WorldWideScience

Sample records for co2 par formation

  1. Novel role for proteinase-activated receptor 2 (PAR2) in membrane trafficking of proteinase-activated receptor 4 (PAR4).

    Science.gov (United States)

    Cunningham, Margaret R; McIntosh, Kathryn A; Pediani, John D; Robben, Joris; Cooke, Alexandra E; Nilsson, Mary; Gould, Gwyn W; Mundell, Stuart; Milligan, Graeme; Plevin, Robin

    2012-05-11

    Proteinase-activated receptors 4 (PAR(4)) is a class A G protein-coupled receptor (GPCR) recognized through the ability of serine proteases such as thrombin and trypsin to mediate receptor activation. Due to the irreversible nature of activation, a fresh supply of receptor is required to be mobilized to the cell surface for responsiveness to agonist to be sustained. Unlike other PAR subtypes, the mechanisms regulating receptor trafficking of PAR(4) remain unknown. Here, we report novel features of the intracellular trafficking of PAR(4) to the plasma membrane. PAR(4) was poorly expressed at the plasma membrane and largely retained in the endoplasmic reticulum (ER) in a complex with the COPI protein subunit β-COP1. Analysis of the PAR(4) protein sequence identified an arginine-based (RXR) ER retention sequence located within intracellular loop-2 (R(183)AR → A(183)AA), mutation of which allowed efficient membrane delivery of PAR(4). Interestingly, co-expression with PAR(2) facilitated plasma membrane delivery of PAR(4), an effect produced through disruption of β-COP1 binding and facilitation of interaction with the chaperone protein 14-3-3ζ. Intermolecular FRET studies confirmed heterodimerization between PAR(2) and PAR(4). PAR(2) also enhanced glycosylation of PAR(4) and activation of PAR(4) signaling. Our results identify a novel regulatory role for PAR(2) in the anterograde traffic of PAR(4). PAR(2) was shown to both facilitate and abrogate protein interactions with PAR(4), impacting upon receptor localization and cell signal transduction. This work is likely to impact markedly upon the understanding of the receptor pharmacology of PAR(4) in normal physiology and disease.

  2. Catholyte-Free Electrocatalytic CO2 Reduction to Formate.

    Science.gov (United States)

    Lee, Wonhee; Kim, Young Eun; Youn, Min Hye; Jeong, Soon Kwan; Park, Ki Tae

    2018-04-16

    Electrochemical reduction of carbon dioxide (CO 2 ) into value-added chemicals is a promising strategy to reduce CO 2 emission and mitigate climate change. One of the most serious problems in electrocatalytic CO 2 reduction (CO 2 R) is the low solubility of CO 2 in an aqueous electrolyte, which significantly limits the cathodic reaction rate. This paper proposes a facile method of catholyte-free electrocatalytic CO 2 reduction to avoid the solubility limitation using commercial tin nanoparticles as a cathode catalyst. Interestingly, as the reaction temperature rises from 303 K to 363 K, the partial current density (PCD) of formate improves more than two times with 52.9 mA cm -2 , despite the decrease in CO 2 solubility. Furthermore, a significantly high formate concentration of 41.5 g L -1 is obtained as a one-path product at 343 K with high PCD (51.7 mA cm -2 ) and high Faradaic efficiency (93.3 %) via continuous operation in a full flow cell at a low cell voltage of 2.2 V. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Modeling of fate and transport of co-injection of H2S with CO2 in deep saline formations

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, W.; Xu, T.; Li, Y.

    2010-12-15

    The geological storage of CO{sub 2} in deep saline formations is increasing seen as a viable strategy to reduce the release of greenhouse gases into the atmosphere. However, costs of capture and compression of CO{sub 2} from industrial waste streams containing small quantities of sulfur and nitrogen compounds such as SO{sub 2}, H{sub 2}S and N{sub 2} are very expensive. Therefore, studies on the co-injection of CO{sub 2} containing other acid gases from industrial emissions are very important. In this paper, numerical simulations were performed to study the co-injection of H{sub 2}S with CO{sub 2} in sandstone and carbonate formations. Results indicate that the preferential dissolution of H{sub 2}S gas (compared with CO{sub 2} gas) into formation water results in the delayed breakthrough of H{sub 2}S gas. Co-injection of H{sub 2}S results in the precipitation of pyrite through interactions between the dissolved H{sub 2}S and Fe{sup 2+} from the dissolution of Fe-bearing minerals. Additional injection of H{sub 2}S reduces the capabilities for solubility and mineral trappings of CO{sub 2} compared to the CO{sub 2} only case. In comparison to the sandstone (siliciclastic) formation, the carbonate formation is less favorable to the mineral sequestration of CO{sub 2}. Different from CO{sub 2} mineral trapping, the presence of Fe-bearing siliciclastic and/or carbonate is more favorable to the H{sub 2}S mineral trapping.

  4. Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

    Science.gov (United States)

    Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

    2017-09-19

    As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

  5. CO2 sequestration using principles of shell formation

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Seung-Woo; Jang, Young-Nam [CO2 Sequestration Research Department, Korea Institute of Geoscience and Mineral Resources (Korea, Republic of); Lee, Si-Hyun; Lim, Kyoung-Soo; Jeong, Soon-Kwan [Energy Conservation Research Department of Clean Energy System Research Center, Korea Institute of Energy Research (Korea, Republic of)

    2011-06-15

    The biomimetic sequestration of carbon dioxide to reduce the CO2 emitted into the atmosphere is introduced in this paper. Bivalve shells are used as a good model of CO2 sequestration in this paper, because the shell is derived from the calcium ions and CO2 in seawater. Carbonic anhydrase, hemocyte from diseased shell (HDS) and extrapallial fluid (EFP) are involved in shell formation. This paper compares the soluble protein extracted from Crassostrea gigas with bovine carbonic anhydrase II in terms of their ability to promote CO2 hydration and the production of calcium precipitates. The result demonstrates that HDS has more functional groups to bind calcium ions in aqueous systems, and a different process of calcium precipitation, than does bovine carbonic anhydrase II. To understand molecular weight and secondary protein structure, mass-spectroscopic analysis (MALDI-TOF) and circular dichroism (CD) analysis were used. With regard to EPF, EPF related to shell formation is composed of several fractions and plays a role in sequestration of CO2.

  6. Formation of Co2P in the combustion regime

    International Nuclear Information System (INIS)

    Muchaik, S.V.; Dubrov, A.N.; Lynchak, K.A.

    1983-01-01

    Combustion of the system Co-P produces the compounds Co 2 P, CoP and CoP 3 , the first two being producible in the combustion regime, while for synthesis of stoichiometric Co 2 P at normal argon pressure, an original mixture with a certain excess of phosphorus is required. The present experiments were performed with electrolytic cobalt powder and red phosphorus. As the Co-P mixture is diluted by the final product (Co 2 P) there is a decrease in combustion temperature and rate, unaccompanied by any of the anomalies seen with dilution by cobalt. It can be suggested that although the combustion in the Co-P system and, possibly, i-- other phosphide systems, is not gasless in its kinetic aspects the combustion mechanism is similar to that in gasless systems. It is shown that formation of the phosphide Co=3''P and specimens wyth composition Co-Co 2 P in the combustion regime occurs with participation of a lIqui] phase of eutectic composition. Combustion occurs in a self-oscillating regime. The temperature for Co 2 P formation is close to its melting point, and the process activation energy comprises 205 kJ/mole

  7. Enthalpies of formation of selected Co{sub 2}YZ Heusler compounds

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Ming, E-mail: myin1@hawk.iit.edu; Chen, Song; Nash, Philip

    2013-11-15

    Highlights: •Enthalpies of formation of selected Co{sub 2}YZ were measured by drop calorimeters. •Enthalpy decreases as the Z element approaches the top right corner of the periodic table. •For the Y element, enthalpy increases on increasing the number of d electrons. •Result of L2{sub 1} structured compounds agrees with first principles data. •Lattice parameters and related phase relationships were consistent with literature data. -- Abstract: Standard enthalpies of formation at 298 K of selected ternary Co{sub 2}-based Heusler compounds Co{sub 2}YZ (Y = Fe, Hf, Mn, Ti, V, Zr; Z = Al, Ga, In, Si, Ge, Sn) were measured by high temperature direct synthesis calorimetry. The measured enthalpies of formation (in kJ/mole of atoms) of the L2{sub 1} compounds are: Co{sub 2}FeGa (−25.8 ± 2.6); Co{sub 2}FeSi (−38.4 ± 2.2); Co{sub 2}FeGe (−11.6 ± 2.1); Co{sub 2}MnGa (−30.1 ± 2.3); Co{sub 2}MnSi (−42.4 ± 1.2); Co{sub 2}MnGe (−31.6 ± 3.0); Co{sub 2}MnSn (−15.6 ± 2.8); Co{sub 2}TiAl (−55.0 ± 3.7); Co{sub 2}TiGa (−54.2 ± 2.6); Co{sub 2}TiSi (−61.4 ± 1.7); Co{sub 2}TiGe (−59.3 ± 3.8); Co{sub 2}TiSn (−38.4 ± 2.0); Co{sub 2}VGa (−28.4 ± 1.1) and for the B2 compounds: Co{sub 2}FeAl (−22.5 ± 2.5), Co{sub 2}MnAl (−27.6 ± 2.7). Values are compared with those from first principles calculation when available and the extended semi-empirical model of Miedema. Trends in enthalpy of formation with element atomic number are discussed. Lattice parameters of the compounds with L2{sub 1} structure are determined by X-ray diffraction analysis.

  8. Complex Formation in a Liquid-Liquid Extraction System Containing Cobalt(II), 4-(2-Pyridylazo)resorcinol, and Nitron

    OpenAIRE

    Racheva, Petya Vassileva; Gavazov, Kiril Blazhev; Lekova, Vanya Dimitrova; Dimitrov, Atanas Nikolov

    2013-01-01

    Complex formation and liquid-liquid extraction were studied in a system containing cobalt(II), 4-(2-pyridylazo)resorcinol (PAR), 1,4-diphenyl-3-(phenylamino)-1H-1,2,4-triazole (Nitron, Nt), water, and chloroform. The effect of some experimental parameters (pH, shaking time, concentration of PAR, and concentration of Nt) was systematically investigated, and the optimum conditions for cobalt extraction as an ion-association complex, (NtH+)[Co3+(PAR)2], were found. The following key equilibrium ...

  9. Formation and decomposition of siderite for CO2 treatment

    Science.gov (United States)

    Y Mora, E.; Sarmiento, A.; Vera, E.; Drozd, V.; Durigyn, A.; Saxena, S.

    2017-12-01

    In this research work, we studied the conditions for formation and decomposition of siderite FeCO3 from hematite Fe2O3 along with carbon dioxide CO2 at suitable thermodynamic conditions. As reductant agents were used mixtures of two elements, metallic iron and graphite. Best levels of carbonation were found in mixtures with bigger amounts of metallic iron. It was demonstrated that CO2 capture capacity by hematite depends of temperature, CO2 pressure, and reaction time. Temperatures between 100 and 150°C, pressures between 10 and 30bar and reaction times between 1 and 4h were adjusted for analyse the carbonation behaviour; siderite formation was improved by increases of these three variables. There was no carbonation without water in the mixtures, due to kinetic limitations. CO2 capture capacity was calculated from Rietveld refinement results. Using vacuum system and Dielectric Barrier Discharge, DBD plasma, the siderite was decomposed at 300°C, and 320°C respectively. Techniques as X-ray diffraction, and surface area analysis were employed to study the material.

  10. Martian Gullies: Formation by CO2 Fluidification

    Science.gov (United States)

    Cedillo-Flores, Y.; Durand-Manterola, H. J.

    2006-12-01

    Some of the geomorphological features in Mars are the gullies. Some theories developed tried explain its origin, either by liquid water, liquid carbon dioxide or flows of dry granular material. We made a comparative analysis of the Martian gullies with the terrestrial ones. We propose that the mechanism of formation of the gullies is as follows: In winter CO2 snow mixed with sand falls in the terrain. In spring the CO2 snow sublimate and gaseous CO2 make fluid the sand which flows like liquid eroding the terrain and forming the gullies. By experimental work with dry granular material, we simulated the development of the Martian gullies injecting air in the granular material. We present the characteristics of some terrestrial gullies forms at cold environment, sited at Nevado de Toluca Volcano near Toluca City, México. We compare them with Martian gullies choose from four different areas, to target goal recognize or to distinguish, (to identify) possible processes evolved in its formation. Also, we measured the lengths of those Martian gullies and the range was from 24 m to 1775 meters. Finally, we present results of our experimental work at laboratory with dry granular material.

  11. A Biomimetic Nickel Complex with a Reduced CO2 Ligand Generated by Formate Deprotonation and its Behaviour towards CO2.

    Science.gov (United States)

    Limberg, Christian; Zimmermann, Philipp; Hoof, Santina; Braun-Cula, Beatrice; Herwig, Christian

    2018-04-10

    Reduced CO2 species are key intermediates in a variety of natural and synthetic processes. In the majority of systems, however, they elude isolation or characterisation due to high reactivity or limited accessibility (heterogeneous systems) and thus formulations often remain uncertain or based on calculations only. We herein report on a Ni-CO22- complex that is unique in many ways. While its structural and electronic features help understanding the CO2 bound state in Ni,Fe carbon monoxide dehydrogenases, its reactivity sheds light on how CO2 can be converted into CO/CO32- by nickel complexes. In addition, the complex has been generated via a rare example of formate β deprotonation, a mechanistical step relevant to nickel catalysed conversion of HxCOyz- at electrodes and formate oxidation in formate dehydrogenases. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Subtask 2.17 - CO2 Storage Efficiency in Deep Saline Formations

    Energy Technology Data Exchange (ETDEWEB)

    Gorecki, Charles D. [Univ. of North Dakota, Grand Forks, ND (United States); Liu, Guoxiang [Univ. of North Dakota, Grand Forks, ND (United States); Braunberger, Jason R. [Univ. of North Dakota, Grand Forks, ND (United States); Klenner, Robert C. L. [Univ. of North Dakota, Grand Forks, ND (United States); Ayash, Scott C. [Univ. of North Dakota, Grand Forks, ND (United States); Dotzenrod, Neil W. [Univ. of North Dakota, Grand Forks, ND (United States); Steadman, Edward N. [Univ. of North Dakota, Grand Forks, ND (United States); Harju, John A. [Univ. of North Dakota, Grand Forks, ND (United States)

    2014-02-01

    As the field of carbon capture and storage (CCS) continues to advance, and large-scale implementation of geologic carbon dioxide (CO2) storage progresses, it will be important to understand the potential of geologic formations to store meaningful amounts of CO2. Geologic CO2 storage in deep saline formations (DSFs) has been suggested as one of the best potential methods for reducing anthropogenic CO2 emission to the atmosphere, and as such, updated storage resource estimation methods will continue to be an important component for the widespread deployment of CCS around the world. While there have been several methodologies suggested in the literature, most of these methods are based on a volumetric calculation of the pore volume of the DSF multiplied by a storage efficiency term and do not consider the effect of site-specific dynamic factors such as injection rate, injection pattern, timing of injection, pressure interference between injection locations, and overall formation pressure buildup. These volumetric methods may be excellent for comparing the potential between particular formations or basins, but they have not been validated through real-world experience or full-formation injection simulations. Several studies have also suggested that the dynamic components of geologic storage may play the most important role in storing CO2 in DSFs but until now have not directly compared CO2 storage resource estimates made with volumetric methodologies to estimates made using dynamic CO2 storage methodologies. In this study, two DSFs, in geographically separate areas with geologically diverse properties, were evaluated with both volumetric and dynamic CO2 storage resource estimation methodologies to compare the results and determine the applicability of both approaches. In the end, it was determined that the dynamic CO2 storage resource potential is timedependent and it

  13. ON THE FORMATION OF CO2 AND OTHER INTERSTELLAR ICES

    International Nuclear Information System (INIS)

    Garrod, R. T.; Pauly, T.

    2011-01-01

    We investigate the formation and evolution of interstellar dust-grain ices under dark-cloud conditions, with a particular emphasis on CO 2 . We use a three-phase model (gas/surface/mantle) to simulate the coupled gas-grain chemistry, allowing the distinction of the chemically active surface from the ice layers preserved in the mantle beneath. The model includes a treatment of the competition between barrier-mediated surface reactions and thermal-hopping processes. The results show excellent agreement with the observed behavior of CO 2 , CO, and water ice in the interstellar medium. The reaction of the OH radical with CO is found to be efficient enough to account for CO 2 ice production in dark clouds. At low visual extinctions, with dust temperatures ∼>12 K, CO 2 is formed by direct diffusion and reaction of CO with OH; we associate the resultant CO 2 -rich ice with the observational polar CO 2 signature. CH 4 ice is well correlated with this component. At higher extinctions, with lower dust temperatures, CO is relatively immobile and thus abundant; however, the reaction of H and O atop a CO molecule allows OH and CO to meet rapidly enough to produce a CO:CO 2 ratio in the range ∼2-4, which we associate with apolar signatures. We suggest that the observational apolar CO 2 /CO ice signatures in dark clouds result from a strongly segregated CO:H 2 O ice, in which CO 2 resides almost exclusively within the CO component. Observed visual-extinction thresholds for CO 2 , CO, and H 2 O are well reproduced by depth-dependent models. Methanol formation is found to be strongly sensitive to dynamical timescales and dust temperatures.

  14. Effect of high temperature deposition on CoSi2 phase formation

    International Nuclear Information System (INIS)

    Comrie, C. M.; Ahmed, H.; Smeets, D.; Demeulemeester, J.; Vantomme, A.; Turner, S.; Van Tendeloo, G.; Detavernier, C.

    2013-01-01

    This paper discusses the nucleation behaviour of the CoSi to CoSi 2 transformation from cobalt silicide thin films grown by deposition at elevated substrate temperatures ranging from 375 °C to 600 °C. A combination of channelling, real-time Rutherford backscattering spectrometry, real-time x-ray diffraction, and transmission electron microscopy was used to investigate the effect of the deposition temperature on the subsequent formation temperature of CoSi 2 , its growth behaviour, and the epitaxial quality of the CoSi 2 thus formed. The temperature at which deposition took place was observed to exert a significant and systematic influence on both the formation temperature of CoSi 2 and its growth mechanism. CoSi films grown at the lowest temperatures were found to increase the CoSi 2 nucleation temperature above that of CoSi 2 grown by conventional solid phase reaction, whereas the higher deposition temperatures reduced the nucleation temperature significantly. In addition, a systematic change in growth mechanism of the subsequent CoSi 2 growth occurs as a function of deposition temperature. First, the CoSi 2 growth rate from films grown at the lower reactive deposition temperatures is substantially lower than that grown at higher reactive deposition temperatures, even though the onset of growth occurs at a higher temperature, Second, for deposition temperatures below 450 °C, the growth appears columnar, indicating nucleation controlled growth. Elevated deposition temperatures, on the other hand, render the CoSi 2 formation process layer-by-layer which indicates enhanced nucleation of the CoSi 2 and diffusion controlled growth. Our results further indicate that this observed trend is most likely related to stress and changes in microstructure introduced during reactive deposition of the CoSi film. The deposition temperature therefore provides a handle to tune the CoSi 2 growth mechanism.

  15. Protease-activated receptor (PAR2, but not PAR1, is involved in collateral formation and anti-inflammatory monocyte polarization in a mouse hind limb ischemia model.

    Directory of Open Access Journals (Sweden)

    Lisa G van den Hengel

    Full Text Available AIMS: In collateral development (i.e. arteriogenesis, mononuclear cells are important and exist as a heterogeneous population consisting of pro-inflammatory and anti-inflammatory/repair-associated cells. Protease-activated receptor (PAR1 and PAR2 are G-protein-coupled receptors that are both expressed by mononuclear cells and are involved in pro-inflammatory reactions, while PAR2 also plays a role in repair-associated responses. Here, we investigated the physiological role of PAR1 and PAR2 in arteriogenesis in a murine hind limb ischemia model. METHODS AND RESULTS: PAR1-deficient (PAR1-/-, PAR2-deficient (PAR2-/- and wild-type (WT mice underwent femoral artery ligation. Laser Doppler measurements revealed reduced post-ischemic blood flow recovery in PAR2-/- hind limbs when compared to WT, while PAR1-/- mice were not affected. Upon ischemia, reduced numbers of smooth muscle actin (SMA-positive collaterals and CD31-positive capillaries were found in PAR2-/- mice when compared to WT mice, whereas these parameters in PAR1-/- mice did not differ from WT mice. The pool of circulating repair-associated (Ly6C-low monocytes and the number of repair-associated (CD206-positive macrophages surrounding collaterals in the hind limbs were increased in WT and PAR1-/- mice, but unaffected in PAR2-/- mice. The number of repair-associated macrophages in PAR2-/- hind limbs correlated with CD11b- and CD115-expression on the circulating monocytes in these animals, suggesting that monocyte extravasation and M-CSF-dependent differentiation into repair-associated cells are hampered. CONCLUSION: PAR2, but not PAR1, is involved in arteriogenesis and promotes the repair-associated response in ischemic tissues. Therefore, PAR2 potentially forms a new pro-arteriogenic target in coronary artery disease (CAD patients.

  16. Optimizing geologic CO2 sequestration by injection in deep saline formations below oil reservoirs

    International Nuclear Information System (INIS)

    Han, Weon Shik; McPherson, Brian J.

    2009-01-01

    The purpose of this research is to present a best-case paradigm for geologic CO 2 storage: CO 2 injection and sequestration in saline formations below oil reservoirs. This includes the saline-only section below the oil-water contact (OWC) in oil reservoirs, a storage target neglected in many current storage capacity assessments. This also includes saline aquifers (high porosity and permeability formations) immediately below oil-bearing formations. While this is a very specific injection target, we contend that most, if not all, oil-bearing basins in the US contain a great volume of such strata, and represent a rather large CO 2 storage capacity option. We hypothesize that these are the best storage targets in those basins. The purpose of this research is to evaluate this hypothesis. We quantitatively compared CO 2 behavior in oil reservoirs and brine formations by examining the thermophysical properties of CO 2 , CO 2 -brine, and CO 2 -oil in various pressure, temperature, and salinity conditions. In addition, we compared the distribution of gravity number (N), which characterizes a tendency towards buoyancy-driven CO 2 migration, and mobility ratio (M), which characterizes the impeded CO 2 migration, in oil reservoirs and brine formations. Our research suggests competing advantages and disadvantages of CO 2 injection in oil reservoirs vs. brine formations: (1) CO 2 solubility in oil is significantly greater than in brine (over 30 times); (2) the tendency of buoyancy-driven CO 2 migration is smaller in oil reservoirs because density contrast between oil and CO 2 is smaller than it between brine and oil (the approximate density contrast between CO 2 and crude oil is ∼100 kg/m 3 and between CO 2 and brine is ∼350 kg/m 3 ); (3) the increased density of oil and brine due to the CO 2 dissolution is not significant (about 7-15 kg/m 3 ); (4) the viscosity reduction of oil due to CO 2 dissolution is significant (from 5790 to 98 mPa s). We compared these competing

  17. Carbon Disulfide (CS2) Mechanisms in Formation of Atmospheric Carbon Dioxide (CO2) Formation from Unconventional Shale Gas Extraction and Processing Operations and Global Climate Change.

    Science.gov (United States)

    Rich, Alisa L; Patel, Jay T

    2015-01-01

    Carbon disulfide (CS2) has been historically associated with the production of rayon, cellophane, and carbon tetrachloride. This study identifies multiple mechanisms by which CS2 contributes to the formation of CO2 in the atmosphere. CS2 and other associated sulfide compounds were found by this study to be present in emissions from unconventional shale gas extraction and processing (E&P) operations. The breakdown products of CS2; carbonyl sulfide (COS), carbon monoxide (CO), and sulfur dioxide (SO2) are indirect greenhouse gases (GHGs) that contribute to CO2 levels in the atmosphere. The heat-trapping nature of CO2 has been found to increase the surface temperature, resulting in regional and global climate change. The purpose of this study is to identify five mechanisms by which CS2 and the breakdown products of CS2 contribute to atmospheric concentrations of CO2. The five mechanisms of CO2 formation are as follows: Chemical Interaction of CS2 and hydrogen sulfide (H2S) present in natural gas at high temperatures, resulting in CO2 formation;Combustion of CS2 in the presence of oxygen producing SO2 and CO2;Photolysis of CS2 leading to the formation of COS, CO, and SO2, which are indirect contributors to CO2 formation;One-step hydrolysis of CS2, producing reactive intermediates and ultimately forming H2S and CO2;Two-step hydrolysis of CS2 forming the reactive COS intermediate that reacts with an additional water molecule, ultimately forming H2S and CO2. CS2 and COS additionally are implicated in the formation of SO2 in the stratosphere and/or troposphere. SO2 is an indirect contributor to CO2 formation and is implicated in global climate change.

  18. Molecular mechanism of bundle formation by the bacterial actin ParM

    Energy Technology Data Exchange (ETDEWEB)

    Popp, David, E-mail: dpopp@imcb.a-star.edu.sg [ERATO ' Actin Filament Dynamics' Project, Japan Science and Technology Corporation, c/o RIKEN Harima Institute at Spring 8, 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Institute of Molecular and Cell Biology, 61 Biopolis Drive, Proteos, 138673 Singapore (Singapore); Narita, Akihiro [ERATO ' Actin Filament Dynamics' Project, Japan Science and Technology Corporation, c/o RIKEN Harima Institute at Spring 8, 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Nagoya University Graduate School of Science, Structural Biology Research Center and Division of Biological Sciences, Furo-cho, Chikusa-ku, Nagoya 464-8601 (Japan); Iwasa, Mitsusada [ERATO ' Actin Filament Dynamics' Project, Japan Science and Technology Corporation, c/o RIKEN Harima Institute at Spring 8, 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Maeda, Yuichiro [ERATO ' Actin Filament Dynamics' Project, Japan Science and Technology Corporation, c/o RIKEN Harima Institute at Spring 8, 1-1-1 Kouto, Sayo, Hyogo 679-5148 (Japan); Nagoya University Graduate School of Science, Structural Biology Research Center and Division of Biological Sciences, Furo-cho, Chikusa-ku, Nagoya 464-8601 (Japan); Robinson, Robert C. [Institute of Molecular and Cell Biology, 61 Biopolis Drive, Proteos, 138673 Singapore (Singapore)

    2010-01-22

    The actin homolog ParM plays a microtubule-like role in segregating DNA prior to bacterial cell division. Fluorescence and cryo-electron microscopy have shown that ParM forms filament bundles between separating DNA plasmids in vivo. Given the lack of ParM bundling proteins it remains unknown how ParM bundles form at the molecular level. Here we show using time-lapse TIRF microscopy, under in vitro molecular crowding conditions, that ParM-bundle formation consists of two distinct phases. At the onset of polymerization bundle thickness and shape are determined in the form of nuclei of short helically disordered filaments arranged in a liquid-like lattice. These nuclei then undergo an elongation phase whereby they rapidly increase in length. At steady state, ParM bundles fuse into one single large aggregate. This behavior had been predicted by theory but has not been observed for any other cytomotive biopolymer, including F-actin. We employed electron micrographs of ParM rafts, which are 2-D analogs of 3-D bundles, to identify the main molecular interfilament contacts within these suprastructures. The interface between filaments is similar for both parallel and anti-parallel orientations and the distribution of filament polarity is random within a bundle. We suggest that the interfilament interactions are not due to the interactions of specific residues but rather to long-range, counter ion mediated, electrostatic attractive forces. A randomly oriented bundle ensures that the assembly is rigid and that DNA may be captured with equal efficiency at both ends of the bundle via the ParR binding protein.

  19. Activated protein C (APC) can increase bone anabolism via a protease-activated receptor (PAR)1/2 dependent mechanism.

    Science.gov (United States)

    Shen, Kaitlin; Murphy, Ciara M; Chan, Ben; Kolind, Mille; Cheng, Tegan L; Mikulec, Kathy; Peacock, Lauren; Xue, Meilang; Park, Sang-Youel; Little, David G; Jackson, Chris J; Schindeler, Aaron

    2014-12-01

    Activated Protein C (APC) is an anticoagulant with strong cytoprotective properties that has been shown to promote wound healing. In this study APC was investigated for its potential orthopedic application using a Bone Morphogenetic Protein 2 (rhBMP-2) induced ectopic bone formation model. Local co-administration of 10 µg rhBMP-2 with 10 µg or 25 µg APC increased bone volume at 3 weeks by 32% (N.S.) and 74% (pAPC are largely mediated by its receptors endothelial protein C receptor (EPCR) and protease-activated receptors (PARs). Cultured pre-osteoblasts and bone nodule tissue sections were shown to express PAR1/2 and EPCR. When pre-osteoblasts were treated with APC, cell viability and phosphorylation of ERK1/2, Akt, and p38 were increased. Inhibition with PAR1 and sometimes PAR2 antagonists, but not with EPCR blocking antibodies, ameliorated the effects of APC on cell viability and kinase phosphorylation. These data indicate that APC can affect osteoblast viability and signaling, and may have in vivo applications with rhBMP-2 for bone repair. © 2014 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

  20. Formation of ternary CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) complexes under neutral to weakly alkaline conditions.

    Science.gov (United States)

    Lee, Jun-Yeop; Yun, Jong-Il

    2013-07-21

    The chemical behavior of ternary Ca-UO2-CO3 complexes was investigated by using time-resolved laser fluorescence spectroscopy (TRLFS) in combination with EDTA complexation at pH 7-9. A novel TRLFS revealed two distinct fluorescence lifetimes of 12.7 ± 0.2 ns and 29.2 ± 0.4 ns for uranyl complexes which were formed increasingly dependent upon the calcium ion concentration, even though nearly indistinguishable fluorescence peak shapes and positions were measured for both Ca-UO2-CO3 complexes. For identifying the stoichiometric number of complexed calcium ions, slope analysis in terms of relative fluorescence intensity versus calcium concentration was employed in a combination with the complexation reaction of CaEDTA(2-) by adding EDTA. The formation of CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) was identified under given conditions and their formation constants were determined at I = 0.1 M Na/HClO4 medium, and extrapolated to infinitely dilute solution using specific ion interaction theory (SIT). As a result, the formation constants for CaUO2(CO3)3(2-) and Ca2UO2(CO3)3(aq) were found to be log β113(0) = 27.27 ± 0.14 and log β213(0) = 29.81 ± 0.19, respectively, providing that the ternary Ca-UO2-CO3 complexes were predominant uranium(vi) species at neutral to weakly alkaline pH in the presence of Ca(2+) and CO3(2-) ions.

  1. Dense CO2 as a Solute, Co-Solute or Co-Solvent in Particle Formation Processes: A Review

    Directory of Open Access Journals (Sweden)

    Ana V. M. Nunes

    2011-11-01

    Full Text Available The application of dense gases in particle formation processes has attracted great attention due to documented advantages over conventional technologies. In particular, the use of dense CO2 in the process has been subject of many works and explored in a variety of different techniques. This article presents a review of the current available techniques in use in particle formation processes, focusing exclusively on those employing dense CO2 as a solute, co-solute or co-solvent during the process, such as PGSS (Particles from gas-saturated solutions®, CPF (Concentrated Powder Form®, CPCSP (Continuous Powder Coating Spraying Process, CAN-BD (Carbon dioxide Assisted Nebulization with a Bubble Dryer®, SEA (Supercritical Enhanced Atomization, SAA (Supercritical Fluid-Assisted Atomization, PGSS-Drying and DELOS (Depressurization of an Expanded Liquid Organic Solution. Special emphasis is given to modifications introduced in the different techniques, as well as the limitations that have been overcome.

  2. Methane production from formate, acetate and H2/CO2; focusing on kinetics and microbial characterization

    DEFF Research Database (Denmark)

    Pan, Xiaofang; Angelidaki, Irini; Alvarado-Morales, Merlin

    2016-01-01

    For evaluating the methanogenesis from typical methanogenic precursors (formate, acetate and H-2/CO2), CH4 production kinetics were investigated at 37 +/- 1 degrees C in batch anaerobic digestion tests and stimulated by modified Gompertz model. The results showed that maximum methanation rate from...... formate, acetate and H-2/CO2 were 19.58 +/- 0.49, 42.65 +/- 1.17 and 314.64 +/- 3.58 N mL/gVS/d in digested manure system and 6.53 +/- 0.31, 132.04 +/- 3.96 and 640.16 +/- 19.92 N mL/gVS/d in sewage sludge system during second generation incubation. Meanwhile the model could not fit well in granular...... sludge system, while the rate of formate methanation was faster than from H-2/CO2 and acetate. Considering both the kinetic results and microbial assay we could conclude that H-2/CO2 methanation was the fastest methanogenic step in digested manure and sewage sludge system with Methanomicrobiales...

  3. Geological Sequestration of CO2 by Hydrous Carbonate Formation with Reclaimed Slag

    Energy Technology Data Exchange (ETDEWEB)

    Von L. Richards; Kent Peaslee; Jeffrey Smith

    2008-02-06

    The concept of this project is to develop a process that improves the kinetics of the hydrous carbonate formation reaction enabling steelmakers to directly remove CO2 from their furnace exhaust gas. It is proposed to bring the furnace exhaust stream containing CO2 in contact with reclaimed steelmaking slag in a reactor that has an environment near the unit activity of water resulting in the production of carbonates. The CO2 emissions from the plant would be reduced by the amount sequestered in the formation of carbonates. The main raw materials for the process are furnace exhaust gases and specially prepared slag.

  4. Measuring permanence of CO2 storage in saline formations: The Frio experiment

    Science.gov (United States)

    Hovorka, Susan D.; Benson, Sally M.; Doughty, Christine; Freifeild, Barry M.; Sakurai, Shinichi; Daley, Thomas M.; Kharaka, Yousif K.; Holtz, Mark H.; Trautz, Robert C.; Nance, H. Seay; Myer, Larry R.; Knauss, Kevin G.

    2006-01-01

    If CO2 released from fossil fuel during energy production is returned to the subsurface, will it be retained for periods of time significant enough to benefit the atmosphere? Can trapping be assured in saline formations where there is no history of hydrocarbon accumulation? The Frio experiment in Texas was undertaken to provide answers to these questions.One thousand six hundred metric tons of CO2 were injected into the Frio Formation, which underlies large areas of the United States Gulf Coast. Reservoir characterization and numerical modeling were used to design the experiment, as well as to interpret the results through history matching. Closely spaced measurements in space and time were collected to observe the evolution of immiscible and dissolved CO2 during and after injection. The high-permeability, steeply dipping sandstone allowed updip flow of supercritical CO2 as a result of the density contrast with formation brine and absence of a local structural trap.The front of the CO2 plume moved more quickly than had been modeled. By the end of the 10-day injection, however, the plume geometry in the plane of the observation and injection wells had thickened to a distribution similar to the modeled distribution. As expected, CO2 dissolved rapidly into brine, causing pH to fall and calcite and metals to be dissolved.Postinjection measurements, including time-lapse vertical seismic profiling transects along selected azimuths, cross-well seismic topography, and saturation logs, show that CO2 migration under gravity slowed greatly 2 months after injection, matching model predictions that significant CO2 is trapped as relative permeability decreases.

  5. CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane.

    Science.gov (United States)

    Khadka, Nimesh; Dean, Dennis R; Smith, Dayle; Hoffman, Brian M; Raugei, Simone; Seefeldt, Lance C

    2016-09-06

    The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild-type nitrogenase and a nitrogenase with amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by two or eight electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it is demonstrated that nitrogenase preferentially reduces CO2 by two electrons/protons to formate (HCOO(-)) at rates >10 times higher than rates of CO2 reduction to CO and CH4. Quantum mechanical calculations on the doubly reduced FeMo-cofactor with a Fe-bound hydride and S-bound proton (E2(2H) state) favor a direct reaction of CO2 with the hydride ("direct hydride transfer" reaction pathway), with facile hydride transfer to CO2 yielding formate. In contrast, a significant barrier is observed for reaction of Fe-bound CO2 with the hydride ("associative" reaction pathway), which leads to CO and CH4. Remarkably, in the direct hydride transfer pathway, the Fe-H behaves as a hydridic hydrogen, whereas in the associative pathway it acts as a protic hydrogen. MoFe proteins with amino acid substitutions near FeMo-cofactor (α-70(Val→Ala), α-195(His→Gln)) are found to significantly alter the distribution of products between formate and CO/CH4.

  6. Favourable Formations for CO{sub 2} Storage in the Almazan Basin; Formaciones Favorables para el Almacenamiento de CO{sub 2} en la Cuenca de Almazan

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz Rivas, C.; Lomba Falcon, L.

    2008-04-10

    Geological storage of carbon dioxide is one of the technological options that have been considered nowadays for global climate change mitigation. Underground CO{sub 2} storage requires the selection and identification of deep geological formations which must meet criteria for health and environmental safety in the middle-term of one thousand years. Deep permeable formations, depleted oil and gas fields, unminable coal seams and saline rocks are possible geological formations for CO{sub 2} storage. Some areas in our country have been selected to search potential CO{sub 2} reservoirs. Among these areas, sedimentary basins are highlighted because of their thick stratigraphic sequences and the availability of extensive geological data which are coming from fossil fuel exploration. In this report, the identification and selection of favourable geological formations in the Almazan basin is presented. A 3D simplified subsurface basin geological model that was based on a Geographic Information System is included as well. The report also includes suitable CO{sub 2} injection areas in the surface for the selected geological formations. Finally, a preliminary CO{sub 2} storage capacity estimation of a potential structural trap has been calculated, considering only physical CO{sub 2} trapping. This work has been undertaken in the framework of the Geological CO{sub 2} Storage Project which is within the Singular Strategic Project of the Ministry of Education and Science Generation, Capture and Storage advanced technologies of CO{sub 2}. (Author) 84 refs.

  7. Le coût par QALY rapporté au PIB (CQP): suggestion d'un nouvel ...

    African Journals Online (AJOL)

    Le coût par QALY rapporté au PIB (CQP): suggestion d'un nouvel indice économique évaluant l'impact réel du coût du bénéfice des molécules onéreuses en oncologie par rapport aux moyens économique d'un pays.

  8. Underground CO{sub 2} Storage: Approach for Favourable Formations in Ebro Basin; AGP de CO{sub 2}: Seleccion de Formaciones Favorables en la Cuenca del Ebro

    Energy Technology Data Exchange (ETDEWEB)

    Campos, R.; Perucha, A.; Recreo, F.

    2008-04-10

    The study of the possibilities of conducting Deep Geological CO{sub 2} Storage inside Spanish territory is being performed through the Strategic Singular Project PS-120000-2005-2 of the National Program of Energy from the Education and Science Ministry, and called CO{sub 2} generation, sequestration and storage advanced technologies, sub project N3 CO{sub 2} Geological Storage This report studies the possibilities the Ebro basin offers for definitive CO{sub 2} storage as one of the Spanish selected areas from previous studies. The study and reinterpretation of the information obtained from the hydrocarbon exploration accomplished in the area has lead to the selection of a series of geological formations. These formations have been chosen attending certain characteristics such as their disposition, extension, depth and porosity. The study has also been conducted considering the characteristics of the geological formations above the CO{sub 2} storage formations so as to guarantee the sealing of the storage. The study includes the approximate estimation of the storage capacity for each of the formations in Megatons of CO{sub 2}, which can be useful in future decision making. Deep geological storage is one of the more relevant international initiatives in order to eliminate or reduce the anthropogenic CO{sub 2} emissions to the atmosphere. (Author) 68 refs.

  9. Ultrathin Co3O4 Layers Realizing Optimized CO2 Electroreduction to Formate.

    Science.gov (United States)

    Gao, Shan; Jiao, Xingchen; Sun, Zhongti; Zhang, Wenhua; Sun, Yongfu; Wang, Chengming; Hu, Qitao; Zu, Xiaolong; Yang, Fan; Yang, Shuyang; Liang, Liang; Wu, Ju; Xie, Yi

    2016-01-11

    Electroreduction of CO2 into hydrocarbons could contribute to alleviating energy crisis and global warming. However, conventional electrocatalysts usually suffer from low energetic efficiency and poor durability. Herein, atomic layers for transition-metal oxides are proposed to address these problems through offering an ultralarge fraction of active sites, high electronic conductivity, and superior structural stability. As a prototype, 1.72 and 3.51 nm thick Co3O4 layers were synthesized through a fast-heating strategy. The atomic thickness endowed Co3O4 with abundant active sites, ensuring a large CO2 adsorption amount. The increased and more dispersed charge density near Fermi level allowed for enhanced electronic conductivity. The 1.72 nm thick Co3O4 layers showed over 1.5 and 20 times higher electrocatalytic activity than 3.51 nm thick Co3O4 layers and bulk counterpart, respectively. Also, 1.72 nm thick Co3O4 layers showed formate Faradaic efficiency of over 60% in 20 h. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. The formation mechanism of a textured ceramic of thermoelectric [Ca2CoO3](0.62)[CoO2] on beta-Co(OH)2 templates through in situ topotactic conversion.

    Science.gov (United States)

    Itahara, Hiroshi; Seo, Won-Seon; Lee, Sujeong; Nozaki, Hiroshi; Tani, Toshihiko; Koumoto, Kunihito

    2005-05-04

    We investigated the formation mechanism of thermoelectric [Ca(2)CoO(3)](0.62)[CoO(2)] (CCO) on beta-Co(OH)(2) templates with maintained orientations by identifying the intermediate phases and specifying the relationship between their crystallographic orientations. We mixed beta-Co(OH)(2) templates with the complementary reactant CaCO(3) and prepared a compact by tape casting, with the developed (001) plane of the templates aligned along the casting plane. High-temperature XRD of the compact revealed that beta-Co(OH)(2) decomposed into Co(3)O(4) by 873 K, and Co(3)O(4) reacted with CaO to form CCO by 1193 K via the formation of the newly detected intermediate phase beta-Na(x)()CoO(2)-type Ca(x)()CoO(2) at 913-973 K. Pole figure measurements and SEM and TEM observations revealed that the relationship between the crystallographic planes was (001) beta-Co(OH)(2)//{111} Co(3)O(4)//(001) Ca(x)()CoO(2)//(001) CCO. The crystal structures of the four materials possess the common CoO(2) layer (or similar), which is composed of edge-sharing CoO(6) octahedra, parallel to the planes. The cross-sectional HRTEM analysis of an incompletely reacted specimen showed transient lattice images from Ca(x)()CoO(2) into CCO, in which every other CoO(2) layer of Ca(x)()CoO(2) was preserved. Thus, it was demonstrated that a textured CCO ceramic is produced through a series of in situ topotactic conversion reactions with a preserved CoO(2) layer of its template.

  11. Preliminary Study of Favourable Formations for CO2 Subsurface Storage in Spain

    International Nuclear Information System (INIS)

    Zapatero, M. A.; Reyes, J. L.; Martinez, R.; Suarez, I.; Arenillas, A.; Perucha, M. A.

    2009-01-01

    This report is a synthesis of the possibilities of CO 2 storage in the Spanish subsurface. Compilation and analysis of geological information has been carried out, looking at surface and subsurface, in order to make a pre-selection of potential favourable units for CO 2 storage, taking in account that each of this storages needs a confining formation to seal the storage. Before the storage selection, a general description of the great geological units of the Iberian Peninsula is done. Afterwards, borehole logging from petroleum exploration is analysed in these units, formations and areas of interest. The aim is to finally obtain a description of selected units and their possibilities of CO 2 storage. (Author) 17 refs

  12. Pre injection characterisation and evaluation of CO{sub 2} sequestration potential in the Haizume formation, Niigata basin, Japan; Caracterisation avant injection et evaluation du potentiel de sequestration de CO{sub 2} dans la formation de Haizume, bassin de Niigata, Japon. Modelisation geochimique des interactions eau-mineraux-CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Zwingmann, N. [CSIRO Petroleum, ARRC, Bentley, WA (Australia); Mito, S.; Sorai, M.; Ohsumi, T. [RITE, Kyoto (Japan); Zwingmann, N. [Western, Univ. (Australia); Sorai, M. [Mitsubishi Research Institute, Inc. (Japan)

    2005-03-15

    The Research Institute of Innovative Technology for the Earth (RITE) is carrying out a small-scale CO{sub 2} injection field experiment to investigate the feasibility of geological sequestration of CO{sub 2} greenhouse gas in the south-west of Nagaoka City, Niigata Prefecture, Japan. Prior to the injection geochemical reactions caused by CO{sub 2} injections were investigated using the geochemical modelling code (EQ3/6). The injection formation is the sedimentary marine Haizume Formation (Pleistocene) in the Uonuma Group, which is covered by a mud-stone seal. The formation is mainly composed of quartz, plagioclase, feldspar, pyroxene, and clays (smectite, chlorite). The sandstone shows minor consolidation and grain size is medium to coarse sand. The total dissolved solid (TDS) of the formation water is approximately 6100 mg/l and the water contains a high Ca{sup 2+} ({>=} 20% of Na{sup +} concentration). The geochemical model was used for an initial adjustment of the formation water chemistry to the formation conditions and a modelling of the formation water-mineral-CO{sub 2} reactions. The modelling results showed a high reactivity of the minerals in the CO{sub 2} rich environment and high mineral conversion rate within the formation. At the final state, approximately 23 mol of CO{sub 2} were taken into 1 kg of formation water and more than 90% of this was stored within carbonate minerals. In this simulation, some uncertainty is associated with the time scale and a more detailed investigation is planned and will address accurate evaluation. (authors)

  13. C60-pentacene network formation by 2-D co-crystallization.

    Science.gov (United States)

    Jin, Wei; Dougherty, Daniel B; Cullen, William G; Robey, Steven; Reutt-Robey, Janice E

    2009-09-01

    We report experiments highlighting the mechanistic role of mobile pentacene precursors in the formation of a network C(60)-pentacene co-crystalline structure on Ag(111). This co-crystalline arrangement was first observed by low temperature scanning tunneling microscopy (STM) by Zhang et al. (Zhang, H. L.; Chen, W.; Huang, H.; Chen, L.; Wee, A. T. S. J. Am. Chem. Soc. 2008, 130, 2720-2721). We now show that this structure forms readily at room temperature from a two-dimensional (2-D) mixture. Pentacene, evaporated onto Ag(111) to coverages of 0.4-1.0 ML, produces a two-dimensional (2-D) gas. Subsequently deposited C(60) molecules combine with the pentacene 2-D gas to generate a network structure, consisting of chains of close-packed C(60) molecules, spaced by individual C(60) linkers and 1 nm x 2.5 nm pores containing individual pentacene molecules. Spontaneous formation of this stoichiometric (C(60))(4)-pentacene network from a range of excess pentacene surface coverage (0.4 to 1.0 ML) indicates a self-limiting assembly process. We refine the structure model for this phase and discuss the generality of this co-crystallization mechanism.

  14. Interdisciplinary Investigation of CO2 Sequestration in Depleted Shale Gas Formations

    Energy Technology Data Exchange (ETDEWEB)

    Zoback, Mark D. [Stanford Univ., CA (United States); Kovscek, Anthony R. [Stanford Univ., CA (United States); Wilcox, Jennifer [Stanford Univ., CA (United States)

    2013-09-30

    This project investigates the feasibility of geologic sequestration of CO2 in depleted shale gas reservoirs from an interdisciplinary viewpoint. It is anticipated that over the next two decades, tens of thousands of wells will be drilled in the 23 states in which organic-rich shale gas deposits are found. This research investigates the feasibility of using these formations for sequestration. If feasible, the number of sites where CO2 can be sequestered increases dramatically. The research embraces a broad array of length scales ranging from the ~10 nanometer scale of the pores in the shale formations to reservoir scale through a series of integrated laboratory and theoretical studies.

  15. Avis 6 sur la formation à et par la recherche

    OpenAIRE

    Centre de Coopération Internationale en Recherche Agronomique pour le Développement

    2015-01-01

    La formation à et par la recherche s’appuie sur la démarche scientifique, les savoirs, les connaissances à transmettre, tout autant que l’acquisition de compétences en gestion de projet, de capacités au travail en équipe, d’une ouverture d’esprit qui favorisera la créativité. Elle doit permettre de prendre conscience de la responsabilité endossée par la communauté scientifique vis-à-vis de la société et de l’environnement, mais aussi préparer l’avenir professionnel de celle ou de celui qu...

  16. Complex Formation in a Liquid-Liquid Extraction System Containing Cobalt(II, 4-(2-Pyridylazoresorcinol, and Nitron

    Directory of Open Access Journals (Sweden)

    Petya Vassileva Racheva

    2013-01-01

    Full Text Available Complex formation and liquid-liquid extraction were studied in a system containing cobalt(II, 4-(2-pyridylazoresorcinol (PAR, 1,4-diphenyl-3-(phenylamino-1H-1,2,4-triazole (Nitron, Nt, water, and chloroform. The effect of some experimental parameters (pH, shaking time, concentration of PAR, and concentration of Nt was systematically investigated, and the optimum conditions for cobalt extraction as an ion-association complex, (NtH+[Co3+(PAR2], were found. The following key equilibrium constants were calculated: constant of association (Log β=4.77±0.06, constant of distribution (LogKD=1.34±0.01, and constant of extraction (LogKex=6.11±0.07. Beer’s law was obeyed for Co concentrations up to 1.7 μg mL−1 with a molar absorptivity of 6.0×104 L mol−1 cm−1 at λmax=520 nm. Some additional characteristics, such as limit of detection, limit of quantification, and Sandell’s sensitivity, were estimated as well.

  17. Optimizing and Quantifying CO2 Storage Resource in Saline Formations and Hydrocarbon Reservoirs

    Energy Technology Data Exchange (ETDEWEB)

    Bosshart, Nicholas W. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Ayash, Scott C. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Azzolina, Nicholas A. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Peck, Wesley D. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Gorecki, Charles D. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Ge, Jun [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Jiang, Tao [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Burton-Kelly, Matthew E. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Anderson, Parker W. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Dotzenrod, Neil W. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center; Gorz, Andrew J. [Univ. of North Dakota, Grand Folks, ND (United States). Energy & Environmental Research Center

    2017-06-30

    In an effort to reduce carbon dioxide (CO2) emissions from large stationary sources, carbon capture and storage (CCS) is being investigated as one approach. This work assesses CO2 storage resource estimation methods for deep saline formations (DSFs) and hydrocarbon reservoirs undergoing CO2 enhanced oil recovery (EOR). Project activities were conducted using geologic modeling and simulation to investigate CO2 storage efficiency. CO2 storage rates and efficiencies in DSFs classified by interpreted depositional environment were evaluated at the regional scale over a 100-year time frame. A focus was placed on developing results applicable to future widespread commercial-scale CO2 storage operations in which an array of injection wells may be used to optimize storage in saline formations. The results of this work suggest future investigations of prospective storage resource in closed or semiclosed formations need not have a detailed understanding of the depositional environment of the reservoir to generate meaningful estimates. However, the results of this work also illustrate the relative importance of depositional environment, formation depth, structural geometry, and boundary conditions on the rate of CO2 storage in these types of systems. CO2 EOR occupies an important place in the realm of geologic storage of CO2, as it is likely to be the primary means of geologic CO2 storage during the early stages of commercial implementation, given the lack of a national policy and the viability of the current business case. This work estimates CO2 storage efficiency factors using a unique industry database of CO2 EOR sites and 18 different reservoir simulation models capturing fluvial clastic and shallow shelf carbonate depositional environments for reservoir depths of 1219 and 2438 meters (4000 and 8000 feet) and 7.6-, 20-, and 64-meter (25-, 66

  18. Stereochemistry and mechanism of the reduction of some bicyclo (2-2-1-) heptane-2-ones by metals dissolved in liquid ammonia; Stereochimie et mecanisme de la reduction de quelques bicyclo (2-2-1) heptanones-2 par les metaux dissous dans l'ammoniac liquide

    Energy Technology Data Exchange (ETDEWEB)

    Coulombeau, A [Commissariat a l' Energie Atomique, Grenoble (France). Centre d' Etudes Nucleaires

    1969-07-01

    A systematic experimental study of the reduction of four bicyclo(2-2-1)hepta n-2-ones by dissolved alkaline and alkaline-earth metals in liquid ammonia is reported. Chapter one: models of metal-ammonia solutions and mechanisms of the reduction of ketones by these solutions are rapidly recalled. Chapter two: results obtained in the thermodynamic equilibration of three pairs of epimeric alcohols which formally derive from three of the starting ketones are presented. Chapter three: deals with the results obtained in the reduction of the ketones in the absence or the presence of a proton source. A new interpretation of these results is given and is based upon two different effects: - the torsional interaction created by the bridgehead substituent on the C-O bond which favours the formation of the endo alcohol; - the difference of steric hindrance between the two sides (exo and endo) defined by the plane of the carbonyl group of the starting molecule, which favours the attack of the metal cation from one side or the other, and therefore the formation of the exo or the endo epimer. This mechanism is generalised in a model which is tested by means of some examples published in the literature. It then appears able to construe correctly the obtained results. (author) [French] Une etude experimentale systematique de la reduction de quatre bicyclo-(2-2-1)heptanones-2 par les metaux alcalins et alcalino-terreux dissous dans l'ammoniac liquide a ete effectuee. 1er chapitre: on y rappelle rapidement les modeles proposes pour la structure des solutions metalliques dans l'ammoniac liquide, ainsi que les mecanismes de reduction des cetones par ces solutions. 2eme chapitre: on y presente les resultats obtenus lors de l'equilibration thermodynamique de trois couples d'alcools epimeres derivant de trois des cetones reduites. 3eme chapitre: il concerne les resultats obtenus lors de la reduction des cetones en l'absence ou en presence de donneurs de protons. Une interpretation nouvelle

  19. Numerical modeling of injection and mineral trapping of CO2 withH2S and SO2 in a Sandstone Formation

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Tianfu; Apps, John A.; Pruess, Karsten; Yamamoto, Hajime

    2004-09-07

    Carbon dioxide (CO{sub 2}) injection into deep geologic formations could decrease the atmospheric accumulation of this gas from anthropogenic sources. Furthermore, by co-injecting H{sub 2}S or SO{sub 2}, the products respectively of coal gasification or combustion, with captured CO{sub 2}, problems associated with surface disposal would be mitigated. We developed models that simulate the co-injection of H{sub 2}S or SO{sub 2} with CO{sub 2} into an arkose formation at a depth of about 2 km and 75 C. The hydrogeology and mineralogy of the injected formation are typical of those encountered in Gulf Coast aquifers of the United States. Six numerical simulations of a simplified 1-D radial region surrounding the injection well were performed. The injection of CO{sub 2} alone or co-injection with SO{sub 2} or H{sub 2}S results in a concentrically zoned distribution of secondary minerals surrounding a leached and acidified region adjacent to the injection well. Co-injection of SO{sub 2} with CO{sub 2} results in a larger and more strongly acidified zone, and alteration differs substantially from that caused by the co-injection of H{sub 2}S or injection of CO{sub 2} alone. Precipitation of carbonates occurs within a higher pH (pH > 5) peripheral zone. Significant quantities of CO{sub 2} are sequestered by ankerite, dawsonite, and lesser siderite. The CO{sub 2} mineral-trapping capacity of the formation can attain 40-50 kg/m{sup 3} medium for the selected arkose. In contrast, secondary sulfates precipitate at lower pH (pH < 5) within the acidified zone. Most of the injected SO{sub 2} is transformed and immobilized through alunite precipitation with lesser amounts of anhydrite and minor quantities of pyrite. The dissolved CO{sub 2} increases with time (enhanced solubility trapping). The mineral alteration induced by injection of CO{sub 2} with either SO{sub 2} or H{sub 2}S leads to corresponding changes in porosity. Significant increases in porosity occur in the acidified

  20. Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO{sub 2} to formate

    Energy Technology Data Exchange (ETDEWEB)

    Lv, Weixin; Zhou, Jing; Bei, Jingjing [School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng, 224051 (China); Zhang, Rui, E-mail: zhangrui@ycit.cn [School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng, 224051 (China); Wang, Lei [Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education of the People’s Republic of China, Heilongjiang University, Harbin, 150080 (China); Xu, Qi [School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng, 224051 (China); Wang, Wei, E-mail: wangw@ycit.edu.cn [School of Chemistry and Chemical Engineering, Yancheng Institute of Technology, Yancheng, 224051 (China)

    2017-01-30

    Highlights: • Bi/Cu electrode was prepared by depositing nano-sized Bi catalyst on Cu foil. • The Bi/Cu electrode can reduce CO{sub 2} to formate with a low overpotential. • The energy efficiency for reduction of CO{sub 2} to formate can reach to 50%. • A Tafel slope of 128 mV decade{sup −1} was observed for producing formate. - Abstract: Electrochemical reduction of carbon dioxide (CO{sub 2}) to formate is energetically inefficient because high overpotential is required for reduction of CO{sub 2} to formate on most traditional catalysts. In this paper, a novel nano-sized Bi-based electrocatalyst deposited on a Cu foil has been synthesized, which can be used as a cathode for electrochemical reduction of CO{sub 2} to formate with a low overpotential (0.69 V) and a high selectivity (91.3%). The electrocatalyst can show excellent catalytic performance toward reduction of CO{sub 2} which can probably be attributed to the nano-sized structure and the surface oxide layer. The energy efficiency for reduction of CO{sub 2} to formate can reach to 50% when an Ir{sub x}Sn{sub y}Ru{sub z}O{sub 2}/Ti electrode is used as anode, it is one of the highest values found in the literatures and very practicable for sustainable fuel synthesis.

  1. CO_2 capture from flue gas using clathrate formation in the presence of thermodynamic promoters

    International Nuclear Information System (INIS)

    Kim, Soyoung; Choi, Sung-Deuk; Seo, Yongwon

    2017-01-01

    Tetrahydrofuran (THF) as a water-soluble sII clathrate former, cyclopentane (CP) as a water-insoluble sII clathrate former, and tetra n-butyl ammonium chloride (TBAC) as a water-soluble semiclathrate former were used to investigate their thermodynamic promotion effects on clathrate-based CO_2 capture from simulated flue gas. The phase equilibria of CO_2 (20%) + N_2 (80%) + promoter clathrates at different promoter concentrations revealed that the presence of THF, CP, and TBAC could significantly reduce the clathrate formation pressure. THF solutions provided the highest gas uptake and steepest CO_2 concentration changes in the vapor phase, whereas TBAC solutions showed the highest CO_2 selectivity (∼61%) in the clathrate phase. CP solutions exhibited a slower formation rate, but their final gas uptake and CO_2 selectivity in the clathrate phase were comparable to the THF solutions. Raman spectroscopy confirmed the enclathration of both CO_2 and N_2 in the clathrate cages and a structural transition due to the inclusion of promoters in the clathrate phase. The overall experimental results indicate that TBAC is a viable thermodynamic promoter for clathrate-based CO_2 capture from simulated flue gas, considering the lower pressure requirement for clathrate formation, higher CO_2 enrichment in the clathrate phase, non-toxicity, and non-volatility. - Highlights: • Clathrate-based CO_2 capture was investigated in the presence of thermodynamic promoters. • THF, CP, and TBAC demonstrated a significant thermodynamic promotion for CO_2 (20%) + N_2 (80%) clathrates. • The highest gas uptake was observed for the THF (5.6 mol%) solution. • TBAC solutions showed the highest CO_2 selectivity in the clathrate phase (∼61%). • Raman spectroscopy confirmed the guest gas enclathration and clathrate structure.

  2. An assessment on CO2 geosequestration in deep saline formations in the Taihsi Basin, central Taiwan

    Science.gov (United States)

    Cai, Mo-Si; Lin, Andrew T.; Fan, Jhen-Huei

    2015-04-01

    Geological storage of carbon dioxide (CO2) is to inject and store a large amount of anthropogenic CO2 in deep and sealed porous rocks in order to mitigate the aggravated threat of global climate changes. Borehole and reflection seismic data are used to understand the spatial distribution of suitable CO2 reservoirs and cap rocks in the Taihsi Basin, central Taiwan, where the level of seismicity is low. The Taihsi Basin was a rift basin during the Paleocene to Eocene, followed by a phase of post-rift subsidence during late Oligocene to late Miocene. The loading of the Taiwan mountain belt since late Miocene has turned the Taihsi Basin into a peripheral foreland basin, with strata gently dipping toward the mountain belts in the east. The coastal plain in central Taiwan (Changhua and Yunlin Counties) and its adjacent offshore areas are close to major CO2 emission sources and no active geological structures are found in these areas, making the study area a favorable CO2 storage site. Spatial distribution of formation thickness and depth for CO2 reservoirs and cap rocks indicates three CO2 storage systems existed in the study area. They are: (1) late Miocene to Pliocene Nanchuang Formation and Kueichulin Formation (reservoirs)-Chinshui Shale (seals) system (hereafter abbreviated as NK-C system), (2) early to middle Miocene Shihti Formation and Peiliao Formation (reservoirs)-Talu Shale (seals) system (SP-T system), (3) early Miocene Mushan Formation (reservoirs)-Piling Shale (seals) system (M-P system). The NK-C system contains multiple layers of porous sandstones from Nanchuang and Kueichulin formations, with total thickness around 210-280 m. In the vicinity of the northern bank of the Jhuoshuei River, reservoir top reaches a depth around 1850 m, with 60 m thick seal formation, the Chinshui Shale. However, the Chinshui Shale becomes sand-prone in the Changhua coastal and nearshore areas due to facies changes. The SP-T system consists of two porous sandstone layers from

  3. How Sodium Chloride Salt Inhibits the Formation of CO2 Gas Hydrates.

    Science.gov (United States)

    Holzammer, Christine; Finckenstein, Agnes; Will, Stefan; Braeuer, Andreas S

    2016-03-10

    We present an experimental Raman study on how the addition of sodium chloride to CO2-hydrate-forming systems inhibits the hydrate formation thermodynamically. For this purpose, the molar enthalpy of reaction and the molar entropy of reaction for the reaction of weakly hydrogen-bonded water molecules to strongly hydrogen bonded water molecules are determined for different salinities from the Raman spectrum of the water-stretching vibration. Simultaneously, the influence of the salinity on the solubility of CO2 in the liquid water-rich phase right before the start of hydrate formation is analyzed. The results demonstrate that various mechanisms contribute to the inhibition of gas hydrate formation. For the highest salt concentration of 20 wt % investigated, the temperature of gas hydrate formation is lowered by 12 K. For this concentration the molar enthalpy and entropy of reaction become smaller by 50 and 20%, respectively. Concurrently, the solubility of carbon dioxide is reduced by 70%. These results are compared with data in literature for systems of sodium chloride in water (without carbon dioxide).

  4. Formation, stability and structural characterization of ternary MgUO{sub 2}(CO{sub 3}){sub 3}{sup 2-} and Mg{sub 2}UO{sub 2}(CO{sub 3}){sub 3}(aq) complexes

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Jun-Yeop; Yun, Jong-Il [KAIST, Daejeon (Korea, Republic of). Dept. of Nuclear and Quantum Engineering; Vespa, Marika; Gaona, Xavier; Dardenne, Kathy; Rothe, Joerg; Rabung, Thomas; Altmaier, Marcus [Karlsruhe Institute of Technology, Karlsruhe (Germany). Inst. for Nuclear Waste Disposal

    2017-06-01

    The formation of ternary Mg-UO{sub 2}-CO{sub 3} complexes under weakly alkaline pH conditions was investigated by time-resolved laser fluorescence spectroscopy (TRLFS) and extended X-ray absorption fine structure (EXAFS) and compared to Ca-UO{sub 2}-CO{sub 3} complexes. The presence of two different Mg-UO{sub 2}-C{sub 3} complexes was identified by means of two distinct fluorescence lifetimes of 17±2 ns and 51±2 ns derived from the multi-exponential decay of the fluorescence signal. Slope analysis in terms of fluorescence intensity coupled with fluorescence intensity factor as a function of log [Mg(II)] was conducted for the identification of the Mg-UO{sub 2}-CO{sub 3} complexes forming. For the first time, the formation of both MgUO{sub 2}(CO{sub 3}){sub 3}{sup 2-} and Mg{sub 2}UO{sub 2}(CO{sub 3}){sub 3}(aq) species was confirmed and the corresponding equilibrium constants were determined as log β {sub 113}=25.8±0.3 and β {sub 213}=27.1±0.6, respectively. Complementarily, fundamental structural information for both Ca-UO{sub 2}-CO{sub 3} and Mg-UO{sub 2}-CO{sub 3} complexes was gained by extended EXAFS revealing very similar structures between these two species, except for the clearly shorter U-Mg distance (3.83 Aa) compared with U-Ca distance (4.15 Aa). These results confirmed the inner-sphere character of the Ca/Mg-UO{sub 2}-CO{sub 3} complexes. The formation constants determined for MgUO{sub 2}(CO{sub 3}){sub 3}{sup 2-} and Mg{sub 2}UO{sub 2}(CO{sub 3}){sub 3}(aq) species indicate that ternary Mg-UO{sub 2}-CO{sub 3} complexes contribute to the relevant uranium species in carbonate saturated solutions under neutral to weakly alkaline pH conditions in the presence of Mg(II) ions, which will induce notable influences on the U(VI) chemical species under seawater conditions.

  5. Enhancement of CO(3-2)/CO(1-0) ratios and star formation efficiencies in supergiant H II regions

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Rie E.; Espada, Daniel; Komugi, Shinya; Nakanishi, Kouichiro; Sawada, Tsuyoshi; Fujii, Kosuke; Kawabe, Ryohei [National Astronomical Observatory of Japan, 2-21-1 Osawa, Mitaka, Tokyo 181-8588 (Japan); Kohno, Kotaro [Institute of Astronomy, School of Science, The University of Tokyo, Osawa, Mitaka, Tokyo 181-0015 (Japan); Tosaki, Tomoka [Joetsu University of Education, Yamayashiki-machi, Joetsu, Niigata 943-8512 (Japan); Hirota, Akihiko; Minamidani, Tetsuhiro [Nobeyama Radio Observatory, Minamimaki, Minamisaku, Nagano 384-1805 (Japan); Okumura, Sachiko K. [Department of Mathematical and Physical Sciences, Faculty of Science, Japan Woman' s University, Mejirodai 2-8-1, Bunkyo, Tokyo 112-8681 (Japan); Kuno, Nario [Department of Astronomical Science, The Graduate University for Advanced Studies (Sokendai), 2-21-1 Osawa, Mitaka, Tokyo 181-0015 (Japan); Muraoka, Kazuyuki; Onodera, Sachiko [Osaka Prefecture University, Gakuen 1-1, Sakai, Osaka 599-8531 (Japan); Kaneko, Hiroyuki, E-mail: rie.miura@nao.ac.jp [Department of Physics, Meisei University, Hino, Tokyo 191-8506 (Japan)

    2014-06-20

    We present evidence that super giant H II regions (GHRs) and other disk regions of the nearby spiral galaxy, M33, occupy distinct locations in the correlation between molecular gas, Σ{sub H{sub 2}}, and the star formation rate surface density, Σ{sub SFR}. This result is based on wide-field and high-sensitivity CO(3-2) observations at 100 pc resolution. Star formation efficiencies (SFEs), defined as Σ{sub SFR}/Σ{sub H{sub 2}}, in GHRs are found to be ∼1 dex higher than in other disk regions. The CO(3-2)/CO(1-0) integrated intensity ratio, R {sub 3-2/1-0}, is also higher than the average over the disk. Such high SFEs and R {sub 3-2/1-0} can reach the values found in starburst galaxies, which suggests that GHRs may be the elements building up a larger-scale starburst region. Three possible contributions to high SFEs in GHRs are investigated: (1) the I {sub CO}-N(H{sub 2}) conversion factor, (2) the dense gas fraction traced by R {sub 3-2/1-0}, and (3) the initial mass function (IMF). We conclude that these starburst-like properties in GHRs can be interpreted by a combination of both a top-heavy IMF and a high dense gas fraction, but not by changes in the I {sub CO}-N(H{sub 2}) conversion factor.

  6. A Hydromechanic-Electrokinetic Model for CO2 Sequestration in Geological Formations

    NARCIS (Netherlands)

    Al-Khoury, R.I.N.; Talebian, M.; Sluys, L.J.

    2013-01-01

    In this contribution, a finite element model for simulating coupled hydromechanic and electrokinetic flow in a multiphase domain is outlined. The model describes CO2 flow in a deformed, unsaturated geological formation and its associated streaming potential flow. The governing field equations are

  7. Formation and dissociation of CO{sub 2} and CO{sub 2}-THF hydrates compared to CH{sub 4} and CH{sub 4}-THF hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Giavarini, C.; Maccioni, F.; Broggi, A. [Roma Univ. La Sapienza, Roma (Italy). Dept. of Chemical Engineering; Politi, M. [ENEL-RICERCHE, Brindisi (Italy)

    2008-07-01

    Carbon sequestration involves the removal of greenhouse gases from industrial or utility plant streams and their long term storage so that they cannot interact with the climate system. Different methods for selective carbon dioxide (CO{sub 2}) removal are in commercial use and are based on, gas absorption, membrane process, and cryogenic fractionation. In addition, disposal of captured CO{sub 2} in the ocean and in geological reservoirs has been proposed by researchers. Another challenge is to take advantage of the properties of CO{sub 2} hydrates for carbon sequestration since it could have a number of uses such as chemical production. As such, it is important to understand the hydrate decomposition kinetics during storage, transportation, and disposal. This paper presented a project that involved the separation of carbon dioxide from the flue gases of powers plants, in the form of hydrate. The project also involved the storage, use, and disposal of the hydrate. The purpose of the study was to evaluate the decomposition kinetics of CO{sub 2} hydrate containing different quantities of ice, at low pressures and temperatures between -3 and 0 degrees Celsius. In addition, in order to evaluate the tetrahydrofuran (THF) stabilization effect, the study examined the influence of THF on the formation and decomposition kinetics of mixed THF-methane (CH{sub 4}) and THF-CO{sub 2} hydrates. Preservation tests were conducted to determine the best pressure and temperature conditions for the mixed-hydrates conservation, with reference to the simple hydrates. The paper described the apparatus for the formation and dissociation tests which consisted of a jacketed stainless steel reactor, equipped with stirrer. The paper also described the hydrate formation procedure as well as hydrate characterization. Last, the paper discussed the hydrate dissociation tests that were conducted immediately after hydrate formation in the reactor. It was concluded that the hydrophilic and hydrophobic

  8. Micropore Formation of [Zn2(Oxac) (Taz)2]·(H2O)2.5 via CO2 Adsorption.

    Science.gov (United States)

    Zubir, Moondra; Hamasaki, Atom; Iiyama, Taku; Ohta, Akira; Ohki, Hiroshi; Ozeki, Sumio

    2017-01-24

    As-synthesized [Zn 2 (Oxac) (Taz) 2 ]·(H 2 O) 2.5 , referred to as ZOTW 2.5 , was prepared from aqueous methanol solutions of Zn 5 (CO 3 ) 2 (OH) 6 and two kinds of ligands of 1,2,4-triazole (Taz) and oxalic acid (Oxac) at 453 K for 12 h. The crystal structure was determined by the Rietveld method. As-synthesized ZOTW 2.5 was pretreated at 383 K and 1 mPa for t pt h, ZOTW x (t pt h). ZOTW x (≥3h) showed a type I adsorption isotherm for N 2 at 77 K having a saturation amount (V s ) of 180 mg/g, but that pretreated shortly showed only 1/10 in V s . CO 2 was adsorbed at 303 K in sigmoid on nonporous ZOTW x (≤2h) and in Langmuir-type on ZOTW x (≥3h) to reach the adsorption amount of 120 mg/g at 700 Torr. N 2 adsorption on ZOTW x (≤2h)deCO 2 , degassed after CO 2 adsorption on ZOTW x (≤2h), was promoted 5-fold from 180 mg/g on ZOTW x (t pt h) and ZOTW x (≥3h)deCO 2 up to ca. 1000 mg/g. The interaction of CO 2 and H 2 O molecules in micropores may lead to a new route for micropore formation.

  9. O vacancy formation in (Pr/Gd)BaCo2O5.5 and the role of antisite defects

    KAUST Repository

    Omotayo Akande, Salawu; Chroneos, Alexander; Schwingenschlö gl, Udo

    2017-01-01

    that O vacancy formation is significantly easier in PrBaCo2O5.5 than in GdBaCo2O5.5, the difference in formation energy being hardly modified by antisite defects. While pyramidally coordinated Co atoms are not affected, we show that the presence

  10. Formation reactions and thermal stability of Ca/sub 2/NbCoO/sub 6/ and Ca/sub 2/TaCoO/sub 6/

    Energy Technology Data Exchange (ETDEWEB)

    Kuleshova, T B; Razumovskaya, O N; Belyaev, I N; Salei, V S [Rostovskij-na-Donu Gosudarstvennyj Univ. (USSR)

    1979-11-01

    Ca/sub 2/M/sup 5/CoO/sub 6/ compounds and reactions of their formation from oxides were investigated by thermogravimetric and X-ray phase analysis methods. Optimum conditions for synthesizing the above compounds have been found, and the degree of oxidation of Co therein, determined. The thermal stability of the compounds was also studied. It was shown, that the stability of Co (3) in Ca/sub 2/NbCaO/sub 6/ Ca/sub 2/TaCoO/sub 6/ is higher than that in similar compounds containing Pb. The resultant compounds are pure perovskites. Presented are the calculated and the experimental values of perovskite cell parameters.

  11. Concomitant carboxylate and oxalate formation from the activation of CO{sub 2} by a thorium(III) complex

    Energy Technology Data Exchange (ETDEWEB)

    Formanuik, Alasdair; Ortu, Fabrizio; Mills, David P. [School of Chemistry, The University of Manchester (United Kingdom); Inman, Christopher J. [Department of Chemistry and Biochemistry, School of Life Sciences, University of Sussex, Brighton (United Kingdom); Kerridge, Andrew [Department of Chemistry, Lancaster University (United Kingdom); Castro, Ludovic; Maron, Laurent [LPCNO, CNRA et INSA, Universite Paul Sabatier, Toulouse (France)

    2016-12-12

    Improving our comprehension of diverse CO{sub 2} activation pathways is of vital importance for the widespread future utilization of this abundant greenhouse gas. CO{sub 2} activation by uranium(III) complexes is now relatively well understood, with oxo/carbonate formation predominating as CO{sub 2} is readily reduced to CO, but isolated thorium(III) CO{sub 2} activation is unprecedented. We show that the thorium(III) complex, [Th(Cp''){sub 3}] (1, Cp''={C_5H_3(SiMe_3)_2-1,3}), reacts with CO{sub 2} to give the mixed oxalate-carboxylate thorium(IV) complex [{Th(Cp'')_2[κ"2-O_2C{C_5H_3-3,3'-(SiMe_3)_2}]}{sub 2}(μ-κ{sup 2}:κ{sup 2}-C{sub 2}O{sub 4})] (3). The concomitant formation of oxalate and carboxylate is unique for CO{sub 2} activation, as in previous examples either reduction or insertion is favored to yield a single product. Therefore, thorium(III) CO{sub 2} activation can differ from better understood uranium(III) chemistry. (copyright 2016 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  12. Effects of cyclopentane on CO2 hydrate formation and dissociation as a co-guest molecule for desalination

    International Nuclear Information System (INIS)

    Zheng, Jia-nan; Yang, Ming-jun; Liu, Yu; Wang, Da-yong; Song, Yong-chen

    2017-01-01

    Highlights: • CP decreases CO 2 hydrate phase equilibrium pressure by forming CO 2 -CP hydrates. • The increase of CP can’t decrease hydrates phase equilibrium pressure unlimitedly. • Higher CP concentration lowers CO 2 hydrate gas uptake. • The optimal CP molar ratio is 0.01 based on hydrate phase equilibrium and gas uptake. - Abstract: Cyclopentane (CP) is considered to be a potential co-guest molecule in carbon dioxide (CO 2 ) hydrate-based desalination. The experimental thermodynamic data of CO 2 -CP hydrates were measured for a salt solution, where CP was chosen as a hydrate promoter. Seven experimental cases (62 cycles) were studied with different molar ratios of CP/water (0, 0.0025, 0.005, 0.0075, 0.01, 0.02, and 0.03). Hydrate phase equilibrium data were generated using an isochoric method, and the hydrate saturations were calculated based on gas uptake. The results indicated that the increase in CP concentration significantly decreased the CO 2 hydrate equilibrium pressure to a certain limit; the hydrate saturation also decreased during this process. Also, it was determined that CP encouraged the formation of s-II double CO 2 -CP hydrates, which are different from s-I simple CO 2 hydrate. The CO 2 -CP guest provides a strengthened stability and moderate hydrate phase equilibrium conditions for hydrate-based desalination. The recommended optimal molar ratio of CP is 0.01 when the increase in equilibrium was more than 10 K, and the decrease in hydrate saturation was less than 2%.

  13. Novel CO2 Foam Concepts and Injection Schemes for Improving CO2 Sweep Efficiency in Sandstone and Carbonate Hydrocarbon Formations

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Quoc [Univ. of Texas, Austin, TX (United States). Department of Petroleum & Geosystems Engineering; Hirasaki, George [Rice Univ., Houston, TX (United States). Department of Chemical Engineering; Johnston, Keith [Univ. of Texas, Austin, TX (United States). Department of Chemical Engineering

    2015-02-05

    We explored cationic, nonionic and zwitterionic surfactants to identify candidates that have the potential to satisfy all the key requirements for CO2 foams in EOR. We have examined the formation, texture, rheology and stability of CO2 foams as a function of the surfactant structure and formulation variables including temperature, pressure, water/CO2 ratio, surfactant concentration, salinity and concentration of oil. Furthermore, the partitioning of surfactants between oil and water as well as CO2 and water was examined in conjunction with adsorption measurements on limestone by the Hirasaki lab to develop strategies to optimize the transport of surfactants in reservoirs.

  14. PmaCO2 Project: Porosity and CO2 Trapping Mechanisms The Utrillas Formation in SD-1 borehole (Tejada - Burgos): Porosity and Porous Media Modelling

    International Nuclear Information System (INIS)

    Campos, R.; Barrios, I.; Gonzalez, A. M.

    2013-02-01

    The aim of PmaCO 2 project, supported by the Secretary of State and Research MINECO (CGL2011-24768) is to increase the knowledge of the microstructure of porous storage formations and thus contribute to the viability of CO 2 sequestration in geological formations. The microporous structure plays an important role not only in the prevalence of a particular trapping mechanism, but also on the amount of CO 2 immobilized. Utrillas facies are investigated in this project as representatives of a deep saline aquifer storage. This publication is a summary of the work done in the first year of the project. We present a study on microstructure of sandstones Utrillas, sampled in borehole, by applying the mercury intrusion porosimetry technique for the experimental determination of porosity and associated parameters. The porous medium was modeled with the PoreCor simulation code based in intrusion-extrusion curves. (Author) 78 refs.

  15. A rigorous mechanistic model for predicting gas hydrate formation kinetics: The case of CO2 recovery and sequestration

    International Nuclear Information System (INIS)

    ZareNezhad, Bahman; Mottahedin, Mona

    2012-01-01

    Highlights: ► A mechanistic model for predicting gas hydrate formation kinetics is presented. ► A secondary nucleation rate model is proposed for the first time. ► Crystal–crystal collisions and crystal–impeller collisions are distinguished. ► Simultaneous determination of nucleation and growth kinetics are established. ► Important for design of gas hydrate based energy storage and CO 2 recovery systems. - Abstract: A rigorous mechanistic model for predicting gas hydrate formation crystallization kinetics is presented and the special case of CO 2 gas hydrate formation regarding CO 2 recovery and sequestration processes has been investigated by using the proposed model. A physical model for prediction of secondary nucleation rate is proposed for the first time and the formation rates of secondary nuclei by crystal–crystal collisions and crystal–impeller collisions are formulated. The objective functions for simultaneous determination of nucleation and growth kinetics are presented and a theoretical framework for predicting the dynamic behavior of gas hydrate formation is presented. Predicted time variations of CO 2 content, total number and surface area of produced hydrate crystals are in good agreement with the available experimental data. The proposed approach can have considerable application for design of gas hydrate converters regarding energy storage and CO 2 recovery processes.

  16. Formation of nanoscale networks: selectively swelling amphiphilic block copolymers with CO2-expanded liquids.

    Science.gov (United States)

    Gong, Jianliang; Zhang, Aijuan; Bai, Hua; Zhang, Qingkun; Du, Can; Li, Lei; Hong, Yanzhen; Li, Jun

    2013-02-07

    Polymeric films with nanoscale networks were prepared by selectively swelling an amphiphilic diblock copolymer, polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP), with the CO(2)-expanded liquid (CXL), CO(2)-methanol. The phase behavior of the CO(2)-methanol system was investigated by both theoretical calculation and experiments, revealing that methanol can be expanded by CO(2), forming homogeneous CXL under the experimental conditions. When treated with the CO(2)-methanol system, the spin cast compact PS-b-P4VP film was transformed into a network with interconnected pores, in a pressure range of 12-20 MPa and a temperature range of 45-60 °C. The formation mechanism of the network, involving plasticization of PS and selective swelling of P4VP, was proposed. Because the diblock copolymer diffusion process is controlled by the activated hopping of individual block copolymer chains with the thermodynamic barrier for moving PVP segments from one to another, the formation of the network structures is achieved in a short time scale and shows "thermodynamically restricted" character. Furthermore, the resulting polymer networks were employed as templates, for the preparation of polypyrrole networks, by an electrochemical polymerization process. The prepared porous polypyrrole film was used to fabricate a chemoresistor-type gas sensor which showed high sensitivity towards ammonia.

  17. O vacancy formation in (Pr/Gd)BaCo2O5.5 and the role of antisite defects

    KAUST Repository

    Omotayo Akande, Salawu

    2017-04-20

    In search for materials for intermediate temperature solid oxide fuel cells, (Pr/Gd)BaCo2O5.5 is investigated by first principles calculations. Antisite defects are considered as they may modify the electronic and O diffusion properties but are rarely studied in double perovskite oxides. Octahedrally coordinated Co atoms are shown to realize intermediate and high spin states for PrBaCo2O5.5 and GdBaCo2O5.5, respectively, while pyramidally coordinated Co atoms always have high spin. It turns out that O vacancy formation is significantly easier in PrBaCo2O5.5 than in GdBaCo2O5.5, the difference in formation energy being hardly modified by antisite defects. While pyramidally coordinated Co atoms are not affected, we show that the presence of antisite defects causes parts of the octahedrally coordinated Co atoms to switch from intermediate to high spin.

  18. Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298K from Quantum Mechanics Free Energy Calculations with Explicit Water.

    Science.gov (United States)

    Cheng, Tao; Xiao, Hai; Goddard, William A

    2016-10-11

    Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions are not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out Quantum Mechanics (QM) calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2RR conditions) to examine the initial reaction pathways to form CO and formate (HCOO - ) from CO 2 through free energy calculations at 298K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ- ), with a free energy barrier of ΔG ‡ =0.43 eV, the rate determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 eV and 0.30 eV, respectively. HCOO - formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO - formation occurs in the first electron transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution we need to control this first step of CO 2 binding, which might involve alloying or changing the structure at the nanoscale.

  19. Studies of phase formation in CoSi2 buried layers fabricated using ion implantation

    International Nuclear Information System (INIS)

    Galaev, A.A.; Parkhomenko, Yu.N.; Podgornyi, D.A.; Shcherbachev, K.D.

    1998-01-01

    The processes of the formation of cobalt disilicide buried layers in silicon are studied under different conditions of implantation with Co. In particular, the effects of the implantation dose and the postimplantation annealing temperature on the state of the Co-implanted layer are considered. Two types of heteroepitaxial Si/CoSi 2 /Si structures are obtained with the conducting layers of thicknesses 70 and 90 nm buried at the depths 80 and 10 nm, respectively

  20. Methanogenesis from acetate by Methanosarcina barkeri: Catalysis of acetate formation from methyl iodide, CO/sub 2/, and H/sub 2/ by the enzyme system involved

    Energy Technology Data Exchange (ETDEWEB)

    Laufer, K; Eikmanns, B; Frimmer, U; Thauer, R K

    1987-04-01

    Cell suspensions of Methanosarcina barkeri grown on acetate catalyze the formation of methane and CO/sub 2/ from acetate as well as an isotopic exchange between the carboxyl group of acetate and CO/sub 2/. Here we report that these cells also mediate the synthesis of acetate from methyl iodide, CO/sub 2/, and reducing equivalents (H/sub 2/ or CO), the methyl group of acetate being derived from methyl iodide and the carboxyl group from CO/sub 2/. Methyl chloride and methyltosylate but not methanol can substitute for methyl iodide in this reaction. Acetate formation from methyl iodide, CO/sub 2/, and reducing equivalents is coupled with the phosphorylation of ADP. Evidence is presented that methyl iodide is incorporated into the methyl group of acetate via a methyl corrinoid intermediate (deduced from inhibition experiments with propyl iodide) and that CO/sub 2/ is assimilated into the carboxyl group via a C/sub 1/ intermediate which does not exchange with free formate or free CO. The effects of protonophores, of the proton-translocating ATPase inhibitor N,N'-dicyclohexylcarbodiimide, and of arsenate on acetate formation are interpreted to indicate that the reduction of CO/sub 2/ to the oxidation level of the carboxyl group of acetate requires the presence of an electrochemical proton potential and that acetyl-CoA or acetyl-phosphate rather than free acetate is the immediate product of the condensation reaction. These results are dicsussed with respect to the mechanism of methanogenesis from acetate.

  1. Experimental study and thermodynamic modeling of CO2 gas hydrate formation in presence of zinc oxide nanoparticles

    International Nuclear Information System (INIS)

    Mohammadi, Mohsen; Haghtalab, Ali; Fakhroueian, Zahra

    2016-01-01

    Highlights: • Nanofluids enhance heat and mass transfer and affect on kinetic and thermodynamics. • The ZnO nanoparticles in liquid affect on kinetics and P-T curve of CO 2 hydrate. • ZnO nanoparticles enhance the growth rate and gas storage in CO 2 hydrate. • A thermodynamic modeling of CO 2 hydrate proposed in the presence of nanoparticles. • Water activity in ZnO + nanofluid was affected by enhancement of the CO 2 solubility. - Abstract: The effect of synthesized zinc oxide (ZnO) nanoparticles was investigated on the kinetic and thermodynamic equilibrium conditions of CO 2 hydrate formation. The amount of the gas consumption was measured and compared for the four sample fluids: pure water, aqueous solution of sodium dodecyl sulfate (SDS), water-based ZnO-nanofluid and water-based ZnO-nanofluid in the presence of SDS (0.001 mass fraction). The time of hydrate growth decreased and the amount of the storage gas enhanced in the presence of nanoparticles. Moreover, the nanoparticles size effect besides the CO 2 solubility enhancement in ZnO-nanofluid led to the reduction of water activity, so that the equilibrium curve of hydrate formation was shifted to higher pressures. A new correlation for Henry’s law constant was obtained using CO 2 -solubility data in ZnO-nanofluid. Finally using this correlation, the water activity was calculated through the Chen–Guo approach to propose a thermodynamic method for prediction of the equilibrium hydrate formation conditions in the presence of the nanoparticles.

  2. Biological CO2 conversion to acetate in subsurface coal-sand formation using a high-pressure reactor system

    Science.gov (United States)

    Ohtomo, Y.; Ijiri, A.; Ikegawa, Y.; Tsutsumi, M.; Imachi, H.; Uramoto, G.; Hoshino, T.; Morono, Y.; Tanikawa, W.; Hirose, T.; Inagaki, F.

