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Sample records for hybrid sulfur thermochemical

  1. Development of the Hybrid Sulfur Thermochemical Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Summers, William A.; Steimke, John L

    2005-09-23

    The production of hydrogen via the thermochemical splitting of water is being considered as a primary means for utilizing the heat from advanced nuclear reactors to provide fuel for a hydrogen economy. The Hybrid Sulfur (HyS) Process is one of the baseline candidates identified by the U.S. Department of Energy [1] for this purpose. The HyS Process is a two-step hybrid thermochemical cycle that only involves sulfur, oxygen and hydrogen compounds. Recent work has resulted in an improved process design with a calculated overall thermal efficiency (nuclear heat to hydrogen, higher heating value basis) approaching 50%. Economic analyses indicate that a nuclear hydrogen plant employing the HyS Process in conjunction with an advanced gas-cooled nuclear reactor system can produce hydrogen at competitive prices. Experimental work has begun on the sulfur dioxide depolarized electrolyzer, the major developmental component in the cycle. Proof-of-concept tests have established proton-exchange-membrane cells (a state-of-the-art technology) as a viable approach for conducting this reaction. This is expected to lead to more efficient and economical cell designs than were previously available. Considerable development and scale-up issues remain to be resolved, but the development of a viable commercial-scale HyS Process should be feasible in time to meet the commercialization schedule for Generation IV gas-cooled nuclear reactors.

  2. Materials study supporting thermochemical hydrogen cycle sulfuric acid decomposer design

    Science.gov (United States)

    Peck, Michael S.

    Increasing global climate change has been driven by greenhouse gases emissions originating from the combustion of fossil fuels. Clean burning hydrogen has the potential to replace much of the fossil fuels used today reducing the amount of greenhouse gases released into the atmosphere. The sulfur iodine and hybrid sulfur thermochemical cycles coupled with high temperature heat from advanced nuclear reactors have shown promise for economical large-scale hydrogen fuel stock production. Both of these cycles employ a step to decompose sulfuric acid to sulfur dioxide. This decomposition step occurs at high temperatures in the range of 825°C to 926°C dependent on the catalysis used. Successful commercial implementation of these technologies is dependent upon the development of suitable materials for use in the highly corrosive environments created by the decomposition products. Boron treated diamond film was a potential candidate for use in decomposer process equipment based on earlier studies concluding good oxidation resistance at elevated temperatures. However, little information was available relating the interactions of diamond and diamond films with sulfuric acid at temperatures greater than 350°C. A laboratory scale sulfuric acid decomposer simulator was constructed at the Nuclear Science and Engineering Institute at the University of Missouri-Columbia. The simulator was capable of producing the temperatures and corrosive environments that process equipment would be exposed to for industrialization of the sulfur iodide or hybrid sulfur thermochemical cycles. A series of boron treated synthetic diamonds were tested in the simulator to determine corrosion resistances and suitability for use in thermochemical process equipment. These studies were performed at twenty four hour durations at temperatures between 600°C to 926°C. Other materials, including natural diamond, synthetic diamond treated with titanium, silicon carbide, quartz, aluminum nitride, and Inconel

  3. ALTERNATIVE FLOWSHEETS FOR THE SULFUR-IODINE THERMOCHEMICAL HYDROGEN CYCLE

    Energy Technology Data Exchange (ETDEWEB)

    BROWN,LC; LENTSCH,RD; BESENBRUCH,GE; SCHULTZ,KR; FUNK,JE

    2003-02-01

    OAK-B135 A hydrogen economy will need significant new sources of hydrogen. Unless large-scale carbon sequestration can be economically implemented, use of hydrogen reduces greenhouse gases only if the hydrogen is produced with non-fossil energy sources. Nuclear energy is one of the limited options available. One of the promising approaches to produce large quantities of hydrogen from nuclear energy efficiently is the Sulfur-Iodine (S-I) thermochemical water-splitting cycle, driven by high temperature heat from a helium Gas-Cooled Reactor. They have completed a study of nuclear-driven thermochemical water-splitting processes. The final task of this study was the development of a flowsheet for a prototype S-I production plant. An important element of this effort was the evaluation of alternative flowsheets and selection of the reference design.