    2013-12-01

    The geological CO2 sequestration into subsurface unmineable oil/gas fields and coal formations has been considered as one of the possible ways to reduce dispersal of anthropogenic greenhouse gasses into the atmosphere. However, feasibility of CO2 injection largely depends on a variety of geological and economical settings, and its ecological consequences have remained largely unpredictable. To address these issues, we developed a new flow-through-type CO2 injection system designated as the 'geobio-reactor system' to examine possible geophysical, geochemical and microbiological impact caused by CO2 injection under in-situ pressure (0-100 MPa) and temperature (0-70°C) conditions. In this study, we investigated Eocene bituminous coal-sandstones in the northwestern Pacific coast, Hokkaido, Japan, using the geobio-reactor system. Anaerobic artificial fluid and CO2 (flow rate: 0.002 and 0.00001 mL/min, respectively) were continuously supplemented into the coal-sand column under the pore pressure of 40 MPa (confined pressure: 41 MPa) at 40°C for 56 days. Molecular analysis of bacterial 16S rRNA genes showed that predominant bacterial components were physically dispersed from coal to sand as the intact form during experiment. Cultivation experiments from sub-sampling fluids indicated that some terrestrial microbes could preserve their survival in subsurface condition. Molecular analysis of archaeal 16S rRNA genes also showed that no methanogens were activated during experiment. We also anaerobically incubated the coal sample using conventional batch-type cultivation technique with a medium for methanogens. After one year of the batch incubation at 20°C, methane could be detected from the cultures except for the acetate-fed culture. The sequence of archaeal 16S rRNA genes via PCR amplification obtained from the H2 plus formate-fed culture was affiliated with a hydrogenotrophic methanogen within the genus Methanobacterium, whereas the methanol plus trimethylamine culture

  3. Observations of CO{sub 2} clathrate hydrate formation and dissolution under deep-ocean disposal conditions

    Energy Technology Data Exchange (ETDEWEB)

    Warzinski, R.P.; Cugini, A.V. [Department of Energy, Pittsburgh, PA (United States); Holder, G.D. [Univ. of Pittsburgh, Pittsburgh, PA (United States)

    1995-11-01

    Disposal of anthropogenic emissions of CO{sub 2} may be required to mitigate rises in atmospheric levels of this greenhouse gas if other measures are ineffective and the worst global warming scenarios begin to occur. Long-term storage of large quantities of CO{sub 2} has been proposed, but the feasibility of large land and ocean disposal options remains to be established. Determining the fate of liquid CO{sub 2} injected into the ocean at depths greater than 500 m is complicated by uncertainties associated with the physical behavior of CO{sub 2} under these conditions, in particular the possible formation of the ice-like CO{sub 2} clathrate hydrate. Resolving this issue is key to establishing the technical feasibility of this option. Experimental and theoretical work in this area is reported.

  4. Formation of Aqueous MgUO2(CO3)32- Complex and Uranium Anion Exchange Mechanism onto an Exchange Resin

    International Nuclear Information System (INIS)

    Dong, Wenming; Brooks, Scott C

    2008-01-01

    The formation of and stability constants for aqueous Mg-UO2-CO3 complexes were determined using an anion exchange method. Magnesium concentration was varied (up to 20 mmol/L) at constant ionic strength (I = 0.101, 0.202, 0.304, 0.406, and 0.509 mol/kg NaNO3), pH = 8.1, total [U(VI)] = 10.4 mol/L under equilibrium with atmospheric CO2. The results indicate that only the MgUO2(CO3)32- complex is formed. The cumulative formation constant extrapolated to zero ionic strength is similar regardless of the activity correction convention used: log = 25.8 b 0.5 using Davies equation and = 25.02 b 0.08 using specific ion interaction theory (SIT). Uranium sorption onto the exchange resin decreased in the presence of Mg putatively due to the formation of MgUO2(CO3)32- that had a lower affinity for the resin than UO2(CO3)34-. Uranium sorption results are consistent with an equivalent anion exchange reaction between NO3- and UO2(CO3)34- species to retain charge neutrality regardless of Mg concentration. No Mg was associated with the anion exchange resin indicating that the MgUO2(CO3)32- complex did not sorb

  5. Adsorbed Carbon Formation and Carbon Hydrogenation for CO_2 Methanation on the Ni(111) Surface: ASED-MO Study

    International Nuclear Information System (INIS)

    Choe, Sang Joon; Kang, Hae Jin; Kim, Su Jin; Park, Sung Bae; Park, Dong Ho; Huh, Do Sung

    2005-01-01

    Using the ASED-MO (Atom Superposition and Electron Delocalization-Molecular Orbital) theory, we investigated carbon formation and carbon hydrogenation for CO_2 methanation on the Ni (111) surface. For carbon formation mechanism, we calculated the following activation energies, 1.27 eV for CO_2 dissociation, 2.97 eV for the CO, 1.93 eV for 2CO dissociation, respectively. For carbon methanation mechanism, we also calculated the following activation energies, 0.72 eV for methylidyne, 0.52 eV for methylene and 0.50 eV for methane, respectively. We found that the calculated activation energy of CO dissociation is higher than that of 2CO dissociation on the clean surface and base on these results that the CO dissociation step are the ratedetermining of the process. The C-H bond lengths of CH_4 the intermediate complex are 1.21 A, 1.31 A for the C···H_(_1_), and 2.82 A for the height, with angles of 105 .deg. for H_(_1_)CH and 98 .deg. for H_(_1_)CH_(_1_)

  6. ParA and ParB coordinate chromosome segregation with cell elongation and division during Streptomyces sporulation

    Science.gov (United States)

    Donczew, Magdalena; Mackiewicz, Paweł; Wróbel, Agnieszka; Flärdh, Klas; Zakrzewska-Czerwińska, Jolanta

    2016-01-01

    In unicellular bacteria, the ParA and ParB proteins segregate chromosomes and coordinate this process with cell division and chromosome replication. During sporulation of mycelial Streptomyces, ParA and ParB uniformly distribute multiple chromosomes along the filamentous sporogenic hyphal compartment, which then differentiates into a chain of unigenomic spores. However, chromosome segregation must be coordinated with cell elongation and multiple divisions. Here, we addressed the question of whether ParA and ParB are involved in the synchronization of cell-cycle processes during sporulation in Streptomyces. To answer this question, we used time-lapse microscopy, which allows the monitoring of growth and division of single sporogenic hyphae. We showed that sporogenic hyphae stop extending at the time of ParA accumulation and Z-ring formation. We demonstrated that both ParA and ParB affect the rate of hyphal extension. Additionally, we showed that ParA promotes the formation of massive nucleoprotein complexes by ParB. We also showed that FtsZ ring assembly is affected by the ParB protein and/or unsegregated DNA. Our results indicate the existence of a checkpoint between the extension and septation of sporogenic hyphae that involves the ParA and ParB proteins. PMID:27248800

  7. Protease-activated receptor (PAR)-2 is required for PAR-1 signalling in pulmonary fibrosis

    NARCIS (Netherlands)

    Lin, Cong; von der Thüsen, Jan; Daalhuisen, Joost; ten Brink, Marieke; Crestani, Bruno; van der Poll, Tom; Borensztajn, Keren; Spek, C. Arnold

    2015-01-01

    Idiopathic pulmonary fibrosis is the most devastating diffuse fibrosing lung disease of unknown aetiology. Compelling evidence suggests that both protease-activated receptor (PAR)-1 and PAR-2 participate in the development of pulmonary fibrosis. Previous studies have shown that bleomycin-induced

  8. Pore-scale studies of multiphase flow and reaction involving CO2 sequestration in geologic formations

    Science.gov (United States)

    Kang, Q.; Wang, M.; Lichtner, P. C.

    2008-12-01

    In geologic CO2 sequestration, pore-scale interfacial phenomena ultimately govern the key processes of fluid mobility, chemical transport, adsorption, and reaction. However, spatial heterogeneity at the pore scale cannot be resolved at the continuum scale, where averaging occurs over length scales much larger than typical pore sizes. Natural porous media, such as sedimentary rocks and other geological media encountered in subsurface formations, are inherently heterogeneous. This pore-scale heterogeneity can produce variabilities in flow, transport, and reaction processes that take place within a porous medium, and can result in spatial variations in fluid velocity, aqueous concentrations, and reaction rates. Consequently, the unresolved spatial heterogeneity at the pore scale may be important for reactive transport modeling at the larger scale. In addition, current continuum models of surface complexation reactions ignore a fundamental property of physical systems, namely conservation of charge. Therefore, to better understand multiphase flow and reaction involving CO2 sequestration in geologic formations, it is necessary to quantitatively investigate the influence of the pore-scale heterogeneity on the emergent behavior at the field scale. We have applied the lattice Boltzmann method to simulating the injection of CO2 saturated brine or supercritical CO2 into geological formations at the pore scale. Multiple pore-scale processes, including advection, diffusion, homogeneous reactions among multiple aqueous species, heterogeneous reactions between the aqueous solution and minerals, ion exchange and surface complexation, as well as changes in solid and pore geometry are all taken into account. The rich pore scale information will provide a basis for upscaling to the continuum scale.

  9. Preliminary Study of Favourable Formations for CO{sub 2} Subsurface Storage in Spain; Estudio Preliminar de las Formaciones Favorables para el Almacenamiento Subterraneo de CO{sub 2} en Espana

    Energy Technology Data Exchange (ETDEWEB)

    Zapatero, M. A.; Reyes, J. L.; Martinez, R.; Suarez, I.; Arenillas, A.; Perucha, M. A.

    2009-10-12

    This report is a synthesis of the possibilities of CO{sub 2} storage in the Spanish subsurface. Compilation and analysis of geological information has been carried out, looking at surface and subsurface, in order to make a pre-selection of potential favourable units for CO{sub 2} storage, taking in account that each of this storages needs a confining formation to seal the storage. Before the storage selection, a general description of the great geological units of the Iberian Peninsula is done. Afterwards, borehole logging from petroleum exploration is analysed in these units, formations and areas of interest. The aim is to finally obtain a description of selected units and their possibilities of CO{sub 2} storage. (Author) 17 refs.

  10. Physical Property Changes During CO2 Injection into Sandstone from Pukpyeong Formation, South Korea: Pore-scale Approach

    Science.gov (United States)

    Han, J.; Keehm, Y.

    2010-12-01

    Carbon dioxide is believed to be responsible for global warming and climate change, and Korea government puts a great effort in CCS (Carbon Capture and Storage). The geological sequestration is regarded as one viable option and we are looking for prospecting formations for carbon storage. In this paper, we present a new approach to determine physical property changes during CO2 injection and preliminary results from applying the method to one of prospective Tertiary formation in South Korea. The so-called computational rock physics method is composed of three steps: 1) acquisition of high-resolution pore microstructures by X-ray micro-tomography; 2) CO2 injection simulation using lattice-Boltzmann (LB) two-phase flow simulation; and 3) FEM property simulations (electrical and elastic) at different CO2 saturations during the injection. We have been shown the viability of the method last year. This year we applied this method to one of CS (carbon storage) target area, Pukpyeong formation located in north-eastern part of South Korea. From thin section analysis, we found that the formation is composed of mudstone, sandstone and conglomerate, and most of them are poorly consolidated. The mudstone and poorly-sorted conglomerate are believed to have very low permeability, and the effect of CO2 injection would be significant. Thus we focus on sandstone units and get pore microstructure of those units. We then performed the computational rock physics analysis, and present the relations of Vp - CO2 saturation, and electrical conductivity - CO2 saturation for a few sand units. We also present the preliminary upscaling results by putting combined sandstone and mudstone units into FEM modeling. The modeling results implies that the new computational approach can be very useful to characterizing the CS sites especially in early stage. Acknowledgement: This work was supported by the Energy R&D program of the Korea Institute of Energy Technology Evaluation and Planning (KETEP

  11. CO2-Water-Rock Wettability: Variability, Influencing Factors, and Implications for CO2 Geostorage.

    Science.gov (United States)

    Iglauer, Stefan

    2017-05-16

    Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO 2 is captured from large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO 2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO 2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO 2 cannot percolate), (2) residual trapping (where the CO 2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO 2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO 2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO 2 through the rock are strongly influenced by the CO 2 -brine-rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO 2 -wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO 2 -wet. Note that CO 2 -wet surfaces dramatically reduce CO 2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO 2 -wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO 2 -wettability and the

  12. Profiling gene expression induced by protease-activated receptor 2 (PAR2 activation in human kidney cells.

    Directory of Open Access Journals (Sweden)

    Jacky Y Suen

    Full Text Available Protease-Activated Receptor-2 (PAR2 has been implicated through genetic knockout mice with cytokine regulation and arthritis development. Many studies have associated PAR2 with inflammatory conditions (arthritis, airways inflammation, IBD and key events in tumor progression (angiogenesis, metastasis, but they have relied heavily on the use of single agonists to identify physiological roles for PAR2. However such probes are now known not to be highly selective for PAR2, and thus precisely what PAR2 does and what mechanisms of downstream regulation are truly affected remain obscure. Effects of PAR2 activation on gene expression in Human Embryonic Kidney cells (HEK293, a commonly studied cell line in PAR2 research, were investigated here by comparing 19,000 human genes for intersecting up- or down-regulation by both trypsin (an endogenous protease that activates PAR2 and a PAR2 activating hexapeptide (2f-LIGRLO-NH(2. Among 2,500 human genes regulated similarly by both agonists, there were clear associations between PAR2 activation and cellular metabolism (1,000 genes, the cell cycle, the MAPK pathway, HDAC and sirtuin enzymes, inflammatory cytokines, and anti-complement function. PAR-2 activation up-regulated four genes more than 5 fold (DUSP6, WWOX, AREG, SERPINB2 and down-regulated another six genes more than 3 fold (TXNIP, RARG, ITGB4, CTSD, MSC and TM4SF15. Both PAR2 and PAR1 activation resulted in up-regulated expression of several genes (CD44, FOSL1, TNFRSF12A, RAB3A, COPEB, CORO1C, THBS1, SDC4 known to be important in cancer. This is the first widespread profiling of specific activation of PAR2 and provides a valuable platform for better understanding key mechanistic roles of PAR2 in human physiology. Results clearly support the development of both antagonists and agonists of human PAR2 as potential disease modifying therapeutic agents.

  13. The importance of nodule CO2 fixation for the efficiency of symbiotic nitrogen fixation in pea at vegetative growth and during pod formation.

    Science.gov (United States)

    Fischinger, Stephanie Anastasia; Schulze, Joachim

    2010-05-01

    Nodule CO2 fixation is of pivotal importance for N2 fixation. The process provides malate for bacteroids and oxaloacetate for nitrogen assimilation. The hypothesis of the present paper was that grain legume nodules would adapt to higher plant N demand and more restricted carbon availability at pod formation through increased nodule CO2 fixation and a more efficient N2 fixation. Growth, N2 fixation, and nodule composition during vegetative growth and at pod formation were studied in pea plants (Pisum sativum L.). In parallel experiments, 15N2 and 13CO2 uptake, as well as nodule hydrogen and CO2 release, was measured. Plants at pod formation showed higher growth rates and N2 fixation per plant when compared with vegetative growth. The specific activity of active nodules was about 25% higher at pod formation. The higher nodule activity was accompanied by higher amino acid concentration in nodules and xylem sap with a higher share of asparagine. Nodule 13CO2 fixation was increased at pod formation, both per plant and per 15N2 fixed unit. However, malate concentration in nodules was only 40% of that during vegetative growth and succinate was no longer detectable. The data indicate that increased N2 fixation at pod formation is connected with strongly increased nodule CO2 fixation. While the sugar concentration in nodules at pod formation was not altered, the concentration of organic acids, namely malate and succinate, was significantly lower. It is concluded that strategies to improve the capability of nodules to fix CO2 and form organic acids might prolong intensive N2 fixation into the later stages of pod formation and pod filling in grain legumes.

  14. Surface and Subsurface Geochemical Monitoring of an EOR-CO2 Field: Buracica, Brazil Monitoring géochimique en surface et sub-surface d’un gisement en production par récupération assistée et injection de CO2 : le champ de Buracica, Brésil

    Directory of Open Access Journals (Sweden)

    Magnier C.

    2012-04-01

    Full Text Available This paper presents a surface and subsurface geochemical survey of the Buracica EOR-CO2 field onshore Brazil. We adopted a methodology coupling the stable isotopes of carbon with noble gases to investigate the adequacy of geochemical monitoring to track deep fluid leakage at the surface. Three campaigns of CO2 flux and concentration in soils were performed to understand the CO2 variability across the field. The distribution of the CO2 soil contents between 0.8 and 14% is in great part controlled by the properties of the soil, with a first-order topographic dependency. These results, together with a δ13CCO2 between –15 and –23‰, suggest that the bulk of the soil CO2 flux is biological. The gas injected and produced at numerous wells across the field showed a great spatial and somewhat temporal heterogeneity with respect to molecular, δ13CCO2 and noble gas compositions. This heterogeneity is a consequence of the EOR-induced sweeping of the petroleum fluids by the injected CO2, producing a heterogeneous mixing controlled by the production scheme and the distribution in reservoir permeability. In light of the δ13CCO2 found in the reservoir, the stable isotopic composition of carbon was insufficient to track CO2 leaks at the surface. We demonstrate how noble gases may be powerful leak discriminators, even for CO2 abundances in soils in the bottom range of the biological baseline (~1%. The results presented in this study show the potential of geochemical monitoring techniques, involving stable isotopes and noble gases at the reservoir and soil levels, for tracing CO2 in CCS projects. Le monitoring géochimique du gisement de Buracica, qui produit des hydrocarbures par récupération assistée et injection de dioxyde de carbone, est présenté dans cet article. Une méthodologie permettant de coupler l’utilisation des isotopes stables du carbone et des isotopes des gaz rares pour étudier la faisabilité de traçage d’une fuite de CO2 du r

  15. Numerical simulation of CO2 geological storage in saline aquifers – case study of Utsira formation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zheming; Agarwal, Ramesh K. [Department of Mechanical Engineering and Materials Science, Washington University, St. Louis, MO 63130 (United States)

    2013-07-01

    CO2 geological storage (CGS) is one of the most promising technologies to address the issue of excessive anthropogenic CO2 emissions in the atmosphere due to fossil fuel combustion for electricity generation. In order to fully exploit the storage potential, numerical simulations can help in determining injection strategies before the deployment of full scale sequestration in saline aquifers. This paper presents the numerical simulations of CO2 geological storage in Utsira saline formation where the sequestration is currently underway. The effects of various hydrogeological and numerical factors on the CO2 distribution in the topmost hydrogeological layer of Utsira are discussed. The existence of multiple pathways for upward mobility of CO2 into the topmost layer of Utsira as well as the performance of the top seal are also investigated.

  16. Effect of carbonic anhydrase on silicate weathering and carbonate formation at present day CO2 concentrations compared to primordial values

    Science.gov (United States)

    Xiao, Leilei; Lian, Bin; Hao, Jianchao; Liu, Congqiang; Wang, Shijie

    2015-01-01

    It is widely recognized that carbonic anhydrase (CA) participates in silicate weathering and carbonate formation. Nevertheless, it is still not known if the magnitude of the effect produced by CA on surface rock evolution changes or not. In this work, CA gene expression from Bacillus mucilaginosus and the effects of recombination protein on wollastonite dissolution and carbonate formation under different conditions are explored. Real-time fluorescent quantitative PCR was used to explore the correlation between CA gene expression and sufficiency or deficiency in calcium and CO2 concentration. The results show that the expression of CA genes is negatively correlated with both CO2 concentration and ease of obtaining soluble calcium. A pure form of the protein of interest (CA) is obtained by cloning, heterologous expression, and purification. The results from tests of the recombination protein on wollastonite dissolution and carbonate formation at different levels of CO2 concentration show that the magnitudes of the effects of CA and CO2 concentration are negatively correlated. These results suggest that the effects of microbial CA in relation to silicate weathering and carbonate formation may have increased importance at the modern atmospheric CO2 concentration compared to 3 billion years ago. PMID:25583135

  17. Formation of Anhydrite due to Interaction Between Water Soluble CO2 (aq) and Calcite Mineral During Enhanced Oil Recovery

    DEFF Research Database (Denmark)

    Chakravarty, Krishna Hara; Fosbøl, Philip Loldrup; Thomsen, Kaj

    2015-01-01

    In the Low Salinity based EOR method, formation and migration of fines have proved to have profound effect on the displacement efficiency of residual oil. Salinity variations of injected brines have also been shown to affect oil recovery for WAG-CO2 processes. But the effect of fines in EOR during...... simulations were conducted over a temperature range of 50°C to 250°C and a pressure range of 5 bars to 500 bars. The amounts of fines formation taking place for different LSWAG-CO2 processes were correlated to the described oil recovery. It is observed that significant amounts of fines formation can take...... with the available SO42- ions. The salinity and composition of brines present in pore space shows direct correlation with the amount of fines produced during CO2 injection. With increase in temperature and pressure, the amount fines formation increased significantly. The described oil recovery for different LSWAG...

  18. Formate-Dependent Microbial Conversion of CO2 and the Dominant Pathways of methanogenesis in production water of high-temperature oil reservoirs amended with bicarbonate

    Directory of Open Access Journals (Sweden)

    Guang-Chao eYang

    2016-03-01

    Full Text Available CO2 sequestration in deep-subsurface formations including oil reservoirs is a potential measure to reduce the CO2 concentration in the atmosphere. However, the fate of the CO2 and the ecological influences in Carbon Dioxide Capture and Storage (CDCS facilities is not understood clearly. In the current study, the fate of CO2 (in bicarbonate form (0~90 mM with 10 mM of formate as electron donor and carbon source was investigated with high-temperature production water from oilfield in China. The isotope data showed that bicarbonate could be reduced to methane by methanogens and major pathway of methanogenesis could be syntrophic formate oxidation coupled with CO2 reduction and formate methanogenesis under the anaerobic conditions. The bicarbonate addition induced the shift of microbial community. Addition of bicarbonate and formate was associated with a decrease of Methanosarcinales, but promotion of Methanobacteriales in all treatments. Thermodesulfovibrio was the major group in all the samples and Thermacetogenium dominated in the high bicarbonate treatments. The results indicated that CO2 from CDCS could be transformed to methane and the possibility of microbial CO2 conversion for enhanced microbial energy recovery in oil reservoirs.

  19. Distinctive G Protein-Dependent Signaling by Protease-Activated Receptor 2 (PAR2 in Smooth Muscle: Feedback Inhibition of RhoA by cAMP-Independent PKA.

    Directory of Open Access Journals (Sweden)

    Wimolpak Sriwai

    Full Text Available We examined expression of protease-activated receptors 2 (PAR2 and characterized their signaling pathways in rabbit gastric muscle cells. The PAR2 activating peptide SLIGRL (PAR2-AP stimulated Gq, G13, Gi1, PI hydrolysis, and Rho kinase activity, and inhibited cAMP formation. Stimulation of PI hydrolysis was partly inhibited in cells expressing PAR2 siRNA, Gaq or Gai minigene and in cells treated with pertussis toxin, and augmented by expression of dominant negative regulator of G protein signaling (RGS4(N88S. Stimulation of Rho kinase activity was abolished by PAR-2 or Ga13 siRNA, and by Ga13 minigene. PAR2-AP induced a biphasic contraction; initial contraction was selectively blocked by the inhibitor of PI hydrolysis (U73122 or MLC kinase (ML-9, whereas sustained contraction was selectively blocked by the Rho kinase inhibitor (Y27632. PAR2-AP induced phosphorylation of MLC20, MYPT1 but not CPI-17. PAR2-AP also caused a decrease in the association of NF-kB and PKA catalytic subunit: the effect of PAR2-AP was blocked by PAR2 siRNA or phosphorylation-deficient RhoA (RhoA(S188A. PAR2-AP-induced degradation of IkBa and activation of NF-kB were abolished by the blockade of RhoA activity by Clostridium botulinum C3 exoenzyme suggesting RhoA-dependent activation of NF-kB. PAR2-AP-stimulated Rho kinase activity was significantly augmented by the inhibitors of PKA (myristoylated PKI, IKK2 (IKKIV or NF-kB (MG132, and in cells expressing dominant negative mutants of IKK (IKK(K44A, IkBa (IkBa (S32A/S36A or RhoA(S188A, suggesting feedback inhibition of Rho kinase activity via PKA derived from NF-kB pathway. PAR2-AP induced phosphorylation of RhoA and the phosphorylation was attenuated in cells expressing phosphorylation-deficient RhoA(S188A. Our results identified signaling pathways activated by PAR2 to mediate smooth muscle contraction and a novel pathway for feedback inhibition of PAR2-stimulated RhoA. The pathway involves activation of the NF-kB to

  20. Instrument for continuous supervision of the radioactivity of CO{sub 2} coolant in piles - DCCA -CO{sub 2} (1960); Dispositif de controle continu de la radioactivite du CO{sub 2} de refroidissement des piles - DCCA - CO{sub 2} (1960)

    Energy Technology Data Exchange (ETDEWEB)

    Fitoussi, L. [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    This paper describes an apparatus for continuous measurement of CO{sub 2} activity, which can be used on piles cooled by circulation of gas. The first part is devoted mainly to describing the apparatus used and the character of the radioactivity and thermodynamic measurements carried out, and giving the general characteristics of the gas circuit required if the instrument is to be suitably gas-tight. In the second part theoretical calculations are given, particularly on the determination of the ionisation current in an ionisation chamber with circulating gas. Several parameters enter into this determination, such as the mean path of {beta} particles in the ionisation chamber, the linear number of ion pairs formed in the gas by these {beta} particles as a function of their energy, the temperature and pressure of the gas in the ionisation chamber. This part also evaluates the sensitivity areas of the apparatus for measuring the concentrations of radioactive gases such as argon-41 and fission gases from uranium-235 in the CO{sub 2} coolant. In the last part are described the results of measurements performed with such an apparatus on the pile EL2, the special investigations carried out on the CO{sub 2} coolant of this pile, and the information gained during normal operation and during accidents. The DCCA - CO{sub 2} which has just been put in operation at G2 is briefly presented. In the conclusion the possibilities offered by this apparatus are underlined. (author) [French] Ce rapport a pour but de presenter le Dispositif de Controle continu de l'Activite du CO{sub 2} pouvant etre utilise aupres des piles refroidies par une circulation de gaz. La premiere partie du rapport consiste essentiellement a decrire l'ensemble de l'appareillage mis en oeuvre, a preciser la nature des mesures de radioactivite et de thermodynamique effectuees et a citer les caracteristiques generales du circuit de gaz pour avoir un dispositif presentant une etancheite efficace

  1. Instrument for continuous supervision of the radioactivity of CO{sub 2} coolant in piles - DCCA -CO{sub 2} (1960); Dispositif de controle continu de la radioactivite du CO{sub 2} de refroidissement des piles - DCCA - CO{sub 2} (1960)

    Energy Technology Data Exchange (ETDEWEB)

    Fitoussi, L [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1960-07-01

    This paper describes an apparatus for continuous measurement of CO{sub 2} activity, which can be used on piles cooled by circulation of gas. The first part is devoted mainly to describing the apparatus used and the character of the radioactivity and thermodynamic measurements carried out, and giving the general characteristics of the gas circuit required if the instrument is to be suitably gas-tight. In the second part theoretical calculations are given, particularly on the determination of the ionisation current in an ionisation chamber with circulating gas. Several parameters enter into this determination, such as the mean path of {beta} particles in the ionisation chamber, the linear number of ion pairs formed in the gas by these {beta} particles as a function of their energy, the temperature and pressure of the gas in the ionisation chamber. This part also evaluates the sensitivity areas of the apparatus for measuring the concentrations of radioactive gases such as argon-41 and fission gases from uranium-235 in the CO{sub 2} coolant. In the last part are described the results of measurements performed with such an apparatus on the pile EL2, the special investigations carried out on the CO{sub 2} coolant of this pile, and the information gained during normal operation and during accidents. The DCCA - CO{sub 2} which has just been put in operation at G2 is briefly presented. In the conclusion the possibilities offered by this apparatus are underlined. (author) [French] Ce rapport a pour but de presenter le Dispositif de Controle continu de l'Activite du CO{sub 2} pouvant etre utilise aupres des piles refroidies par une circulation de gaz. La premiere partie du rapport consiste essentiellement a decrire l'ensemble de l'appareillage mis en oeuvre, a preciser la nature des mesures de radioactivite et de thermodynamique effectuees et a citer les caracteristiques generales du circuit de gaz pour avoir un dispositif presentant une etancheite efficace. Dans la seconde

  2. CO2 capture by gas hydrate crystallization: Application on the CO2-N2 mixture

    International Nuclear Information System (INIS)

    Bouchemoua, A.

    2012-01-01

    CO 2 capture and sequestration represent a major industrial and scientific challenge of this century. There are different methods of CO 2 separation and capture, such as solid adsorption, amines adsorption and cryogenic fractionation. Although these processes are well developed at industrial level, they are energy intensive. Hydrate formation method is a less energy intensive and has an interesting potential to separate carbon dioxide. Gas hydrates are Document crystalline compounds that consist of hydrogen bonded network of water molecules trapping a gas molecule. Gas hydrate formation is favored by high pressure and low temperature. This study was conducted as a part of the SECOHYA ANR Project. The objective is to study the thermodynamic and kinetic conditions of the process to capture CO 2 by gas hydrate crystallization. Firstly, we developed an experimental apparatus to carry out experiments to determine the thermodynamic and kinetic formation conditions of CO 2 -N 2 gas hydrate mixture in water as liquid phase. We showed that the operative pressure may be very important and the temperature very low. For the feasibility of the project, we used TBAB (Tetrabutylammonium Bromide) as thermodynamic additive in the liquid phase. The use of TBAB may reduce considerably the operative pressure. In the second part of this study, we presented a thermodynamic model, based on the van der Waals and Platteeuw model. This model allows the estimation of thermodynamic equilibrium conditions. Experimental equilibrium data of CO 2 -CH 4 and CO 2 -N 2 mixtures are presented and compared to theoretical results. (author)

  3. Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

    DEFF Research Database (Denmark)

    Plampin, Michael R.; Lassen, Rune Nørbæk; Sakaki, Toshihiro

    2014-01-01

    sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2......, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been...... quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test...

  4. 4D Joint Stratigraphic Inversion of Prestack Seismic Data: Application to the CO2 Storage Reservoir (Utsira Sand Formation at Sleipner Site Inversion stratigraphique jointe 4D de données sismiques avant sommation : application au réservoir de stockage de CO2 (Formation Utsira du site de Sleipner

    Directory of Open Access Journals (Sweden)

    Labat K.

    2012-04-01

    éservoirs au cours de leur production. Nous présentons ici une méthodologie d'inversion stratigraphique 4D qui fournit une estimation des variations d'impédances des ondes P et S dans le réservoir, par inversion de données de sismiques répétées avant-sommation. L'inversion 4D est implémentée dans le domaine temps et nécessite une loi de mise à l'échelle des temps de trajets pour chaque jeu de données de sismique répétée (aussi appelé "millésime" afin de mettre en correspondance les temps d'arrivée d'événements homologues observés sur les jeux de données appelés référence et monitors. Cette opération est souvent appelée "warping". L'inversion 4D est une méthodologie qui comporte trois étapes : la première étape consiste à inverser chaque millésime sismique séparément, pour produire autant de distributions en impédances P et S que de jeux de données considérés. La seconde étape utilise l'information des impédances P disponibles pour résoudre le problème du warping, qui est un point clé pour la troisième et dernière étape : l'inversion jointe de tous les millésimes sismiques disponibles. Cette séquence d'inversion 4D a été appliquée aux jeux de données enregistrés sur le réservoir de stockage de CO2 du site norvégien de Sleipner (Mer du Nord. Ce dernier est devenu un site industriel de référence pour le stockage à long terme du dioxyde de carbone (CO2 dans un aquifère salin, la formation des sables de l'Utsira. Nous avons focalisé notre étude sur l'inversion 4D des millésimes 1994 et 2006, acquise respectivement avant et dix ans après le début de l'injection de CO2. Le warping a fourni une loi de mise à l'échelle des temps de propagation avec un retard maximum d'environ 45 ms à la base de l'aquifère Utsira. L'inversion 4D jointe a donné des résultats plus cohérents que les inversions 3D : l'inversion 4D fournit en particulier des impédances P pour les grès saturés en CO2 qui sont très proches des

  5. Preliminary Simulations of CO2 Transport in the Dolostone Formations in the Ordos Basin, China

    Energy Technology Data Exchange (ETDEWEB)

    Hao, Y; Wolery, T; Carroll, S

    2009-04-30

    This report summarizes preliminary 2-D reactive-transport simulations on the injection, storage and transport of supercritical CO{sub 2} in dolostone formations in the Ordos Basin in China. The purpose of the simulations was to evaluate the role that basin heterogeneity, permeability, CO{sub 2} flux, and geochemical reactions between the carbonate geology and the CO{sub 2} equilibrated brines have on the evolution of porosity and permeability in the storage reservoir. The 2-D simulation of CO{sub 2} injection at 10{sup 3} ton/year corresponds to CO{sub 2} injection at a rate of 3 x 10{sup 5} ton/year in a 3-D, low permeable rock. An average permeability of 10 md was used in the simulation and reflects the upper range of permeability reported for the Ordos Basin Majiagou Group. Transport and distribution of CO{sub 2} between in the gas, aqueous, and solid phases were followed during a 10-year injection phase and a 10-year post injection phase. Our results show that CO{sub 2} flux and the spatial distribution of reservoir permeability will dictate the transport of CO{sub 2} in the injection and post injection phases. The injection rate of supercritical CO{sub 2} into low permeable reservoirs may need to be adjusted to avoid over pressure and mechanical damage to the reservoir. Although it should be noted that 3-D simulations are needed to more accurately model pressure build-up in the injection phase. There is negligible change in porosity and permeability due to carbonate mineral dissolution or anhydrite precipitation because a very small amount of carbonate dissolution is required to reach equilibrium with respect these phases. Injected CO{sub 2} is stored largely in supercritical and dissolved phases. During the injection phase, CO{sub 2} is transport driven by pressure build up and CO{sub 2} buoyancy.

  6. Metal-Organic Framework-Stabilized CO2/Water Interfacial Route for Photocatalytic CO2 Conversion.

    Science.gov (United States)

    Luo, Tian; Zhang, Jianling; Li, Wei; He, Zhenhong; Sun, Xiaofu; Shi, Jinbiao; Shao, Dan; Zhang, Bingxing; Tan, Xiuniang; Han, Buxing

    2017-11-29

    Here, we propose a CO 2 /water interfacial route for photocatalytic CO 2 conversion by utilizing a metal-organic framework (MOF) as both an emulsifier and a catalyst. The CO 2 reduction occurring at the CO 2 /water interface produces formate with remarkably enhanced efficiency as compared with that in conventional solvent. The route is efficient, facile, adjustable, and environmentally benign, which is applicable for the CO 2 transformation photocatalyzed by different kinds of MOFs.

  7. Protection of G2 and G3 against CO{sub 2}; La protection contre le CO{sub 2} des ensembles G.2 et G.3

    Energy Technology Data Exchange (ETDEWEB)

    Chassany, J Ph; Rodier, J [Commissariat a l' Energie Atomique, Service de Protection contre les Radiations, Marcoule (France). Centre d' Etudes Nucleaires

    1961-07-01

    The presence of 60.000 m{sup 3} of CO{sub 2} at 15 kg/cm{sup 2} pressure has made necessary to set up a detection and protection system on a scale equal to that used for ionising radiations. Instruments to check CO and CO{sub 2} in the atmosphere carry out measurements continuously, alarm systems give warning if the CO{sub 2} content increases, and the working areas may be surveyed by a whole series of portable instruments. The order for evacuation is given by sirens, and respiratory units are placed at strategic points along the exit paths. (author) [French] La presence de 60000 m{sup 3} de CO{sub 2} a 15 kg/cm{sup 2} de pression a exige la mise en place d'un dispositif de detection et de protection aussi important que celui realise pour les radiations ionisantes. Des appareils de controle d'ambiance pour le CO et le CO{sub 2} effectuent des mesures en permanence, des appareils d'alarme donnent l'alerte en cas d'augmentation de la teneur en CO{sub 2} et tout une serie d'appareils portatifs permettant la surveillance des chantiers. L'evacuation est demandee par sirene et des appareils respiratoires autonomes jalonnent les trajets vers les sorties. (auteur)

  8. Geological Storage of CO2. Site Selection Criteria; Almacenamiento Geologico de CO2. Criterios de Seleccion de Emplazamientos

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz, C; Martinez, R; Recreo, F; Prado, P; Campos, R; Pelayo, M; Losa, A de la; Hurtado, A; Lomba, L; Perez del Villar, L; Ortiz, G; Sastre, J

    2006-07-01

    In year 2002 the Spanish Parliament unanimously passed the ratification of the Kyoto Protocol, signed December 1997, compromising to limiting the greenhouse gas emissions increase. Later on, the Environment Ministry submitted the Spanish National Assignment Emissions Plan to the European Union and in year 2005 the Spanish Greenhouse Gas market started working, establishing taxes to pay in case of exceeding the assigned emissions limits. So, the avoided emissions of CO2 have now an economic value that is promoting new anthropogenic CO2 emissions reduction technologies. Carbon Capture and Storage (CCS) are among these new technological developments for mitigating or eliminate climate change. CO2 can be stored in geological formations such as depleted oil or gas fields, deep permeable saline water saturated formations and unmineable coal seams, among others. This report seeks to establish the selection criteria for suitable geological formations for CO2 storage in the Spanish national territory, paying attention to both the operational and performance requirements of these storage systems. The report presents the physical and chemical properties and performance of CO2 under storage conditions, the transport and reaction processes of both supercritical and gaseous CO2, and CO2 trapping mechanisms in geological formations. The main part of the report is devoted to geological criteria at watershed, site and formation scales. (Author) 100 ref.

  9. PAR-2 expression in the gingival crevicular fluid reflects chronic periodontitis severity

    Directory of Open Access Journals (Sweden)

    Henrique FUKUSHIMA

    Full Text Available Abstract Recent studies investigating protease-activated receptor type 2 (PAR-2 suggest an association between the receptor and periodontal inflammation. It is known that gingipain, a bacterial protease secreted by the important periodontopathogen Porphyromonas gingivalis can activate PAR-2. Previous studies by our group found that PAR-2 is overexpressed in the gingival crevicular fluid (GCF of patients with moderate chronic periodontitis (MP. The present study aimed at evaluating whether PAR-2 expression is associated with chronic periodontitis severity. GCF samples and clinical parameters, including plaque and bleeding on probing indices, probing pocket depth and clinical attachment level, were collected from the control group (n = 19 at baseline, and from MP patients (n = 19 and severe chronic periodontitis (SP (n = 19 patients before and 6 weeks after periodontal non-surgical treatment. PAR-2 and gingipain messenger RNA (mRNA in the GCF of 4 periodontal sites per patient were evaluated by Reverse Transcription Polymerase Chain Reaction (RT-qPCR. PAR-2 and gingipain expressions were greater in periodontitis patients than in control group patients. In addition, the SP group presented increased PAR-2 and gingipain mRNA levels, compared with the MP group. Furthermore, periodontal treatment significantly reduced (p <0.05 PAR-2 expression in patients with periodontitis. In conclusion, PAR-2 is associated with chronic periodontitis severity and with gingipain levels in the periodontal pocket, thus suggesting that PAR-2 expression in the GCF reflects the severity of destruction during periodontal infection.

  10. Natural Analogues of CO2 Geological Storage; Analogos Naturales del Almacenamiento Geologico de CO2

    Energy Technology Data Exchange (ETDEWEB)

    Perez del Villar, L; Pelayo, M; Recreo, F

    2007-07-20

    Geological storage of carbon dioxide is nowadays, internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize the global climate change universally accepted. Nevertheless, the possible risks derived of this long-term storage have a direct influence on its public acceptance. Among the favourable geological formations to store CO2, depleted oil and gas fields, deep saline reservoirs, and unamiable coal seams are highlighted. One of the most important objectives of the R and D projects related to the CO2 geological storage is the evaluation of the CO2 leakage rate through the above mentioned geological formations. Therefore, it is absolutely necessary to increase our knowledge on the interaction among CO2, storage and sealing formations, as well as on the flow paths and the physical resistance of the sealing formation. The quantification of the CO2 leakage rate is essential to evaluate the effects on the human and animal health, as well as for the ecosystem and water quality. To achieve these objectives, the study of the natural analogues is very useful in order to know the natural leakage rate to the atmosphere, its flow paths, the physical, chemical and mineralogical modifications due to the long term interaction processes among the CO2 and the storage and sealing formations, as well as the effects on the groundwaters and ecosystems. In this report, we have tried to summarise the main characteristics of the natural reservoirs and surficial sources of CO2, which are both natural analogues of the geological storage and CO2 leakage, studied in EEUU, Europe and Australia. The main objective of this summary is to find the possible applications for long-term risk prediction and for the performance assessment by means of conceptual and numerical modelling, which will allow to validate the predictive models of the CO2 storage behaviour, to design and develop suitable monitoring techniques to control the CO2 behaviour

  11. Advances in Geological CO{sub 2} Sequestration and Co-Sequestration with O{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Verba, Circe A; O& #x27; Connor, William K.; Ideker, J.H.

    2012-10-28

    The injection of CO{sub 2} for Enhanced Oil Recovery (EOR) and sequestration in brine-bearing formations for long term storage has been in practice or under investigation in many locations globally. This study focused on the assessment of cement wellbore seal integrity in CO{sub 2}- and CO{sub 2}-O{sub 2}-saturated brine and supercritical CO{sub 2} environments. Brine chemistries (NaCl, MgCl{sub 2}, CaCl{sub 2}) at various saline concentrations were investigated at a pressure of 28.9 MPa (4200 psi) at both 50{degree}C and 85{degree}C. These parameters were selected to simulate downhole conditions at several potential CO{sub 2} injection sites in the United States. Class H portland cement is not thermodynamically stable under these conditions and the formation of carbonic acid degrades the cement. Dissociation occurs and leaches cations, forming a CaCO{sub 3} buffered zone, amorphous silica, and other secondary minerals. Increased temperature affected the structure of C-S-H and the hydration of the cement leading to higher degradation rates.

  12. Dolomite decomposition under CO2

    International Nuclear Information System (INIS)

    Guerfa, F.; Bensouici, F.; Barama, S.E.; Harabi, A.; Achour, S.

    2004-01-01

    Full text.Dolomite (MgCa (CO 3 ) 2 is one of the most abundant mineral species on the surface of the planet, it occurs in sedimentary rocks. MgO, CaO and Doloma (Phase mixture of MgO and CaO, obtained from the mineral dolomite) based materials are attractive steel-making refractories because of their potential cost effectiveness and world wide abundance more recently, MgO is also used as protective layers in plasma screen manufacture ceel. The crystal structure of dolomite was determined as rhombohedral carbonates, they are layers of Mg +2 and layers of Ca +2 ions. It dissociates depending on the temperature variations according to the following reactions: MgCa (CO 3 ) 2 → MgO + CaO + 2CO 2 .....MgCa (CO 3 ) 2 → MgO + Ca + CaCO 3 + CO 2 .....This latter reaction may be considered as a first step for MgO production. Differential thermal analysis (DTA) are used to control dolomite decomposition and the X-Ray Diffraction (XRD) was used to elucidate thermal decomposition of dolomite according to the reaction. That required samples were heated to specific temperature and holding times. The average particle size of used dolomite powders is 0.3 mm, as where, the heating temperature was 700 degree celsius, using various holding times (90 and 120 minutes). Under CO 2 dolomite decomposed directly to CaCO 3 accompanied by the formation of MgO, no evidence was offered for the MgO formation of either CaO or MgCO 3 , under air, simultaneous formation of CaCO 3 , CaO and accompanied dolomite decomposition

  13. Experimental hydrate formation and gas production scenarios based on CO{sub 2} sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, J.C.; Howard, J.J. [ConocoPhillips, Bartlesville, OK (United States). Reservoir Laboratories; Baldwin, B.A. [Green Country Petrophysics LLC, Dewey, OK (United States); Ersland, G.; Husebo, J.; Graue, A. [Bergen Univ., Bergen (Norway). Dept. of Physics and Technology

    2008-07-01

    Gas hydrate production strategies have focused on depressurization or thermal stimulation of the reservoir, which in turn leads to hydrate dissociation. In order to evaluate potential production scenarios, the recovery efficiency of the natural gas from hydrate must be known along with the corresponding amounts of produced water. This study focused on the exchange of carbon dioxide (CO{sub 2}) with the natural gas hydrate and the subsequent release of free methane (CH{sub 4}). Laboratory experiments that investigated the rates and mechanisms of hydrate formation in coarse-grained porous media have shown the significance of initial water saturation and salinity on forming methane hydrates. Many of the experiments were performed in a sample holder fitted with an MRI instrument for monitoring hydrate formation. Hydrate-saturated samples were subjected to different procedures to release methane. The rates and efficiency of the exchange process were reproducible over a series of initial conditions. The exchange process was rapid and efficient in that no free water was observed in the core with MRI measurements. Injection of CO{sub 2} into the whole-core hydrate-saturated pore system resulted in methane production at the outlet end. Permeability measurements on these hydrate saturated cores during hydrate formation decreased to low values, but enough for gas transport. The lower permeability values remained constant during the methane-carbon dioxide exchange process in the hydrate structure. 12 refs., 9 figs.

  14. Bacterial Community Profiling of H2/CO2 or Formate-Utilizing Acetogens Enriched from Diverse Ecosystems

    Science.gov (United States)

    Han, R.; Zhang, L.; Fu, B.; Liu, H.

    2014-12-01

    Synthetic gases are usually generated from either cellulosic agricultural waste combustion or industrial release and could be subsequently transformed into acetate, ethanol, and/or butyrate by homoacetogenic bacteria, which commonly possess reductive acetyl-CoA synthesis pathway. Homoacetogen-based syngas fermentation technology provides an alternative solution to link greenhouse gas emission control and cellulosic solid waste treatment with biofuels production. The objective of our current project is to hunt for homoacetogens with capabilities of highly efficiently converting syngases to chemical solvents. In this study, we evaluated homoacetogens population dynamics during enrichments and pinpointed dominant homoacetogens representing diverse ecosystems enriched by different substrates. We enriched homoacetogens from four different samples including waste activate sludge, freshwater sediment, anaerobic methanogenic sludge, and cow manure using H2/CO2 (4:1) or formate as substrate for homoacetogen enrichment. Along with the formyltetrahydrofolate synthetase (FTHFS) gene (fhs gene)-specific real time qPCR assay and Terminal Restriction Fragment Length Polymorphism (T-RFLP) analysis, 16S rRNA based 454 high-throughput pyrosequencing was applied to reveal the population dynamic and community structure during enrichment from different origins. Enrichment of homoacetogenic populations coincided with accumulations of short chain fatty acids such as acetate and butyrate. 454 high-throughput pyrosequencing revealed Firmicutes and Spirochaetes populations became dominant while the overall microbial diversity decreased after enrichment. The most abundant sequences among the four origins belonged to the following phyla: Firmicutes, Spirochaetes, Proteobacteria, and Bacteroidetes, accounting for 62.1%-99.1% of the total reads. The major putative homoacetogenic species enriched on H2/CO2 or formate belonged to Clostridium spp., Acetobacterium spp., Acetoanaerobium spp

  15. Uncertainty studies and risk assessment for CO2 storage in geological formations

    International Nuclear Information System (INIS)

    Walter, Lena Sophie

    2013-01-01

    Carbon capture and storage (CCS) in deep geological formations is one possible option to mitigate the greenhouse gas effect by reducing CO 2 emissions into the atmosphere. The assessment of the risks related to CO 2 storage is an important task. Events such as CO 2 leakage and brine displacement could result in hazards for human health and the environment. In this thesis, a systematic and comprehensive risk assessment concept is presented to investigate various levels of uncertainties and to assess risks using numerical simulations. Depending on the risk and the processes, which should be assessed, very complex models, large model domains, large time scales, and many simulations runs for estimating probabilities are required. To reduce the resulting high computational costs, a model reduction technique (the arbitrary polynomial chaos expansion) and a method for model coupling in space are applied. The different levels of uncertainties are: statistical uncertainty in parameter distributions, scenario uncertainty, e.g. different geological features, and recognized ignorance due to assumptions in the conceptual model set-up. Recognized ignorance and scenario uncertainty are investigated by simulating well defined model set-ups and scenarios. According to damage values, which are defined as a model output, the set-ups and scenarios can be compared and ranked. For statistical uncertainty probabilities can be determined by running Monte Carlo simulations with the reduced model. The results are presented in various ways: e.g., mean damage, probability density function, cumulative distribution function, or an overall risk value by multiplying the damage with the probability. If the model output (damage) cannot be compared to provided criteria (e.g. water quality criteria), analytical approximations are presented to translate the damage into comparable values. The overall concept is applied for the risks related to brine displacement and infiltration into drinking water

  16. PAR-2 expression in the gingival crevicular fluid reflects chronic periodontitis severity.

    Science.gov (United States)

    Fukushima, Henrique; Alves, Vanessa Tubero Euzebio; Carvalho, Verônica Franco de; Ambrósio, Lucas Macedo Batitucci; Eichler, Rosangela Aparecida Dos Santos; Carvalho, Maria Helena Catelli de; Saraiva, Luciana; Holzhausen, Marinella

    2017-01-26

    Recent studies investigating protease-activated receptor type 2 (PAR-2) suggest an association between the receptor and periodontal inflammation. It is known that gingipain, a bacterial protease secreted by the important periodontopathogen Porphyromonas gingivalis can activate PAR-2. Previous studies by our group found that PAR-2 is overexpressed in the gingival crevicular fluid (GCF) of patients with moderate chronic periodontitis (MP). The present study aimed at evaluating whether PAR-2 expression is associated with chronic periodontitis severity. GCF samples and clinical parameters, including plaque and bleeding on probing indices, probing pocket depth and clinical attachment level, were collected from the control group (n = 19) at baseline, and from MP patients (n = 19) and severe chronic periodontitis (SP) (n = 19) patients before and 6 weeks after periodontal non-surgical treatment. PAR-2 and gingipain messenger RNA (mRNA) in the GCF of 4 periodontal sites per patient were evaluated by Reverse Transcription Polymerase Chain Reaction (RT-qPCR). PAR-2 and gingipain expressions were greater in periodontitis patients than in control group patients. In addition, the SP group presented increased PAR-2 and gingipain mRNA levels, compared with the MP group. Furthermore, periodontal treatment significantly reduced (p periodontitis. In conclusion, PAR-2 is associated with chronic periodontitis severity and with gingipain levels in the periodontal pocket, thus suggesting that PAR-2 expression in the GCF reflects the severity of destruction during periodontal infection.

  17. Formation of hydroxyl radicals and kinetic study of 2-chlorophenol photocatalytic oxidation using C-doped TiO2, N-doped TiO2, and C,N Co-doped TiO2 under visible light.

    Science.gov (United States)

    Ananpattarachai, Jirapat; Seraphin, Supapan; Kajitvichyanukul, Puangrat

    2016-02-01

    This work reports on synthesis, characterization, adsorption ability, formation rate of hydroxyl radicals (OH(•)), photocatalytic oxidation kinetics, and mineralization ability of C-doped titanium dioxide (TiO2), N-doped TiO2, and C,N co-doped TiO2 prepared by the sol-gel method. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy were used to analyze the titania. The rate of formation of OH(•) for each type of titania was determined, and the OH-index was calculated. The kinetics of as-synthesized TiO2 catalysts in photocatalytic oxidation of 2-chlorophenol (2-CP) under visible light irradiation were evaluated. Results revealed that nitrogen was incorporated into the lattice of titania with the structure of O-Ti-N linkages in N-doped TiO2 and C,N co-doped TiO2. Carbon was joined to the Ti-O-C bond in the C-doped TiO2 and C,N co-doped TiO2. The 2-CP adsorption ability of C,N co-doped TiO2 and C-doped TiO2 originated from a layer composed of a complex carbonaceous mixture at the surface of TiO2. C,N co-doped TiO2 had highest formation rate of OH(•) and photocatalytic activity due to a synergistic effect of carbon and nitrogen co-doping. The order of photocatalytic activity per unit surface area was the same as that of the formation rate of OH(•) unit surface area in the following order: C,N co-doped TiO2 > C-doped TiO2 > N-doped TiO2 > undoped TiO2.

  18. Effect of atmospheric CO{sub 2} on surface segregation and phase formation in La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ} thin films

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Yang [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Luo, Heng [Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States); Cetin, Deniz [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Lin, Xi [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States); Ludwig, Karl [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Physics, Boston University, Boston, MA 02215 (United States); Pal, Uday; Gopalan, Srikanth [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States); Basu, Soumendra, E-mail: basu@bu.edu [Division of Materials Science and Engineering, Boston University, Brookline, MA 02446 (United States); Department of Mechanical Engineering, Boston University, Boston, MA 02215 (United States)

    2014-12-30

    Highlights: • LSCF exhibits Sr surface segregation on high-temperature annealing. • The presence of atmospheric CO{sub 2} enhances the kinetics of Sr surface segregation. • At high-CO{sub 2} partial pressures, there is a significant coverage of the surface by Sr-rich phases. • The increase in kinetics is attributed to increased thermodynamic driving force for SrCO{sub 3} formation. - Abstract: The effects of atmospheric CO{sub 2} on surface segregation and phase formation in La{sub 0.6}Sr{sub 0.4}Co{sub 0.2}Fe{sub 0.8}O{sub 3−δ} (LSCF-6428) were investigated. (0 0 1)-oriented LSCF-6428 thin films were deposited on lattice matched (1 1 0)-oriented NdGaO{sub 3} (NGO) substrates by pulsed laser deposition (PLD). Using the synchrotron technique of total reflection X-ray fluorescence (TXRF), it was found that the kinetics of Sr surface segregation was enhanced when annealing at 800 °C in a high-CO{sub 2} partial pressure, as compared to a similar anneal in a CO{sub 2}-free atmosphere, with the oxygen partial pressure being constant in both cases. Hard X-ray photoelectron spectroscopy (HAXPES) measurements showed that the contribution of the surface carbonate to surface oxide phases increased significantly for the sample annealed in the high-CO{sub 2} atmosphere. Atomic force microscopy (AFM) studies showed enhanced surface phase formation during the high-CO{sub 2} partial pressure anneal. Density functional theory (DFT) calculations provide a thermodynamic basis for the enhanced kinetics of surface segregation in the presence of atmospheric CO{sub 2}.

  19. Bacterial mitosis: Partitioning protein ParA oscillates in spiral-shaped structures and positions plasmids at mid-cell

    DEFF Research Database (Denmark)

    Ebersbach, G.; Gerdes, Kenn

    2004-01-01

    The par2 locus of Escherichia coli plasmid pB171 encodes oscillating ATPase ParA, DNA binding protein ParB and two cis-acting DNA regions to which ParB binds (parC1 and parC2). Three independent techniques were used to investigate the subcellular localization of plasmids carrying par2. In cells......A-GFP oscillated in spiral-shaped structures. Amino acid substitutions in ParA simultaneously abolished ParA spiral formation, oscillation and either plasmid localization or plasmid separation at mid-cell. Therefore, our results suggest that ParA spirals position plasmids at the middle of the bacterial nucleoid...

  20. Modeling of CO2 storage in aquifers

    International Nuclear Information System (INIS)

    Savioli, Gabriela B; Santos, Juan E

    2011-01-01

    Storage of CO 2 in geological formations is a means of mitigating the greenhouse effect. Saline aquifers are a good alternative as storage sites due to their large volume and their common occurrence in nature. The first commercial CO 2 injection project is that of the Sleipner field in the Utsira Sand aquifer (North Sea). Nevertheless, very little was known about the effectiveness of CO 2 sequestration over very long periods of time. In this way, numerical modeling of CO 2 injection and seismic monitoring is an important tool to understand the behavior of CO 2 after injection and to make long term predictions in order to prevent CO 2 leaks from the storage into the atmosphere. The description of CO 2 injection into subsurface formations requires an accurate fluid-flow model. To simulate the simultaneous flow of brine and CO 2 we apply the Black-Oil formulation for two phase flow in porous media, which uses the PVT data as a simplified thermodynamic model. Seismic monitoring is modeled using Biot's equations of motion describing wave propagation in fluid-saturated poroviscoelastic solids. Numerical examples of CO 2 injection and time-lapse seismics using data of the Utsira formation show the capability of this methodology to monitor the migration and dispersal of CO 2 after injection.

  1. Biological CO2 conversion to acetate in subsurface coal-sand formation using a high-pressure reactor system

    Directory of Open Access Journals (Sweden)

    Yoko eOhtomo

    2013-12-01

    Full Text Available Geological CO2 sequestration in unmineable subsurface oil/gas fields and coal formations has been proposed as a means of reducing anthropogenic greenhouse gasses in the atmosphere. However, the feasibility of injecting CO2 into subsurface depends upon a variety of geological and economic conditions, and the ecological consequences are largely unpredictable. In this study, we developed a new flow-through-type reactor system to examine potential geophysical, geochemical and microbiological impacts associated with CO2 injection by simulating in situ pressure (0–100 MPa and temperature (0–70°C conditions. Using the reactor system, anaerobic artificial fluid and CO2 (flow rate: 0.002 and 0.00001 mL/min, respectively were continuously supplemented into a column comprised of bituminous coal and sand under a pore pressure of 40 MPa (confined pressure: 41 MPa at 40°C for 56 days. 16S rRNA gene analysis of the bacterial components showed distinct spatial separation of the predominant taxa in the coal and sand over the course of the experiment. Cultivation experiments using sub-sampled fluids revealed that some microbes survived, or were metabolically active, under CO2-rich conditions. However, no methanogens were activated during the experiment, even though hydrogenotrophic and methylotrophic methanogens were obtained from conventional batch-type cultivation at 20°C. During the reactor experiment, the acetate and methanol concentration in the fluids increased while the δ13Cacetate, H2 and CO2 concentrations decreased, indicating the occurrence of homo-acetogenesis. 16S rRNA genes of homo-acetogenic spore-forming bacteria related to the genus Sporomusa were consistently detected from the sandstone after the reactor experiment. Our results suggest that the injection of CO2 into a natural coal-sand formation preferentially stimulates homo-acetogenesis rather than methanogenesis, and that this process is accompanied by biogenic CO2 conversion to

  2. Effect of Co crystallinity on Co/CNT catalytic activity in CO/CO{sub 2} hydrogenation and CO disproportionation

    Energy Technology Data Exchange (ETDEWEB)

    Chernyak, Sergei A., E-mail: chernyak.msu@gmail.com [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation); Suslova, Evgeniya V.; Egorov, Alexander V.; Maslakov, Konstantin I. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Savilov, Serguei V.; Lunin, Valery V. [Lomonosov Moscow State University, Department of Chemistry, Leninskiye Gory 1-3, Moscow 119991 (Russian Federation); Kurnakov Institute of General and Inorganic Chemistry of the Russian Academy of Sciences, Department of Physical Chemistry, Leninsky Avenue 31, Moscow 119991 (Russian Federation)

    2016-05-30

    Highlights: • Amorphous and crystalline Co supported on CNTs were obtained by tuning of CNT surface. • CO and CO{sub 2} hydrogenation does not occur on amorphous Co particles. • Thermal activation of amorphous Co led to crystallization of metal. • Amorphous Co promotes CO disproportionation. • Carbon shells around the amorphous metal particles after the CO hydrogenation. - Abstract: Carbon nanotubes (CNTs) with different degree of surface oxidation were used as supports for 5 wt.% Co catalysts. CNTs and Co/CNT catalysts were analyzed by XPS, nitrogen adsorption, TEM and electron diffraction to reveal their structure. High oxidation degree of CNT surface (8.6 at.% of O) and low Co loading led to predominantly amorphous Co species. This resulted in the absence of catalytic activity in both CO and CO{sub 2} hydrogenation in opposite to the catalyst supported on less oxidized CNTs (5.4 at.% of O) where Co species were found to be crystalline. Thermal treatment of inactive catalyst in H{sub 2} and He led to the formation of Co crystal phase which was active in catalysis. Co particle size in catalyst supported on strongly oxidized CNTs was unchanged during CO hydrogenation in opposite to Co supported on less oxidized CNTs. Carbon shell formation on the surface of amorphous Co particles during CO hydrogenation was revealed, which testified CO disproportionation. Qualitative mechanism of CO hydrogenation on small Co particles was proposed.

  3. Site characterization of the highest-priority geologic formations for CO2 storage in Wyoming

    Energy Technology Data Exchange (ETDEWEB)

    Surdam, Ronald C. [Univ. of Wyoming, Laramie, WY (United States); Bentley, Ramsey [Univ. of Wyoming, Laramie, WY (United States); Campbell-Stone, Erin [Univ. of Wyoming, Laramie, WY (United States); Dahl, Shanna [Univ. of Wyoming, Laramie, WY (United States); Deiss, Allory [Univ. of Wyoming, Laramie, WY (United States); Ganshin, Yuri [Univ. of Wyoming, Laramie, WY (United States); Jiao, Zunsheng [Univ. of Wyoming, Laramie, WY (United States); Kaszuba, John [Univ. of Wyoming, Laramie, WY (United States); Mallick, Subhashis [Univ. of Wyoming, Laramie, WY (United States); McLaughlin, Fred [Univ. of Wyoming, Laramie, WY (United States); Myers, James [Univ. of Wyoming, Laramie, WY (United States); Quillinan, Scott [Univ. of Wyoming, Laramie, WY (United States)

    2013-12-07

    This study, funded by U.S. Department of Energy National Energy Technology Laboratory award DE-FE0002142 along with the state of Wyoming, uses outcrop and core observations, a diverse electric log suite, a VSP survey, in-bore testing (DST, injection tests, and fluid sampling), a variety of rock/fluid analyses, and a wide range of seismic attributes derived from a 3-D seismic survey to thoroughly characterize the highest-potential storage reservoirs and confining layers at the premier CO2 geological storage site in Wyoming. An accurate site characterization was essential to assessing the following critical aspects of the storage site: (1) more accurately estimate the CO2 reservoir storage capacity (Madison Limestone and Weber Sandstone at the Rock Springs Uplift (RSU)), (2) evaluate the distribution, long-term integrity, and permanence of the confining layers, (3) manage CO2 injection pressures by removing formation fluids (brine production/treatment), and (4) evaluate potential utilization of the stored CO2

  4. [Roles of protease-activated receptor-2 (PAR-2), a G protein-coupled receptor, in modulation of exocrine gland functions].

    Science.gov (United States)

    Nishikawa, Hiroyuki

    2006-07-01

    Protease-activated receptor-2 (PAR-2), a G protein-coupled receptor, is activated by proteolytic unmasking of the N-terminal extracellular tethered ligand that presumably binds to the extracellular loop 2 of the receptor itself. PAR-2 is widely distributed in the mammalian body and plays various roles in biological events in the cardiovascular, respiratory, alimentary, and central neurons systems. PAR-2-activating peptides administered systemically to mice and rats trigger prompt salivation in vivo. In an in vitro study, PAR-2 agonists including the endogenous PAR-2 activator trypsin induce secretion of amylase and mucin from isolated rat parotid glands and sublingual glands, respectively. PAR-2-activating peptides administered systemically also modulate pancreatic exocrine secretion in vivo as well as in vitro. In the gastric mucosa, PAR-2 stimulation enhances secretion of mucus and pepsinogen and suppresses acid secretion. Tear secretion can also be caused by PAR-2-related peptides in PAR-2-dependent and -independent manners. PAR-2 thus plays a general or key role in the regulation of exocrine secretion. This review focuses on the physiologic and/or pathophysiologic roles of PAR-2 in glandular exocrine secretion. The possibility of PAR-2 as a target for drug development is also discussed.

  5. Geological Storage of CO2. Site Selection Criteria; Almacenamiento Geologico de CO2. Criterios de Selecci0n de Emplazamientos

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz, C; Martinez, R; Recreo, F; Prado, P; Campos, R; Pelayo, M; Losa, A de la; Hurtado, A; Lomba, L; Perez del Villar, L; Ortiz, G; Sastre, J; Zapatero, M A; Suarez, I; Arenillas, A

    2007-09-18

    In year 2002 the Spanish Parliament unanimously passed the ratification of the Kyoto Protocol, signed December 1997, compromising to limiting the greenhouse gas emissions increase. Later on, the Environment Ministry submitted the Spanish National Assignment Emissions Plan to the European Union and in year 2005 the Spanish Greenhouse Gas market started working, establishing taxes to pay in case of exceeding the assigned emissions limits. So, the avoided emissions of CO2 have now an economic value that is promoting new anthropogenic CO2 emissions reduction technologies. Carbon Capture and Storage (CCS) are among these new technological developments for mitigating or eliminate climate change. CO2 can be stored in geological formations such as depleted oil or gas fields, deep permeable saline water saturated formations and unmailable coal seams, among others. This report seeks to establish the selection criteria for suitable geological formations for CO2 storage in the Spanish national territory, paying attention to both the operational and performance requirements of these storage systems. The report presents the physical and chemical properties and performance of CO2 under storage conditions, the transport and reaction processes of both supercritical and gaseous CO2, and CO2 trapping mechanisms in geological formations. The main part of the report is devoted to geological criteria at watershed, site and formation scales. (Author) 100 refs.

  6. Dynamic Filament Formation by a Divergent Bacterial Actin-Like ParM Protein.

    Directory of Open Access Journals (Sweden)

    Anthony J Brzoska

    Full Text Available Actin-like proteins (Alps are a diverse family of proteins whose genes are abundant in the chromosomes and mobile genetic elements of many bacteria. The low-copy-number staphylococcal multiresistance plasmid pSK41 encodes ParM, an Alp involved in efficient plasmid partitioning. pSK41 ParM has previously been shown to form filaments in vitro that are structurally dissimilar to those formed by other bacterial Alps. The mechanistic implications of these differences are not known. In order to gain insights into the properties and behavior of the pSK41 ParM Alp in vivo, we reconstituted the parMRC system in the ectopic rod-shaped host, E. coli, which is larger and more genetically amenable than the native host, Staphylococcus aureus. Fluorescence microscopy showed a functional fusion protein, ParM-YFP, formed straight filaments in vivo when expressed in isolation. Strikingly, however, in the presence of ParR and parC, ParM-YFP adopted a dramatically different structure, instead forming axial curved filaments. Time-lapse imaging and selective photobleaching experiments revealed that, in the presence of all components of the parMRC system, ParM-YFP filaments were dynamic in nature. Finally, molecular dissection of the parMRC operon revealed that all components of the system are essential for the generation of dynamic filaments.

  7. Polymeric cobalt(ii) thiolato complexes - syntheses, structures and properties of [Co(SMes)2] and [Co(SPh)2NH3].

    Science.gov (United States)

    Eichhöfer, Andreas; Buth, Gernot

    2016-11-01

    Reactions of [Co(N(SiMe 3 ) 2 ) 2 thf] with 2.1 equiv. of MesSH (Mes = C 6 H 2 -2,4,6-(CH 3 ) 3 ) yield dark brown crystals of the one dimensional chain compound [Co(SMes) 2 ]. In contrast reactions of [Co(N(SiMe 3 ) 2 ) 2 thf] with 2.1 equiv. of PhSH result in the formation of a dark brown almost X-ray amorphous powder of 'Co(SPh) 2 '. Addition of aliquots of CH 3 OH to the latter reaction resulted in the almost quantitative formation of crystalline ammonia thiolato complexes either [Co(SPh) 2 (NH 3 ) 2 ] or [Co(SPh) 2 NH 3 ]. Single crystal XRD reveals that [Co(SPh) 2 NH 3 ] forms one-dimensional chains in the crystal via μ 2 -SPh bridges whereas [Co(SPh) 2 (NH 3 ) 2 ] consists at a first glance of isolated distorted tetrahedral units. Magnetic measurements suggest strong antiferromagnetic coupling for the two chain compounds [Co(SMes) 2 ] (J = -38.6 cm -1 ) and [Co(SPh) 2 NH 3 ] (J = -27.1 cm -1 ). Interestingly, also the temperature dependence of the susceptibility of tetrahedral [Co(SPh) 2 (NH 3 ) 2 ] shows an antiferromagnetic transition at around 6 K. UV-Vis-NIR spectra display d-d bands in the NIR region between 500 and 2250 nm. Thermal gravimetric analysis of [Co(SPh) 2 (NH 3 ) 2 ] and [Co(SPh) 2 NH 3 ] reveals two well separated cleavage processes for NH 3 and SPh 2 upon heating accompanied by the stepwise formation of 'Co(SPh) 2 ' and cobalt sulfide.

  8. Well technologies for CO2 geological storage: CO2-resistant cement

    International Nuclear Information System (INIS)

    Barlet-Gouedard, V.; Rimmele, G.; Porcherie, O.; Goffe, B.

    2007-01-01

    Storing carbon dioxide (CO 2 ) underground is considered the most effective way for long-term safe and low-cost CO 2 sequestration. This recent application requires long-term well-bore integrity. A CO 2 leakage through the annulus may occur much more rapidly than geologic leakage through the formation rock, leading to economic loss, reduction of CO 2 storage efficiency, and potential compromise of the field for storage. The possibility of such leaks raises considerable concern about the long-term well-bore isolation and the durability of hydrated cement that is used to isolate the annulus across the producing/injection intervals in CO 2 -storage wells. We propose a new experimental procedure and methodology to study reactivity of CO 2 -Water-Cement systems in simulating the interaction of the set cement with injected supercritical CO 2 under downhole conditions. The conditions of experiments are 90 deg. C under 280 bars. The evolution of mechanical, physical and chemical properties of Portland cement with time is studied up to 6 months. The results are compared to equivalent studies on a new CO 2 -resistant material; the comparison shows significant promise for this new material. (authors)

  9. Solid state synthesis of stoichiometric LiCoO2 from mechanically activated Co-Li2CO3 mixtures

    International Nuclear Information System (INIS)

    Berbenni, Vittorio; Milanese, Chiara; Bruni, Giovanna; Marini, Amedeo

    2006-01-01

    Stoichiometric lithium cobalt oxide (LiCoO 2 ) has been synthesized by solid state reaction of mixtures of the system Co-0.5Li 2 CO 3 after mechanical activation by high energy milling. The differences in the reaction mechanism and in product stoichiometry with respect to what happens when starting from the non activated (physical) system have been brought into evidence by TG analysis. Furthermore it has been shown that stoichiometric LiCoO 2 is obtained by a 200 h annealing of the activated mixture at temperatures as low as 400 deg. C. Finally, it has been revealed that longer activation times (150 h) result in Co oxidation to Co 3 O 4 that, in turn, hampers the formation of stoichiometric LiCoO 2

  10. Decontamination of solid matrices using supercritical CO{sub 2}: study of contaminant-additives-CO{sub 2}; Decontamination de matrices organiques solides par CO{sub 2} supercritique: etude des interactions contaminant-additifs-CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Galy, J

    2006-11-15

    This work deals with the decontamination of solid matrices by supercritical CO{sub 2} and more particularly with the study of the interactions between the surfactants and the CO{sub 2} in one part, and with the interactions between the contaminant and the surfactants in another part. The first part of this study has revealed the different interactions between the Pluronics molecules and the supercritical CO{sub 2}. The diagrams graphs have shown that the pluronics (PE 6100, PE 8100 and PE 10100) present a solubility in the supercritical CO{sub 2} low but sufficient (0.1% m/m at 25 MPa and 313 K) for the studied application: the treatment of weak quantities of cerium oxide (or plutonium). An empirical approach based on the evolutions of the slops value and of the origin ordinates of the PT diagrams has been carried out to simulate the phase diagrams PT of the Pluronics. A modeling based on the state equations 'SAFT' (Statistical Associating Fluid Theory) has been studied in order to confirm the experimental results of the disorder points and to understand the role of the different blocks 'PEO' and 'PPO' in the behaviour of Pluronics; this modeling confirms the evolution of the slopes value with the 'CO{sub 2}-phily' of the system. The measure of the surface tension in terms of the Pluronics concentration (PE 6100, 81000 and 10100) has shown different behaviours. For the PE 6100, the surface tension decreases when the surfactant concentration increases (at constant pressure and temperature); on the other hand, for the PE 8100 a slop rupture appears and corresponds to the saturation of the interface water/CO{sub 2} and allows then to determine the Interface Saturation Concentration (ISC). The ISC value (at constant pressure and temperature) increases with an increase of the 'CO{sub 2}-phily'). The model hydrophilous medium being an approximation, it has been replaced by a solid polar phase of CeO{sub 2}. A parallel has

  11. Geological Storage of CO2. Site Selection Criteria

    International Nuclear Information System (INIS)

    Ruiz, C.; Martinez, R.; Recreo, F.; Prado, P.; Campos, R.; Pelayo, M.; Losa, A. de la; Hurtado, A.; Lomba, L.; Perez del Villar, L.; Ortiz, G.; Sastre, J.; Zapatero, M. A.; Suarez, I.; Arenillas, A.

    2007-01-01

    In year 2002 the Spanish Parliament unanimously passed the ratification of the Kyoto Protocol, signed December 1997, compromising to limiting the greenhouse gas emissions increase. Later on, the Environment Ministry submitted the Spanish National Assignment Emissions Plan to the European Union and in year 2005 the Spanish Greenhouse Gas market started working, establishing taxes to pay in case of exceeding the assigned emissions limits. So, the avoided emissions of CO2 have now an economic value that is promoting new anthropogenic CO2 emissions reduction technologies. Carbon Capture and Storage (CCS) are among these new technological developments for mitigating or eliminate climate change. CO2 can be stored in geological formations such as depleted oil or gas fields, deep permeable saline water saturated formations and unmailable coal seams, among others. This report seeks to establish the selection criteria for suitable geological formations for CO2 storage in the Spanish national territory, paying attention to both the operational and performance requirements of these storage systems. The report presents the physical and chemical properties and performance of CO2 under storage conditions, the transport and reaction processes of both supercritical and gaseous CO2, and CO2 trapping mechanisms in geological formations. The main part of the report is devoted to geological criteria at watershed, site and formation scales. (Author) 100 refs

  12. Geological Storage of CO2. Site Selection Criteria

    International Nuclear Information System (INIS)

    Ruiz, C.; Martinez, R.; Recreo, F.; Prado, P.; Campos, R.; Pelayo, M.; Losa, A. de la; Hurtado, A.; Lomba, L.; Perez del Villar, L.; Ortiz, G.; Sastre, J.

    2006-01-01

    In year 2002 the Spanish Parliament unanimously passed the ratification of the Kyoto Protocol, signed December 1997, compromising to limiting the greenhouse gas emissions increase. Later on, the Environment Ministry submitted the Spanish National Assignment Emissions Plan to the European Union and in year 2005 the Spanish Greenhouse Gas market started working, establishing taxes to pay in case of exceeding the assigned emissions limits. So, the avoided emissions of CO2 have now an economic value that is promoting new anthropogenic CO2 emissions reduction technologies. Carbon Capture and Storage (CCS) are among these new technological developments for mitigating or eliminate climate change. CO2 can be stored in geological formations such as depleted oil or gas fields, deep permeable saline water saturated formations and unmineable coal seams, among others. This report seeks to establish the selection criteria for suitable geological formations for CO2 storage in the Spanish national territory, paying attention to both the operational and performance requirements of these storage systems. The report presents the physical and chemical properties and performance of CO2 under storage conditions, the transport and reaction processes of both supercritical and gaseous CO2, and CO2 trapping mechanisms in geological formations. The main part of the report is devoted to geological criteria at watershed, site and formation scales. (Author) 100 ref

  13. Dissociative photo-multiple-ionisation of CO and CO2

    International Nuclear Information System (INIS)

    Bapat, B; Sharma, Vandana; Prajapati, I A; Subramanian, K P; Singh, R K; Lodha, G S

    2007-01-01

    In a photoelectron-photoion coincidence experiment on CO and CO 2 , we have observed the formation and fragmentation of singly to triply charged CO 2 and singly to quadruply charged CO at various energies. Doubly charged cations of both molecules are found to have unstable as well as stable states. Cations with higher charge are found to dissociate promptly. The energy dependence of the relative partial cross-sections in the energy range 125-310 eV are presented

  14. Towards CO2 sequestration and applications of CO2 hydrates: the effects of tetrahydrofuran on the phase equilibria of CO2 hydrates

    International Nuclear Information System (INIS)

    Khalik, M.S.; Peters, C.J.

    2006-01-01

    The increasing quantity of carbon dioxide (CO 2 ) in the atmosphere has caused widespread global concerns. Capturing CO 2 from its sources and stored it in the form of gas hydrates and application of CO 2 hydrates are among the proposed methods to overcome this problem. In order to make hydrate-based process more attractive, the use of cyclic ethers as promoters is suggested to reduce the required hydrate formation pressure and enhancing the corresponding kinetic rate. In the present work, tetrahydrofuran (THF) is chosen as a hydrate promoter, participating in forming hydrates and produces mixed hydrate together with CO 2 . The pressure and temperature ranges of hydrate stability region are carefully determined through phase equilibrium measurement of the ternary CO 2 , tetrahydrofuran (THF) and water systems. From the experimental results, it is confirmed that the presence of THF in CO 2 + water systems will extend the hydrate formation region to higher temperature at a constant pressure. The extension of the hydrate stability region is depended on the overall concentration of the ternary system. Moreover, four-phase equilibrium of H-Lw-Lv-V is observed in the system, which may be due to a liquid phase split. In the region where the four-phase equilibrium exists, the ternary system loses its concentration dependency of the hydrate equilibrium conditions. (Author)

  15. Improved Characterization and Modeling of Tight Oil Formations for CO2 Enhanced Oil Recovery Potential and Storage Capacity Estimation

    Energy Technology Data Exchange (ETDEWEB)

    Sorensen, James [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Smith, Steven [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Kurz, Bethany [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Hawthorne, Steven [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Jin, Lu [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Bosshart, Nicholas [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Torres, Jose [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Nyberg, Carolyn [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Heebink, Loreal [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC); Hurley, John [Univ. of North Dakota, Grand Forks, ND (United States). Energy & Environmental Research Center (EERC)

    2018-03-09

    Tight oil formations such as those in the Bakken petroleum system are known to hold hundreds of billions of barrels of oil in place; however, the primary recovery factor for these plays is typically less than 10%. Tight oil formations, including the Bakken Formation, therefore, may be attractive candidates for enhanced oil recovery (EOR) using CO2. Multiphase fluid behavior and flow in fluid-rich shales can vary substantially depending on the size of pore throats, and properties such as fluid viscosity and density are much different in nanoscale pores than in macroscale pores. Thus it is critical to understand the nature and distribution of nano-, micro-, and macroscale pores and fracture networks. To address these issues, the Energy & Environmental Research Center (EERC) has been conducting a research program entitled “Improved Characterization and Modeling of Tight Oil Formations for CO2 Enhanced Oil Recovery Potential and Storage Capacity Estimation.” The objectives of the project are 1) the use of advanced characterization methods to better understand and quantify the petrophysical and geomechanical factors that control CO2 and oil mobility within tight oil formation samples, 2) the determination of CO2 permeation and oil extraction rates in tight reservoir rocks and organic-rich shales of the Bakken, and 3) the integration of the laboratory-based CO2 permeation and oil extraction data and the characterization data into geologic models and dynamic simulations to develop predictions of CO2 storage resource and EOR in the Bakken tight oil formation. A combination of standard and advanced petrophysical characterization techniques were applied to characterize samples of Bakken Formation tight reservoir rock and shales from multiple wells. Techniques included advanced computer tomography (CT) imaging, scanning electron microscopy (SEM) techniques, whole-core and micro x-ray CT imaging, field

  16. Heterogeneity-enhanced gas phase formation in shallow aquifers during leakage of CO2-saturated water from geologic sequestration sites

    Science.gov (United States)

    Plampin, Michael R.; Lassen, Rune N.; Sakaki, Toshihiro; Porter, Mark L.; Pawar, Rajesh J.; Jensen, Karsten H.; Illangasekare, Tissa H.

    2014-12-01

    A primary concern for geologic carbon storage is the potential for leakage of stored carbon dioxide (CO2) into the shallow subsurface where it could degrade the quality of groundwater and surface water. In order to predict and mitigate the potentially negative impacts of CO2 leakage, it is important to understand the physical processes that CO2 will undergo as it moves through naturally heterogeneous porous media formations. Previous studies have shown that heterogeneity can enhance the evolution of gas phase CO2 in some cases, but the conditions under which this occurs have not yet been quantitatively defined, nor tested through laboratory experiments. This study quantitatively investigates the effects of geologic heterogeneity on the process of gas phase CO2 evolution in shallow aquifers through an extensive set of experiments conducted in a column that was packed with layers of various test sands. Soil moisture sensors were utilized to observe the formation of gas phase near the porous media interfaces. Results indicate that the conditions under which heterogeneity controls gas phase evolution can be successfully predicted through analysis of simple parameters, including the dissolved CO2 concentration in the flowing water, the distance between the heterogeneity and the leakage location, and some fundamental properties of the porous media. Results also show that interfaces where a less permeable material overlies a more permeable material affect gas phase evolution more significantly than interfaces with the opposite layering.

  17. Uncertainty studies and risk assessment for CO{sub 2} storage in geological formations

    Energy Technology Data Exchange (ETDEWEB)

    Walter, Lena Sophie

    2013-07-01

    Carbon capture and storage (CCS) in deep geological formations is one possible option to mitigate the greenhouse gas effect by reducing CO{sub 2} emissions into the atmosphere. The assessment of the risks related to CO{sub 2} storage is an important task. Events such as CO{sub 2} leakage and brine displacement could result in hazards for human health and the environment. In this thesis, a systematic and comprehensive risk assessment concept is presented to investigate various levels of uncertainties and to assess risks using numerical simulations. Depending on the risk and the processes, which should be assessed, very complex models, large model domains, large time scales, and many simulations runs for estimating probabilities are required. To reduce the resulting high computational costs, a model reduction technique (the arbitrary polynomial chaos expansion) and a method for model coupling in space are applied. The different levels of uncertainties are: statistical uncertainty in parameter distributions, scenario uncertainty, e.g. different geological features, and recognized ignorance due to assumptions in the conceptual model set-up. Recognized ignorance and scenario uncertainty are investigated by simulating well defined model set-ups and scenarios. According to damage values, which are defined as a model output, the set-ups and scenarios can be compared and ranked. For statistical uncertainty probabilities can be determined by running Monte Carlo simulations with the reduced model. The results are presented in various ways: e.g., mean damage, probability density function, cumulative distribution function, or an overall risk value by multiplying the damage with the probability. If the model output (damage) cannot be compared to provided criteria (e.g. water quality criteria), analytical approximations are presented to translate the damage into comparable values. The overall concept is applied for the risks related to brine displacement and infiltration into

  18. Risk Assessment and Management for Long-Term Storage of CO2 in Geologic Formations — United States Department of Energy R&D

    Directory of Open Access Journals (Sweden)

    Dawn Deel

    2007-02-01

    Full Text Available Concern about increasing atmospheric concentrations of carbon dioxide (CO2 and other greenhouse gases (GHG and their impact on the earth's climate has grown significantly over the last decade. Many countries, including the United States, wrestle with balancing economic development and meeting critical near-term environmental goals while minimizing long-term environmental risks. One promising solution to the buildup of GHGs in the atmosphere, being pursued by the U.S. Department of Energy's (DOE National Energy Technology Laboratory (NETL and its industrial and academic partners, is carbon sequestration—a process of permanent storage of CO2 emissions in underground geologic formations, thus avoiding CO2 release to the atmosphere. This option looks particularly attractive for point source emissions of GHGs, such as fossil fuel fired power plants. CO2 would be captured, transported to a sequestration site, and injected into an appropriate geologic formation. However, sequestration in geologic formations cannot achieve a significant role in reducing GHG emissions unless it is acceptable to stakeholders, regulators, and the general public, i.e., unless the risks involved are judged to be acceptable. One tool that can be used to achieve acceptance of geologic sequestration of CO2 is risk assessment, which is a proven method to objectively manage hazards in facilities such as oil and natural gas fields, pipelines, refineries, and chemical plants. Although probabilistic risk assessment (PRA has been applied in many areas, its application to geologic CO2 sequestration is still in its infancy. The most significant risk from geologic carbon sequestration is leakage of CO2. Two types of CO2 releases are possible—atmospheric and subsurface. High concentrations of CO2 caused by a release to the atmosphere would pose health risks to humans and animals, and any leakage of CO2 back into the atmosphere negates the effort expended to sequester the CO2

  19. Carbon dioxide induced bubble formation in a CH4-CO2-H2O ternary system: a molecular dynamics simulation study.

    Science.gov (United States)

    Sujith, K S; Ramachandran, C N

    2016-02-07

    The extraction of methane from its hydrates using carbon dioxide involves the decomposition of the hydrate resulting in a CH4-CO2-H2O ternary solution. Using classical molecular dynamics simulations, we investigate the evolution of dissolved gas molecules in the ternary system at different concentrations of CO2. Various compositions considered in the present study resemble the solution formed during the decomposition of methane hydrates at the initial stages of the extraction process. We find that the presence of CO2 aids the formation of CH4 bubbles by causing its early nucleation. Elucidation of the composition of the bubble revealed that in ternary solutions with high concentration of CO2, mixed gas bubbles composed of CO2 and CH4 are formed. To understand the role of CO2 in the nucleation of CH4 bubbles, the structure of the bubble formed was analyzed, which revealed that there is an accumulation of CO2 at the interface of the bubble and the surrounding water. The aggregation of CO2 at the bubble-water interface occurs predominantly when the concentration of CO2 is high. Radial distribution function for the CH4-CO2 pair indicates that there is an increasingly favorable direct contact between dissolved CH4 and CO2 molecules in the bubble-water interface. It is also observed that the presence of CO2 at the interface results in the decrease in surface tension. Thus, CO2 leads to greater stability of the bubble-water interface thereby bringing down the critical size of the bubble nuclei. The results suggest that a rise in concentration of CO2 helps in the removal of dissolved CH4 thereby preventing the accumulation of methane in the liquid phase. Thus, the presence of CO2 is predicted to assist the decomposition of methane hydrates in the initial stages of the replacement process.

  20. Fuzzy Logic Approach for the Prediction of Dross Formation in CO2 Laser Cutting of Mild Steel

    Directory of Open Access Journals (Sweden)

    Miloš Madić

    2015-11-01

    Full Text Available Dross free laser cutting is very important in the application of laser cutting technology. This paper focuses on the development of a fuzzy logic model to predict dross formation in CO2 laser oxygen cutting of mild steel. Laser cutting experiment, conducted according to Taguchi’s experimental design using L25 orthogonal array, provided a set of data for the development of a fuzzy rule base. The predicting fuzzy logic model is based on using Mamdani-type inference system. Developed fuzzy logic model considered the cutting speed, laser power and assist gas pressure as inputs. Using this model the effects of the selected laser cutting parameters on the dross formation were investigated. Additionally, 3-D surface plots were generated to study the interaction effects of the laser cutting parameters. The analysis revealed that the cutting speed has the most significant effect, followed by laser power and assist gas pressure. The results indicated that the fuzzy logic modeling approach can be effectively used for the dross formation prediction in CO2 laser cutting of mild steel.

  1. Fingerprinting captured CO2 using natural tracers: Determining CO2 fate and proving ownership

    Science.gov (United States)

    Flude, Stephanie; Gilfillan, Stuart; Johnston, Gareth; Stuart, Finlay; Haszeldine, Stuart

    2016-04-01

    In the long term, captured CO2 will most likely be stored in large saline formations and it is highly likely that CO2 from multiple operators will be injected into a single saline formation. Understanding CO2 behavior within the reservoir is vital for making operational decisions and often uses geochemical techniques. Furthermore, in the event of a CO2 leak, being able to identify the owner of the CO2 is of vital importance in terms of liability and remediation. Addition of geochemical tracers to the CO2 stream is an effective way of tagging the CO2 from different power stations, but may become prohibitively expensive at large scale storage sites. Here we present results from a project assessing whether the natural isotopic composition (C, O and noble gas isotopes) of captured CO2 is sufficient to distinguish CO2 captured using different technologies and from different fuel sources, from likely baseline conditions. Results include analytical measurements of CO2 captured from a number of different CO2 capture plants and a comprehensive literature review of the known and hypothetical isotopic compositions of captured CO2 and baseline conditions. Key findings from the literature review suggest that the carbon isotope composition will be most strongly controlled by that of the feedstock, but significant fractionation is possible during the capture process; oxygen isotopes are likely to be controlled by the isotopic composition of any water used in either the industrial process or the capture technology; and noble gases concentrations will likely be controlled by the capture technique employed. Preliminary analytical results are in agreement with these predictions. Comparison with summaries of likely storage reservoir baseline and shallow or surface leakage reservoir baseline data suggests that C-isotopes are likely to be valuable tracers of CO2 in the storage reservoir, while noble gases may be particularly valuable as tracers of potential leakage.

  2. Feasibility of storing CO2 in the Utsira formation as part of a long term Dutch CCS strategy. An evaluation based on a GIS/MARKAL toolbox

    International Nuclear Information System (INIS)

    Van den Broek, M.A.; Ramirez-Ramirez, A.; Turkenburg, W.; Faaij, A; Groenenberg, H.; Neele, F.P.; Viebahn, P.

    2009-09-01

    This study provides insight into the feasibility of a CO2 trunkline from the Netherlands to the Utsira formation in the Norwegian part of the North Sea, which is a large geological storage reservoir for CO2. The feasibility is investigated in competition with CO2 storage in onshore and near-offshore sinks in the Netherlands. Least-cost modelling with a MARKAL model in combination with ArcGIS was used to assess the cost-effectiveness of the trunkline as part of a Dutch greenhouse gas emission reduction strategy for the Dutch electricity sector and CO2 intensive industry. The results show that under the condition that a CO2 permit price increases from 25 euro per tCO2 in 2010 to 60 euro per tCO2 in 2030, and remains at this level up to 2050, CO2 emissions in the Netherlands could reduce with 67% in 2050 compared to 1990, and investment in the Utsira trunkline may be cost-effective from 2020-2030 provided that Belgian and German CO2 is transported and stored via the Netherlands as well. In this case, by 2050 more than 2.1 GtCO2 would have been transported from the Netherlands to the Utsira formation. However, if the Utsira trunkline is not used for transportation of CO2 from Belgium and Germany, it may become cost-effective 10 years later, and less than 1.3 GtCO2 from the Netherlands would have been stored in the Utsira formation by 2050. On the short term, CO2 storage in Dutch fields appears more cost-effective than in the Utsira formation, but as yet there are major uncertainties related to the timing and effective exploitation of the Dutch offshore storage opportunities.

  3. Spatially selective Er/Yb-doped CaF2 crystal formation by CO2 laser exposure

    International Nuclear Information System (INIS)

    Kim, Dong-Seon; Lee, Jin-Ho; Lim, Ki-Soo

    2014-01-01

    Highlights: • Oxyfluoride glass–ceramics containing CaF 2 nanocrystals doped with Er 3+ and Yb 3+ ions were formed on the glass surface by CO 2 laser and a heat gun exposure. • Most of Er and Yb ions were distributed inside CaF 2 nanocrystals and fluorine loss was observed in the EDS element maps. • IR-to-VIS upconversion emission efficiency of laser annealed glass ceramics was much increased and compared with that of the furnace-annealed glass ceramics. • Distributed volume of the glass ceramics were estimated by a confocal fluorescence microscope imaging. - Abstract: We report the glass–ceramic precipitation on the oxyfluoride glass surface by spatially selective annealing with a CO 2 laser and a heat gun exposure. X-ray diffraction analysis showed the formation of major CaF 2 and miner Ca 2 SiO 4 nanoparticles. We observed ∼100 nm nanoparticle aggregation by tunneling electron microscopy and element distribution in glass and crystal phases. Spatial distribution of glass ceramics near the glass surface was probed by confocal fluorescence microscope by using much enhanced emission from the Er ions in the laser-treated area. Strong emissions at 365 nm excitation and visible up-conversion emissions at 980 nm excitation also indicated well incorporation of Er and Yb ions into a crystalline environment

  4. Spatially selective Er/Yb-doped CaF2 crystal formation by CO2 laser exposure

    International Nuclear Information System (INIS)

    Kim, Dong-Seon; Lee, Jin-Ho; Lim, Ki-Soo

    2015-01-01

    Highlights: • Oxyfluoride glass–ceramics containing CaF 2 nanocrystals doped with Er 3+ and Yb 3+ ions were formed on the glass surface by CO 2 laser and a heat gun exposure. • Most of Er and Yb ions were distributed inside CaF 2 nanocrystals and fluorine loss was observed in the EDS element maps. • IR-to-VIS upconversion emission efficiency of laser annealed glass ceramics was much increased and compared with that of the furnace-annealed glass ceramics. • Distributed volume of the glass ceramics were estimated by a confocal fluorescence microscope imaging. - Abstract: We report the glass–ceramic precipitation on the oxyfluoride glass surface by spatially selective annealing with a CO 2 laser and a heat gun exposure. X-ray diffraction analysis showed the formation of major CaF 2 and miner Ca 2 SiO 4 nanoparticles. We observed ∼100 nm nanoparticle aggregation by tunneling electron microscopy and element distribution in glass and crystal phases. Spatial distribution of glass ceramics near the glass surface was probed by confocal fluorescence microscope by using much enhanced emission from the Er ions in the laser-treated area. Strong emissions at 365 nm excitation and visible up-conversion emissions at 980 nm excitation also indicated well incorporation of Er and Yb ions into a crystalline environment

  5. Effet de la substitution du cuivre par du lithium sur les proprietes de l'oxyde spinelle lithium(x)cuivre(y-x)cobalt(3-y)oxygen(4) etudie pour l'electrocatalyse de la reaction de degagement de l'oxygene en milieu alcalin

    Science.gov (United States)

    Fatih, Khalid

    L'electrolyse de l'eau demeure la seule technologie industrielle de generation de l'hydrogene et de l'oxygene tres purs sans rejet de CO2 dans l'atmosphere, ce qui le rend tres attrayant par rapport a la combustion de carburants fossiles qui provoque presentement de serieux problemes environnementaux. Dans le but d'ameliorer le rendement de ce procede, nous avons developpe de nouveaux materiaux d'anode peu couteux, a base de l'oxyde mixte CuyCo3-yO 4, qui possedent une cinetique rapide pour la reaction de degagement de l'oxygene (RDO). Cette reaction suscite un interet particulier en raison de la surtension d'activation relativement elevee a l'anode qui cause la principale perte de rendement du procede. Une etude systematique a ete effectuee sur la substitution du Cu par du Li (0 a 40%), afin d'elucider les proprietes electrocatalytiques des oxydes LixCuy-xCo3-yO4. Ces oxydes, prepares sous forme de poudres par decomposition thermique des nitrates precurseurs entre 300 et 500°C, ont montre (DRX et FTIR) une structure spinelle inverse non-stcechiometrique avec une diminution du volume de la maille cristalline. La surface specifique par BET est d'environ 6 m2 g-1. Le pcn, obtenu par titrage acido-basique, a indique une diminution de la force du lien M-OH avec le taux du Li dans l'oxyde. Les analyses par XPS, realisees sur des films d'oxyde prepares par nebulisation reactive sur un substrat lisse de nickel, revelent un enrichissement de la surface en Cu a partir de 30% Li, et la presence des cations de surface Co2+, Co3+, Cu +, Cu2+ et Cu3+. La concentration de ce dernier montre un maximum a 10 et 20% Li. Suite a la substitution du Cu par du Li, la compensation de la charge serait assuree principalement par la formation d'especes Cu3+ pour les oxydes contenant jusqu'a 20% Li, et par la formation d'especes Co3+ aux taux de substitution superieurs. Les micrographies MEB montrent une morphologie hemispherique des particules d'oxyde reparties uniformement sur le substrat

  6. The Geomechanics of CO2 Storage in Deep Sedimentary Formations

    Energy Technology Data Exchange (ETDEWEB)

    Rutqvist, Jonny [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-01-12

    This study provides a review of the geomechanics and modeling of geomechanics associated with geologic carbon storage (GCS), focusing on storage in deep sedimentary formations, in particular saline aquifers. The paper first introduces the concept of storage in deep sedimentary formations, the geomechanical processes and issues related with such an operation, and the relevant geomechanical modeling tools. This is followed by a more detailed review of geomechanical aspects, including reservoir stress-strain and microseismicity, well integrity, caprock sealing performance, and the potential for fault reactivation and notable (felt) seismic events. Geomechanical observations at current GCS field deployments, mainly at the In Salah CO2 storage project in Algeria, are also integrated into the review. The In Salah project, with its injection into a relatively thin, low-permeability sandstone is an excellent analogue to the saline aquifers that might be used for large scale GCS in parts of Northwest Europe, the U.S. Midwest, and China. Some of the lessons learned at In Salah related to geomechanics are discussed, including how monitoring of geomechanical responses is used for detecting subsurface geomechanical changes and tracking fluid movements, and how such monitoring and geomechanical analyses have led to preventative changes in the injection parameters. Recently, the importance of geomechanics has become more widely recognized among GCS stakeholders, especially with respect to the potential for triggering notable (felt) seismic events and how such events could impact the long-term integrity of a CO2 repository (as well as how it could impact the public perception of GCS). As described in the paper, to date, no notable seismic event has been reported from any of the current CO2 storage projects, although some unfelt microseismic activities have been detected by geophones. However, potential future commercial GCS operations from large

  7. PmaCO{sub 2} Project: Porosity and CO{sub 2} Trapping Mechanisms The Utrillas Formation in SD-1 borehole (Tejada - Burgos): Porosity and Porous Media Modelling; PROYECTO PmaCO{sub 2}: Porosidad y Mecanismos de Atrapamiento de CO{sub 2} La Formacion Utrillas en el Sondeo SD-1 (Tejada - Burgos): Porosidad y Modelizacion del Sistema Poroso

    Energy Technology Data Exchange (ETDEWEB)

    Campos, R.; Barrios, I.; Gonzalez, A. M.

    2013-03-01

    The aim of PmaCO{sub 2} project, supported by the Secretary of State and Research MINECO (CGL2011-24768) is to increase the knowledge of the microstructure of porous storage formations and thus contribute to the viability of CO{sub 2} sequestration in geological formations. The microporous structure plays an important role not only in the prevalence of a particular trapping mechanism, but also on the amount of CO{sub 2} immobilized. Utrillas facies are investigated in this project as representatives of a deep saline aquifer storage. This publication is a summary of the work done in the first year of the project. We present a study on microstructure of sandstones Utrillas, sampled in borehole, by applying the mercury intrusion porosimetry technique for the experimental determination of porosity and associated parameters. The porous medium was modeled with the PoreCor simulation code based in intrusion-extrusion curves. (Author) 78 refs.

  8. A methodology for the geological and numerical modelling of CO2 storage in deep saline formations

    Science.gov (United States)

    Guandalini, R.; Moia, F.; Ciampa, G.; Cangiano, C.

    2009-04-01

    Several technological options have been proposed to stabilize and reduce the atmospheric concentrations of CO2 among which the most promising are the CCS technologies. The remedy proposed for large stationary CO2 sources as thermoelectric power plants is to separate the flue gas, capturing CO2 and to store it into deep subsurface geological formations. In order to support the identification of potential CO2 storage reservoirs in Italy, the project "Identification of Italian CO2 geological storage sites", financed by the Ministry of Economic Development with the Research Fund for the Italian Electrical System under the Contract Agreement established with the Ministry Decree of march 23, 2006, has been completed in 2008. The project involves all the aspects related to the selection of potential storage sites, each carried out in a proper task. The first task has been devoted to the data collection of more than 6800 wells, and their organization into a geological data base supported by GIS, of which 1911 contain information about the nature and the thickness of geological formations, the presence of fresh, saline or brackish water, brine, gas and oil, the underground temperature, the seismic velocity and electric resistance of geological materials from different logs, the permeability, porosity and geochemical characteristics. The goal of the second task was the set up of a numerical modelling integrated tool, that is the in order to allow the analysis of a potential site in terms of the storage capacity, both from solubility and mineral trapping points of view, in terms of risk assessment and long-term storage of CO2. This tool includes a fluid dynamic module, a chemical module and a module linking a geomechanical simulator. Acquirement of geological data, definition of simulation parameter, run control and final result analysis can be performed by a properly developed graphic user interface, fully integrated and calculation platform independent. The project is then

  9. Kinetics of the Formation and Dissociation of Gas Hydrates from CO2-CH4 Mixtures

    Directory of Open Access Journals (Sweden)

    Devinder Mahajan

    2012-07-01

    Full Text Available Sequestration of carbon dioxide (CO2 in the form of its hydrates in natural methane (CH4 hydrate reservoirs, via CO2/CH4 exchange, is an attractive pathway that also yields valuable CH4 gas as product. In this paper, we describe a macroscale experiment to form CO2 and CH4-CO2 hydrates, under seafloor-mimic conditions, in a vessel fitted with glass windows that provides visualization of hydrates throughout formation and dissociation processes. Time resolved pressure and temperature data as well as images of hydrates are presented. Quantitative gas conversions with pure CO2, calculated from gas chromatographic measurements yielded values that range from 23 – 59% that correspond to the extent of formed hydrates. In CH4-rich CH4-CO2 mixed gas systems, CH4 hydrates were found to form preferentially.

  10. Barium isotope fractionation during experimental formation of the double carbonate BaMn[CO3](2) at ambient temperature.

    Science.gov (United States)

    Böttcher, Michael E; Geprägs, Patrizia; Neubert, Nadja; von Allmen, Katja; Pretet, Chloé; Samankassou, Elias; Nägler, Thomas F

    2012-09-01

    In this study, we present the first experimental results for stable barium (Ba) isotope ((137)Ba/(134)Ba) fractionation during low-temperature formation of the anhydrous double carbonate BaMn[CO(3)](2). This investigation is part of an ongoing work on Ba fractionation in the natural barium cycle. Precipitation at a temperature of 21±1°C leads to an enrichment of the lighter Ba isotope described by an enrichment factor of-0.11±0.06‰ in the double carbonate than in an aqueous barium-manganese(II) chloride/sodium bicarbonate solution, which is within the range of previous reports for synthetic pure BaCO (3) (witherite) formation.

  11. Natural Analogues of CO2 Geological Storage

    International Nuclear Information System (INIS)

    Perez del Villar, L.; Pelayo, M.; Recreo, F.

    2007-01-01

    Geological storage of carbon dioxide is nowadays, internationally considered as the most effective method for greenhouse gas emission mitigation, in order to minimize the global climate change universally accepted. Nevertheless, the possible risks derived of this long-term storage have a direct influence on its public acceptance. Among the favourable geological formations to store CO2, depleted oil and gas fields, deep saline reservoirs, and unamiable coal seams are highlighted. One of the most important objectives of the R and D projects related to the CO2 geological storage is the evaluation of the CO2 leakage rate through the above mentioned geological formations. Therefore, it is absolutely necessary to increase our knowledge on the interaction among CO2, storage and sealing formations, as well as on the flow paths and the physical resistance of the sealing formation. The quantification of the CO2 leakage rate is essential to evaluate the effects on the human and animal health, as well as for the ecosystem and water quality. To achieve these objectives, the study of the natural analogues is very useful in order to know the natural leakage rate to the atmosphere, its flow paths, the physical, chemical and mineralogical modifications due to the long term interaction processes among the CO2 and the storage and sealing formations, as well as the effects on the groundwaters and ecosystems. In this report, we have tried to summarise the main characteristics of the natural reservoirs and surficial sources of CO2, which are both natural analogues of the geological storage and CO2 leakage, studied in EEUU, Europe and Australia. The main objective of this summary is to find the possible applications for long-term risk prediction and for the performance assessment by means of conceptual and numerical modelling, which will allow to validate the predictive models of the CO2 storage behaviour, to design and develop suitable monitoring techniques to control the CO2 behaviour

  12. Coupled Hydro-Mechanical Simulations of CO2 Storage Supported by Pressure Management Demonstrate Synergy Benefits from Simultaneous Formation Fluid Extraction

    Directory of Open Access Journals (Sweden)

    Kempka Thomas

    2015-04-01

    Full Text Available We assessed the synergetic benefits of simultaneous formation fluid extraction during CO2 injection for reservoir pressure management by coupled hydro-mechanical simulations at the prospective Vedsted storage site located in northern Denmark. Effectiveness of reservoir pressure management was investigated by simulation of CO2 storage without any fluid extraction as well as with 66% and 100% equivalent volume formation fluid extraction from four wells positioned for geothermal heat recovery. Simulation results demonstrate that a total pressure reduction of up to about 1.1 MPa can be achieved at the injection well. Furthermore, the areal pressure perturbation in the storage reservoir can be significantly decreased compared to the simulation scenario without any formation fluid extraction. Following a stress regime analysis, two stress regimes were considered in the coupled hydro-mechanical simulations indicating that the maximum ground surface uplift is about 0.24 m in the absence of any reservoir pressure management. However, a ground uplift mitigation of up to 37.3% (from 0.24 m to 0.15 m can be achieved at the injection well by 100% equivalent volume formation fluid extraction. Well-based adaptation of fluid extraction rates can support achieving zero displacements at the proposed formation fluid extraction wells located close to urban infrastructure. Since shear and tensile failure do not occur under both stress regimes for all investigated scenarios, it is concluded that a safe operation of CO2 injection with simultaneous formation fluid extraction for geothermal heat recovery can be implemented at the Vedsted site.

  13. Reactions of solid CaSO{sub 4} and Na{sub 2}CO{sub 3} and formation of sodium carbonate sulfate double salts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jinsheng; Wu, Yinghai; Anthony, Edward J. [CANMET Energy Technology Centre, Natural Resources Canada, 1 Haanel Dr., Ottawa, Ontario K1A 1M1 (Canada)

    2007-07-01

    High-temperature chemical reactions in mixtures of solid CaSO{sub 4} and Na{sub 2}CO{sub 3} were investigated in order to explore the mechanisms of enhanced sulfur capture by limestones doped with Na{sub 2}CO{sub 3} in fluidized bed combustion. Drastic weight loss of the mixtures was observed in a thermogravimetric analyzer near the melting temperature of Na{sub 2}CO{sub 3}, indicating chemical reaction. X-ray diffraction analysis for a mixture of the solids following a heat treatment at 850 C revealed the existence of two sodium carbonate sulfate double salts that have not been reported before for the present system. The formation of Na{sub 2}SO{sub 4} in the melt of Na{sub 2}CO{sub 3} appears to precede the formation of the double salts. The two double salts are believed to have high porosity and specific surface area similar to those of a better-known double salt, burkeite. The implications of these findings for the enhancement of limestone sulfation by Na{sub 2}CO{sub 3} are also discussed. (author)

  14. Reactions of solid CaSO{sub 4} and Na{sub 2}CO{sub 3} and formation of sodium carbonate sulfate double salts

    Energy Technology Data Exchange (ETDEWEB)

    Wang Jinsheng [CANMET Energy Technology Centre, Natural Resources Canada, 1 Haanel Dr., Ottawa, Ontario K1A 1M1 (Canada)]. E-mail: jiwang@nrcan.gc.ca; Wu Yinghai [CANMET Energy Technology Centre, Natural Resources Canada, 1 Haanel Dr., Ottawa, Ontario K1A 1M1 (Canada); Anthony, Edward J. [CANMET Energy Technology Centre, Natural Resources Canada, 1 Haanel Dr., Ottawa, Ontario K1A 1M1 (Canada)

    2007-07-01

    High-temperature chemical reactions in mixtures of solid CaSO{sub 4} and Na{sub 2}CO{sub 3} were investigated in order to explore the mechanisms of enhanced sulfur capture by limestones doped with Na{sub 2}CO{sub 3} in fluidized bed combustion. Drastic weight loss of the mixtures was observed in a thermogravimetric analyzer near the melting temperature of Na{sub 2}CO{sub 3}, indicating chemical reaction. X-ray diffraction analysis for a mixture of the solids following a heat treatment at 850 deg. C revealed the existence of two sodium carbonate sulfate double salts that have not been reported before for the present system. The formation of Na{sub 2}SO{sub 4} in the melt of Na{sub 2}CO{sub 3} appears to precede the formation of the double salts. The two double salts are believed to have high porosity and specific surface area similar to those of a better-known double salt, burkeite. The implications of these findings for the enhancement of limestone sulfation by Na{sub 2}CO{sub 3} are also discussed.

  15. Enthalpies of formation of layered LiNixMnxCo1-2xO2 (0 ≤ x ≤ 0.5) compounds as lithium ion battery cathode materials

    International Nuclear Information System (INIS)

    Masoumi, Maryam; Cupid, Damian M.; Reichmann, Thomas L.; Seifert, Hans J.; Chang, Keke; Music, Denis; Schneider, Jochen M.

    2017-01-01

    Layer-structured mixed transition metal oxides with the formula LiNi x Mn x Co 1-2x O 2 (0 ≤ x ≤ 0.5) are considered as important cathode materials for lithium-ion batteries. In an effort to evaluate the relative thermodynamic stabilities of individual compositions in this series, the enthalpies of formation of selected stoichiometries are determined by high temperature oxide melt drop solution calorimetry and verified by ab-initio calculations. The measured and calculated data are in good agreement with each other, and the results show that LiCoO 2 -LiNi 0.5 Mn 0.5 O 2 solid solution approaches ideal behavior. By increasing x, i.e. by equimolar substitution of Mn 4+ and Ni 2+ for Co 3+ , the enthalpy of formation of LiNi x Mn x Co 1-2x O 2 from the elements becomes more exothermic, implying increased energetic stability. This conclusion is in agreement with the literature results showing improved structural stability and cycling performance of Ni/Mn-rich LiNi x Mn x Co 1-2x O 2 compounds cycled to higher cut-off voltages.

  16. Controlling selectivities in CO2 reduction through mechanistic understanding

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiang; Shi, Hui; Szanyi, János

    2017-09-11

    Catalytic CO2 conversion to energy carriers and intermediates is of utmost importance to energy and environmental goals. However, the lack of fundamental understanding of the reaction mechanism renders designing a selective catalyst inefficient. We performed operando FTIR/SSITKA experiments to understand the correlation between the kinetics of product formation and that of surface species conversion during CO2 reduction over Pd/Al2O3 catalysts. We found that the rate-determining step for CO formation is the conversion of adsorbed formate, while that for CH4 formation is the hydrogenation of adsorbed carbonyl. The balance of the hydrogenation kinetics between adsorbed formates and carbonyls governs the selectivities to CH4 and CO. We demonstrated how this knowledge can be used to design catalysts to achieve high selectivities to desired products.

  17. A Comparison of national CCS strategies for Northwest Europe, with a focus on the potential of common CO2 storage at the Utsira formation

    DEFF Research Database (Denmark)

    Ramirez, Andrea; Hoefnagels, Ric; van den Broek, Machteld

    2011-01-01

    Mega structures for CO2 storage, such as the Utsira formation in the North Sea, could theoretically supply CO2 storage capacity for several countries for a period of several decades. Their use could increase the cost-effectiveness of CCS in a region while minimizing opposition from the public to CO...... region Pan European TIMES model (PET). In the models scenarios, assumptions and parameters that are not country dependent (e.g. costs related with CO2 capture technology development) have been harmonized. The results indicate that with stringent climate targets, CCS appears as a key mitigation option...... in the national portfolio of measures. Within the CCS portfolio, storage of CO2 in the Utsira formation can indeed be a cost effective option for North Europe and it represents a valuable CO2 storage option at the regional level. For instance, the United Kingdom will profit from the comparably short transport...

  18. Theoretical Insights into a CO Dimerization Mechanism in CO2 Electroreduction.

    Science.gov (United States)

    Montoya, Joseph H; Shi, Chuan; Chan, Karen; Nørskov, Jens K

    2015-06-04

    In this work, we present DFT simulations that demonstrate the ability of Cu to catalyze CO dimerization in CO2 and CO electroreduction. We describe a previously unreported CO dimer configuration that is uniquely stabilized by a charged water layer on both Cu(111) and Cu(100). Without this charged water layer at the metal surface, the formation of the CO dimer is prohibitively endergonic. Our calculations also demonstrate that dimerization should have a lower activation barrier on Cu(100) than Cu(111), which, along with a more exergonic adsorption energy and a corresponding higher coverage of *CO, is consistent with experimental observations that Cu(100) has a high activity for C-C coupling at low overpotentials. We also demonstrate that this effect is present with cations other than H(+), a finding that is consistent with the experimentally observed pH independence of C2 formation on Cu.

  19. Probabilistic modeling and global sensitivity analysis for CO 2 storage in geological formations: a spectral approach

    KAUST Repository

    Saad, Bilal Mohammed

    2017-09-18

    This work focuses on the simulation of CO2 storage in deep underground formations under uncertainty and seeks to understand the impact of uncertainties in reservoir properties on CO2 leakage. To simulate the process, a non-isothermal two-phase two-component flow system with equilibrium phase exchange is used. Since model evaluations are computationally intensive, instead of traditional Monte Carlo methods, we rely on polynomial chaos (PC) expansions for representation of the stochastic model response. A non-intrusive approach is used to determine the PC coefficients. We establish the accuracy of the PC representations within a reasonable error threshold through systematic convergence studies. In addition to characterizing the distributions of model observables, we compute probabilities of excess CO2 leakage. Moreover, we consider the injection rate as a design parameter and compute an optimum injection rate that ensures that the risk of excess pressure buildup at the leaky well remains below acceptable levels. We also provide a comprehensive analysis of sensitivities of CO2 leakage, where we compute the contributions of the random parameters, and their interactions, to the variance by computing first, second, and total order Sobol’ indices.

  20. Probabilistic modeling and global sensitivity analysis for CO 2 storage in geological formations: a spectral approach

    KAUST Repository

    Saad, Bilal Mohammed; Alexanderian, Alen; Prudhomme, Serge; Knio, Omar

    2017-01-01

    This work focuses on the simulation of CO2 storage in deep underground formations under uncertainty and seeks to understand the impact of uncertainties in reservoir properties on CO2 leakage. To simulate the process, a non-isothermal two-phase two-component flow system with equilibrium phase exchange is used. Since model evaluations are computationally intensive, instead of traditional Monte Carlo methods, we rely on polynomial chaos (PC) expansions for representation of the stochastic model response. A non-intrusive approach is used to determine the PC coefficients. We establish the accuracy of the PC representations within a reasonable error threshold through systematic convergence studies. In addition to characterizing the distributions of model observables, we compute probabilities of excess CO2 leakage. Moreover, we consider the injection rate as a design parameter and compute an optimum injection rate that ensures that the risk of excess pressure buildup at the leaky well remains below acceptable levels. We also provide a comprehensive analysis of sensitivities of CO2 leakage, where we compute the contributions of the random parameters, and their interactions, to the variance by computing first, second, and total order Sobol’ indices.

  1. Regulation of Coordination Number over Single Co Sites: Triggering the Efficient Electroreduction of CO2.

    Science.gov (United States)

    Wang, Xiaoqian; Chen, Zhao; Zhao, Xuyan; Yao, Tao; Chen, Wenxing; You, Rui; Zhao, Changming; Wu, Geng; Wang, Jing; Huang, Weixin; Yang, Jinlong; Hong, Xun; Wei, Shiqiang; Wu, Yuen; Li, Yadong

    2018-02-12

    The design of active, selective, and stable CO 2 reduction electrocatalysts is still challenging. A series of atomically dispersed Co catalysts with different nitrogen coordination numbers were prepared and their CO 2 electroreduction catalytic performance was explored. The best catalyst, atomically dispersed Co with two-coordinate nitrogen atoms, achieves both high selectivity and superior activity with 94 % CO formation Faradaic efficiency and a current density of 18.1 mA cm -2 at an overpotential of 520 mV. The CO formation turnover frequency reaches a record value of 18 200 h -1 , surpassing most reported metal-based catalysts under comparable conditions. Our experimental and theoretical results demonstrate that lower a coordination number facilitates activation of CO 2 to the CO 2 .- intermediate and hence enhances CO 2 electroreduction activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Investigations into the influence of some synergists of 2,4-dioxo-hexahydro-1,3,5-triazine (DHT) on the formation of 14CO2 from [2,4-14C]DHT

    International Nuclear Information System (INIS)

    Byhan, O.; Schuster, G.

    1986-01-01

    Combined treatment with DHT and N-phenyl-N'-p-carboxyphenyl-thiourea reduced the formation of 14 CO 2 from [2,4- 14 C]DHT. Contrary to this, combined treatments with N-phenyl-N'-p-carboxyphenyl-urea, cyanoguanidine and, above all, guanidine carbonate increased the formation of 14 CO 2 from [2,4- 14 C]DHT. Thus, retardation of the breakdown of DHT and, beside this, maintenance of a high concentration of DHT, can only be the reason for the augmentation of the antiphytoviral activities of DHT by N-phenyl-N'-p-carboxyphenylthiourea, but not for that by the other 3 substances. An alternative hypothesis is discussed. (author)

  3. Liquid-liquid extraction of ion-association complexes of cobalt(II-4-(2-pyridylazoresorcinol with ditetrazolium salts

    Directory of Open Access Journals (Sweden)

    Divarova Vidka V.

    2015-01-01

    Full Text Available The formation and liquid-liquid extraction of ion-association complexes between Co(II-4-(2-Pyridylazoresorcinol (PAR anionic chelates and cations of three ditetrazolium chlorides were studied: Blue Tetrazolium chloride (BTC, Neotetrazolium chloride (NTC and Nitro Blue Tetrazolium chloride (NBT. The optimum conditions for the formation and solvent extraction of the ion-association comlpex chelates were determined. It has been found that in the systems of Co(II-PAR-DTS, the reactants are reacted in molar ratios 1:2:1 and the general formula of complexes was suggested. The extraction equilibria were investigated and quantitatively characterized by the equilibrium constants and the recovery factors. The analytical characteristics of the complexes were calculated.

  4. Simulation of CO2–water–rock interactions on geologic CO2 sequestration under geological conditions of China

    International Nuclear Information System (INIS)

    Wang, Tianye; Wang, Huaiyuan; Zhang, Fengjun; Xu, Tianfu

    2013-01-01

    Highlights: • We determined the feasibilities of geologic CO 2 sequestration in China. • We determined the formation of gibbsite suggested CO 2 can be captured by rocks. • We suggested the mechanisms of CO 2 –water–rock interactions. • We found the corrosion and dissolution of the rock increased as temperature rose. -- Abstract: The main purpose of this study focused on the feasibility of geologic CO 2 sequestration within the actual geological conditions of the first Carbon Capture and Storage (CCS) project in China. This study investigated CO 2 –water–rock interactions under simulated hydrothermal conditions via physicochemical analyses and scanning electron microscopy (SEM). Mass loss measurement and SEM showed that corrosion of feldspars, silica, and clay minerals increased with increasing temperature. Corrosion of sandstone samples in the CO 2 -containing fluid showed a positive correlation with temperature. During reaction at 70 °C, 85 °C, and 100 °C, gibbsite (an intermediate mineral product) formed on the sample surface. This demonstrated mineral capture of CO 2 and supported the feasibility of geologic CO 2 sequestration. Chemical analyses suggested a dissolution–reprecipitation mechanism underlying the CO 2 –water–rock interactions. The results of this study suggested that mineral dissolution, new mineral precipitation, and carbonic acid formation-dissociation are closely interrelated in CO 2 –water–rock interactions

  5. Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

    Science.gov (United States)

    Qasim, D.; Chuang, K.-J.; Fedoseev, G.; Ioppolo, S.; Boogert, A. C. A.; Linnartz, H.

    2018-04-01

    Context. The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. Aims: This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. Methods: CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. Results: CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH → CH3 + H2O and CH3 + OH → CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation Lamberts et al. (2017, A&A, 599, A132). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

  6. In situ synchrotron X-ray diffraction study of scale formation during CO2 corrosion of carbon steel in sodium and magnesium chloride solutions

    International Nuclear Information System (INIS)

    Ingham, B.; Ko, M.; Laycock, N.; Burnell, J.; Kappen, P.; Kimpton, J.A.; Williams, D.E.

    2012-01-01

    Highlights: ► We studied the scale formation processes of carbon steel in CO 2 saturated brine at 80 °C. ► Protective scales were formed in all tests. ► Only FeCO 3 formed in saturated brine while Fe(OH) 2 CO 3 detected with presence of MgCl 2 . ► MgCl 2 accelerates the onset of siderite precipitation. - Abstract: In situ synchrotron X-ray diffraction was used to follow the formation of corrosion products on carbon steel in CO 2 saturated NaCl solution and mixed NaCl/magnesium chloride (MgCl 2 ) at 80 °C. Siderite (FeCO 3 ) was the only phase formed in NaCl solution, while Fe(OH) 2 CO 3 was also detected when MgCl 2 was present. The proposed model is that siderite precipitation, occurring once the critical supersaturation was exceeded within a defined boundary layer, caused local acidification which accelerated the anodic dissolution of iron. The current fell once a complete surface scale was formed. It is suggested that MgCl 2 addition decreased the required critical supersaturation for precipitation.

  7. Leakage and Seepage of CO2 from Geologic Carbon Sequestration Sites: CO2 Migration into Surface Water

    International Nuclear Information System (INIS)

    Oldenburg, Curt M.; Lewicki, Jennifer L.

    2005-01-01

    Geologic carbon sequestration is the capture of anthropogenic carbon dioxide (CO 2 ) and its storage in deep geologic formations. One of the concerns of geologic carbon sequestration is that injected CO 2 may leak out of the intended storage formation, migrate to the near-surface environment, and seep out of the ground or into surface water. In this research, we investigate the process of CO 2 leakage and seepage into saturated sediments and overlying surface water bodies such as rivers, lakes, wetlands, and continental shelf marine environments. Natural CO 2 and CH 4 fluxes are well studied and provide insight into the expected transport mechanisms and fate of seepage fluxes of similar magnitude. Also, natural CO 2 and CH 4 fluxes are pervasive in surface water environments at levels that may mask low-level carbon sequestration leakage and seepage. Extreme examples are the well known volcanic lakes in Cameroon where lake water supersaturated with respect to CO 2 overturned and degassed with lethal effects. Standard bubble formation and hydrostatics are applicable to CO 2 bubbles in surface water. Bubble-rise velocity in surface water is a function of bubble size and reaches a maximum of approximately 30 cm s -1 at a bubble radius of 0.7 mm. Bubble rise in saturated porous media below surface water is affected by surface tension and buoyancy forces, along with the solid matrix pore structure. For medium and fine grain sizes, surface tension forces dominate and gas transport tends to occur as channel flow rather than bubble flow. For coarse porous media such as gravels and coarse sand, buoyancy dominates and the maximum bubble rise velocity is predicted to be approximately 18 cm s -1 . Liquid CO 2 bubbles rise slower in water than gaseous CO 2 bubbles due to the smaller density contrast. A comparison of ebullition (i.e., bubble formation) and resulting bubble flow versus dispersive gas transport for CO 2 and CH 4 at three different seepage rates reveals that

  8. NETL CO2 Storage prospeCtive Resource Estimation Excel aNalysis (CO2-SCREEN) User's Manual

    Energy Technology Data Exchange (ETDEWEB)

    Sanguinito, Sean M. [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Goodman, Angela [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States); Levine, Jonathan [National Energy Technology Lab. (NETL), Pittsburgh, PA, (United States)

    2017-04-03

    This user’s manual guides the use of the National Energy Technology Laboratory’s (NETL) CO2 Storage prospeCtive Resource Estimation Excel aNalysis (CO2-SCREEN) tool, which was developed to aid users screening saline formations for prospective CO2 storage resources. CO2- SCREEN applies U.S. Department of Energy (DOE) methods and equations for estimating prospective CO2 storage resources for saline formations. CO2-SCREEN was developed to be substantive and user-friendly. It also provides a consistent method for calculating prospective CO2 storage resources that allows for consistent comparison of results between different research efforts, such as the Regional Carbon Sequestration Partnerships (RCSP). CO2-SCREEN consists of an Excel spreadsheet containing geologic inputs and outputs, linked to a GoldSim Player model that calculates prospective CO2 storage resources via Monte Carlo simulation.

  9. Assessment of CO2 Mineralization and Dynamic Rock Properties at the Kemper Pilot CO2 Injection Site

    Science.gov (United States)

    Qin, F.; Kirkland, B. L.; Beckingham, L. E.

    2017-12-01

    CO2-brine-mineral reactions following CO2 injection may impact rock properties including porosity, permeability, and pore connectivity. The rate and extent of alteration largely depends on the nature and evolution of reactive mineral interfaces. In this work, the potential for geochemical reactions and the nature of the reactive mineral interface and corresponding hydrologic properties are evaluated for samples from the Lower Tuscaloosa, Washita-Fredericksburg, and Paluxy formations. These formations have been identified as future regionally extensive and attractive CO2 storage reservoirs at the CO2 Storage Complex in Kemper County, Mississippi, USA (Project ECO2S). Samples from these formations were obtained from the Geological Survey of Alabama and evaluated using a suite of complementary analyses. The mineral composition of these samples will be determined using petrography and powder X-ray Diffraction (XRD). Using these compositions, continuum-scale reactive transport simulations will be developed and the potential CO2-brine-mineral interactions will be examined. Simulations will focus on identifying potential reactive minerals as well as the corresponding rate and extent of reactions. The spatial distribution and accessibility of minerals to reactive fluids is critical to understanding mineral reaction rates and corresponding changes in the pore structure, including pore connectivity, porosity and permeability. The nature of the pore-mineral interface, and distribution of reactive minerals, will be determined through imaging analysis. Multiple 2D scanning electron microscopy (SEM) backscattered electron (BSE) images and energy dispersive x-ray spectroscopy (EDS) images will be used to create spatial maps of mineral distributions. These maps will be processed to evaluate the accessibility of reactive minerals and the potential for flow-path modifications following CO2 injection. The "Establishing an Early CO2 Storage Complex in Kemper, MS" project is funded by

  10. Modelling of gas diffusion limitations in Ni/YSZ electrode material in CO2 and co-electrolysis

    DEFF Research Database (Denmark)

    Duhn, Jakob Dragsbæk; Jensen, Anker Degn; Wedel, Stig

    2016-01-01

    Carbon formation during CO2 and co-electrolysis (combined electrolysis of H2O and CO2)has been observed in recent studies, under operating conditions where carbon formation,based on the bulk gas composition, should be thermodynamically unfavorable. The carboncan principally be formed by the Boudo...

  11. Protease-activated receptor 2 (PAR2) is upregulated by Acanthamoeba plasminogen activator (aPA) and induces proinflammatory cytokine in human corneal epithelial cells.

    Science.gov (United States)

    Tripathi, Trivendra; Abdi, Mahshid; Alizadeh, Hassan

    2014-05-29

    Acanthamoeba plasminogen activator (aPA) is a serine protease elaborated by Acanthamoeba trophozoites that facilitates the invasion of trophozoites to the host and contributes to the pathogenesis of Acanthamoeba keratitis (AK). The aim of this study was to explore if aPA stimulates proinflammatory cytokine in human corneal epithelial (HCE) cells via the protease-activated receptors (PARs) pathway. Acanthamoeba castellanii trophozoites were grown in peptone-yeast extract glucose for 7 days, and the supernatants were collected and centrifuged. The aPA was purified using the fast protein liquid chromatography system, and aPA activity was determined by zymography assays. Human corneal epithelial cells were incubated with or without aPA (100 μg/mL), PAR1 agonists (thrombin, 10 μM; TRAP-6, 10 μM), and PAR2 agonists (SLIGRL-NH2, 100 μM; AC 55541, 10 μM) for 24 and 48 hours. Inhibition of PAR1 and PAR2 involved preincubating the HCE cells for 1 hour with the antagonist of PAR1 (SCH 79797, 60 μM) and PAR2 (FSLLRY-NH2, 100 μM) with or without aPA. Human corneal epithelial cells also were preincubated with PAR1 and PAR2 antagonists and then incubated with or without PAR1 agonists (thrombin and TRAP-6) and PAR2 agonists (SLIGRL-NH2 and AC 55541). Expression of PAR1 and PAR2 was examined by quantitative RT-PCR (qRT-PCR), flow cytometry, and immunocytochemistry. Interleukin-8 expression was quantified by qRT-PCR and ELISA. Human corneal epithelial cells constitutively expressed PAR1 and PAR2 mRNA. Acanthamoeba plasminogen activator and PAR2 agonists significantly upregulated PAR2 mRNA expression (1- and 2-fold, respectively) (P aPA, and PAR2 agonists induced PAR2 mRNA expression in HCE cells (P aPA, significantly upregulated PAR1 mRNA expression, which was significantly inhibited by PAR1 antagonist in HCE cells. Acanthamoeba plasminogen activator and PAR2 agonists stimulated IL-8 mRNA expression and protein production, which is significantly diminished by PAR2 antagonist

  12. Carbon Deposition in Solid Oxide Cells during Co-Electrolysis of H2O and CO2

    DEFF Research Database (Denmark)

    Tao, Youkun; Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

    2014-01-01

    current densities from 1.5 to 2.25 A/cm2 and reactant (H2O + CO2) conversion of up to 67%. Delamination and carbon nano-fibers were observed at the Ni-YSZ|YSZ interface for two cells with a dense microstructure operated at electrolysis current densities of 2.0 and 2.25 A/cm2 and a conversion of 59% and 67...... and the active Ni-YSZ electrode. Carbon nano-fibers were only observed close to the YSZ electrolyte, indicating a very reducing atmosphere and a large over-potential gradient in the active electrode, being highest at the interface to the bulk electrolyte and decreasing toward the Ni-YSZ support.......Carbon formation during co-electrolysis of H2O and CO2 in Ni-YSZ supported Solid Oxide Electrolysis Cells (SOECs) may occur, especially at high current density and high conversion. In order to evaluate the carbon formation limits, five galvanostatic tests were performed in this work at electrolysis...

  13. New Ru(II)N'NN'-type pincer complexes: synthesis, characterization and the catalytic hydrogenation of CO_2 or bicarbonates to formate salts

    International Nuclear Information System (INIS)

    Zengjin Dai; Qi Luo; Hengjiang Cong; Jing Zhang; Tianyou Peng

    2017-01-01

    [RuCl(L1)(MeCN)_2]Cl (1) and [RuCl(L2)(MeCN)_2]Cl (2) complexes were prepared through the reaction of [RuCl2(p-cymene)]_2 with 2,6-bis(benzimidazole-2-yl)-4-hydroxy-pyridine (L1) or 2,6-bis(benzimidazole- 2-yl) pyridine (L2) in acetonitrile, respectively. The treatment of [Ru(OTf)(L2)(MeCN)_2]OTf (3) with 1 equivalent of PPh_3 in ethanol resulted in the formation of [Ru(L2"-"1)(MeCN)(PPh_3)_2]OTf (4), in which one of the N-H moieties of L2 is deprotonated to give an anionic ligand (L2"-"1). It was found that complex 1 can catalyze the hydrogenation of CO_2 to formate salts, producing sodium formate in 34.0% yield with a turnover number (TON) of 407 under the optimized conditions. Further investigations revealed that complexes 1-4 can efficiently catalyze the hydrogenation of sodium bicarbonate to sodium formate, and the catalytic activity follows the order 4 ≥ 1 ≥ 2 ≅ 3. In particular, sodium formate was obtained in good yield (77%) with a high TON (1530) when complex 4 was used as the catalyst. The present results illustrate a new example of Ru(II) complexes bearing a rigid N'NN' framework for the efficient hydrogenation of CO_2 to formate salts in a homogeneous system. (authors)

  14. mTORC2 activation is regulated by the urokinase receptor (uPAR) in bladder cancer.

    Science.gov (United States)

    Hau, Andrew M; Leivo, Mariah Z; Gilder, Andrew S; Hu, Jing-Jing; Gonias, Steven L; Hansel, Donna E

    2017-01-01

    Mammalian target of rapamycin complex 2 (mTORC2) has been identified as a major regulator of bladder cancer cell migration and invasion. Upstream pathways that mediate mTORC2 activation remain poorly defined. Urokinase-type plasminogen activator receptor (uPAR) is a GPI-anchored membrane protein and known activator of cell-signaling. We identified increased uPAR expression in 94% of invasive human bladder cancers and in 54-71% of non-invasive bladder cancers, depending on grade. Normal urothelium was uPAR-immunonegative. Analysis of publicly available datasets identified uPAR gene amplification or mRNA upregulation in a subset of bladder cancer patients with reduced overall survival. Using biochemical approaches, we showed that uPAR activates mTORC2 in bladder cancer cells. Highly invasive bladder cancer cell lines, including T24, J82 and UM-UC-3 cells, showed increased uPAR mRNA expression and protein levels compared with the less aggressive cell lines, UROtsa and RT4. uPAR gene-silencing significantly reduced phosphorylation of Serine-473 in Akt, an mTORC2 target. uPAR gene-silencing also reduced bladder cancer cell migration and Matrigel invasion. S473 phosphorylation was observed by immunohistochemistry in human bladder cancers only when the tumors expressed high levels of uPAR. S473 phosphorylation was not controlled by uPAR in bladder cancer cell lines that are PTEN-negative; however, this result probably did not reflect altered mTORC2 regulation. Instead, PTEN deficiency de-repressed alternative kinases that phosphorylate S473. Our results suggest that uPAR and mTORC2 are components of a single cell-signaling pathway. Targeting uPAR or mTORC2 may be beneficial in patients with bladder cancer. Copyright © 2016. Published by Elsevier Inc.

  15. Par-4-mediated recruitment of Amida to the actin cytoskeleton leads to the induction of apoptosis

    International Nuclear Information System (INIS)

    Boosen, Meike; Vetterkind, Susanne; Koplin, Ansgar; Illenberger, Susanne; Preuss, Ute

    2005-01-01

    Par-4 (prostate apoptosis response-4) sensitizes cells to apoptotic stimuli, but the exact mechanisms are still poorly understood. Using Par-4 as bait in a yeast two-hybrid screen, we identified Amida as a novel interaction partner, a ubiquitously expressed protein which has been suggested to be involved in apoptotic processes. Complex formation of Par-4 and Amida occurs in vitro and in vivo and is mediated via the C-termini of both proteins, involving the leucine zipper of Par-4. Amida resides mainly in the nucleus but displays nucleo-cytoplasmic shuttling in heterokaryons. Upon coexpression with Par-4 in REF52.2 cells, Amida translocates to the cytoplasm and is recruited to actin filaments by Par-4, resulting in enhanced induction of apoptosis. The synergistic effect of Amida/Par-4 complexes on the induction of apoptosis is abrogated when either Amida/Par-4 complex formation or association of these complexes with the actin cytoskeleton is impaired, indicating that the Par-4-mediated relocation of Amida to the actin cytoskeleton is crucial for the pro-apoptotic function of Par-4/Amida complexes in REF52.2 cells. The latter results in enhanced phosphorylation of the regulatory light chain of myosin II (MLC) as has previously been shown for Par-4-mediated recruitment of DAP-like kinase (Dlk), suggesting that the recruitment of nuclear proteins involved in the regulation of apoptotic processes to the actin filament system by Par-4 represents a potent mechanism how Par-4 can trigger apoptosis

  16. CO{sub 2} sequestration technologies

    Energy Technology Data Exchange (ETDEWEB)

    Ketzer, Marcelo [Brazilian Carbon Storage Research Center (Brazil)

    2008-07-15

    In this presentation the importance of the capture and sequestration of CO{sub 2} is outlined for the reduction of gas discharges of greenhouse effect; then the principles of CO{sub 2} storage in geologic formations are reviewed; afterwards, the analogs for the CO{sub 2} storage are commented, such as the storage of the acid gas, the natural gas storage and the natural CO{sub 2} deposits. Also it is spoken on the CO{sub 2} storage in coal, in water-bearing saline deposits and in oil fields, and finally the subject of the safety and monitoring of the CO{sub 2} storage is reviewed. [Spanish] En esta presentacion se expone la importancia de la captura y secuestro de CO{sub 2} para la reduccion de emisiones de gases de efecto invernadero; luego se tratan los principios de almacenamiento de CO{sub 2} en formaciones geologicas; despues se comentan los analogos para el almacenamiento de CO{sub 2} como el almacenamiento del gas acido, el almacenamiento de gas natural y los yacimientos naturales de CO{sub 2}. Tambien se habla sobre el almacenamiento de CO{sub 2} en carbon, acuiferos salinos y yacimientos petroliferos y por ultimo se toca el tema de la seguridad y monitoreo del almacenamiento de CO{sub 2}.

  17. Formation and characterization of nanoparticles formed by sequential ion implantation of Au and Co into SiO2

    International Nuclear Information System (INIS)

    Kluth, P.; Hoy, B.; Johannessen, B.; Dunn, S.G.; Foran, G.J.; Ridgway, M.C.

    2007-01-01

    Nanoparticles (NPs) were formed by sequential ion implantation of Au and Co into thin SiO 2 . After Au implantation and annealing, Co implantations were carried out at room temperature (RT) and 400 deg. C, respectively, with no subsequent annealing. The NPs were investigated by means of Rutherford backscattering spectroscopy (RBS), transmission electron microscopy (TEM) and extended X-ray absorption fine structure spectroscopy (EXAFS). TEM shows the formation of Co-Au core-shell NPs for the Co implantation at 400 deg. C. EXAFS measurements indicate significant strain in the NPs and a bond-length expansion of the Co-Co bonds in the NP core with a concomitant contraction of the Au-Au bonds in the Au shells. NPs are also observed by TEM for the Co implantation performed at RT, however, a lack of crystallinity is apparent from electron diffraction and EXAFS measurements

  18. CO{sub 2} solubility in brines of sedimentary basins. Application to CO{sub 2} sequestration (greenhouse gas); Solubilite de CO{sub 2} dans les saumures des bassins sedimentaires. Application au stockage de CO{sub 2} (gaz a effet de serre)

    Energy Technology Data Exchange (ETDEWEB)

    Portier, S.

    2005-04-01

    Large scale combustion of fossil energy leads today to a production of 20 billions tons of CO{sub 2} annually. This increases continuously the CO{sub 2} concentration in the atmosphere, responsible of the observed climatic increase of the temperature since one century. One of the most acceptable solutions consists in the so called CO{sub 2} sequestration in natural geological formations. The control of the process and the prediction of the final quantity of CO{sub 2} trapped in the deep saline aquifers depend on the knowledge of the solubility of acid gas in natural brines in the in situ temperature and pressure conditions. The possible dissolution of acid gases in aqueous phases brings a new complexity, owing to the fact that they behave like electrolytes in aqueous mediums A thermodynamic model for CO{sub 2} solubility is presented. The vapour phase is described by a cubic state equation. The aqueous phase is described by apparent constants of CO{sub 2} dissolution and dissociation, adjusted on literature data. This model is validated by measurements of the British Geological Survey (CO{sub 2} sequestration at Sleipner oil field, North Sea). The results of this study made it possible to calculate the impact of a CO{sub 2} injection on the solubility of calcite by acidification of formation water. The consequences in terms of CO{sub 2} storage capacity of deep saline aquifers are estimated. (author)

  19. Catalytic conversion of CO, NO and SO2 on supported sulfide catalysts. Part 2. Catalytic reduction of NO and SO2 by CO

    International Nuclear Information System (INIS)

    Zhuang, S.-X.; Yamazaki, M.; Omata, K.; Takahashi, Y.; Yamada, M.

    2001-01-01

    To investigate the possibility of simultaneous catalytic reduction of NO and SO 2 by CO, reactions of NO, NO-CO, and NO-SO 2 -CO were performed on γ-alumina-supported sulfides of transition metals including Co, Mo, CoMo and FeMo. NO was decomposed into N 2 O and N 2 accompanied with the formation of SO 2 ; this serious oxidation of lattice sulfur resulted in the deactivation of the catalysts. The addition of CO to the NO stream suppressed SO 2 formation and yielded COS instead. A stoichiometric conversion of NO and CO to N 2 and CO 2 was observed above 350C on the CoMo and the FeMo catalysts. Although the CO addition lengthened catalyst life, it was not enough to maintain activity. After the NO-CO reaction, an XPS analysis showed the growth of Mo 6+ and SO 4 2- peaks, especially for the sulfided FeMo/Al 2 O 3 ; the FeMo catalyst underwent strong oxidation in the NO-CO reaction. The NO and the NO-CO reactions proceeded non-catalytically, consuming catalyst lattice sulfur to yield SO 2 or COS. The addition of SO 2 in the NO-CO system enabled in situ regeneration of the catalysts; the catalysts oxidized through abstraction of lattice sulfur experienced anew reduction and sulfurization through the SO 2 -CO reaction at higher temperature. NO and SO 2 were completely and catalytically converted at 400C on the sulfided CoMo/Al 2 O 3 . By contrast, the sulfided FeMo/Al 2 O 3 was easily oxidized by NO and hardly re-sulfided under the test conditions. Oxidation states of the metals before and after the reactions were determined. Silica and titania-supported CoMo catalysts were also evaluated to study support effects

  20. Intermediate Scale Laboratory Testing to Understand Mechanisms of Capillary and Dissolution Trapping during Injection and Post-Injection of CO2 in Heterogeneous Geological Formations

    Energy Technology Data Exchange (ETDEWEB)

    Illangasekare, Tissa [Colorado School of Mines, Golden, CO (United States); Trevisan, Luca [Colorado School of Mines, Golden, CO (United States); Agartan, Elif [Colorado School of Mines, Golden, CO (United States); Mori, Hiroko [Colorado School of Mines, Golden, CO (United States); Vargas-Johnson, Javier [Colorado School of Mines, Golden, CO (United States); Gonzalez-Nicolas, Ana [Colorado School of Mines, Golden, CO (United States); Cihan, Abdullah [Colorado School of Mines, Golden, CO (United States); Birkholzer, Jens [Colorado School of Mines, Golden, CO (United States); Zhou, Quanlin [Colorado School of Mines, Golden, CO (United States)

    2015-03-31

    Carbon Capture and Storage (CCS) represents a technology aimed to reduce atmospheric loading of CO2 from power plants and heavy industries by injecting it into deep geological formations, such as saline aquifers. A number of trapping mechanisms contribute to effective and secure storage of the injected CO2 in supercritical fluid phase (scCO2) in the formation over the long term. The primary trapping mechanisms are structural, residual, dissolution and mineralization. Knowledge gaps exist on how the heterogeneity of the formation manifested at all scales from the pore to the site scales affects trapping and parameterization of contributing mechanisms in models. An experimental and modeling study was conducted to fill these knowledge gaps. Experimental investigation of fundamental processes and mechanisms in field settings is not possible as it is not feasible to fully characterize the geologic heterogeneity at all relevant scales and gathering data on migration, trapping and dissolution of scCO2. Laboratory experiments using scCO2 under ambient conditions are also not feasible as it is technically challenging and cost prohibitive to develop large, two- or three-dimensional test systems with controlled high pressures to keep the scCO2 as a liquid. Hence, an innovative approach that used surrogate fluids in place of scCO2 and formation brine in multi-scale, synthetic aquifers test systems ranging in scales from centimeter to meter scale developed used. New modeling algorithms were developed to capture the processes controlled by the formation heterogeneity, and they were tested using the data from the laboratory test systems. The results and findings are expected to contribute toward better conceptual models, future improvements to DOE numerical codes, more accurate assessment of storage capacities, and optimized placement strategies. This report presents the experimental and modeling methods

  1. Interactions between CO2, saline water and minerals during geological storage of CO2

    International Nuclear Information System (INIS)

    Hellevang, Helge

    2006-06-01

    The topic of this thesis is to gain a better understanding of interactions between injected CO 2 , aqueous solutions and formation mineralogies. The main focus is concerned with the potential role mineral reactions play in safe long term storage of CO 2 . The work is divided into an experimental part concentrated on the potential of dawsonite (NaAl(OH) 2 CO 3 ) as a permanent storage host of CO 2 , and the development of a new geochemical code ACCRETE that is coupled with the ATHENA multiphase flow simulator. The thesis is composed of two parts: (I) the first part introducing CO 2 storage, geochemical interactions and related work; and (II) the second part that consists of the papers. Part I is composed as follows: Chapter 2 gives a short introduction to geochemical reactions considered important during CO 2 storage, including a thermodynamic framework. Chapter 3 presents objectives of numerical work related to CO 2 -water-rock interactions including a discussion of factors that influence the outcome of numerical simulations. Chapter 4 presents the main results from paper A to E. Chapter 5 give some details about further research that we propose based on the present work and related work in the project. Several new activities have emerged from research on CO 2 -water-rock interaction during the project. Several of the proposed activities are already initiated. Papers A to F are then listed in Part II of the thesis after the citation list. The thesis presents the first data on the reaction kinetics of dawsonite at different pH (Paper A), and comprehensive numerical simulations, both batch- and large scale 3D reactive transport, that illustrate the role different carbonates have for safe storage of CO 2 in geological formations (Papers C to F). The role of dawsonite in CO 2 storage settings is treated throughout the study (Papers A to E) After the main part of the thesis (Part I and II), two appendices are included: Appendix A lists reactions that are included in the

  2. Petrophysical characterization of the Dolomitic Member of the Boñar Formation (Upper Cretaceous; Duero Basin, Spain) as a potential CO2 reservoir

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Gonzalez, A.; Kovacs, C.; Herrero-Hernandez, A.; Gomez-Fernandez, F.

    2016-07-01

    Boñar Formation (Upper Cretaceous) is a mainly carbonate succession, which outcrops in the North of Duero Basin (Spain). According to the existing data, the Dolomitic Member of this formation appears to be the most suitable for geological storage of CO2. The main objective of this study is to find evidence to support, clarify and specify –at an initial level– the potential of the Dolomitic Member of the Boñar Formation as a geological reservoir. The study covers density, porosity and permeability tests on samples obtained from the outcrop of the succession near the village of Boñar (León). According to the analysis and interpretation of the mentioned petrophysical properties, the porosity of the Dolomitic Member is within the acceptable range for CO2 geological storage, but the permeability values are far too low. This minimizes the possibilities of the Dolomitic Member –and probably of the whole Boñar Formation– to become an appropriate CO2 reservoir. (Author)

  3. Effects of C3H8 on hydrate formation and dissociation for integrated CO2 capture and desalination technology

    International Nuclear Information System (INIS)

    Yang, Mingjun; Zheng, Jianan; Liu, Weiguo; Liu, Yu; Song, Yongchen

    2015-01-01

    Hydrate-based technology has been developing for decades to meet the demands in industrial applications. With the global demands for reduced carbon dioxide (CO 2 ) emissions and more fresh water, CHBD (CO 2 hydrate-based desalination) was proposed and has developed rapidly. In this study, to provide basic data for the improvement of CHBD, the thermodynamic and kinetic characteristics of CO 2 and propane (C 3 H 8 ) mixed-gas hydrates in salt solution were experimentally investigated in which C 3 H 8 was chosen as the hydrate formation promoter. We studied nine experimental cases (54 cycles) with different C 3 H 8 proportions (ranging from 0 to 13%) and different initial solution saturations (30%, 40% and 50%). The hydrate phase equilibrium data were generated using the isochoric method, and the hydrate formation saturations were calculated using the relative gas uptake equation. The results indicated that the increase in the C 3 H 8 proportion significantly decreases the gas mixture hydrate equilibrium pressure. Additionally, the relative gas uptake was reduced as the C 3 H 8 proportion increased. A lower relative gas uptake was obtained at a lower gas pressure for the same gas mixture. The initial solution saturation exhibited an insignificant effect on the hydrate phase equilibrium conditions. When the initial solution saturations increased from 30% to 50%, the relative gas uptake decreased. - Highlights: • C 3 H 8 improves the thermodynamics and kinetics of CO 2 hydrates formation. • Hydrates equilibrium pressure decreases with the increase of C 3 H 8 proportion. • Higher C 3 H 8 proportion and/or solution saturation decrease relative gas uptake. • Initial pressure and solution saturation has interactive effect on gas uptake.

  4. Downhole fluid injection systems, CO2 sequestration methods, and hydrocarbon material recovery methods

    Science.gov (United States)

    Schaef, Herbert T.; McGrail, B. Peter

    2015-07-28

    Downhole fluid injection systems are provided that can include a first well extending into a geological formation, and a fluid injector assembly located within the well. The fluid injector assembly can be configured to inject a liquid CO2/H2O-emulsion into the surrounding geological formation. CO2 sequestration methods are provided that can include exposing a geological formation to a liquid CO2/H2O-emulsion to sequester at least a portion of the CO2 from the emulsion within the formation. Hydrocarbon material recovery methods are provided that can include exposing a liquid CO2/H2O-emulsion to a geological formation having the hydrocarbon material therein. The methods can include recovering at least a portion of the hydrocarbon material from the formation.

  5. CO2 point sources and subsurface storage capacities for CO2 in aquifers in Norway

    International Nuclear Information System (INIS)

    Boee, Reidulv; Magnus, Christian; Osmundsen, Per Terje; Rindstad, Bjoern Ivar

    2002-01-01

    The GESTCO project comprises a study of the distribution and coincidence of thermal CO 2 emission sources and location/quality of geological storage capacity in Europe. Four of the most promising types of geological storage are being studied. 1. Onshore/offshore saline aquifers with or without lateral seal. 2. Low entalpy geothermal reservoirs. 3. Deep methane-bearing coal beds and abandoned coal and salt mines. 4. Exhausted or near exhausted hydrocarbon structures. In this report we present an inventory of CO 2 point sources in Norway (1999) and the results of the work within Study Area C: Deep saline aquifers offshore/near shore Northern and Central Norway. Also offshore/near shore Southern Norway has been included while the Barents Sea is not described in any detail. The most detailed studies are on the Tilje and Aare Formations on the Troendelag Platform off Mid-Norway and on the Sognefjord, Fensfjord and Krossfjord Formations, southeast of the Troll Field off Western Norway. The Tilje Formation has been chosen as one of the cases to be studied in greater detail (numerical modelling) in the project. This report shows that offshore Norway, there are concentrations of large CO 2 point sources in the Haltenbanken, the Viking Graben/Tampen Spur area, the Southern Viking Graben and the central Trough, while onshore Norway there are concentrations of point sources in the Oslofjord/Porsgrund area, along the coast of western Norway and in the Troendelag. A number of aquifers with large theoretical CO 2 storage potential are pointed out in the North Sea, the Norwegian Sea and in the Southern Barents Sea. The storage capacity in the depth interval 0.8 - 4 km below sea level is estimated to be ca. 13 Gt (13000000000 tonnes) CO 2 in geological traps (outside hydrocarbon fields), while the storage capacity in aquifers not confined to traps is estimated to be at least 280 Gt CO 2 . (Author)

  6. Synthesis, Structure, Bonding, and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2 }2 {μ-η22 -B2 H4 }] and [{Cp*M(CO)2 }2 B2 H2 M(CO)4 ], M=Mo,W.

    Science.gov (United States)

    Mondal, Bijan; Bag, Ranjit; Ghorai, Sagar; Bakthavachalam, K; Jemmis, Eluvathingal D; Ghosh, Sundargopal

    2018-04-26

    The reaction of [(Cp*Mo) 2 (μ-Cl) 2 B 2 H 6 ] (1) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO) 2 } 2 {μ-η 22 -B 2 H 4 }] (2). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum-alkyne complex [{CpMo(CO) 2 } 2 C 2 H 2 ]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO) 4 ] fragment, [{Cp*Mo(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (3) was isolated upon treatment with [W(CO) 5 ⋅thf]. Compound 3 shows the intriguing presence of [B 2 H 2 ] with a short B-B length of 1.624(4) Å. We isolated the tungsten analogues of 3, [{Cp*W(CO) 2 } 2 B 2 H 2 W(CO) 4 ] (4) and [{Cp*W(CO) 2 } 2 B 2 H 2 Mo(CO) 4 ] (5), which provided direct proof of the existence of the tungsten analogue of 2. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Implantation of energetic D{sup +} ions into carbon dioxide ices and implications for our solar system: formation of D{sub 2}O and D{sub 2}CO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Bennett, Chris J.; Ennis, Courtney P.; Kaiser, Ralf I., E-mail: ralfk@hawaii.edu [Department of Chemistry, University of Hawai' i at Mānoa, Honolulu, HI 96822 (United States)

    2014-10-10

    Carbon dioxide (CO{sub 2}) ices were irradiated with energetic D{sup +} ions to simulate the exposure of oxygen-bearing solar system ices to energetic protons from the solar wind and magnetospheric sources. The formation of species was observed online and in situ by exploiting FTIR spectroscopy. Molecular products include ozone (O{sub 3}), carbon oxides (CO{sub 3}(C {sub 2v}, D {sub 3h}), CO{sub 4}, CO{sub 5}, CO{sub 6}), D2-water (D{sub 2}O), and D2-carbonic acid (D{sub 2}CO{sub 3}). Species released into the gas phase were sampled via a quadrupole mass spectrometer, and possible minor contributions from D2-formaldehyde (D{sub 2}CO), D4-methanol (CD{sub 3}OD), and D2-formic acid (DCOOD) were additionally identified. The feasibility of several reaction networks was investigated by determining their ability to fit the observed temporal column densities of 10 key species that were quantified during the irradiation period. Directly relevant to the CO{sub 2}-bearing ices of comets, icy satellites in the outer solar system, and the ice caps on Mars, this work illustrates for the first time that D2-water is formed as a product of the exposure of CO{sub 2} ices to D{sup +} ions. These findings provide strong support for water formation from oxygen-bearing materials via non-thermal hydrogen atoms, and predict reaction pathways that are likely to be unfolding on the surfaces of asteroids and the Moon.

  8. Inhibiting trophoblast PAR-1 overexpression suppresses sFlt-1-induced anti-angiogenesis and abnormal vascular remodeling: a possible therapeutic approach for preeclampsia.

    Science.gov (United States)

    Zhao, Yin; Zheng, YanFang; Liu, XiaoXia; Luo, QingQing; Wu, Di; Liu, XiaoPing; Zou, Li

    2018-03-01

    Is it possible to improve vascular remodeling by inhibiting the excessive expression of protease-activated receptor 1 (PAR-1) in trophoblast of abnormal placenta? Inhibition of trophoblast PAR-1 overexpression may promote placental angiogenesis and vascular remodeling, offering an alternative therapeutic approach for preeclampsia. PAR-1 is high-affinity receptor of thrombin. Thrombin increases sFlt-1 secretion in trophoblast via the activation of PAR-1. It is reported that the expression of both thrombin and PAR-1 expression are increased in placentas of preeclampsia patients compared with normal placentas. Trophoblast cells were transfected with PAR-1 short hairpin RNA (shRNA) or PAR-1 overexpression plasmids in vitro. Tube formation assays and a villus-decidua co-culture system were used to study the effect of PAR-1 inhibition on placental angiogenesis and vascular remodeling, respectively. Placentas from rats with preeclampsia were transfected with PAR-1 shRNA to confirm the effect of inhibiting PAR-1 overexpression in placenta. The trophoblast cell line HTR-8/SVneo was transfected with PAR-1 shRNA or PAR-1 overexpression plasmids. After 48 h, supernatant was collected and the level of sFlt-1 secretion was measured by ELISA. Human umbilical cord epithelial cells and a villus-decidua co-culture system were treated with conditioned media to study the effect of PAR-1 inhibition on tube formation and villi vascular remodeling. A preeclampsia rat model was established by intraperitoneal injection of L-NAME. Plasmids were injected into the placenta of the preeclampsia rats and systolic blood pressure was measured on Days 15 and 19. The effect of different treatments was evaluated by proteinuria, placental weights, fetal weights and fetal numbers in study and control groups. The level of serum sFlt-1 in rats with preeclampsia was also measured. Changes in the placenta microvessels were studied by histopathological staining. PAR-1 shRNA inhibited PAR-1 expression and

  9. Phase formation in K2O(K2CO3)-CdO-MoO3 system

    International Nuclear Information System (INIS)

    Tsirenova, G.D.; Tsybikova, B.A.; Bazarova, Zh.G.; Solodovnikov, S.F.; Zolotova, E.S.

    2000-01-01

    Phase formation in K 2 O(K 2 CO 3 )-CdO-MoO 3 system are studied by the methods of x-ray diffraction, thermal and crystal optical analyses. Three potassium-cadmium molybdates are detected: K 4 Cd(MoO 4 ) 3 with a new structure, alluodite-like K 4-2x Cd 1+x (MoO 4 ) 3 (0.26≤x≤0.38 at 470 Deg C) and K 4 CdMo 4 O 15 of K 4 MnMo 4 O 15 type. First of them decomposes in solid phase at 580 Deg C, and others melt incongruently at 720 and 515 Deg C correspondingly. It is established that K 4-2x Cd 1+x (MoO 4 ) 3 compound undergoes phase transition of the second type in the temperature interval of 500-550 Deg C. Phase diagram of quasibinary cross section K 2 MoO 4 -CdMoO 4 is plotted [ru

  10. CO2 capture. Two new structures in the 2-amino-2-methyl-1-propanol (AMP) – water – CO2 system

    DEFF Research Database (Denmark)

    Ståhl, Kenny; Neerup, Randi; Fosbøl, Philip Loldrup

    2016-01-01

    Energy production and transportation is responsible for more than 60 % of our CO2 emission. In particular coal-fired power plants are big contributors. However, these large scale facilities offer the possibility to effective CO2 capture through post-combustion processes. There are several options...... studied the 2-amino-2-methyl-1-propanol (AMP) and the AMP-water phase diagramand its ability for CO2 capture. The first crystal structure in the AMP – water system has been solved from powder diffraction data: AMP trihydrate (triclinic, P-1, a = 6.5897(3), b = 6.399 (2), c = 6.3399(2) Å and α = 92.40 (3...... for such CO2 capture. The problem is to make the absorption/desorption processes energetically and thereby economically viable. One process under investigation involves alkanoamines as absorbents in aqueous solutions. In these systems CO2 is captured either by carbonate and/orcarbamate formation. We have...

  11. Effects of ocean acidification with pCO2 diurnal fluctuations on survival and larval shell formation of Ezo abalone, Haliotis discus hannai.

    Science.gov (United States)

    Onitsuka, Toshihiro; Takami, Hideki; Muraoka, Daisuke; Matsumoto, Yukio; Nakatsubo, Ayumi; Kimura, Ryo; Ono, Tsuneo; Nojiri, Yukihiro

    2018-03-01

    This study assessed the effects of constant and diurnally fluctuating pCO 2 on development and shell formation of larval abalone Haliotis discus hannai. The larvae was exposed to different pCO 2 conditions; constant [450, 800, or 1200 μatm in the first experiment (Exp. I), 450 or 780 μatm in the second experiment (Exp. II)] or diurnally fluctuating pCO 2 (800 ± 400 or 1200 ± 400 μatm in Exp. I, 450 ± 80, 780 ± 200 or 780 ± 400 μatm in Exp. II). Mortality, malformation rates or shell length of larval abalone were not significantly different among the 450, 800, and 800 ± 400 μatm pCO 2 treatments. Meanwhile, significantly higher malformation rates and smaller shells were detected in the 1200 and 1200 ± 400 μatm pCO 2 treatments than in the 450 μatm pCO 2 treatment. The negative impacts were greater in the 1200 ± 400 μatm than in the 1200 μatm. Shell length and malformation rate of larval abalone were related with aragonite saturation state (Ω-aragonite) in experimental seawater, and greatly changed around 1.1 of Ω-aragonite which corresponded to 1000-1300 μatm pCO 2 . These results indicate that there is a pCO 2 threshold associated with Ω-aragonite in the seawater, and that pCO 2 fluctuations produce additional negative impacts on abalone when above the threshold. Clear relationships were detected between abalone fitness and the integrated pCO 2 value over the threshold, indicating that the effects of OA on development and shell formation of larval abalone can be determined by intensity and time of exposure to pCO 2 over the threshold. Copyright © 2017 Elsevier Ltd. All rights reserved.

  12. Challenges in the Greener Production of Formates/Formic Acid, Methanol, and DME by Heterogeneously Catalyzed CO2 Hydrogenation Processes

    KAUST Repository

    Álvarez, Andrea

    2017-06-28

    The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.

  13. CO2 Accounting and Risk Analysis for CO2 Sequestration at Enhanced Oil Recovery Sites.

    Science.gov (United States)

    Dai, Zhenxue; Viswanathan, Hari; Middleton, Richard; Pan, Feng; Ampomah, William; Yang, Changbing; Jia, Wei; Xiao, Ting; Lee, Si-Yong; McPherson, Brian; Balch, Robert; Grigg, Reid; White, Mark

    2016-07-19

    Using CO2 in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce sequestration costs in the absence of emissions policies that include incentives for carbon capture and storage. This study develops a multiscale statistical framework to perform CO2 accounting and risk analysis in an EOR environment at the Farnsworth Unit (FWU), Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil/gas-water flow and transport in the Morrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2/water injection/production rates, cumulative net CO2 storage, cumulative oil/gas productions, and CO2 breakthrough time. The median and confidence intervals are estimated for quantifying uncertainty ranges of the risk metrics. A response-surface-based economic model has been derived to calculate the CO2-EOR profitability for the FWU site with a current oil price, which suggests that approximately 31% of the 1000 realizations can be profitable. If government carbon-tax credits are available, or the oil price goes up or CO2 capture and operating expenses reduce, more realizations would be profitable. The results from this study provide valuable insights for understanding CO2 storage potential and the corresponding environmental and economic risks of commercial-scale CO2-sequestration in depleted reservoirs.

  14. Experimental and theoretical investigations on the carbon dioxide gas hydrate formation kinetics at the onset of turbidity regarding CO2 capture and sequestration processes

    International Nuclear Information System (INIS)

    ZareNezhad, Bahman; Mottahedin, Mona; Varaminian, Farshad

    2013-01-01

    The carbon dioxide gas hydrate formation kinetics at the onset of turbidity is experimentally and theoretically investigated. It is shown that the time-dependent heterogeneous nucleation and growth kinetics are simultaneously governing the hydrate formation process at the onset of turbidity. A new approach is also presented for determination of gas hydrate-liquid interfacial tension. The CO 2 hydrate-liquid interfacial tension according to the suggested heterogeneous nucleation mechanism is found to be about 12.7 mJ/m 2 . The overall average absolute deviation between predicted and measured CO 2 molar consumption is about 0.61%, indicating the excellent accuracy of the proposed model for studying the hydrate-based CO 2 capture and sequestration processes over wide ranges of pressures and temperatures

  15. Effect of Mineral Dissolution/Precipitation and CO2 Exsolution on CO2 transport in Geological Carbon Storage.

    Science.gov (United States)

    Xu, Ruina; Li, Rong; Ma, Jin; He, Di; Jiang, Peixue

    2017-09-19

    Geological carbon sequestration (GCS) in deep saline aquifers is an effective means for storing carbon dioxide to address global climate change. As the time after injection increases, the safety of storage increases as the CO 2 transforms from a separate phase to CO 2 (aq) and HCO 3 - by dissolution and then to carbonates by mineral dissolution. However, subsequent depressurization could lead to dissolved CO 2 (aq) escaping from the formation water and creating a new separate phase which may reduce the GCS system safety. The mineral dissolution and the CO 2 exsolution and mineral precipitation during depressurization change the morphology, porosity, and permeability of the porous rock medium, which then affects the two-phase flow of the CO 2 and formation water. A better understanding of these effects on the CO 2 -water two-phase flow will improve predictions of the long-term CO 2 storage reliability, especially the impact of depressurization on the long-term stability. In this Account, we summarize our recent work on the effect of CO 2 exsolution and mineral dissolution/precipitation on CO 2 transport in GCS reservoirs. We place emphasis on understanding the behavior and transformation of the carbon components in the reservoir, including CO 2 (sc/g), CO 2 (aq), HCO 3 - , and carbonate minerals (calcite and dolomite), highlight their transport and mobility by coupled geochemical and two-phase flow processes, and consider the implications of these transport mechanisms on estimates of the long-term safety of GCS. We describe experimental and numerical pore- and core-scale methods used in our lab in conjunction with industrial and international partners to investigate these effects. Experimental results show how mineral dissolution affects permeability, capillary pressure, and relative permeability, which are important phenomena affecting the input parameters for reservoir flow modeling. The porosity and the absolute permeability increase when CO 2 dissolved water is

  16. Spatially selective Er/Yb-doped CaF{sub 2} crystal formation by CO{sub 2} laser exposure

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong-Seon; Lee, Jin-Ho; Lim, Ki-Soo, E-mail: kslim@chungbuk.ac.kr

    2014-10-30

    Highlights: • Oxyfluoride glass–ceramics containing CaF{sub 2} nanocrystals doped with Er{sup 3+} and Yb{sup 3+} ions were formed on the glass surface by CO{sub 2} laser and a heat gun exposure. • Most of Er and Yb ions were distributed inside CaF{sub 2} nanocrystals and fluorine loss was observed in the EDS element maps. • IR-to-VIS upconversion emission efficiency of laser annealed glass ceramics was much increased and compared with that of the furnace-annealed glass ceramics. • Distributed volume of the glass ceramics were estimated by a confocal fluorescence microscope imaging. - Abstract: We report the glass–ceramic precipitation on the oxyfluoride glass surface by spatially selective annealing with a CO{sub 2} laser and a heat gun exposure. X-ray diffraction analysis showed the formation of major CaF{sub 2} and miner Ca{sub 2}SiO{sub 4} nanoparticles. We observed ∼100 nm nanoparticle aggregation by tunneling electron microscopy and element distribution in glass and crystal phases. Spatial distribution of glass ceramics near the glass surface was probed by confocal fluorescence microscope by using much enhanced emission from the Er ions in the laser-treated area. Strong emissions at 365 nm excitation and visible up-conversion emissions at 980 nm excitation also indicated well incorporation of Er and Yb ions into a crystalline environment.

  17. Spatially selective Er/Yb-doped CaF{sub 2} crystal formation by CO{sub 2} laser exposure

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Dong-Seon; Lee, Jin-Ho; Lim, Ki-Soo, E-mail: kslim@chungbuk.ac.kr

    2015-04-15

    Highlights: • Oxyfluoride glass–ceramics containing CaF{sub 2} nanocrystals doped with Er{sup 3+} and Yb{sup 3+} ions were formed on the glass surface by CO{sub 2} laser and a heat gun exposure. • Most of Er and Yb ions were distributed inside CaF{sub 2} nanocrystals and fluorine loss was observed in the EDS element maps. • IR-to-VIS upconversion emission efficiency of laser annealed glass ceramics was much increased and compared with that of the furnace-annealed glass ceramics. • Distributed volume of the glass ceramics were estimated by a confocal fluorescence microscope imaging. - Abstract: We report the glass–ceramic precipitation on the oxyfluoride glass surface by spatially selective annealing with a CO{sub 2} laser and a heat gun exposure. X-ray diffraction analysis showed the formation of major CaF{sub 2} and miner Ca{sub 2}SiO{sub 4} nanoparticles. We observed ∼100 nm nanoparticle aggregation by tunneling electron microscopy and element distribution in glass and crystal phases. Spatial distribution of glass ceramics near the glass surface was probed by confocal fluorescence microscope by using much enhanced emission from the Er ions in the laser-treated area. Strong emissions at 365 nm excitation and visible up-conversion emissions at 980 nm excitation also indicated well incorporation of Er and Yb ions into a crystalline environment.

  18. Daily variation in net primary production and net calcification in coral reef communities exposed to elevated pCO2

    Directory of Open Access Journals (Sweden)

    S. Comeau

    2017-07-01

    Full Text Available The threat represented by ocean acidification (OA for coral reefs has received considerable attention because of the sensitivity of calcifiers to changing seawater carbonate chemistry. However, most studies have focused on the organismic response of calcification to OA, and only a few have addressed community-level effects, or investigated parameters other than calcification, such as photosynthesis. Light (photosynthetically active radiation, PAR is a driver of biological processes on coral reefs, and the possibility that these processes might be perturbed by OA has important implications for community function. Here we investigate how CO2 enrichment affects the relationships between PAR and community net O2 production (Pnet, and between PAR and community net calcification (Gnet, using experiments on three coral communities constructed to match (i the back reef of Mo'orea, French Polynesia, (ii the fore reef of Mo'orea, and (iii the back reef of O'ahu, Hawaii. The results were used to test the hypothesis that OA affects the relationship between Pnet and Gnet. For the three communities tested, pCO2 did not affect the Pnet–PAR relationship, but it affected the intercept of the hyperbolic tangent curve fitting the Gnet–PAR relationship for both reef communities in Mo'orea (but not in O'ahu. For the three communities, the slopes of the linear relationships between Pnet and Gnet were not affected by OA, although the intercepts were depressed by the inhibitory effect of high pCO2 on Gnet. Our result indicates that OA can modify the balance between net calcification and net photosynthesis of reef communities by depressing community calcification, but without affecting community photosynthesis.

  19. In situ synchrotron X-ray diffraction study of scale formation during CO{sub 2} corrosion of carbon steel in sodium and magnesium chloride solutions

    Energy Technology Data Exchange (ETDEWEB)

    Ingham, B. [Industrial Research Limited, P.O. Box 31-310, Lower Hutt 5045 (New Zealand); MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, P.O. Box 600, Wellington 6140 (New Zealand); Ko, M., E-mail: m.ko@questintegrity.com [MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, P.O. Box 600, Wellington 6140 (New Zealand); Quest Integrity Group, P.O. Box 38-096, Lower Hutt 5045 (New Zealand); School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1022 (New Zealand); Laycock, N. [Quest Integrity Group, P.O. Box 38-096, Lower Hutt 5045 (New Zealand); Burnell, J. [Industrial Research Limited, P.O. Box 31-310, Lower Hutt 5045 (New Zealand); Kappen, P. [Centre for Materials and Surface Science, Department of Physics, La Trobe University, Bundoora, VIC 3086 (Australia); Kimpton, J.A. [Australian Synchrotron, 800 Blackburn Road, Clayton, VIC 3168 (Australia); Williams, D.E. [MacDiarmid Institute for Advanced Materials and Nanotechnology, Victoria University of Wellington, P.O. Box 600, Wellington 6140 (New Zealand); School of Chemical Sciences, University of Auckland, Private Bag 92019, Auckland 1022 (New Zealand)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer We studied the scale formation processes of carbon steel in CO{sub 2} saturated brine at 80 Degree-Sign C. Black-Right-Pointing-Pointer Protective scales were formed in all tests. Black-Right-Pointing-Pointer Only FeCO{sub 3} formed in saturated brine while Fe(OH){sub 2}CO{sub 3} detected with presence of MgCl{sub 2}. Black-Right-Pointing-Pointer MgCl{sub 2} accelerates the onset of siderite precipitation. - Abstract: In situ synchrotron X-ray diffraction was used to follow the formation of corrosion products on carbon steel in CO{sub 2} saturated NaCl solution and mixed NaCl/magnesium chloride (MgCl{sub 2}) at 80 Degree-Sign C. Siderite (FeCO{sub 3}) was the only phase formed in NaCl solution, while Fe(OH){sub 2}CO{sub 3} was also detected when MgCl{sub 2} was present. The proposed model is that siderite precipitation, occurring once the critical supersaturation was exceeded within a defined boundary layer, caused local acidification which accelerated the anodic dissolution of iron. The current fell once a complete surface scale was formed. It is suggested that MgCl{sub 2} addition decreased the required critical supersaturation for precipitation.

  20. Determining CO2 storage potential during miscible CO2 enhanced oil recovery: Noble gas and stable isotope tracers

    Science.gov (United States)

    Shelton, Jenna L.; McIntosh, Jennifer C.; Hunt, Andrew; Beebe, Thomas L; Parker, Andrew D; Warwick, Peter D.; Drake, Ronald; McCray, John E.

    2016-01-01

    Rising atmospheric carbon dioxide (CO2) concentrations are fueling anthropogenic climate change. Geologic sequestration of anthropogenic CO2 in depleted oil reservoirs is one option for reducing CO2 emissions to the atmosphere while enhancing oil recovery. In order to evaluate the feasibility of using enhanced oil recovery (EOR) sites in the United States for permanent CO2 storage, an active multi-stage miscible CO2flooding project in the Permian Basin (North Ward Estes Field, near Wickett, Texas) was investigated. In addition, two major natural CO2 reservoirs in the southeastern Paradox Basin (McElmo Dome and Doe Canyon) were also investigated as they provide CO2 for EOR operations in the Permian Basin. Produced gas and water were collected from three different CO2 flooding phases (with different start dates) within the North Ward Estes Field to evaluate possible CO2 storage mechanisms and amounts of total CO2retention. McElmo Dome and Doe Canyon were sampled for produced gas to determine the noble gas and stable isotope signature of the original injected EOR gas and to confirm the source of this naturally-occurring CO2. As expected, the natural CO2produced from McElmo Dome and Doe Canyon is a mix of mantle and crustal sources. When comparing CO2 injection and production rates for the CO2 floods in the North Ward Estes Field, it appears that CO2 retention in the reservoir decreased over the course of the three injections, retaining 39%, 49% and 61% of the injected CO2 for the 2008, 2010, and 2013 projects, respectively, characteristic of maturing CO2 miscible flood projects. Noble gas isotopic composition of the injected and produced gas for the flood projects suggest no active fractionation, while δ13CCO2 values suggest no active CO2dissolution into formation water, or mineralization. CO2 volumes capable of dissolving in residual formation fluids were also estimated along with the potential to store pure-phase supercritical CO2. Using a combination

  1. System-level modeling for geological storage of CO2

    OpenAIRE

    Zhang, Yingqi; Oldenburg, Curtis M.; Finsterle, Stefan; Bodvarsson, Gudmundur S.

    2006-01-01

    One way to reduce the effects of anthropogenic greenhouse gases on climate is to inject carbon dioxide (CO2) from industrial sources into deep geological formations such as brine formations or depleted oil or gas reservoirs. Research has and is being conducted to improve understanding of factors affecting particular aspects of geological CO2 storage, such as performance, capacity, and health, safety and environmental (HSE) issues, as well as to lower the cost of CO2 capture and related p...

  2. Modulating calcium phosphate formation using CO2 laser engineering of a polymeric material

    International Nuclear Information System (INIS)

    Waugh, D.G.; Lawrence, J.