  4. Commercial Alloys for Sulfuric Acid Vaporization in Thermochemical Hydrogen Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Thomas M. Lillo; Karen M. Delezene-Briggs

    2005-10-01

    Most thermochemical cycles being considered for producing hydrogen include a processing stream in which dilute sulfuric acid is concentrated, vaporized and then decomposed over a catalyst. The sulfuric acid vaporizer is exposed to highly aggressive conditions. Liquid sulfuric acid will be present at a concentration of >96 wt% (>90 mol %) H2SO4 and temperatures exceeding 400oC [Brown, et. al, 2003]. The system will also be pressurized, 0.7-3.5 MPa, to keep the sulfuric acid in the liquid state at this temperature and acid concentration. These conditions far exceed those found in the commercial sulfuric acid generation, regeneration and handling industries. Exotic materials, e.g. ceramics, precious metals, clad materials, etc., have been proposed for this application [Wong, et. al., 2005]. However, development time, costs, reliability, safety concerns and/or certification issues plague such solutions and should be considered as relatively long-term, optimum solutions. A more cost-effective (and relatively near-term) solution would be to use commercially-available metallic alloys to demonstrate the cycle and study process variables. However, the corrosion behavior of commercial alloys in sulfuric acid is rarely characterized above the natural boiling point of concentrated sulfuric acid (~250oC at 1 atm). Therefore a screening study was undertaken to evaluate the suitability of various commercial alloys for concentration and vaporization of high-temperature sulfuric acid. Initially alloys were subjected to static corrosion tests in concentrated sulfuric acid (~95-97% H2SO4) at temperatures and exposure times up to 200oC and 480 hours, respectively. Alloys with a corrosion rate of less than 5 mm/year were then subjected to static corrosion tests at a pressure of 1.4 MPa and temperatures up to 375oC. Exposure times were shorter due to safety concerns and ranged from as short as 5 hours up to 144 hours. The materials evaluated included nickel-, iron- and cobalt

  5. Hydrogen production via thermochemical cycles based on sulfur chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Soliman, M.A.; Conger, W.L.; Carty, R.H.; Funk, J.E.; Cox, K.E.

    1976-01-01

    A class of closed thermochemical cycles for hydrogen production based on sulfur chemistry is presented. This class is described by the following set of chemical reactions: M + H/sub 2/O reversible MO + H/sub 2/ (low temperature); MO + 0.5S reversible M + 0.5SO/sub 2/ (high temperature); M'O + 1.5SO/sub 2/ reversible M'SO/sub 4/ + 0.5S (low temperature); and M'SO/sub 4/ reversible M'O + SO/sub 2/ + 0.5O/sub 2/ (high temperature). Experimental investigation of some of the reactions is presented. Thermodynamic analysis indicates efficiencies of the range of 40 to 50 percent and sometimes higher. Not all of the reactions in the proposed cycles have been verified in the literature or through experimentation.

  6. The role of labile sulfur compounds in thermochemical sulfate reduction

    Science.gov (United States)

    Amrani, A.; Zhang, T.; Ma, Q.; Ellis, G.S.; Tang, Y.

    2008-01-01

    The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n-octane and CaSO4 in the presence of reduced sulfur (e.g. H2S, S??, organic S) at temperatures of 330 and 356 ??C under a constant confining pressure. The in-situ pH was buffered to 3.5 (???6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H2S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n-octane, which is comparable to the concentration of organic S that is common in many oils (???0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H2S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H2S. Second, we considered the generation of olefines in association with the elimination of H2S during thermal degradation of thiols because olefines are much more reactive than n-alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of

  7. The role of labile sulfur compounds in thermochemical sulfate reduction

    Science.gov (United States)

    Amrani, Alon; Zhang, Tongwei; Ma, Qisheng; Ellis, Geoffrey S.; Tang, Yongchun

    2008-06-01

    The reduction of sulfate to sulfide coupled with the oxidation of hydrocarbons to carbon dioxide, commonly referred to as thermochemical sulfate reduction (TSR), is an important abiotic alteration process that most commonly occurs in hot carbonate petroleum reservoirs. In the present study we focus on the role that organic labile sulfur compounds play in increasing the rate of TSR. A series of gold-tube hydrous pyrolysis experiments were conducted with n-octane and CaSO4 in the presence of reduced sulfur (e.g. H2S, S°, organic S) at temperatures of 330 and 356 °C under a constant confining pressure. The in-situ pH was buffered to 3.5 (∼6.3 at room temperature) with talc and silica. For comparison, three types of oil with different total S and labile S contents were reacted under similar conditions. The results show that the initial presence of organic or inorganic sulfur compounds increases the rate of TSR. However, organic sulfur compounds, such as 1-pentanethiol or diethyldisulfide, were significantly more effective in increasing the rate of TSR than H2S or elemental sulfur (on a mole S basis). The increase in rate is achieved at relatively low concentrations of 1-pentanethiol, less than 1 wt% of the total n-octane, which is comparable to the concentration of organic S that is common in many oils (∼0.3 wt%). We examined several potential reaction mechanisms to explain the observed reactivity of organic LSC. First, the release of H2S from the thermal degradation of thiols was discounted as an important mechanism due to the significantly greater reactivity of thiol compared to an equivalent amount of H2S. Second, we considered the generation of olefines in association with the elimination of H2S during thermal degradation of thiols because olefines are much more reactive than n-alkanes during TSR. In our experiments, olefines increased the rate of TSR, but were less effective than 1-pentanethiol and other organic LSC. Third, the thermal decomposition of