    2012-01-01

    The use of simulated body fluid (SBF) is widely used as a screening technique to assess the ability of materials to promote calcium phosphate formation. This paper details the use of CO 2 laser surface treatment of nylon® 6,6 to modulate calcium phosphate formation following immersion in SBF for 14 days. Through white light interferometry (WLI) it was determined that the laser surface processing gave rise to maximum Ra and Sa parameters of 1.3 and 4.4 μm, respectively. The use of X-ray photoelectron spectroscopy (XPS) enabled a maximum increase in surface oxygen content of 5.6%at. to be identified. The laser-induced surface modifications gave rise to a modulation in the wettability characteristics such that the contact angle, θ, decreased for the whole area processed samples, as expected, and increased for the patterned samples. The increase in θ can be attributed to a transition in wetting nature to a mixed-state wetting regime. It was seen for all samples that calcium phosphate formed on each surface following 14 days. The largest increase in mass, Δg, owed to calcium phosphate formation, was brought about by the whole area processed sample irradiated with a fluence of 51 J cm −2 . No correlation between the calcium phosphate formation and the laser patterned surface properties was determined due to the likely affect of the mixed-state wetting regime. Strong correlations between θ, the surface energy parameters and the calcium phosphate formation for the whole area processed samples allow one to realize the potential for this surface treatment technique in predicting the bone forming ability of laser processed materials. - Highlights: ► Surface modifications brought about a modulation in the wetting of nylon 6,6. ► An increase in θ can be attributed to a mixed-state wetting regime. ► Laser surface treatment modulated the ability to promote apatite formation. ► Mixed-state wetting regime affected the promotion of uniform apatite formation.

  3. The PHREEQC modeling of CO{sub 2} transport in highly saline solutions of a final radioactive waste repository; PHREEQC. Modellierung des Transportes von CO{sub 2} in hochsalinaren Loesungen eines Endlagers

    Energy Technology Data Exchange (ETDEWEB)

    Weyand, Torben [Bonn Univ. (Germany); Gesellschaft fuer Reaktorsicherheit mbH (GRS), Koeln (Germany); Bracke, Guido [Gesellschaft fuer Reaktorsicherheit mbH (GRS), Koeln (Germany); Reichert, Barbara [Bonn Univ. (Germany)

    2014-03-15

    The safe confinement of radioactive materials in the containment providing zone of the host rock (CPRZ) over a period of one million years is required for a final repository for highly radioactive heat-generating waste (BMU 2010). In order to assess the safe containment of radionuclides in the CPRZ a sound understanding of the ongoing processes in a repository is necessary. These processes include the transport and chemical interactions of the radionuclide {sup 14}C in the gas phase and in highly saline solutions in a final repository for radioactive waste. The geochemical code PHREEQC /PAR 13/ was used to study the chemical interactions of CO{sub 2} and {sup 14}C as {sup 14}CO{sub 2} during transport in the gas phase and highly saline solutions. The model and scenario was based on the concept for a repository in Gorleben /BOL 11/. A gas generation of CO{sub 2} containing {sup 14}C was assumed since the disposed containers with the radioactive waste corrode /LAR 13/. The advective transport is triggered by gas generation. The physical dissolution of CO{sub 2}, chemical equilibria with aquatic carbon-containing species (e. g. HCO{sub 3}{sup -}(aq), CO{sub 3}{sup 2-}(aq)) and solid phases (e. g. magnesite, MgCO{sub 3}) coupled with transport were modelled. Due to the addition of dissolved MgCl{sub 2} in the crushed salt backfill of the main drift the aquatic species MgCO{sub 3}(aq) and the mineral MgCO{sub 3}(s) is formed. The influence of CO{sub 2} partial pressure and the chemical interactions in the presence of dissolved Fe{sup 2+}, Ca{sup 2+}, Mg{sup 2+} and K{sup +} were studied. Due to the physical solution, the CO{sub 2} partial pressure has a major influence on the transport of {sup 14}C. In the presence of calcium CaCO{sub 3}(aq), the minerals calcite (CaCO{sub 3}(s)) and dolomite (MgCa(CO{sub 3}){sub 2}(s)) were formed in the highly saline solutions. No siderite (FeCO{sub 3}) in the presence of Fe{sup 2+} was formed. The transport of {sup 14}C was delayed

  4. The Arizona Radio Observatory CO Mapping Survey of Galactic Molecular Clouds. V. The Sh2-235 Cloud in CO J=2-1, 13CO J=2-1, and CO J=3-2

    Science.gov (United States)

    Bieging, John H.; Patel, Saahil; Peters, William L.; Toth, L. Viktor; Marton, Gábor; Zahorecz, Sarolta

    2016-09-01

    We present the results of a program to map the Sh2-235 molecular cloud complex in the CO and 13CO J = 2 - 1 transitions using the Heinrich Hertz Submillimeter Telescope. The map resolution is 38″ (FWHM), with an rms noise of 0.12 K brightness temperature, for a velocity resolution of 0.34 km s-1. With the same telescope, we also mapped the CO J = 3 - 2 line at a frequency of 345 GHz, using a 64 beam focal plane array of heterodyne mixers, achieving a typical rms noise of 0.5 K brightness temperature with a velocity resolution of 0.23 km s-1. The three spectral line data cubes are available for download. Much of the cloud appears to be slightly sub-thermally excited in the J = 3 level, except for in the vicinity of the warmest and highest column density areas, which are currently forming stars. Using the CO and 13CO J = 2 - 1 lines, we employ an LTE model to derive the gas column density over the entire mapped region. Examining a 125 pc2 region centered on the most active star formation in the vicinity of Sh2-235, we find that the young stellar object surface density scales as approximately the 1.6-power of the gas column density. The area distribution function of the gas is a steeply declining exponential function of gas column density. Comparison of the morphology of ionized and molecular gas suggests that the cloud is being substantially disrupted by expansion of the H II regions, which may be triggering current star formation.

  5. Unexpected inhibition of CO2 gas hydrate formation in dilute TBAB solutions and the critical role of interfacial water structure

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Ngoc N.; Nguyen, Anh V.; Nguyen, Khoi T.; Rintoul, Llew; Dang, Liem X.

    2016-12-01

    Gas hydrates formed under moderated conditions open up novel approaches to tackling issues related to energy supply, gas separation, and CO2 sequestration. Several additives like tetra-n-butylammonium bromide (TBAB) have been empirically developed and used to promote gas hydrate formation. Here we report unexpected experimental results which show that TBAB inhibits CO2 gas hydrate formation when used at minuscule concentration. We also used spectroscopic techniques and molecular dynamics simulation to gain further insights and explain the experimental results. They have revealed the critical role of water alignment at the gas-water interface induced by surface adsorption of tetra-n-butylammonium cation (TBA+) which gives rise to the unexpected inhibition of dilute TBAB solution. The water perturbation by TBA+ in the bulk is attributed to the promotion effect of high TBAB concentration on gas hydrate formation. We explain our finding using the concept of activation energy of gas hydrate formation. Our results provide a step toward to mastering the control of gas hydrate formation.

  6. Modeling of Gas Diffusion in Ni/YSZ Electrodes in CO2 and Co-electrolysis

    DEFF Research Database (Denmark)

    Duhn, Jakob Dragsbæk; Jensen, Anker Degn; Wedel, Stig

    2017-01-01

    Carbon formation may occur during CO2 and CO2/H2O electrolysis using solid oxide electrolyzer cells due to the Boudouard reaction (2CO →  CO2 + C(s)). Formed carbon may disintegrate the cell structure and it is therefore of importance to be able to predict when carbon is formed, and take actions...

  7. Active sites of ligand-protected Au25 nanoparticle catalysts for CO2 electroreduction to CO

    Science.gov (United States)

    Alfonso, Dominic R.; Kauffman, Douglas; Matranga, Christopher

    2016-05-01

    Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO2) into CO at atomically precise negatively charged Au25- nanoclusters. The studies showed CO2 conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO2 reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO2 reduction catalyst because formation of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO2 reduction at gold nanocluster catalysts.

  8. Método para determinação de parâmetros de gravação e corte a laser CO2 com aplicação na joalheria contemporânea

    Directory of Open Access Journals (Sweden)

    Mariana Kuhl Cidade

    2016-12-01

    Full Text Available A tecnologia de gravação e corte a laser CO2 é um dos principais processos de fabricação da atualidade, unindo versatilidade, precisão e velocidade, sendo uma importante ferramenta para o design de joias contemporâneas. A utilização do equipamento depende de diversas variáveis relacionadas aos materiais utilizados ou aos projetos executados. Contudo, a obtenção dos melhores parâmetros frequentemente é realizada de forma empírica, tornando a padronização imprecisa e prejudicando a qualidade das peças. Na joalheria contemporânea, é essencial a busca por peças com grande nível de acabamento e que mesclem a utilização de materiais nobres com alternativas não-convencionais. Esta pesquisa trata do desenvolvimento de um método para a obtenção de parâmetros ideais para a utilização da tecnologia de gravação e corte a laser CO2, com desenhos vetoriais, através de etapas que considerem as variáveis do projeto, do material e do equipamento do tipo galvanométrico. Para aplicação, o método foi empregado no desenvolvimento de joias utilizando-se borracha EPDM com prata. Foram conduzidos testes de aplicação de velocidades e número de passadas de feixe laser, determinando a configuração ideal para utilização deste processo no material. Imagens analisadas via MEV auxiliaram na avaliação dos efeitos do feixe laser no elastômero, como a zona de abrangência térmica e a efetividade do corte. Com um método para obtenção dos parâmetros para boa definição de corte e uniformidade do traço, essa pesquisa objetiva auxiliar estudantes, profissionais e indústrias na execução de seus projetos.

  9. INFLUENCE OF METRONIDAZOLE, CO, CO2, AND METHANOGENS ON THE FERMENTATIVE METABOLISM OF THE ANAEROBIC FUNGUS NEOCALLIMASTIX SP STRAIN L2

    NARCIS (Netherlands)

    MARVINSIKKEMA, FD; REES, E; KRAAK, MN; GOTTSCHAL, JC; PRINS, RA

    The effects of metronidazole, CO, methanogens, and CO, on the fermentation of glucose by the anaerobic fungus Neocallimastix sp. strain L2 were investigated. Both metronidazole and CO caused a shift in the fermentation products from predominantly H-2, acetate, and formate to lactate as the major

  10. Vote par sondage uniforme incorruptible

    OpenAIRE

    Blanchard , Nicolas

    2016-01-01

    International audience; Introduit en 2012 par David Chaum, le vote par sondage uniforme (random-sample voting) est un protocole de vote basé sur un choix d'une sous-population représentative , permettant de limiter les coûts tout en ayant de nombreux avantages, principalement lorsqu'il est couplé a d'autres techniques comme ThreeBallot. Nous analysons un problème de corruptibilité potentielle où les votants peuvent vendre leur vote au plus offrant et proposons une variation du protocole reméd...

  11. Catalytic hydrogenation of CO2 to formates by lutidine-derived Ru-CNC pincer complex : theoretical insight into unrealized potential

    NARCIS (Netherlands)

    Filonenko, G.; Smykowski, D.; Szyja, B.M.; Li, G.; Szczygiel, J.; Hensen, E.J.M.; Pidko, E.A.

    2015-01-01

    Metal-ligand cooperative properties of a bis-N-heterocyclic carbene ruthenium CNC-pincer catalyst and its activity in CO2 hydrogenation to formates were studied by DFT calculations complemented by NMR spectroscopy and kinetic measurements. The dearomatized Ru-CNC* pincer (1*) is significantly more

  12. Interface characteristics in Co2MnSi/Ag/Co2MnSi trilayer

    International Nuclear Information System (INIS)

    Li, Yang; Chen, Hong; Wang, Guangzhao; Yuan, Hongkuan

    2016-01-01

    Highlights: • Inferface DO 3 disorder is most favorable in Co 2 MnSi/Ag/Co 2 MnSi trilayer. • Interface itself and inferface DO 3 disorder destroy the half-metallicity of interface layers. • Magnetoresistance is reduced by the interface itself and interface disorder. • Magnetotransport coefficient is largely reduced by the interface itself and interface disorder. - Abstract: Interface characteristics of Co 2 MnSi/Ag/Co 2 MnSi trilayer have been investigated by means of first-principles. The most likely interface is formed by connecting MnSi-termination to the bridge site between two Ag atoms. As annealed at high temperature, the formation of interface DO 3 disorder is most energetically favorable. The spin polarization is reduced by both the interface itself and interface disorder due to the interface state occurs in the minority-spin gap. As a result, the magneto-resistance ratio has a sharp drop based on the estimation of a simplified modeling.

  13. Application of rank annihilation factor analysis to the spectrophotometric determination of the formation constant of complex of a new synthesized tripodal ligand with Co2+

    Directory of Open Access Journals (Sweden)

    Reza Golbedaghi

    2017-05-01

    Full Text Available The complex formation between a new synthesized tripodal ligand (L22py and the cation Co2+ in water was studied spectrophotometrically using rank annihilation factor analysis (RAFA. According to molar ratio data the stoichiometry of complexation between the ligand and the cation Co2+ was 1:1. Formation constant of this complex was derived using RAFA on spectrophotometric data. In this process the contribution of ligand is removed from the absorbance data matrix when the complex stability constant acts as an optimizing object and simply combined with the pure spectrum of ligand, the rank of original data matrix can be reduced by one by annihilating the information of the ligand from the original data matrix. The effect of ethanol, dimethylformamide (DMF and acetonitrile (AN was investigated on the formation constant of the Co2+ complex. Complex formation constant in water was estimated as log Kf = 5.09 ± 0.02. In mixtures of solvents of water and DMF and water and AN, the formation constant of the complex was increased because of lowering donor number of the solvent and in mixture of water and ethanol, the complex formation constant was decreased because of lowering of dielectric constant of the solvent.

  14. A novel CO2 sequestration system for environmentally producing hydrogen from fossil-fuels

    International Nuclear Information System (INIS)

    Eucker IV, W.

    2007-01-01

    Aqueous monoethanolamine (MEA) scrubbers are currently used to capture carbon dioxide (CO 2 ) from industrial flue gases in various fossil-fuel based energy production systems. MEA is a highly volatile, corrosive, physiologically toxic, and foul-smelling chemical that requires replacement after 1000 operational hours. Room temperature ionic liquids (RTILs), a novel class of materials with negligible vapor pressures and potentiality as benign solvents, may be the ideal replacement for MEA. Ab initio computational modeling was used to investigate the molecular interactions of ILs with CO 2 . The energetic and thermodynamic parameters of the RTILs as CO 2 solvents are on par with MEA. As viable competitors to the present CO 2 separation technology, RTILs may economize the fossil-fuel decarbonization process with the ultimate aim of realizing a green hydrogen economy

  15. Natural CO2 migrations in the South-Eastern Basin of France: implications for the CO2 storage in sedimentary formations

    International Nuclear Information System (INIS)

    Rubert, Y.

    2009-03-01

    Study of natural CO 2 analogues brings key informations on the factors governing the long term stability/instability of future anthropogenic CO 2 storages. The main objective of this work, through the study of cores from V.Mo.2 well crosscutting the Montmiral natural reservoir (Valence Basin, France), is to trace the deep CO 2 migrations in fractures. Petrographic, geochemical and micro-thermometric studies of the V.Mo.2 cores were thus performed in order: 1) to describe the reservoir filling conditions and 2) to detect possible CO 2 -leakage through the sediments overlying the reservoir. Fluid inclusions from the Paleozoic crystalline basement record the progressive unmixing of a hot homogeneous aquo-carbonic fluid. The Montmiral reservoir was therefore probably fed by a CO 2 -enriched gas component at the Late Cretaceous-Paleogene. The study of the sedimentary column in V.Mo.2 well, demonstrates that the CO 2 did not migrate towards the surface through the thick marly unit (Domerian-Middle Oxfordian). These marls have acted as an impermeable barrier that prevented the upward migration of fluids. Two main stages of fluid circulation have been recognized: 1) an ante- Callovian one related to the Tethysian extension 2) a tertiary stage during which the upper units underwent a karstification, with CO 2 leakage related but which remained confined into the deeper parts of the Valence Basin. Since the Paleogene, the Montmiral reservoir has apparently remained stable, despite the Pyrenean and alpine orogeneses. This is mainly due to the efficient seal formed by the thick marly levels and also to the local structuration in faulted blocks which apparently acted as efficient lateral barriers. (author)

  16. Corrosion of low alloy steel containing 0.5% chromium in supercritical CO2-saturated brine and water-saturated supercritical CO2 environments

    Science.gov (United States)

    Wei, Liang; Gao, Kewei; Li, Qian

    2018-05-01

    The corrosion behavior of P110 low-Cr alloy steel in supercritical CO2-saturated brine (aqueous phase) and water-saturated supercritical CO2 (SC CO2 phase) was investigated. The results show that P110 steel primarily suffered general corrosion in the aqueous phase, while severe localized corrosion occurred in the SC CO2 phase. The formation of corrosion product scale on P110 steel in the aqueous phase divided into three stages: formation of the initial corrosion layer containing amorphous Cr(OH)3, FeCO3 and a small amount of Fe3C; transformation of initial corrosion layer to mixed layer, which consisted of FeCO3 and a small amount of Cr(OH)3 and Fe3C; growth and dissolution of the mixed layer. Finally, only a single mixed layer covered on the steel in the aqueous phase. However, the scale formed in SC CO2 phase consisted of two layers: the inner mixed layer and the dense outer FeCO3 crystalline layer.

  17. Modification of Ga2O3 by an Ag-Cr core-shell cocatalyst enhances photocatalytic CO evolution for the conversion of CO2 by H2O.

    Science.gov (United States)

    Pang, Rui; Teramura, Kentaro; Tatsumi, Hiroyuki; Asakura, Hiroyuki; Hosokawa, Saburo; Tanaka, Tsunehiro

    2018-01-25

    A core-shell structure of Ag-Cr dual cocatalyst loaded-Ga 2 O 3 was found to significantly enhance the formation rate of CO and selectivity toward CO evolution for the photocatalytic conversion of CO 2 where H 2 O is used as an electron donor.

  18. Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

    Science.gov (United States)

    Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

    2014-12-01

    The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E

  19. Photosynthesis of Scenedesmus obliquus in outdoor open thin-layer cascade system in high and low CO2 in Belgium.

    Science.gov (United States)

    de Marchin, Thomas; Erpicum, Michel; Franck, Fabrice

    2015-12-10

    Two outdoor open thin-layer cascade systems operated as batch cultures with the alga Scenedesmus obliquus were used to compare the productivity and photosynthetic acclimations in control and CO2 supplemented cultures in relation with the outdoor light irradiance. We found that the culture productivity was limited by CO2 availability. In the CO2 supplemented culture, we obtained a productivity of up to 24gdwm(-2)day(-1) and found a photosynthetic efficiency (value based on the PAR solar radiation energy) of up to 5%. In the CO2 limited culture, we obtained a productivity of up to 10gdwm(-2)day(-1) while the photosynthetic efficiency was up to 3.3% and decreased to 2.1% when the integrated daily PAR increased. Fluorescence and oxygen evolution measurements showed that ETR and oxygen evolution light saturation curves, as well as light-dependent O2 uptake were similar in algal samples from both cultures when the CO2 limitation was removed. In contrast, we found that CO2 limitation conducted to a decreased PSII photochemical efficiency and an increased light-induced heat-dissipation in the control culture compared to the CO2 supplemented culture. These features are in line with a lower light use efficiency and may therefore contribute to the lower productivity observed in absence of CO2 supplementation in outdoor mass cultures of S. obliquus. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. EFP1 is an ER stress-induced glycoprotein which interacts with the pro-apoptotic protein Par-4

    Directory of Open Access Journals (Sweden)

    Sarah Appel

    2009-05-01

    Full Text Available Sarah Appel1,2,6, Susanne Vetterkind1,2,6, Ansgar Koplin1,3, Barbara Maertens1,4, Meike Boosen1,5, Ute Preuss11The Institute of Genetics, University of Bonn, Bonn, Germany; 2Department of Health Sciences, Sargent College of Health and Rehabilitation Sciences, Boston University, Boston, MA, USA; 3Center for Molecular Biology Heidelberg (ZMBH, Heidelberg, Germany; 4Institute of Biochemistry II, University of Cologne, Cologne, Germany; 5Institute of Pharmacology and Toxicology, University Hospital of Johann Wolfgang Goethe-University Frankfurt am Main, Frankfurt am Main, Germany; 6These authors contributed equally to this work.Abstract: We have isolated the rat ortholog of EFP1 (EF-hand binding protein 1 as a novel interaction partner of the pro-apoptotic protein Par-4 (prostate apoptosis response-4. Rat EFP1 contains two thioredoxin domains, the COOH-terminal one harboring a CGFC motif, and has a similar protein domain structure as members of the protein disulfide isomerase (PDI family. In REF52.2 and CHO cells, EFP1 colocalized with the endoplasmic reticulum (ER marker PDI. Furthermore, EFP1 possesses catalytic activity as demonstrated by an insulin disulfide reduction assay. Western blot analysis revealed two EFP1 protein bands of approximately 136 and 155 kDa, representing different glycosylation states of the protein. Complex formation between EFP1 and Par-4 was confirmed in vitro and in vivo by co-immunoprecipitation, dot blot overlay and pull-down experiments. In CHO cells, coexpression of EFP1 and Par-4 resulted in enhanced Par-4-mediated apoptosis, which required the catalytic activity of EFP1. Interestingly, EFP1 was specifically upregulated in NIH3T3 cells after induction of ER stress by thapsigargin, tunicamycin, and brefeldin A, but not by agents that induce oxidative stress or ER-independent apoptosis. Furthermore, we could show that the induction of apoptosis by Ca2+ stress-inducing agents was significantly decreased after si

  1. Numerical Study on CO2-Brine-Rock Interaction of Enhanced Geothermal Systems with CO2 as Heat Transmission Fluid

    Directory of Open Access Journals (Sweden)

    Wan Yuyu

    2016-01-01

    Full Text Available Enhanced Geothermal Systems (EGS with CO2 instead of water as heat transmission fluid is an attractive concept for both geothermal resources development and CO2 geological sequestration. Previous studies show that CO2 has lots of favorable properties as heat transmission fluid and also can offer geologic storage of CO2 as an ancillary benefit. However, after CO2 injection into geological formations, chemical reaction between brine and rock can change chemical characteristics of saline and properties of rock such as porosity and permeability. Is this advantage or disadvantage for EGS operating? To answer this question, we have performed chemically reactive transport modeling to investigate fluid-rock interactions and CO2 mineral carbonation of Enhanced Geothermal Systems (EGS site at Desert Peak (Nevada operated with CO2. The simulation results show that (1 injection CO2 can create a core zone fulfilled with CO2 as main working domain for EGS, and (2 CO2 storage can induced self-enhancing alteration of EGS.

  2. Formation of sulphite, cysteic acid and taurine from sulphate by the egg embryo; Formation de sulfite, d'acide cysteique et de taurine a partir de sulfate par l'oeuf embryonne

    Energy Technology Data Exchange (ETDEWEB)

    Chapeville, F; Fromageot, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires

    1959-07-01

    It is shown that the formation of taurine from sulphate by the chicken embryo involves the reduction of sulphate to sulphite (I), the synthesis of cysteic acid (II) and its decarboxylation (Ill). The reaction (I) takes place in the vitellin sac. The reaction (II) results from the condensation of the sulphite with a-amino-acrylic acid and is carried out by the yolk. The enzymes responsible for the decarboxylation (III) are distributed both in the embryo and in its appendages. (author) [French] On demontre que la formation de taurine a partir de sulfate par l'embryon de poulet implique la reduction du sulfate en sulfite (1), la synthese de l'acide cysteique (Il) et sa decarboxylation (III). La reaction (I) a lieu dans le sac vitellin. La reaction (II) resulte de la condensation du sulfite avec l'acide a-amino-acrylique et est realisee par le jaune. Les enzymes assurant la decarboxylation (III) sont repartis aussi bien dans l'embryon que dans ses annexes. (auteur)

  3. CO{sub 2} separation from exhaust gas; CO{sub 2} separasjon fra eksosgass

    Energy Technology Data Exchange (ETDEWEB)

    Magelssen, Paul Fr. [Saga Petroleum A/S, Forus (Norway)

    1998-07-01

    When Saga wanted to reduce the CO{sub 2} emissions from Snorre B, cleaning of CO{sub 2} from exhaust gas was one of several options considered. CO{sub 2} cleaning using membrane/amine technology is under development. Saga required that the technology should be qualified and that the yield of the Snorre B project should not be reduced. This presentation discusses qualification of combined membrane/amine technology, environmental issues, economic issues and implementation on the Snorre B platform. Flue gas from the gas turbine is passed to a CO{sub 2} absorption and desorption stage from which the CO{sub 2} is passed on for compression and disposal while the cleaned flue is let out. The membrane is situated between the flue gas and the absorbent liquid. The pores are large enough for the CO{sub 2} to pass through quickly and small enough to prevent the liquid from penetrating into the pores. The packing factor is high, 500 - 1000 m2/m3, there is no formation of froth, ducts or entrainment of the liquid. New technology implies 65 - 70% size reduction of the main equipment and 39 - 40% reduction of the energy consumption. Research on amines brings out new chemicals which imply 80% reduction in the consumption of chemicals and the quantity of special waste produced. If a CO{sub 2} cleaning plant is installed on a LM 2500, the CO{sub 2} emissions can be reduced by 97,200 ton/year given the right operational conditions. Although it was decided in 1998 not to install the module with the CO{sub 2} pilot cleaning plant, Snorre B is still a good environmental project having CO{sub 2} emission within the values set by Miljoesok.

  4. Ternary CoS{sub 2}/MoS{sub 2}/RGO electrocatalyst with CoMoS phase for efficient hydrogen evolution

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Yan-Ru; Shang, Xiao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Gao, Wen-Kun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Dong, Bin, E-mail: dongbin@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); College of Science, China University of Petroleum (East China), Qingdao 266580 (China); Chi, Jing-Qi; Li, Xiao; Yan, Kai-Li; Chai, Yong-Ming [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Yun-Qi, E-mail: liuyq@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China); Liu, Chen-Guang [State Key Laboratory of Heavy Oil Processing, China University of Petroleum (East China), Qingdao 266580 (China)

    2017-08-01

    Highlights: • Ternary CoS{sub 2}/MoS{sub 2}/RGO with CoMoS phase as electrocatalyst for HER was prepared. • CoMoS phase have the metallic nature and highly intrinsic activity for HER. • RGO support ensures good distribution of CoMoS phase and enhances the conductivity. • The introduction of CoMoS and RGO may be a novel strategy for efficient HER of MoS{sub 2}. - Abstract: CoMoS phase with metallic character plays crucial role on enhancing the activity of MoS{sub 2} electrocatalysts for hydrogen evolution reaction (HER). However, only Co atoms located in the edges of MoS{sub 2} can create CoMoS phase, so it is a challenge to obtain CoMoS phase with homogeneous distribution limited by the layered MoS{sub 2} and doping method of Co. Herein, we reported a simple one-pot hydrothermal method to prepare novel ternary CoS{sub 2}/MoS{sub 2}/RGO with CoMoS phase for HER using reduced graphene oxide (RGO) as support. XPS proves the formation of CoMoS phase, implying the enhanced activity for HER. RGO support ensures the well distribution of CoMoS phase and enhances the conductivity of CoS{sub 2}/MoS{sub 2}/RGO. Compared to CoS{sub 2}/RGO, MoS{sub 2}/RGO and CoS{sub 2}/MoS{sub 2}, the obtained CoS{sub 2}/MoS{sub 2}/RGO shows superior activity for HER with an onset overpotential of −80 mV (vs. RHE), small Tafel slope of 56 mV dec{sup −1}, high exchange current density of 11.4 μA cm{sup −2} and rigid electrochemical durability. The enhanced performances for HER may be ascribed to the formation of CoMoS phase with high activity and the existence of RGO support with good electrical conductivitys in ternary CoS{sub 2}/MoS{sub 2}/RGO. Therefore, the introduction of CoMoS phase and RGO into MoS{sub 2} could effectively enhance electrocatalytic properties for HER.

  5. Rocky Mountain Regional CO{sub 2} Storage Capacity and Significance

    Energy Technology Data Exchange (ETDEWEB)

    Laes, Denise; Eisinger, Chris; Esser, Richard; Morgan, Craig; Rauzi, Steve; Scholle, Dana; Matthews, Vince; McPherson, Brian

    2013-08-30

    The purpose of this study includes extensive characterization of the most promising geologic CO{sub 2} storage formations on the Colorado Plateau, including estimates of maximum possible storage capacity. The primary targets of characterization and capacity analysis include the Cretaceous Dakota Formation, the Jurassic Entrada Formation and the Permian Weber Formation and their equivalents in the Colorado Plateau region. The total CO{sub 2} capacity estimates for the deep saline formations of the Colorado Plateau region range between 9.8 metric GT and 143 metric GT, depending on assumed storage efficiency, formations included, and other factors.

  6. The FP7 ULTimateCO2 project: a study of the long term fate of CO2

    Science.gov (United States)

    Audigane, Pascal; Waldmann, Svenja; Pearce, Jonathan; Dimier, Alain; Le Gallo, Yann; Frykman, Peter; Maurand, Nicolas; Gherardi, Fabrizio; Yalamas, Thierry; Cremer, Holger; Spiers, Chris; Nussbaum, Christophe

    2014-05-01

    The objectives of the European FP7 ULTimateCO2 project are to study specific processes that could influence the long-term fate of geologically stored CO2, mainly: the trapping mechanisms occurring in the storage reservoir, the influence of fluid-rock interactions on mechanical integrity of caprock and well vicinity, and also the modifications induced at the regional scale (brine displacement, fault reactivation, hydrogeology changes...). A comprehensive approach combining laboratory experiments, numerical modeling and natural analogue studies is developed to assess all the processes mentioned above. A collection of data has been generated from natural and industrial (oil industry) analogues on the fluid flow and mechanical properties, structure, and mineralogy of faults and fractures that could affect the long-term storage capacity of underground CO2 storage sites. To address geochemical trapping at reservoir scale, an experimental approach is developed using sandstone core materials in batch reactive mode with CO2 and impurities at reservoir pressure and temperature conditions. Three inter-related lines of laboratory experiments investigate the long-term evolution of the mechanical properties and sealing integrity of fractured and faulted caprocks using Opalinus clay of Mont Terri Gallery (Switzerland), an analogue for caprock well investigated in the past for nuclear waste disposal purpose. To evaluate the interactions between CO2 (and formation fluid) and the well environment (formation, cement, casing) and to assess the consequences of these interactions on the transport properties of well materials, a 1 to 1 scale experiment has been set in the Mont Terri Gallery Opalinus clay to reproduce classical well objects (cemented annulus, casing and cement plug) perforating caprock formations. An extensive program of numerical modeling is also developed to calibrate, to reproduce and to extrapolate the experimental results at longer time scales including uncertainty

  7. Numerical Simulation of Multiphase Hydromechanical Processes Induced by CO2 Injection into Deep Saline Aquifers Simulation numérique des processus hydromécaniques polyphasiques provoqués par l’injection de CO2 dans des aquifères salins profonds

    Directory of Open Access Journals (Sweden)

    Goerke U.-J.

    2011-02-01

    Full Text Available In this paper, the conceptual modeling and the numerical simulation of two-phase flow during CO2 injection into deep saline aquifers is presented. The work focuses on isothermal short-term processes in the vicinity of the injection well. Governing differential equations are based on balance laws for mass and momentum, and completed by constitutive relations for the fluid and solid phases as well as their mutual interactions. Constraint conditions for the partial saturations and the pressure fractions of CO2 and brine are defined. To characterize the stress state in the solid matrix, the effective stress principle is applied. The coupled problem is solved using the inhouse scientific code OpenGeoSys (an open source finite element code and verified with benchmarks. Cet article présente le concept de la modélisation ainsi que la simulation numérique d’écoulement biphasé lors de l’injection de CO2 dans des aquifères salins profonds. L’étude se concentre sur des processus à court terme dans la proximité de puits d’injection dans les conditions isothermes. Les équations différentielles principales sont dérivées des équations de bilan de masse et de la quantité de mouvement, et elles sont complétées par des relations constitutives pour des phases solides et fluides ainsi que leur interaction. Les conditions de contrainte sont définies pour la saturation partielle, les fractions de pression de CO2 et l’eau salée. Pour caractériser l’état de contrainte dans la matrice solide, le principe de contrainte effective est appliqué. Le problème couplé considéré est résolu en utilisant le logiciel scientifique interne OpenGeoSys (un logiciel d’éléments finis libre d’accès et vérifié avec des exemples pour les processus concernés.

  8. Coupled multiphase reactive flow and mineral dissolution-precipitation kinetics: Examples of long-term CO2 sequestration in Utsira Sand, Norway and Mt. Simon Formation, Midwest USA

    Science.gov (United States)

    Zhang, Y.; Zhang, G.; Lu, P.; Hu, B.; Zhu, C.

    2017-12-01

    The extent of CO2 mineralization after CO2 injection into deep saline aquifers is a result of the complex coupling of multiphase fluid flow, mass transport, and brine-mineral reactions. The effects of dissolution rate laws and groundwater flow on the long-term fate of CO2 have been seriously overlooked. To investigate these effects, we conducted multiphase (CO2 and brine) coupled reactive transport modeling of CO2 storage in two sandy formations (Utsira Sand, Norway1,2 and Mt. Simon formation, USA 3) using ToughReact and simulated a series of scenarios. The results indicated that: (1) Different dissolution rate laws for feldspars can significantly affect the amount of CO2 mineralization. Increased feldspar dissolution will promote CO2 mineral trapping through the coupling between feldspar dissolution and carbonate mineral precipitation at raised pH. The predicted amount of CO2 mineral trapping when using the principle of detailed balancing-based rate law for feldspar dissolution is about twice as much as that when using sigmoidal rate laws in the literature. (2) Mineral trapping is twice as much when regional groundwater flow is taken into consideration in long-term simulations (e.g., 10,000 years) whereas most modeling studies neglected the regional groundwater flow back and effectively simulated a batch reactor process. Under the influence of regional groundwater flow, the fresh brine from upstream continuously dissolves CO2 at the tail of CO2 plume, generating a large acidified area where large amount of CO2 mineralization takes place. The upstream replenishment of groundwater results in ˜22% mineral trapping at year 10,000, compared to ˜4% when this effect is ignored. Refs: 1Zhang, G., Lu, P., Wei, X., Zhu, C. (2016). Impacts of Mineral Reaction Kinetics and Regional Groundwater Flow on Long-Term CO2 Fate at Sleipner. Energy & Fuels, 30(5), 4159-4180. 2Zhu, C., Zhang, G., Lu, P., Meng, L., Ji, X. (2015). Benchmark modeling of the Sleipner CO2 plume

  9. Influence of the cation substitution on the magnetic properties of LiCo2O4 and Li(Me,Co2O4 spinels

    Directory of Open Access Journals (Sweden)

    Gautier, J. L.

    2004-08-01

    Full Text Available Lithium-based cells LiCo2O4 have been characterized by magnetic techniques, looking at the influence of the partial substitution of cobalt by 3d or 4d transition metal elements (Fe, Ni, Cu, Cr, Mo. The non-substituted compound LiCo2O4 behaves as an antiferromagnet, with a Néel temperature TN of 30 K, although antiferromagnetic interactions are much more important, as suggested by a Weiss parameter Θ of the order of ‑225 K. In the solid solution Li(NixCo2‑xO4 the Weiss parameter Θ changes with x(Ni, reaching large positive values (e.g., Θ ~ +230 K, for x = 0.5. This phenomenon suggests the existence of a canted‑antiferromagnetic or ferrimagnetic structures with large ferromagnetic components. Substitution of cobalt by other 3d or 4d transition metals in the LiMe0.5Co1.5O4 series shows dramatic effects with respect to the non-substituted LiCo2O4 compound : copper completely suppresses the magnetic order, while iron increases TN to almost room temperature. No modifications are observed when molybdenum substitutes cobalt, while chromium transforms the AF order in a ferromagnetic one, with Tc of about 90 K.Se ha caracterizado por técnicas magnéticas, el efecto de la sustitución parcial de Co por elementos de transición 3d o 4d (Fe, Ni, Cu, Cr, Mo en celdas LiCo2O4 a base de litio. El compuesto no sustituído LiCo2O4, se comporta como un antiferromagneto de temperatura de Néel TN de 30 K, aunque existen interacciones antiferromagnéticas mucho más importantes, como lo indica un parámetro de Weiss Θ del orden de -225K. En la solución sólida Li(NixCo2‑xO4, el parámetro de Weiss Θ cambia con x(Ni, alcanzando valores positivos altos (e.g., Θ ~ +230K, para x=0.5. Este fenómeno sugiere la existencia de una estructura antiferromagnética inclinada (“AF-canted” o de una estructura ferrimagnética, donde predominan componentes ferromagnéticas importantes. La sustitución del cobalto por otros elementos de transición 3d o 4d en

  10. CO2 laser photolysis of clustered ions, (1)

    International Nuclear Information System (INIS)

    Ikezoe, Yasumasa; Soga, Takeshi; Suzuki, Kazuya; Ohno, Shin-ichi.

    1990-09-01

    Vibrational excitation and the following decomposition of cluster ions by CO 2 laser photons are studied. Characteristics of the cluster ion and the CO 2 laser photon are summarized in their relation to the photolysis of cluster ions. An apparatus was installed, which is composed of (1) corona discharge-jet expansion section (formation of cluster ions), (2) CO 2 laser section (photolysis of cluster ions), and (3) mass spectrometer section. Experimental results of ammonia cluster ions were described. Effects of repeller voltage, shape of repellers, and adiabatic cooling are examined on the formation of ammonia cluster ions by corona discharge-jet expansion method. Collisional dissociation of cluster ions was observed at high repeller voltages. Size distribution of the ammonia cluster ion is discussed in connection with the temperature of cluster ions. Intensity of CO 2 laser was related to decomposition yield of cluster ions. (author)

  11. A Geochemical Approach for Monitoring a CO2 Pilot Site: Rousse, France. A Major gases, CO2-Carbon Isotopes and Noble Gases Combined Approach Une méthode géochimique pour la surveillance d’un site pilote de stockage de CO2 : Rousse, France. Approche combinant les gaz majeurs, l’isotopie du carbone du CO2 et les gaz rares

    Directory of Open Access Journals (Sweden)

    Garcia B.

    2012-02-01

    storage pilot suggest that noble gas compositions produced by oxyfuel process are sufficiently exotic compared to compositions found in nature (reservoir, aquifer and air to be directly used as tracers of the injected CO2, and to detect and quantify leaks at soil and aquifer levels. Ce papier presente la caracterisation geochimique des differents gaz, naturels et anthropogeniques, impliques dans un pilote de stockage de CO2 en champ de gaz naturel appauvri (Rousse, France. Dans ce pilote, le CO2 est produit par oxycombustion d’un gaz naturel transforme en gaz domestique a l’usine de Lacq. Ce CO2 est transporte dans un pipeline de 30 km de longueur jusqu’au reservoir de gaz appauvri de Rousse. Les gaz produits a Rousse avant injection de CO2, le gaz commercial de Lacq et le CO2 resultant de l’oxycombustion ont ete echantillonnes, ainsi que les gaz situes dans un puits de surveillance (a une profondeur de 45 m et les gaz du sol situes au voisinage de Rousse. Pour tous ces echantillons, la composition en gaz majeurs, la signature isotopique du carbone ainsi que l’abondance et signature isotopique des gaz rares ont ete determinees. Les compositions gazeuses du gaz naturel de Rousse sont comparables a celle du gaz domestique de Lacq avec le methane comme compose principal et la fraction C2-C5 et CO2 comme gaz residuels. Les gaz des sols refletent typiquement des melanges entre l’air (pole pur et le CO2 d’origine biogenique (avec des teneurs maximales de l’ordre de 9-10 %, tandis que les gaz presents dans le puits de monitoring refletent typiquement la composition de l’air sans exces de CO2. Le gaz de Rousse et le gaz domestique du site de Lacq ont une composition isotopique δ13CCH4 egale a –41,0 ‰ et –43,0 ‰ respectivement. Le CO2 injecte sur Rousse a une composition isotopique δ13CCO2 egale a –40,0 ‰ a la sortie de la chambre d’oxycombustion, tandis que la composition isotopique δ13CCO2 des gaz des sols est comprise entre –15 et –25

  12. Hydronium-Induced Switching between CO2 Electroreduction Pathways.

    Science.gov (United States)

    Seifitokaldani, Ali; Gabardo, Christine M; Burdyny, Thomas; Dinh, Cao-Thang; Edwards, Jonathan P; Kibria, Md Golam; Bushuyev, Oleksandr S; Kelley, Shana O; Sinton, David; Sargent, Edward H

    2018-03-21

    Over a broad range of operating conditions, many CO 2 electroreduction catalysts can maintain selectivity toward certain reduction products, leading to materials and surfaces being categorized according to their products; here we ask, is product selectivity truly a property of the catalyst? Silver is among the best electrocatalysts for CO in aqueous electrolytes, where it reaches near-unity selectivity. We consider the hydrogenations of the oxygen and carbon atoms via the two proton-coupled-electron-transfer processes as chief determinants of product selectivity; and find using density functional theory (DFT) that the hydronium (H 3 O + ) intermediate plays a key role in the first oxygen hydrogenation step and lowers the activation energy barrier for CO formation. When this hydronium influence is removed, the activation energy barrier for oxygen hydrogenation increases significantly, and the barrier for carbon hydrogenation is reduced. These effects make the formate reaction pathway more favorable than CO. Experimentally, we then carry out CO 2 reduction in highly concentrated potassium hydroxide (KOH), limiting the hydronium concentration in the aqueous electrolyte. The product selectivity of a silver catalyst switches from entirely CO under neutral conditions to over 50% formate in the alkaline environment. The simulated and experimentally observed selectivity shift provides new insights into the role of hydronium on CO 2 electroreduction processes and the ability for electrolyte manipulation to directly influence transition state (TS) kinetics, altering favored CO 2 reaction pathways. We argue that selectivity should be considered less of an intrinsic catalyst property, and rather a combined product of the catalyst and reaction environment.

  13. Electronic structure and O vacancy formation/migration in La0.825(Mg/Ca/Ba)0.125CoO3

    KAUST Repository

    Omotayo Akande, Salawu

    2016-05-05

    The effect of A-site hole doping (Mg2+, Ca2+ or Ba2+) on the electronic and magnetic properties as well as the O vacancy formation and migration in perovskite LaCoO3 is studied using first-principles calculations. All three dopants are found to facilitate O vacancy formation. Substitution of La3+ with Ba2+/Mg2+ yields the lowest O vacancy formation energy for low/intermediate spin Co, implying that not only the structure but also the spin state of Co is a key parameter. Only for low spin Co the ionic radius is correlated with the O migration barrier. Enhanced migration for intermediate spin Co is ascribed to the availability of additional space at the transition state. © CopyrightEPLA, 2016.

  14. Thermodynamics of CoAl2O4-CoGa2O4 solid solutions

    International Nuclear Information System (INIS)

    Lilova, Kristina I.; Navrotsky, Alexandra; Melot, Brent C.; Seshadri, Ram

    2010-01-01

    CoAl 2 O 4 , CoGa 2 O 4 , and their solid solution Co(Ga z Al 1-z ) 2 O 4 have been studied using high temperature oxide melt solution calorimetry in molten 2PbO.B 2 O 3 at 973 K. There is an approximately linear correlation between lattice parameters, enthalpy of formation from oxides, and the Ga content. The experimental enthalpy of mixing is zero within experimental error. The cation distribution parameters are calculated using the O'Neill and Navrotsky thermodynamic model. The enthalpies of mixing calculated from these parameters are small and consistent with the calorimetric data. The entropies of mixing are calculated from site occupancies and compared to those for a random mixture of Ga and Al ions on octahedral site with all Co tetrahedral and for a completely random mixture of all cations on both sites. Despite a zero heat of mixing, the solid solution is not ideal in that activities do not obey Raoult's Law because of the more complex entropy of mixing. - Graphical abstract: Measured enthalpies of mixing of CoAl 2 O 4 -CoGa 2 O 4 solid solutions are close to zero but entropies of mixing reflect the complex cation distribution, so the system is not an ideal solution.

  15. High-permeance crosslinked PTMSP thin-film composite membranes as supports for CO2 selective layer formation

    Directory of Open Access Journals (Sweden)

    Stepan D. Bazhenov

    2016-10-01

    Full Text Available In the development of the composite gas separation membranes for post-combustion CO2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology. The primary requirements to the membrane supports are concerned with their high CO2 permeance. In this work, the membrane supports with desired characteristics were developed as high-permeance gas separation thin film composite (TFC membranes with the thin defect-free layer from the crosslinked highly permeable polymer, poly[1-(trimethylsilyl-1-propyne] (PTMSP. This layer is insoluble in chloroform and can be used as a gutter layer for the further deposition of the СО2-selective materials from the organic solvents. Crosslinking of PTMSP was performed using polyethyleneimine (PEI and poly (ethyleneglycol diglycidyl ether (PEGDGE as crosslinking agents. Optimal concentrations of PEI in PTMSP and PEGDGE in methanol were selected in order to diminish the undesirable effect on the final membrane gas transport characteristics. The conditions of the kiss-coating technique for the deposition of the thin defect-free PTMSP-based layer, namely, composition of the casting solution and the speed of movement of the porous commercial microfiltration-grade support, were optimized. The procedure of post-treatment with alcohols and alcohol solutions was shown to be crucial for the improvement of gas permeance of the membranes with the crosslinked PTMSP layer having thickness ranging within 1–2.5 μm. The claimed membranes showed the following characteristics: CO2 permeance is equal to 50–54 m3(STP/(m2 h bar (18,500–20,000 GPU, ideal CO2/N2 selectivity is 3.6–3.7, and their selective layers are insoluble in chloroform. Thus, the developed high-permeance TFC membranes are considered as a promising supports for further modification by enhanced CO2 selective layer formation. Keywords: Thin-film composite membrane

  16. Satellite-derived SIF and CO2 Observations Show Coherent Responses to Interannual Climate Variations

    Science.gov (United States)

    Butterfield, Z.; Hogikyan, A.; Kulawik, S. S.; Keppel-Aleks, G.

    2017-12-01

    Gross primary production (GPP) is the single largest carbon flux in the Earth system, but its sensitivity to changes in climate is subject to significant uncertainty. Satellite measurements of solar-induced chlorophyll fluorescence (SIF) offer insight into spatial and temporal patterns in GPP at a global scale and, combined with other satellite-derived datasets, provide unprecedented opportunity to explore interactions between atmospheric CO2, GPP, and climate variability. To explore potential drivers of GPP in the Northern Hemisphere (NH), we compare monthly-averaged SIF data from the Global Ozone Monitoring Experiment 2 (GOME-2) with observed anomalies in temperature (T; CRU-TS), liquid water equivalent (LWE) from the Gravity Recovery and Climate Experiment (GRACE), and photosynthetically active radiation (PAR; CERES SYN1deg). Using observations from 2007 through 2015 for several NH regions, we calculate month-specific sensitivities of SIF to variability in T, LWE, and PAR. These sensitivities provide insight into the seasonal progression of how productivity is affected by climate variability and can be used to effectively model the observed SIF signal. In general, we find that high temperatures are beneficial to productivity in the spring, but detrimental in the summer. The influences of PAR and LWE are more heterogeneous between regions; for example, higher LWE in North American temperate forest leads to decreased springtime productivity, while exhibiting a contrasting effect in water-limited regions. Lastly, we assess the influence of variations in terrestrial productivity on atmospheric carbon using a new lower tropospheric CO2 product derived from the Greenhouse Gases Observing Satellite (GOSAT). Together, these data shed light on the drivers of interannual variability in the annual cycle of NH atmospheric CO2, and may provide improved constraints on projections of long-term carbon cycle responses to climate change.

  17. Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

    Science.gov (United States)

    Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

    2017-06-27

    A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

  18. Electronic structures and stability of Ni/Bi2Te3 and Co/Bi2Te3 interfaces

    International Nuclear Information System (INIS)

    Xiong Ka; Wang Weichao; Alshareef, Husam N; Gupta, Rahul P; Gnade, Bruce E; Cho, Kyeongjae; White, John B

    2010-01-01

    We investigate the electronic structures and stability for Ni/Bi 2 Te 3 , NiTe/Bi 2 Te 3 , Co/Bi 2 Te 3 and CoTe 2 /Bi 2 Te 3 interfaces by first-principles calculations. It is found that the surface termination strongly affects the band alignment. Ni and Co are found to form Ohmic contacts to Bi 2 Te 3 . The interface formation energy for Co/Bi 2 Te 3 interfaces is much lower than that of Ni/Bi 2 Te 3 interfaces. Furthermore, we found that NiTe on Bi 2 Te 3 is more stable than Ni, while the formation energies for Co and CoTe 2 on Bi 2 Te 3 are comparable.

  19. First Modelling Results of the EM Response of a CO2 Storage in the Paris Basin Premières modélisations de la réponse EM d’un stockage de CO2 dans le bassin Parisien

    Directory of Open Access Journals (Sweden)

    Bourgeois B.

    2010-07-01

    Full Text Available We study the feasibility of using electrical/EM methods for monitoring the injection of supercritical CO2 at a depth of 1700 m in a saline aquifer of the Paris Basin (Dogger carbonates. We first establish the theoretical interest of resistivity methods for CO2 monitoring through the basic laws of electrical physics in porous sedimentary rocks, assuming that supercritical CO2 is a perfect insulator. Various combinations of EM sources and sensors are discussed and it is shown that the best type of array consists of a galvanic source (i.e. injection of current via a pair of electrodes A and B and of a grid of electric (and possibly magnetic sensors at the ground surface. Given the usual depth and thinness of CO2 storage layers, current injection at depth was investigated in order to increase the current density in the reservoir and thus enhance the CO2 response. Point injection at the reservoir depth in the so-called “Mise À la Masse” (MAM configuration is generally impossible in deep wells due to the presence of metallic casings. Therefore, the possibility of using a deep metallic casing as a long electrode distributing the current all along a borehole is studied. This kind of source is named “LEMAM” (Long Electrode Mise À la Masse in order to differentiate it from the conventional MAM. Numerical simulations are presented for the LEMAM array and for the gradient or rectangle array (RECT, for which the current is injected by a pair of point electrodes at the ground surface. The geoelectric model used is based on an area close to the Saint-Martin-de-Bossenay (SMB oilfield, in the south-east of the Paris Basin. The storage reservoir considered in this study is the 75-m-thick “Oolithe Blanche” formation (Mid Jurassic or Dogger, Bathonian age, located at a depth of about 1700 m below ground surface. In the models presented, the CO2 plume is simplified to a square horizontal slab of 2 km side, 70 m thick, floating at the top of the oolite

  20. Promoting Ethylene Selectivity from CO2 Electroreduction on CuO Supported onto CO2 Capture Materials.

    Science.gov (United States)

    Yang, Hui-Juan; Yang, Hong; Hong, Yu-Hao; Zhang, Peng-Yang; Wang, Tao; Chen, Li-Na; Zhang, Feng-Yang; Wu, Qi-Hui; Tian, Na; Zhou, Zhi-You; Sun, Shi-Gang

    2018-03-09

    Cu is a unique catalyst for CO 2 electroreduction, since it can catalyze CO 2 reduction to a series of hydrocarbons, alcohols, and carboxylic acids. Nevertheless, such Cu catalysts suffer from poor selectivity. High pressure of CO 2 is considered to facilitate the activity and selectivity of CO 2 reduction. Herein, a new strategy is presented for CO 2 reduction with improved C 2 H 4 selectivity on a Cu catalyst by using CO 2 capture materials as the support at ambient pressure. N-doped carbon (N x C) was synthesized through high-temperature carbonization of melamine and l-lysine. We observed that the CO 2 uptake capacity of N x C depends on both the microporous area and the content of pyridinic N species, which can be controlled by the carbonization temperature (600-800 °C). The as-prepared CuO/N x C catalysts exhibit a considerably higher C 2 H 4 faradaic efficiency (36 %) than CuO supported on XC-72 carbon black (19 %), or unsupported CuO (20 %). Moreover, there is a good linear relationship between the C 2 H 4 faradaic efficiency and CO 2 uptake capacity of the supports for CuO. The local high CO 2 concentration near Cu catalysts, created by CO 2 capture materials, was proposed to increase the coverage of CO intermediate, which is favorable for the coupling of two CO units in the formation of C 2 H 4 . This study demonstrates that pairing Cu catalysts with CO 2 capture supports is a promising approach for designing highly effective CO 2 reduction electrocatalysts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Nitrous Oxide Formation and Destruction by Industrial No Abatement Techniques Including Scr Emissions des protoxides d'azote par des techniques industrielles d'abattement de NO y compris le SCR

    Directory of Open Access Journals (Sweden)

    De Soete G. G.

    2006-11-01

    , respectivement : NCO + NO -> N2O + CO (1 N2O + H -> N2 + OH (2 Une élévation de la température favorise la transformation du précurseur CNO en NO et NH, tout en intensifiant la réaction (2 par l'accroissement de la concentration en radicaux H; une augmentation de l'excès d'oxygène par contre diminue cette concentration. 2. Formation de N2O lors de l'injection d'ammoniac (NCSR Dans cette partie de l'étude, la fraction F2 est de l'argon dopé avec de l'ammoniac ou avec un mélange d'ammoniac et de NO. Il est à remarquer que l'ammoniac à lui seul se transforme partiellement en NO et en N2O (fig. 7 et 8; l'acide cyanhydrique présente le même comportement de manière encore plus accentué en ce qui concerne la formation de N2O (fig. 9. Dans ces figures, Fn->no désigne la fraction d'atomes d'azote transformés en NO, Fn->n2o la fraction d'atomes d'azote transformés en N2O, tandis que Fm désigne la fraction de l'espèce azoté M décomposée. L'injection de NO seul ne forme pas de N2O (fig. 10; l'injection de N2O seul ne forme que des quantités négligeables de NO (fig. 11. La figure 12 résume ces observations et donne également la valeur des températures au point d'injection (Tx en fonction de la distance X. Le NO apparaît comme un produit primaire formé à partir de NH3, tandis que le protoxyde d'azote est formé à partir d'une réaction entre NH3 et NO. Lors de l'injection de NH3 en présence de NO, il faudra donc s'attendre à une compétition de (1 la réduction de NO par l'ammoniac et (2 la formation de NO à partir de l'ammoniac. Ceci est confirmé par les expériences (fig. 14 et 15. 3. Formation et destruction de N2O pendant la réduction catalytique de NO (SCR. Cette partie de l'étude a été effectuée en lit fixe sur un grand nombre d'oxydes métalliques. L'identification des voies réactionnelles est illustrée par les figures 16 à 22, avec le vanadium pentoxyde comme catalyseur. Une vue schématique du mécanisme réactionnel global est pr

  2. Carbon dioxide (CO2) sequestration in deep saline aquifers and formations: Chapter 3

    Science.gov (United States)

    Rosenbauer, Robert J.; Thomas, Burt

    2010-01-01

    Carbon dioxide (CO2) capture and sequestration in geologic media is one among many emerging strategies to reduce atmospheric emissions of anthropogenic CO2. This chapter looks at the potential of deep saline aquifers – based on their capacity and close proximity to large point sources of CO2 – as repositories for the geologic sequestration of CO2. The petrochemical characteristics which impact on the suitability of saline aquifers for CO2 sequestration and the role of coupled geochemical transport models and numerical tools in evaluating site feasibility are also examined. The full-scale commercial CO2 sequestration project at Sleipner is described together with ongoing pilot and demonstration projects.

  3. The surface chemistry of Cu in the presence of CO2 and H2O

    Energy Technology Data Exchange (ETDEWEB)

    Deng, Xingyi; Verdaguer, Albert; Herranz, Tirma; Weis, Christoph; Bluhm, Hendrik; Salmeron, Miquel

    2008-07-16

    The chemical nature of copper and copper oxide (Cu{sub 2}O) surfaces in the presence of CO{sub 2} and H{sub 2}O at room temperature was investigated using ambient pressure x-ray photoelectron spectroscopy. The studies reveal that in the presence of 0.1 torr CO{sub 2} several species form on the initially clean Cu, including carbonate CO{sub 3}{sup 2}, CO{sub 2}{sup {delta}-} and C{sup 0}, while no modifications occur on an oxidized surface. The addition of 0.1 ML Zn to the Cu results in the complete conversion of CO{sub 2}{sup {delta}-} to carbonate. In a mixture of 0.1 torr H{sub 2}O and 0.1 torr CO{sub 2}, new species are formed, including hydroxyl, formate and methoxy, with H{sub 2}O providing the hydrogen needed for the formation of hydrogenated species.

  4. The effect of a fourth element (Co, Cu, Fe, Pd) on the standard enthalpy of formation of the Heusler compound Ni{sub 2}MnSn

    Energy Technology Data Exchange (ETDEWEB)

    Yin, Ming, E-mail: myin1@hawk.iit.edu; Nash, Philip

    2016-05-15

    The standard enthalpies of formation of quaternary Heusler compounds (X, Ni){sub 2}MnSn (X = Co, Cu, Fe, Pd) were investigated experimentally using high temperature direct reaction calorimetry. Lattice parameters of these compounds were determined using X-ray diffraction analysis. Microstructures were identified using scanning electron microscopy and energy dispersive spectroscopy. The effect of an additional X element on the standard enthalpy of formation of the Heusler compound Ni{sub 2}MnSn is discussed. - Highlights: • Enthalpies of formation of (X,Ni){sub 2}YZ (X = Co, Cu, Fe, Pd) were measured by drop calorimeters. • Magnetic contribution to enthalpy of formation plays an important role. • Introducing a fourth element could stabilize an unstable Heusler structure. • Lattice parameters do not necessarily obey the Vegard's law. • It is possible to tailor properties of Heusler compounds with enough background information.

  5. MgCo2-D2 and MgCoNi-D2 systems synthesized at high pressures and interaction mechanism during the HDDR processing

    Directory of Open Access Journals (Sweden)

    Chubin Wan

    2017-02-01

    MgCo2 is a new example of the hydrogen storage alloy, in which a successful HDDR processing results in the reversible formation of the initial intermetallic at much lower temperatures than in the equilibrium phase diagram of the Mg-Co system.

  6. TEOA-mediated formation of hollow core-shell structured CoNi2S4 nanospheres as a high-performance electrode material for supercapacitors

    Science.gov (United States)

    Liang, Jun; Li, Meng; Chai, Yao; Luo, Min; Li, Li

    2017-09-01

    In this study, we report for the first time a cost-effective and general approach for the high-yield synthesis of a hierarchical core-shell and hollow structure of ternary CoNi2S4 in a triethanolamine (TEOA)-assisted hydrothermal system. It is found that a continuous increase in TEOA usages facilitates the formation and transformation of hierarchical CoNi2S4 hollow nanospheres, and the formation mechanism of the unique structure is revealed to be assembly-then-inside-out evacuation and Ostwald ripening mechanism during the sulfidation process. More importantly, when used as faradaic electrode for supercapacitors, the hierarchical hollow CoNi2S4 nanospheres display not only exceptional pseudocapacitve performance with high specific capacitance (2035 Fg-1 at 1 Ag-1) and excellent rate capability (1215 Fg-1 at 20 Ag-1), but also superior cycling stability, with only about 8.7% loss over 3000 cycles at 10 Ag-1. This work can provide some guidance for us in the structural and compositional tuning of mixed binary-metal sulfides toward many desired applications.

  7. Modulating calcium phosphate formation using CO{sub 2} laser engineering of a polymeric material

    Energy Technology Data Exchange (ETDEWEB)

    Waugh, D.G., E-mail: Dwaugh@lincoln.ac.uk; Lawrence, J.

    2012-02-01

    The use of simulated body fluid (SBF) is widely used as a screening technique to assess the ability of materials to promote calcium phosphate formation. This paper details the use of CO{sub 2} laser surface treatment of nylon Registered-Sign 6,6 to modulate calcium phosphate formation following immersion in SBF for 14 days. Through white light interferometry (WLI) it was determined that the laser surface processing gave rise to maximum Ra and Sa parameters of 1.3 and 4.4 {mu}m, respectively. The use of X-ray photoelectron spectroscopy (XPS) enabled a maximum increase in surface oxygen content of 5.6%at. to be identified. The laser-induced surface modifications gave rise to a modulation in the wettability characteristics such that the contact angle, {theta}, decreased for the whole area processed samples, as expected, and increased for the patterned samples. The increase in {theta} can be attributed to a transition in wetting nature to a mixed-state wetting regime. It was seen for all samples that calcium phosphate formed on each surface following 14 days. The largest increase in mass, {Delta}g, owed to calcium phosphate formation, was brought about by the whole area processed sample irradiated with a fluence of 51 J cm{sup -2}. No correlation between the calcium phosphate formation and the laser patterned surface properties was determined due to the likely affect of the mixed-state wetting regime. Strong correlations between {theta}, the surface energy parameters and the calcium phosphate formation for the whole area processed samples allow one to realize the potential for this surface treatment technique in predicting the bone forming ability of laser processed materials. - Highlights: Black-Right-Pointing-Pointer Surface modifications brought about a modulation in the wetting of nylon 6,6. Black-Right-Pointing-Pointer An increase in {theta} can be attributed to a mixed-state wetting regime. Black-Right-Pointing-Pointer Laser surface treatment modulated the

  8. THE INFLUENCE OF CO2 ON WELL CEMENT

    Directory of Open Access Journals (Sweden)

    Nediljka Gaurina-Međimurec

    2010-12-01

    Full Text Available Carbon capture and storage is one way to reduce emissions of greenhouse gases in the atmosphere. Underground gas storage operations and CO2 sequestration in aquifers relay on both the proper wellbore construction and sealing properties of the cap rock. CO2 injection candidates may be new wells or old wells. In both cases, the long-term wellbore integrity (up to 1 000 years is one of the key performance criteria in the geological storage of CO2. The potential leakage paths are the migration CO2 along the wellbore due to poor cementation and flow through the cap rock. The permeability and integrity of the set cement will determine how effective it is in preventing the leakage. The integrity of the cap rock is assured by an adequate fracture gradient and by sufficient set cement around the casing across the cap rock and without a micro-annulus. CO2 storage in underground formations has revived the researc of long term influence of the injected CO2 on Portland cements and methods for improving the long term efficiency of the wellbore sealant. Some researchers predicted that set cement will fail when exposed to CO2 leading to potential leakage to the atmosphere or into underground formations that may contain potable water. Other researchers show set cement samples from 30 to 50 year-old wells (CO2 EOR projects that have maintained sealing integrity and prevented CO2 leakage, in spite of some degree of carbonation. One of reasons for the discrepancy between certain research lab tests and actual field performance measurements is the absence of standard protocol for CO2 resistance-testing devices, conditions, or procedures. This paper presents potential flow paths along the wellbore, CO2 behaviour under reservoir conditions, and geochemical alteration of hydrated Portland cement due to supercritical CO2 injection.

  9. Electronic structures and stability of Ni/Bi2Te3 and Co/Bi2Te3 interfaces

    KAUST Repository

    Xiong, Ka; Wang, Weichao; Alshareef, Husam N.; Gupta, Rahul P.; White, John B.; Gnade, Bruce E.; Cho, Kyeongjae

    2010-01-01

    We investigate the electronic structures and stability for Ni/Bi 2Te3, NiTe/Bi2Te3, Co/Bi 2Te3 and CoTe2/Bi2Te3 interfaces by first-principles calculations. It is found that the surface termination strongly affects the band alignment. Ni and Co are found to form Ohmic contacts to Bi2Te3. The interface formation energy for Co/Bi2Te3 interfaces is much lower than that of Ni/Bi2Te3 interfaces. Furthermore, we found that NiTe on Bi2Te3 is more stable than Ni, while the formation energies for Co and CoTe2 on Bi2Te3 are comparable. © 2010 IOP Publishing Ltd.

  10. Electronic structures and stability of Ni/Bi2Te3 and Co/Bi2Te3 interfaces

    KAUST Repository

    Xiong, Ka

    2010-03-04

    We investigate the electronic structures and stability for Ni/Bi 2Te3, NiTe/Bi2Te3, Co/Bi 2Te3 and CoTe2/Bi2Te3 interfaces by first-principles calculations. It is found that the surface termination strongly affects the band alignment. Ni and Co are found to form Ohmic contacts to Bi2Te3. The interface formation energy for Co/Bi2Te3 interfaces is much lower than that of Ni/Bi2Te3 interfaces. Furthermore, we found that NiTe on Bi2Te3 is more stable than Ni, while the formation energies for Co and CoTe2 on Bi2Te3 are comparable. © 2010 IOP Publishing Ltd.

  11. Combustion characteristics and air pollutant formation during oxy-fuel co-combustion of microalgae and lignite.

    Science.gov (United States)

    Gao, Yuan; Tahmasebi, Arash; Dou, Jinxiao; Yu, Jianglong

    2016-05-01

    Oxy-fuel combustion of solid fuels is seen as one of the key technologies for carbon capture to reduce greenhouse gas emissions. The combustion characteristics of lignite coal, Chlorella vulgaris microalgae, and their blends under O2/N2 and O2/CO2 conditions were studied using a Thermogravimetric Analyzer-Mass Spectroscopy (TG-MS). During co-combustion of blends, three distinct peaks were observed and were attributed to C. vulgaris volatiles combustion, combustion of lignite, and combustion of microalgae char. Activation energy during combustion was calculated using iso-conventional method. Increasing the microalgae content in the blend resulted in an increase in activation energy for the blends combustion. The emissions of S- and N-species during blend fuel combustion were also investigated. The addition of microalgae to lignite during air combustion resulted in lower CO2, CO, and NO2 yields but enhanced NO, COS, and SO2 formation. During oxy-fuel co-combustion, the addition of microalgae to lignite enhanced the formation of gaseous species. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Graphene and TiO_2 co-modified flower-like Bi_2O_2CO_3: A novel multi-heterojunction photocatalyst with enhanced photocatalytic activity

    International Nuclear Information System (INIS)

    Ao, Yanhui; Xu, Liya; Wang, Peifang; Wang, Chao; Hou, Jun; Qian, Jin; Li, Yi

    2015-01-01

    Graphical abstract: A novel multi-heterojunction photocatalyst (graphene and TiO_2 co-modified flower-like Bi_2O_2CO_3) was prepared for the first time. The as-obtained samples showed much higher activity compared to pure Bi_2O_2CO_3, TiO_2 and GR–Bi_2O_2CO_3 for dye degradation, which is almost 14 times higher than that of pure Bi_2O_2CO_3 and also much higher than the sum of graphene–Bi_2O_2CO_3 and TiO_2. - Highlights: • Graphene and TiO_2 co-modified flower-like Bi_2O_2CO_3 was prepared for the first time. • The sample shows enhanced photocatalytic activity due to the formation of multi-heterojunction. • The sample also exhibits a synergetic effect of graphene and TiO_2. • The composite photocatalyst shows a good stability for dye degradation. - Abstract: In this paper, graphene (GR) and titania co-modified flower-like Bi_2O_2CO_3 multi-heterojunction composite photocatalysts were prepared by a simple and feasible two step hydrothermal process. The prepared samples were analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM), transmission electron microscopy (TEM), UV–vis diffuse reflectance spectrometry (DRS), photoluminescence (PL), N_2 adsorption–desorption isotherm, and photo-induced current. The photocatalytic activity was investigated by the degradation of MO under UV light irradiation. The as prepared multi-heterojunction GR/Bi_2O_2CO_3/TiO_2 composites exhibited much higher photocatalytic activity than pure Bi_2O_2CO_3, TiO_2 and GR–Bi_2O_2CO_3. The higher performance of GR/Bi_2O_2CO_3/TiO_2 can be ascribed to the formation of multi-heterojunctions, which promote the effective separation of photo-induced electron–hole pairs. Moreover, the higher photocatalytic activity can also be ascribed to the high surface area of GR and TiO_2, which offers more active sites for the photodegradation reaction. Furthermore, the photocatalytic activity of GR/Bi_2O_2CO_3/TiO_2 remained without striking decrease after five cycles

  13. Separation and capture of CO2 from large stationary sources and sequestration in geological formations--coalbeds and deep saline aquifers.

    Science.gov (United States)

    White, Curt M; Strazisar, Brian R; Granite, Evan J; Hoffman, James S; Pennline, Henry W

    2003-06-01

    The topic of global warming as a result of increased atmospheric CO2 concentration is arguably the most important environmental issue that the world faces today. It is a global problem that will need to be solved on a global level. The link between anthropogenic emissions of CO2 with increased atmospheric CO2 levels and, in turn, with increased global temperatures has been well established and accepted by the world. International organizations such as the United Nations Framework Convention on Climate Change (UNFCCC) and the Intergovernmental Panel on Climate Change (IPCC) have been formed to address this issue. Three options are being explored to stabilize atmospheric levels of greenhouse gases (GHGs) and global temperatures without severely and negatively impacting standard of living: (1) increasing energy efficiency, (2) switching to less carbon-intensive sources of energy, and (3) carbon sequestration. To be successful, all three options must be used in concert. The third option is the subject of this review. Specifically, this review will cover the capture and geologic sequestration of CO2 generated from large point sources, namely fossil-fuel-fired power gasification plants. Sequestration of CO2 in geological formations is necessary to meet the President's Global Climate Change Initiative target of an 18% reduction in GHG intensity by 2012. Further, the best strategy to stabilize the atmospheric concentration of CO2 results from a multifaceted approach where sequestration of CO2 into geological formations is combined with increased efficiency in electric power generation and utilization, increased conservation, increased use of lower carbon-intensity fuels, and increased use of nuclear energy and renewables. This review covers the separation and capture of CO2 from both flue gas and fuel gas using wet scrubbing technologies, dry regenerable sorbents, membranes, cryogenics, pressure and temperature swing adsorption, and other advanced concepts. Existing

  14. Visible-light-driven methane formation from CO2 with a molecular iron catalyst

    Science.gov (United States)

    Rao, Heng; Schmidt, Luciana C.; Bonin, Julien; Robert, Marc

    2017-08-01

    Converting CO2 into fuel or chemical feedstock compounds could in principle reduce fossil fuel consumption and climate-changing CO2 emissions. One strategy aims for electrochemical conversions powered by electricity from renewable sources, but photochemical approaches driven by sunlight are also conceivable. A considerable challenge in both approaches is the development of efficient and selective catalysts, ideally based on cheap and Earth-abundant elements rather than expensive precious metals. Of the molecular photo- and electrocatalysts reported, only a few catalysts are stable and selective for CO2 reduction; moreover, these catalysts produce primarily CO or HCOOH, and catalysts capable of generating even low to moderate yields of highly reduced hydrocarbons remain rare. Here we show that an iron tetraphenylporphyrin complex functionalized with trimethylammonio groups, which is the most efficient and selective molecular electro- catalyst for converting CO2 to CO known, can also catalyse the eight-electron reduction of CO2 to methane upon visible light irradiation at ambient temperature and pressure. We find that the catalytic system, operated in an acetonitrile solution containing a photosensitizer and sacrificial electron donor, operates stably over several days. CO is the main product of the direct CO2 photoreduction reaction, but a two-pot procedure that first reduces CO2 and then reduces CO generates methane with a selectivity of up to 82 per cent and a quantum yield (light-to-product efficiency) of 0.18 per cent. However, we anticipate that the operating principles of our system may aid the development of other molecular catalysts for the production of solar fuels from CO2 under mild conditions.

  15. 40 CFR Figure C-1 to Subpart C of... - Suggested Format for Reporting Test Results for Methods for SO 2, CO, O 3, NO 2

    Science.gov (United States)

    2010-07-01

    ... Results for Methods for SO 2, CO, O 3, NO 2 C Figure C-1 to Subpart C of Part 53 Protection of Environment... Pt. 53, Subpt. C, Fig. C-1 Figure C-1 to Subpart C of Part 53—Suggested Format for Reporting Test... Difference Table C-1 spec. Pass or fail Low 1 ____ ppm 2 to ____ ppm 3 4 5 6 Medium 1 ____ ppm 2 to ____ ppm...

  16. Alberta industrial synergy CO2 programs initiative

    International Nuclear Information System (INIS)

    Yildirim, E.

    1998-01-01

    The various industrial sectors within Alberta produce about 350,000 tonnes of CO 2 per day. This presentation was concerned with how this large volume and high concentration of CO 2 can be used in industrial and agricultural applications, because every tonne of CO 2 used for such purposes is a tonne that does not end up in the atmosphere. There is a good potential for an industrial synergy between the producers and users of CO 2 . The Alberta Industrial Synergy CO 2 Programs Initiative was established to ultimately achieve a balance between the producers of CO 2 and the users of CO 2 by creating ways to use the massive quantities of CO 2 produced by Alberta's hydrocarbon-based economy. The Alberta CO 2 Research Steering Committee was created to initiate and support CO 2 programs such as: (1) CO 2 use in enhanced oil recovery, (2) creation of a CO 2 production inventory, (3) survey of CO 2 users and potential users, (4) investigation of process issues such as power generation, oil sands and cement manufacturing, and (5) biofixation by plants, (6) other disposal options (e.g. in depleted oil and gas reservoirs, in aquifers, in tailings ponds, in coal beds). The single most important challenge was identified as 'rationalizing the formation of the necessary infrastructure'. Failing to do that will greatly impede efforts directed towards CO 2 utilization

  17. Titanium Insertion into CO Bonds in Anionic Ti-CO2 Complexes.

    Science.gov (United States)

    Dodson, Leah G; Thompson, Michael C; Weber, J Mathias

    2018-03-22

    We explore the structures of [Ti(CO 2 ) y ] - cluster anions using infrared photodissociation spectroscopy and quantum chemistry calculations. The existence of spectral signatures of metal carbonyl CO stretching modes shows that insertion of titanium atoms into C-O bonds represents an important reaction during the formation of these clusters. In addition to carbonyl groups, the infrared spectra show that the titanium center is coordinated to oxalato, carbonato, and oxo ligands, which form along with the metal carbonyls. The presence of a metal oxalato ligand promotes C-O bond insertion in these systems. These results highlight the affinity of titanium for C-O bond insertion processes.

  18. Modelling of the Duero Sedimentary Basin and Selection of Deep Favourable Geological Formations for Supercritical CO{sub 2} Storage; Modelizacion del Subsuelo de la Cuenca del Duero y Seleccion de Formaciones Favorables para el Almacenamiento de CO{sub 2} en Estado Supercritico

    Energy Technology Data Exchange (ETDEWEB)

    Prado, A. J.; Perez del Villar, L.; Pelayo, M.; Recreo, F.

    2008-04-10

    Currently, the Deep Geological Storage is the internationally most accepted option to store CO{sub 2}, whose main goal is to reduce the CO{sub 2} emissions to the atmosphere. This work, which has been carried out in the frame of The Strategic Singular Project entitled: CO{sub 2} generation, capture and storage advanced technologies summarizes a general methodology focused on the selection and modelling of favourable formations to store CO{sub 2} and to estimate their storage capacity. To conclude, the Duero basin suitability to allocate a CO{sub 2} storage plant has been quantified by integrating the Multi-criteria Evaluation Methods with the corresponding developed Geographical Information Systems. (Author) 45 refs.

  19. Splenectomy after partial hepatectomy accelerates liver regeneration in mice by promoting tight junction formation via polarity protein Par 3-aPKC.

    Science.gov (United States)

    Liu, Guoxing; Xie, Chengzhi; Fang, Yu; Qian, Ke; Liu, Qiang; Liu, Gao; Cao, Zhenyu; Du, Huihui; Fu, Jie; Xu, Xundi

    2018-01-01

    Several experimental studies have demonstrated that removal of the spleen accelerates liver regeneration after partial hepatectomy. While the mechanism of splenectomy promotes liver regeneration by the improvement of the formation of tight junction and the establishment of hepatocyte polarity is still unknown. We analyzed the cytokines, genes and proteins expression between 70% partial hepatectomy mice (PHx) and simultaneous 70% partial hepatectomy and splenectomy mice (PHs) at predetermined timed points. Compared with the PHx group mice, splenectomy accelerated hepatocyte proliferation in PHs group. The expression of Zonula occludens-1 (ZO-1) indicated that splenectomy promotes the formation of tight junction during liver regeneration. TNF-α, IL-6, HGF, TSP-1 and TGF-β1 were essential factors for the formation of tight junction and the establishment of hepatocytes polarity in liver regeneration. After splenectomy, Partitioning defective 3 homolog (Par 3) and atypical protein kinase C (aPKC) regulate hepatocyte localization and junctional structures in regeneration liver. Our data suggest that the time course expression of TNF-α, IL-6, HGF, TSP-1, and TGF-β1 and the change of platelets take part in liver regeneration. Combination with splenectomy accelerates liver regeneration by improvement of the tight junction formation which may help to establish hepatocyte polarity via Par 3-aPKC. This may provide a clue for us that splenectomy could accelerate liver regeneration after partial hepatectomy of hepatocellular carcinoma and living donor liver transplantation. Copyright © 2017 Elsevier Inc. All rights reserved.

  20. Numerical Investigation into the Impact of CO2-Water-Rock Interactions on CO2 Injectivity at the Shenhua CCS Demonstration Project, China

    Directory of Open Access Journals (Sweden)

    Guodong Yang

    2017-01-01

    Full Text Available A 100,000 t/year demonstration project for carbon dioxide (CO2 capture and storage in the deep saline formations of the Ordos Basin, China, has been successfully completed. Field observations suggested that the injectivity increased nearly tenfold after CO2 injection commenced without substantial pressure build-up. In order to evaluate whether this unique phenomenon could be attributed to geochemical changes, reactive transport modeling was conducted to investigate CO2-water-rock interactions and changes in porosity and permeability induced by CO2 injection. The results indicated that using porosity-permeability relationships that include tortuosity, grain size, and percolation porosity, other than typical Kozeny-Carman porosity-permeability relationship, it is possible to explain the considerable injectivity increase as a consequence of mineral dissolution. These models might be justified in terms of selective dissolution along flow paths and by dissolution or migration of plugging fines. In terms of geochemical changes, dolomite dissolution is the largest source of porosity increase. Formation physical properties such as temperature, pressure, and brine salinity were found to have modest effects on mineral dissolution and precipitation. Results from this study could have practical implications for a successful CO2 injection and enhanced oil/gas/geothermal production in low-permeability formations, potentially providing a new basis for screening of storage sites and reservoirs.

  1. Chemical and Molecular Descriptors for the Reactivity of Amines with CO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Anita S.; Kitchin, John R.

    2012-10-24

    Amine-based solvents are likely to play an important role in CO{sub 2} capture applications in the future, and the identification of amines with superior performance will facilitate their use in CO{sub 2} capture. While some improvements in performance will be achieved through process modifications, modifying the CO{sub 2} capture performance of an amine also implies in part an ability to modify the reactions between the amine and CO{sub 2} through development of new functionalized amines. We present a computational study of trends in the reactions between CO{sub 2} and functionalized amines with a focus on identifying molecular descriptors that determine trends in reactivity. We examine the formation of bicarbonate and carbamate species on three classes of functionalized amines: alkylamines, alkanolamines, and fluorinated alkylamines including primary, secondary and tertiary amines in each class. These functional groups span electron-withdrawing to donating behavior, hydrogen-bonding, extent of functionalization, and proximity effects of the functional groups. Electron withdrawing groups tend to destabilize CO{sub 2} reaction products, whereas electron-donating groups tend to stabilize CO{sub 2} reaction products. Hydrogen bonding stabilizes CO{sub 2} reaction products. Electronic structure descriptors based on electronegativity were found to describe trends in the bicarbonate formation energy. A chemical correlation was observed between the carbamate formation energy and the carbamic acid formation energy. The local softness on the reacting N in the amine was found to partially explain trends carbamic acid formation energy.

  2. Enclathration of CO2 as a co-guest of structure H hydrates and its implications for CO2 capture and sequestration

    International Nuclear Information System (INIS)

    Lee, Yohan; Lee, Dongyoung; Lee, Jong-Won; Seo, Yongwon

    2016-01-01

    Highlights: • We examine sH hydrates with CO 2 + N 2 + neohexane for CO 2 capture and sequestration. • The structural transition occurs in the CO 2 (40%) + N 2 (60%) + neohexane system. • CO 2 molecules are enclathrated into sH hydrates in the N 2 -rich systems. • CO 2 selectivity in sH hydrates is slightly lower than that in sI hydrates. • ΔH d values provide information on the structural transition of sH to sI hydrates. - Abstract: In this study, the thermodynamic behaviors, cage-specific guest distributions, structural transition, and dissociation enthalpies of sH hydrates with CO 2 + N 2 gas mixtures were investigated for their potential applications to hydrate-based CO 2 capture and sequestration. The stability conditions of the CO 2 + N 2 + water systems and the CO 2 + N 2 + neohexane (2,2-dimethylbutane, NH) + water systems indicated that the gas mixtures in the range of flue gas compositions could form sH hydrates, thereby mitigating the pressure and temperature required for gas hydrate formation. Structure identification using powder X-ray diffraction (PXRD) revealed the coexistence of sI and sH hydrates in the CO 2 (40%) + N 2 (60%) + NH system and the hydrate structure transformed from sH into sI as the CO 2 concentration increased. In addition, the Raman analysis clearly demonstrated that CO 2 molecules were enclathrated into the cages of sH hydrates in the N 2 -rich systems. It was found from direct CO 2 composition measurements that CO 2 selectivity in the sH hydrate phase was slightly lower than that in the corresponding sI hydrate phase. Dissociation enthalpy (ΔH d ) measurements using a high-pressure micro-differential scanning calorimeter (HP μ-DSC) indicated that the ΔH d values could also provide valuable information on the structural transition of sH to sI hydrates with respect to the CO 2 concentration in the feed gas. This study provides a better understanding of the thermodynamic and physicochemical background for CO 2

  3. Possible use of Fe/CO2 fuel cells for CO2 mitigation plus H2 and electricity production

    International Nuclear Information System (INIS)

    Rau, Greg H.

    2004-01-01

    The continuous oxidation of scrap iron in the presence of a constant CO 2 -rich waste gas stream and water is evaluated as a means of sequestering anthropogenic CO 2 as well as generating hydrogen gas and electricity. The stoichiometry of the net reaction, Fe 0 + CO 2 + H 2 O → FeCO 3 + H 2 , and assumptions about reaction rates, reactant and product prices/values and overhead costs suggest that CO 2 might be mitigated at a net profit in excess of $30/tonne CO 2 . The principle profit center of the process would be hydrogen production, alone providing a gross income of >$160/tonne CO 2 reacted. However, the realization of such fuel cell economics depends on a number of parameters including: (1) the rate at which the reaction can be sustained, (2) the areal and volumetric density with which H 2 and electricity can be produced, (3) the purity of the H 2 produced, (4) the transportation costs of the reactants (Fe, CO 2 and H 2 O) and products (FeCO 3 or Fe(HCO 3 ) 2 ) to/from the cells and (5) the cost/benefit trade-offs of optimizing the preceding variables in a given market and regulatory environment. Because of the carbon intensity of conventional iron metal production, a net carbon sequestration benefit for the process can be realized only when waste (rather than new) iron and steel are used as electrodes and/or when Fe(HCO 3 ) 2 is the end product. The used electrolyte could also provide a free source of Fe 2+ ions for enhancing iron-limited marine photosynthesis and, thus, greatly increasing the CO 2 sequestration potential of the process. Alternatively, the reaction of naturally occurring iron oxides (iron ore) with CO 2 can be considered for FeCO 3 formation and sequestration, but this foregoes the benefits of hydrogen and electricity production. Use of Fe/CO 2 fuel cells would appear to be particularly relevant for fossil fuel gasification/steam reforming systems given the highly concentrated CO 2 they generate and given the existing infrastructure they

  4. Numerical analysis of capillary entrapment for effective CO{sub 2} aquifer storage

    Energy Technology Data Exchange (ETDEWEB)

    Uelker, B.; Pusch, G. [Technische Univ. Clausthal (Germany). Inst. fuer Erdoel- und Erdgastechnik; May, F. [Bundesanstalt fuer Geowissenschaften und Rohstoffe, Hannover (Germany)

    2007-09-13

    The success of underground CO{sub 2} sequestration projects relies on the ability of keeping CO{sub 2} immobilized. The risk of CO{sub 2} leakage into the atmosphere through faults, cap rock formations or wellbore must be evaluated for the long term safety of storage. In case of CO{sub 2} sequestration in a saline aquifer capillary trapping of CO{sub 2} is one of the essential mechanisms controlling the upward and lateral migration of CO{sub 2} plumes after the injection phase. Therefore, assessment of CO{sub 2} immobilization requires accurate modelling of multi phase flow performance. A generic reservoir model was created to examine the impact of the relative permeabilities and capillary forces on capillary trapping. This study reveals how the mechanism of capillary trapping is affected by varying the CO{sub 2} injection rate, hysteresis between drainage and imbibition processes and residual phase saturations. The leakage risk of injected CO{sub 2} in vertical and horizontal wells was also compared to identify the effective injection geometry. Vertical injection across the entire storage formation interval leads to extensive contact with cap rock and leakage through it. Horizontal wells located in the lower part of the formation both increase the aquifer utilization and eliminate contact with cap rock immediately. Thus horizontal wells can be an alternative to inject more CO{sub 2} and minimize leakage. (orig.)

  5. Predictive value of 14CO2 breath tests for clinical use of 13CO2 breath tests

    International Nuclear Information System (INIS)

    Glaubitt, D.M.H.

    1975-01-01

    The knowledge of the efficiency of 14 CO 2 breath tests makes possible the comparison of the efficiency of analogous tests using the stable isotope 13 C. 14 CO 2 exhalation studies render overall information. After parenteral administration of a 14 C labeled substrate, 14 CO 2 breath tests permit insight into the metabolism of the 14 C substrate and the associated intermediary metabolism. If the 14 C substrate is given orally or by intraduodenal instillation, 14 CO 2 breath tests supply information not only about gastrointenstinal absorption and digestion but also about the intermediary metabolism yielding 14 CO 2 , after the administered substrate or its degradation products have been absorbed in the gastrointestinal tract. The fraction of 14 CO 2 arising from absorption, digestion and intermediary metabolism can be estimated only by additional methods. 14 CO 2 breath tests are unable to delineate single metabolic reactions involved in the formation of carbon dioxide. Under these considerations the clinical application of 14 CO 2 breath tests may provide diagnostically useful results, especially in internal medicine and surgery. The tests are suitable for intraindividual assessment of the course of a disease and of therapeutic effects. They may be important in the research of the metabolism of 14 C labeled substrates

  6. Blowing loop in the EL-4 reactor: CO{sub 2} flow control analogue study; Boucle de soufflage de la centrale EL-4 - regulation du debit CO{sub 2} - etude analogique

    Energy Technology Data Exchange (ETDEWEB)

    Chazal, G; Merle, J P; Guillemard, B [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires; Leroy, C; Robin, L; Jacquin, J C; Cornudet, A [Societe INDATOM, France (France)

    1966-07-01

    This report describes one study which contributed to the construction of the Monts d'Arree nuclear power station: EL-4. The reactor is cooled by a CO{sub 2} current provided by 3 turbo-blower groups. The priming vapour for the turbines is taken at the exit of the main CO{sub 2} - H{sub 2}O exchangers. The operation of EL 4 is based on a high degree of centralization of the controls which attributes an important role to the general regulation circuits. This general regulation includes in particular an internal blowing loop which controls the CO{sub 2} flow. The study of the control of this CO{sub 2} flow is made up of 3 parts: - analogue representation of the reactors cooling circuit and of the turbo blower unit. - first test campaign using the analogue computer describing the natural behaviour of the system in the absence of control. theoretical determination of the regulation factors; definition of the regulation using an analogue computer and second test campaign for recording the performances of the blowing loop. The 4. part of the report deals with the analogue study: analogue equations - development. (authors) [French] Ce rapport prend place parmi les etudes de realisation de la Centrale des Monts d'Arree EL-4. Le reacteur est refroidi par une circulation de CO{sub 2} assuree par 3 groupes turbosoufflantes. La vapeur d'entrainement des turbines est prelevee a la sortie des echangeurs principaux CO{sub 2} - H{sub 2}O. L'exploitation de EL-4 repose sur une centralisation poussee des moyens de controle-commande qui attribue un role essentiel aux circuits de regulation generale. Cette regulation generale comporte en particulier une boucle interne de soufflage qui realise un asservissement du debit de CO{sub 2}. L'etude de cette regulation du debit CO{sub 2} comprend 3 parties: - representation analogique du circuit de refroidissement du reacteur et de l'ensemble turbine-soufflante. - premiere campagne d'essais sur calculateur analogique decrivant le comportement

  7. Sequential sputtered Co-HfO{sub 2} granular films

    Energy Technology Data Exchange (ETDEWEB)

    Chadha, M.; Ng, V.

    2017-03-15

    A systematic study of magnetic, magneto-transport and micro-structural properties of Co-HfO{sub 2} granular films fabricated by sequential sputtering is presented. We demonstrate reduction in ferromagnetic-oxide formation by using HfO{sub 2} as the insulting matrix. Microstructure evaluation of the films showed that the film structure consisted of discrete hcp-Co grains embedded in HfO{sub 2} matrix. Films with varying compositions were prepared and their macroscopic properties were studied. We correlate the variation in these properties to the variation in film microstructure. Our study shows that Co-HfO{sub 2} films with reduced cobalt oxide and varying properties can be prepared using sequential sputtering technique. - Highlights: • Co-HfO{sub 2} granular films were prepared using sequential sputtering. • A reduction in ferromagnetic-oxide formation is observed. • Co-HfO{sub 2} films display superparamagnetism and tunnelling magneto-resistance. • Varying macroscopic properties were achieved by changing film composition. • Applications can be found in moderate MR sensors and high –frequency RF devices.

  8. The Abundance of Atmospheric CO{sub 2} in Ocean Exoplanets: a Novel CO{sub 2} Deposition Mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Levi, A.; Sasselov, D. [Harvard-Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Podolak, M., E-mail: amitlevi.planetphys@gmail.com [Dept. of Geosciences, Tel Aviv University, Tel Aviv, 69978 (Israel)

    2017-03-20

    We consider super-Earth sized planets which have a water mass fraction large enough to form an external mantle composed of high-pressure water-ice polymorphs and also lack a substantial H/He atmosphere. We consider such planets in their habitable zone, so that their outermost condensed mantle is a global, deep, liquid ocean. For these ocean planets, we investigate potential internal reservoirs of CO{sub 2}, the amount of CO{sub 2} dissolved in the ocean for the various saturation conditions encountered, and the ocean-atmosphere exchange flux of CO{sub 2}. We find that, in a steady state, the abundance of CO{sub 2} in the atmosphere has two possible states. When wind-driven circulation is the dominant CO{sub 2} exchange mechanism, an atmosphere of tens of bars of CO{sub 2} results, where the exact value depends on the subtropical ocean surface temperature and the deep ocean temperature. When sea-ice formation, acting on these planets as a CO{sub 2} deposition mechanism, is the dominant exchange mechanism, an atmosphere of a few bars of CO{sub 2} is established. The exact value depends on the subpolar surface temperature. Our results suggest the possibility of a negative feedback mechanism, unique to water planets, where a reduction in the subpolar temperature drives more CO{sub 2} into the atmosphere to increase the greenhouse effect.

  9. Reactivity of micas and cap-rock in wet supercritical CO_2 with SO_2 and O_2 at CO_2 storage conditions

    International Nuclear Information System (INIS)

    Pearce, Julie K.; Dawson, Grant K.W.; Law, Alison C.K.; Biddle, Dean; Golding, Suzanne D.

    2016-01-01

    Seal or cap-rock integrity is a safety issue during geological carbon dioxide capture and storage (CCS). Industrial impurities such as SO_2, O_2, and NOx, may be present in CO_2 streams from coal combustion sources. SO_2 and O_2 have been shown recently to influence rock reactivity when dissolved in formation water. Buoyant water-saturated supercritical CO_2 fluid may also come into contact with the base of cap-rock after CO_2 injection. Supercritical fluid-rock reactions have the potential to result in corrosion of reactive minerals in rock, with impurity gases additionally present there is the potential for enhanced reactivity but also favourable mineral precipitation. The first observation of mineral dissolution and precipitation on phyllosilicates and CO_2 storage cap-rock (siliciclastic reservoir) core during water-saturated supercritical CO_2 reactions with industrial impurities SO_2 and O_2 at simulated reservoir conditions is presented. Phyllosilicates (biotite, phlogopite and muscovite) were reacted in contact with a water-saturated supercritical CO_2 containing SO_2, or SO_2 and O_2, and were also immersed in the gas-saturated bulk water. Secondary precipitated sulfate minerals were formed on mineral surfaces concentrated at sheet edges. SO_2 dissolution and oxidation resulted in solution pH decreasing to 0.74 through sulfuric acid formation. Phyllosilicate dissolution released elements to solution with ∼50% Fe mobilized. Geochemical modelling was in good agreement with experimental water chemistry. New minerals nontronite (smectite), hematite, jarosite and goethite were saturated in models. A cap-rock core siltstone sample from the Surat Basin, Australia, was also reacted in water-saturated supercritical CO_2 containing SO_2 or in pure supercritical CO_2. In the presence of SO_2, siderite and ankerite were corroded, and Fe-chlorite altered by the leaching of mainly Fe and Al. Corrosion of micas in the cap-rock was however not observed as the pH was

  10. Experimental investigation of CO2-brine-rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

    Science.gov (United States)

    Rosenbauer, R.J.; Koksalan, T.; Palandri, J.L.

    2005-01-01

    Deep-saline aquifers are potential repositories for excess CO2, currently being emitted to the atmosphere from anthropogenic activities, but the reactivity of supercritical CO2 with host aquifer fluids and formation minerals needs to be understood. Experiments reacting supercritical CO2 with natural and synthetic brines in the presence and absence of limestone and plagioclase-rich arkosic sandstone showed that the reaction of CO2-saturated brine with limestone results in compositional, mineralogical, and porosity changes in the aquifer fluid and rock that are dependent on initial brine composition, especially dissolved calcium and sulfate. Experiments reacting CO2-saturated, low-sulfate brine with limestone dissolved 10% of the original calcite and increased rock porosity by 2.6%. Experiments reacting high-sulfate brine with limestone, both in the presence and absence of supercritical CO2, were characterized by the precipitation of anhydrite, dolomitization of the limestone, and a final decrease in porosity of 4.5%. However, based on favorable initial porosity changes of about 15% due to the dissolution of calcite, the combination of CO2 co-injection with other mitigation strategies might help alleviate some of the well-bore scale and formation-plugging problems near the injection zone of a brine disposal well in Paradox Valley, Colorado, as well as provide a repository for CO2. Experiments showed that the solubility of CO2 is enhanced in brine in the presence of limestone by 9% at 25 ??C and 6% at 120 ??C and 200 bar relative to the brine itself. The solubility of CO2 is enhanced also in brine in the presence of arkosic sandstone by 5% at 120 ??C and 300 bar. The storage of CO 2 in limestone aquifers is limited to only ionic and hydraulic trapping. However, brine reacted with supercritical CO2 and arkose yielded fixation and sequestration of CO2 in carbonate mineral phases. Brine desiccation was observed in all experiments containing a discrete CO2 phase

  11. Nitrogen-based catalysts for the electrochemical reduction of CO2 to CO.

    Science.gov (United States)

    Tornow, Claire E; Thorson, Michael R; Ma, Sichao; Gewirth, Andrew A; Kenis, Paul J A

    2012-12-05

    The synthesis and application of carbon-supported, nitrogen-based organometallic silver catalysts for the reduction of CO(2) is studied using an electrochemical flow reactor. Their performance toward the selective formation of CO is similar to the performance achieved when using Ag as the catalyst, but comparatively at much lower silver loading. Faradaic efficiencies of the organometallic catalyst are higher than 90%, which are comparable to those of Ag. Furthermore, with the addition of an amine ligand to Ag/C, the partial current density for CO increases significantly, suggesting a possible co-catalyst mechanism. Additional improvements in activity and selectivity may be achieved as greater insight is obtained on the mechanism of CO(2) reduction and on how these complexes assemble on the carbon support.

  12. Reaction of silanes in supercritical CO2 with TiO2 and Al2O3.

    Science.gov (United States)

    Gu, Wei; Tripp, Carl P

    2006-06-20

    Infrared spectroscopy was used to investigate the reaction of silanes with TiO2 and Al2O3 using supercritical CO2 (Sc-CO2) as a solvent. It was found that contact of Sc-CO2 with TiO2 leads to partial removal of the water layer and to the formation of carbonate, bicarbonate, and carboxylate species on the surface. Although these carbonate species are weakly bound to the TiO2 surface and can be removed by a N2 purge, they poison the surface, resulting in a lower level of reaction of silanes with TiO2. Specifically, the amount of hexamethyldisilazane adsorbed on TiO2 is about 10% of the value obtained when the reaction is performed from the gas phase. This is not unique to TiO2, as the formation of carbonate species also occurs upon contact of Al2O3 with Sc-CO2 and this leads to a lower level of reaction with hexamethyldisilazane. This is in contrast to reactions of silanes on SiO2 where Sc-CO2 has several advantages over conventional gaseous or nonaqueous methods. As a result, caution needs to be applied when using Sc-CO2 as a solvent for silanization reactions on oxides other than SiO2.

  13. Catalytic conversion of 11CO2 and 11CO into synthesis precursors for 11C labelling

    International Nuclear Information System (INIS)

    Patt, J.T.

    1994-03-01

    The positron emitter carbon-11 (T 1/2 =20.3 min) is an ideal radio nuclide for tracers in positron emission tomography (PET). In this study catalytic methods for the synthesis of [ 11 C]alcohols have been investigated. The formation of [ 11 C]methanol has been studied on Pd/Al 2 O 3 and Cu/ZnO/Al 2 O 3 catalysts with respect to CO and CO 2 carrier addition to the synthesis gas. Carbon monoxide was identified as the precursor of methanol formation on the Pd/Al 2 O 3 -catalyst. In contrast on the Cu/ZnO/Al 2 O 3 -catalyst methanol was formed on a reaction pathway via an adsorbed CO 2 -species. A n.c.a.-[ 11 C]methanol synthesis basing on the Cu/ZnO/Al 2 O 3 -catalyst has been developed by substitution of the oxygen containing components CO and CO 2 in the synthesis gas by N 2 O. The radiochemical yield, the low selectivity of [ 11 C]methanol production and the rather slow kinetics of this process were arguments against the practical use of this process in the synthesis of 11 C-labelling agents. (orig.)

  14. Research Project on CO2 Geological Storage and Groundwater Resources: Water Quality Effects Caused by CO2 Intrusion into Shallow Groundwater

    Energy Technology Data Exchange (ETDEWEB)

    Birkholzer, Jens; Apps, John; Zheng, Liange; Zhang, Yingqi; Xu, Tianfu; Tsang, Chin-Fu

    2008-10-01

    One promising approach to reduce greenhouse gas emissions is injecting CO{sub 2} into suitable geologic formations, typically depleted oil/gas reservoirs or saline formations at depth larger than 800 m. Proper site selection and management of CO{sub 2} storage projects will ensure that the risks to human health and the environment are low. However, a risk remains that CO{sub 2} could migrate from a deep storage formation, e.g. via local high-permeability pathways such as permeable faults or degraded wells, and arrive in shallow groundwater resources. The ingress of CO{sub 2} is by itself not typically a concern to the water quality of an underground source of drinking water (USDW), but it will change the geochemical conditions in the aquifer and will cause secondary effects mainly induced by changes in pH, in particular the mobilization of hazardous inorganic constituents present in the aquifer minerals. Identification and assessment of these potential effects is necessary to analyze risks associated with geologic sequestration of CO{sub 2}. This report describes a systematic evaluation of the possible water quality changes in response to CO{sub 2} intrusion into aquifers currently used as sources of potable water in the United States. Our goal was to develop a general understanding of the potential vulnerability of United States potable groundwater resources in the event of CO{sub 2} leakage. This goal was achieved in two main tasks, the first to develop a comprehensive geochemical model representing typical conditions in many freshwater aquifers (Section 3), the second to conduct a systematic reactive-transport modeling study to quantify the effect of CO{sub 2} intrusion into shallow aquifers (Section 4). Via reactive-transport modeling, the amount of hazardous constituents potentially mobilized by the ingress of CO{sub 2} was determined, the fate and migration of these constituents in the groundwater was predicted, and the likelihood that drinking water

  15. Mechano-chemical pathways to H2O and CO2 splitting

    Science.gov (United States)

    Vedadi, Mohammad H.; Haas, Stephan

    2011-10-01

    The shock-induced collapse of CO2-filled nanobubbles is investigated using molecular dynamics simulations based on a reactive force field. The energetic nanojet and high-pressure water hammer shock formed during and after collapse of the nanobubble trigger mechano-chemical H2O-CO2 reactions, some of which lead to splitting of water and formation of O2 molecules. The dominant pathways through which splitting of water molecules occur are identified.

  16. DFT+U study of polaronic conduction in Li2O2 and Li2CO3

    DEFF Research Database (Denmark)

    García Lastra, Juan Maria; Myrdal, J.S.G.; Christensen, Rune

    2013-01-01

    The main discharge products formed at the cathode of nonaqueous Li-air batteries are known to be Li2O2 and residual Li2CO3. Recent experiments indicate that the charge transport through these materials is the main limiting factor for the battery performance. It has been also shown...... that the performance of the battery decreases drastically when the amount of Li2CO3 at the cathode increases with respect to Li2O2. In this work, we study the formation and transport of hole and electron polarons in Li2O2 and Li2CO3 using density functional theory (DFT) within the PBE+U approximation. For both...... materials, we find that the formation of polarons (both hole and electron) is stabilized with respect to the delocalized states for all physically relevant values of U. We find a much higher mobility for hole polarons than for the electron polarons, and we show that the poor charge transport in Li2CO3...

  17. First identification and thermodynamic characterization of the ternary U(VI) species, UO2(O2)(CO3)2(4-), in UO2-H2O2-K2CO3 solutions.

    Science.gov (United States)

    Goff, George S; Brodnax, Lia F; Cisneros, Michael R; Peper, Shane M; Field, Stephanie E; Scott, Brian L; Runde, Wolfgang H

    2008-03-17

    In alkaline carbonate solutions, hydrogen peroxide can selectively replace one of the carbonate ligands in UO2(CO3)3(4-) to form the ternary mixed U(VI) peroxo-carbonato species UO2(O2)(CO3)2(4-). Orange rectangular plates of K4[UO2(CO3)2(O2)].H2O were isolated and characterized by single crystal X-ray diffraction studies. Crystallographic data: monoclinic, space group P2(1)/ n, a = 6.9670(14) A, b = 9.2158(10) A, c = 18.052(4) A, Z = 4. Spectrophotometric titrations with H 2O 2 were performed in 0.5 M K 2CO 3, with UO2(O2)(CO3)2(4-) concentrations ranging from 0.1 to 0.55 mM. The molar absorptivities (M(-1) cm(-1)) for UO2(CO3)3(4-) and UO2(O2)(CO3)2(4-) were determined to be 23.3 +/- 0.3 at 448.5 nm and 1022.7 +/- 19.0 at 347.5 nm, respectively. Stoichiometric analyses coupled with spectroscopic comparisons between solution and solid state indicate that the stable solution species is UO2(O2)(CO3)2(4-), which has an apparent formation constant of log K' = 4.70 +/- 0.02 relative to the tris-carbonato complex.

  18. CO2 Frost Phenomenon for Binary System of Methane-Carbon Dioxide Mixtures

    Directory of Open Access Journals (Sweden)

    Gede Wibawa

    2015-12-01

    Full Text Available In the present study, the CO2 frost phenomenon of CH4-CO2 mixtures has been observed for the rational design of CO2 removal from natural gas using a controlled freeze out area. The CO2 frost conditions were estimated using the ZNE method and process simulation software (Aspen HYSYS® v7.3. The experiment was carried out using a double pipe heat exchanger (DPHE with the concentration of CO2 in the gas mixture at 5 and 10% and pressure of the gas mixture from 1 to 20 bar. The equilibrium temperature predictions of the ZNE method and the process simulation software only had a slight difference, with a magnitude deviation of less than 1% for pressures below 20 bar and 3% for pressures in the range of 20-30 bar, respectively. In the experimental study, CO2 frost formation was detected at pressures of 1, 5, 10 and 20 bar. The locations of the initial CO2 frost formation were determined using a pressure drop indicator associated with the predicted frost temperatures obtained from the ZNE method and the process simulation software. For all studied variables, the locations of initial CO2 frost formation were found at 0.887-1.531 m from the inlet.

  19. Characterization of Unconventional Reservoirs: CO2 Induced Petrophysics

    Science.gov (United States)

    Verba, C.; Goral, J.; Washburn, A.; Crandall, D.; Moore, J.

    2017-12-01

    As concerns about human-driven CO2 emissions grow, it is critical to develop economically and environmentally effective strategies to mitigate impacts associated with fossil energy. Geologic carbon storage (GCS) is a potentially promising technique which involves the injection of captured CO2 into subsurface formations. Unconventional shale formations are attractive targets for GCS while concurrently improving gas recovery. However, shales are inherently heterogeneous, and minor differences can impact the ability of the shale to effectively adsorb and store CO2. Understanding GCS capacity from such endemic heterogeneities is further complicated by the complex geochemical processes which can dynamically alter shale petrophysics. We investigated the size distribution, connectivity, and type (intraparticle, interparticle, and organic) of pores in shale; the mineralogy of cores from unconventional shale (e.g. Bakken); and the changes to these properties under simulated GCS conditions. Electron microscopy and dual beam focused ion beam scanning electron microscopy were used to reconstruct 2D/3D digital matrix and pore structures. Comparison of pre and post-reacted samples gives insights into CO2-shale interactions - such as the mechanism of CO2 sorption in shales- intended for enhanced oil recovery and GCS initiatives. These comparisons also show how geochemical processes proceed differently across shales based on their initial diagenesis. Results show that most shale pore sizes fall within meso-macro pore classification (> 2 nm), but have variable porosity and organic content. The formation of secondary minerals (calcite, gypsum, and halite) may play a role in the infilling of fractures and pore spaces in the shale, which may reduce permeability and inhibit the flow of fluids.

  20. Multiple isotopes (O, C, Li, Sr) as tracers of CO2 and brine leakage from CO2-enhanced oil recovery activities in Permian Basin, Texas, USA

    Science.gov (United States)

    Phan, T. T.; Sharma, S.; Gardiner, J. B.; Thomas, R. B.; Stuckman, M.; Spaulding, R.; Lopano, C. L.; Hakala, A.

    2017-12-01

    Potential CO2 and brine migration or leakage into shallow groundwater is a critical issue associated with CO2 injection at both enhanced oil recovery (EOR) and carbon sequestration sites. The effectiveness of multiple isotope systems (δ18OH2O, δ13C, δ7Li, 87Sr/86Sr) in monitoring CO2 and brine leakage at a CO2-EOR site located within the Permian basin (Seminole, Texas, USA) was studied. Water samples collected from an oil producing formation (San Andres), a deep groundwater formation (Santa Rosa), and a shallow groundwater aquifer (Ogallala) over a four-year period were analyzed for elemental and isotopic compositions. The absence of any change in δ18OH2O or δ13CDIC values of water in the overlying Ogallala aquifer after CO2 injection indicates that injected CO2 did not leak into this aquifer. The range of Ogallala water δ7Li (13-17‰) overlaps the San Andres water δ7Li (13-15‰) whereas 87Sr/86Sr of Ogallala (0.70792±0.00005) significantly differs from San Andres water (0.70865±0.00003). This observation demonstrates that Sr isotopes are much more sensitive than Li isotopes in tracking brine leakage into shallow groundwater at the studied site. In contrast, deep groundwater δ7Li (21-25‰) is isotopically distinct from San Andres produced water; thus, monitoring this intermitted formation water can provide an early indication of CO2 injection-induced brine migration from the underlying oil producing formation. During water alternating with gas (WAG) operations, a significant shift towards more positive δ13CDIC values was observed in the produced water from several of the San Andres formation wells. The carbon isotope trend suggests that the 13C enriched injected CO2 and formation carbonates became the primary sources of dissolved inorganic carbon in the area surrounding the injection wells. Moreover, one-way ANOVA statistical analysis shows that the differences in δ7Li (F(1,16) = 2.09, p = 0.17) and 87Sr/86Sr (F(1,18) = 4.47, p = 0.05) values of

  1. Late-Onset Inadvertent Bleb Formation following Pars Plana M3 Molteno Implant Tube Obstruction

    Directory of Open Access Journals (Sweden)

    Anmar M. Abdul-Rahman

    2017-01-01

    Full Text Available Purpose: To report a case of inadvertent bleb formation presenting 18 months after pars plana M3 Molteno implant tube obstruction in a patient with mixed mechanism glaucoma. Materials and Methods: An 84-year-old Caucasian male with mixed mechanism glaucoma underwent slit-lamp examination, gonioscopy, colour anterior segment photography and anterior segment optical coherence tomography (AS-OCT. Results: An inadvertent bleb developed 18 months after pars plana implant tube re-positioning with a 6/0 Vicryl tie ligature. The bleb was located in the area anterior to the implant plate; it was characterised by a thin, transparent, avascular and multi-cystic wall, with a visible stoma at the posterior edge of the bleb. The bleb was functioning as demonstrated by an intraocular pressure of 6 mm Hg at presentation and a punctate fluorescein uptake pattern of the bleb wall. The bleb over the plate of the Molteno implant was non-functioning, likely secondary to tube obstruction by vitreous in the early postoperative period. AS-OCT showed a tract from the anterior chamber commencing at an entry wound through a corneal tunnel to the posterior stoma at the base of the inadvertent bleb. Conclusions: We hypothesise that the pathophysiologic factors resulting in an inadvertent bleb are a result of a combination of apoptosis, late-onset wound dehiscence and internal gaping of a centrally placed corneal wound. In addition, aqueous hydrodynamic factors may play a role.

  2. CO2 fluxes near a forest edge

    DEFF Research Database (Denmark)

    Sogachev, Andrey; Leclerc, Monique Y.; Zhang, Gensheng

    2008-01-01

    In contrast with recent advances on the dynamics of the flow at a forest edge, few studies have considered its role on scalar transport and, in particular, on CO2 transfer. The present study addresses the influence of the abrupt roughness change on forest atmosphere CO2 exchange and contrasts...... as a function of both sources/sinks distribution and the vertical structure of the canopy. Results suggest that the ground source plays a major role in the formation of wave-like vertical CO2 flux behavior downwind of a forest edge, despite the fact that the contribution of foliage sources/sinks changes...

  3. Theoretical study of methanol synthesis from CO2 and CO hydrogenation on the surface of ZrO2 supported In2O3 catalyst

    Science.gov (United States)

    Dou, Maobin; Zhang, Minhua; Chen, Yifei; Yu, Yingzhe

    2018-06-01

    The interactions between ZrO2 support and In2O3 catalyst play pivotal role in the catalytic conversion of CO2 to methanol. Herein, a density functional theory study has been conducted to research the mechanism of methanol synthesis from CO2 and CO hydrogenation on the defective ZrO2 supported In2O3(110) surface (D surface). The calculations reveal that methanol is produced mainly via the HCOO reaction pathway from CO2 hydrogenation on D surface, and the hydrogenation of HCOO to form H2COO species with an activation barrier of 1.21 eV plays the rate determining step for the HCOO reaction pathway. The direct dissociation of CO2 to CO on D surface is kinetically and energetically prohibited. Methanol synthesis from CO hydrogenation on D surface is much facile comparing with the elementary steps involved in CO2 hydrogenation. The rate determining step of CO hydrogenation to methanol is the formation of H3CO species on the vacancy site with a barrier of 0.51 eV. ZrO2 support has significant effect on the suppressing of the dissociation of CO2 and stabilization of H2COO species on the surface of In2O3 catalyst.

  4. Synthèse de composés oxygénés à partir de CO et H2 Synthesis of Oxygenated Compounds from CO and H2

    Directory of Open Access Journals (Sweden)

    Chaumette P.

    2006-11-01

    Full Text Available Dans cet article sont passés en revue les principaux produits oxygénés qui peuvent être obtenus en utilisant exclusivement le gaz de synthèse, par voie directe ou par l'intermédiaire du méthanol, aisément synthétisé à partir de CO et H2. Une comparaison est effectuée, qui porte essentiellement sur les modes de synthèse, les différents catalyseurs employés et leurs performances. L'aspect mécanistique est abordé en présentant les divers mécanismes proposés pour ces réactions. Il apparaît, dès à présent, que ces voies d'accès vers les produits oxygénés permettraient de remplacer les procédés utilisant les oléfines par des procédés utilisant le méthanol et le gaz de synthèse. In this article are reviewed the principal oxygenated products that can be produced exclusively from synthesis gas either by a straight-run process or through the use of methanol that can be easily obtained from CO and H2. A comparison is made between the synthesis processes, the different catalysts and their performances. An approach of the mechanistic aspects is undertaken by considering the various mechanistic routes proposed for these reactions. It already now appears that such ways of obtaining these oxygenated products would allow to replace processes using olefins by processes using methanol and synthesis gas.

  5. Attempts To Catalyze the Electrochemical CO2-to-Methanol Conversion by Biomimetic 2e(-) + 2H(+) Transferring Molecules.

    Science.gov (United States)

    Saveant, Jean-Michel; Tard, Cédric

    2016-01-27

    In the context of the electrochemical and photochemical conversion of CO2 to liquid fuels, one of the most important issues of contemporary energy and environmental issues, the possibility of pushing the reduction beyond the CO and formate level and catalytically generate products such as methanol is particularly attractive. Biomimetic 2e(-) + 2H(+) is often viewed as a potential hydride donor. This has been the object of a recent interesting attempt (J. Am. Chem. Soc. 2014, 136, 14007) in which 6,7-dimethyl-4-hydroxy-2-mercaptopteridine was reported as a catalyst of the electrochemical conversion of CO2 to methanol and formate, based on cyclic voltammetric, (13)C NMR, IR, and GC analyses. After checking electrolysis at the reported potential and at a more negative potential to speed up the reaction, it appears, on (1)H NMR and gas chromatographic grounds, that there is neither catalysis nor methanol and nor formate production. (1)H NMR (with H2O presaturation) brings about an unambiguous answer to the eventual production of methanol and formate, much more so than (13)C NMR, which can even be misleading when no internal standard is used as in the above-mentioned paper. IR analysis is even less conclusive. Use of a GC technique with sufficient sensitivity confirmed the lack of methanol formation. The direct or indirect hydride transfer electrochemical reduction of CO2 to formate and to methanol remains an open question. Original ideas and efforts such as those discussed here are certainly worth tempting. However, in view of the importance of the stakes, it appears necessary to carefully check reports in this area.

  6. Formate Formation and Formate Conversion in Biological Fuels Production

    Directory of Open Access Journals (Sweden)

    Bryan R. Crable

    2011-01-01

    Full Text Available Biomethanation is a mature technology for fuel production. Fourth generation biofuels research will focus on sequestering CO2 and providing carbon-neutral or carbon-negative strategies to cope with dwindling fossil fuel supplies and environmental impact. Formate is an important intermediate in the methanogenic breakdown of complex organic material and serves as an important precursor for biological fuels production in the form of methane, hydrogen, and potentially methanol. Formate is produced by either CoA-dependent cleavage of pyruvate or enzymatic reduction of CO2 in an NADH- or ferredoxin-dependent manner. Formate is consumed through oxidation to CO2 and H2 or can be further reduced via the Wood-Ljungdahl pathway for carbon fixation or industrially for the production of methanol. Here, we review the enzymes involved in the interconversion of formate and discuss potential applications for biofuels production.

  7. Enthalpies of formation of layered LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} (0 ≤ x ≤ 0.5) compounds as lithium ion battery cathode materials

    Energy Technology Data Exchange (ETDEWEB)

    Masoumi, Maryam; Cupid, Damian M.; Reichmann, Thomas L.; Seifert, Hans J. [Karlsruhe Institute of Technology, Eggenstein-Leopoldshafen (Germany). Inst. for Applied Materials - Applied Materials Physics; Chang, Keke; Music, Denis; Schneider, Jochen M. [RWTH Aachen Univ. (Germany). Materials Chemistry

    2017-11-15

    Layer-structured mixed transition metal oxides with the formula LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} (0 ≤ x ≤ 0.5) are considered as important cathode materials for lithium-ion batteries. In an effort to evaluate the relative thermodynamic stabilities of individual compositions in this series, the enthalpies of formation of selected stoichiometries are determined by high temperature oxide melt drop solution calorimetry and verified by ab-initio calculations. The measured and calculated data are in good agreement with each other, and the results show that LiCoO{sub 2}-LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} solid solution approaches ideal behavior. By increasing x, i.e. by equimolar substitution of Mn{sup 4+} and Ni{sup 2+} for Co{sup 3+}, the enthalpy of formation of LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} from the elements becomes more exothermic, implying increased energetic stability. This conclusion is in agreement with the literature results showing improved structural stability and cycling performance of Ni/Mn-rich LiNi{sub x}Mn{sub x}Co{sub 1-2x}O{sub 2} compounds cycled to higher cut-off voltages.

  8. Modeling and Simulation on NOx and N2O Formation in Co-combustion of Low-rank Coal and Palm Kernel Shell

    Directory of Open Access Journals (Sweden)

    Mahidin Mahidin

    2012-12-01

    Full Text Available NOx and N2O emissions from coal combustion are claimed as the major contributors for the acid rain, photochemical smog, green house and ozone depletion problems. Based on the facts, study on those emissions formation is interest topic in the combustion area. In this paper, theoretical study by modeling and simulation on NOx and N2O formation in co-combustion of low-rank coal and palm kernel shell has been done. Combustion model was developed by using the principle of chemical-reaction equilibrium. Simulation on the model in order to evaluate the composition of the flue gas was performed by minimization the Gibbs free energy. The results showed that by introduced of biomass in coal combustion can reduce the NOx concentration in considerably level. Maximum NO level in co-combustion of low-rank coal and palm kernel shell with fuel composition 1:1 is 2,350 ppm, low enough compared to single low-rank coal combustion up to 3,150 ppm. Moreover, N2O is less than 0.25 ppm in all cases. Keywords: low-rank coal, N2O emission, NOx emission, palm kernel shell

  9. How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

    Science.gov (United States)

    Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György

    2017-04-01

    Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an

  10. Inert-Gas Condensed Co-W Nanoclusters: Formation, Structure and Magnetic Properties

    Science.gov (United States)

    Golkar-Fard, Farhad Reza

    Rare-earth permanent magnets are used extensively in numerous technical applications, e.g. wind turbines, audio speakers, and hybrid/electric vehicles. The demand and production of rare-earth permanent magnets in the world has in the past decades increased significantly. However, the decrease in export of rare-earth elements from China in recent time has led to a renewed interest in developing rare-earth free permanent magnets. Elements such as Fe and Co have potential, due to their high magnetization, to be used as hosts in rare-earth free permanent magnets but a major challenge is to increase their magnetocrystalline anisotropy constant, K1, which largely drives the coercivity. Theoretical calculations indicate that dissolving the 5d transition metal W in Fe or Co increases the magnetocrystalline anisotropy. The challenge, though, is in creating a solid solution in hcp Co or bcc Fe, which under equilibrium conditions have negligible solubility. In this dissertation, the formation, structure, and magnetic properties of sub-10 nm Co-W clusters with W content ranging from 4 to 24 atomic percent were studied. Co-W alloy clusters with extended solubility of W in hcp Co were produced by inert gas condensation. The different processing conditions such as the cooling scheme and sputtering power were found to control the structural state of the as-deposited Co-W clusters. For clusters formed in the water-cooled formation chamber, the mean size and the fraction crystalline clusters increased with increasing power, while the fraction of crystalline clusters formed in the liquid nitrogen-cooled formation chamber was not as affected by the sputtering power. For the low W content clusters, the structural characterization revealed clusters predominantly single crystalline hcp Co(W) structure, a significant extension of W solubility when compared to the equilibrium solubility, but fcc Co(W) and Co3W structures were observed in very small and large clusters, respectively. At high

  11. Microstructure of buried CoSi2 layers formed by high-dose Co implantation into (100) and (111) Si substrates

    International Nuclear Information System (INIS)

    Bulle-Lieuwma, C.W.T.; Van Ommen, A.H.; Vandenhoudt, D.E.W.; Ottenheim, J.J.M.; de Jong, A.F.

    1991-01-01

    Heteroepitaxial Si/CoSi 2 /Si structures have been synthesized by implanting 170-keV Co + with doses in the range 1--3x10 17 Co + ions/cm 2 into (100) and (111) Si substrates and subsequent annealing. The microstructure of both the as-implanted and annealed structures is investigated in great detail by transmission electron microscopy, high-resolution electron microscopy, and x-ray diffraction. In the as-implanted samples, the Co is present as CoSi 2 precipitates, occurring both in aligned (A-type) and twinned (B-type) orientation. For the highest dose, a continuous layer of stoichiometric CoSi 2 is already formed during implantation. It is found that the formation of a connected layer, already during implantation, is crucial for the formation of a buried CoSi 2 layer upon subsequent annealing. Particular attention is given to the coordination of the interfacial Co atoms at the Si/CoSi 2 (111) interfaces of both types of precipitates. We find that the interfacial Co atoms at the A-type interfaces are fully sevenfold coordinated, whereas at the B-type interfaces they appear to be eightfold coordinated

  12. Regulator of G protein signaling 2 (RGS2 and RGS4 form distinct G protein-dependent complexes with protease activated-receptor 1 (PAR1 in live cells.

    Directory of Open Access Journals (Sweden)

    Sungho Ghil

    Full Text Available Protease-activated receptor 1 (PAR1 is a G-protein coupled receptor (GPCR that is activated by natural proteases to regulate many physiological actions. We previously reported that PAR1 couples to Gi, Gq and G12 to activate linked signaling pathways. Regulators of G protein signaling (RGS proteins serve as GTPase activating proteins to inhibit GPCR/G protein signaling. Some RGS proteins interact directly with certain GPCRs to modulate their signals, though cellular mechanisms dictating selective RGS/GPCR coupling are poorly understood. Here, using bioluminescence resonance energy transfer (BRET, we tested whether RGS2 and RGS4 bind to PAR1 in live COS-7 cells to regulate PAR1/Gα-mediated signaling. We report that PAR1 selectively interacts with either RGS2 or RGS4 in a G protein-dependent manner. Very little BRET activity is observed between PAR1-Venus (PAR1-Ven and either RGS2-Luciferase (RGS2-Luc or RGS4-Luc in the absence of Gα. However, in the presence of specific Gα subunits, BRET activity was markedly enhanced between PAR1-RGS2 by Gαq/11, and PAR1-RGS4 by Gαo, but not by other Gα subunits. Gαq/11-YFP/RGS2-Luc BRET activity is promoted by PAR1 and is markedly enhanced by agonist (TFLLR stimulation. However, PAR1-Ven/RGS-Luc BRET activity was blocked by a PAR1 mutant (R205A that eliminates PAR1-Gq/11 coupling. The purified intracellular third loop of PAR1 binds directly to purified His-RGS2 or His-RGS4. In cells, RGS2 and RGS4 inhibited PAR1/Gα-mediated calcium and MAPK/ERK signaling, respectively, but not RhoA signaling. Our findings indicate that RGS2 and RGS4 interact directly with PAR1 in Gα-dependent manner to modulate PAR1/Gα-mediated signaling, and highlight a cellular mechanism for selective GPCR/G protein/RGS coupling.

  13. Degradation of vinasse in soil under different humidity levels: CO sub 2 liberation, microbial biomass formation and immobilization of added nitrogen. Decomposicao de vinhaca em solo sob diferentes niveis de umidade: liberacao de CO sub 2 , formacao de biomassa microbiana e imobilizacao do nitrogenio adicionado

    Energy Technology Data Exchange (ETDEWEB)

    Minhoni, M T.A. [UNESP, Botucatu, SP (Brazil). Dept. de Defesa Fitossanitaria; Cerri, C C [Centro de Energia Nuclear na Agricultura (CENA), Piracicaba, SP (Brazil)

    1987-01-01

    Degradation of vinasse added to a sandy Red-Yellow Latosol at the rate of 200m{sup 3}/ha and kept at 40,60 and 80% of the holding capacity (w.h.c.), was studied and compared for liberation of CO{sub 2}, formation of microbial biomass and immobilization of nitrogen added. The CO{sub 2} liberated was evaluated by NaOH retention followed by titration with HCl. The microbial biomass was determined by using gamma radiation as biocide. Nitrogen immobilization was determined using the Kjeldahl method and {sup 15}N enrichment according to Rittemberg's method. Soil moisture, which affected the oxygen level of the soil, had a significant influence in CO{sub 2} liberation, formation of microbial biomassa and nitrogen immobilization. Samples kept under drier conditions (40% w.h.c.) showed initially greater Co{sub 2} liberation. However, at the end of 3 month incubation period, total carbon evolved was similar at all misture levels used, with an average of 3805{mu}g C/g soil. The microbial biomass showed greater formation for the drier samples (40% w.h.c.), reaching a maximum of 519{mu}g C/g soil. Immobilization of the N added showed an increasing initial rate, which was greater with dryness of the soil, followed by stabilization. Nevertheless, at the end of 3 month incubation period, the percentages of immobilization were similar and about 40% of total {sup 15}N irrespective of the soil moisture content. Therefore, the increasing rate of carbon assimilation was not totally acompanied by an increasing immobilization for the N added. The greatest intensity was reached by CO{sub 2} liberation in residue degradation, 2/3 of the carbon having evolved to CO{sub 2} and than 1/3 having been immobilized by the microbial biomass. (author).

  14. Alteration of bentonite when contacted with supercritical CO2

    Science.gov (United States)

    Jinseok, K.; Jo, H. Y.; Yun, S. T.

    2014-12-01

    Deep saline formations overlaid by impermeable caprocks with a high sealing capacity are attractive CO2 storage reservoirs. Shales, which consist of mainly clay minerals, are potential caprocks for the CO2 storage reservoirs. The properties of clay minerals in shales may affect the sealing capacity of shales. In this study, changes in clay minerals' properties when contacted with supercritical (SC) CO2 at various conditions were investigated. Bentonite, whichis composed of primarily montmorillonite, was used as the clay material in this study. Batch reactor tests on wet bentonite samples in the presence of SC CO2 with or without aqueous phases were conducted at high pressure (12 MPa) and moderate temperature (50 oC) conditions for a week. Results show that the bentonite samples obtained from the tests with SC CO2 had less change in porosity than those obtained from the tests without SC CO2 (vacuum-drying) at a given reaction time, indicating that the bentonite samples dried in the presence of SC CO2 maintained their structure. These results suggest that CO2 molecules can diffuse into interlayer of montmorillonite, which is a primary mineral of bentonite, and form a single CO2 molecule layer or double CO2 molecule layers. The CO2 molecules can displace water molecules in the interlayer, resulting in maintaining the interlayer spacing when dehydration occurs. Noticeable changes in reacted bentonite samples obtained from the tests with an aqueous phase (NaCl, CaCl2, or sea water) are decreases in the fraction of plagioclase and pyrite and formation of carbonate minerals (i.e., calcite and dolomite) and halite. In addition, no significant exchanges of Na or Ca on the exchangeable complex of the montmorillonite in the presence of SC CO2 occurred, resulting in no significant changes in the swelling capacity of bentonite samples after reacting with SC CO2 in the presence of aqueous phases. These results might be attributed by the CO2 molecule layer, which prevents

  15. Corrosion of N80 carbon steel in oil field formation water containing CO2 in the absence and presence of acetic acid

    International Nuclear Information System (INIS)

    Zhu, S.D.; Fu, A.Q.; Miao, J.; Yin, Z.F.; Zhou, G.S.; Wei, J.F.

    2011-01-01

    Highlights: → Effects of temperature and HAc concentration on N80 carbon steel were investigated. → Temperature increased corrosion rate of N80 and precipitation rate of FeCO 3 . → HAc increased corrosion rate of N80 and enhanced the local corrosion attack (pitting). → FeCO 3 was still the main composition of corrosion products in the presence of HAc. → There was a transition region between CO 2 corrosion control and HAc corrosion control. - Abstract: Corrosion behaviour of N80 carbon steel in formation water containing CO 2 was studied by polarization curve technique, electrochemical impedance spectroscopy, weight loss test, scanning electron microscope, and X-ray diffraction. Effects of temperature and acetic acid concentration on the corrosion behaviour of N80 carbon steel were discussed. The results showed that increasing temperature not only enhanced the dissolution of steel substrate, but also promoted the precipitation of FeCO 3 , the addition of acetic acid enhanced localized corrosion attack on N80 carbon steel. FeCO 3 was the main corrosion product. And there was a transition region between CO 2 corrosion control and HAc corrosion control.

  16. The electrochemical selective reduction of NO using CoSe2@CNTs hybrid.

    Science.gov (United States)

    Liu, Hui; Xiang, Kaisong; Yang, Bentao; Xie, Xiaofeng; Wang, Dongli; Zhang, Cong; Liu, Zhilou; Yang, Shu; Liu, Cao; Zou, Jianping; Chai, Liyuan

    2017-06-01

    Converting the NO from gaseous pollutant into NH 4 + through electrocatalytical reduction using cost-effective materials holds great promise for pollutant purifying and resources recycling. In this work, we developed a highly selective and stable catalyst CoSe 2 nanoparticle hybridized with carbon nanotubes (CoSe 2 @CNTs). The CoSe 2 @CNTs hybrid catalysts performed an extraordinary high selectivity for NH 4 + formation in NO electroreduction with minimal N 2 O production and H 2 evolution. The specific spatial structure of CoSe 2 is conductive to the predominant formation of N-H bond between the N from adsorbed NO and H and inhibition of N-N formation from adjacent adsorbed NO. It was also the first time to convert the coordinated NO into NH 4 + using non-noble metal catalysis. Moreover, the original concept of employing CoSe 2 as eletrocatalyst for NO hydrogenation presented in this work can broaden horizons and provide new dimensions in the design of new highly efficient catalysts for NH 4 + synthesis in aqueous solution.

  17. Formation of Glycerol through Hydrogenation of CO Ice under Prestellar Core Conditions

    Science.gov (United States)

    Fedoseev, G.; Chuang, K.-J.; Ioppolo, S.; Qasim, D.; van Dishoeck, E. F.; Linnartz, H.

    2017-06-01

    Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, I.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic-ray-induced UV photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via nonenergetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the “CO freeze-out stage” in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol—HOCH2CH(OH)CH2OH—a three-carbon-bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical-radical and radical-molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde—HOCH2CH(OH)CHO—is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars.

  18. A Multi-scale Approach for CO2 Accounting and Risk Analysis in CO2 Enhanced Oil Recovery Sites

    Science.gov (United States)

    Dai, Z.; Viswanathan, H. S.; Middleton, R. S.; Pan, F.; Ampomah, W.; Yang, C.; Jia, W.; Lee, S. Y.; McPherson, B. J. O. L.; Grigg, R.; White, M. D.

    2015-12-01

    Using carbon dioxide in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce carbon sequestration costs in the absence of greenhouse gas emissions policies that include incentives for carbon capture and storage. This study develops a multi-scale approach to perform CO2 accounting and risk analysis for understanding CO2 storage potential within an EOR environment at the Farnsworth Unit of the Anadarko Basin in northern Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil-water flow and transport in the Marrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2 injection rate, CO2 first breakthrough time, CO2 production rate, cumulative net CO2 storage, cumulative oil and CH4 production, and water injection and production rates. A global sensitivity analysis indicates that reservoir permeability, porosity, and thickness are the major intrinsic reservoir parameters that control net CO2 injection/storage and oil/CH4 recovery rates. The well spacing (the distance between the injection and production wells) and the sequence of alternating CO2 and water injection are the major operational parameters for designing an effective five-spot CO2-EOR pattern. The response surface analysis shows that net CO2 injection rate increases with the increasing reservoir thickness, permeability, and porosity. The oil/CH4 production rates are positively correlated to reservoir permeability, porosity and thickness, but negatively correlated to the initial water saturation. The mean and confidence intervals are estimated for quantifying the uncertainty ranges of the risk metrics. The results from this study provide useful insights for understanding the CO2 storage potential and the corresponding risks of commercial-scale CO2-EOR fields.

  19. Natural CO2 Analogs for Carbon Sequestration

    Energy Technology Data Exchange (ETDEWEB)

    Scott H. Stevens; B. Scott Tye

    2005-07-31

    The report summarizes research conducted at three naturally occurring geologic CO{sub 2} fields in the US. The fields are natural analogs useful for the design of engineered long-term storage of anthropogenic CO{sub 2} in geologic formations. Geologic, engineering, and operational databases were developed for McElmo Dome in Colorado; St. Johns Dome in Arizona and New Mexico; and Jackson Dome in Mississippi. The three study sites stored a total of 2.4 billion t (46 Tcf) of CO{sub 2} equivalent to 1.5 years of power plant emissions in the US and comparable in size with the largest proposed sequestration projects. The three CO{sub 2} fields offer a scientifically useful range of contrasting geologic settings (carbonate vs. sandstone reservoir; supercritical vs. free gas state; normally pressured vs. overpressured), as well as different stages of commercial development (mostly undeveloped to mature). The current study relied mainly on existing data provided by the CO{sub 2} field operator partners, augmented with new geochemical data. Additional study at these unique natural CO{sub 2} accumulations could further help guide the development of safe and cost-effective design and operation methods for engineered CO{sub 2} storage sites.

  20. Solubility of NaNd(CO3)2.6H2O(c) in concentrated Na2CO3 and NaHCO3 solutions

    International Nuclear Information System (INIS)

    Rao, L.; Rai, D.; Felmy, A.R.; Fulton, R.W.; Novak, C.F.

    1996-01-01

    NaNd(CO 3 ) 2 x 6 H 2 O(c) was identified to be the final equilibrium solid phase in suspensions containing concentrated sodium carbonate (0.1 to 2.0 M) and sodium bicarbonate (0.1 to 1.0 M), with either NaNd(CO 3 ) 2 x 6 H 2 O(c) or Nd 2 (CO 3 ) 3 x xH 2 O(s) as initial solids. A thermodynamic model, based on Pitzer's specific into-interaction approach, was developed to interpret the solubility of NaNd(CO 3 ) 2 x 6 H 2 O(c) as functions of sodium carbonate and sodium bicarbonate concentrations. In this model, the solubility data of NaNd(CO 3 ) 2 x 6 H 2 O(c) were explained by assuming the formation of NdCO 3 + , Nd(CO 3 ) 2 - and Nd(CO 3 ) 3 3- species and invoking the specific ion interactions between Na + and Nd(CO 3 ) 3 3- . Ion interaction parameters for Na + -Nd(CO 3 ) 3 3- were developed to fit the solubility data. Based on the model calculations, Nd(CO 3 ) 3 3- was the predominant aqueous neodymium species in 0.1 to 2 M sodium carbonate and 0.1 to 1 M sodium bicarbonate solutions. The logarithm of the NaNd(CO 3 ) 2 x 6 H 2 O solubility product (NaNd(CO 3 ) 2 x 6 H 2 O(c)=Na + +Nd 3+ +2 CO 3 2- +6 H 2 O) was calculated to be -21.39. This model also provided satisfactory interpretation of the solubility data of the analogous Am(III) system in less concentrated carbonate and bicarbonate solutions. (orig.)

  1. Southern Adriatic sea as a potential area for CO2 geological storage

    International Nuclear Information System (INIS)

    Volpi, V.; Forlin, F.; Donda, F.; Civile, D.; Facchin, L.; Sauli, L.; Merson, B.; Sinza-Mendieta, K.; Shams, A.

    2015-01-01

    The Southern Adriatic Sea is one of the five prospective areas for CO 2 storage being evaluated under the three year (FP7) European SiteChar project dedicated to the characterization of European CO 2 storage sites. The potential reservoir for CO 2 storage is represented by a carbonate formation, the wackstones and packstones of the Scaglia Formation (Upper Cretaceous-Paleogene). In this paper, we present the geological characterization and the 3D modeling that led to the identification of three sites, named Grazia, Rovesti and Grifone, where the Scaglia Formation, with an average thickness of 50 m, reveals good petrophysical characteristics and is overlain by an up to 1 200 thick cap-rock. The vicinity of the selected sites to the Enel - Federico II power plant (one of the major Italian CO 2 emitter) where a pilot plant for CO 2 capture has been already started in April 2010, represents a good opportunity to launch the first Carbon Capture and Storage (CCS) pilot project in Italy and to apply this technology at industrial level, strongly contributing at the same time at reducing the national CO 2 emissions. (authors)

  2. Prediction of CO2 leakage during sequestration into marine sedimentary strata

    International Nuclear Information System (INIS)

    Li, Qi; Wu Zhishen; Li Xiaochun

    2009-01-01

    Deep ocean storage of CO 2 could help reduce the atmospheric level of greenhouse gas as part of a climate change mitigation strategy. In this paper, a multiphase flow model of CO 2 sequestration into deep ocean sediments was designed associated with the formation of CO 2 hydrates. A simplified assumption was proposed to predict the critical time of CO 2 leakage from marine sedimentary strata into seawater. Moreover, some principal parameters, which include the permeability, anisotropy, total injection amount, and length of the injection part of wellbores, were investigated by numerical simulations. The numerical estimates are used to assess the feasibility and effectiveness of CO 2 storage in deep ocean sediments. Accurately predicting the actual fate of liquid CO 2 sequestered into the marine sedimentary strata at depths greater than 500 m is complicated by uncertainties associated with not only the chemical-physical behavior of CO 2 under such conditions but also the geo-environment of disposal sites. Modeling results have shown some implications that the effectiveness of CO 2 ocean sequestration depends mainly on the injection conditions (such as injection rate, total injection amount, and the depth of injection), the site geology (such as permeability and anisotropy of disposal formations), and the chemical-physical behavior of CO 2 in marine environment

  3. Impact of elevated CO_2 concentrations on carbonate mineral precipitation ability of sulfate-reducing bacteria and implications for CO_2 sequestration

    International Nuclear Information System (INIS)

    Paul, Varun G.; Wronkiewicz, David J.; Mormile, Melanie R.

    2017-01-01

    Interest in anthropogenic CO_2 release and associated global climatic change has prompted numerous laboratory-scale and commercial efforts focused on capturing, sequestering or utilizing CO_2 in the subsurface. Known carbonate mineral precipitating microorganisms, such as the anaerobic sulfate-reducing bacteria (SRB), could enhance the rate of conversion of CO_2 into solid minerals and thereby improve long-term storage of captured gasses. The ability of SRB to induce carbonate mineral precipitation, when exposed to atmospheric and elevated pCO_2, was investigated in laboratory scale tests with bacteria from organic-rich sediments collected from hypersaline Lake Estancia, New Mexico. The enriched SRB culture was inoculated in continuous gas flow and batch reactors under variable headspace pCO_2 (0.0059 psi to 20 psi). Solution pH, redox conditions, sulfide, calcium and magnesium concentrations were monitored in the reactors. Those reactors containing SRB that were exposed to pCO_2 of 14.7 psi or less showed Mg-calcite precipitation. Reactors exposed to 20 psi pCO_2 did not exhibit any carbonate mineralization, likely due to the inhibition of bacterial metabolism caused by the high levels of CO_2. Hydrogen, lactate and formate served as suitable electron donors for the SRB metabolism and related carbonate mineralization. Carbon isotopic studies confirmed that ∼53% of carbon in the precipitated carbonate minerals was derived from the CO_2 headspace, with the remaining carbon being derived from the organic electron donors, and the bicarbonate ions available in the liquid medium. The ability of halotolerant SRB to induce the precipitation of carbonate minerals can potentially be applied to the long-term storage of anthropogenic CO_2 in saline aquifers and other ideal subsurface rock units by converting the gas into solid immobile phases. - Highlights: • SRB under study are capable of precipitating calcite up to 14.7 psi pCO_2. • At 20 psi pCO_2, bacterial activity

  4. International Symposium on Site Characterization for CO2Geological Storage

    Energy Technology Data Exchange (ETDEWEB)

    Tsang, Chin-Fu

    2006-02-23

    Several technological options have been proposed to stabilize atmospheric concentrations of CO{sub 2}. One proposed remedy is to separate and capture CO{sub 2} from fossil-fuel power plants and other stationary industrial sources and to inject the CO{sub 2} into deep subsurface formations for long-term storage and sequestration. Characterization of geologic formations for sequestration of large quantities of CO{sub 2} needs to be carefully considered to ensure that sites are suitable for long-term storage and that there will be no adverse impacts to human health or the environment. The Intergovernmental Panel on Climate Change (IPCC) Special Report on Carbon Dioxide Capture and Storage (Final Draft, October 2005) states that ''Site characterization, selection and performance prediction are crucial for successful geological storage. Before selecting a site, the geological setting must be characterized to determine if the overlying cap rock will provide an effective seal, if there is a sufficiently voluminous and permeable storage formation, and whether any abandoned or active wells will compromise the integrity of the seal. Moreover, the availability of good site characterization data is critical for the reliability of models''. This International Symposium on Site Characterization for CO{sub 2} Geological Storage (CO2SC) addresses the particular issue of site characterization and site selection related to the geologic storage of carbon dioxide. Presentations and discussions cover the various aspects associated with characterization and selection of potential CO{sub 2} storage sites, with emphasis on advances in process understanding, development of measurement methods, identification of key site features and parameters, site characterization strategies, and case studies.

  5. Shape-Dependent Electrocatalytic Reduction of CO2 to CO on Triangular Silver Nanoplates.

    Science.gov (United States)

    Liu, Subiao; Tao, Hongbiao; Zeng, Li; Liu, Qi; Xu, Zhenghe; Liu, Qingxia; Luo, Jing-Li

    2017-02-15

    Electrochemical reduction of CO 2 (CO 2 RR) provides great potential for intermittent renewable energy storage. This study demonstrates a predominant shape-dependent electrocatalytic reduction of CO 2 to CO on triangular silver nanoplates (Tri-Ag-NPs) in 0.1 M KHCO 3 . Compared with similarly sized Ag nanoparticles (SS-Ag-NPs) and bulk Ag, Tri-Ag-NPs exhibited an enhanced current density and significantly improved Faradaic efficiency (96.8%) and energy efficiency (61.7%), together with a considerable durability (7 days). Additionally, CO starts to be observed at an ultralow overpotential of 96 mV, further confirming the superiority of Tri-Ag-NPs as a catalyst for CO 2 RR toward CO formation. Density functional theory calculations reveal that the significantly enhanced electrocatalytic activity and selectivity at lowered overpotential originate from the shape-controlled structure. This not only provides the optimum edge-to-corner ratio but also dominates at the facet of Ag(100) where it requires lower energy to initiate the rate-determining step. This study demonstrates a promising approach to tune electrocatalytic activity and selectivity of metal catalysts for CO 2 RR by creating optimal facet and edge site through shape-control synthesis.

  6. Optimization of CO2 Storage in Saline Aquifers Using Water-Alternating Gas (WAG) Scheme - Case Study for Utsira Formation

    Science.gov (United States)

    Agarwal, R. K.; Zhang, Z.; Zhu, C.

    2013-12-01

    For optimization of CO2 storage and reduced CO2 plume migration in saline aquifers, a genetic algorithm (GA) based optimizer has been developed which is combined with the DOE multi-phase flow and heat transfer numerical simulation code TOUGH2. Designated as GA-TOUGH2, this combined solver/optimizer has been verified by performing optimization studies on a number of model problems and comparing the results with brute-force optimization which requires a large number of simulations. Using GA-TOUGH2, an innovative reservoir engineering technique known as water-alternating-gas (WAG) injection has been investigated to determine the optimal WAG operation for enhanced CO2 storage capacity. The topmost layer (layer # 9) of Utsira formation at Sleipner Project, Norway is considered as a case study. A cylindrical domain, which possesses identical characteristics of the detailed 3D Utsira Layer #9 model except for the absence of 3D topography, was used. Topographical details are known to be important in determining the CO2 migration at Sleipner, and are considered in our companion model for history match of the CO2 plume migration at Sleipner. However, simplification on topography here, without compromising accuracy, is necessary to analyze the effectiveness of WAG operation on CO2 migration without incurring excessive computational cost. Selected WAG operation then can be simulated with full topography details later. We consider a cylindrical domain with thickness of 35 m with horizontal flat caprock. All hydrogeological properties are retained from the detailed 3D Utsira Layer #9 model, the most important being the horizontal-to-vertical permeability ratio of 10. Constant Gas Injection (CGI) operation with nine-year average CO2 injection rate of 2.7 kg/s is considered as the baseline case for comparison. The 30-day, 15-day, and 5-day WAG cycle durations are considered for the WAG optimization design. Our computations show that for the simplified Utsira Layer #9 model, the

  7. Growth of CoSi2 on Si(001) by reactive deposition epitaxy

    International Nuclear Information System (INIS)

    Lim, C.W.; Shin, C.-S.; Gall, D.; Zuo, J.M.; Petrov, I.; Greene, J.E.

    2005-01-01

    CaF 2 -structure CoSi 2 layers were formed on Si(001) by reactive deposition epitaxy (RDE) and compared with CoSi 2 layers obtained by conventional solid phase growth (SPG). In both sets of experiments, Co was deposited by ultrahigh-vacuum magnetron sputtering and CoSi 2 formed at 600 deg. C. However, in the case of RDE, CoSi 2 formation occurred during Co deposition while for SPG, Co was deposited at 25 deg. C and silicidation took place during subsequent annealing. X-ray diffraction pole figures and transmission electron microscopy results demonstrate that RDE CoSi 2 layers are epitaxial with a cube-on-cube relationship (001) CoSi 2 parallel (001) Si and [100] CoSi 2 parallel[100] Si . In contrast, SPG films are polycrystalline with an average grain size of ≅1000 A and a mixed 111/002/022/112 orientation. We attribute the striking difference to rapid Co diffusion into the Si(001) substrate during RDE for which the high Co/Si reactivity gives rise to a flux-limited reaction resulting in the direct formation of the disilicide phase. In contrast, sequential nucleation and transformation among increasingly Si-rich phases--from orthorhombic Co 2 Si to cubic CoSi to CoSi 2 --during SPG results in polycrystalline layers with a complex texture

  8. Topotactic synthesis of Co3O4 nanoboxes from Co(OH)2 nanoflakes

    International Nuclear Information System (INIS)

    Tian Li; Huang Kelong; Liu Younian; Liu Suqin

    2011-01-01

    Hollow nanocubes of spinel Co 3 O 4 with the dimension of 20 nm were successfully prepared via a facile and reproducible solvothermal route. The structure and morphology of Co 3 O 4 nanoboxes were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and high-resolution transmission electron microscope (HRTEM) techniques. And a possible growth mechanism of Co 3 O 4 nanoboxes were suggested that solid Co 3 O 4 nanocubes nucleate in-situ and grow epitaxially from hexagonal β-Co(OH) 2 precursors with the structural matching relationship of [0 0 1] β-Co(OH) 2 //[1 1 1] Co 3 O 4 , and then solid Co 3 O 4 nanocubes gradually hollow and convert to single-crystal nanoboxes owing to Ostwald ripening. - Graphical abstract: The formation mechanism of Co 3 O 4 nanoboxes can be expressed as epitaxial growth of Co 3 O 4 nanocubes from β-Co(OH) 2 nanoflakes due to a topotactic transformation and hollowing process owing to Ostwald ripening. Highlights: → Co 3 O 4 nanoboxes were prepared by a convenient, economical and controllable hydrothermal route. → Morphology and structure of Co 3 O 4 nanoboxes were characterized by XRD, SEM, and TEM techniques. → Co 3 O 4 nanoboxes grow epitaxially from Co(OH) 2 by topotactic transformation was suggested.

  9. Carbon balance of CO2-EOR for NCNO classification

    Energy Technology Data Exchange (ETDEWEB)

    Nunez-Lopez, Vanessa [The University of Texas at Austin; Gil-Egui, Ramon; Gonzalez-Nicolas, Ana; Hovorka, Susan D

    2017-03-18

    The question of whether carbon dioxide enhanced oil recovery (CO2-EOR) constitutes a valid alternative for greenhouse gas emission reduction has been frequently asked by the general public and environmental sectors. Through this technology, operational since 1972, oil production is enhanced by injecting CO2 into depleted oil reservoirs in order displace the residual oil toward production wells in a solvent/miscible process. For decades, the CO2 utilized for EOR has been most commonly sourced from natural CO2 accumulations. More recently, a few projects have emerged where anthropogenic CO2 (A-CO2) is captured at an industrial facility, transported to a depleted oil field, and utilized for EOR. If carbon geologic storage is one of the project objectives, all the CO2 injected into the oil field for EOR could technically be stored in the formation. Even though the CO2 is being prevented from entering the atmosphere, and permanently stored away in a secured geologic formation, a question arises as to whether the total CO2 volumes stored in order to produce the incremental oil through EOR are larger than the CO2 emitted throughout the entire CO2-EOR process, including the capture facility, the EOR site, and the refining and burning of the end product. We intend to answer some of these questions through a DOE-NETL funded study titled “Carbon Life Cycle Analysis of CO2-EOR for Net Carbon Negative Oil (NCNO) Classification”. NCNO is defined as oil whose carbon emissions to the atmosphere, when burned or otherwise used, are less than the amount of carbon permanently stored in the reservoir in order to produce the oil. In this paper, we focus on the EOR site in what is referred to as a gate-to-gate system, but are inclusive of the burning of the refined product, as this end member is explicitly stated in the definition of NCNO. Finally, we use Cranfield, Mississippi, as a case study and come to the conclusion that the incremental oil produced is net carbon negative.

  10. Chambers versus Relaxed Eddy Accumulation: an intercomparison study of two methods for short-term measurements of biogenic CO2 fluxes

    Science.gov (United States)

    Jasek, Alina; Zimnoch, Miroslaw; Gorczyca, Zbigniew; Chmura, Lukasz; Necki, Jaroslaw

    2014-05-01

    The presented work is a part of comprehensive study aimed at thorough characterization of carbon cycle in the urban environment of Krakow, southern Poland. In the framework of this study two independent methods were employed to quantify biogenic CO2 flux in the city: (i) closed chambers, and (ii) Relaxed Eddy Accumulation (REA). The results of a three-day intensive intercomparison campaign performed in July 2013 and utilizing both measurement methods are reported here. The chamber method is a widely used approach for measurements of gas exchange between the soil and the atmosphere. The system implemented in this study consisted of a single chamber operating in a closed-dynamic mode, combined with Vaisala CarboCAP infrared CO2 sensor in a mobile setup. An alternative flux measurement method, covering larger area is represented by REA, which is a modification of the eddy covariance method. It consists of a 3D anemometer (Gill Windmaster Pro) and the system collecting updraft and downdraft samples to 5-litre Tedlar bags. The CO2 mixing ratios in the collected samples are measured by Picarro G2101i analyzer. The setup consists of two sets of bags so that the sampling can be performed continuously with 15-min temporal resolution. A 48-hectares open meadow located close the city center was chosen as a test site for comparison of the two methods of CO2 flux measurements outlined above. In the middle of the meadow a 3-metre high tripod was installed with the anemometer and REA inlet system. For a period of 46 hours the system was measuring net CO2 flux from the surrounding area. A meteorological conditions and intensity of photosynthetically active radiation (PAR) were also recorded. In the same time, CO2 flux from several points around the REA inlet was measured with the chamber system, resulting in 93 values for both respiration and net CO2 flux. Chamber results show rather homogenous distribution of the soil CO2 flux (the mean value equal to 40.9 ± 2.2 mmol/m2h), with

  11. In vitro and in vivo inhibition of proangiogenic retinal phenotype by an antisense oligonucleotide downregulating uPAR expression.

    Science.gov (United States)

    Lulli, Matteo; Cammalleri, Maurizio; Granucci, Irene; Witort, Ewa; Bono, Silvia; Di Gesualdo, Federico; Lupia, Antonella; Loffredo, Rosa; Casini, Giovanni; Dal Monte, Massimo; Capaccioli, Sergio

    2017-08-26

    Neoangiogenesis is the main pathogenic event involved in a variety of retinal diseases. It has been recently demonstrated that inhibiting the urokinase-type plasminogen activator receptor (uPAR) results in reduced angiogenesis in a mouse model of oxygen-induced retinopathy (OIR), establishing uPAR as a therapeutic target in proliferative retinopathies. Here, we evaluated in cultured human retinal endothelial cells (HRECs) and in OIR mice the potential of a specific antisense oligodeoxyribonucleotide (ASO) in blocking the synthesis of uPAR and in providing antiangiogenic effects. uPAR expression in HRECs was inhibited by lipofection with the phosphorotioated 5'-CGGCGGGTGACCCATGTG-3' ASO-uPAR, complementary to the initial translation site of uPAR mRNA. Inhibition of uPAR expression via ASO-uPAR was evaluated in HRECs by analyzing VEGF-induced tube formation and migration. In addition, the well-established and reproducible murine OIR model was used to induce retinal neovascularization in vivo. OIR mice were injected intraperitoneally with ASO-uPAR and retinopathy was evaluated considering the extent of the avascular area in the central retina and neovascular tuft formation. The ASO-uPAR specifically decreased uPAR mRNA and protein levels in HRECs and mitigated VEGF-induced tube formation and cell migration. Noteworthy, in OIR mice ASO-uPAR administration reduced both the avascular area and the formation of neovascular tufts. In conclusion, although the extrapolation of these experimental findings to the clinic is not straightforward, ASO-uPAR may be considered a potential therapeutic tool for treatment of proliferative retinal diseases. Copyright © 2017 Elsevier Inc. All rights reserved.

  12. The effect of the substitution of D{sub 2}O for H{sub 2}O on the degradation of myosin {beta} in solution by heat and by {sup 60}Co {gamma} radiation (1962); Effet de la substitution de D{sub 2}O a H{sub 2}O sur l'alteration de la Myosine B en solution par la chaleur et par les rayons {gamma} du {sup 60}CO (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Pinset-Harstrom, I.; Fritsch, A. [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-07-01

    (1) Alterations of myosin B produced by heat or irradiation are shown to be qualitatively identical as demonstrated by analytical centrifugation. (2) A considerable isotope effect was demonstrated using 75 per cent D{sub 2}O in the solvent. The sensitivity of myosin B to heat and irradiation is discussed in the light of this isotope effect. (3) Polymers appearing upon heat treatment of myosin B seem to be of a very different nature than the polymers occurring alter a similar treatment upon myosin A. Polymers obtained from myosin B can be depolymerized by ATP and they appear in a much narrower temperature range than myosin A polymers. This fact indicates a considerable difference in the activation enthalpies in the two reactions. (authors) [French] (1) Cette etude montre que les alterations de la myosine B provoquees par la chaleur et par l'irradiation aux rayons {gamma} sont - telles qu'elles apparaissent a l'ultracentrifugation analytique - qualitativement semblables. (2) Nous avons observe un effet isotopique considerable de la presence de 75 pour cent de D{sub 2}O dans le solvant sur la sensibilite de la myosine B envers ces deux agents, et nous avons presente une tentative d'explication de ce fait. (3) Les polymeres qui apparaissent apres un traitement par la chaleur de la myosine semblent etre d'une nature tres differente des polymeres que l'on voit apparaitre apres un traitement identique de la myosine A. Ceux obtenus a partir de le myosine B sont depolymerisables par l'intermediaire de l'ATP et apparaissent dans une zone de temperature beaucoup plus etroite que celles de la myosine A. Ce dernier fait indique une difference considerable de l'enthalpie d'activation des deux reactions. (auteurs)

  13. The effect of the substitution of D{sub 2}O for H{sub 2}O on the degradation of myosin {beta} in solution by heat and by {sup 60}Co {gamma} radiation (1962); Effet de la substitution de D{sub 2}O a H{sub 2}O sur l'alteration de la Myosine B en solution par la chaleur et par les rayons {gamma} du {sup 60}CO (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Pinset-Harstrom, I; Fritsch, A [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-07-01

    (1) Alterations of myosin B produced by heat or irradiation are shown to be qualitatively identical as demonstrated by analytical centrifugation. (2) A considerable isotope effect was demonstrated using 75 per cent D{sub 2}O in the solvent. The sensitivity of myosin B to heat and irradiation is discussed in the light of this isotope effect. (3) Polymers appearing upon heat treatment of myosin B seem to be of a very different nature than the polymers occurring alter a similar treatment upon myosin A. Polymers obtained from myosin B can be depolymerized by ATP and they appear in a much narrower temperature range than myosin A polymers. This fact indicates a considerable difference in the activation enthalpies in the two reactions. (authors) [French] (1) Cette etude montre que les alterations de la myosine B provoquees par la chaleur et par l'irradiation aux rayons {gamma} sont - telles qu'elles apparaissent a l'ultracentrifugation analytique - qualitativement semblables. (2) Nous avons observe un effet isotopique considerable de la presence de 75 pour cent de D{sub 2}O dans le solvant sur la sensibilite de la myosine B envers ces deux agents, et nous avons presente une tentative d'explication de ce fait. (3) Les polymeres qui apparaissent apres un traitement par la chaleur de la myosine semblent etre d'une nature tres differente des polymeres que l'on voit apparaitre apres un traitement identique de la myosine A. Ceux obtenus a partir de le myosine B sont depolymerisables par l'intermediaire de l'ATP et apparaissent dans une zone de temperature beaucoup plus etroite que celles de la myosine A. Ce dernier fait indique une difference considerable de l'enthalpie d'activation des deux reactions. (auteurs)

  14. Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

    Science.gov (United States)

    Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

    2018-02-01

    Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

  15. Supercritical CO2 uptake by nonswelling phyllosilicates.

    Science.gov (United States)

    Wan, Jiamin; Tokunaga, Tetsu K; Ashby, Paul D; Kim, Yongman; Voltolini, Marco; Gilbert, Benjamin; DePaolo, Donald J

    2018-01-30

    Interactions between supercritical (sc) CO 2 and minerals are important when CO 2 is injected into geologic formations for storage and as working fluids for enhanced oil recovery, hydraulic fracturing, and geothermal energy extraction. It has previously been shown that at the elevated pressures and temperatures of the deep subsurface, scCO 2 alters smectites (typical swelling phyllosilicates). However, less is known about the effects of scCO 2 on nonswelling phyllosilicates (illite and muscovite), despite the fact that the latter are the dominant clay minerals in deep subsurface shales and mudstones. Our studies conducted by using single crystals, combining reaction (incubation with scCO 2 ), visualization [atomic force microscopy (AFM)], and quantifications (AFM, X-ray photoelectron spectroscopy, X-ray diffraction, and off-gassing measurements) revealed unexpectedly high CO 2 uptake that far exceeded its macroscopic surface area. Results from different methods collectively suggest that CO 2 partially entered the muscovite interlayers, although the pathways remain to be determined. We hypothesize that preferential dissolution at weaker surface defects and frayed edges allows CO 2 to enter the interlayers under elevated pressure and temperature, rather than by diffusing solely from edges deeply into interlayers. This unexpected uptake of CO 2 , can increase CO 2 storage capacity by up to ∼30% relative to the capacity associated with residual trapping in a 0.2-porosity sandstone reservoir containing up to 18 mass % of illite/muscovite. This excess CO 2 uptake constitutes a previously unrecognized potential trapping mechanism. Copyright © 2018 the Author(s). Published by PNAS.

  16. Possible impacts of CO2 storage on the marine environment

    International Nuclear Information System (INIS)

    Poremski, H.J.

    2005-01-01

    This study examined the potential impacts of deep-sea carbon dioxide (CO 2 ) sequestration on the marine environment. The upper layers of oceans are currently saturated with CO 2 , while deeper ocean waters remain undersaturated. Arctic and Antarctic waters have higher uptake rates of CO 2 due to their lower temperatures. CO 2 deposited in Arctic and Antarctic waters sinks to the bottom of the ocean, and is then transported to equatorial latitudes, where stored amounts of CO 2 that are not fixed by biochemical processes will be released and enter the atmosphere again after a period of approximately 1000 years. Nearly 50 per cent of CO 2 fixation occurs as a result of phytoplankton growth, which is dependent on the availability of a range of nutrients, essential trace metals, and optimal physical conditions. Fertilization-induced CO 2 fixation in the sediments of southern oceans will result in nutrient depletion of bottom layers, which will in turn result in lower primary production levels at equatorial latitudes. Current modelling approaches to CO 2 injection assume that the injected CO 2 will dissolve in a plume extending 100 m around a riser. Retention times of several hundred years are anticipated. However, further research is needed to investigate the efficacy of CO 2 deep ocean storage technologies. Increased CO 2 uptake can also increase the formation of bicarbonate (HCO 3 ) acidification, decrease pH values, and inhibit the formation of biomass in addition to impacting on the calcification of many organisms. It was concluded that ocean storage by injection or deep storage is an untenable option at present due to the fact that the effects of excessive CO 2 in marine environments are not fully understood. 22 refs., 2 tabs

  17. THE ARIZONA RADIO OBSERVATORY CO MAPPING SURVEY OF GALACTIC MOLECULAR CLOUDS. II. THE W3 REGION IN CO J = 2-1, 13CO J = 2-1, AND CO J = 3-2 EMISSION

    International Nuclear Information System (INIS)

    Bieging, John H.; Peters, William L.

    2011-01-01

    We present fully sampled 38'' resolution maps of the CO and 13 CO J = 2-1 lines in the molecular clouds toward the H II region complex W3. The maps cover a 2. 0 0 x 1. 0 67 section of the galactic plane and span -70 to -20 km s -1 (LSR) in velocity with a resolution of ∼1.3 km s -1 . The velocity range of the images includes all the gas in the Perseus spiral arm. We also present maps of CO J = 3-2 emission for a 0. 0 5 x 0. 0 33 area containing the H II regions W3 Main and W3(OH). The J = 3-2 maps have velocity resolution of 0.87 km s -1 and 24'' angular resolution. Color figures display the peak line brightness temperature, the velocity-integrated intensity, and velocity channel maps for all three lines, and also the (CO/ 13 CO) J = 2-1 line intensity ratios as a function of velocity. The line intensity image cubes are made available in standard FITS format as electronically readable files. We compare our molecular line maps with the 1.1 mm continuum image from the BOLOCAM Galactic Plane Survey (BGPS). From our 13 CO image cube, we derive kinematic information for the 65 BGPS sources in the mapped field, in the form of Gaussian component fits.

  18. Switchable CO2 electroreduction via engineering active phases of Pd nanoparticles

    Institute of Scientific and Technical Information of China (English)

    Dunfeng Gao; Fan Yang; Shu Miao; Jianguo Wang; Guoxiong Wang; Xinhe Bao; Hu Zhou; Fan Cai; Dongniu Wang; Yongfeng Hu; Bei Jiang; Wen-Bin Cai; Xiaoqi Chen; Rui Si

    2017-01-01

    Active-phase engineering is regularly utilized to tune the selectivity of metal nanoparticles (NPs) in heterogeneous catalysis.However,the lack of understanding of the active phase in electrocatalysis has hampered the development of efficient catalysts for CO2 electroreduction.Herein,we report the systematic engineering of active phases of Pd NPs,which are exploited to select reaction pathways for CO2 electroreduction.In situ X-ray absorption spectroscopy,in situ attenuated total reflection-infrared spectroscopy,and density functional theory calculations suggest that the formation of a hydrogen-adsorbed Pd surface on a mixture of the α-and β-phases of a palladium-hydride core (α+β PdHx@PdHx) above-0.2 V (vs.a reversible hydrogen electrode) facilitates formate production via the HCOO* intermediate,whereas the formation of a metallic Pd surface on the β-phase Pd hydride core (β PdHx@Pd) below-0.5 V promotes CO production via the COOH* intermediate.The main product,which is either formate or CO,can be selectively produced with high Faradaic efficiencies (>90%) and mass activities in the potential window of 0.05 to-0.9 V with scalable application demonstration.

  19. Numerical modeling of pore-scale phenomena during CO2 sequestration in oceanic sediments

    International Nuclear Information System (INIS)

    Kang, Qinjun; Tsimpanogiannis, Ioannis N.; Zhang, Dongxiao; Lichtner, Peter C.

    2005-01-01

    Direct disposal of liquid CO 2 on the ocean floor is one of the approaches considered for sequestering CO 2 in order to reduce its concentration in the atmosphere. At oceanic depths deeper than approximately 3000 m, liquid CO 2 density is higher than the density of seawater and CO 2 is expected to sink and form a pool at the ocean floor. In addition to chemical reactions between CO 2 and seawater to form hydrate, fluid displacement is also expected to occur within the ocean floor sediments. In this work, we consider two different numerical models for hydrate formation at the pore scale. The first model consists of the Lattice Boltzmann (LB) method applied to a single-phase supersaturated solution in a constructed porous medium. The second model is based on the Invasion Percolation (IP) in pore networks, applied to two-phase immiscible displacement of seawater by liquid CO 2 . The pore-scale results are upscaled to obtain constitutive relations for porosity, both transverse and for the entire domain, and for permeability. We examine deposition and displacement patterns, and changes in porosity and permeability due to hydrate formation, and how these properties depend on various parameters including a parametric study of the effect of hydrate formation kinetics. According to the simulations, the depth of CO 2 invasion in the sediments is controlled by changes in the pore-scale porosity close to the hydrate formation front. (author)

  20. Formation of Glycerol through Hydrogenation of CO Ice under Prestellar Core Conditions

    Energy Technology Data Exchange (ETDEWEB)

    Fedoseev, G.; Chuang, K.-J.; Qasim, D.; Linnartz, H. [Sackler Laboratory for Astrophysics, Leiden Observatory, Leiden University, P.O. Box 9513, NL-2300 RA Leiden (Netherlands); Ioppolo, S. [School of Physical Sciences, The Open University, Walton Hall, Milton Keynes MK7 6AA (United Kingdom); Dishoeck, E. F. van, E-mail: gfedo@oact.inaf.it [Leiden Observatory, Leiden University, P.O. Box 9513, NL-2300 RA Leiden (Netherlands)

    2017-06-10

    Observational studies reveal that complex organic molecules (COMs) can be found in various objects associated with different star formation stages. The identification of COMs in prestellar cores, i.e., cold environments in which thermally induced chemistry can be excluded and radiolysis is limited by cosmic rays and cosmic-ray-induced UV photons, is particularly important as this stage sets up the initial chemical composition from which ultimately stars and planets evolve. Recent laboratory results demonstrate that molecules as complex as glycolaldehyde and ethylene glycol are efficiently formed on icy dust grains via nonenergetic atom addition reactions between accreting H atoms and CO molecules, a process that dominates surface chemistry during the “CO freeze-out stage” in dense cores. In the present study we demonstrate that a similar mechanism results in the formation of the biologically relevant molecule glycerol—HOCH{sub 2}CH(OH)CH{sub 2}OH—a three-carbon-bearing sugar alcohol necessary for the formation of membranes of modern living cells and organelles. Our experimental results are fully consistent with a suggested reaction scheme in which glycerol is formed along a chain of radical–radical and radical–molecule interactions between various reactive intermediates produced upon hydrogenation of CO ice or its hydrogenation products. The tentative identification of the chemically related simple sugar glyceraldehyde—HOCH{sub 2}CH(OH)CHO—is discussed as well. These new laboratory findings indicate that the proposed reaction mechanism holds much potential to form even more complex sugar alcohols and simple sugars.

  1. Geological storage of CO2 : Mechanical and chemical effects on host and seal formations

    NARCIS (Netherlands)

    Hangx, Suzanne

    2009-01-01

    The socio-economic impact of global warming resulting from anthropogenic CO2 emissions has lead to much attention for carbon mitigation strategies in recent years. One of the most promising ways of disposing of CO2 is through Carbon Capture and Storage (CCS), entailing CO2 capture at source,

  2. In situ synthesis and formation mechanism of ZrC and ZrB2 by combustion synthesis from the Co-Zr-B4C system

    Directory of Open Access Journals (Sweden)

    Mengxian Zhang

    2015-09-01

    Full Text Available ZrC-ZrB2-based composites were prepared by combustion synthesis (CS reaction from 10 wt.% to 50 wt.% Co-Zr-B4C powder mixtures. With increasing Co contents, the particle sizes of near-spherical ZrC and platelet-like ZrB2 decreased from 1 μm to 0.5 μm and from 5 μm to 2 μm, respectively. In addition, the formation mechanism of ZrC and ZrB2 was explored by the phase transition and microstructure evolution on the combustion wave quenched sample in combination with differential scanning calorimeter analysis. The results showed that the production of ZrC was ascribed to the solid-solid reaction between Zr and C and the precipitation from the Co-Zr-B-C melt, while ZrB2 was prepared from the saturated liquid. The low B concentration in the Co-Zr-B-C liquid and high cooling rate during the CS process led to the presence of Co2B and ZrCo3B2 in the composites. The addition of Co in the Co-Zr-B4C system not only prevented ZrC and ZrB2 particulates from growing, but also promoted the occurrence of ZrC-ZrB2-forming reaction.

  3. Exchange coupling behavior in bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

    Energy Technology Data Exchange (ETDEWEB)

    Leite, G.C.P. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Chagas, E.F., E-mail: efchagas@fisica.ufmt.br [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Pereira, R.; Prado, R.J. [Instituto de Fisica, Universidade Federal de Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Terezo, A.J. [Departamento de Quimica, Universidade Federal do Mato Grosso, 78060-900 Cuiaba-MT (Brazil); Alzamora, M.; Baggio-Saitovitch, E. [Centro Brasileiro de Pesquisas Fisicas, Rua Xavier Sigaud 150 Urca, Rio de Janeiro (Brazil)

    2012-09-15

    In this work we report a study of the magnetic behavior of ferrimagnetic oxide CoFe{sub 2}O{sub 4} and ferrimagnetic oxide/ferromagnetic metal CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite. The latter compound is a good system to study hard ferrimagnet/soft ferromagnet exchange coupled. Two steps were followed to synthesize the bimagnetic CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite: (i) first, preparation of CoFe{sub 2}O{sub 4} nanoparticles using a simple hydrothermal method, and (ii) second, reduction reaction of cobalt ferrite nanoparticles using activated charcoal in inert atmosphere and high temperature. The phase structures, particle sizes, morphology, and magnetic properties of CoFe{sub 2}O{sub 4} nanoparticles were investigated by X-Ray diffraction (XRD), Mossbauer spectroscopy (MS), transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM) with applied field up to 3.0 kOe at room temperature and 50 K. The mean diameter of CoFe{sub 2}O{sub 4} particles is about 16 nm. Mossbauer spectra revealed two sites for Fe{sup 3+}. One site is related to Fe in an octahedral coordination and the other one to the Fe{sup 3+} in a tetrahedral coordination, as expected for a spinel crystal structure of CoFe{sub 2}O{sub 4}. TEM measurements of nanocomposite showed the formation of a thin shell of CoFe{sub 2} on the cobalt ferrite and indicate that the nanoparticles increase to about 100 nm. The magnetization of the nanocomposite showed a hysteresis loop that is characteristic of exchange coupled systems. A maximum energy product (BH){sub max} of 1.22 MGOe was achieved at room temperature for CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposites, which is about 115% higher than the value obtained for CoFe{sub 2}O{sub 4} precursor. The exchange coupling interaction and the enhancement of product (BH){sub max} in nanocomposite CoFe{sub 2}O{sub 4}/CoFe{sub 2} are discussed. - Highlights: Black-Right-Pointing-Pointer CoFe{sub 2}O{sub 4}/CoFe{sub 2} nanocomposite

  4. Estimation of the reaction rate for the formation of CH3O from H + H2CO - Implications for chemistry in the solar system

    Science.gov (United States)

    Yung, Yuk L.; Drew, William A.; Pinto, Joseph P.; Friedl, Randall R.

    1988-01-01

    Troe's (1977) approximate theory is presently used in conjunction with transition state theory to estimate the rate coefficient of the reaction by which CO is reduced to CH4; attention is given to the role that may be played in the reduction process by the formation of the CH3O radical from H + H2CO. Attention is given to the implications of such a reaction (1) for the CO chemistry on Jupiter and within the solar nebula, (2) for the interpretation of such experimental results as those of Bar-Nun and Shaviv (1975) and Bar-Nun and Chang (1983), and (3) for organic synthesis in the prebiotic terrestrial atmosphere.

  5. Physicochemical studies of the carbamate-CO2-solvent system

    International Nuclear Information System (INIS)

    Prencipe, M.; Ishida, T.

    1977-08-01

    The formation of carbamate from CO 2 and the various amine solutions has been investigated for the purpose of elucidating the structure of the species generated in the reaction. The amine solutions used were 1 and 2 molar solutions of di-n-butylamine (DNBA) in triethylamine (TEA), pure DNBA and pure TEA. It has been found that the nonaqueous solvent participates in the formation of carbamate in 1 and 2M-DNBA/TEA solutions as a proton acceptor in DNBA-carbamate formation. However, due to the high concentration of the solutions and the basicities of the amines, a significant amount of DNBA which does not form the DNBA-carbamate anion is also found to be participating as a proton acceptor. Pure TEA absorbs only 1 / 60 of the absorption by pure DNBA. The extent of TEA participation in the CO 2 -absorption process other than as a proton acceptor in DNBA-carbamate is negligible. The formation of carbamic acid and zwitterion have been found unlikely. 7 tables, 15 figs

  6. Interfacial Interactions and Wettability Evaluation of Rock Surfaces for CO2 Storage

    NARCIS (Netherlands)

    Shojai Kaveh, N.

    2014-01-01

    To reduce CO2 emissions into the atmosphere, different scenarios are proposed to capture and store carbon dioxide (CO2) in geological formations (CCS). Storage strategies include CO2 injection into deep saline aquifers, depleted gas and oil reservoirs, and unmineable coal seams. To identify a secure

  7. Proposition d'explication de la formation d'hydrogène sulfuré dans les stockages souterrains de gaz naturel par réduction des sulfures minéraux de la roche magasin Proposed Explanation of Hydrogen-Sulfide Formation in Underground Natural-Gas Storage Structures by Reduction of Mineral Sulfides in the Reservoir Rock.

    Directory of Open Access Journals (Sweden)

    Bourgeois J. P.

    2006-11-01

    Full Text Available La formation d'hydrogène sulfuré dans les structures de stockage peu expliquer autrement que par l'action de bactéries sulfato-réductrices. La contenue dans la roche magasin constitue une source de sulfures capable d'alimenter en H2S le gaz naturel. La réduction de la pyrite en sulfures du type Fe 1-x S et l'équilibre de dissolution précipitation, lié principalement à la pression de CO2, dans les structures stockages, constituent un processus de formation d'H2S capable d'expliquer tativement et quantitativement les phénomènes observés sur le terrain. Un modèle simplifié de stockage reprend ce schéma et teste la sensibililté de la teneur en H2S à la valeur des paramètres physiques et chimiques définissant le stockage. Cette étude permet de proposer un certain nombre d'actions susceptibles de limiter la formation d'H2S et d'orienter les choix futurs du couple gaz naturel - structures de stockage. The formation of hydrogen sulfide in storage structures can be explained otherwise thon by the action of sulfate-reducing bacteria. The pyrite contained in the reservoir rock makes up a source of sulfides capable of supplying the natural gas with H2S.Reduction of pyrite ta sulfides of the Fe,-,S type and the dissolution precipitation equilibrium, linked mainly ta C02 pressure in storage structures, make up an H2S for-mation process capable of qualitatively and quantitatively explained phenomena observed in the field.A simplified storage model reflects this scheme and can be used ta test the sensi-tivity of the H2S content ta the value of the physical and chemical parameters defining the storage structure.This investigation can be used to propose various means of action (sable ta "mit H2S formation and ta guide future choices of natural gas/storage-structure pairs.

  8. Catalytic activity of Co/SiO2 and Co/TiO2 nanosized systems in the oxidation of carbon monoxide

    Science.gov (United States)

    Kelyp, A. A.; Smirnova, N. P.; Oleksenko, L. P.; Lutsenko, L. V.; Oranskaya, E. I.; Ripko, A. P.

    2013-06-01

    The effects of the preparation procedure, active component concentration, and conditions of formation of nanosized cobalt-containing systems based on TiO2 and SiO2 mesoporous powders on their catalytic activity in the oxidation of carbon monoxide were studied. The active phase in the systems was cobalt spinel CoCo2O4 found in all samples. High catalytic activity was found in the samples characterized by relatively high contents of surface active centers (cobalt cations with octahedral surroundings).

  9. Glycine formation in CO2:CH4:NH3 ices induced by 0-70 eV electrons

    Science.gov (United States)

    Esmaili, Sasan; Bass, Andrew D.; Cloutier, Pierre; Sanche, Léon; Huels, Michael A.

    2018-04-01

    Glycine (Gly), the simplest amino-acid building-block of proteins, has been identified on icy dust grains in the interstellar medium, icy comets, and ice covered meteorites. These astrophysical ices contain simple molecules (e.g., CO2, H2O, CH4, HCN, and NH3) and are exposed to complex radiation fields, e.g., UV, γ, or X-rays, stellar/solar wind particles, or cosmic rays. While much current effort is focused on understanding the radiochemistry induced in these ices by high energy radiation, the effects of the abundant secondary low energy electrons (LEEs) it produces have been mostly assumed rather than studied. Here we present the results for the exposure of multilayer CO2:CH4:NH3 ice mixtures to 0-70 eV electrons under simulated astrophysical conditions. Mass selected temperature programmed desorption (TPD) of our electron irradiated films reveals multiple products, most notably intact glycine, which is supported by control measurements of both irradiated or un-irradiated binary mixture films, and un-irradiated CO2:CH4:NH3 ices spiked with Gly. The threshold of Gly formation by LEEs is near 9 eV, while the TPD analysis of Gly film growth allows us to determine the "quantum" yield for 70 eV electrons to be about 0.004 Gly per incident electron. Our results show that simple amino acids can be formed directly from simple molecular ingredients, none of which possess preformed C—C or C—N bonds, by the copious secondary LEEs that are generated by ionizing radiation in astrophysical ices.

  10. Assessment of particle size distribution in CO 2 accidental releases

    NARCIS (Netherlands)

    Hulsbosch-Dam, C.E.C.; Spruijt, M.P.N.; Necci, A.; Cozzani, V.

    2012-01-01

    A model was developed to calculate the particle size distribution following the release of pressurised supercritical CO 2. The model combines several sub-models for the different stages of jet break-up and specifically addresses the possible formation of solid particles, which is important for CO 2

  11. Impact of CO{sub 2} hydrates on ocean carbon dioxide deposition options

    Energy Technology Data Exchange (ETDEWEB)

    Lund, P C

    1995-04-01

    The objective of the research project described in this report was to contribute to the research on greenhouse gases and the global environment. The focus is on the concept of storing large amounts of CO{sub 2} in the ocean. The project was divided into three subtasks: (1) a comprehensive study of the thermodynamic, physical and chemical properties of the seawater/CO{sub 2}/hydrate system, (2) establishment of a micro-scale kinetic model for CO{sub 2} hydrate formation and stability, based on (1), and (3) establishment of macro-scale models for various ocean deposition options based on (2). A database of selected thermodynamic functions has been set up. A large database of oceanic data has also been made; for any given coordinates at sea a computer program provides the temperature, salinity and oxygen profiles from the sea surface to the sea floor. The kinetic model predicts the formation and pseudo-stability of a very thin hydrate film which acts as an inhibitor for diffusion of CO{sub 2} into the sea water. The model predicts that the hydrate film reduces the overall flux from a liquid CO{sub 2} source with about 90%. Thermodynamically, pure CO{sub 2} in contact with water might form hydrates at depths below about 400 m, which would indicate that hydrate formation could play a role for all ocean CO{sub 2} deposition options. However, this study shows that other mechanisms significantly reduce the role of hydrate formation. It is finally concluded that although more modelling and experimental work is required within this field of research, the hydrate film may play an important role for all options except from shallow water injection. 86 refs., 32 figs., 16 tabs.

  12. Effect of CaCO_3 addition on ash sintering behaviour during K_2CO_3 catalysed steam gasification of a Chinese lignite

    International Nuclear Information System (INIS)

    Zhang, Jiguang; Li, Jianbo; Mao, Yandong; Bi, Jicheng; Zhu, Mingming; Zhang, Zhezi; Zhang, Li; Zhang, Dongke

    2017-01-01

    Highlights: • K_2CO_3 decreased ash sintering temperature and enhanced ash melting in gasification. • CaCO_3 addition enhanced ash melting and lowered ash sintering temperatures. • CaCO_3 reacted with SiO_2 to form fluxing phases and amorphous materials. • CaCO_3 addition inhibited the potassium aluminium silicate formation. • CaCO_3 addition preserved the catalytic activity of potassium. - Abstract: The ash sintering behaviour of a Chinese lignite (LLI) with different amounts of CaCO_3 addition during K_2CO_3-catalysed gasification was investigated. 0–10 wt% K_2CO_3 was doped into the lignite for catalytic gasification, and CaCO_3 was added into the K_2CO_3-doped samples, varying in the range of 0–20 wt% relative to the lignite, for understanding its impact on ash sintering and catalytic gasification activity. Ash samples were prepared by completely gasifying the lignite samples with steam in a fixed-bed catalytic gasification system operating at 1073 K and atmospheric pressure. Sintering temperature, mineralogy and morphology of the ash samples thus obtained were determined using a pressure-drop sintering device, XRD and SEM-EDS, respectively. The results showed that the ash sintering temperature decreased as the K_2CO_3 addition increased, indicating that K_2CO_3 as the catalyst for gasification would promote ash sintering. SEM imaging analysis showed that all the ash samples from LLI with K_2CO_3 addition were composed of agglomerated particles with smooth surfaces, indicating the ashes had incurred partial melting. The degree of melting became more apparent as the K_2CO_3 addition ratio increased. These molten phases were identified as K-bearing arcanite and kaliophilite, which contributed to the formation of liquid phases at lower temperatures, resulting in lowered ash sintering temperatures. It was also revealed that the addition of CaCO_3 decreased the sintering temperatures of ash samples, indicating that the ash sintering was further

  13. Desarrollo preliminar de una metodología de suministro de CO2 a cultivos de Botryococcus Braunii para la producción de biocombustibles

    Directory of Open Access Journals (Sweden)

    Nestor Andres Jaimes Villarreal

    2015-12-01

    Full Text Available Diversos estudios sobre el cultivo de microalgas a escala laboratorio y piloto han registrado el potencial de estos microorganismos para la producción de materia prima en la elaboración de biocombustibles. El suministro de una fuente de carbono para el cultivo masivo de microalgas representa una de las principales limitantes en el proceso productivo; estas fi jan fotosintéticamente carbono inorgánico (CO2 y sintetizan metabolitos para la producción de biocombustibles. En el presente estudio se evaluó la infl uencia de diversos parámetros de suministro de CO2 sobre cultivos de la especie Botryococcus braunii en fotobiorreactores a escala laboratorio. Se plantearon diseños experimentales centrales compuestos para correlacionar los parámetros a evaluar y determinar su efecto en la dilución de CO2 y producción de metabolitos (biomasa, lípidos e hidrocarburos. Respecto a los parámetros de diseño del fotobiorreactor, alturas > 36cm, diámetros 0,06v/vm suministrado de manera continua son ideales para el crecimiento celular. Por otra parte, concentraciones medias (0,04 – 0,06v/vm de CO2 son ideales para la producción de lípidos y concentraciones bajas de CO2 (≤ 0,02v/vm favorecen la producción de hidrocarburos. Se validó el potencial de la cepa de B. braunii colombiana para la producción de biodiésel gracias a sus altas tasas de síntesis de lípidos.

  14. Vehicle emissions of greenhouse gases and related tracers from a tunnel study: : CO: CO2, N2O: CO2, CH4: CO2, O2: CO2 ratios, and the stable isotopes 13C and 18O in CO2 and CO

    NARCIS (Netherlands)

    Popa, Maria Elena; Vollmer, M. K.; Jordan, A.; Brand, W. A.; Pathirana, S. L.; Rothe, M.; Röckmann, T.

    2014-01-01

    Measurements of CO2, CO, N2O and CH4 mole fractions, O2/N2 ratios and the stable isotopes 13C and 18O in CO2 and CO have been performed in air samples from the Islisberg highway tunnel (Switzerland). The molar CO : CO2 ratios, with an average of (4.15 ± 0.34) ppb:ppm, are lower than reported in

  15. Kinetics of CO2 and methane hydrate formation : an experimental analysis in the bulk phase

    NARCIS (Netherlands)

    He, Y.; Rudolph, E.S.J.; Zitha, P.L.J.; Golombok, M.

    2011-01-01

    Gas resources captured in the form of gas hydrates are by an order of magnitude larger than the resources available from conventional resources. In order to keep the CO2CO2 footprint in the world as small as possible, the idea is to produce methane hydrates and sequestrate CO2CO2 into hydrates in

  16. Geothermal energy combined with CO2 sequestration : An additional benefit

    NARCIS (Netherlands)

    Salimi, H.; Wolf, K.H.A.A.; Bruining, J.

    2012-01-01

    In this transition period from a fossil-fuel based society to a sustainable-energy society, it is expected that CO2 capture and subsequent sequestration in geological formations plays a major role in reducing greenhouse gas emissions. An alternative for CO2 emission reduction is to partially replace

  17. Uma investigação sobre os co-movimentos na volatilidade dos par bonds latino-americanos

    Directory of Open Access Journals (Sweden)

    Igor A.C. de Morais

    2001-04-01

    Full Text Available Este artigo procura aplicar o método de quase-máxima verossimilhança para estimar a volatilidade estocástica multivariada não-estacionária dos preços de compra dos par bonds de quatro países latino-americanos - México, Brasil, Argentina e Venezuela - no período de 9-8-1994 a 15-9-1999. O objetivo é analisar possíveis movimentos comuns nestas variâncias. Os testes feitos revelam que a volatilidade nos modelos univariados não apresentam inclinação, mas possuem alta persistência. A formulação multivariada relaciona bem os dados, obtendo estimativas consistentes e revelando a existência de um comportamento ao longo do tempo similar entre as volatilidades das quatro séries.This paper uses a quasi-maximum likelihood procedure to estimate the non-stationary stochastic volatility for the par bonds of four Latin American countries: Brazil, Argentina, Mexico and Venezuela. The aim is to investigate the possible presence of co-movements in volatility across countries. The estimation period goes from August 1994 to September 1999, including, therefore, the Asian and Russian crises. The estimated volatility for the univariate model does not show any slope and is highly persistent. The multivariate model gives a good fit to the data and shows that there is common movement.

  18. Experimental and simulation studies on mineral trapping of CO2 with brine

    International Nuclear Information System (INIS)

    Soong, Y.; Goodman, A.L.; McCarthy-Jones, J.R.; Baltrus, J.P.

    2004-01-01

    The reaction of carbon dioxide (CO 2 ) with brine samples collected from the Oriskany Formation in Indiana County, PA, was investigated in an autoclave reactor under various conditions. A geochemical code, PHREEQC, was used as to simulate the reaction in the autoclave reactor. The combined experimental and modeling data suggests that pH (pH > 9) plays a key role in the formation of carbonate minerals. The effects of temperature and CO 2 pressure have a lesser impact on the formation of carbonate minerals

  19. Emissions of HC, CO, NOx, CO2, and SO2 from civil aviation in China in 2010

    Science.gov (United States)

    Fan, Weiyi; Sun, Yifei; Zhu, Tianle; Wen, Yi

    2012-09-01

    Civil aviation in China has developed rapidly in recent years, and the effects of civil aviation emissions on the atmospheric environment should not be neglected. The establishment of emission inventories of atmospheric pollutants from civil aviation contributes to related policy formation and pollution control. According to the 2010's China flight schedules, aircraft/engine combination information and revised emission indices from the International Civil Aviation Organization emission data bank based on meteorological data, the fuel consumption and HC, CO, NOx, CO2, SO2 emissions from domestic flights of civil aviation in China (excluding Taiwan Province) in 2010 are estimated in this paper. The results show that fuel consumption in 2010 on domestic flights in China is 12.12 million tons (metric tons), HC, CO, NOx, CO2 and SO2 emissions are 4600 tons, 39,700 tons, 154,100 tons, 38.21 million tons and 9700 tons, respectively. The fuel consumption and pollutant emissions of China Southern Airline are responsible for the largest national proportion of each, accounting for 27% and 25-28%, respectively.

  20. Polyoxometalate-Promoted Electrocatalytic CO2 Reduction at Nanostructured Silver in Dimethylformamide.

    Science.gov (United States)

    Guo, Si-Xuan; Li, Fengwang; Chen, Lu; MacFarlane, Douglas R; Zhang, Jie

    2018-04-18

    Electrochemical reduction of CO 2 is a promising method to convert CO 2 into fuels or useful chemicals, such as carbon monoxide (CO), hydrocarbons, and alcohols. In this study, nanostructured Ag was obtained by electrodeposition of Ag in the presence of a Keggin type polyoxometalate, [PMo 12 O 40 ] 3- (PMo). Metallic Ag is formed upon reduction of Ag + . Adsorption of PMo on the surface of the newly formed Ag lowers its surface energy thus stabilizes the nanostructure. The electrocatalytic performance of this Ag-PMo nanocomposite for CO 2 reduction was evaluated in a CO 2 saturated dimethylformamide medium containing 0.1 M [ n-Bu 4 N]PF 6 and 0.5% (v/v) added H 2 O. The results show that this Ag-PMo nanocomposite can catalyze the reduction of CO 2 to CO with an onset potential of -1.70 V versus Fc 0/+ , which is only 0.29 V more negative than the estimated reversible potential (-1.41 V) for this process and 0.70 V more positive than that on bulk Ag metal. High faradaic efficiencies of about 90% were obtained over a wide range of applied potentials. A Tafel slope of 60 mV dec -1 suggests that rapid formation of *CO 2 •- is followed by the rate-determining protonation step. This is consistent with the voltammetric data which suggest that the reduced PMo interacts strongly with CO 2 (and presumably CO 2 •- ) and hence promotes the formation of CO 2 •- .

  1. Are CO Observations of Interstellar Clouds Tracing the H2?

    Science.gov (United States)

    Federrath, Christoph; Glover, S. C. O.; Klessen, R. S.; Mac Low, M.

    2010-01-01

    Interstellar clouds are commonly observed through the emission of rotational transitions from carbon monoxide (CO). However, the abundance ratio of CO to molecular hydrogen (H2), which is the most abundant molecule in molecular clouds is only about 10-4. This raises the important question of whether the observed CO emission is actually tracing the bulk of the gas in these clouds, and whether it can be used to derive quantities like the total mass of the cloud, the gas density distribution function, the fractal dimension, and the velocity dispersion--size relation. To evaluate the usability and accuracy of CO as a tracer for H2 gas, we generate synthetic observations of hydrodynamical models that include a detailed chemical network to follow the formation and photo-dissociation of H2 and CO. These three-dimensional models of turbulent interstellar cloud formation self-consistently follow the coupled thermal, dynamical and chemical evolution of 32 species, with a particular focus on H2 and CO (Glover et al. 2009). We find that CO primarily traces the dense gas in the clouds, however, with a significant scatter due to turbulent mixing and self-shielding of H2 and CO. The H2 probability distribution function (PDF) is well-described by a log-normal distribution. In contrast, the CO column density PDF has a strongly non-Gaussian low-density wing, not at all consistent with a log-normal distribution. Centroid velocity statistics show that CO is more intermittent than H2, leading to an overestimate of the velocity scaling exponent in the velocity dispersion--size relation. With our systematic comparison of H2 and CO data from the numerical models, we hope to provide a statistical formula to correct for the bias of CO observations. CF acknowledges financial support from a Kade Fellowship of the American Museum of Natural History.

  2. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng; Yang, Xiulin; Li, Henan; Hedhili, Mohamed N.; Huang, Kuo-Wei; Li, Lain-Jong; Zhang, Wenjing

    2017-01-01

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  3. Symmetrical synergy of hybrid CoS2-WS2 electrocatalysts for hydrogen evolution reaction

    KAUST Repository

    Zhou, Xiaofeng

    2017-06-05

    A highly active and stable hybrid electrocatalyst 3D hierarchical CoS2 nanosheets incorporated with WS2 (CoS2@WS2) has been developed via a one-step sulfurization method for the first time, where the contents of WS2 can be adjusted easily. We first prove the addition of small amounts of WS2 enhances the hydrogen evolution reaction (HER) performance of CoS2, and vise versa. In other words, we validated the symmetric synergy for HER between the Co- and W-based sulfide hybrid catalysts. In addition, we confirmed that the formation of nanointerfaces of Co-S-W between CoS2 and WS2 was responsible for the excellent HER activity (an overpotential of -97.2 mV at -10 mA/cm2, a small Tafel slope of 66.0 mV/dec, and prominent electrochemical stability) of hybrid electrocatalyst CoS2@WS2.

  4. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    Science.gov (United States)

    Wang, Mengnan; Zhang, Jiaguang; Yan, Ning

    2013-09-01

    The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs). Ni NPs and eight NiM (M stands for a second metal) NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  5. Le domaine des co-infections et des maladies concomitantes du Réseau canadien pour les essais VIH des IRSC : lignes directrices canadiennes pour la prise en charge et le traitement de la co-infection par le VIH et l’hépatite C chez les adultes

    Science.gov (United States)

    Hull, Mark; Giguère, Pierre; Klein, Marina; Shafran, Stephen; Tseng, Alice; Côté, Pierre; Poliquin, Marc; Cooper, Curtis

    2014-01-01

    HISTORIQUE : De 20 % à 30 % des Canadiens qui vivent avec le VIH sont co-infectés par le virus de l’hépatite C (VHC), lequel est responsable d’une morbidité et d’une mortalité importantes. La prise en charge du VIH et du VHC est plus complexe en raison de l’évolution accélérée de la maladie hépatique, du choix et des critères d’initiation de la thérapie antirétrovirale et du traitement anti-VHC, de la prise en charge de la santé mentale et des toxicomanies, des obstacles socioéconomiques et des interactions entre les nouvelles thérapies antivirales à action directe du VHC et les antirétroviraux OBJECTIF : Élaborer des normes nationales de prise en charge des adultes co-infectés par le VHC et le VIH dans le contexte canadien. MÉTHODOLOGIE : Le Réseau canadien pour les essais VIH des Instituts de recherche en santé du Canada a réuni un groupe d’experts possédant des compétences cliniques en co-infection par le VIH et le VHC pour réviser les publications à jour ainsi que les lignes directrices et les protocoles en place. Après une vaste sollicitation afin d’obtenir des points de vue, le groupe de travail a approuvé des recommandations consensuelles, qu’il a caractérisées au moyen d’une échelle de qualité des preuves fondée sur la classe (bienfaits par rapport aux préjudices) et sur la catégorie (degré de certitude). RÉSULTATS : Toutes les personnes co-infectées par le VIH et le VHC devraient subir une évaluation en vue de recevoir un traitement du VHC. Les personnes qui ne sont pas en mesure d’entreprendre un traitement du VHC devraient être soignées pour le VIH afin de ralentir l’évolution de la maladie hépatique. La norme de traitement du VHC de génotype 1 est un régime comprenant de l’interféron pégylé et de la ribavirine dosée en fonction du poids, associés à un inhibiteur de la protéase du VHC. Pour les génotypes 2 ou 3, une bithérapie classique est recommandée pendant 24 semaines s

  6. Seismic characterization of CO{sub 2} in coals

    Energy Technology Data Exchange (ETDEWEB)

    McCrank, J.; Lawton, D.C. [Calgary Univ., AB (Canada). Dept. of Geoscience, Consortium for Research in Elastic Wave Exploration Seismology

    2008-07-01

    The Mynheer coal seam was targeted for an enhanced coalbed methane (CBM) experiment. During initial testing of the reservoir permeability, 180 tonnes of carbon dioxide (CO{sub 2}) was injected into the seam. The objective of the study was to characterize the coal zones and to determine if the small volume of CO{sub 2} in the thinly bedded and seismically tuned reservoir can be detected in the 3D surface seismic data. The multi-well pilot project took place in the Pembina Field of west-central Alberta. The Ardley coals were tested for CO{sub 2} injection, enhanced CBM production, and CO{sub 2} sequestration. The seismic survey captured the condition of the reservoir after formation permeability tests. It was concluded that the anomalies seen in the seismic data can be attributed to changes in the physical properties of the coal due to CO{sub 2} adsorption. 2 refs., 5 figs.

  7. Waste cleaning using CO2-acid microemulsion

    International Nuclear Information System (INIS)

    Park, Kwangheon; Sung, Jinhyun; Koh, Moonsung; Ju, Minsu

    2011-01-01

    Frequently we need to decontaminate radioactive wastes for volume reduction purposes. Metallic contaminants in wastes can be removed by dissolution to acid; however, this process produces a large amount of liquid acid waste. To reduce this 2ndary liquid waste, we suggest CO 2 -acid emulsion in removing metallic contaminants. Micro- and macro-emulsion of acid in liquid/supercritical CO 2 were successfully made. The formation region of microemulsion (water or acid in CO 2 ) was measured, and stability of the microemulsion was analyzed with respect to surfactant types. We applied micro- and macro-emulsion containing acid to the decontamination of radioactive metallic parts contaminated on the surface. The cleaning methods of micro- and macro-emulsion seemed better compared to the conventional acid cleaning. Moreover, these methods produce very small amount of secondary wastes. (author)

  8. Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries.

    Science.gov (United States)

    Wang, Qin-Chao; Hu, Enyuan; Pan, Yang; Xiao, Na; Hong, Fan; Fu, Zheng-Wen; Wu, Xiao-Jing; Bak, Seong-Min; Yang, Xiao-Qing; Zhou, Yong-Ning

    2017-11-01

    Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na + and vacancy ordering. An interesting structure change of Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 , effectively suppressing the Mn 3+ -induced Jahn-Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 during charge/discharge is contributed by Co 2.2+ /Co 3+ and Mn 3.3+ /Mn 4+ redox couples. This is the first time that the highly reversible Co 2+ /Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

  9. Interfacial phenomena at the compressed co2-water interface

    Directory of Open Access Journals (Sweden)

    B. Bharatwaj

    2006-06-01

    Full Text Available Compressed CO2 is considered to be a viable alternative to toxic volatile organic solvents with potential applications in areas including separation reactions, and materials formation processes. Thus an interest in CO2 stems from the fact that it is very inexpensive, has low toxicity, and is not a regulated. However, compressed CO2 has a zero dipole moment and weak van der Waals forces and thus is a poor solvent for both polar and most high molecular weight solutes, characteristics that severely restrict its applicability. In order to overcome this inherent inability, surfactant-stabilized organic and aqueous dispersions in CO2 have been proposed. This work will discuss fundamentals and recent advances in the design of amphiphiles for the novel CO2-water interface.

  10. Metal-Doped Nitrogenated Carbon as an Efficient Catalyst for Direct CO2 Electroreduction to CO and Hydrocarbons.

    Science.gov (United States)

    Varela, Ana Sofia; Ranjbar Sahraie, Nastaran; Steinberg, Julian; Ju, Wen; Oh, Hyung-Suk; Strasser, Peter

    2015-09-07

    This study explores the kinetics, mechanism, and active sites of the CO2 electroreduction reaction (CO2RR) to syngas and hydrocarbons on a class of functionalized solid carbon-based catalysts. Commercial carbon blacks were functionalized with nitrogen and Fe and/or Mn ions using pyrolysis and acid leaching. The resulting solid powder catalysts were found to be active and highly CO selective electrocatalysts in the electroreduction of CO2 to CO/H2 mixtures outperforming a low-area polycrystalline gold benchmark. Unspecific with respect to the nature of the metal, CO production is believed to occur on nitrogen functionalities in competition with hydrogen evolution. Evidence is provided that sufficiently strong interaction between CO and the metal enables the protonation of CO and the formation of hydrocarbons. Our results highlight a promising new class of low-cost, abundant electrocatalysts for synthetic fuel production from CO2 . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Enhanced electrocatalytic CO2 reduction via field-induced reagent concentration

    Science.gov (United States)

    Liu, Min; Pang, Yuanjie; Zhang, Bo; de Luna, Phil; Voznyy, Oleksandr; Xu, Jixian; Zheng, Xueli; Dinh, Cao Thang; Fan, Fengjia; Cao, Changhong; de Arquer, F. Pelayo García; Safaei, Tina Saberi; Mepham, Adam; Klinkova, Anna; Kumacheva, Eugenia; Filleter, Tobin; Sinton, David; Kelley, Shana O.; Sargent, Edward H.

    2016-09-01

    Electrochemical reduction of carbon dioxide (CO2) to carbon monoxide (CO) is the first step in the synthesis of more complex carbon-based fuels and feedstocks using renewable electricity. Unfortunately, the reaction suffers from slow kinetics owing to the low local concentration of CO2 surrounding typical CO2 reduction reaction catalysts. Alkali metal cations are known to overcome this limitation through non-covalent interactions with adsorbed reagent species, but the effect is restricted by the solubility of relevant salts. Large applied electrode potentials can also enhance CO2 adsorption, but this comes at the cost of increased hydrogen (H2) evolution. Here we report that nanostructured electrodes produce, at low applied overpotentials, local high electric fields that concentrate electrolyte cations, which in turn leads to a high local concentration of CO2 close to the active CO2 reduction reaction surface. Simulations reveal tenfold higher electric fields associated with metallic nanometre-sized tips compared to quasi-planar electrode regions, and measurements using gold nanoneedles confirm a field-induced reagent concentration that enables the CO2 reduction reaction to proceed with a geometric current density for CO of 22 milliamperes per square centimetre at -0.35 volts (overpotential of 0.24 volts). This performance surpasses by an order of magnitude the performance of the best gold nanorods, nanoparticles and oxide-derived noble metal catalysts. Similarly designed palladium nanoneedle electrocatalysts produce formate with a Faradaic efficiency of more than 90 per cent and an unprecedented geometric current density for formate of 10 milliamperes per square centimetre at -0.2 volts, demonstrating the wider applicability of the field-induced reagent concentration concept.

  12. Brine/CO2 Interfacial Properties and Effects on CO2 Storage in Deep Saline Aquifers Propriétés interfaciales saumure/CO2 et effets sur le stockage du CO2 dans des aquifères salins profonds

    Directory of Open Access Journals (Sweden)

    Chalbaud C.

    2010-05-01

    Full Text Available It has been long recognized that interfacial interactions (interfacial tension, wettability, capillarity and interfacial mass transfer govern fluid distribution and behaviour in porous media. Therefore the interfacial interactions between CO2, brine and reservoir oil and/or gas have an important influence on the effectiveness of any CO2 storage operation. There is a lack of experimental data related to interfacial properties for all the geological storage options (oil & gas reservoirs, coalbeds, deep saline aquifers. In the case of deep saline aquifers, there is a gap in data and knowledge of brine-CO2 interfacial properties at storage conditions. More specifically, experimental interfacial tension values and experimental tests in porous media are necessary to better understand the wettability evolution as a function of thermodynamic conditions and it’s effects on fluid flow in the porous media. In this paper, a complete set of experimental values of brine-CO2 Interfaciale Tension (IFT at pressure, temperature and salt concentration conditions representative of those of a CO2 storage operation. A correlation is derived from experimental data published in a companion paper [Chalbaud C., Robin M., Lombard J.-M., Egermann P., Bertin H. (2009 Interfacial Tension Measurements and Wettability Evaluation for Geological CO2 Storage, Adv. Water Resour. 32, 1, 1-109] to model IFT values. This paper pays particular attention to coreflooding experiments showing that the CO2 partially wets the surface in a Intermediate-Wet (IW or Oil-Wet (OW limestone rock. This wetting behavior of CO2 is coherent with observations at the pore scale in glass micromodels and presents a negative impact on the storage capacity of a given site. Il est admis depuis longtemps que les propriétés interfaciales (tension interfaciale, mouillabilité, capillarité et transfert de masse régissent la distribution et le comportement des fluides au sein des milieux poreux. Par cons

  13. Plutonium extraction by the formation of insoluble salts (1960); Extraction du plutonium par formation de sels insolubles (1960)

    Energy Technology Data Exchange (ETDEWEB)

    Ganivet, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1960-06-15

    The aim of this work is to convert Pu IV nitrate in solution into an insoluble salt. Three methods have been studied: 1) the conventional oxalic acid method was improved; 2) precipitation with 8-hydroxyquinoline was tried; 3) the hydrogen peroxide method was adapted to the eluates of the ionic resins from Marcoule. The yield from the oxalic process has been increased (loss of Pu in the mother-liquor brought from 200 mg/l to 20 mg/l). The study of Pu IV precipitation by 8-hydroxyquinoline has shown that the yield is excellent (Pu concentration in the mother-liquor less than 5 mg/h), but decontamination from impurities is nil. Finally, experiments on the precipitation by hydrogen peroxide of Pu IV solutions at the concentrations normally obtained from the anionic resins at Marcoule have given us good yields (Pu concentration in the mother-liquor less than 7 mg/l), and the purification is better than that obtained by oxalic acid (1000 ppm total impurities after a precipitation). (author) [French] L'objet de l'etude est la transformation en sel insoluble du nitrate de Pu IV en solution. Trois procedes ont ete etudies: 1) la methode classique a l'acide oxalique a ete amelioree, 2) la precipitation a la 8-hydroxyquinoleine a ete essayee; 3) le procede a l'eau oxygenee a ete adapte aux solutions d'elution des resines anion de Marcoule. Le rendement du procede oxalique a ete augmente (perte en Pu dans les eaux-meres ramenee de 200 mg/l a 20 mg/l). L'etude de la precipitation du Pu IV par la 8-hydroxyquinoleine a montre que le rendement etait excellent (concentration du Pu dans les eaux-meres inferieure a 5 mg/l), mais la decontamination en impuretes est nulle. Enfin, l'etude et l'application de la precipitation par l'eau oxygenee de solutions de Pu IV de concentrations habituellement obtenues a la sortie des resines anion a Marcoule nous ont permis d'obtenir un bon rendement (concentration de Pu dans les eaux-meres inferieure a 7 mg/l); la purification est meilleure que

  14. Biofunctionalized conductive polymers enable efficient CO2 electroreduction

    Science.gov (United States)

    Coskun, Halime; Aljabour, Abdalaziz; De Luna, Phil; Farka, Dominik; Greunz, Theresia; Stifter, David; Kus, Mahmut; Zheng, Xueli; Liu, Min; Hassel, Achim W.; Schöfberger, Wolfgang; Sargent, Edward H.; Sariciftci, Niyazi Serdar; Stadler, Philipp

    2017-01-01

    Selective electrocatalysts are urgently needed for carbon dioxide (CO2) reduction to replace fossil fuels with renewable fuels, thereby closing the carbon cycle. To date, noble metals have achieved the best performance in energy yield and faradaic efficiency and have recently reached impressive electrical-to-chemical power conversion efficiencies. However, the scarcity of precious metals makes the search for scalable, metal-free, CO2 reduction reaction (CO2RR) catalysts all the more important. We report an all-organic, that is, metal-free, electrocatalyst that achieves impressive performance comparable to that of best-in-class Ag electrocatalysts. We hypothesized that polydopamine—a conjugated polymer whose structure incorporates hydrogen-bonded motifs found in enzymes—could offer the combination of efficient electrical conduction, together with rendered active catalytic sites, and potentially thereby enable CO2RR. Only by developing a vapor-phase polymerization of polydopamine were we able to combine the needed excellent conductivity with thin film–based processing. We achieve catalytic performance with geometric current densities of 18 mA cm−2 at 0.21 V overpotential (−0.86 V versus normal hydrogen electrode) for the electrosynthesis of C1 species (carbon monoxide and formate) with continuous 16-hour operation at >80% faradaic efficiency. Our catalyst exhibits lower overpotentials than state-of-the-art formate-selective metal electrocatalysts (for example, 0.5 V for Ag at 18 mA cm−1). The results confirm the value of exploiting hydrogen-bonded sequences as effective catalytic centers for renewable and cost-efficient industrial CO2RR applications. PMID:28798958

  15. Formation of freestanding ZrO{sub 2} nanotubes for Cr(VI) removal

    Energy Technology Data Exchange (ETDEWEB)

    Bashirom, Nurulhuda, E-mail: nurulhuda.usm2014@gmail.com; Ye, Beh Chin, E-mail: cyebeh@gmail.com; Razak, Khairunisak Abdul, E-mail: khairunisak@usm.my; Lockman, Zainovia, E-mail: zainovia@usm.my [School of Materials & Mineral Resources Engineering, Universiti Sains Malaysia, 14300 Seri Ampangan, Nibong Tebal, Seberang Prai Selatan, Pulau Pinang (Malaysia)

    2016-07-06

    Freestanding ZrO{sub 2} nanotubes (ZNTs) were produced using a simple anodization method in fluorinated ethylene glycol electrolyte containing 1 ml 1 M K{sub 2}CO{sub 3}. The pH of the bath was kept constant at 8. The potassium carbonate (K{sub 2}CO{sub 3}) was added into electrolyte to promote the detachment of anodic ZrO{sub 2} film from the underlying zirconium (Zr) substrate. The poor adherence of ZNTs layer was due to generation of CO{sub 2} gas that was thought to occur between metal|oxide interfaces. The effect of anodization voltages towards the detachment of ZNTs layer was systematically studied at 20 V, 40 V, 50 V and 60 V for 1 hour. The formation of CO{sub 2} gas is a function of anodization voltage, in which at 60 V, a good anodic film separation seen due to higher formation of CO{sub 2} gas. A preliminary study shown the capability of ZNTs in removing 5 ppm of Cr(VI) aqueous solution under illumination of UV light.

  16. Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial–brine–rock–CO2 interactions

    Science.gov (United States)

    Shelton, Jenna L.; McIntosh, Jennifer C.; Warwick, Peter D.; Lee Zhi Yi, Amelia

    2014-01-01

    The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO2, including the possibility of enhanced microbial conversion of CO2 to CH4 via methanogenesis. Stable carbon isotopes of CO2, CH4 and DIC, together with mol% CO2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO2. The dominant fate of the injected CO2appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ13C-CO2 and δ13C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

  17. Exploring the Phase Diagram SiO2-CO2 at High Pressures and Temperatures

    Science.gov (United States)

    Kavner, A.

    2015-12-01

    CO2 is an important volatile system relevant for planetary sciences and fundamental chemistry. Molecular CO2 has doubly bonded O=C=O units but high pressure-high temperature (HP-HT) studies have recently shown its transformation into a three-dimensional network of corner-linked [CO4] units analogous to the silica mineral polymorphs, through intermediate non-molecular phases. Here, we report P-V-T data on CO2-IV ice from time-of-flight neutron diffraction experiments, which allow determining the compressibility and thermal expansivity of this intermediate molecular-to-non-molecular phase.1 Aditionally, we have explored the SiO2-CO2 phase diagram and the potential formation of silicon carbonate compounds. New data obtained by laser-heating diamond-anvil experiments in CO2-filled microporous silica polymorphs will be shown. In particular, these HP-HT experiments explore the existence of potential CO2/SiO2 compounds with tetrahedrally-coordinated C/Si atoms by oxygens, which are predicted to be stable (or metastable) by state-of-the-art ab initio simulations.2,3 These theoretical predictions were supported by a recent study that reports the formation of a cristobalite-type Si0.4C0.6O2 solid solution at high-pressures and temperatures, which can be retained as a metastable solid down to ambient conditions.4 Entirely new families of structures could exist based on [CO4]4- units in various degrees of polymerisation, giving rise to a range of chain, sheet and framework solids like those found in silicate chemistry. References[1] S. Palaich et al., Am. Mineral. Submitted (2015) [2] A. Morales-Garcia et al., Theor. Chem. Acc. 132, 1308 (2013) [3] R. Zhou et al., Phys. Rev. X, 4, 011030 (2014) [4] M. Santoro et al. Nature Commun. 5, 3761 (2014)

  18. Evaluation of hydrogen production from CO2 corrosion of steel drums in SFR, Part 2

    International Nuclear Information System (INIS)

    Dugstad, A.; Videm, K.

    1987-06-01

    An experimental program has been carried out for the investigation of the hydrogen formation due to corrosion of steel by water containing CO 2 produced by microbiologic decomposition of paper in waste drums. The hydrogen production will be limited by a limited rate of CO 2 production, as CO 2 is consumed by corrosive reactions producing carbonate containing corrosion products. Experiments indicated that also iron oxide and hydroxides were formed together with FeCO 3 at low CO 2 partial pressures but at a rate which leads to a rather slow increase in hydrogen production. Hydrogen evaluation has been overestimated in previous reports on this subject. (authors)

  19. Maximization of permanent trapping of CO{sub 2} and co-contaminants in the highest-porosity formations of the Rock Springs Uplift (Southwest Wyoming): experimentation and multi-scale modeling

    Energy Technology Data Exchange (ETDEWEB)

    Piri, Mohammad

    2014-03-31

    Under this project, a multidisciplinary team of researchers at the University of Wyoming combined state-of-the-art experimental studies, numerical pore- and reservoir-scale modeling, and high performance computing to investigate trapping mechanisms relevant to geologic storage of mixed scCO{sub 2} in deep saline aquifers. The research included investigations in three fundamental areas: (i) the experimental determination of two-phase flow relative permeability functions, relative permeability hysteresis, and residual trapping under reservoir conditions for mixed scCO{sub 2}-­brine systems; (ii) improved understanding of permanent trapping mechanisms; (iii) scientifically correct, fine grid numerical simulations of CO{sub 2} storage in deep saline aquifers taking into account the underlying rock heterogeneity. The specific activities included: (1) Measurement of reservoir-­conditions drainage and imbibition relative permeabilities, irreducible brine and residual mixed scCO{sub 2} saturations, and relative permeability scanning curves (hysteresis) in rock samples from RSU; (2) Characterization of wettability through measurements of contact angles and interfacial tensions under reservoir conditions; (3) Development of physically-­based dynamic core-­scale pore network model; (4) Development of new, improved high-­performance modules for the UW-­team simulator to provide new capabilities to the existing model to include hysteresis in the relative permeability functions, geomechanical deformation and an equilibrium calculation (Both pore-­ and core-­scale models were rigorously validated against well-­characterized core-­ flooding experiments); and (5) An analysis of long term permanent trapping of mixed scCO{sub 2} through high-­resolution numerical experiments and analytical solutions. The analysis takes into account formation heterogeneity, capillary trapping, and relative permeability hysteresis.

  20. Modeling CO2-facilitated transport across a diethanolamine liquid membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lihong Bao; Michael C. Trachtenberg [Carbozyme Inc., Monmouth Junction, NJ (United States)

    2005-12-15

    We compared experimental and model data for the facilitated transport of CO2 from a CO2-air mixture across an aqueous solution of diethanolamine (DEA) via a hollow fiber, contained liquid membrane (HFCLM) permeator. A two-step carbamate formation model was devised to analyze the data instead of the one-step mechanism used by previous investigators. The effects of DEA concentration, liquid membrane thickness and feed CO2 concentration were also studied. With a 20% (wt) DEA liquid membrane and feed of 15% CO2 in CO2-air mixture at atmosphere pressure, the permeance reached 1.51E-8 mol/m{sup 2} s Pa with a CO2/N2 selectivity of 115. Model predictions compared well with the experimental results at CO2 concentrations of industrial importance. Short-term stability of the HFCLM permeator performance was examined. The system was stable during 5-days of testing.

  1. Spin-Glass Transition and Giant Paramagnetism in Heavily Hole-Doped Bi2Sr2Co2Oy

    Science.gov (United States)

    Hsu, Hung Chang; Lee, Wei-Li; Lin, Jiunn-Yuan; Young, Ben-Li; Kung, Hsiang-Hsi; Huang, Jian; Chou, Fang Cheng

    2014-02-01

    Hole-doped single crystals of misfit-layered cobaltate Bi2-xPbxSr2-zCo2Oy (x = 0-0.61, y = 8.28-8.62, and z = 0.01-0.22) have been successfully grown using the optical floating-zone method. Heavier hole doping has been achieved through both Pb substitution in the Bi site and the more effective Sr vacancy formation. The Co4+ : Co3+ ratio can be raised significantly from its original ˜1 : 1 to 4.5 : 1, as confirmed by iodometric titration. A spin-glass transition temperature of Tg ˜ 70 K is confirmed by ac susceptibility measurement when the Co4+ : Co3+ ratio becomes higher than 2 : 1, presumably owing to the significantly increased probability of triangular geometrical frustration among antiferromagnetically coupled localized Co4+ spins.

  2. Influence of Operational Parameters on the Photocatalytic Activity of Powdered TiO2 for the Reduction of CO2

    Directory of Open Access Journals (Sweden)

    Oman Zuas

    2014-07-01

    Full Text Available In this report, the results from a study on the influence of operational parameters on TiO2 photocatalytic activity for CO2 reduction under an ultraviolet-visible (UV-vis illumination are presented. The results indicated that the TiO2 was found to be active for CO2 reduction with CH3OH as the major products, while other minor products (CO, CH4, and C2H4 were also detected. In addition, the formation of such reduction products was obviously influenced by the operational parameters. Under this study, the optimum operational parameters for CO2 reduction at 298 °K were determined to be: NaOH concentration 0.2 M, TiO2 dosage 2 g/L, volume of the reaction media 75 mL, the pressure of system 800 kPa. It was also found that the increase in UV-vis illumination time have increased the yield of product formation. A possible reaction pathway for the formation of the reduction products is also discussed.

  3. Comparison of Dry Gas Seasonal Storage with CO2 Storage and Re-Use Potential

    OpenAIRE

    Killerud, Marie

    2013-01-01

    To make large-scale CO2 storage economic, many groups have proposed using CO2in EOR projects to create value for CO2 storage. However, CO2 EOR projectsgenerally require a large and variable supply of CO2 and consequently may requiretemporary storage of CO2 in geological formations. In order to store CO2 atoffshore sites as a source for CO2 EOR projects, the CO2 needs to be extractedfrom a storage site to a certain extent. Alternatively, CO2 EOR projects maybe developed alongside saline aquife...

  4. Degradation of solid oxide cells during co-electrolysis of H2O and CO2: Carbon deposition under high current densities

    DEFF Research Database (Denmark)

    Tao, Youkun; Ebbesen, Sune Dalgaard; Mogensen, Mogens Bjerg

    2012-01-01

    conversions of the reactants were no more than 66.8 %. Ni-YSZ electrode delamination and carbon nano-fibers could be observed after test at the Ni-YSZ | YSZ electrolyte interface for two of the cells. Thermodynamic calculation shows that the reactant conversion needed for carbon formation is above 99 %, far...... above the experimental conversions. The observed carbon formation may be caused by the gas diffusion limitations at high current densities. Carbon nano-fibers were only observed close to the YSZ electrolyte indicating a large overpotential gradient at the TPBs close to the electrolyte......During co-electrolysis of H2O and CO2 using solid oxide cells (SOCs) the risk of carbon deposition in the Ni-YSZ electrode under high current densities (∼ 2.0 A/cm2) was studied in this work. Five galvanostatic tests were performed at current density between 1.5 and 2.25 A/cm2 and the average...

  5. CCS in the North Sea region: A comparison on the cost-effectiveness of storing CO2 in the Utsira formation at regional and national scales

    DEFF Research Database (Denmark)

    Strachan, N.; Hoefnagels, R.; Ramirez, A.

    2011-01-01

    The potential scale of carbon dioxide capture and storage (CCS) under long-term decarbonisation scenarios means that analysis on the contribution of large international CO2 storage reservoirs is critical. This paper compares the potentially key role of CCS within cost-optimizing energy systems...... formation as a common North Sea CO2 storage resource. A robust finding is that low carbon electricity is a primary decarbonisation pathway and that CCS plays a key role (32–40%) within this portfolio. This paper confirms that the overall driver of the amount of CCS utilized is the climate policy...... the CO2 storage cost curve, with the Netherlands and the UK being the largest contributors, followed by transboundary flows of CO2 from other countries. However, overall regional CCS flows may be larger (for example under low fossil fuel prices) than the estimated (and uncertain) maximum annual injection...

  6. Mathematical models as tools for probing long-term safety of CO2 storage

    Energy Technology Data Exchange (ETDEWEB)

    Pruess, Karsten; Birkholzer, Jens; Zhou, Quanlin

    2009-02-01

    Subsurface reservoirs being considered for storing CO{sub 2} include saline aquifers, oil and gas reservoirs, and unmineable coal seams (Baines and Worden, 2004; IPCC, 2005). By far the greatest storage capacity is in saline aquifers (Dooley et al., 2004), and our discussion will focus primarily on CO{sub 2} storage in saline formations. Most issues for safety and security of CO{sub 2} storage arise from the fact that, at typical temperature and pressure conditions encountered in terrestrial crust, CO{sub 2} is less dense than aqueous fluids. Accordingly, CO{sub 2} will experience an upward buoyancy force in most subsurface environments, and will tend to migrate upwards whenever (sub-)vertical permeable pathways are available, such as fracture zones, faults, or improperly abandoned wells (Bachu, 2008; Pruess, 2008a, b; Tsang et al., 2008). CO{sub 2} injection will increase fluid pressures in the target formation, thereby altering effective stress distributions, and potentially triggering movement along fractures and faults that could increase their permeability and reduce the effectiveness of a caprock in containing CO{sub 2} (Rutqvist et al., 2008; Chiaramonte et al., 2008). Induced seismicity as a consequence of fluid injection is also a concern (Healy et al., 1968; Raleigh et al., 1976; Majer et al., 2007). Dissolution of CO{sub 2} in the aqueous phase generates carbonic acid, which may induce chemical corrosion (dissolution) of minerals with associated increase in formation porosity and permeability, and may also mediate sequestration of CO{sub 2} as solid carbonate (Gaus et al., 2008). Chemical dissolution of caprock minerals could promote leakage of CO{sub 2} from a storage reservoir (Gherardi et al., 2007). Chemical dissolution and geomechanical effects could reinforce one another in compromising CO{sub 2} containment. Additional issues arise from the potential of CO{sub 2} to mobilize hazardous chemical species (Kharaka et al., 2006), and from migration of

  7. Starch and sucrose synthesis in Phaseolus vulgaris as affected by light, CO2, and abscisic acid

    International Nuclear Information System (INIS)

    Sharkey, T.D.; Berry, J.A.; Raschke, K.

    1985-01-01

    Phaseolus vulgaris L. leaves were subjected to various light, CO 2 , and O 2 levels and abscisic acid, then given a 10 minute pulse of 14 CO 2 followed by a 5 minute chase with unlabeled CO 2 . After the chase period, very little label remained in the ionic fractions except at low CO 2 partial pressure. Most label was found in the neutral, alcohol soluble fraction or in the insoluble fraction digestable by amyloglucosidase. Sucrose formation was linearly related to assimilation rate. Starch formation increased linearly with assimilation rate, but did not occur if the assimilation rate was below 4 micromoles per square meter per second. Neither abscisic acid, nor high CO 2 in combination with low O 2 caused significant perturbations of the sucrose/starch formation ratio. These studies indicate that the pathways for starch and sucrose synthesis both are controlled by the rate of net CO 2 assimilation, with sucrose the preferred product at very low assimilation rates

  8. Effects of substrate temperature and Cu underlayer thickness on the formation of SmCo5(0001) epitaxial thin films

    International Nuclear Information System (INIS)

    Ohtake, Mitsuru; Nukaga, Yuri; Futamoto, Masaaki; Kirino, Fumiyoshi

    2010-01-01

    SmCo 5 (0001) epitaxial thin films were prepared on Cu(111) underlayers heteroepitaxially grown on Al 2 O 3 (0001) single-crystal substrates by molecular beam epitaxy. The effects of substrate temperature and Cu underlayer thickness on the crystallographic properties of SmCo 5 (0001) epitaxial films were investigated. The Cu atoms of underlayer diffuse into the SmCo 5 film and substitute the Co sites in SmCo 5 structure forming an alloy compound of Sm(Co,Cu) 5 . The ordered phase formation is enhanced with increasing the substrate temperature and with increasing the Cu underlayer thickness. The Cu atom diffusion into the SmCo 5 film is assisting the formation of Sm(Co,Cu) 5 ordered phase.

  9. Transformation of Sodium Bicarbonate and CO2 into Sodium Formate over NiPd Nanoparticle Catalyst

    Directory of Open Access Journals (Sweden)

    Mengnan eWang

    2013-09-01

    Full Text Available The present research systematically investigated, for the first time, the transformation of sodium bicarbonate and CO2 into sodium formate over a series of Ni based metal nanoparticles (NPs. Ni NPs and eight NiM (M stands for a second metal NPs were prepared by a facile wet chemical process and then their catalytic performance were evaluated in sodium bicarbonate hydrogenation. Bimetallic NiPd NPs with a composition of 7:3 were found to be superior for this reaction, which are more active than both pure Ni and Pd NPs. Hot filtration experiment suggested the NPs to be the truly catalytic active species and kinetic analysis indicated the reaction mechanism to be different than most homogeneous catalysts. The enhanced activity of the bimetallic nanoparticles may be attributed to their smaller size and improved stability.

  10. Pars plana Ahmed valve and vitrectomy in patients with glaucoma associated with posterior segment disease.

    Science.gov (United States)

    Wallsh, Josh O; Gallemore, Ron P; Taban, Mehran; Hu, Charles; Sharareh, Behnam

    2013-01-01

    To assess the safety and efficacy of a modified technique for pars plana placement of the Ahmed valve in combination with pars plana vitrectomy in the treatment of glaucoma associated with posterior segment disease. Thirty-nine eyes with glaucoma associated with posterior segment disease underwent pars plana vitrectomy combined with Ahmed valve placement. All valves were placed in the pars plana using a modified technique, without the pars plana clip, and using a scleral patch graft. The 24 eyes diagnosed with neovascular glaucoma had an improvement in intraocular pressure from 37.6 mmHg to 13.8 mmHg and best-corrected visual acuity from 2.13 logarithm of minimum angle of resolution to 1.40 logarithm of minimum angle of resolution. Fifteen eyes diagnosed with steroid-induced glaucoma had an improvement in intraocular pressure from 27.9 mmHg to 14.1 mmHg and best-corrected visual acuity from 1.38 logarithm of minimum angle of resolution to 1.13 logarithm of minimum angle of resolution. Complications included four cases of cystic bleb formation and one case of choroidal detachment and explantation for hypotony. Ahmed valve placement through the pars plana during vitrectomy is an effective option for managing complex cases of glaucoma without the use of the pars plana clip.

  11. Facile formation of 2D Co2P@Co3O4 microsheets through in-situ toptactic conversion and surface corrosion: Bifunctional electrocatalysts towards overall water splitting

    Science.gov (United States)

    Yao, Lihua; Zhang, Nan; Wang, Yin; Ni, Yuanman; Yan, Dongpeng; Hu, Changwen

    2018-01-01

    Exploring efficient non-precious electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is crucial for many renewable energy conversion processes. In this work, we report that 2D Co2P@Co3O4 microsheets can be prepared through an in-situ toptactic conversion from single-crystal β-Co(OH)2 microplatelets, associated with a surface phosphatization and corrosion process. The resultant Co2P@Co3O4 2D hybrid materials can further serve as self-supported bifunctional catalytic electrodes to drive the overall water splitting for HER and OER simultaneously, with low overpotentials and high long-term stability. Furthermore, a water electrolyzer based on Co2P@Co3O4 hybrid as both anode and cathode is fabricated, which achieves 10 mA cm-2 current at only 1.57 V during water splitting process. Therefore, this work provides a facile strategy to obtain 2D Co2P-based micro/nanostructures, which act as low-cost and highly active electrocatalysts towards overall water splitting application.

  12. Investigation of Co nanoparticle formation using time-dependent and spatially-resolved X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zinoveva, S

    2008-04-15

    A crucial step towards controlled synthesis of nanoparticles is the detailed understanding of the various chemical processes that take place during the synthesis. X-ray Absorption Spectroscopy (XAS) is especially suitable for elucidating the type and structure of the intermediate metal species. It is applicable to materials that have no long range order and provides information on both electronic and geometric structures. Here a comparative study is reported of the formation of cobalt nanoparticles via thermolysis of two organometallic precursors dicobalt octacarbonyl (DCO) and alkyne-bridged dicobalt hexacarbonyl (ADH) in the presence of aluminum organics. Using time-dependent XAS a reaction pathway different from both the atom based La Mer model and the Watzky and Finsky autocatalytic surface growth model is observed. Where prior to the nucleation several intermediates are formed and the initial nucleus is composed of Co atoms coordinated with ligands Co{sub n}(CO){sub m} with n=2-3, m=3-5. The formation of Co nanoparticles was also investigated using a reaction different from thermolysis of cobalt carbonyls, namely reduction of Co (II) acetate by sodium borohydrate. Here the combination of microreactor system and spatially resolved XAS allowed ''in situ'' monitoring of the wet chemical synthesis. Several steps of the reaction were spatially resolved in the microreactor. The vertical size of the X-ray beam (50 {mu}m) focused with Kirkpatrick-Baez mirror system, determines the time resolution (better than 2 ms). The results provide direct insight into rapid process of nanoparticles formation and demonstrate the potential of this new technique for the fundamental studies of such type of processes where miniaturization and timeresolution are important. Like in the carbonyls thermolysis no evidence for the reduction of the starting complex to isolated Co{sup 0} atoms followed by nucleation of Co{sup 0} atoms was observed. (orig.)

  13. Investigation of Co nanoparticle formation using time-dependent and spatially-resolved X-ray absorption spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Zinoveva, S.

    2008-04-15

    A crucial step towards controlled synthesis of nanoparticles is the detailed understanding of the various chemical processes that take place during the synthesis. X-ray Absorption Spectroscopy (XAS) is especially suitable for elucidating the type and structure of the intermediate metal species. It is applicable to materials that have no long range order and provides information on both electronic and geometric structures. Here a comparative study is reported of the formation of cobalt nanoparticles via thermolysis of two organometallic precursors dicobalt octacarbonyl (DCO) and alkyne-bridged dicobalt hexacarbonyl (ADH) in the presence of aluminum organics. Using time-dependent XAS a reaction pathway different from both the atom based La Mer model and the Watzky and Finsky autocatalytic surface growth model is observed. Where prior to the nucleation several intermediates are formed and the initial nucleus is composed of Co atoms coordinated with ligands Co{sub n}(CO){sub m} with n=2-3, m=3-5. The formation of Co nanoparticles was also investigated using a reaction different from thermolysis of cobalt carbonyls, namely reduction of Co (II) acetate by sodium borohydrate. Here the combination of microreactor system and spatially resolved XAS allowed ''in situ'' monitoring of the wet chemical synthesis. Several steps of the reaction were spatially resolved in the microreactor. The vertical size of the X-ray beam (50 {mu}m) focused with Kirkpatrick-Baez mirror system, determines the time resolution (better than 2 ms). The results provide direct insight into rapid process of nanoparticles formation and demonstrate the potential of this new technique for the fundamental studies of such type of processes where miniaturization and timeresolution are important. Like in the carbonyls thermolysis no evidence for the reduction of the starting complex to isolated Co{sup 0} atoms followed by nucleation of Co{sup 0} atoms was observed. (orig.)

  14. Confined release of CO{sub 2} into the ocean

    Energy Technology Data Exchange (ETDEWEB)

    Adams, E.E.; Zhang, X.Y.; Herzog, H.J. [Massachusetts Inst. of Technology, Cambridge, MA (United States)] [and others

    1993-12-31

    To help reduce global warming, it has been proposed to sequester some CO{sub 2} in the deep ocean. However, current pipe technology is limited to about 600-650 m{sup 4}, so deeper transport requires other means. Recently, it was suggested that CO{sub 2} could be released at depths of 200 - 400 m as a concentrated seawater solution. The dense solution would form a negatively buoyant gravity current and sink to greater depth. In the following we expand our previous calculations showing that an unconfined release of CO{sub 2} will not create sufficient concentration or negative buoyancy. However, release of either compressed gaseous or liquid CO{sub 2} into an appropriately designed confinement vessel could produce sufficient concentration to transport the current to deeper water. Furthermore, such a scheme may facilitate formation of CO{sub 2} hydrate particles that are heavier than seawater, causing further sinking. A recently completed Research Needs assessment study which we conducted for DOE concludes that shallow water disposal of CO{sub 2} may be the most promising CO{sub 2} disposal option.

  15. The magnetic and colloidal properties of CoFe2O4 nanoparticles synthesized by co-precipitation.

    Science.gov (United States)

    Gyergyek, Sašo; Drofenik, Miha; Makovec, Darko

    2014-01-01

    Magnetic CoFe(2)O(4) nanoparticles were synthesized by co-precipitation at 80 °C. This co-precipitation was achieved by the rapid addition of a strong base to an aqueous solution of cations. The investigation of the samples that were quenched at different times after the addition of the base, using transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDXS) and X-ray powder diffractometry, revealed the formation of a Co-deficient amorphous phase and Co(OH)(2), which rapidly reacted to form small CoFe(2)O(4) nanoparticles. The nanoparticles grew with the time of aging at elevated temperature. The colloidal suspensions of the nanoparticles were prepared in both an aqueous medium and in a non-polar organic medium, with the adsorption of citric acid and ricinoleic acid on the nanoparticles, respectively. The measurements of the room-temperature magnetization revealed the ferrimagnetic state of the CoFe(2)O(4) nanoparticles, while their suspensions displayed superparamagnetic behaviour.

  16. CO2 condensation and the climate of early Mars.

    Science.gov (United States)

    Kasting, J F

    1991-01-01

    A one-dimensional, radiative-convective climate model was used to reexamine the question of whether early Mars could have been kept warm by the greenhouse effect of a dense, CO2 atmosphere. The new model differs from previous models by considering the influence of CO2 clouds on the convective lapse rate and on the the planetary radiation budget. Condensation of CO2 decreases the lapse rate and, hence, reduces the magnitude of the greenhouse effect. This phenomenon becomes increasingly important at low solar luminosities and may preclude warm (0 degree C), globally averaged surface temperatures prior to approximately 2 billion years ago unless other greenhouse gases were present in addition to CO2 and H2O. Alternative mechanisms for warming early Mars and explaining channel formation are discussed.

  17. DNA degradation by bleomycin: evidence for 2'R-proton abstraction and for C-O bond cleavage accompanying base propenal formation

    International Nuclear Information System (INIS)

    Ajmera, S.; Wu, J.C.; Worth, L. Jr.; Rabow, L.E.; Stubbe, J.; Kozarich, J.W.

    1986-01-01

    Reaction of poly(dA-[2'S- 3 H]dU) with activated bleomycin yields [ 3 H] uracil propenal that completely retains the tritium label. In contrast, the authors have previously shown that reaction of poly(dA-[2'R- 3 H]dU) with activated bleomycin affords unlabeled uracil propenal. They have also prepared both cis- and trans-thymine propenals by chemical synthesis and have observed that the trans isomer is the exclusive product of the bleomycin reaction. Moreover, the cis isomer was found to be stable to the conditions of bleomycin-induced DNA degradation. Taken together, these results establish that the formation of trans-uracil propenal occurs via an anti-elimination mechanism with the stereospecific abstraction of the 2R proton. The question of phosphodiester bond cleavage during base propenal formation has also been addressed by the analysis of the fate of oxygen-18 in poly(dA-[3'- 18 O]dT) upon reaction with activated bleomycin. The 5'-monophosphate oligonucleotide ends produced from thymine propenal formation have been converted to inorganic phosphate by the action of alkaline phosphatase, and the phosphate has been analyzed for 18 O content by 31 P NMR spectroscopy. The oxygen-18 is retained in the inorganic phosphate, establishing that the formation of thymine propenal by activated bleomycin proceeds with C-O bond cleavage at the 3-position

  18. Density-Driven Flow Simulation in Anisotropic Porous Media: Application to CO2 Geological Sequestration

    KAUST Repository

    Negara, Ardiansyah; Salama, Amgad; Sun, Shuyu

    2014-01-01

    Carbon dioxide (CO2) sequestration in saline aquifers is considered as one of the most viable and promising ways to reduce CO2 concentration in the atmosphere. CO2 is injected into deep saline formations at supercritical state where its density

  19. CO2 Reduction Catalyzed by Nitrogenase: Pathways to Formate, Carbon Monoxide, and Methane

    OpenAIRE

    Khadka, Nimesh; Dean, Dennis R.; Smith, Dayle; Hoffman, Brian M.; Raugei, Simone; Seefeldt, Lance C.

    2016-01-01

    The reduction of N2 to NH3 by Mo-dependent nitrogenase at its active-site metal cluster FeMo-cofactor utilizes reductive elimination (re) of Fe-bound hydrides with obligatory loss of H2 to activate the enzyme for binding/reduction of N2. Earlier work showed that wild type nitrogenase and a nitrogenase having amino acid substitutions in the MoFe protein near FeMo-cofactor can catalytically reduce CO2 by 2 or 8 electrons/protons to carbon monoxide (CO) and methane (CH4) at low rates. Here, it i...

  20. Microwave-assisted nitric acid treatment of sepiolite and functionalization with polyethylenimine applied to CO{sub 2} capture and CO{sub 2}/N{sub 2} separation

    Energy Technology Data Exchange (ETDEWEB)

    Vilarrasa-García, E., E-mail: enrique@gpsa.ufc.br [Department of Chemical Engineering, Universidade Federal do Ceará, Campus do Pici, bl. 709, 60455-760 Fortaleza (Brazil); Cecilia, J.A., E-mail: jacecilia@uma.es [Department of Inorganic Chemistry, Cristallography and Mineralogy, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga (Spain); Bastos-Neto, M., E-mail: mbn@ufc.br [Department of Chemical Engineering, Universidade Federal do Ceará, Campus do Pici, bl. 709, 60455-760 Fortaleza (Brazil); Cavalcante, C.L., E-mail: celio@gpsa.ufc.br [Department of Chemical Engineering, Universidade Federal do Ceará, Campus do Pici, bl. 709, 60455-760 Fortaleza (Brazil); Azevedo, D.C.S., E-mail: diana@gpsa.ufc.br [Department of Chemical Engineering, Universidade Federal do Ceará, Campus do Pici, bl. 709, 60455-760 Fortaleza (Brazil); Rodríguez-Castellón, E., E-mail: castellon@uma.es [Department of Inorganic Chemistry, Cristallography and Mineralogy, Universidad de Málaga, Campus de Teatinos s/n, 29071 Málaga (Spain)

    2017-07-15

    Highlights: • Textural properties of sepiolite can be enhanced by microwave assisted acid treatment. • CO{sub 2} uptake of sepiolite improved significantly after amine modification. • The highest CO{sub 2}/N{sub 2} selectivity is 440 mol CO{sub 2}/mol N{sub 2} at 338 K and low pressures. - Abstract: Sepiolite was treated in HNO{sub 3} solutions with the assistance of microwave radiation. This treatment caused the progressive depletion of Mg{sup 2+}, the gradual degradation of the sepiolite structure and the formation of an amorphous silica phase, which contributes to a noticeable increase of the surface area. The use of microwaves during acid treatment, after few minutes, led to materials with similar S{sub BET} to those obtained after 48 h with conventional heating methods. The influence of mineralogical impurities, crystallinity and chemical composition in the reactivity of sepiolite to this treatment was also studied. The obtained materials were impregnated with polyethylenimine and assessed for CO{sub 2} capture and CO{sub 2}/N{sub 2} selectivity at different temperatures. Experimental equilibrium data were fitted to Langmuir and Sips models. The adsorption data revealed that sepiolite can be an interesting adsorbent for CO{sub 2} capture, achieving a capacity of 1.70 mmol g{sup −1} at 338 K and 1 bar, providing a high CO{sub 2}/N{sub 2} selectivity (440 mol CO{sub 2}/mol N{sub 2}).

  1. Comparison of the Wymark CO2 Reservoir with the Midale Beds at the Weyburn CO2 Injection Project

    International Nuclear Information System (INIS)

    Ryerson, F.; Johnson, J.

    2010-01-01

    The Devonian carbonates of the Duperow Formation on the western flank of the Williston Basin in southwest Saskatchewan contain natural accumulations of CO 2 , and may have done so for as long as 50 m.y. in the views of some investigations. These carbonate sediments are characterized by a succession of carbonate cycles capped by anhydrite-rich evaporites that are thought to act as seals to fluid migration. The Weyburn CO 2 injection site lies 400 km to the east in a series of Mississippian carbonates that were deposited in a similar depositional environment. That natural CO 2 can be stored long-term within carbonate strata has motivated the investigation of the Duperow rocks as a potential natural analogue to storage of anthropogenic CO 2 that may ultimately provide additional confidence for CO 2 sequestration in carbonate lithologies. For the Duperow strata to represent a legitimate analog for Midale injection and storage, the similarity in lithofacies, whole rock compositions, mineral compositions and porosity with the Midale Beds must be established. Previous workers have demonstrated the similarity of the lithofacies at both sites. Here we compare the whole rock compositions, mineralogy and mineral compositions. The major mineral phases at both locales are calcite, dolomite and anhydrite. In addition, accessory pyrite, fluorite and celestine are also observed. The distribution of porosity in the Midale Vuggy units is virtually identical to that of the Duperow Formation, but the Marly units of the Midale have significantly higher porosity. The Duperow Formation is topped by the Dinesmore evaporite that is particularly rich in anhydrite, and often contains authigenic K-feldspar. The chemistry of dolomite and calcite from the two localities also overlaps. Silicate minerals are in low abundance within the analyzed Duperow samples, < 3 wt% on a normative basis, with quartz the only phase identifiable in x-ray diffraction patterns. The Midale Beds contain

  2. CO2 reforming of methane: valorizing CO2 by means of Dielectric Barrier Discharge

    Science.gov (United States)

    Machrafi, H.; Cavadias, S.; Amouroux, J.

    2011-03-01

    The impact of pollution on the environment is causing several problems that are to be reduced as much as possible. One important example is the production of CO2 that is emitted by many transport and industrial applications. An interesting solution is to view CO2 as a source instead of a product that can be stocked. The case considered in this work is the CO2 reformation of methane producing hydrogen and CO. It is an endothermic reaction, for which the activition barrier needs to be overcome. The method of Dielectric Barrier Discharge can do this efficiently. The process relies on the collision of electrons, which are accelerated under an electrical field that is created in the discharge area. This leads to the formation of reactive species, which facilitate the abovementioned reaction. The determination of the electron density is performed by PLASIMO. The study is subsequently continued using the Reaction Engineering module in COMSOL (with an incorporated kinetic mechanism) in order to model the discharge phase. Then COMSOL (continuity and Navier-Stokes equations) is used to model the flow in the post-discharge phase. The results showed that both a 2D and 3D model can be used to model the chemical-plasma process. These methods need strongly reduced kinetic mechanism, which in some cases can cause loss of precision. It is also observed that the present experimental set-up that is modeled needs to be improved. A suggestion is made.

  3. LABORATORY EXPERIMENTS TO SIMULATE CO2 OCEAN DISPOSAL

    Energy Technology Data Exchange (ETDEWEB)

    Stephen M. Masutani

    1999-12-31

    This Final Technical Report summarizes the technical accomplishments of an investigation entitled ''Laboratory Experiments to Simulate CO{sub 2} Ocean Disposal'', funded by the U.S. Department of Energy's University Coal Research Program. This investigation responds to the possibility that restrictions on greenhouse gas emissions may be imposed in the future to comply with the Framework Convention on Climate Change. The primary objective of the investigation was to obtain experimental data that can be applied to assess the technical feasibility and environmental impacts of oceanic containment strategies to limit release of carbon dioxide (CO{sub 2}) from coal and other fossil fuel combustion systems into the atmosphere. A number of critical technical uncertainties of ocean disposal of CO{sub 2} were addressed by performing laboratory experiments on liquid CO{sub 2} jet break-up into a dispersed droplet phase, and hydrate formation, under deep ocean conditions. Major accomplishments of this study included: (1) five jet instability regimes were identified that occur in sequence as liquid CO{sub 2} jet disintegration progresses from laminar instability to turbulent atomization; (2) linear regression to the data yielded relationships for the boundaries between the five instability regimes in dimensionless Ohnesorge Number, Oh, and jet Reynolds Number, Re, space; (3) droplet size spectra was measured over the full range of instabilities; (4) characteristic droplet diameters decrease steadily with increasing jet velocity (and increasing Weber Number), attaining an asymptotic value in instability regime 5 (full atomization); and (5) pre-breakup hydrate formation appears to affect the size distribution of the droplet phase primary by changing the effective geometry of the jet.

  4. Formation of Silica-Lysozyme Composites Through Co-Precipitation and Adsorption

    Directory of Open Access Journals (Sweden)

    Daniela B. van den Heuvel

    2018-04-01

    Full Text Available Interactions between silica and proteins are crucial for the formation of biosilica and the production of novel functional hybrid materials for a range of industrial applications. The proteins control both precipitation pathway and the properties of the resulting silica–organic composites. Here, we present data on the formation of silica–lysozyme composites through two different synthesis approaches (co-precipitation vs. adsorption and show that the chemical and structural properties of these composites, when analyzed using a combination of synchrotron-based scattering (total scattering and small-angle X-ray scattering, spectroscopic, electron microscopy, and potentiometric methods vary dramatically. We document that while lysozyme was not incorporated into nor did its presence alter the molecular structure of silica, it strongly enhanced the aggregation of silica particles due to electrostatic and potentially hydrophobic interactions, leading to the formation of composites with characteristics differing from pure silica. The differences increased with increasing lysozyme content for both synthesis approaches. Yet, the absolute changes differ substantially between the two sets of composites, as lysozyme did not just affect aggregation during co-precipitation but also particle growth and likely polymerization during co-precipitation. Our results improve the fundamental understanding of how organic macromolecules interact with dissolved and nanoparticulate silica and how these interactions control the formation pathway of silica–organic composites from sodium silicate solutions, a widely available and cheap starting material.

  5. Formation of Silica-Lysozyme Composites Through Co-Precipitation and Adsorption

    Science.gov (United States)

    van den Heuvel, Daniela B.; Stawski, Tomasz M.; Tobler, Dominique J.; Wirth, Richard; Peacock, Caroline L.; Benning, Liane G.

    2018-04-01

    Interactions between silica and proteins are crucial for the formation of biosilica and the production of novel functional hybrid materials for a range of industrial applications. The proteins control both precipitation pathway and the properties of the resulting silica-organic composites. Here we present data on the formation of silica-lysozyme composites through two different synthesis approaches (co-precipitation vs. adsorption) and show that the chemical and structural properties of these composites, when analyzed using a combination of synchrotron-based scattering (total scattering and SAXS), spectroscopic, electron microscopy and potentiometric methods vary dramatically. We document that while lysozyme was not incorporated into nor did its presence alter the molecular structure of silica, it strongly enhanced the aggregation of silica particles due to electrostatic and potentially hydrophobic interactions, leading to the formation of composites with characteristics differing from pure silica. The differences increased with increasing lysozyme content for both synthesis approaches. Yet, the absolute changes differ substantially between the two sets of composites, as lysozyme did not just affect aggregation during co-precipitation but also particle growth and likely polymerization during co-precipitation. Our results improve the fundamental understanding of how organic macromolecules interact with dissolved and nanoparticulate silica and how these interactions control the formation pathway of silica-organic composites from sodium silicate solutions, a widely available and cheap starting material.

  6. THE DISTRIBUTION AND CHEMISTRY OF H2CO IN THE DM TAU PROTOPLANETARY DISK

    International Nuclear Information System (INIS)

    Loomis, Ryan A.; Öberg, Karin I.; Guzman, Viviana V.; Cleeves, L. Ilsedore; Andrews, Sean M.

    2015-01-01

    H 2 CO ice on dust grains is an important precursor of complex organic molecules (COMs). H 2 CO gas can be readily observed in protoplanetary disks and may be used to trace COM chemistry. However, its utility as a COM probe is currently limited by a lack of constraints on the relative contributions of two different formation pathways: on icy grain surfaces and in the gas phase. We use archival Atacama Large (sub-)Millimeter Array observations of the resolved distribution of H 2 CO emission in the disk around the young low-mass star DM Tau to assess the relative importance of these formation routes. The observed H 2 CO emission has a centrally peaked and radially broad brightness profile (extending out to 500 AU). We compare these observations with disk chemistry models with and without grain-surface formation reactions and find that both gas and grain-surface chemistry are necessary to explain the spatial distribution of the emission. Gas-phase H 2 CO production is responsible for the observed central peak, while grain-surface chemistry is required to reproduce the emission exterior to the CO snow line (where H 2 CO mainly forms through the hydrogenation of CO ice before being non-thermally desorbed). These observations demonstrate that both gas and grain-surface pathways contribute to the observed H 2 CO in disks and that their relative contributions depend strongly on distance from the host star

  7. CO2 activation on bimetallic CuNi nanoparticles

    Directory of Open Access Journals (Sweden)

    Natalie Austin

    2016-10-01

    Full Text Available Density functional theory calculations have been performed to investigate the structural, electronic, and CO2 adsorption properties of 55-atom bimetallic CuNi nanoparticles (NPs in core-shell and decorated architectures, as well as of their monometallic counterparts. Our results revealed that with respect to the monometallic Cu55 and Ni55 parents, the formation of decorated Cu12Ni43 and core-shell Cu42Ni13 are energetically favorable. We found that CO2 chemisorbs on monometallic Ni55, core-shell Cu13Ni42, and decorated Cu12Ni43 and Cu43Ni12, whereas, it physisorbs on monometallic Cu55 and core-shell Cu42Ni13. The presence of surface Ni on the NPs is key in strongly adsorbing and activating the CO2 molecule (linear to bent transition and elongation of C˭O bonds. This activation occurs through a charge transfer from the NPs to the CO2 molecule, where the local metal d-orbital density localization on surface Ni plays a pivotal role. This work identifies insightful structure-property relationships for CO2 activation and highlights the importance of keeping a balance between NP stability and CO2 adsorption behavior in designing catalytic bimetallic NPs that activate CO2.

  8. Oleic-acid-coated CoFe2O4 nanoparticles synthesized by co-precipitation and hydrothermal synthesis

    International Nuclear Information System (INIS)

    Gyergyek, Sašo; Drofenik, Miha; Makovec, Darko

    2012-01-01

    Highlights: ► Synthesis of oleic-acid-coated CoFe 2 O 4 nanoparticles from an aqueous solution. ► During the co-precipitation of Co 2+ /Fe 3+ single-phase spinel forms. ► During the co-precipitation of Co 2+ /Fe 2+ , feroxyhyte forms in addition to spinel. ► Oleic acid increases the spinel formation temperature and limits particle growth. ► Colloidal suspensions of ferrimagnetic CoFe 2 O 4 were prepared. - Abstract: Oleic-acid-coated CoFe 2 O 4 nanoparticles were synthesized by co-precipitation and hydrothermal synthesis. The coprecipitation of the nanoparticles was achieved by the rapid addition of a strong base to an aqueous solution of cations in the presence of the oleic acid surfactant, or without this additive. The nanoparticles were also synthesized by a hydrothermal treatment of suspensions of the precipitates, coprecipitated at room temperature in the presence of the oleic acid, or without it. The influence of the synthesis conditions, such as the valence state of the iron cation in the starting aqueous solution, the temperature of the treatment and the presence of oleic acid, on the particles size was systematically studied. X-ray powder diffractometry (XRD) and transmission electron microscopy (TEM) coupled with energy-dispersive X-ray spectroscopy (EDS) revealed that, although spinel forms at room temperature, a substantial amount of Co was incorporated within the secondary, feroxyhyte-like phase when the iron cation was in the 2+ state. In contrast, when iron was in the 3+ state, the spinel forms at elevated temperatures of approximately 60 °C. The presence of the oleic acid further increased the formation temperature for the stoichiometric spinel. Moreover, the oleic acid impeded the particles’ growth and enabled the preparation of colloidal suspensions of the nanoparticles in non-polar organic solvents. The nanoparticles’ size was successfully controlled by the temperature of the synthesis in the region where superparamagnetism

  9. Organic chemistry in a CO2 rich early Earth atmosphere

    Science.gov (United States)

    Fleury, Benjamin; Carrasco, Nathalie; Millan, Maëva; Vettier, Ludovic; Szopa, Cyril

    2017-12-01

    The emergence of life on the Earth has required a prior organic chemistry leading to the formation of prebiotic molecules. The origin and the evolution of the organic matter on the early Earth is not yet firmly understood. Several hypothesis, possibly complementary, are considered. They can be divided in two categories: endogenous and exogenous sources. In this work we investigate the contribution of a specific endogenous source: the organic chemistry occurring in the ionosphere of the early Earth where the significant VUV contribution of the young Sun involved an efficient formation of reactive species. We address the issue whether this chemistry can lead to the formation of complex organic compounds with CO2 as only source of carbon in an early atmosphere made of N2, CO2 and H2, by mimicking experimentally this type of chemistry using a low pressure plasma reactor. By analyzing the gaseous phase composition, we strictly identified the formation of H2O, NH3, N2O and C2N2. The formation of a solid organic phase is also observed, confirming the possibility to trigger organic chemistry in the upper atmosphere of the early Earth. The identification of Nitrogen-bearing chemical functions in the solid highlights the possibility for an efficient ionospheric chemistry to provide prebiotic material on the early Earth.

  10. Structures of actin-like ParM filaments show architecture of plasmid-segregating spindles.

    Science.gov (United States)

    Bharat, Tanmay A M; Murshudov, Garib N; Sachse, Carsten; Löwe, Jan

    2015-07-02

    Active segregation of Escherichia coli low-copy-number plasmid R1 involves formation of a bipolar spindle made of left-handed double-helical actin-like ParM filaments. ParR links the filaments with centromeric parC plasmid DNA, while facilitating the addition of subunits to ParM filaments. Growing ParMRC spindles push sister plasmids to the cell poles. Here, using modern electron cryomicroscopy methods, we investigate the structures and arrangements of ParM filaments in vitro and in cells, revealing at near-atomic resolution how subunits and filaments come together to produce the simplest known mitotic machinery. To understand the mechanism of dynamic instability, we determine structures of ParM filaments in different nucleotide states. The structure of filaments bound to the ATP analogue AMPPNP is determined at 4.3 Å resolution and refined. The ParM filament structure shows strong longitudinal interfaces and weaker lateral interactions. Also using electron cryomicroscopy, we reconstruct ParM doublets forming antiparallel spindles. Finally, with whole-cell electron cryotomography, we show that doublets are abundant in bacterial cells containing low-copy-number plasmids with the ParMRC locus, leading to an asynchronous model of R1 plasmid segregation.

  11. Simulation of CO2 Injection in Porous Media with Structural Deformation Effect

    KAUST Repository

    Negara, Ardiansyah

    2011-01-01

    Carbon dioxide (CO2) sequestration is one of the most attractive methods to reduce the amount of CO2 in the atmosphere by injecting it into the geological formations. Furthermore, it is also an effective mechanism for enhanced oil recovery

  12. Competitive Adsorption-Assisted Formation of One-Dimensional Cobalt Nanochains with High CO Hydrogenation Activity

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Xin [State; Ren, Zhibo [State; Institute; Zhu, Xiaolin [State; Zhang, Qinwei [State; Mei, Donghai [Institute; Chen, Biaohua [State

    2017-10-31

    In the present work, cobalt nanochains have been successfully synthesized by a novel co assisted self-assembling formation strategy. A dramatic morphology transformation from cobalt nanoparticles to nanochains are observed when co molecules were introduced into the synthetic system. DFT calculations further confirm that competitive co-adsorbed co and oleylamine over the cobalt nanoparticles facilitates the formation of cobalt nanochains, which show higher co hydrogenation performance. The present work provides a new strategic and promising method for controllable synthesis of catalyst nanomaterials with the preferred surface structure and morphology.

  13. CFD Recombiner Modelling and Validation on the H2-Par and Kali-H2 Experiments

    International Nuclear Information System (INIS)

    Mimouni, S.; Mechitoua, N.; Ouraou, M.

    2011-01-01

    A large amount of Hydrogen gas is expected to be released within the dry containment of a pressurized water reactor (PWR), shortly after the hypothetical beginning of a severe accident leading to the melting of the core. According to local gas concentrations, the gaseous mixture of hydrogen, air and steam can reach the flammability limit, threatening the containment integrity. In order to prevent mechanical loads resulting from a possible conflagration of the gas mixture, French and German reactor containments are equipped with passive autocatalytic recombiners (PARs) which preventively oxidize hydrogen for concentrations lower than that of the flammability limit. The objective of the paper is to present numerical assessments of the recombiner models implemented in CFD solvers NEPTUNE C FD and Code S aturne. Under the EDF/EPRI agreement, CEA has been committed to perform 42 tests of PARs. The experimental program named KALI-H 2 , consists checking the performance and behaviour of PAR. Unrealistic values for the gas temperature are calculated if the conjugate heat transfer and the wall steam condensation are not taken into account. The combined effects of these models give a good agreement between computational results and experimental data

  14. Method and apparatus for efficient injection of CO2 in oceans

    Science.gov (United States)

    West, Olivia R.; Tsouris, Constantinos; Liang, Liyuan

    2003-07-29

    A liquid CO.sub.2 injection system produces a negatively buoyant consolidated stream of liquid CO.sub.2, CO.sub.2 hydrate, and water that sinks upon release at ocean depths in the range of 700-1500 m. In this approach, seawater at a predetermined ocean depth is mixed with the liquid CO.sub.2 stream before release into the ocean. Because mixing is conducted at depths where pressures and temperatures are suitable for CO.sub.2 hydrate formation, the consolidated stream issuing from the injector is negatively buoyant, and comprises mixed CO.sub.2 -hydrate/CO.sub.2 -liquid/water phases. The "sinking" characteristic of the produced stream will prolong the metastability of CO.sub.2 ocean sequestration by reducing the CO.sub.2 dissolution rate into water. Furthermore, the deeper the CO.sub.2 hydrate stream sinks after injection, the more stable it becomes internally, the deeper it is dissolved, and the more dispersed is the resulting CO.sub.2 plume. These factors increase efficiency, increase the residence time of CO2 in the ocean, and decrease the cost of CO.sub.2 sequestration while reducing deleterious impacts of free CO.sub.2 gas in ocean water.

  15. Spontaneous passivation observations during scale formation on mild steel in CO{sub 2} brines

    Energy Technology Data Exchange (ETDEWEB)

    Han Jiabin, E-mail: jhan@lanl.gov [Institute for Corrosion and Multiphase Technology, Department of Chemical and Biomolecular Engineering, Ohio University, 342 West State Street, Athens, OH 45701 (United States); Nesic, Srdjan, E-mail: nesic@ohio.edu [Institute for Corrosion and Multiphase Technology, Department of Chemical and Biomolecular Engineering, Ohio University, 342 West State Street, Athens, OH 45701 (United States); Yang Yang; Brown, Bruce N. [Institute for Corrosion and Multiphase Technology, Department of Chemical and Biomolecular Engineering, Ohio University, 342 West State Street, Athens, OH 45701 (United States)

    2011-06-01

    Highlights: > We observed spontaneous passivation was at pH > 7. A higher open circuit potential was achieved comparing to bare surface or FeCO{sub 3} scaled surface. > Effects of pH, temperature, CO{sub 2}/FeCO{sub 3} on spontaneous passivation were systematically investigated. > TEM analysis determined the structure and chemistry of the passive film is Fe{sub 3}O{sub 4} instead of FeCO{sub 3}. > Root cause of the galvanic mechanism of localized CO{sub 2} corrosion is clarified. - Abstract: Previous study revealed localized corrosion in CO{sub 2} environments was driven by a galvanic cell established between pit surfaces and scaled surrounding area. In order to underpin the understanding of the galvanic mechanism of localized corrosion, the root cause of potential differences between these two surfaces, passivation of mild steel, in CO{sub 2} environments was investigated using transmission electron microscopy technique and electrochemical techniques including potentiodynamic polarization, cyclic polarization and open circuit potential techniques. Potentiodynamic polarization experiments showed that the passivation of the carbon steel surface favorably occurred at pH > 7 and facilitated with the presence of FeCO{sub 3} scale. Cyclic polarization tests showed that polarization rate had an important influence on passivation behavior. At a slower polarization rate, lower passivation potential and current density were observed. Spontaneous passivation was evidenced by a significant increase of corrosion resistance and an open circuit potential without any externally applied current or potential during electrode immersion. This process is affected by pH, temperature, presence of CO{sub 2} and iron carbonate. Nevertheless, iron carbonate film is not the only one responsible for passivation, as demonstrated from depassivation tests where passivity was lost without losing the existing iron carbonate film. Transmission electron microscopy technique was used to determine

  16. Autotrophic fixation of geogenic CO2 by microorganisms contributes to soil organic matter formation and alters isotope signatures in a wetland mofette

    DEFF Research Database (Denmark)

    Beulig, Felix

    2015-01-01

    To quantify the contribution of autotrophic microorganisms to organic matter (OM) formation in soils, we investigated natural CO2 vents (mofettes) situated in a wetland in northwest Bohemia (Czech Republic). Mofette soils had higher soil organic matter (SOM) concentrations than reference soils due...... of radiocarbon and enriched in 13C compared to atmospheric CO2. Together, these isotopic signals allow us to distinguish C fixed by plants from C fixed by autotrophic microorganisms using their differences in 13C discrimination. We can then estimate that up to 27 % of soil organic matter in the 0–10 cm layer...... ranged up to 1.59 ± 0.16 μg gdw−1 d−1. We inferred that the negative δ13C shift was caused by the activity of autotrophic microorganisms using the Calvin–Benson–Bassham (CBB) cycle, as indicated from quantification of cbbL/cbbM marker genes encoding for RubisCO by quantitative polymerase chain reaction...

  17. Direct Measurements of Leaf Level CH4 and CO2 Exchange in a Boreal Forest

    Science.gov (United States)

    Crill, P.; Lindroth, A.; Vestin, P.; Båth, A.

    2008-12-01

    Reports of aerobic CH4 sources from leaves and litter of a variety of forests and plant functional types have added a potential mystery to our understanding of CH4 dynamics especially if these sources contribute enough to have a significant impact on the global budget. We have made direct measurements of leaf level CH4 and CO2 exchange using a quartz branch cuvette in a boreal forest in Norunda, Sweden since August of this year. The cuvette was temperature controlled and was designed to close for 5 minutes every 30 minutes. Air was circulated to a Los Gatos CH4/CO2 infrared absorption laser spectrometer. Air and cuvette temperatures, PAR and UV radiation (Kipp and Zonen, CUV4; spectral range 300-380 nm) were measured at the branch chamber. The study was made in the Norunda 100 years old stand consisting of a mixture of Scots pine (Pinus sylvestris L.) , Birch (Betula sp.) and Norway spruce (Picea abies (L.) Karst.). The cuvette was moved between trees at roughly 5 day intervals. A null empty cuvette period was included in the rotation. The initial data show the expected CO2 uptake correlated with incident PAR and low rates of emission at night. However, there was no clear pattern of emissions detectable in the CH4. We estimate that we should be able to resolve a change of 0.5 ppbv CH4 min- 1 with our analytical setup. Both the daytime (1000-1600) and nighttime (2200-0400) averages were less than our detection. Even on very sunny days with high PAR and UV flux values, no consistent pattern was detectable. The lack of a distinct signal may be due to the fact that the past month has been very rainy, it is late in the growth season at these latitudes and sun angles are increasing quickly. The trees were at the northern edge of a clearing and we were also measuring mid height (2-3 m) leaves and branches of young trees. The branch cuvette design can also be optimized to improve its sensitivity.

  18. Net ecosystem CO2 exchange over a larch forest in Hokkaido, Japan

    International Nuclear Information System (INIS)

    Huimin Wang; Saigusa, Nobuko; Yamamoto, Susumu; Kondo, Hiroaki; Hirano, Takashi; Toriyama, Atsushi; Fujinuma, Yasumi

    2004-01-01

    Larch forests are distributed extensively in the east Eurasian continent and are expected to play a significant role in the terrestrial ecosystem carbon cycling process. In view of the fact that studies on carbon exchange for this important biome have been very limited, we have initiated a long-term flux observation in a larch forest ecosystem in Hokkaido in northern Japan since 2000. The net ecosystem CO 2 exchange (NEE) showed large seasonal and diurnal variation. Generally, the larch forest ecosystem released CO 2 in nighttime and assimilated CO 2 in daytime during the growing season from May to October. The ecosystem started to become a net carbon sink in May, reaching a maximum carbon uptake as high as 186 g C m -2 month -1 in June. With the yellowing, senescing and leaf fall, the ecosystem turned into a carbon source in November. During the non-growing season, the larch forest ecosystem became a net source of CO 2 , releasing an average of 16.7 g C m -2 month -1 . Overall, the ecosystem sequestered 141-240 g C m -2 yr -1 in 2001. The NEE was significantly influenced by environmental factors. Respiration of the ecosystem, for example, was exponentially dependent on air temperature, while photosynthesis was related to the incident PAR in a manner consistent with the Michaelis-Menten model. Although the vapor pressure deficit (VPD) was scarcely higher than 15 hPa, the CO 2 uptake rate was also depressed when VPD surpassed 10 hPa (Author)

  19. A combined methodology using electrical resistivity tomography, ordinary kriging and porosimetry for quantifying total C trapped in carbonate formations associated with natural analogues for CO2 leakage

    Science.gov (United States)

    Prado-Pérez, A. J.; Aracil, E.; Pérez del Villar, L.

    2014-06-01

    Currently, carbon deep geological storage is one of the most accepted methods for CO2 sequestration, being the long-term behaviour assessment of these artificial systems absolutely essential to guarantee the safety of the CO2 storage. In this sense, hydrogeochemical modelling is being used for evaluating any artificial CO2 deep geological storage as a potential CO2 sinkhole and to assess the leakage processes that are usually associated with these engineered systems. Carbonate precipitation, as travertines or speleothems, is a common feature in the CO2 leakage scenarios and, therefore, is of the utmost importance to quantify the total C content trapped as a stable mineral phase in these carbonate formations. A methodology combining three classical techniques such as: electrical resistivity tomography, geostatistical analysis and mercury porosimetry is described in this work, which was developed for calculating the total amount of C trapped as CaCO3 associated with the CO2 leakages in Alicún de las Torres natural analogue (Granada, Spain). The proposed methodology has allowed estimating the amount of C trapped as calcite, as more than 1.7 Mt. This last parameter, focussed on an artificial CO2 deep geological storage, is essential for hydrogeochemical modellers when evaluating whether CO2 storages constitute or not CO2 sinkholes. This finding is extremely important when assessing the long-term behaviour and safety of any artificial CO2 deep geological storage.

  20. Spatial control of bone formation using a porous polymer scaffold co-delivering anabolic rhBMP-2 and anti-resorptive agents

    Directory of Open Access Journals (Sweden)

    NYC Yu

    2014-01-01

    Full Text Available Current clinical delivery of recombinant human bone morphogenetic proteins (rhBMPs utilises freeze-dried collagen. Despite effective new bone generation, rhBMP via collagen can be limited by significant complications due to inflammation and uncontrolled bone formation. This study aimed to produce an alternative rhBMP local delivery system to permit more controllable and superior rhBMP-induced bone formation. Cylindrical porous poly(lactic-co-glycolic acid (PLGA scaffolds were manufactured by thermally-induced phase separation. Scaffolds were encapsulated with anabolic rhBMP-2 (20 µg ± anti-resorptive agents: zoledronic acid (5 µg ZA, ZA pre-adsorbed onto hydroxyapatite microparticles, (5 µg ZA/2 % HA or IkappaB kinase (IKK inhibitor (10 µg PS-1145. Scaffolds were inserted in a 6-mm critical-sized femoral defect in Wistar rats, and compared against rhBMP-2 via collagen. The regenerate region was examined at 6 weeks by 3D microCT and descriptive histology. MicroCT and histology revealed rhBMP-induced bone was more restricted in the PLGA scaffolds than collagen scaffolds (-92.3 % TV, p < 0.01. The regenerate formed by PLGA + rhBMP-2/ZA/HA showed comparable bone volume to rhBMP-2 via collagen, and bone mineral density was +9.1 % higher (p < 0.01. Local adjunct ZA/HA or PS-1145 significantly enhanced PLGA + rhBMP-induced bone formation by +78.2 % and +52.0 %, respectively (p ≤ 0.01. Mechanistically, MG-63 human osteoblast-like cells showed cellular invasion and proliferation within PLGA scaffolds. In conclusion, PLGA scaffolds enabled superior spatial control of rhBMP-induced bone formation over clinically-used collagen. The PLGA scaffold has the potential to avoid uncontrollable bone formation-related safety issues and to customise bone shape by scaffold design. Moreover, local treatment with anti-resorptive agents incorporated within the scaffold further augmented rhBMP-induced bone formation.

  1. Improvement of heat transfer by the use of corrugated surfaces; Amelioration du transfert de chaleur par l'emploi de surfaces corruguees

    Energy Technology Data Exchange (ETDEWEB)

    Gargaud, J; Paumard, G [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    This experimental work is designed to determine the friction coefficient and the Margoulis number of internally or externally corrugated cans cooled by air or CO{sub 2} under forced convection, when the Reynolds' number is between 1.5 * 10{sup 4} and 3.5 * 10{sup 6} Different corrugation profiles have been examined; they are made up of variously shaped threading, of rings, of transverse fins, of very small 'herring-bone fins, of undulations. Two types of test have been carried out: 1. tests in annular spaces using CO{sub 2} or air, where the gas circulates between an electrically heated corrugated nucleus having a constant flux and a smooth exterior channel. 2. tests on internally corrugated tubes heated by an external water current and cooled by an internal current of pressurized CO{sub 2}. The first type of test requires probe-measurement of the speeds and the temperatures in the fluid in order to obtain a friction coefficient and a Margoulis' number which are characteristic of the corrugated surface. These coefficients, on the other hand, are given directly by the second, type of test. This work shows the role and the importance of the various geometric and aerodynamic parameters such as relative roughness, the reduced pitch (ratio of the pitches at the height of the corrugation) and the Reynolds' number. (authors) [French] Ce travail experimental a pour objet la determination du coefficient de frottement et du nombre de Margoulis de gaines corruguees exterieurement ou interieurement, refroidies par de l'air ou du CO{sub 2} en convection forcee turbulente, pour des nombres de Reynolds compris entre 1,5.10{sup 4} et 3,5.10{sup 6}. Divers profils de corrugations ont ete examines; ils comprennent des filetages de formes variees, des anneaux, des ailettes transversales et des ailettes en chevrons de tres petites dimensions, des ondulations. Deux types d'essais ont ete realises: 1. des essais en espace annulaire, au CO{sub 2} ou a l'air, ou le gaz circule entre un

  2. Centromere pairing by a plasmid-encoded type I ParB protein

    DEFF Research Database (Denmark)

    Ringgaard, Simon; Löwe, Jan; Gerdes, Kenn

    2007-01-01

    The par2 locus of Escherichia coli plasmid pB171 encodes two trans-acting proteins, ParA and ParB, and two cis-acting sites, parC1 and parC2, to which ParB binds cooperatively. ParA is related to MinD and oscillates in helical structures and thereby positions ParB/parC-carrying plasmids regularly......, hence identifying the N terminus of ParB as a requirement for ParB-mediated centromere pairing. These observations suggest that centromere pairing is an important intermediate step in plasmid partitioning mediated by the common type I loci....

  3. Design of experimental system for supercritical CO2 fracturing under confining pressure conditions

    Science.gov (United States)

    Wang, H.; Lu, Q.; Li, X.; Yang, B.; Zheng, Y.; Shi, L.; Shi, X.

    2018-03-01

    Supercritical CO2 has the characteristics of low viscosity, high diffusion and zero surface tension, and it is considered as a new fluid for non-polluting and non-aqueous fracturing which can be used for shale gas development. Fracturing refers to a method of utilizing the high-pressure fluid to generate fractures in the rock formation so as to improve the oil and gas flow conditions and increase the oil and gas production. In this article, a new type of experimental system for supercritical CO2 fracturing under confining pressure conditions is designed, which is based on characteristics of supercritical CO2, shale reservoir and down-hole environment. The experimental system consists of three sub-systems, including supercritical CO2 generation system, supercritical CO2 fracturing system and data analysis system. It can be used to simulate supercritical CO2 fracturing under geo-stress conditions, thus to study the rock initiation pressure, the formation of the rock fractures, fractured surface morphology and so on. The experimental system has successfully carried out a series of supercritical CO2 fracturing experiments. The experimental results confirm the feasibility of the experimental system and the high efficiency of supercritical CO2 in fracturing tight rocks.

  4. Numerical Simulation of Natural Convection in Heterogeneous Porous media for CO2 Geological Storage

    NARCIS (Netherlands)

    Ranganathan, P.; Farajzadeh, R.; Bruining, J.; Zitha, P.L.J.

    2012-01-01

    We report a modeling and numerical simulation study of density-driven natural convection during geological CO2 storage in heterogeneous formations. We consider an aquifer or depleted oilfield overlain by gaseous CO2, where the water density increases due to CO2 dissolution. The heterogeneity of the

  5. Modelling the aqueous and nonaqueous interfaces for CO2 electro-reduction over Sn catalysts

    Science.gov (United States)

    Sheng, Tian; Sun, Shi-Gang

    2018-01-01

    In CO2 electroreduction, Sn catalysts with a high overpotential for hydrogen evolution reaction and a high selectivity towards formic acid formation are very attractive. Many efforts have been made for improving the catalytic performance and for understanding the mechanisms. In electrochemistry, the role of solvents for surface reactions was deserved to be investigated, in particular for some nonaqueous solvents. Here, we have modeled the aqueous (water) and nonaqueous (acetonitrile and dichloromethane) for investigation of CO2 electroreduction on Sn surface, by constrained ab initio molecular dynamics simulations and thermodynamic integrations, including a number of explicit solvent molecules in computational models. It was found that CO2 reduction is initiated from formate formation and solvents, in particular, water can effectively facilitate the reaction.

  6. Efficient Electrocatalytic Reduction of CO2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes - A Step Towards the Electrochemical CO2 Refinery

    KAUST Repository

    Wang, Hong; Jia, Jia; Song, Pengfei; Wang, Qiang; Li, Debao; Min, Shixiong; Qian, Chenxi; Wang, Lu; Li, Young Feng; Ma, Chun; Wu, Tao; Yuan, Jiayin; Antonietti, Markus; Ozin, Geoffrey A.

    2017-01-01

    The search for earth abundant, efficient and stable electrocatalysts that can enable the chemical reduction of CO2 to value-added chemicals and fuels at an industrially relevant scale, is a high priority for the development of a global network of renewable energy conversion and storage systems that can meaningfully impact greenhouse gas induced climate change. Here we introduce a straightforward, low cost, scalable and technologically relevant method to manufacture an all-carbon, electroactive, nitrogen-doped nanoporous carbon-carbon nanotube composite membrane. The membrane is demonstrated to function as a binder-free, high-performance electrode for the electrocatalytic reduction of CO2 to formate. The Faradaic efficiency for the production of formate is 81%. Furthermore, the robust structural and electrochemical properties of the membrane endow it with excellent long-term stability.

  7. Efficient Electrocatalytic Reduction of CO2 by Nitrogen-Doped Nanoporous Carbon/Carbon Nanotube Membranes - A Step Towards the Electrochemical CO2 Refinery

    KAUST Repository

    Wang, Hong

    2017-05-12

    The search for earth abundant, efficient and stable electrocatalysts that can enable the chemical reduction of CO2 to value-added chemicals and fuels at an industrially relevant scale, is a high priority for the development of a global network of renewable energy conversion and storage systems that can meaningfully impact greenhouse gas induced climate change. Here we introduce a straightforward, low cost, scalable and technologically relevant method to manufacture an all-carbon, electroactive, nitrogen-doped nanoporous carbon-carbon nanotube composite membrane. The membrane is demonstrated to function as a binder-free, high-performance electrode for the electrocatalytic reduction of CO2 to formate. The Faradaic efficiency for the production of formate is 81%. Furthermore, the robust structural and electrochemical properties of the membrane endow it with excellent long-term stability.

  8. Contribution to the study of a method for measuring continuously the isotopic effect. The search for an isotopic effect during the reduction of cuprous oxide by a {sup 12}CO - {sup 14}CO mixture (1962); Contribution a l'etude d'une methode de mesure continue de l'effet isotopique. Recherche d'un effet isotopique dans la reduction de l'oxyde cuivreux par le melange {sup 12}CO - {sup 14}CO (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Richard, J [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-15

    The determination of an isotopic effect between the two reactions: {sup 12}CO + Cu{sub 2}O {yields} {sup 12}CO{sub 2} + 2 Cu 'light' reaction {sup 14}CO + Cu{sub 2}O {yields} {sup 14}C{sub O}2 + 2 Cu 'heavy' reaction is possible if the respective kinetics are known. The condensation, during the reaction, of the carbon dioxide formed, and the measurement as a function of time of the residual carbon monoxide pressure, makes it possible to deduce, uninterruptedly, the 'light' reaction kinetics. The 'heavy' reaction kinetics are obtained by measuring continuously, in situ, the radioactivity of the residual reactant gas as a function of the time. The apparatus used for this is a plastic scintillator counter. A calibration curve of the measured radioactivity as a function of the reactant gas pressure in the absence of reaction makes it possible to compare the kinetics of the 'light' and 'heavy' reactions. The reaction temperature is chosen such that the reaction rate is sufficiently slow, so that the variation of the radioactivity during unit counting time is negligible. (author) [French] La determination d'un effet isotopique entre les deux reactions: {sup 12}CO + Cu{sub 2}O {yields} {sup 12}CO{sub 2} + 2 Cu reaction 'legere' {sup 14}CO + Cu{sub 2}O {yields} {sup 14}C{sub O}2 + 2 Cu reaction 'lourde' est rendue possible par la connaissance de leurs cinetiques respectives. La condensation, au cours de la reaction, du gaz carbonique forme et la mesure en fonction du temps de la pression de l'oxyde de carbone residuel, permet d'obtenir, de facon continue, la cinetique de la reaction 'legere'. La cinetique de la reaction lourde est determinee par la mesure continue, in situ, du taux de radioactivite du reactif gazeux residuel en fonction du temps. Le dispositif employe dans ce but est un compteur a scintillateur plastique. Une courbe d'etalonnage, du taux mesure de radioactivite en fonction de la pression du gaz reactif, en l'absence de reaction, permet de comparer les

  9. Oxidation of iron and steels by carbon dioxide under pressure (1962); Oxydation du fer et des aciers par l'anhydride carbonique sous pression (1962)

    Energy Technology Data Exchange (ETDEWEB)

    Colombie, M [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1962-07-01

    After having developed one of the first thermo-balances to operate under pressure, we have studied the influence of the pressure on the corrosion of iron and steels by carbon dioxide. The corrosion was followed by three different methods simultaneously: by the oxidation kinetics, by micrographs, and by radiocrystallography. We have been able to show that the influence of the pressure is not negligible and we have provided much experimental evidence: oxidation kinetics, micrographic aspects, surface precipitation of carbon, metal carburization, the texture of the magnetite layer. All these phenomena are certainly modified by changes in the carbon dioxide pressure. In order to interpret most of our results we have been led to believe that the phenomenon of corrosion by CO{sub 2} depends on secondary reactions localised at the oxide-gas interface. This would constitute a major difference between the oxidation by CO{sub 2} and that by oxygen. (author) [French] Apres avoir etudie et mis au point une des premieres thermobalances fonctionnant sous pression, nous avons etudie l'influence de la pression sur la corrosion du fer et des aciers par l'anhydride carbonique. Notre etude a ete conduite simultanement sur trois plans differents: etude des cinetiques d'oxydation, etude micrographique et etude radiocristallographique. Nous avons pu montrer que l'influence de la pression n'etait pas negligeable et nous en avons fourni un faisceau de preuves experimentales important: cinetiques d'oxydation, aspect micrographique, precipitation superficielle de carbone, carburation du metal, texture de la couche de magnetite. Tous ces phenomenes sont sans aucun doute modifies par une variation de pression du gaz carbonique. Pour interpreter la plupart de nos resultats, nous avons ete conduits a penser que le phenomene de corrosion par CO{sub 2} etait tributaire de reactions secondaires localisees a l'interface oxyde-gaz. Ce serait la une des differences fondamentales entre l'oxydation par

  10. Element mobilization and immobilization from carbonate rocks between CO 2 storage reservoirs and the overlying aquifers during a potential CO 2 leakage

    Energy Technology Data Exchange (ETDEWEB)

    Lawter, Amanda R.; Qafoku, Nikolla P.; Asmussen, R. Matthew; Kukkadapu, Ravi K.; Qafoku, Odeta; Bacon, Diana H.; Brown, Christopher F.

    2018-04-01

    Despite the numerous studies on changes within the reservoir following CO2 injection and the effects of CO2 release into overlying aquifers, little or no literature is available on the effect of CO2 release on rock between the storage reservoirs and subsurface. To address this knowledge gap, relevant rock materials, temperatures and pressures were used to study mineralogical and elemental changes in this intermediate zone. After rocks reacted with CO2, liquid analysis showed an increase of major elements (e.g., Ca, and Mg) and variable concentrations of potential contaminants (e.g., Sr and Ba); lower concentrations were observed in N2 controls. In experiments with As/Cd and/or organic spikes, representing potential contaminants in the CO2 plume originating in the storage reservoir, most or all of these contaminants were removed from the aqueous phase. SEM and Mössbauer spectroscopy results showed the formation of new minerals and Fe oxides in some CO2-reacted samples, indicating potential for contaminant removal through mineral incorporation or adsorption onto Fe oxides. These experiments show the interactions between the CO2-laden plume and the rock between storage reservoirs and overlying aquifers have the potential to affect the level of risk to overlying groundwater, and should be considered during site selection and risk evaluation.

  11. Catalytic conversion of CO2 into valuable products

    International Nuclear Information System (INIS)

    Pham-Huu, C.; Ledoux, M.J.

    2008-01-01

    Complete text of publication follows: Synthesis gas, a mixture of H 2 and CO, is an important feed-stock for several chemical processes operated in the production of methanol and synthetic fuels through a Fischer- Tropsch synthesis. Synthesis gas is produced via an endothermic steam reforming of methane (CH 4 + H 2 O → CO + 3H 2 , ΔH = +225.4 kJ.mol -1 ), catalytic or direct partial oxidation of methane (CH 4 + (1/2)O 2CO + 2H 2 , ΔH -38 kJ.mol -1 ) and CO 2 reforming of methane (CH 4 + CO 22CO + 2H 2 , ΔH= +247 kJ.mol -1 ). The main disadvantage of these processes is the high coke formation, essentially in the nano-filament form, which may cause severe deactivation of the catalyst by pore or active site blocking and sometimes, physical disintegration of the catalyst body causing a high pressure drop along the catalyst bed and even, in some cases, inducing damage to the reactor itself. Previous results obtained in the catalytic partial oxidation of methane have shown that due to the hot spot and carbon nano-filaments formation, especially in the case of the CO 2 reforming, the alumina-based catalyst in an extrudate form was broken into powder which induces a significant pressure drop across the catalytic bed. In the case of endothermic reactions, steam and CO 2 reforming, the temperature drop within the catalyst bed could also modified the activity of the catalyst. Silicon carbide (SiC) exhibits a high thermal conductivity, a high resistance towards oxidation, a high mechanical strength, and chemical inertness, all of which make it a good candidate for use as catalyst support in several endothermic and exothermic reactions such as dehydrogenation, selective partial oxidation, and Fischer-Tropsch synthesis. The gas-solid reaction allows the preparation of SiC with medium surface area, i.e. 10 to 40 m 2 .g -1 , and controlled macroscopic shape, i.e. grains, extrudates or foam, for it subsequence use as catalyst support. In addition, due to its chemical

  12. Cu-Sn Bimetallic Catalyst for Selective Aqueous Electroreduction of CO2 to CO

    KAUST Repository

    Sarfraz, Saad

    2016-03-23

    We report a selective and stable electrocatalyst utilizing non-noble metals consisting of Cu and Sn for the efficient and selective reduction of CO2 to CO over a wide potential range. The bimetallic electrode was prepared through the electrodeposition of Sn species on the surface of oxide-derived copper (OD-Cu). The Cu surface, when decorated with an optimal amount of Sn, resulted in a Faradaic efficiency (FE) for CO greater than 90% and a current density of −1.0 mA cm−2 at −0.6 V vs. RHE, compared to the CO FE of 63% and −2.1 mA cm−2 for OD-Cu. Excess Sn on the surface caused H2 evolution with a decreased current density. X-ray diffraction (XRD) suggests the formation of Cu-Sn alloy. Auger electron spectroscopy of the sample surface exhibits zero-valent Cu and Sn after the electrodeposition step. Density functional theory (DFT) calculations show that replacing a single Cu atom with a Sn atom leaves the d-band orbitals mostly unperturbed, signifying no dramatic shifts in the bulk electronic structure. However, the Sn atom discomposes the multi-fold sites on pure Cu, disfavoring the adsorption of H and leaving the adsorption of CO relatively unperturbed. Our catalytic results along with DFT calculations indicate that the presence of Sn on reduced OD-Cu diminishes the hydrogenation capability—i.e., the selectivity towards H2 and HCOOH—while hardly affecting the CO productivity. While the pristine monometallic surfaces (both Cu and Sn) fail to selectively reduce CO2, the Cu-Sn bimetallic electrocatalyst generates a surface that inhibits adsorbed H*, resulting in improved CO FE. This study presents a strategy to provide a low-cost non-noble metals that can be utilized as a highly selective electrocatalyst for the efficient aqueous reduction of CO2.

  13. RESOLUTION DU PROBLEME DE PREDICTION LINEAIRE PAR LA METHODE ULV. APPLICATION AU SIGNAL FID

    Directory of Open Access Journals (Sweden)

    M KHELIF

    2003-06-01

    Full Text Available Dans le cadre de la spectroscopie RMN, notre objectif est de déterminer le spectre d'absorption du signal de précession libre FID par la méthode de prédiction linéaire (PL. Ceci revient à résoudre le problème de prédiction linéaire en exploitant la méthode de corrélation par l'utilisation de la décomposition en valeurs singulières SVD pour l'inversion de la matrice de corrélation. Or, cette technique est la source d'un certain nombre de problèmes lorsque le signal est noyé dans du bruit. Aussi sera-t-elle coûteuse en temps lorsque les dimensions de la matrice de corrélation sont importantes. Afin de résoudre ce problème, nous exploitons les propriétés d'une nouvelle technique dérivée de la SVD, la décomposition ULV pour minimiser le coût du traitement et assurer une inversion correcte de la matrice de corrélation. Dans ce but, nous déterminons le spectre d'absorption par la technique ULV et nous le comparons avec le spectre déterminé par la SVD et  la FFT. Nous comparons par la suite la qualité des spectres obtenus par rapport au spectre d'absorption idéal  déterminé par FFT.

  14. Localized corrosion of carbon steel in a CO{sub 2}-saturated oilfield formation water

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, G.A. [Department of Mechanical and Manufacturing Engineering, University of Calgary, Calgary, AB, T2N 1N4 (Canada); Cheng, Y.F., E-mail: fcheng@ucalgary.c [Department of Mechanical and Manufacturing Engineering, University of Calgary, Calgary, AB, T2N 1N4 (Canada)

    2011-01-01

    In this work, corrosion and localized corrosion behavior of X65 pipeline steel were studied in a simulated, CO{sub 2}-saturated oilfield formation water by various electrochemical measurement techniques, including electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves, galvanic current and localized EIS (LEIS). The morphology and composition of the formed corrosion scale were characterized by scanning electron microscopy and energy-dispersive X-ray analysis. A conceptual model was developed to illustrate the occurrence of localized corrosion of the steel under scale. Both galvanic current and LEIS measurements showed that a galvanic effect existed between the bare steel and the scale-covered region. The scale-covered region served as cathode and the bare steel site as the anode. The big cathode vs. small anode geometry accelerated the local corrosion reaction. At an elevated temperature, a compact, crystalline scale was formed on the steel surface, enhancing the galvanic effect. Moreover, the stability of the scale was increased with time, and localized corrosion of the steel under scale experienced mechanistic changes with time.

  15. Enhanced Photocatalytic Reduction of CO2 to CO through TiO2 Passivation of InP in Ionic Liquids.

    Science.gov (United States)

    Zeng, Guangtong; Qiu, Jing; Hou, Bingya; Shi, Haotian; Lin, Yongjing; Hettick, Mark; Javey, Ali; Cronin, Stephen B

    2015-09-21

    A robust and reliable method for improving the photocatalytic performance of InP, which is one of the best known materials for solar photoconversion (i.e., solar cells). In this article, we report substantial improvements (up to 18×) in the photocatalytic yields for CO2 reduction to CO through the surface passivation of InP with TiO2 deposited by atomic layer deposition (ALD). Here, the main mechanisms of enhancement are the introduction of catalytically active sites and the formation of a pn-junction. Photoelectrochemical reactions were carried out in a nonaqueous solution consisting of ionic liquid, 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM]BF4), dissolved in acetonitrile, which enables CO2 reduction with a Faradaic efficiency of 99% at an underpotential of +0.78 V. While the photocatalytic yield increases with the addition of the TiO2 layer, a corresponding drop in the photoluminescence intensity indicates the presence of catalytically active sites, which cause an increase in the electron-hole pair recombination rate. NMR spectra show that the [EMIM](+) ions in solution form an intermediate complex with CO2(-), thus lowering the energy barrier of this reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Experimental evidence for carbonate precipitation and CO 2 degassing during sea ice formation

    Science.gov (United States)

    Papadimitriou, S.; Kennedy, H.; Kattner, G.; Dieckmann, G. S.; Thomas, D. N.

    2004-04-01

    Chemical and stable carbon isotopic modifications during the freezing of artificial seawater were measured in four 4 m 3 tank incubations. Three of the four incubations were inoculated with a nonaxenic Antarctic diatom culture. The 18 days of freezing resulted in 25 to 27 cm thick ice sheets overlying the residual seawater. The ice phase was characterized by a decrease in temperature from -1.9 to -2.2°C in the under-ice seawater down to -6.7°C in the upper 4 cm of the ice sheet, with a concurrent increase in the salinity of the under-ice seawater and brine inclusions of the ice sheet as a result of physical concentration of major dissolved salts by expulsion from the solid ice matrix. Measurements of pH, total dissolved inorganic carbon (C T) and its stable isotopic composition (δ 13C T) all exhibited changes, which suggest minimal effect by biological activity during the experiment. A systematic drop in pH and salinity-normalized C T by up to 0.37 pH SWS units and 376 μmol C kg -1 respectively at the lowest temperature and highest salinity part of the ice sheet were coupled with an equally systematic 13C enrichment of the C T. Calculations based on the direct pH and C T measurements indicated a steady increase in the in situ concentration of dissolved carbon dioxide (CO 2(aq)) with time and increasing salinity within the ice sheet, partly due to changes in the dissociation constants of carbonic acid in the low temperature-high salinity range within sea ice. The combined effects of temperature and salinity on the solubility of CO 2 over the range of conditions encountered during this study was a slight net decrease in the equilibrium CO 2(aq) concentration as a result of the salting-out overriding the increase in solubility with decreasing temperature. Hence, the increase in the in situ CO 2(aq) concentration lead to saturation or supersaturation of the brine inclusions in the ice sheet with respect to atmospheric pCO 2 (≈3.5 × 10 -4 atm). When all physico

  17. International and European legal aspects on underground geological storage of CO2

    International Nuclear Information System (INIS)

    Wall, C.; Olvstam, M.-L.; Bernstone, C.

    2005-01-01

    The often disconnected international and European legal rules regarding carbon dioxide (CO 2 ) storage in geological formations create legal uncertainty and a slow down in investments. Existing rules for waste dumping, such as the OSPAR and London Conventions implies that CO 2 storage in sub seabed geological formations is not permitted for climate change mitigating purposes. This paper emphasized that even in cases when complete certainty about the exact application of a legal rule is not possible, it is necessary to know if an activity is lawful. It also emphasized that CO 2 storage should be a priority in the international agenda. The current gaps in knowledge concerning the relevant international and European legislation directly related to CO 2 storage were identified in this paper, including long-term liability for risk of damages caused during the injection phase of the well. The current relevant legislation that is not directly concerned with CO 2 storage but which might have an impact on future legislation was also discussed along with relevant legal principles that might influence future legislation. Some of the many ongoing projects concerning CO 2 storage were reviewed along with papers and reports on regulating CO 2 storage. It was concluded that if CO 2 capture and storage is going to be a large-scale concept for mitigating climate change, the legal issues and requirements need to be an area of priority. 16 refs

  18. LDRD final report on "Pumping up CO2 and conversion into useful molecules" (LDRD 105932).

    Energy Technology Data Exchange (ETDEWEB)

    Kemp, Richard Alan; Stewart, Constantine A.; Dickie, Diane A. (University of New Mexico, Albuquerque, NM)

    2009-11-01

    Group 12 metal cyclam complexes and their derivatives as well as (octyl){sub 2}Sn(OMe){sub 2} were examined as potential catalysts for the production of dimethyl carbonate (DMC) using CO{sub 2} and methanol. The zinc cyclams will readily take up carbon dioxide and methanol at room temperature and atmospheric pressure to give the metal methyl carbonate. The tin exhibited an improvement in DMC yields. Studies involving the reaction of bis-phosphino- and (phosphino)(silyl)-amido group 2 and 12 complexes with CO{sub 2} and CS{sub 2} were performed. Notable results include formation of phosphino-substituted isocyanates, fixation of three moles of CO{sub 2} in an unprecedented [N(CO{sub 2}){sub 3}]{sup 3-} anion, and rapid splitting of CS{sub 2} by main group elements under extremely mild conditions. Similar investigations of divalent group 14 silyl amides led to room temperature splitting of CO{sub 2} into CO and metal oxide clusters, and the formation of isocyanates and carbodiimides.

  19. Numerical modeling of CO2 mineralisation during storage in deep saline aquifers

    NARCIS (Netherlands)

    Ranganathan, P.; Van Hemert, P.; Rudolph, S.J.; Zitha, P.L.J.

    2011-01-01

    Simulations are performed to evaluate the feasibility of a potential site within the Rotliegend sandstone formation in the Dutch subsurface at a depth of around 3000 m for CO2 sequestration using the numerical simulator CMG-GEM. Three CO2 storage trapping mechanisms are studied: (1) mobility

  20. Photo-conversion of CO2 using titanium dioxide: enhancements by plasmonic and co-catalytic nanoparticles

    International Nuclear Information System (INIS)

    Mankidy, Bijith D; Joseph, Babu; Gupta, Vinay K

    2013-01-01

    Converting carbon dioxide (CO 2 ) to hydrocarbons that can be used as fuels is beneficial from both environmental and economic points of view. In this study, nanoparticles are designed to enhance the photoreduction of CO 2 on a titanium dioxide (TiO 2 ) catalyst. An increase in catalytic activity is reported when silver (Ag), platinum (Pt) or bimetallic Ag–Pt and core–shell Ag@silica (SiO 2 ) nanoparticles are used with the TiO 2 semiconductor catalyst. Nanoparticles with different elemental composition or geometrical structure facilitate successive photo-excitation steps—generation, transport, storage and interfacial transfer of electrons and holes. Results show that while the addition of either type of nanoparticles augments product formation rates, bimetallic co-catalysts improve product selectivity. When both bimetallic co-catalysts and Ag@SiO 2 nanoparticles are used in combination, product yields are enhanced more than seven fold in comparison to native TiO 2 and high selectivity for methane (CH 4 ) is observed. When the bimetallic Ag–Pt co-catalysts are tuned, a selectivity of CH 4 of approximately 80%, as compared to 20% with only TiO 2 , can be achieved. (paper)

  1. Temperature-programmed reaction of CO2 reduction in the presence of hydrogen over Fe/Al2O3, Re/Al2O3 and Cr-Mn-O/Al2O3 catalysts

    International Nuclear Information System (INIS)

    Mirzabekova, S.R.; Mamedov, A.B.; Krylov, O.V.

    1996-01-01

    Regularities in CO 2 reduction have been studied using the systems Fe/Al 2 O 3 , Re/Al 2 O 3 and Cr-Mn-O/Al 2 O 3 under conditions of thermally programmed reaction by way of example. A sharp increase in the reduction rate in the course of CO 2 interaction with reduced Fe/Al 2 O 3 and Re/Al 2 O 3 , as well as with carbon fragments with addition in CO 2 flow of 1-2%H 2 , has been revealed. The assumption is made on intermediate formation of a formate in the process and on initiating effect of hydrogen on CO 2 reduction by the catalyst. Refs. 26, figs. 10

  2. Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

    Science.gov (United States)

    Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan; Graves, Christopher

    2018-01-01

    Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate the problem, but only to a certain extent. This work shows that a typical SOEC stack converting CO2 to CO and O2 is limited to as little as 15-45% conversion due to risk of carbon formation. Furthermore, cells operated in CO2-electrolysis mode are poisoned by reactant gases containing ppb-levels of sulfur, in contrast to ppm-levels for operation in fuel cell mode.

  3. Cryogenic-SEM investigation of CO{sub 2} hydrate morphologies

    Energy Technology Data Exchange (ETDEWEB)

    Camps, A.P.; Milodowski, A.; Rochelle, C.; Williams, J.F.; Jackson, P. D. [British Geological Survey, Keyworth, Nottinghamshire (United Kingdom); Camps, A.P; Lovell, M.; Williams, J.F. [Leicester Univ., Leicester (United Kingdom). Dept. of Geology

    2008-07-01

    Gas hydrates occur naturally around the world in the shallow-marine geosphere, and are seen as a drilling hazard in the petroleum industry due to their role in the carbon cycle, and their possible contribution in past and present climate change. Hydrates are ice-like structures composed of cages of water molecules containing one or more guest molecules, such as methane and carbon dioxide (CO{sub 2}). CO{sub 2} hydrates also occur naturally on earth and are being investigated for their potential to store large volumes of CO{sub 2} to reduce atmospheric emissions of greenhouse gases as a climate change mitigation strategy. However, the mineralogy and formation processes of hydrates are relatively poorly understood. Different imaging techniques have been utilized to study gas hydrates, such as nuclear magnetic resonance, magnetic resonance imaging, and x-ray computed tomography. Scanning Electron Microscopy (SEM) at cryogenic temperatures is another technique to study hydrates, and has been used successfully for investigation of methane and CO{sub 2} hydrates. This paper presented a study that investigated CO{sub 2} hydrates formed in laboratories, using a cryogenic-SEM. The paper presented the study methods and observations, including euhedral crystalline carbon dioxide hydrate; acicular carbon dioxide hydrate; granoblastic carbon dioxide hydrate; and gas rich carbon dioxide hydrate. It was concluded that the investigation produced various different hydrate morphologies resulting from different formation conditions. Morphologies ranged from well-defined euhedral crystals to acicular needles, and more complex, intricate forms. 22 refs., 6 figs., 1 appendix.

  4. Directed and persistent movement arises from mechanochemistry of the ParA/ParB system.

    Science.gov (United States)

    Hu, Longhua; Vecchiarelli, Anthony G; Mizuuchi, Kiyoshi; Neuman, Keir C; Liu, Jian

    2015-12-22

    The segregation of DNA before cell division is essential for faithful genetic inheritance. In many bacteria, segregation of low-copy number plasmids involves an active partition system composed of a nonspecific DNA-binding ATPase, ParA, and its stimulator protein ParB. The ParA/ParB system drives directed and persistent movement of DNA cargo both in vivo and in vitro. Filament-based models akin to actin/microtubule-driven motility were proposed for plasmid segregation mediated by ParA. Recent experiments challenge this view and suggest that ParA/ParB system motility is driven by a diffusion ratchet mechanism in which ParB-coated plasmid both creates and follows a ParA gradient on the nucleoid surface. However, the detailed mechanism of ParA/ParB-mediated directed and persistent movement remains unknown. Here, we develop a theoretical model describing ParA/ParB-mediated motility. We show that the ParA/ParB system can work as a Brownian ratchet, which effectively couples the ATPase-dependent cycling of ParA-nucleoid affinity to the motion of the ParB-bound cargo. Paradoxically, this resulting processive motion relies on quenching diffusive plasmid motion through a large number of transient ParA/ParB-mediated tethers to the nucleoid surface. Our work thus sheds light on an emergent phenomenon in which nonmotor proteins work collectively via mechanochemical coupling to propel cargos-an ingenious solution shaped by evolution to cope with the lack of processive motor proteins in bacteria.

  5. Improvement of CO sub 2 flood performance

    Energy Technology Data Exchange (ETDEWEB)

    Martin, D.F.; Heller, J.P.

    1991-06-01

    This is the final report of a six-year research project devoted to the study of processes of oil displacement using dense carbon dioxide. The topics studied have included phase behavior and physical properties of mixtures of crude oil with CO{sub 2}, the phenomena involved in the displacement of oil through reservoir rock under oilfield conditions, the influence of stabilized lamella or CO{sub 2}-foam on this displacement and the development of computer programs to simulate the displacement. In addition, the occurrence of nonuniformities in the displacement pattern has also been considered. The effect on displacement of permeability heterogeneities in the reservoir have been studied geostatistically and by direct numerical modelling. Displacement nonuniformities that are induced by viscosity and density differences between displaced and displacing fluids have also been considered, and efforts are described for the development of two different types of additive for purposes of mobility control of CO{sub 2} floods. One of these is the so-called CO{sub 2}-foam, formed by simultaneous flow through the formation of dense CO{sub 2} with a water solution of a special surfactant. The second type under development in the project is known as direct thickener, and consists of a polymer that is soluble in dense CO{sub 2} and able to viscosify it. Significant progress is reported on all of the topics mentioned above. 174 refs., 186 figs., 41 tabs.

  6. Leaching of organic acids from macromolecular organic matter by non-supercritical CO2

    Science.gov (United States)

    Sauer, P.; Glombitza, C.; Kallmeyer, J.

    2012-04-01

    The storage of CO2 in underground reservoirs is discussed controversly in the scientific literature. The worldwide search for suitable storage formations also considers coal-bearing strata. CO2 is already injected into seams for enhanced recovery of coal bed methane. However, the effects of increased CO2 concentration, especially on organic matter rich formations, are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Huge amounts of low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced by the acidic porewater. Recent investigations outlined the importance of LMWOAs as a feedstock for microbial life in the subsurface [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effect of high concentrations of dissolved CO2 on the release of LMWOAs from coal we developed an inexpensive high-pressure high temperature system that allows manipulating the partial pressure of dissolved gases at pressures and temperatures up to 60 MPa and 120° C, respectively. In a reservoir vessel, gases are added to saturate the extraction medium to the desired level. Inside the extraction vessel hangs a flexible and inert PVDF sleeve (polyvinylidene fluoride, almost impermeable for gases), holding the sample and separating it from the pressure fluid. The flexibility of the sleeve allows for subsampling without loss of pressure. Coal samples from the DEBITS-1 well, Waikato Basin, NZ (R0 = 0.29, TOC = 30%). were extracted at 90° C and 5 MPa, either with pure or CO2-saturated water. Subsamples were taken at different time points during the extraction. The extracted LMWOAs such as formate, acetate and oxalate were analysed by ion chromatography. Yields of LMWOAs were higher with pure water than with CO2

  7. Demonstrating storage of CO2 in geological reservoirs: the Sleipner and SACS projects

    International Nuclear Information System (INIS)

    Torp, T.A.; Gale, J.

    2004-01-01

    At the Sleipner gas field in the North Sea, CO 2 has been stripped from the produced natural gas and injected into a sand layer called the Utsira formation. Injection started in October 1996, to date nearly 8 million tonnes of CO 2 have been injected without any significant operational problems observed in the capture plant or in the injection well. The Sleipner project is the first commercial application of CO 2 storage in deep saline aquifers in the world. To monitor the injected CO 2 , a separate project called the saline aquifer CO 0 2 storage (SACS) project was established in 1998. As part of the SACS project, 3D seismic surveying has been used to successfully monitor the CO 2 in the Utsira formation, an industry first. Repeat seismic surveys have successfully imaged movement of the injected CO 2 within the reservoir. Reservoir simulation tools have been successfully adapted to describe the migration of the CO 2 in the reservoir. The simulation packages have been calibrated against the repeat seismic surveys and shown themselves to be capable of replicating the position of the CO 2 in the reservoir. The possible reactions between minerals within the reservoir sand and the injected CO 2 have been studied by laboratory experiments and simulations. The cumulative experiences of the Sleipner and SACS projects will be embodied in a Best Practice Manual to assist other organisations planning CO 2 injection projects to take advantage of the learning processes undertaken and to assist in facilitating new projects of this type. (author)

  8. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration - Literature Review

    International Nuclear Information System (INIS)

    Krupka, Kenneth M.; Cantrell, Kirk J.; McGrail, B. Peter

    2010-01-01

    Permanent storage of anthropogenic CO 2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO 2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO 2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO 2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO 2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO 2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO 2 sequestration. A review of thermodynamic data for CO 2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO 2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO 2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO 2 and CH 4 gases, carbonate aqueous species, and carbonate minerals. Values of Δ f G 298 o and/or log K r,298 o are available for essentially all of these compounds. However, log K r,T o or heat capacity values at temperatures above 298 K exist

  9. Cs2CO3-promoted polycondensation of CO2with diols and dihalides for the synthesis of miscellaneous polycarbonates

    KAUST Repository

    Chen, Zuliang

    2016-07-12

    A one-pot protocol for the direct synthesis of polycarbonates through polycondensation of diols, dihalides and CO2 in the presence of Cs2CO3 is described. The conditions were optimized by studying the polycondensation of CO2 with 1,4-phenylenedimethanol and 1,4-dibromobutane as model monomers. Then, diols and dihalides with different spacers between the reactive groups including aliphatic, aromatic and poly(ethylene glycol) were tested under optimal conditions. Miscellaneous polycarbonates exhibiting molar masses in the range of 43 000 g mol-1 (GPC) and conversion higher than 96% could be obtained. The proposed mechanism rules out the possibility of ether linkage formation during polycondensation and accounts for the creation of carbonate linkages in two different ways. The thermal properties of the synthesized polycarbonates were unveiled by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). © 2016 The Royal Society of Chemistry.

  10. Wellbore integrity analysis of a natural CO2 producer

    KAUST Repository

    Crow, Walter

    2010-03-01

    Long-term integrity of existing wells in a CO2-rich environment is essential for ensuring that geological sequestration of CO2 will be an effective technology for mitigating greenhouse gas-induced climate change. The potential for wellbore leakage depends in part on the quality of the original construction as well as geochemical and geomechanical stresses that occur over its life-cycle. Field data are essential for assessing the integrated effect of these factors and their impact on wellbore integrity, defined as the maintenance of isolation between subsurface intervals. In this report, we investigate a 30-year-old well from a natural CO2 production reservoir using a suite of downhole and laboratory tests to characterize isolation performance. These tests included mineralogical and hydrological characterization of 10 core samples of casing/cement/formation, wireline surveys to evaluate well conditions, fluid samples and an in situ permeability test. We find evidence for CO2 migration in the occurrence of carbonated cement and calculate that the effective permeability of an 11′-region of the wellbore barrier system was between 0.5 and 1 milliDarcy. Despite these observations, we find that the amount of fluid migration along the wellbore was probably small because of several factors: the amount of carbonation decreased with distance from the reservoir, cement permeability was low (0.3-30 microDarcy), the cement-casing and cement-formation interfaces were tight, the casing was not corroded, fluid samples lacked CO2, and the pressure gradient between reservoir and caprock was maintained. We conclude that the barrier system has ultimately performed well over the last 3 decades. These results will be used as part of a broader effort to develop a long-term predictive simulation tool to assess wellbore integrity performance in CO2 storage sites. © 2009 Elsevier Ltd. All rights reserved.

  11. Process-based approach for the detection of CO2 injectate leakage

    Science.gov (United States)

    Romanak, Katherine; Bennett, Philip C.

    2017-11-14

    The present invention includes a method for distinguishing between a natural source of deep gas and gas leaking from a CO.sub.2 storage reservoir at a near surface formation comprising: obtaining one or more surface or near surface geological samples; measuring a CO.sub.2, an O.sub.2, a CH.sub.4, and an N.sub.2 level from the surface or near surface geological sample; determining the water vapor content at or above the surface or near surface geological samples; normalizing the gas mixture of the CO.sub.2, the O.sub.2, the CH.sub.4, the N.sub.2 and the water vapor content to 100% by volume or 1 atmospheric total pressure; determining: a ratio of CO.sub.2 versus N.sub.2; and a ratio of CO.sub.2 to N.sub.2, wherein if the ratio is greater than that produced by a natural source of deep gas CO.sub.2 or deep gas methane oxidizing to CO.sub.2, the ratio is indicative of gas leaking from a CO.sub.2 storage reservoir.

  12. A sensitivity analysis on seismic tomography data with respect to CO2 saturation of a CO2 geological sequestration field

    Science.gov (United States)

    Park, Chanho; Nguyen, Phung K. T.; Nam, Myung Jin; Kim, Jongwook

    2013-04-01

    Monitoring CO2 migration and storage in geological formations is important not only for the stability of geological sequestration of CO2 but also for efficient management of CO2 injection. Especially, geophysical methods can make in situ observation of CO2 to assess the potential leakage of CO2 and to improve reservoir description as well to monitor development of geologic discontinuity (i.e., fault, crack, joint, etc.). Geophysical monitoring can be based on wireline logging or surface surveys for well-scale monitoring (high resolution and nallow area of investigation) or basin-scale monitoring (low resolution and wide area of investigation). In the meantime, crosswell tomography can make reservoir-scale monitoring to bridge the resolution gap between well logs and surface measurements. This study focuses on reservoir-scale monitoring based on crosswell seismic tomography aiming describe details of reservoir structure and monitoring migration of reservoir fluid (water and CO2). For the monitoring, we first make a sensitivity analysis on crosswell seismic tomography data with respect to CO2 saturation. For the sensitivity analysis, Rock Physics Models (RPMs) are constructed by calculating the values of density and P and S-wave velocities of a virtual CO2 injection reservoir. Since the seismic velocity of the reservoir accordingly changes as CO2 saturation changes when the CO2 saturation is less than about 20%, while when the CO2 saturation is larger than 20%, the seismic velocity is insensitive to the change, sensitivity analysis is mainly made when CO2 saturation is less than 20%. For precise simulation of seismic tomography responses for constructed RPMs, we developed a time-domain 2D elastic modeling based on finite difference method with a staggered grid employing a boundary condition of a convolutional perfectly matched layer. We further make comparison between sensitivities of seismic tomography and surface measurements for RPMs to analysis resolution

  13. Osteogenesis differentiation of human periodontal ligament cells by CO2 laser-treatment stimulating macrophages via BMP2 signalling pathway

    International Nuclear Information System (INIS)

    Hsieh, Wen-Hui; Chen, Yi-Jyun; Hung, Chi-Jr; Huang, Tsui-Hsien; Kao, Chia-Tze; Shie, Ming-You

    2014-01-01

    Immune reactions play an important role in determining the biostimulation of bone formation, either in new bone formation or inflammatory fibrous tissue encapsulation. Macrophage cell, the important effector cells in the immune reaction, which are indispensable for osteogenesis and their heterogeneity and plasticity, render macrophages a primer target for immune system modulation. However, there are very few studies about the effects of macrophage cells on laser treatment-regulated osteogenesis. In this study, we used CO 2 laser as a model biostimulation to investigate the role of macrophage cells on the CO 2 laser stimulated osteogenesis. Bone morphogenetic protein 2 (BMP2) was also significantly up regulated by the CO 2 laser stimulation, indicating that macrophage may participate in the CO 2 laser stimulated osteogenesis. Interestingly, when laser treatment macrophage-conditioned medium were applied to human periodontal ligament cells (hPDLs), the osteogenesis differentiation of hPDLs was significantly enhanced, indicating the important role of macrophages in CO 2 laser-induced osteogenesis. These findings provided valuable insights into the mechanism of CO 2 laser-stimulated osteogenic differentiation, and a strategy to optimize the evaluation system for the in vitro osteogenesis capacity of laser treatment. (paper)

  14. Liberation of microbial substrates from macromolecular organic matter by non-supercritical CO2

    Science.gov (United States)

    Sauer, P.; Glombitza, C.; Kallmeyer, J.

    2012-12-01

    The worldwide search for suitable underground storage formations for CO2 also considers coal-bearing strata. CO2 is already injected into coal seams for enhanced recovery of coal bed methane. However, the geochemical and microbiological effects of increased CO2 concentrations on organic matter rich formations are rarely investigated. The injected CO2 will dissolve in the pore water, causing a decrease in pH and resulting in acidic formation waters. Low molecular weight organic acids (LMWOAs) are chemically bound to the macromolecular matrix of sedimentary organic matter and may be liberated by hydrolysis, which is enhanced under acidic conditions. Recent investigations outlined the importance of LMWOAs as a feedstock for subsurface microbial life [1]. Therefore, injection of CO2 into coal formations may result in enhanced nutrient supply for subsurface microbes. To investigate the effects of highly CO2-saturated waters on the release of LMWOAs from coal, we developed an inexpensive high-pressure-high-temperature system that allows manipulating the concentration of dissolved gases up to 60 MPa and 120°C, respectively. The sample is placed in a flexible, gas-tight and inert PVDF sleeve, separating it from the pressure fluid and allowing for subsampling without loss of pressure. Lignite samples from the DEBITS-1 well, Waikato Basin, NZ and the Welzow-Süd open-cast mine, Niederlausitz, Germany, were extracted at 90° C and 5 MPa, with either pure water, CO2-saturated water, CO2/NO2 or CO2/SO2-saturated water. Subsamples were taken at different time points during the 72 hrs. long extraction. Extraction of LMWOAs from coal samples with our pressurised system resulted in yields that were up to four times higher than those reported for Soxhlet extraction [2]. These higher yields may be explained by the fact that during Soxhlet extraction the sample only gets into contact with freshly distilled water, whereas in our system the extraction fluid is circulated, resulting in

  15. Screening and ranking framework (SRF) for geologic CO2 storagesite selection on the basis of HSE risk

    Energy Technology Data Exchange (ETDEWEB)

    Oldenburg, Curtis M.

    2006-11-27

    A screening and ranking framework (SRF) has been developedto evaluate potential geologic carbon dioxide (CO2) storage sites on thebasis of health, safety, and environmental (HSE) risk arising from CO2leakage. The approach is based on the assumption that CO2 leakage risk isdependent on three basic characteristics of a geologic CO2 storage site:(1) the potential for primary containment by the target formation; (2)the potential for secondary containment if the primary formation leaks;and (3) the potential for attenuation and dispersion of leaking CO2 ifthe primary formation leaks and secondary containment fails. Theframework is implemented in a spreadsheet in which users enter numericalscores representing expert opinions or published information along withestimates of uncertainty. Applications to three sites in Californiademonstrate the approach. Refinements and extensions are possible throughthe use of more detailed data or model results in place of propertyproxies.

  16. PVTx properties of the CO2-H2O and CO2-H2O-NaCl systems below 647 K: assessment of experimental data and thermodynamic models

    Science.gov (United States)

    Hu, Jiawen; Duan, Zhenhao; Zhu, Chen; Chou, I.-Ming

    2007-01-01

    Evaluation of CO2 sequestration in formation brine or in seawater needs highly accurate experimental data or models of pressure–volume–temperature-composition (PVTx) properties for the CO2–H2O and CO2–H2O–NaCl systems. This paper presents a comprehensive review of the experimental PVTx properties and the thermodynamic models of these two systems. The following conclusions are drawn from the review: (1) About two-thirds of experimental data are consistent with each other, where the uncertainty in liquid volumes is within 0.5%, and that in gas volumes within 2%. However, this accuracy is not sufficient for assessing CO2 sequestration. Among the data sets for liquids, only a few are available for accurate modeling of CO2 sequestration. These data have an error of about 0.1% on average, roughly covering from 273 to 642 K and from 1 to 35 MPa; (2) There is a shortage of volumetric data of saturated vapor phase. (3) There are only a few data sets for the ternary liquids, and they are inconsistent with each other, where only a couple of data sets can be used to test a predictive density model for CO2 sequestration; (4) Although there are a few models with accuracy close to that of experiments, none of them is accurate enough for CO2 sequestration modeling, which normally needs an accuracy of density better than 0.1%. Some calculations are made available on www.geochem-model.org.

  17. A community standard format for the representation of protein affinity reagents

    DEFF Research Database (Denmark)

    Gloriam, David Erik Immanuel; Orchard, Sandra; Bertinetti, Daniela

    2010-01-01

    Protein affinity reagents (PARs), most commonly antibodies, are essential reagents for protein characterization in basic research, biotechnology, and diagnostics as well as the fastest growing class of therapeutics. Large numbers of PARs are available commercially; however, their quality is often...... that facilitates easy comparison of their cost and quality. However, in contrast to, for example, nucleotide databases among which data are synchronized between the major data providers, current PAR producers, quality control centers, and commercial companies all use incompatible formats, hindering data exchange....... Here we propose Proteomics Standards Initiative (PSI)-PAR as a global community standard format for the representation and exchange of protein affinity reagent data. The PSI-PAR format is maintained by the Human Proteome Organisation PSI and was developed within the context of Proteome...

  18. Investigation of the conversion mechanism of nanosized CoF2

    International Nuclear Information System (INIS)

    Teng, Yin Ting; Pramana, Stevin S.; Ding, Junfeng; Wu, Tom; Yazami, Rachid

    2013-01-01

    Highlights: • First report on synthesis of nanosized cobalt fluoride via precipitation. • CoF x formation during recharging commences at the interface between cobalt and lithium fluoride. • Valance change of cobalt in cobalt fluoride electrode upon discharging and recharging is shown from EELS and XPS. • Lithiation of CoF 2 leads to formation of superparamagnetic nanosized cobalt particles. • Morphology of the conductive carbon addictives used plays a crucial factor in determining the capacity retention ability. -- Abstract: Nanoparticles (∼20 nm) of tetragonal (P42/mnm) cobalt fluoride (CoF 2 ) has been synthesized by precipitation using cobalt nitrate and ammonium fluoride solution at room temperature, followed by annealing at 400 °C under argon atmosphere. The morphology and structure have been studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). The electrochemical lithiation of CoF 2 and its structural and valence changes during conversion have been investigated. Electrochemical measurements revealed a discharge specific capacity close to theoretical specific capacity of 553 mAh g −1 and charge specific capacities ranging from 250 to 450 mAh g −1 in the first cycle, depending on the type of conductive carbon addictive used. Lithiation of CoF 2 occurs without any intercalation, but via conversion reaction CoF 2 + 2Li + + 2e − → Co(0) + 2LiF. During lithiation, CoF 2 is fully reduced to Co(0) and breaks down into smaller particles of ∼2 nm. Upon recharging, CoF x is formed instead of CoF 2 . XPS and EELS studies show that only the surface of the electrode is reconverted back to CoF x during recharging. In addition, recharging to form CoF x commences at the interface between the cobalt and lithium fluoride. These results offer the experimental evidence explaining the lack of cycle stability of metal fluorides that undergo a conversion reaction with lithium such

  19. Two-Phase Reactive Transport Model CO2-Brine at Hontomín Technological Development Plant (Burgos)

    International Nuclear Information System (INIS)

    Rodrigo-Naharro, J.; Recreo-Jiménez, F.

    2015-01-01

    The option of storing CO2 in carbonate formations is a minority in the literature on CO2 Deep Geological Storage (CO2-DGS). However, there is sufficient bibliography on systems where CO2 natural accumulations have remained for centuries in carbonate formations (e.g. McElmo Dome, USA), as well as projects related to the enhanced oil recovery (Weyburn Project, Canada). Both cases can represent natural or industrial analogues of a CO2-DGS. The Technological Development Plant (TDP) at Hontomín (Burgos) was initially designed to inject supercritical CO2 or dissolved CO2 in a Lower Jurassic limestone-dolomite formation of the Burgos Platform, at 1500 m depth approximately. The Dogger Aquifer in the Paris Basin, together with the overlying Albian aquifer, is one of these potential analogues of the Underground Structure of Hontomín due to their stratigraphic, lithological and hydrogeological similarities. However, the drilling of the wells HI (injection) and HA (auscultation) in the TDP at Hontomín in 2014, which have allowed to access to the storage and seal formations, as well as the petrophysical measurements performed by CIUDEN and Fundación Instituto Petrofísico on core samples from both wells, and the hydraulic tests for the dynamic reservoir characterisation, have advised to include the more permeable formation levels of the Norian-Rhaetian “carniolas” in the initially selected storage formation. This formation is located at the bottom of the Sopeña dolomitic Fm., at a depth of 1595-1605 m in the well HI. The existence of sulphates (anhydrite and gypsum) in these levels introduces lithological and geochemical features not present in the Dogger aquifer of the Paris Basin which, in turn, advises to consider the lessons learned from the Weyburn Project. In this report a study of the system CO2–brine–storage rock, close to the well HI, is presented, where the deep aquifer of the Underground Structure of Hontomín could be affected in the chemical

  20. Exceptional Lithium Storage in a Co(OH) 2 Anode: Hydride Formation

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Hyunchul; Choi, Woon Ih [Samsung Advanced Institute of Technology, Samsung Electronics, 130 Samsung-ro, Suwon 16678, South Korea; Jang, Yoonjung; Balasubramanian, Mahalingam [Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States; Lee, Wontae; Park, Gwi Ok; Park, Su Bin; Yoo, Jaeseung; Hong, Jin Seok [Samsung Advanced Institute of Technology, Samsung Electronics, 130 Samsung-ro, Suwon 16678, South Korea; Choi, Youn-Suk [Samsung Advanced Institute of Technology, Samsung Electronics, 130 Samsung-ro, Suwon 16678, South Korea; Lee, Hyo Sug [Samsung Advanced Institute of Technology, Samsung Electronics, 130 Samsung-ro, Suwon 16678, South Korea; Bae, In Tae; Kim, Ji Man; Yoon, Won-Sub

    2018-02-26

    Current lithium ion battery technology is tied in with conventional reaction mechanisms such as insertion, conversion, and alloying reactions even though most future applications like EVs demand much higher energy densities than current ones. Exploring the exceptional reaction mechanism and related electrode materials can be critical for pushing current battery technology to a next level. Here, we introduce an exceptional reaction with a Co(OH)(2) material which exhibits an initial charge capacity of 1112 mAh g(-1), about twice its theoretical value based on known conventional conversion reaction, and retains its first cycle capacity after 30 cycles. The combined results of synchrotron X-ray diffraction and X-ray absorption spectroscopy indicate that nanosized Co metal particles and LiOH are generated by conversion reaction at high voltages, and CoxHy, Li2O, and LiH are subsequently formed by hydride reaction between Co metal, LiOH, and other lithium species at low voltages, resulting in a anomalously high capacity beyond the theoretical capacity of Co(OH)(2). This is further corroborated by AIMD simulations, localized STEM, and XPS. These findings will provide not only further understanding of exceptional lithium storage of recent nanostructured materials but also valuable guidance to develop advanced electrode materials with high energy density for next-generation batteries.

  1. Characterization and Catalytic Activity of Mn-Co/TiO2 Catalysts for NO Oxidation to NO2 at Low Temperature

    Directory of Open Access Journals (Sweden)

    Lu Qiu

    2016-01-01

    Full Text Available A series of Mn-Co/TiO2 catalysts were prepared by wet impregnation method and evaluated for the oxidation of NO to NO2. The effects of Co amounts and calcination temperature on NO oxidation were investigated in detail. The catalytic oxidation ability in the temperature range of 403–473 K was obviously improved by doping cobalt into Mn/TiO2. These samples were characterized by nitrogen adsorption-desorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscope (TEM and hydrogen temperature programmed reduction (H2-TPR. The results indicated that the formation of dispersed Co3O4·CoMnO3 mixed oxides through synergistic interaction between Mn-O and Co-O was directly responsible for the enhanced activities towards NO oxidation at low temperatures. Doping of Co enhanced Mn4+ formation and increased chemical adsorbed oxygen amounts, which also accelerated NO oxidation.

  2. Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

    Science.gov (United States)

    Lobo-Lapidus, Rodrigo J; Gates, Bruce C

    2010-10-04

    Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

  3. The synthesis of higher alcohols from CO2 hydrogenation with Co, Cu, Fe-based catalysts

    International Nuclear Information System (INIS)

    Ji, Qinqin

    2017-01-01

    CO 2 is a clean carbon source for the chemical reactions, many researchers have studied the utilization of CO 2 . Higher alcohols are clean fuel additives. The synthesis of higher alcohols from CO hydrogenation has also been studied by many researchers, but there are few literatures about the synthesis of higher alcohols from CO 2 hydrogenation, which is a complex and difficult reaction. The catalysts that used for higher alcohols synthesis need at least two active phases and good cooperation. In our study, we tested the Co. Cu. Fe spinel-based catalysts and the effect of supports (CNTs and TUD-1) and promoters (K, Na, Cs) to the HAS reaction. We found that catalyst CuFe-precursor-800 is beneficial for the synthesis of C2+ hydrocarbons and higher alcohols. In the CO 2 hydrogenation, Co acts as a methanation catalyst rather than acting as a FT catalyst, because of the different reaction mechanism between CO hydrogenation and CO 2 hydrogenation. In order to inhibit the formation of huge amount of hydrocarbons, it is better to choose catalysts without Co in the CO 2 hydrogenation reaction. Compared the functions of CNTs and TUD-1, we found that CNTs is a perfect support for the synthesis of long-chain products (higher alcohols and C2+ hydrocarbons). The TUD-1 support are more suitable for synthesis of single-carbon products (methane and methanol).The addition of alkalis as promoters does not only lead to increase the conversion of CO 2 and H 2 , but also sharply increased the selectivity to the desired products, higher alcohols. The catalyst 0.5K30CuFeCNTs owns the highest productivities (370.7 g.kg -1 .h -1 ) of higher alcohols at 350 C and 50 bar. (author) [fr

  4. Experimental Ion Mobility measurements in Ne-CO$_2$ and CO$_2$-N$_2$ mixtures

    CERN Document Server

    Encarnação, P.M.C.C.; Veenhof, R.; Neves, P.N.B.; Santos, F.P.; Trindade, A.M.F.; Borges, F.I.G.M.; Conde, C.A.N.

    2016-01-01

    In this paper we present the experimental results for the mobility, K0, of ions in neon-carbon dioxide (Ne-CO2) and carbon dioxide-nitrogen (CO2-N2) gaseous mixtures for total pressures ranging from 8–12 Torr, reduced electric fields in the 10–25 Td range, at room temperature. Regarding the Ne-CO2 mixture only one peak was observed for CO2 concentrations above 25%, which has been identified as an ion originated in CO2, while below 25% of CO2 a second-small peak appears at the left side of the main peak, which has been attributed to impurities. The mobility values for the main peak range between 3.51 ± 0.05 and 1.07 ± 0.01 cm2V−1s−1 in the 10%-99% interval of CO2, and from 4.61 ± 0.19 to 3.00 ± 0.09 cm2V−1s−1 for the second peak observed (10%–25% of CO2). For the CO2-N2, the time-of-arrival spectra displayed only one peak for CO2 concentrations above 10%, which was attributed to ions originated in CO2, namely CO2+(CO2), with a second peak appearing for CO2 concentrations below 10%. This secon...

  5. Characterization of magnetic nano particles of CoFe{sub 2}O{sub 4} and CoZnFe{sub 2}O{sub 4} prepared by the chemical co-precipitation method; Caracterizacion de nanoparticulas magneticas de CoFe{sub 2}O{sub 4} y CoZnFe{sub 2}O{sub 4} preparadas por el metodo de coprecipitacion quimica

    Energy Technology Data Exchange (ETDEWEB)

    Lopez, J.; Zambrano, G.; Gomez, M. E. [Universidad del Valle, Departamento de Fisica, Laboratorio de Peliculas Delgadas, Ciudad Universitaria Melendez, 25360 Cali (Colombia); Prieto, P. [Universidad del Valle, Centro de Excelencia en Nuevos Materiales, Ciudad Universitaria Melendez, 25360 Cali (Colombia); Espinoza B, F. J., E-mail: javierlo21@gmail.com [IPN, Centro de Investigacion y de Estudios Avanzados, Unidad Queretaro, Libramiento Norponiente No. 2000, Fracc. Real de Juriquilla, 76230 Queretaro (Mexico)

    2012-07-01

    Magnetic cobalt ferrite nanoparticles of CoFe{sub 2}O{sub 4} and CoZnFe{sub 2}O{sub 4} were prepared by co-precipitation technique from aqueous salt solutions of Co (II), ZnSO{sub 4} and Fe (III), in an alkaline medium. CoFe{sub 2}O{sub 4} powder samples were structurally characterized by X-ray diffraction, showing the presence of the most intense peat at 2{theta} = 413928{sup o} (Co K{alpha}1) corresponding to the (311) crystallographic orientation of the CoFe{sub 2}O{sub 4} spinel phase. The mean size of the crystalline of CoFe{sub 2}O{sub 4} and CoZnFe{sub 2}O{sub 4} nanoparticles determined from the full width at half maximum of the strongest reflection of the (311) peak by using the Scherrer approximation was calculated to be 11.4 and 7.0 ({+-} o.2) nm, respectively. Transmission electron microscopy studies permitted determining nanoparticle size of CoZnFe{sub 2}O{sub 4}. Fourier transform infrared spectroscopy was used to confirm the formation of Fe-O bonds, allowing identifying the presence of ferrite spinel structure. Magnetic properties were investigated with the aid of a vibrating sample magnetometer at room temperature Herein, the sample showed superparamagnetic behavior, determined by the hysteresis loop finally, due to the hysteresis loop of the CoZnFe{sub 2}O{sub 4} is very small, our magnetic nanoparticles can be considered as a soft magnetic material. These magnetic nanoparticles have interesting technological applications in biomedicine given their biocompatibility, in nano technology, and in ferro fluid preparation. (Author)

  6. Electrocatalytic Production of C3-C4 Compounds by Conversion of CO2 on a Chloride-Induced Bi-Phasic Cu2O-Cu Catalyst.

    Science.gov (United States)

    Lee, Seunghwa; Kim, Dahee; Lee, Jaeyoung

    2015-12-01

    Electrocatalytic conversion of carbon dioxide (CO2) has recently received considerable attention as one of the most feasible CO2 utilization techniques. In particular, copper and copper-derived catalysts have exhibited the ability to produce a number of organic molecules from CO2. Herein, we report a chloride (Cl)-induced bi-phasic cuprous oxide (Cu2O) and metallic copper (Cu) electrode (Cu2OCl) as an efficient catalyst for the formation of high-carbon organic molecules by CO2 conversion, and identify the origin of electroselectivity toward the formation of high-carbon organic compounds. The Cu2OCl electrocatalyst results in the preferential formation of multi-carbon fuels, including n-propanol and n-butane C3-C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. U.S. Department of Energy's site screening, site selection, and initial characterization for storage of CO2 in deep geological formations

    Science.gov (United States)

    Rodosta, T.D.; Litynski, J.T.; Plasynski, S.I.; Hickman, S.; Frailey, S.; Myer, L.

    2011-01-01

    The U.S. Department of Energy (DOE) is the lead Federal agency for the development and deployment of carbon sequestration technologies. As part of its mission to facilitate technology transfer and develop guidelines from lessons learned, DOE is developing a series of best practice manuals (BPMs) for carbon capture and storage (CCS). The "Site Screening, Site Selection, and Initial Characterization for Storage of CO2 in Deep Geological Formations" BPM is a compilation of best practices and includes flowchart diagrams illustrating the general decision making process for Site Screening, Site Selection, and Initial Characterization. The BPM integrates the knowledge gained from various programmatic efforts, with particular emphasis on the Characterization Phase through pilot-scale CO2 injection testing of the Validation Phase of the Regional Carbon Sequestration Partnership (RCSP) Initiative. Key geologic and surface elements that suitable candidate storage sites should possess are identified, along with example Site Screening, Site Selection, and Initial Characterization protocols for large-scale geologic storage projects located across diverse geologic and regional settings. This manual has been written as a working document, establishing a framework and methodology for proper site selection for CO2 geologic storage. This will be useful for future CO2 emitters, transporters, and storage providers. It will also be of use in informing local, regional, state, and national governmental agencies of best practices in proper sequestration site selection. Furthermore, it will educate the inquisitive general public on options and processes for geologic CO2 storage. In addition to providing best practices, the manual presents a geologic storage resource and capacity classification system. The system provides a "standard" to communicate storage and capacity estimates, uncertainty and project development risk, data guidelines and analyses for adequate site characterization, and

  8. Interfacial stability of CoSi2/Si structures grown by molecular beam epitaxy

    Science.gov (United States)

    George, T.; Fathauer, R. W.

    1992-01-01

    The stability of CoSi2/Si interfaces was examined in this study using columnar silicide structures grown on (111) Si substrates. In the first set of experiments, Co and Si were codeposited using MBE at 800 C and the resulting columnar silicide layer was capped by epitaxial Si. Deposition of Co on the surface of the Si capping layer at 800 C results in the growth of the buried silicide columns. The buried columns grow by subsurface diffusion of the deposited Co, suppressing the formation of surface islands of CoSi2. The column sidewalls appear to be less stable than the top and bottom interfaces, resulting in preferential lateral growth and ultimately in the coalescence of the columns to form a continuous buried CoSi2 layer. In the second set of experiments, annealing of a 250 nm-thick buried columnar layer at 1000 C under a 100 nm-thick Si capping layer results in the formation of a surface layer of CoSi2 with a reduction in the sizes of the CoSi2 columns. For a sample having a thicker Si capping layer the annealing leads to Ostwald ripening producing buried equiaxed columns. The high CoSi2/Si interfacial strain could provide the driving force for the observed behavior of the buried columns under high-temperature annealing.

  9. CO 2 breakthrough—Caprock sealing efficiency and integrity for carbon geological storage

    KAUST Repository

    Espinoza, D. Nicolas

    2017-10-23

    Small pores in high specific surface clay-rich caprocks give rise to high capillary entry pressures and high viscous drag that hinder the migration of buoyant carbon dioxide CO2. We measured the breakthrough pressure and ensuing CO2 permeability through sediment plugs prepared with sand, silt, kaolinite and smectite, and monitored their volumetric deformation using high-pressure oedometer cells. The data show water expulsion and volumetric contraction prior to CO2 breakthrough, followed by preferential CO2 flow thereafter. Our experimental results and data gathered from previous studies highlight the inverse relationship between breakthrough pressure and pore size, as anticipated by Laplace’s equation. In terms of macro-scale parameters, the breakthrough pressure increases as the sediment specific surface increases and the porosity decreases. The breakthrough pressure is usually lower than the values predicted with average pore size estimations; it can reach ∼6.2MPa in argillaceous formations, and 11.2MPa in evaporites. The CO2 permeability after breakthrough is significantly lower than the absolute permeability, but it may increase in time due to water displacement and desiccation. Leakage will be advection-controlled once percolation takes place at most storage sites currently being considered. Diffusive and advective CO2 leaks through non-fractured caprocks will be minor and will not compromise the storage capacity at CO2 injection sites. The “sealing number” and the “stability number” combine the initial fluid pressure, the buoyant pressure caused by the CO2 plume, the capillary breakthrough pressure of the caprock, and the stress conditions at the reservoir depth; these two numbers provide a rapid assessment of potential storage sites. Unexpected CO2 migration patterns emerge due to the inherent spatial variability and structural discontinuities in geological formations; sites with redundant seal layers should be sought for the safe and long

  10. ULTimateCO2 - State of the art report. Dealing with uncertainty associated with long-term CO2 geological storage

    International Nuclear Information System (INIS)

    2014-01-01

    ULTimateCO2, a four-year collaborative project financed by the 7. Framework Programme and coordinated by BRGM, aims to shed more light on the long-term processes associated with the geological storage of CO 2 . ULTimateCO2 unites 12 partners (research institutes, universities, industrialists) and a varied panel of experts (NGOs, national authority representatives, IEAGHG,...). Based on a multidisciplinary approach, and bringing together laboratory experiments, numerical modelling and natural analogue field studies, ULTimateCO2 will increase our understanding of the long-term effects of CO 2 Capture and Storage (CCS) in terms of hydrodynamics, geochemistry, mechanics of the storage formations and their vicinity. The report contains the partners' pooled knowledge and provides a view of the current state-of-the-art for the issues addressed by this project: - The long-term reservoir trapping efficiency (WP3); - The long-term sealing integrity of faulted and fractured cap-rock (WP4); - The near-well leakage characterisation and chemical processes (WP5); - The long-term behavior of stored CO 2 looking at the basin scale (WP2); - Uncertainty assessment (WP6). Each chapter is divided into two sections: (i) a summary which explains in 'simple words' the main issues and objectives of the WP, and (ii) a current state of the art section which provides a more sound review on the specific studied processes. The aim is to provide answers to pertinent questions from a variety of users, particularly project owners, site operators and national authorities, about their exposure to uncertainty downstream of closure of a CO 2 geological storage site

  11. Rapid solubility and mineral storage of CO2 in basalt

    DEFF Research Database (Denmark)

    Gislason, Sigurdur R.; Broecker, W.S.; Gunnlaugsson, E.

    2014-01-01

    The long-term security of geologic carbon storage is critical to its success and public acceptance. Much of the security risk associated with geological carbon storage stems from its buoyancy. Gaseous and supercritical CO2 are less dense than formation waters, providing a driving force for it to ......The long-term security of geologic carbon storage is critical to its success and public acceptance. Much of the security risk associated with geological carbon storage stems from its buoyancy. Gaseous and supercritical CO2 are less dense than formation waters, providing a driving force...... for it to escape back to the surface. This buoyancy can be eliminated by the dissolution of CO2 into water prior to, or during its injection into the subsurface. The dissolution makes it possible to inject into fractured rocks and further enhance mineral storage of CO2 especially if injected into silicate rocks...... rich in divalent metal cations such as basalts and ultra-mafic rocks. We have demonstrated the dissolution of CO2 into water during its injection into basalt leading to its geologic solubility storage in less than five minutes and potential geologic mineral storage within few years after injection [1...

  12. Do carboximide–carboxylic acid combinations form co-crystals? The role of hydroxyl substitution on the formation of co-crystals and eutectics

    Directory of Open Access Journals (Sweden)

    Ramanpreet Kaur

    2015-05-01

    Full Text Available Carboxylic acids, amides and imides are key organic systems which provide understanding of molecular recognition and binding phenomena important in biological and pharmaceutical settings. In this context, studies of their mutual interactions and compatibility through co-crystallization may pave the way for greater understanding and new applications of their combinations. Extensive co-crystallization studies are available for carboxylic acid/amide combinations, but only a few examples of carboxylic acid/imide co-crystals are currently observed in the literature. The non-formation of co-crystals for carboxylic acid/imide combinations has previously been rationalized, based on steric and computed stability factors. In the light of the growing awareness of eutectic mixtures as an alternative outcome in co-crystallization experiments, the nature of various benzoic acid/cyclic imide combinations is established in this paper. Since an additional functional group can provide sites for new intermolecular interactions and, potentially, promote supramolecular growth into a co-crystal, benzoic acids decorated with one or more hydroxyl groups have been systematically screened for co-crystallization with one unsaturated and two saturated cyclic imides. The facile formation of an abundant number of hydroxybenzoic acid/cyclic carboximide co-crystals is reported, including polymorphic and variable stoichiometry co-crystals. In the cases where co-crystals did not form, the combinations are shown invariably to result in eutectics. The presence or absence and geometric disposition of hydroxyl functionality on benzoic acid is thus found to drive the formation of co-crystals or eutectics for the studied carboxylic acid/imide combinations.

  13. Synthesis and thermoelectric properties of Sb{sub 0.20}CoSb{sub 2.80} skutterudite

    Energy Technology Data Exchange (ETDEWEB)

    Figueirêdo, C.A., E-mail: camila_fig@hotmail.com [Universidade Federal do Rio Grande do Sul, PGCIMAT, Instituto de Física, 91501-970 Porto Alegre, RS (Brazil); Gallas, M.R. [Universidade Federal do Rio Grande do Sul, PGCIMAT, Instituto de Física, 91501-970 Porto Alegre, RS (Brazil); Institute for Multiscale Simulations, Friedrich-Alexander-Universität, Nägelsbachstrasse 49b, 91052 Erlangen (Germany); Zorzi, J.E. [Universidade de Caxias do Sul, Instituto de Materiais Cerâmicos, 95765-000 Bom Princípio, RS (Brazil); Perottoni, C.A. [Universidade Federal do Rio Grande do Sul, PGCIMAT, Instituto de Física, 91501-970 Porto Alegre, RS (Brazil); Universidade de Caxias do Sul, Instituto de Materiais Cerâmicos, 95765-000 Bom Princípio, RS (Brazil)

    2014-06-15

    Highlights: • A HP-HT Sb{sub 0.20}CoSb{sub 2.80} phase was prepared by processing cobalt antimonide at 7.7 GPa and 550 °C, for (at least) 5 min. • The mechanism of formation of this phase involves (i) decomposition of cobalt antimonide into CoSb{sub 2} and Sb, and (ii) insertion of Sb into the remaining cobalt antimonide. • The mechanism of formation is qualitatively different from that responsible for the formation of the high pressure (greater than 20 GPa) phase. - Abstract: Polycrystalline samples of cobalt antimonide (CoSb{sub 2.79}) were submitted to different conditions of pressure, temperature and processing time, in a high-pressure toroidal-type chamber, aiming to maximize the production of the high pressure phase previously observed in experiments with a diamond anvil cell. Rietveld refinements of X-ray powder diffraction data were performed to determine the phase composition and structural parameters. The maximum yield, 89(2) wt.% of Sb{sub x}CoSb{sub 3−x} phase, was obtained at 7.7 GPa, 550 °C and (at least) 5 min of processing time. The mechanism behind the formation of Sb{sub x}CoSb{sub 3−x} at high pressure and high temperature is actually not the same as that previously inferred from experiments at higher pressures (20 GPa) and room temperature with the diamond anvil cell. Indeed, evidences suggest that, at high pressure and high temperature, Sb{sub x}CoSb{sub 3−x} is formed by insertion of Sb resulting from decomposition of cobalt antimonide. Thermal conductivity, Seebeck coefficient and electrical conductivity were estimated for CoSb{sub 2.79} and Sb{sub 0.20}CoSb{sub 2.80}. The thermoelectric figure of merit at room temperature for Sb{sub 0.20}CoSb{sub 2.80} resulted 33% greater than that for CoSb{sub 2.79}.

  14. Microstructural and strength improvements through the use of Na{sub 2}CO{sub 3} in a cementless Ca(OH){sub 2}-activated Class F fly ash system

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, Dongho; Jun, Yubin; Jeong, Yeonung; Oh, Jae Eun, E-mail: ohjaeeun@unist.ac.kr

    2015-01-15

    This study explores the beneficial effects of Na{sub 2}CO{sub 3} as an additive for microstructural and strength improvements in a Ca(OH){sub 2}-activated fly ash system. NaOH-activated fly ash samples were also tested to compare the effect of Na{sub 2}CO{sub 3}. Compressive strength testing, XRD, SEM/BSE/EDS, {sup 29}Si/{sup 27}Al MAS-NMR, MIP and TGA were performed. The testing results indicate that the use of Na{sub 2}CO{sub 3} for Ca(OH){sub 2}-activation led to a noticeable improvement in strength and microstructure, primarily due to (1) more dissolution of raw fly ash at an early age, (2) more formation of C–S–H [or C–S–H(I)], (3) porosity reduction, and (4) pore-size refinement. We also found that (1) an early high alkalinity from the NaOH formation was not a major cause of strength, (2) geopolymer was not formed despite the early NaOH formation, and (3) no visible pore-filling action of CaCO{sub 3} was observed. However, Na{sub 2}CO{sub 3} did not produce any improvement in strength for NaOH-activated fly ash. -- Highlights: •The use of Na{sub 2}CO{sub 3} significantly improved strength and microstructure. •The use of Na{sub 2}CO{sub 3} induced more dissolution of raw fly ash at early ages. •The use of Na{sub 2}CO{sub 3} promoted more C–S–H [or C–S–H(I)] formation. •The use of Na{sub 2}CO{sub 3} reduced total porosity and refined pore-size distribution. •The use of Na{sub 2}CO{sub 3} produced neither geopolymer formations nor pore-filling actions from CaCO{sub 3}.

  15. CO{sub 2} direct cycles suitable for AGR type reactors; Cycles directs de gaz carbonique applicables aux reacteurs du genre AGR

    Energy Technology Data Exchange (ETDEWEB)

    Maillet, E [Commissariat a l' Energie Atomique. Centre d' Etudes Nucleaires de Saclay, 91 - Gif-sur-Yvette (France)

    1967-10-01

    The perspectives given by the gas turbines under pressure, to build simple nuclear power plants and acieving significantly high yield, are specified. The CO{sub 2} is characterised by by good efficiency under moderate temperature (500 to 750 Celsius degrees), compactness and the simpleness of machines and the safe exploitation (supply, storage, relief cooling, thermosyphon). The revision of thermal properties of the CO{sub 2} and loss elements show that several direct cycles would fit in particular to the AGR type reactors. Cycles that would diverge a little from classical models and able to lead to power and heat generation can lead by simple means to the best results. Several satisfying solutions present for the starting up, the power regulation and the stopping. The nuclear power plant components and the functioning safety are equally considered in the present report. The conclusions stimulate the studies and realizations of carbon dioxide gas turbines in when approprite. [French] Les perspectives offertes par la turbine a gaz sous pression, pour construire des centrales nucleaires simples et de rendement progressivement eleve, se precisent actuellement. le CO{sub 2} se distingue par sa bonne efficacite a temperature moderee (500 a 750 degres celsius), la compacite et la simplicite des machines, et la surete qu'il apporte a l'exploitation ( approvisionnement, stockage, refroidissement de secours, thermosiphon). La revision des proprietes thermophysiques du CO{sub 2} et des elements de pertes montre que divers cycles directs conviendraient en particulier aux reacteurs agr ou derives. Des cycles s'ecartant peu des modeles classiques, et se pretant ulterieurement a la production simultanee d'electricite et de chaleur, peuvent conduire par des moyens simples aux meilleurs resultats d'ensemble. Plusieurs solutions satisfaisantes se presentent pour le demarrage, le reglage de la puissance et l'arret. Les composants de la centrale et la surete de fonctionnement sont

  16. Overcoming double-step CO2 adsorption and minimizing water co-adsorption in bulky diamine-appended variants of Mg2(dobpdc).

    Science.gov (United States)

    Milner, Phillip J; Martell, Jeffrey D; Siegelman, Rebecca L; Gygi, David; Weston, Simon C; Long, Jeffrey R

    2018-01-07

    Alkyldiamine-functionalized variants of the metal-organic framework Mg 2 (dobpdc) (dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising for CO 2 capture applications owing to their unique step-shaped CO 2 adsorption profiles resulting from the cooperative formation of ammonium carbamate chains. Primary , secondary (1°,2°) alkylethylenediamine-appended variants are of particular interest because of their low CO 2 step pressures (≤1 mbar at 40 °C), minimal adsorption/desorption hysteresis, and high thermal stability. Herein, we demonstrate that further increasing the size of the alkyl group on the secondary amine affords enhanced stability against diamine volatilization, but also leads to surprising two-step CO 2 adsorption/desorption profiles. This two-step behavior likely results from steric interactions between ammonium carbamate chains induced by the asymmetrical hexagonal pores of Mg 2 (dobpdc) and leads to decreased CO 2 working capacities and increased water co-adsorption under humid conditions. To minimize these unfavorable steric interactions, we targeted diamine-appended variants of the isoreticularly expanded framework Mg 2 (dotpdc) (dotpdc 4- = 4,4''-dioxido-[1,1':4',1''-terphenyl]-3,3''-dicarboxylate), reported here for the first time, and the previously reported isomeric framework Mg-IRMOF-74-II or Mg 2 (pc-dobpdc) (pc-dobpdc 4- = 3,3'-dioxidobiphenyl-4,4'-dicarboxylate, pc = para -carboxylate), which, in contrast to Mg 2 (dobpdc), possesses uniformally hexagonal pores. By minimizing the steric interactions between ammonium carbamate chains, these frameworks enable a single CO 2 adsorption/desorption step in all cases, as well as decreased water co-adsorption and increased stability to diamine loss. Functionalization of Mg 2 (pc-dobpdc) with large diamines such as N -( n -heptyl)ethylenediamine results in optimal adsorption behavior, highlighting the advantage of tuning both the pore shape and the diamine size for the development of

  17. Rechargeable Al-CO2 Batteries for Reversible Utilization of CO2.

    Science.gov (United States)

    Ma, Wenqing; Liu, Xizheng; Li, Chao; Yin, Huiming; Xi, Wei; Liu, Ruirui; He, Guang; Zhao, Xian; Luo, Jun; Ding, Yi

    2018-05-21

    The excessive emission of CO 2 and the energy crisis are two major issues facing humanity. Thus, the electrochemical reduction of CO 2 and its utilization in metal-CO 2 batteries have attracted wide attention because the batteries can simultaneously accelerate CO 2 fixation/utilization and energy storage/release. Here, rechargeable Al-CO 2 batteries are proposed and realized, which use chemically stable Al as the anode. The batteries display small discharge/charge voltage gaps down to 0.091 V and high energy efficiencies up to 87.7%, indicating an efficient battery performance. Their chemical reaction mechanism to produce the performance is revealed to be 4Al + 9CO 22Al 2 (CO 3 ) 3 + 3C, by which CO 2 is reversibly utilized. These batteries are envisaged to effectively and safely serve as a potential CO 2 fixation/utilization strategy with stable Al. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. CO2 Capture by Carbon Aerogel–Potassium Carbonate Nanocomposites

    Directory of Open Access Journals (Sweden)

    Guang Yang

    2016-01-01

    Full Text Available Recently, various composites for reducing CO2 emissions have been extensively studied. Because of their high sorption capacity and low cost, alkali metal carbonates are recognized as a potential candidate to capture CO2 from flue gas under moist conditions. However, undesirable effects and characteristics such as high regeneration temperatures or the formation of byproducts lead to high energy costs associated with the desorption process and impede the application of these materials. In this study, we focused on the regeneration temperature of carbon aerogel–potassium carbonate (CA–KC nanocomposites, where KC nanocrystals were formed in the mesopores of the CAs. We observed that the nanopore size of the original CA plays an important role in decreasing the regeneration temperature and in enhancing the CO2 capture capacity. In particular, 7CA–KC, which was prepared from a CA with 7 nm pores, exhibited excellent performance, reducing the desorption temperature to 380 K and exhibiting a high CO2 capture capacity of 13.0 mmol/g-K2CO3, which is higher than the theoretical value for K2CO3 under moist conditions.

  19. Binding CO2 from Air by a Bulky Organometallic Cation Containing Primary Amines.

    Science.gov (United States)

    Luo, Yang-Hui; Chen, Chen; Hong, Dan-Li; He, Xiao-Tong; Wang, Jing-Wen; Ding, Ting; Wang, Bo-Jun; Sun, Bai-Wang

    2018-03-21

    The organometallic cation 1 (Fe(bipy-NH 2 ) 3 2+ , bipy-NH 2 = 4,4'-diamino-2,2'-bipyridine), which was constructed in situ in solution, can bind CO 2 from air effectively with a stoichiometric ratio of 1:4 (1/CO 2 ), through the formation of "H-bonded CO 2 " species: [CO 2 -OH-CO 2 ] - and [CO 2 -CO 2 -OH] - . These two species, along with the captured individual CO 2 molecules, connected 1 into a novel 3D (three-dimensional) architecture, that was crystal 1·2(OH - )·4(CO 2 ). The adsorption isotherms, recycling investigations, and the heat capacity of 1 have been investigated; the results revealed that the organometallic cation 1 can be recycled at least 10 times for the real-world CO 2 capture applications. The strategies presented here may provide new hints for the development of new alkanolamine-related absorbents or technologies for CO 2 capture and sequestration.

  20. Synthesis of polyglycocarbonates through polycondensation of glucopyranosides with CO2

    KAUST Repository

    Pati, Debasis

    2017-03-17

    Starting from α-methyl D-glucopyranoside (MDG), three strategies of synthesis of polyglycocarbonates through direct polycondensation with CO2 were tried. Using unprotected MDG for reaction with CO2, water soluble oligoglycocarbonates could be obtained; α-methyl-2,3-di-O-methyl D-glucopyranoside (MDMG) which had its hydroxyls in the C2 and C3 positions protected was also subjected to polycondensation with CO2, affording polyglycocarbonates of limited molar mass due to an equilibrium that prevented the progress of the condensation reaction as in the previous case. Lastly, the polycondensation of MDMG with CO2 and aliphatic or aromatic dihalides was carried out in the presence of Cs2CO3; this resulted in the formation of polyglycocarbonates of rather high molar mass containing either aliphatic or aromatic linkers. The structures of the synthesized monomers and polyglycocarbonates were thoroughly characterized. The thermal properties of the obtained polyglycocarbonates were further investigated by TGA and DSC.

  1. Synthesis of polyglycocarbonates through polycondensation of glucopyranosides with CO2

    KAUST Repository

    Pati, Debasis; Chen, Zuliang; Feng, Xiaoshuang; Hadjichristidis, Nikolaos; Gnanou, Yves

    2017-01-01

    Starting from α-methyl D-glucopyranoside (MDG), three strategies of synthesis of polyglycocarbonates through direct polycondensation with CO2 were tried. Using unprotected MDG for reaction with CO2, water soluble oligoglycocarbonates could be obtained; α-methyl-2,3-di-O-methyl D-glucopyranoside (MDMG) which had its hydroxyls in the C2 and C3 positions protected was also subjected to polycondensation with CO2, affording polyglycocarbonates of limited molar mass due to an equilibrium that prevented the progress of the condensation reaction as in the previous case. Lastly, the polycondensation of MDMG with CO2 and aliphatic or aromatic dihalides was carried out in the presence of Cs2CO3; this resulted in the formation of polyglycocarbonates of rather high molar mass containing either aliphatic or aromatic linkers. The structures of the synthesized monomers and polyglycocarbonates were thoroughly characterized. The thermal properties of the obtained polyglycocarbonates were further investigated by TGA and DSC.

  2. Monitoring CO2 Intrusion in shallow aquifer using complex electrical methods and a novel CO2 sensitive Lidar-based sensor

    Science.gov (United States)

    Leger, E.; Dafflon, B.; Thorpe, M.; Kreitinger, A.; Laura, D.; Haivala, J.; Peterson, J.; Spangler, L.; Hubbard, S. S.

    2016-12-01

    While subsurface storage of CO2 in geological formations offers significant potential to mitigate atmospheric greenhouse gasses, approaches are needed to monitor the efficacy of the strategy as well as possible negative consequences, such as leakage of CO2 or brine into groundwater or release of fugitive gaseous CO2. Groundwater leakages can cause subsequent reactions that may also be deleterious. For example, a release of dissolved CO2 into shallow groundwatersystems can decrease groundwater pH which can potentiallymobilize naturally occurring trace metals and ions. In this perspective, detecting and assessing potential leak requires development of novel monitoring techniques.We present the results of using surface electrical resistivity tomography (ERT) and a novel CO2 sensitive Lidar-based sensor to monitor a controlled CO2 release at the ZeroEmission Research and Technology Center (Bozeman, Montana). Soil temperature and moisture sensors, wellbore water quality measurements as well as chamber-based CO2 flux measurements were used in addition to the ERT and a novel Lidar-based sensor to detect and assess potential leakage into groundwater, vadose zone and atmosphere. The three-week release wascarried out in the vadose and the saturated zones. Well sampling of pH and conductivity and surface CO2 fluxes and concentrations measurements were acquired during the release and are compared with complex electricalresistivity time-lapse measurements. The novel Lidar-based image of the CO2 plume were compared to chamber-based CO2 flux and concentration measurements. While a continuous increase in subsurface ERT and above ground CO2 was documented, joint analysis of the above and below ground data revealed distinct transport behavior in the vadose and saturated zones. Two type of transport were observed, one in the vadoze zone, monitored by CO2 flux chamber and ERT, and the other one in the saturated zone, were ERT and wellsampling were carried. The experiment suggests how

  3. PAR-2 activation enhances weak acid-induced ATP release through TRPV1 and ASIC sensitization in human esophageal epithelial cells.

    Science.gov (United States)

    Wu, Liping; Oshima, Tadayuki; Shan, Jing; Sei, Hiroo; Tomita, Toshihiko; Ohda, Yoshio; Fukui, Hirokazu; Watari, Jiro; Miwa, Hiroto

    2015-10-15

    Esophageal visceral hypersensitivity has been proposed to be the pathogenesis of heartburn sensation in nonerosive reflux disease. Protease-activated receptor-2 (PAR-2) is expressed in human esophageal epithelial cells and is believed to play a role in inflammation and sensation. PAR-2 activation may modulate these responses through adenosine triphosphate (ATP) release, which is involved in transduction of sensation and pain. The transient receptor potential vanilloid receptor 1 (TRPV1) and acid-sensing ion channels (ASICs) are both acid-sensitive nociceptors. However, the interaction among these molecules and the mechanisms of heartburn sensation are still not clear. We therefore examined whether ATP release in human esophageal epithelial cells in response to acid is modulated by TRPV1 and ASICs and whether PAR-2 activation influences the sensitivity of TRPV1 and ASICs. Weak acid (pH 5) stimulated the release of ATP from primary human esophageal epithelial cells (HEECs). This effect was significantly reduced after pretreatment with 5-iodoresiniferatoxin (IRTX), a TRPV1-specific antagonist, or with amiloride, a nonselective ASIC blocker. TRPV1 and ASIC3 small interfering RNA (siRNA) transfection also decreased weak acid-induced ATP release. Pretreatment of HEECs with trypsin, tryptase, or a PAR-2 agonist enhanced weak acid-induced ATP release. Trypsin treatment led to the phosphorylation of TRPV1. Acid-induced ATP release enhancement by trypsin was partially blocked by IRTX, amiloride, or a PAR-2 antagonist. Conversely, acid-induced ATP release was augmented by PAR-2 activation through TRPV1 and ASICs. These findings suggested that the pathophysiology of heartburn sensation or esophageal hypersensitivity may be associated with the activation of PAR-2, TRPV1, and ASICs. Copyright © 2015 the American Physiological Society.

  4. Monolayer dispersion of CoO on Al2O3 probed by positronium atom

    International Nuclear Information System (INIS)

    Liu, Z.W.; Zhang, H.J.; Chen, Z.Q.

    2014-01-01

    CoO/Al 2 O 3 catalysts were prepared by wet impregnation method with CoO contents ranging from 0 wt% to 24 wt%. X-ray diffraction and X-ray photoelectron spectroscopy measurements suggest formation of CoO after calcined in N 2 . Quantitative X-ray diffraction analysis indicates monolayer dispersion capacity of CoO in CoO/Al 2 O 3 catalysts to be about 3 wt%. Positron annihilation lifetime and coincidence Doppler broadening measurements were performed to study the dispersion state of CoO on Al 2 O 3 . The positron lifetime measurements reveal two long lifetime components τ 3 and τ 4 , which correspond to ortho-positronium annihilation lifetime in microvoids and large pores, respectively. It was found that the positronium atom is very sensitive to the dispersion state of CoO on Al 2 O 3 . The presence of CoO significantly decreases both the lifetime and the intensity of τ 4 . Detailed analysis of the coincidence Doppler broadening measurements suggests that with the CoO content lower than the monolayer dispersion, spin conversion reaction of positronium is induced by CoO. When the cobalt content is higher than the monolayer dispersion capacity, inhibition of positronium formation becomes the dominate effect.

  5. L'initiative Agua Limpia para Perú est dirigée par un ancien titulaire ...

    International Development Research Centre (IDRC) Digital Library (Canada)

    9 juil. 2014 ... Au Pérou, de nombreuses sources d'eau sont contaminées par de ... l'accès à une eau propre et la formation sur l'assainissement, les eaux usées et les ... par AguaSAN Perú aux fins du traitement des eaux (en espagnol).

  6. Synthesis and electrical properties of (Pb,Co)Sr2(Y,Ca)Cu2Oz

    Science.gov (United States)

    Tashiro, T.; Maeda, T.; Abe, R.; Takechi, S.; Takahashi, T.; Haruta, M.; Horii, S.

    One of related materials to high-temperature superconductors (HTSC's) with nominal compositions of (Pb0.5Co0.5)Sr2(Y1xCax)Cu2Oz (x=0∼0.6) is synthesized and characterized. All samples are nearly single-phase, and its crystal structure is likely to be so-called "1-2-1-2" type which is one of typical structures of HTSC's. Electrical resistivity is decreased as x increases. While superconductivity is not observed at temperatures between room-temperature and 20 K for all samples, temperature dependence of the resistivity exhibits metallic behavior down to 150 K for x=0.5. Phase formation and transport behavior are discussed focusing on mixed valence-state of Co2+ and Co3+.

  7. Dynamic simulation and optimization of an industrial-scale absorption tower for CO2 capturing from ethane gas

    Directory of Open Access Journals (Sweden)

    Babak Pouladi

    2016-11-01

    Full Text Available This article considers a process technology based on absorption for CO2 capturing of ethane gas in phase 9 and 10 of south pars in Iran using diethanolamine (DEA as absorbent solvent. This CO2 capture plant was designed to achieve 85% CO2 recovery and obtain 19 ppm the CO2 concentration in the outlet of absorber. ASPEN–HYSYS software was used for the dynamic simulation of a commercial-scale CO2 capture plant and amine Pkg equation was chosen from the fluid property package for calculating the thermodynamic properties of the process. A static approach for optimization was used to evaluate the optimum conditions. This research revealed that pressure variation does not have any considerable changes in the absorption process, while both amine inlet temperature and volumetric flow rate increment enhance the absorption tower efficiency. The effect of temperature was very significant as shown in the dynamic study plots. The optimum condition for CO2 absorption from a stream of ethane gas with molar flow rate of 2118 kg mol h−1 was obtained 75 m3  h−1 of amine at 53 °C and 24 bar. This optimized condition is acceptable from economical, safe as well as feasible point of view.

  8. A Review of Hazardous Chemical Species Associated with CO2 Capturefrom Coal-Fired Power Plants and Their Potential Fate in CO2 GeologicStorage

    Energy Technology Data Exchange (ETDEWEB)

    Apps, J.A.

    2006-02-23

    Conventional coal-burning power plants are major contributors of excess CO2 to the atmospheric inventory. Because such plants are stationary, they are particularly amenable to CO2 capture and disposal by deep injection into confined geologic formations. However, the energy penalty for CO2 separation and compression is steep, and could lead to a 30-40 percent reduction in useable power output. Integrated gas combined cycle (IGCC) plants are thermodynamically more efficient, i.e.,produce less CO2 for a given power output, and are more suitable for CO2 capture. Therefore, if CO2 capture and deep subsurface disposal were to be considered seriously, the preferred approach would be to build replacement IGCC plants with integrated CO2 capture, rather than retrofit existing conventional plants. Coal contains minor quantities of sulfur and nitrogen compounds, which are of concern, as their release into the atmosphere leads to the formation of urban ozone and acid rain, the destruction of stratospheric ozone, and global warming. Coal also contains many trace elements that are potentially hazardous to human health and the environment. During CO2 separation and capture, these constituents could inadvertently contaminate the separated CO2 and be co-injected. The concentrations and speciation of the co-injected contaminants would differ markedly, depending on whether CO2 is captured during the operation of a conventional or an IGCC plant, and the specific nature of the plant design and CO2 separation technology. However, regardless of plant design or separation procedures, most of the hazardous constituents effectively partition into the solid waste residue. This would lead to an approximately two order of magnitude reduction in contaminant concentration compared with that present in the coal. Potential exceptions are Hg in conventional plants, and Hg and possibly Cd, Mo and Pb in IGCC plants. CO2 capture and injection disposal could afford an opportunity to deliberately capture

  9. Bimolecular reaction of CH3 + CO in solid p-H2: Infrared absorption of acetyl radical (CH3CO) and CH3-CO complex

    Science.gov (United States)

    Das, Prasanta; Lee, Yuan-Pern

    2014-06-01

    We have recorded infrared spectra of acetyl radical (CH3CO) and CH3-CO complex in solid para-hydrogen (p-H2). Upon irradiation at 248 nm of CH3C(O)Cl/p-H2 matrices, CH3CO was identified as the major product; characteristic intense IR absorption features at 2990.3 (ν9), 2989.1 (ν1), 2915.6 (ν2), 1880.5 (ν3), 1419.9 (ν10), 1323.2 (ν5), 836.6 (ν7), and 468.1 (ν8) cm-1 were observed. When CD3C(O)Cl was used, lines of CD3CO at 2246.2 (ν9), 2244.0 (ν1), 1866.1 (ν3), 1046.7 (ν5), 1029.7 (ν4), 1027.5 (ν10), 889.1 (ν6), and 723.8 (ν7) cm-1 appeared. Previous studies characterized only three vibrational modes of CH3CO and one mode of CD3CO in solid Ar. In contrast, upon photolysis of a CH3I/CO/p-H2 matrix with light at 248 nm and subsequent annealing at 5.1 K before re-cooling to 3.2 K, the CH3-CO complex was observed with characteristic IR features at 3165.7, 3164.5, 2150.1, 1397.6, 1396.4, and 613.0 cm-1. The assignments are based on photolytic behavior, observed deuterium isotopic shifts, and a comparison of observed vibrational wavenumbers and relative IR intensities with those predicted with quantum-chemical calculations. This work clearly indicates that CH3CO can be readily produced from photolysis of CH3C(O)Cl because of the diminished cage effect in solid p-H2 but not from the reaction of CH3 + CO because of the reaction barrier. Even though CH3 has nascent kinetic energy greater than 87 kJ mol-1 and internal energy ˜42 kJ mol-1 upon photodissociation of CH3I at 248 nm, its energy was rapidly quenched so that it was unable to overcome the barrier height of ˜27 kJ mol-1 for the formation of CH3CO from the CH3 + CO reaction; a barrierless channel for formation of a CH3-CO complex was observed instead. This rapid quenching poses a limitation in production of free radicals via bimolecular reactions in p-H2.

  10. Engaging pediatric intensive care unit (PICU) clinical staff to lead practice improvement: the PICU participatory action research project (PICU-PAR).

    Science.gov (United States)

    Collet, Jean-Paul; Skippen, Peter W; Mosavianpour, Mir Kaber; Pitfield, Alexander; Chakraborty, Bubli; Hunte, Garth; Lindstrom, Ronald; Kissoon, Niranjan; McKellin, William H

    2014-01-08

    Despite considerable efforts, engaging staff to lead quality improvement activities in practice settings is a persistent challenge. At British Columbia Children's Hospital (BCCH), the pediatric intensive care unit (PICU) undertook a new phase of quality improvement actions based on the Community of Practice (CoP) model with Participatory Action Research (PAR). This approach aims to mobilize the PICU 'community' as a whole with a focus on practice; namely, to create a 'community of practice' to support reflection, learning, and innovation in everyday work. An iterative two-stage PAR process using mixed methods has been developed among the PICU CoP to describe the environment (stage 1) and implement specific interventions (stage 2). Stage 1 is ethnographic description of the unit's care practice. Surveys, interviews, focus groups, and direct observations describe the clinical staff's experiences and perspectives around bedside care and quality endeavors in the PICU. Contrasts and comparisons across participants, time and activities help understanding the PICU culture and experience. Stage 2 is a succession of PAR spirals, using results from phase 1 to set up specific interventions aimed at building the staff's capability to conduct QI projects while acquiring appropriate technical skills and leadership capacity (primary outcome). Team communication, information, and interaction will be enhanced through a knowledge exchange (KE) and a wireless network of iPADs. Lack of leadership at the staff level in order to improve daily practice is a recognized challenge that faces many hospitals. We believe that the PAR approach within a highly motivated CoP is a sound method to create the social dynamic and cultural context within which clinical teams can grow, reflect, innovate and feel proud to better serve patients.

  11. CuZn Alloy- Based Electrocatalyst for CO2 Reduction

    KAUST Repository

    Alazmi, Amira

    2014-06-01

    ABSTRACT CuZn Alloy- Based Electrocatalyst for CO2 Reduction Amira Alazmi Carbon dioxide (CO2) is one of the major greenhouse gases and its emission is a significant threat to global economy and sustainability. Efficient CO2 conversion leads to utilization of CO2 as a carbon feedstock, but activating the most stable carbon-based molecule, CO2, is a challenging task. Electrochemical conversion of CO2 is considered to be the beneficial approach to generate carbon-containing fuels directly from CO2, especially when the electronic energy is derived from renewable energies, such as solar, wind, geo-thermal and tidal. To achieve this goal, the development of an efficient electrocatalyst for CO2 reduction is essential. In this thesis, studies on CuZn alloys with heat treatments at different temperatures have been evaluated as electrocatalysts for CO2 reduction. It was found that the catalytic activity of these electrodes was strongly dependent on the thermal oxidation temperature before their use for electrochemical measurements. The polycrystalline CuZn electrode without thermal treatment shows the Faradaic efficiency for CO formation of only 30% at applied potential ~−1.0 V vs. RHE with current density of ~−2.55 mA cm−2. In contrast, the reduction of oxide-based CuZn alloy electrode exhibits 65% Faradaic efficiency for CO at lower applied potential about −1.0 V vs. RHE with current density of −2.55 mA cm−2. Furthermore, stable activity was achieved over several hours of the reduction reaction at the modified electrodes. Based on electrokinetic studies, this improvement could be attributed to further stabilization of the CO2•− on the oxide-based Cu-Zn alloy surface.

  12. Adsorption of Dissolved Gases (CH4, CO2, H2, Noble Gases) by Water-Saturated Smectite Clay Minerals

    Science.gov (United States)

    Bourg, I. C.; Gadikota, G.; Dazas, B.

    2016-12-01

    Adsorption of dissolved gases by water-saturated clay minerals plays important roles in a range of fields. For example, gas adsorption in on clay minerals may significantly impact the formation of CH4 hydrates in fine-grained sediments, the behavior of CH4 in shale, CO2 leakage across caprocks of geologic CO2 sequestration sites, H2 leakage across engineered clay barriers of high-level radioactive waste repositories, and noble gas geochemistry reconstructions of hydrocarbon migration in the subsurface. Despite its importance, the adsorption of gases on clay minerals remains poorly understood. For example, some studies have suggested that clay surfaces promote the formation of CH4 hydrates, whereas others indicate that clay surfaces inhibit the formation of CH4 hydrates. Here, we present molecular dynamics (MD) simulations of the adsorption of a range of gases (CH4, CO2, H2, noble gases) on clay mineral surfaces. Our results indicate that the affinity of dissolved gases for clay mineral surfaces has a non-monotone dependence on the hydrated radius of the gas molecules. This non-monotone dependence arises from a combination of two effects: the polar nature of certain gas molecules (in particular, CO2) and the templating of interfacial water structure by the clay basal surface, which results in the presence of interfacial water "cages" of optimal size for intermediate-size gas molecules (such as Ne or Ar).

  13. Biofilm formation by designed co-cultures of Caldicellulosiruptor species as a means to improve hydrogen productivity.

    Science.gov (United States)

    Pawar, Sudhanshu S; Vongkumpeang, Thitiwut; Grey, Carl; van Niel, Ed Wj

    2015-01-01

    Caldicellulosiruptor species have gained a reputation as being among the best microorganisms to produce hydrogen (H2) due to possession of a combination of appropriate features. However, due to their low volumetric H2 productivities (Q H2), Caldicellulosiruptor species cannot be considered for any viable biohydrogen production process yet. In this study, we evaluate biofilm forming potential of pure and co-cultures of Caldicellulosiruptor saccharolyticus and Caldicellulosiruptor owensensis in continuously stirred tank reactors (CSTR) and up-flow anaerobic (UA) reactors. We also evaluate biofilms as a means to retain biomass in the reactor and its influence on Q H2. Moreover, we explore the factors influencing the formation of biofilm. Co-cultures of C. saccharolyticus and C. owensensis form substantially more biofilm than formed by C. owensensis alone. Biofilms improved substrate conversion in both of the reactor systems, but improved the Q H2 only in the UA reactor. When grown in the presence of each other's culture supernatant, both C. saccharolyticus and C. owensensis were positively influenced on their individual growth and H2 production. Unlike the CSTR, UA reactors allowed retention of C. saccharolyticus and C. owensensis when subjected to very high substrate loading rates. In the UA reactor, maximum Q H2 (approximately 20 mmol · L(-1)  · h(-1)) was obtained only with granular sludge as the carrier material. In the CSTR, stirring negatively affected biofilm formation. Whereas, a clear correlation was observed between elevated (>40 μM) intracellular levels of the secondary messenger bis-(3'-5')-cyclic dimeric guanosine monophosphate (c-di-GMP) and biofilm formation. In co-cultures C. saccharolyticus fortified the trade of biofilm formation by C. owensensis, which was mediated by elevated levels of c-di-GMP in C. owensensis. These biofilms were effective in retaining biomass of both species in the reactor and improving Q H2 in a UA reactor using

  14. A One-Step Route to CO2 -Based Block Copolymers by Simultaneous ROCOP of CO2 /Epoxides and RAFT Polymerization of Vinyl Monomers.

    Science.gov (United States)

    Wang, Yong; Zhao, Yajun; Ye, Yunsheng; Peng, Haiyan; Zhou, Xingping; Xie, Xiaolin; Wang, Xianhong; Wang, Fosong

    2018-03-26

    The one-step synthesis of well-defined CO 2 -based diblock copolymers was achieved by simultaneous ring-opening copolymerization (ROCOP) of CO 2 /epoxides and RAFT polymerization of vinyl monomers using a trithiocarbonate compound bearing a carboxylic group (TTC-COOH) as the bifunctional chain transfer agent (CTA). The double chain-transfer effect allows for independent and precise control over the molecular weight of the two blocks and ensures narrow polydispersities of the resultant block copolymers (1.09-1.14). Notably, an unusual axial group exchange reaction between the aluminum porphyrin catalyst and TTC-COOH impedes the formation of homopolycarbonates. By taking advantage of the RAFT technique, it is able to meet the stringent demand for functionality control to well expand the application scopes of CO 2 -based polycarbonates. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Electrochemical reactivity of Co-Li2S nanocomposite for lithium-ion batteries

    International Nuclear Information System (INIS)

    Zhou, Yongning; Wu, Changliang; Zhang, Hua; Wu, Xiaojing; Fu, Zhengwen

    2007-01-01

    The fabrication of Co-Li 2 S nanocomposite thin film is reported by pulsed laser deposition (PLD) for the first time. Li 2 S-Co nanocomposite thin film is used as storing Li electrodes that have led to promising electrochemical activity and good electrochemical performance. The releasing Li process from the as-deposited Li 2 S-Co nanocomposite thin films is confirmed by the ex situ high resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) measurements and may come from the decomposition of Li 2 S with and without the interaction of metal Co into CoS 2 and S. The electrochemical reaction mechanism of Co-Li 2 S nanocomposite film electrode involving both the formation and decomposition of Li 2 S and the lithium extraction/insertion of CoS 2 after the initial charging process is proposed. Our results demonstrate the advantages of using Co-Li 2 S nanocomposite in storage lithium materials

  16. Improved Satellite-based Photosysnthetically Active Radiation (PAR) for Air Quality Studies

    Science.gov (United States)

    Pour Biazar, A.; McNider, R. T.; Cohan, D. S.; White, A.; Zhang, R.; Dornblaser, B.; Doty, K.; Wu, Y.; Estes, M. J.

    2015-12-01

    One of the challenges in understanding the air quality over forested regions has been the uncertainties in estimating the biogenic hydrocarbon emissions. Biogenic volatile organic compounds, BVOCs, play a critical role in atmospheric chemistry, particularly in ozone and particulate matter (PM) formation. In southeastern United States, BVOCs (mostly as isoprene) are the dominant summertime source of reactive hydrocarbon. Despite significant efforts in improving BVOC estimates, the errors in emission inventories remain a concern. Since BVOC emissions are particularly sensitive to the available photosynthetically active radiation (PAR), model errors in PAR result in large errors in emission estimates. Thus, utilization of satellite observations to estimate PAR can help in reducing emission uncertainties. Satellite-based PAR estimates rely on the technique used to derive insolation from satellite visible brightness measurements. In this study we evaluate several insolation products against surface pyranometer observations and offer a bias correction to generate a more accurate PAR product. The improved PAR product is then used in biogenic emission estimates. The improved biogenic emission estimates are compared to the emission inventories over Texas and used in air quality simulation over the period of August-September 2013 (NASA's Discover-AQ field campaign). A series of sensitivity simulations will be performed and evaluated against Discover-AQ observations to test the impact of satellite-derived PAR on air quality simulations.

  17. CO2 sequestration

    International Nuclear Information System (INIS)

    Favre, E.; Jammes, L.; Guyot, F.; Prinzhofer, A.; Le Thiez, P.

    2009-01-01

    This document presents the summary of a conference-debate held at the Academie des Sciences (Paris, France) on the topic of CO 2 sequestration. Five papers are reviewed: problems and solutions for the CO 2 sequestration; observation and surveillance of reservoirs; genesis of carbonates and geological storage of CO 2 ; CO 2 sequestration in volcanic and ultra-basic rocks; CO 2 sequestration, transport and geological storage: scientific and economical perspectives

  18. Effects of N2-O2 and CO2-O2 tensions on growth of fungi isolated from damaged flue-cured tobacco.

    Science.gov (United States)

    Yang, H; Lucas, G B

    1970-02-01

    Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N(2)-O(2) or CO(2)-O(2). A 1 to 5% concentration of O(2) in an N(2) atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O(2) for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O(2). High O(2) concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O(2) in the N(2) atmosphere, furrows formed in mycelial mats between 5 and 40% O(2) in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O(2) decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO(2)-O(2) mixtures radial growth of all species increased with each quantitative decrease of CO(2). All species except A. niger grew faster in air than in 10% CO(2). In contrast to N(2)-O(2) mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O(2) concentrations.

  19. Extraction of some acids using aliphatic amines; Extraction de quelques acides par des amines aliphatiques

    Energy Technology Data Exchange (ETDEWEB)

    Matutano, L [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-06-01

    Hydrochloric, nitric, sulphuric, perchloric, phosphoric, acetic and formic acids in aqueous solution (0.05 to 10 M) are extracted by amberlite LA2 and trilaurylamine in solution, 5 per cent by volume, in kerosene and xylene respectively. The extraction process consists of: neutralization of the amine salt; a 'molecular extraction', i.e. an extraction using an excess of acid with respect to the stoichiometry of the amine salt. According to the behaviour of the acid during the extraction, three groups may be distinguished: completely dissociated acids, carboxylic acids, phosphoric acid. This classification is also valid for the extraction of the water which occurs simultaneously with that of the acid. An extraction mechanism is put forward for formic acid and the formation constant of its amine salt is calculated. (author) [French] Les acides chlorhydrique, nitrique, sulfurique, perchlorique, phosphorique, acetique et formique, en solution aqueuse - 0,05 a 10 M - sont extraits par l'amberlite LA2 et la trilaurylamine en solution, a 5 pour cent en volume, dans le kerosene et le xylene respectivement. L'extraction comprend: une neutralisation de l'amine par l'acide avec formation d'un sel d'amine; une 'extraction moleculaire', c'est-a-dire une extraction d'acide en exces par rapport a la stoechiometrie du sel d'amine. Suivant le comportement des acides au cours de l'extraction nous distinguons trois groupes: acides entierement dissocies, acides carboxyliques, acide phosphorique. Cette classification est egalement valable pour l'extraction de l'eau qui est simultanee a celle de l'acide. Un mecanisme d'extraction pour l'acide formique est propose et nous calculons la constante de formation de son sel d'amine. (auteur)

  20. Two-Nozzle Flame Spray Pyrolysis (FSP) Synthesis of CoMo/Al2O3 Hydrotreating Catalysts

    DEFF Research Database (Denmark)

    Høj, Martin; Pham, David K.; Brorson, Michael

    2013-01-01

    and the hydrodenitrogenation activity improved from 70 to 90 % relative activity. This suggests that better promotion of the active molybdenum sulfide phase was achieved when using two-nozzle FSP synthesis, probably due to less formation of the undesired phase CoAl2O4, which makes Co unavailable for promotion.......Two-nozzle frame spray analysis (FSP) synthesis of CoMo/Al2O3 where Co and Al are sprayed in separate flames was applied to minimize the formation of CoAl2O4 observed in one-nozzle flame spray pyrolysis (FSP) synthesis and the materials were characterized by N2-adsorption (BET), X-ray diffraction...... (XRD), UV–vis diffuse reflectance spectroscopy, Raman spectroscopy, transmission electron microscopy, and catalytic performances in hydrotreating. By varying the flame mixing distances (81–175 mm) the amount of CoAl2O4 could be minimized. As evidenced by UV–vis spectroscopy, CoAl2O4 was detected only...

  1. Thermodynamic Data for Geochemical Modeling of Carbonate Reactions Associated with CO2 Sequestration – Literature Review

    Energy Technology Data Exchange (ETDEWEB)

    Krupka, Kenneth M. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Cantrell, Kirk J. [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); McGrail, B. Peter [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

    2010-09-01

    Permanent storage of anthropogenic CO2 in deep geologic formations is being considered as a means to reduce the concentration of atmospheric CO2 and thus its contribution to global climate change. To ensure safe and effective geologic sequestration, numerous studies have been completed of the extent to which the CO2 migrates within geologic formations and what physical and geochemical changes occur in these formations when CO2 is injected. Sophisticated, computerized reservoir simulations are used as part of field site and laboratory CO2 sequestration studies. These simulations use coupled multiphase flow-reactive chemical transport models and/or standalone (i.e., no coupled fluid transport) geochemical models to calculate gas solubility, aqueous complexation, reduction/oxidation (redox), and/or mineral solubility reactions related to CO2 injection and sequestration. Thermodynamic data are critical inputs to modeling geochemical processes. The adequacy of thermodynamic data for carbonate compounds has been identified as an important data requirement for the successful application of these geochemical reaction models to CO2 sequestration. A review of thermodynamic data for CO2 gas and carbonate aqueous species and minerals present in published data compilations and databases used in geochemical reaction models was therefore completed. Published studies that describe mineralogical analyses from CO2 sequestration field and natural analogue sites and laboratory studies were also reviewed to identify specific carbonate minerals that are important to CO2 sequestration reactions and therefore require thermodynamic data. The results of the literature review indicated that an extensive thermodynamic database exists for CO2 and CH4 gases, carbonate aqueous species, and carbonate minerals. Values of ΔfG298° and/or log Kr,298° are available for essentially all of these compounds. However, log Kr,T° or heat capacity values at temperatures above 298 K exist for less than

  2. STIMULATION PAR LES CYTOKININES DE L’ACCUMULATION ALCALOÏDIQUE DANS DES SUSPENSIONS CELLULAIRES: IMPLICATION DE L’ETHYLENE COMME SECOND MESSAGER ?

    Directory of Open Access Journals (Sweden)

    A YAHIA

    1999-12-01

    Full Text Available Dans ce travail, nous avons cherché à savoir si l’éthylène pouvait être impliquée lors de la stimulation de la production alcaloïdique par les cytokinines dans les suspensions cellulaires de Catharanthus roseus. La stratégie expérimentale a été double: 1 modifier les teneurs en éthylène endogène en traitant les cellules par différents agonistes ou antagonistes de la voie de biosynthèse de l’éthylène, 2 soumettre les cellules à des apports exogène d’éthylène.      Les résultats obtenus montrent que les inhibiteurs de l’éthylène AVG, Co+2  bloquent partiellement la stimulation alcaloïdique dans les cellules traitées par les cytokinines alors que le précurseur de l’éthylène ACC n’a pas d’effet sur la production alcaloïdique dans les cellules non traitées par les cytokinines. En revanche, lorsque l’éthylène est apporté de manière exogène (traitement par l’éthephon, la production alcaloïdique est multipliée par quatre.

  3. Cascade catalysis in membranes with enzyme immobilization for multienzymatic conversion of CO2 to methanol

    DEFF Research Database (Denmark)

    Luo, Jianquan; Meyer, Anne S.; Mateiu, Ramona Valentina

    2015-01-01

    .e. by directing membrane fouling formation), without any addition of organic solvent. Such coimmobilization and sequential immobilization systems were examined for the production of methanol from CO2 with formate dehydrogenase (FDH), formaldehyde dehydrogenase (FaldDH) and alcohol dehydrogenase (ADH). Enzyme...... for multi-enzymatic cascade systems, but also reveals the reaction bottleneck and provides possible solutions for the bioconversion of CO2 to methanol....

  4. Capture and geological sequestration of CO{sub 2}: fighting against global warming; Capture et stockage geologique du CO{sub 2}: lutter contre le rechauffement planetaire

    Energy Technology Data Exchange (ETDEWEB)

    Czernichowski-Lauriol, I

    2006-07-01

    In order to take up the global warming challenge, a set of emergency measures is to be implemented: energy saving, clean transportation systems, development of renewable energy sources.. CO{sub 2} sequestration of massive industrial emission sources inside deep geologic formations is another promising solution, which can contribute to the division by two of the world CO{sub 2} emissions between today and 2050. The CO{sub 2} capture and sequestration industry is developing. Research projects and pilot facilities are on the increase over the world. Their aim is to warrant the efficiency and security of this technology over the centuries to come. (J.S.)

  5. Mathematical Analysis of High-Temperature Co-electrolysis of CO2 and O2 Production in a Closed-Loop Atmosphere Revitalization System

    Energy Technology Data Exchange (ETDEWEB)

    Michael G. McKellar; Manohar S. Sohal; Lila Mulloth; Bernadette Luna; Morgan B. Abney

    2010-03-01

    NASA has been evaluating two closed-loop atmosphere revitalization architectures based on Sabatier and Bosch carbon dioxide, CO2, reduction technologies. The CO2 and steam, H2O, co-electrolysis process is another option that NASA has investigated. Utilizing recent advances in the fuel cell technology sector, the Idaho National Laboratory, INL, has developed a CO2 and H2O co-electrolysis process to produce oxygen and syngas (carbon monoxide, CO and hydrogen, H2 mixture) for terrestrial (energy production) application. The technology is a combined process that involves steam electrolysis, CO2 electrolysis, and the reverse water gas shift (RWGS) reaction. A number of process models have been developed and analyzed to determine the theoretical power required to recover oxygen, O2, in each case. These models include the current Sabatier and Bosch technologies and combinations of those processes with high-temperature co-electrolysis. The cases of constant CO2 supply and constant O2 production were evaluated. In addition, a process model of the hydrogenation process with co-electrolysis was developed and compared. Sabatier processes require the least amount of energy input per kg of oxygen produced. If co-electrolysis replaces solid polymer electrolyte (SPE) electrolysis within the Sabatier architecture, the power requirement is reduced by over 10%, but only if heat recuperation is used. Sabatier processes, however, require external water to achieve the lower power results. Under conditions of constant incoming carbon dioxide flow, the Sabatier architectures require more power than the other architectures. The Bosch, Boudouard with co-electrolysis, and the hydrogenation with co-electrolysis processes require little or no external water. The Bosch and hydrogenation processes produce water within their reactors, which aids in reducing the power requirement for electrolysis. The Boudouard with co-electrolysis process has a higher electrolysis power requirement because carbon

  6. Sol-gel system study of Zr O2- Co3 O-4

    International Nuclear Information System (INIS)

    Cerri, J.A.; Matos, E.M.R.; Longo, E.; Varela, J.A.; Santos, C.O.P.

    1992-01-01

    Phases present in the system Zr O 2 + Co 3 O 4 were studied through X-Ray diffraction. The processing of the powder was developed through a modified sol-gel method, where the precursors Zr O (N O 3)2 and Co (N O 3)2 were in an ethanol solution. To verify the influence of CO 3 O 4 on the stabilization and phases formation, the crystallite size and the lattice parameter were determined considering as standard, the system without cobalt. (author)

  7. Sequestering CO2 by mineralization into useful nesquehonite-based products

    Directory of Open Access Journals (Sweden)

    Fredrik Paul Glasser

    2016-02-01

    Full Text Available The precipitation of magnesium hydroxy-carbonate hydrates has been suggested as a route to sequester CO2 into solids. We report the development of self-cementing compositions based on nesquehonite, MgCO3·3H2O, that are made from CO2-containing gas streams, the CO2 being separated from other gases by its high solubility in alkaline water, while magnesium is typically provided by waste desalination brines. Precipitation conditions are adjusted to optimize the formation of nesquehonite and the crystalline solid can readily be washed free of chloride. Products can be prepared to achieve self-cementation following two routes: (i thermal activation of the nesquehonite then rehydration of the precursor or (ii direct curing of a slurry of nesquehonite. The products thus obtained contain ~ 30 wt% CO2 and could form the basis for a new generation of lightweight, thermally insulating boards, blocks and panels, with sufficient strength for general construction.

  8. Role of Li2O2@Li2CO3 Interfaces on Charge Transport in Nonaqueous Li−Air Batteries

    DEFF Research Database (Denmark)

    Mekonnen, Yedilfana Setarge; García Lastra, Juan Maria; Hummelshøj, Jens S.

    2015-01-01

    The formation and oxidation of the main discharge product in nonaqueous secondary Li−O2 batteries, that is, Li2O2, has been studied intensively, but less attention has been given to the formation of cathode−electrolyte interfaces, which can significantly influence the performance of the Li−O2...... battery. Here we apply density functional theory with the Hubbard U correction (DFT+U) and nonequilibrium Green’s function (NEGF) methods to investigate the role of Li2O2@Li2CO3 interface layers on the ionic and electronic transport properties at the oxygen electrode. We show that, for example, lithium...... vacancies accumulate at the peroxide part of the interface during charge, reducing the coherent electron transport by two to three orders of magnitude compared with pristine Li2O2. During discharge, Li2O2@Li2CO3 interfaces may, however, provide an alternative in-plane channel for fast electron polaron...

  9. Patērētāju uzvedības pētījums par ēdienu piegādes portālu Hungryhouse.co.uk kā e-komercijas dalībnieku.

    OpenAIRE

    Dembovska, Gerda

    2013-01-01

    Darba tēma -patērētāju uzvedības pētījums par ēdienu piegādes portālu Hungryhouse.co.uk kā e-komercijas dalībnieku. Autore apraksta patērētāja uzvedības izpētes un e-komercijas teorētiskos aspektus,analizē uzņēmuma Hungryhouse.co.uk. darbību Lielbritānijā,veic aptauju par Hungryhouse.co.uk.pastāvēšanas iespējām Latvijā. Darba mērķis -pamatojoties uz patērētāju uzvedības un e-komercijas teorētiskām atziņām,kā arī uz iedzīvotāju aptaujas rezultātiem, izpētīt ēdiena piegādes portāla Hungryho...

  10. Surface studies of UFe2 and evaluation of its catalytic properties with a 2H2:CO mixture

    International Nuclear Information System (INIS)

    Schultz, J.; Naegele, J.; Spirlet, J.C.; Colmenares, C.

    1987-01-01

    The reactivity of UFe 2 with O 2 , CO and CO 2 were studied using x-ray photoelectron spectroscopy (XPS). Adsorption of O 2 on clean UFe 2 surfaces (Fe/U ≅ 2.0), produced by argon-ion sputtering, leads to the formation of UO 2 and depletion of Fe from the surface layer probed by XPS (Fe/U ≅ 0.8). The oxidation state of Fe in this layer, as determined by XPS (Fe 2p/sub 3/2/ = 710.4 eV), is between Fe +2 and Fe +3 of pure Fe oxides. Exposure of sputtered-clean UFe 2 to CO and CO 2 results in a slight broadening of the U 4f peaks, indicating U oxidation, and some Fe depletion in the analyzed layer (Fe/U ≅ 1.7). The O ls (530.2 and 530.4 eV for CO and CO 2 , respectively) and C ls (282.7 and 282.6 eV for CO and CO 2 , respectively) indicate that dissociative chemisorption to O and C atoms occurs. UFe 2 ground into a fine powder was tested as a catalyst in a differential high-pressure flow reactor with a 2H 2 :CO gas mixture. A significant amount of methanol and hydrocarbons are produced at 577K; while hydrocarbons are the main products (>99%) at 739K. XPS analysis of the used catalyst indicates that U is present as UO/sub 2+x/ and Fe as Fe 2 O 3

  11. Investigating CO2 Reservoirs at Gale Crater and Evidence for a Dense Early Atmosphere

    Science.gov (United States)

    Niles, P. B.; Archer, P. D.; Heil, E.; Eigenbrode, J.; McAdam, A.; Sutter, B.; Franz, H.; Navarro-Gonzalez, R.; Ming, D.; Mahaffy, P. R.; hide

    2015-01-01

    One of the most compelling features of the Gale landing site is its age. Based on crater counts, the formation of Gale crater is dated to be near the beginning of the Hesperian near the pivotal Hesperian/Noachian transition. This is a time period on Mars that is linked to increased fluvial activity through valley network formation and also marks a transition from higher erosion rates/clay mineral formation to lower erosion rates with mineralogies dominated by sulfate minerals. Results from the Curiosity mission have shown extensive evidence for fluvial activity within the crater suggesting that sediments on the floor of the crater and even sediments making up Mt. Sharp itself were the result of longstanding activity of liquid water. Warm/wet conditions on early Mars are likely due to a thicker atmosphere and increased abundance of greenhouse gases including the main component of the atmosphere, CO2. Carbon dioxide is minor component of the Earth's atmosphere yet plays a major role in surface water chemistry, weathering, and formation of secondary minerals. An ancient martian atmosphere was likely dominated by CO2 and any waters in equilibrium with this atmosphere would have different chemical characteristics. Studies have noted that high partial pressures of CO2 would result in increased carbonic acid formation and lowering of the pH so that carbonate minerals are not stable. However, if there were a dense CO2 atmosphere present at the Hesperian/Noachian transition, it would have to be stored in a carbon reservoir on the surface or lost to space. The Mt. Sharp sediments are potentially one of the best places on Mars to investigate these CO2 reservoirs as they are proposed to have formed in the early Hesperian, from an alkaline lake, and record the transition to an aeolian dominated regime near the top of the sequence. The total amount of CO2 in the Gale crater soils and sediments is significant but lower than expected if a thick atmosphere was present at the

  12. FooPar

    DEFF Research Database (Denmark)

    Hargreaves, F. P.; Merkle, D.

    2013-01-01

    We present FooPar, an extension for highly efficient Parallel Computing in the multi-paradigm programming language Scala. Scala offers concise and clean syntax and integrates functional programming features. Our framework FooPar combines these features with parallel computing techniques. Foo......, results based on a empirical analysis on two supercomputers are given. We achieve close-to-optimal performance wrt. theoretical peak performance. Based on this result we conclude that FooPar allows programmers to fully access Scalas design features without suffering from performance drops when compared...

  13. AREA 2: Novel Materials for Robust Repair of Leaky Wellbores in CO2 Storage Formations

    Energy Technology Data Exchange (ETDEWEB)

    Balhoff, Matthew [Univ. of Texas, Austin, TX (United States); Tavassoli, Shayan [Univ. of Texas, Austin, TX (United States); Fei Ho, Jostine [Univ. of Texas, Austin, TX (United States)

    2016-01-31

    The potential leakage of hydrocarbon fluids or CO2 out of subsurface formations through wells with fractured cement or debonded microannuli is a primary concern in oil and gas production and CO2 storage. The presence of fractures in a cement annulus with apertures on the order of 10–300 microns can pose a significant leakage danger with effective permeability in the range of 0.1–1 mD (millidarcy). Leakage pathways with small apertures are often difficult to repair using conventional oilfield cement, thus a low-viscosity sealant that can be easily placed into these fractures while providing an effective seal is desired. The development of a novel application using pH-triggered polymeric sealants could potentially be the solution to plugging these fractures and that was the research aim of this study. The application is based on the transport and reaction of a low-pH poly(acrylic acid) polymer through fractures in strongly alkaline cement. The pH-sensitive microgels viscosify upon neutralization with cement to become highly swollen gels with substantial yield stress that can block fluid flow. Experiments in a cement fracture determined the effects of the viscosification and gel deposition via real-time visual observation and measurements of pressure gradient and effluent pH. While the pH-triggered gelling mechanism and rheology measurements of the neutralized polymer gel show promising results, the polymer solution in contact with cement undergoes an undesirable reaction known as polymer syneresis. Syneresis is caused by the release of calcium cation from cement that collapses the polymer network. Syneresis produces an unstable calcium-precipitation byproduct that is detrimental to the strength and stability of the gel in place. As a result, gel-sealed leakage pathways that subjected to various degrees of syneresis often failed to hold back pressures. Several chemicals were studied to inhibit polymer syneresis and tested for pretreatment of

  14. Progress and Perspective of Electrocatalytic CO2 Reduction for Renewable Carbonaceous Fuels and Chemicals.

    Science.gov (United States)

    Zhang, Wenjun; Hu, Yi; Ma, Lianbo; Zhu, Guoyin; Wang, Yanrong; Xue, Xiaolan; Chen, Renpeng; Yang, Songyuan; Jin, Zhong

    2018-01-01

    The worldwide unrestrained emission of carbon dioxide (CO 2 ) has caused serious environmental pollution and climate change issues. For the sustainable development of human civilization, it is very desirable to convert CO 2 to renewable fuels through clean and economical chemical processes. Recently, electrocatalytic CO 2 conversion is regarded as a prospective pathway for the recycling of carbon resource and the generation of sustainable fuels. In this review, recent research advances in electrocatalytic CO 2 reduction are summarized from both experimental and theoretical aspects. The referred electrocatalysts are divided into different classes, including metal-organic complexes, metals, metal alloys, inorganic metal compounds and carbon-based metal-free nanomaterials. Moreover, the selective formation processes of different reductive products, such as formic acid/formate (HCOOH/HCOO - ), monoxide carbon (CO), formaldehyde (HCHO), methane (CH 4 ), ethylene (C 2 H 4 ), methanol (CH 3 OH), ethanol (CH 3 CH 2 OH), etc. are introduced in detail, respectively. Owing to the limited energy efficiency, unmanageable selectivity, low stability, and indeterminate mechanisms of electrocatalytic CO 2 reduction, there are still many tough challenges need to be addressed. In view of this, the current research trends to overcome these obstacles in CO 2 electroreduction field are summarized. We expect that this review will provide new insights into the further technique development and practical applications of CO 2 electroreduction.

  15. Impact of CO_2 on the Evolution of Microbial Communities Exposed to Carbon Storage Conditions, Enhanced Oil Recovery, and CO_2 Leakage

    International Nuclear Information System (INIS)

    Gulliver, Djuna M.; Gregory, Kelvin B.; Lowry, Gregory V.

    2016-01-01

    Geologic carbon storage (GCS) is a crucial part of a proposed mitigation strategy to reduce the anthropogenic carbon dioxide (CO_2) emissions to the atmosphere. During this process, CO_2 is injected as super critical carbon dioxide (SC-CO_2) in confined deep subsurface storage units, such as saline aquifers and depleted oil reservoirs. The deposition of vast amounts of CO_2 in subsurface geologic formations could unintentionally lead to CO_2 leakage into overlying freshwater aquifers. Introduction of CO_2 into these subsurface environments will greatly increase the CO_2 concentration and will create CO_2 concentration gradients that drive changes in the microbial communities present. While it is expected that altered microbial communities will impact the biogeochemistry of the subsurface, there is no information available on how CO_2 gradients will impact these communities. The overarching goal of this project is to understand how CO_2 exposure will impact subsurface microbial communities at temperatures and pressures that are relevant to GCS and CO_2 leakage scenarios. To meet this goal, unfiltered, aqueous samples from a deep saline aquifer, a depleted oil reservoir, and a fresh water aquifer were exposed to varied concentrations of CO_2 at reservoir pressure and temperature. The microbial ecology of the samples was examined using molecular, DNA-based techniques. The results from these studies were also compared across the sites to determine any existing trends. Results reveal that increasing CO_2 leads to decreased DNA concentrations regardless of the site, suggesting that microbial processes will be significantly hindered or absent nearest the CO_2 injection/leakage plume where CO_2 concentrations are highest. At CO_2 exposures expected downgradient from the CO_2 plume, selected microorganisms emerged as dominant in the CO_2 exposed conditions. Results suggest that the altered microbial community was site specific and highly dependent on pH. The site

  16. Opportunities for low-cost CO2 storage demonstration projects in China

    International Nuclear Information System (INIS)

    Meng, Kyle C.; Williams, Robert H.; Celia, Michael A.

    2007-01-01

    Several CO 2 storage demonstration projects are needed in a variety of geological formations worldwide to prove the viability of CO 2 capture and storage as a major option for climate change mitigation. China has several low-cost CO 2 sources at sites that produce NH 3 from coal via gasification. At these plants, CO 2 generated in excess of the amount needed for other purposes (e.g., urea synthesis) is vented as a relatively pure stream. These CO 2 sources would potentially be economically interesting candidates for storage demonstration projects if there are suitable storage sites nearby. In this study a survey was conducted to estimate CO 2 availability at modern Chinese coal-fed ammonia plants. Results indicate that annual quantities of available, relatively pure CO 2 per site range from 0.6 to 1.1 million tonnes. The CO 2 source assessment was complemented by analysis of possible nearby opportunities for CO 2 storage. CO 2 sources were mapped in relation to China's petroliferous sedimentary basins where prospective CO 2 storage reservoirs possibly exist. Four promising pairs of sources and sinks were identified. Project costs for storage in deep saline aquifers were estimated for each pairing ranging from $15-21/t of CO 2 . Potential enhanced oil recovery and enhanced coal bed methane recovery opportunities near each prospective source were also considered

  17. NOVEL CONCEPTS RESEARCH IN GEOLOGIC STORAGE OF CO2 PHASE III

    Energy Technology Data Exchange (ETDEWEB)

    Neeraj Gupta

    2006-01-23

    As part of the Department of Energy's (DOE) initiative on developing new technologies for storage of carbon dioxide in geologic reservoirs, Battelle has been investigating the feasibility of CO{sub 2} sequestration in the deep saline reservoirs in the Ohio River Valley region. In addition to the DOE, the project is being sponsored by American Electric Power (AEP), BP, The Ohio Coal Development Office (OCDO) of the Ohio Air Quality Development Authority, Schlumberger, and Battelle. The main objective of the project is to demonstrate that CO{sub 2} sequestration in deep formations is feasible from engineering and economic perspectives, as well as being an inherently safe practice and one that will be acceptable to the public. In addition, the project is designed to evaluate the geology of deep formations in the Ohio River Valley region in general and in the vicinity of AEP's Mountaineer Power Plant in particular, in order to determine their potential use for conducting a long-term test of CO{sub 2} disposal in deep saline formations. The current technical progress report summarizes activities completed for the October through December 2005 period of the project. As discussed in the following report, the main field activity was reservoir testing in the Copper Ridge ''B-zone'' in the AEP No.1 well. In addition reservoir simulations were completed to assess feasibility of CO{sub 2} injection for the Mountaineer site. These reservoir testing and computer simulation results suggest that injection potential may be substantially more than anticipated for the Mountaineer site. Work also continued on development of injection well design options, engineering assessment of CO{sub 2} capture systems, permitting, and assessment of monitoring technologies as they apply to the project site. Overall, the current design feasibility phase project is proceeding according to plans.

  18. Spectroscopic analysis of PMMA/PVC blends containing CoCl2

    Directory of Open Access Journals (Sweden)

    N.S. Alghunaim

    2015-01-01

    Full Text Available Composites of polymethyl methacrylate (PMMA and polyvinyl chloride (PVC polymer blend containing different concentrations (⩽10 wt. of cobalt chloride (CoCl2 were prepared by casting techniques. The changes of the structural, spectroscopic, optical and thermal parameters of the samples are studied using different tools. FT-IR spectroscopy confirmed the complexation between the blends and Co+2-ions. The decrease or increase of IR band intensity with some shifts of other bands suggests an interaction and compatibility between PMMA/PVC blends with CoCl2 take place. The Ultra violet and visible (UV/Vis spectra indicated that the presence of band gap energy depends on increasing of CoCl2 contents. The absorption intensity of the samples doped with CoCl2 becomes faint lower than the pure blend. The values of energy gap for direct and indirect transition decreases with the increase of CoCl2 due to the presence of charge transfer between PMMA/PVC and CoCl2. The thermogravimetric analysis (TGA curves for all the samples have the same behavior and more steps of decomposition were observed. The reduction of mass loss for samples containing CoCl2 compared to the pure blend was observed and it was attributed to crosslink formation between the blend and CoCl2.

  19. CO{sub 2} electroreduction: conversion into formic acid and mechanistic aspect in aqueous medium; Electroreduction du CO{sub 2}: conversion en acide formique et aspect mecanistique en milieu aqueux

    Energy Technology Data Exchange (ETDEWEB)

    Innocent, B.; Pasquier, D.; Ropital, F. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France); Hahn, F.; Leger, J.M.; Kokoh, B. [Poitiers Univ., LaCCO, Equipe Electrocatalyse, UMR 6503 CNRS, 86 (France)

    2007-07-01

    The CO{sub 2} release reduction is nowadays considered as a necessity to limit the climatic change phenomena due to the greenhouse effect. For that, a part of CO{sub 2} could be transformed by its electrochemical reduction on a hydrogen overvoltage electrode as lead. According to the nature of the electrode material and of the electrolyte, CO{sub 2} can be electro catalytically hydrogenated or dimerized. In the conditions presented here (basic aqueous medium, lead electrode), the reagent is in majority reduced into formate, the parasite faradic reaction being the solvent transformation into dihydrogen. The studies carried out by cyclic voltametry have shown that the reducible form of CO{sub 2} is the hydrogeno-carbonate ion; its reduction begins at -1.2 V and reaches a maximum for an electrode potential of -1.6 V vs. ECS. Long intentiostatic electrolyses have then been carried out in an electrolytic circulation cell of 'filter-press' type. The cathode is a lead sheet of 20 cm{sup 2} and a current intensity of -100 mA has been imposed. The chromatographic analyses of the electrolytic solution have allowed to show that the formate selectivity is of 90%. The electroreduction process induces an acido-basic disequilibrium which induces a decrease of the reaction yield. A pH correction is then necessary to obtain great conversions of CO{sub 2} in alkaline medium (pH{>=}7) as follows: HCO{sub 3}{sup -} + H{sub 2}O + 2e{sup -} {yields} HCOO{sup -} + 2 HO{sup -}. In situ reflexion infrared spectroscopy studies, carried out in deuterated aqueous medium and by chrono-amperometry, have shown characteristic bands due to the hydrogeno-carbonate ion (weakly adsorbed) and to the formate produced, required for the understanding of the reactional mechanism. (O.M.)

  20. Uncertainty in geochemical modelling of CO2 and calcite dissolution in NaCl solutions due to different modelling codes and thermodynamic databases

    International Nuclear Information System (INIS)

    Haase, Christoph; Dethlefsen, Frank; Ebert, Markus; Dahmke, Andreas

    2013-01-01

    Highlights: • CO 2 and calcite dissolution is calculated. • The codes PHREEQC, Geochemist’s Workbench, EQ3/6, and FactSage are used. • Comparison with Duan and Li (2008) shows lowest deviation using phreeqc.dat and wateq4f.dat. • Using Pitzer databases does not improve accurate calculations. • Uncertainty in dissolved CO 2 is largest using the geochemical models. - Abstract: A prognosis of the geochemical effects of CO 2 storage induced by the injection of CO 2 into geologic reservoirs or by CO 2 leakage into the overlaying formations can be performed by numerical modelling (non-invasive) and field experiments. Until now the research has been focused on the geochemical processes of the CO 2 reacting with the minerals of the storage formation, which mostly consists of quartzitic sandstones. Regarding the safety assessment the reactions between the CO 2 and the overlaying formations in the case of a CO 2 leakage are of equal importance as the reactions in the storage formation. In particular, limestone formations can react very sensitively to CO 2 intrusion. The thermodynamic parameters necessary to model these reactions are not determined explicitly through experiments at the total range of temperature and pressure conditions and are thus extrapolated by the simulation code. The differences in the calculated results lead to different calcite and CO 2 solubilities and can influence the safety issues. This uncertainty study is performed by comparing the computed results, applying the geochemical modelling software codes The Geochemist’s Workbench, EQ3/6, PHREEQC and FactSage/ChemApp and their thermodynamic databases. The input parameters (1) total concentration of the solution, (2) temperature and (3) fugacity are varied within typical values for CO 2 reservoirs, overlaying formations and close-to-surface aquifers. The most sensitive input parameter in the system H 2 O–CO 2 –NaCl–CaCO 3 for the calculated range of dissolved calcite and CO 2 is the

  1. Soil gas (222Rn, CO2, 4He) behaviour over a natural CO2 accumulation, Montmiral area (Drome, France): geographical, geological and temporal relationships

    International Nuclear Information System (INIS)

    Gal, Frederick; Joublin, Franck; Haas, Hubert; Jean-prost, Veronique; Ruffier, Veronique

    2011-01-01

    The south east basin of France shelters deep CO 2 reservoirs often studied with the aim of better constraining geological CO 2 storage operations. Here we present new soil gas data, completing an existing dataset (CO 2 , 222 Rn, 4 He), together with mineralogical and physical characterisations of soil columns, in an attempt to better understand the spatial distribution of gas concentrations in the soils and to rule on the sealed character of the CO 2 reservoir at present time. Anomalous gas concentrations were found but did not appear to be clearly related to geological structures that may drain deep gases up to the surface, implying a dominant influence of near surface processes as indicated by carbon isotope ratios. Coarse grained, quartz-rich soils favoured the existence of high CO 2 concentrations. Fine grained clayey soils preferentially favoured the existence of 222 Rn but not CO 2 . Soil formations did not act as barriers preventing gas migrations in soils, either due to water content or due to mineralogical composition. No abundant leakage from the Montmiral reservoir can be highlighted by the measurements, even near the exploitation well. As good correlation between CO 2 and 222 Rn concentrations still exist, it is suggested that 222 Rn migration is also CO 2 dependent in non-leaking areas - diffusion dominated systems.

  2. Toxic emissions and devalued CO2-neutrality

    DEFF Research Database (Denmark)

    Czeskleba-Dupont, Rolf

    With reference to the paradigme shift regarding the formation of dioxins in municiplan solid waste incinerators experimental results are taken into account which lead to the suspicion that the same mechanism of de-novo-synthesis also applies to fireplace chimneys. This can explain the dioxin...... friendly effects of substituting wood burning for fossil fuels. With reference to Bent Sørensen's classical work on 'Renewable Energy' the assumption of CO2-neutrality regarding incineration is problematised when applied to plants with long rotation periods as trees. Registered CO2-emissions from wood...... burning are characterised together with particle and PAH emissions. The positive treatment of wood stove-technology in the Danish strategy for sustainable development (draft 2007) is critically evaluated and approaches to better regulation are identified....

  3. Molecular simulations of CO2 at interfaces

    DEFF Research Database (Denmark)

    Silvestri, Alessandro

    trapping mechanisms that act over dierent time scales, where eectiveness is determined by phenomena that occur at the interfaces between CO2, pore uids and the pore surfaces. Solid theoretical understanding of the nanoscale interactions that result from the interplay of intermolecular and surface forces...... variety of conditions: pressure, temperature, pore solution salinity and various mineral surfaces. However, achieving representative subsurface conditions in experiments is challenging and reported data are aected by experimental uncertainties and sometimes are contradictory. Molecular modelling...... rock record and the formations are generally porous so their probable response to CO2 sequestration needs to be investigated. However, despite the large number of geologic sequestration publications on water{rock interactions over the last decade, studies on carbonate reservoirs remain scarce...

  4. Noble gas geochemistry to monitor CO2 geological storages

    International Nuclear Information System (INIS)

    Lafortune, St.

    2007-11-01

    According to the last IPCC (Intergovernmental Panel on Climate Change) report, a probability of 90 % can be now established for the responsibility of the anthropogenic CO 2 emissions for the global climate change observed since the beginning of the 20. century. To reduce these emissions and keep producing energy from coal, oil or gas combustions, CO 2 could be stored in geological reservoirs like aquifers, coal beds, and depleted oil or gas fields. Storing CO 2 in geological formations implies to control the efficiency and to survey the integrity of the storages, in order to be able to detect the possible leaks as fast as possible. Here, we study the feasibility of a geochemical monitoring through noble gas geochemistry. We present (1) the development of a new analytical line, Garodiox, developed to extract quantitatively noble gas from water samples, (2) the testing of Garodiox on samples from a natural CO 2 storage analogue (Pavin lake, France) and (3) the results of a first field work on a natural CO 2 accumulation (Montmiral, France). The results we obtain and the conclusions we draw, highlight the interest of the geochemical monitoring we suggest. (author)

  5. Formation of trans-caffeoyl-CoA from trans-4-coumaroyl-CoA by Zn2+-dependent enzymes in cultured plant cells and its activation by an elicitor-induced pH shift

    NARCIS (Netherlands)

    Kneusel, R.; Matern, U.; Nicolaij, K.

    1989-01-01

    A novel hydroxylase activity catalyzing the formation of trans-caffeoyl-CoA from trans-4-coumaroyl-CoA was identified in crude extracts from cultured parsley cells. The extracts were less active (Vmax/Km) in converting trans-4-coumaric to trans-caffeic acid. Optimal hydroxylase activity was found at

  6. Capture and geological sequestration of CO2: fighting against global warming

    International Nuclear Information System (INIS)

    Czernichowski-Lauriol, I.

    2006-01-01

    In order to take up the global warming challenge, a set of emergency measures is to be implemented: energy saving, clean transportation systems, development of renewable energy sources.. CO 2 sequestration of massive industrial emission sources inside deep geologic formations is another promising solution, which can contribute to the division by two of the world CO 2 emissions between today and 2050. The CO 2 capture and sequestration industry is developing. Research projects and pilot facilities are on the increase over the world. Their aim is to warrant the efficiency and security of this technology over the centuries to come. (J.S.)

  7. Thermal formation of mesoporous single-crystal Co3O4 nano-needles and their lithium storage properties

    KAUST Repository

    Lou, Xiong Wen; Deng, Da; Lee, Jim Yang; Archer, Lynden A.

    2008-01-01

    In this work, we report the simple solid-state formation of mesoporous Co3O4 nano-needles with a 3D single-crystalline framework. The synthesis is based on controlled thermal oxidative decomposition and re-crystallization of precursor β-Co(OH)2 nano-needles. Importantly, after thermal treatment, the needle-like morphology can be completely preserved, despite the fact that there is a large volume contraction accompanying the process: β-Co(OH)2Co3O 4. Because of the intrinsic crystal contraction, a highly mesoporous structure with high specific surface area has been simultaneously created. The textual properties can be easily tailored by varying the annealing temperature between 200-400 °C. Interestingly, thermal re-crystallization at higher temperatures leads to the formation of a perfect 3D single-crystalline framework. Thus derived mesoporous Co3O4 nano-needles serve as a good model system for the study of lithium storage properties. The optimized sample manifests very low initial irreversible loss (21%), ultrahigh capacity, and excellent cycling performance. For example, a reversible capacity of 1079 mA h g-1 can be maintained after 50 cycles. The superior electrochemical performance and ease of synthesis may suggest their practical use in lithium-ion batteries. © The Royal Society of Chemistry 2008.

  8. Gross primary production of a semiarid grassland is enhanced by six years of exposure to elevated atmospheric CO2, warming, and irrigation.

    Science.gov (United States)

    Ryan, E.; Ogle, K.; Peltier, D.; Williams, D. G.; Pendall, E.

    2014-12-01

    The goal of this study was to quantify interannual variation of gross primary production (GPP) and evaluate potential drivers of GPP with global change using the Prairie Heating and CO2 Enrichment (PHACE) experiment in semiarid grassland in southeastern Wyoming. PHACE consists of the treatments: control, warming only, elevated CO2 (eCO2) only, eCO2 and warming, and irrigation only. We expected that GPP would be most strongly influenced by interannual variability in precipitation under all PHACE treatments, soil water availability under eCO2, and nitrogen availability. GPP data were obtained from paired measurements of net ecosystem exchange (NEE) and ecosystem respiration (Reco; GPP = Reco - NEE) made on 2-4 week intervals over six growing seasons (2007-2012). Soil temperature (T), soil water content (SWC), vapor pressure deficit (VPD), and photosynthetically active radiation (PAR) were continuously recorded at the plot (T, SWC) and site (VPD, PAR) scales. Annual, plot-level aboveground plant nitrogen content (N) was measured during peak biomass. We fit a non-linear light-response model to the GPP data within a Bayesian framework, and modeled the maximum GPP rate (Gmax) and canopy light-use efficiency (Q) as functions of N and current and antecedent SWC, T, and VPD. The model fit the GPP data well (R2 = 0.64), and regardless of the PHACE treatment the most important drivers of GPP were N (for Gmax), VPD (Gmax and Q), antecedent T (Gmax), and antecedent VPD (Q). Model simulations predicted that annual GPP increased on average by about 16% with eCO2, 14% with warming, 12% with eCO2 and warming, and 23% with irrigation. For four of the six years, annual GPP was significantly affected by either eCO2 alone or when combined with warming. The increase in annual GPP under irrigation was similar to the increase under eCO2 during a dry year (2012), but irrigation stimulated GPP to a greater degree than eCO2 during wet years (2008, 2009). Hence, increases in GPP under eCO2

  9. Carbon deposition and sulfur poisoning during CO2 electrolysis in nickel-based solid oxide cell electrodes

    DEFF Research Database (Denmark)

    Skafte, Theis Løye; Blennow, Peter; Hjelm, Johan

    2017-01-01

    is investigated systematically using simple current-potential experiments. Due to variations of local conditions, it is shown that higher current density and lower fuel electrode porosity will cause local carbon formation at the electrochemical reaction sites despite operating with a CO outlet concentration...... outside the thermodynamic carbon formation region. Attempts at mitigating the issue by coating the composite nickel/yttria-stabilized zirconia electrode with carbon-inhibiting nanoparticles and by sulfur passivation proved unsuccessful. Increasing the fuel electrode porosity is shown to mitigate......Reduction of CO2 to CO and O2 in the solid oxide electrolysis cell (SOEC) has the potential to play a crucial role in closing the CO2 loop. Carbon deposition in nickel-based cells is however fatal and must be considered during CO2 electrolysis. Here, the effect of operating parameters...

  10. Numerical simulation of CO2 leakage from a geologic disposal reservoir, including transitions from super- to sub-critical conditions, and boiling of liquid of CO2

    International Nuclear Information System (INIS)

    Pruess, Karsten

    2003-01-01

    The critical point of CO 2 is at temperature and pressure conditions of T crit = 31.04 C, P crit = 73.82 bar. At lower (subcritical) temperatures and/or pressures, CO 2 can exist in two different phase states, a liquid and a gaseous state, as well as in two-phase mixtures of these states. Disposal of CO 2 into brine formations would be made at supercritical pressures. However, CO 2 escaping from the storage reservoir may migrate upwards towards regions with lower temperatures and pressures, where CO 2 would be in subcritical conditions. An assessment of the fate of leaking CO 2 requires a capability to model not only supercritical but also subcritical CO 2 , as well as phase changes between liquid and gaseous CO 2 in sub-critical conditions. We have developed a methodology for numerically simulating the behavior of water-CO 2 mixtures in permeable media under conditions that may include liquid, gaseous, and supercritical CO 2 . This has been applied to simulations of leakage from a deep storage reservoir in which a rising CO 2 plume undergoes transitions from supercritical to subcritical conditions. We find strong cooling effects when liquid CO 2 rises to elevations where it begins to boil and evolve a gaseous CO 2 phase. A three-phase zone forms (aqueous - liquid - gas), which over time becomes several hundred meters thick as decreasing temperatures permit liquid CO 2 to advance to shallower elevations. Fluid mobilities are reduced in the three-phase region from phase interference effects. This impedes CO 2 upflow, causes the plume to spread out laterally, and gives rise to dispersed CO 2 discharge at the land surface. Our simulation suggests that temperatures along a CO 2 leakage path may decline to levels low enough so that solid water ice and CO 2 hydrate phases may be formed

  11. Phosphorylation of Mycobacterium tuberculosis ParB participates in regulating the ParABS chromosome segregation system.

    Science.gov (United States)

    Baronian, Grégory; Ginda, Katarzyna; Berry, Laurence; Cohen-Gonsaud, Martin; Zakrzewska-Czerwińska, Jolanta; Jakimowicz, Dagmara; Molle, Virginie

    2015-01-01

    Here, we present for the first time that Mycobacterium tuberculosis ParB is phosphorylated by several mycobacterial Ser/Thr protein kinases in vitro. ParB and ParA are the key components of bacterial chromosome segregation apparatus. ParB is a cytosolic conserved protein that binds specifically to centromere-like DNA parS sequences and interacts with ParA, a weak ATPase required for its proper localization. Mass spectrometry identified the presence of ten phosphate groups, thus indicating that ParB is phosphorylated on eight threonines, Thr32, Thr41, Thr53, Thr110, Thr195, and Thr254, Thr300, Thr303 as well as on two serines, Ser5 and Ser239. The phosphorylation sites were further substituted either by alanine to prevent phosphorylation or aspartate to mimic constitutive phosphorylation. Electrophoretic mobility shift assays revealed a drastic inhibition of DNA-binding by ParB phosphomimetic mutant compared to wild type. In addition, bacterial two-hybrid experiments showed a loss of ParA-ParB interaction with the phosphomimetic mutant, indicating that phosphorylation is regulating the recruitment of the partitioning complex. Moreover, fluorescence microscopy experiments performed in the surrogate Mycobacterium smegmatis ΔparB strain revealed that in contrast to wild type Mtb ParB, which formed subpolar foci similar to M. smegmatis ParB, phoshomimetic Mtb ParB was delocalized. Thus, our findings highlight a novel regulatory role of the different isoforms of ParB representing a molecular switch in localization and functioning of partitioning protein in Mycobacterium tuberculosis.

  12. Phosphorylation of Mycobacterium tuberculosis ParB participates in regulating the ParABS chromosome segregation system.

    Directory of Open Access Journals (Sweden)

    Grégory Baronian

    Full Text Available Here, we present for the first time that Mycobacterium tuberculosis ParB is phosphorylated by several mycobacterial Ser/Thr protein kinases in vitro. ParB and ParA are the key components of bacterial chromosome segregation apparatus. ParB is a cytosolic conserved protein that binds specifically to centromere-like DNA parS sequences and interacts with ParA, a weak ATPase required for its proper localization. Mass spectrometry identified the presence of ten phosphate groups, thus indicating that ParB is phosphorylated on eight threonines, Thr32, Thr41, Thr53, Thr110, Thr195, and Thr254, Thr300, Thr303 as well as on two serines, Ser5 and Ser239. The phosphorylation sites were further substituted either by alanine to prevent phosphorylation or aspartate to mimic constitutive phosphorylation. Electrophoretic mobility shift assays revealed a drastic inhibition of DNA-binding by ParB phosphomimetic mutant compared to wild type. In addition, bacterial two-hybrid experiments showed a loss of ParA-ParB interaction with the phosphomimetic mutant, indicating that phosphorylation is regulating the recruitment of the partitioning complex. Moreover, fluorescence microscopy experiments performed in the surrogate Mycobacterium smegmatis ΔparB strain revealed that in contrast to wild type Mtb ParB, which formed subpolar foci similar to M. smegmatis ParB, phoshomimetic Mtb ParB was delocalized. Thus, our findings highlight a novel regulatory role of the different isoforms of ParB representing a molecular switch in localization and functioning of partitioning protein in Mycobacterium tuberculosis.

  13. Sea ice contribution to the air-sea CO{sub 2} exchange in the Arctic and Southern Oceans

    Energy Technology Data Exchange (ETDEWEB)

    Rysgaard, Soeren (Greenland Climate Research Centre, Greenland Inst. of Natural Resources, Nuuk, Greenland (Denmark); Centre for Earth Observation Science, CHR Faculty of Environment Earth and Resources, Univ. of Manitoba, Winnipeg (Canada)), e-mail: rysgaard@natur.gl; Bendtsen, Joergen (Greenland Climate Research Centre, Greenland Inst. of Natural Resources, Nuuk, Greenland (Denmark); Centre for Ice and Climate, Niels Bohr Inst., Univ. of Copenhagen, Copenhagen O (Denmark)); Delille, Bruno (Unit' e d' Oceanographie Chimique, Interfacultary Centre for Marine Research, Universite de Liege, Liege (Belgium)); Dieckmann, Gerhard S. (Alfred Wegener Inst. for Polar and Marine Research, Bremerhaven (Germany)); Glud, Ronnie N. (Greenland Climate Research Centre, Greenland Inst. of Natural Resources, Nuuk, Greenland (Denmark); Scottish Association of Marine Sciences, Scotland UK, Southern Danish Univ. and NordCee, Odense M (Denmark)); Kennedy, Hilary; Papadimitriou, Stathys (School of Ocean Sciences, Bangor Univ., Menai Bridge, Anglesey, Wales (United Kingdom)); Mortensen, John (Greenland Climate Research Centre, Greenland Inst. of Natural Resources, Nuuk, Greenland (Denmark)); Thomas, David N. (School of Ocean Sciences, Bangor Univ., Menai Bridge, Anglesey, Wales (United Kingdom); Finnish Environment Inst. (SYKE), Marine Research Centre, Helsinki (Finland)); Tison, Jean-Louis (Glaciology Unit, Dept. of Earth and Environmental Sciences, Universite Libre de Bruxelles, Bruxelles, (Belgium))

    2011-11-15

    Although salt rejection from sea ice is a key process in deep-water formation in ice-covered seas, the concurrent rejection of CO{sub 2} and the subsequent effect on air-sea CO{sub 2} exchange have received little attention. We review the mechanisms by which sea ice directly and indirectly controls the air-sea CO{sub 2} exchange and use recent measurements of inorganic carbon compounds in bulk sea ice to estimate that oceanic CO{sub 2} uptake during the seasonal cycle of sea-ice growth and decay in ice-covered oceanic regions equals almost half of the net atmospheric CO{sub 2} uptake in ice-free polar seas. This sea-ice driven CO{sub 2} uptake has not been considered so far in estimates of global oceanic CO{sub 2} uptake. Net CO{sub 2} uptake in sea-ice-covered oceans can be driven by; (1) rejection during sea-ice formation and sinking of CO{sub 2}-rich brine into intermediate and abyssal oceanic water masses, (2) blocking of air-sea CO{sub 2} exchange during winter, and (3) release of CO{sub 2}-depleted melt water with excess total alkalinity during sea-ice decay and (4) biological CO{sub 2} drawdown during primary production in sea ice and surface oceanic waters

  14. Rational Design of a Hierarchical Tin Dendrite Electrode for Efficient Electrochemical Reduction of CO2.

    Science.gov (United States)

    Won, Da Hye; Choi, Chang Hyuck; Chung, Jaehoon; Chung, Min Wook; Kim, Eun-Hee; Woo, Seong Ihl

    2015-09-21

    Catalysis is a key technology for the synthesis of renewable fuels through electrochemical reduction of CO2 . However, successful CO2 reduction still suffers from the lack of affordable catalyst design and understanding the factors governing catalysis. Herein, we demonstrate that the CO2 conversion selectivity on Sn (or SnOx /Sn) electrodes is correlated to the native oxygen content at the subsurface. Electrochemical analyses show that the reduced Sn electrode with abundant oxygen species effectively stabilizes a CO2 (.-) intermediate rather than the clean Sn surface, and consequently results in enhanced formate production in the CO2 reduction. Based on this design strategy, a hierarchical Sn dendrite electrode with high oxygen content, consisting of a multi-branched conifer-like structure with an enlarged surface area, was synthesized. The electrode exhibits a superior formate production rate (228.6 μmol h(-1)  cm(-2) ) at -1.36 VRHE without any considerable catalytic degradation over 18 h of operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Modulation of magmatic processes by CO2 flushing

    Science.gov (United States)

    Caricchi, Luca; Sheldrake, Tom E.; Blundy, Jon

    2018-06-01

    Magmatic systems are the engines driving volcanic eruptions and the source of fluids responsible for the formation of porphyry-type ore deposits. Sudden variations of pressure, temperature and volume in magmatic systems can produce unrest, which may culminate in a volcanic eruption and/or the abrupt release of ore-forming fluids. Such variations of the conditions within magmatic systems are commonly ascribed to the injection of new magma from depth. However, as magmas fractionating at depth or rising to the upper crust release CO2-rich fluids, the interaction between carbonic fluids and H2O-rich magmas stored in the upper crust (CO2 flushing), must also be a common process affecting the evolution of subvolcanic magma reservoirs. Here, we investigate the effect of gas injection on the stability and chemical evolution of magmatic systems. We calculate the chemical and physical evolution of magmas subjected to CO2-flushing using rhyolite-MELTS. We compare the calculations with a set of melt inclusion data for Mt. St. Helens, Merapi, Etna, and Stromboli volcanoes. We provide an approach that can be used to distinguish between melt inclusions trapped during CO2 flushing, magma ascent and decompression, or those affected by post-entrapment H2O-loss. Our results show that CO2 flushing is a widespread process in both felsic and mafic magmatic systems. Depending upon initial magma crystallinity and duration of CO2 input, flushing can either lead to volcanic eruption or fluid release. We suggest that CO2 flushing is a fundamental process modulating the behaviour and chemical evolution of crustal magmatic systems.

  16. Mineralogical controls on porosity and water chemistry during O_2-SO_2-CO_2 reaction of CO_2 storage reservoir and cap-rock core

    International Nuclear Information System (INIS)

    Pearce, Julie K.; Golab, Alexandra; Dawson, Grant K.W.; Knuefing, Lydia; Goodwin, Carley; Golding, Suzanne D.

    2016-01-01

    -rocks could be expected to act as baffles to fluids preventing vertical fluid migration. Concentrations of dissolved elements including Ca, Fe, Mn, and Ni increased during reactions of several core samples, with Mn, Mg, Co, and Zn correlated with Ca from cap-rock cores. Precipitation of gypsum, Fe-oxides and clays on seal core samples sequestered dissolved elements including Fe through co-precipitation or adsorption. A conceptual model of impure CO_2-water-rock interactions for a siliciclastic reservoir is discussed. - Highlights: • O_2-SO_2-CO_2 experiments on CO_2 sequestration site reservoir and cap-rock cores. • Coupled micro CT and geochemical characterization before and after reactions. • Strong acidification with reservoir core, no change in porosity. • Formation of open porosity in calcite cemented core, with buffered pH. • Dissolved Mn, Mg, Co, and Zn correlated with Ca from cap-rocks.

  17. Oxygen, hydrogen, ethylene and CO 2 development in lithium-ion batteries

    Science.gov (United States)

    Holzapfel, M.; Würsig, A.; Scheifele, W.; Vetter, J.; Novák, P.

    Gas evolution has been examined for different types of battery-related electrode materials via in situ differential electrochemical mass spectrometry (DEMS). Besides standard graphite also a novel silicon-based negative electrode was examined and it was shown that the evolution of hydrogen and ethylene is considerably reduced on this material compared to graphite. Oxygen evolution was proven to happen on the oxidative reaction of a Li 2O 2 electrode, besides a certain oxidation of the electrolyte. The 4.5 V plateau upon the oxidation of Li[Ni 0.2Li 0.2Mn 0.6]O 2 was likewise proven to be linked to oxygen evolution. Also in this case electrolyte oxidation was shown to be a side reaction. Layered positive electrode materials Li(Ni,Co,Al)O 2 and Li(Ni,Mn,Co)O 2 were also examined. The influence of different parameters on the CO 2 evolution in lithium-ion batteries was shown up. The amount of CO 2 formation is increased by high temperatures and cell voltages, while the addition of vinylene carbonate (VC) decreases it. Li(Ni,Mn,Co)O 2 shows much less CO 2 evolution than Li(Ni,Co,Al)O 2.

  18. Effects of N2-O2 and CO2-O2 Tensions on Growth of Fungi Isolated from Damaged Flue-Cured Tobacco 1

    Science.gov (United States)

    Yang, H.; Lucas, G. B.

    1970-01-01

    Ten fungi, Aspergillus niger, A. flavus, A. ochraceus, A. ruber, A. repens, A. amstelodami, Alternaria tenuis, Penicillium brevi-compactum, Cladosporium herbarum, and Chaetomium dolicotrichum, were isolated from moldy flue-cured tobacco and grown in various mixtures of N2-O2 or CO2-O2. A 1 to 5% concentration of O2 in an N2 atmosphere caused the greatest change in growth of the nine species, and a 10 to 20% concentration of O2 for A. flavus. All species, except A. amstelodami and A. ruber, grew faster in air than in mixtures containing 10% O2. High O2 concentrations generally inhibited furrow production in the mycelial mats. In an atmosphere of 5 to 40% O2 in the N2 atmosphere, furrows formed in mycelial mats between 5 and 40% O2 in the species except for A. ruber, A. repens, and A. amstelodami, which produced none in any concentration. As O2 decreased below 20%, spore production was progressively decreased, colony color faded to white, and cleistothecia formation was suppressed. In CO2-O2 mixtures radial growth of all species increased with each quantitative decrease of CO2. All species except A. niger grew faster in air than in 10% CO2. In contrast to N2-O2 mixtures, the fungi formed furrows, sporulation and cleistothecial formation were suppressed, and colony color changed to white in higher O2 concentrations. PMID:5461786

  19. NO2-initiated multiphase oxidation of SO2 by O2 on CaCO3 particles

    Science.gov (United States)

    Yu, Ting; Zhao, Defeng; Song, Xiaojuan; Zhu, Tong

    2018-05-01

    The reaction of SO2 with NO2 on the surface of aerosol particles has been suggested to be important in sulfate formation during severe air pollution episodes in China. However, we found that the direct oxidation of SO2 by NO2 was slow and might not be the main reason for sulfate formation in ambient air. In this study, we investigated the multiphase reaction of SO2 with an O2 / NO2 mixture on single CaCO3 particles using Micro-Raman spectroscopy. The reaction converted the CaCO3 particle to a Ca(NO3)2 droplet, with CaSO4 ⚫ 2H2O solid particles embedded in it, which constituted a significant fraction of the droplet volume at the end of the reaction. The reactive uptake coefficient of SO2 for sulfate formation was on the order of 10-5, which was higher than that for the multiphase reaction of SO2 directly with NO2 by 2-3 orders of magnitude. According to our observations and the literature, we found that in the multiphase reaction of SO2 with the O2 / NO2 mixture, O2 was the main oxidant of SO2 and was necessary for radical chain propagation. NO2 acted as the initiator of radical formation, but not as the main oxidant. The synergy of NO2 and O2 resulted in much faster sulfate formation than the sum of the reaction rates with NO2 and with O2 alone. We estimated that the multiphase oxidation of SO2 by O2 initiated by NO2 could be an important source of sulfate and a sink of SO2, based on the calculated lifetime of SO2 regarding the loss through the multiphase reaction versus the loss through the gas-phase reaction with OH radicals. Parameterization of the reactive uptake coefficient of the reaction observed in our laboratory for further model simulation is needed, as well as an integrated assessment based on field observations, laboratory study results, and model simulations to evaluate the importance of the reaction in ambient air during severe air pollution episodes, especially in China.

  20. Assessment of CO2 Storage Potential in Naturally Fractured Reservoirs With Dual-Porosity Models

    Science.gov (United States)

    March, Rafael; Doster, Florian; Geiger, Sebastian

    2018-03-01

    Naturally Fractured Reservoirs (NFR's) have received little attention as potential CO2 storage sites. Two main facts deter from storage projects in fractured reservoirs: (1) CO2 tends to be nonwetting in target formations and capillary forces will keep CO2 in the fractures, which typically have low pore volume; and (2) the high conductivity of the fractures may lead to increased spatial spreading of the CO2 plume. Numerical simulations are a powerful tool to understand the physics behind brine-CO2 flow in NFR's. Dual-porosity models are typically used to simulate multiphase flow in fractured formations. However, existing dual-porosity models are based on crude approximations of the matrix-fracture fluid transfer processes and often fail to capture the dynamics of fluid exchange accurately. Therefore, more accurate transfer functions are needed in order to evaluate the CO2 transfer to the matrix. This work presents an assessment of CO2 storage potential in NFR's using dual-porosity models. We investigate the impact of a system of fractures on storage in a saline aquifer, by analyzing the time scales of brine drainage by CO2 in the matrix blocks and the maximum CO2 that can be stored in the rock matrix. A new model to estimate drainage time scales is developed and used in a transfer function for dual-porosity simulations. We then analyze how injection rates should be limited in order to avoid early spill of CO2 (lost control of the plume) on a conceptual anticline model. Numerical simulations on the anticline show that naturally fractured reservoirs may be used to store CO2.