  8. Sulfur Based Thermochemical Heat Storage for Baseload Concentrated Solar Power Generation

    Energy Technology Data Exchange (ETDEWEB)

    wong, bunsen

    2014-11-20

    This project investigates the engineering and economic feasibility of supplying baseload power using a concentrating solar power (CSP) plant integrated with sulfur based thermochemical heat storage. The technology stores high temperature solar heat in the chemical bonds of elemental sulfur. Energy is recovered as high temperature heat upon sulfur combustion. Extensive developmental and design work associated with sulfur dioxide (SO2) disproportionation and sulfuric acid (H2SO4) decomposition chemical reactions used in this technology had been carried out in the two completed phases of this project. The feasibility and economics of the proposed concept was demonstrated and determined.

  9. Sulfur Based Thermochemical Heat Storage for Baseload Concentrated Solar Power Generation

    Energy Technology Data Exchange (ETDEWEB)

    Wong, Bunsen [General Atomics, San Diego, CA (United States)

    2014-11-01

    This project investigates the engineering and economic feasibility of supplying baseload power using a concentrating solar power (CSP) plant integrated with sulfur based thermochemical heat storage. The technology stores high temperature solar heat in the chemical bonds of elemental sulfur. Energy is recovered as high temperature heat upon sulfur combustion. Extensive developmental and design work associated with sulfur dioxide (SO2) disproportionation and sulfuric acid (H2SO4) decomposition chemical reactions used in this technology had been carried out in the two completed phases of this project. The feasibility and economics of the proposed concept was demonstrated and determined.

  10. Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

    Science.gov (United States)

    Ota, K.; Conger, W. L.

    1977-01-01

    The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

  11. An exergetic/energetic/economic analysis of three hydrogen production processes - Electrolysis, hybrid, and thermochemical

    Science.gov (United States)

    Funk, J. E.; Eisermann, W.

    This paper presents the results of a combined first and second law analysis, along with capital and operating costs, for hydrogen production from water by means of electrolytic, hybrid, and thermochemical processes. The processes are SPE and Lurgi electrolysis with light water reactor power generation and sulfur cycle hybrid, thermochemical and SPE electrolysis with a very high temperature reactor primary energy source. Energy and Exergy (2nd law) flow diagrams for the process are shown along with the location and magnitude of the process irreversibilities. The overall process thermal (1st law) efficiencies vary from 25 to 51% and the exergetic (2nd law) efficiencies, referred to the fuel for the primary energy source, vary from 22 to 45%. Capital and operating costs, escalated to 1979 dollars, are shown for each process for both the primary energy source and the hydrogen production plant. All costs were taken from information available in the open literature and are for a plant capacity of 100 x 10 to the 6th SCF/day. Production costs vary from 10 to 18 $/GJ, based on the higher heating value of hydrogen, and are based on a 90% plant operating factor with a 21% annual charge on total capital costs.

  12. Sulfur Solubility In Silicate Melts: A Thermochemical Model

    Science.gov (United States)

    Moretti, R.; Ottonello, G.

    A termochemical model for calculating sulfur solubility of simple and complex silicate melts has been developed in the framework of the Toop-Samis polymeric approach combined with a Flood - Grjotheim theoretical treatment of silicate slags [1,2]. The model allows one to compute sulfide and sulfate content of silicate melts whenever fugacity of gaseous sulphur is provided. "Electrically equivalent ion fractions" are needed to weigh the contribution of the various disproportion reactions of the type: MOmelt + 1/2S2 ,gas MSmelt+1/2O2 ,gas (1) MOmelt + 1/2S2 ,gas + 3/2O2 ,gas MSO4 ,melt (2) Eqs. 1 and 2 account for the oxide-sulfide and the oxide-sulfate disproportiona- tion in silicate melt. Electrically equivalent ion fractions are computed, in a fused salt Temkin notation, over the appropriate matrixes (anionic and cationic). The extension of such matrixes is calculated in the framework of a polymeric model previously developed [1,2,3] and based on a parameterization of acid-base properties of melts. No adjustable parameters are used and model activities follow the raoultian behavior implicit in the ion matrix solution of the Temkin notation. The model is based on a huge amount of data available in literature and displays a high heuristic capability with virtually no compositional limits, as long as the structural role assigned to each oxide holds. REFERENCES: [1] Ottonello G., Moretti R., Marini L. and Vetuschi Zuccolini M. (2001), Chem. Geol., 174, 157-179. [2] Moretti R. (2002) PhD Thesis, University of Pisa. [3] Ottonello G. (2001) J. Non-Cryst. Solids, 282, 72-85.

  13. RECENT ADVANCES IN THE DEVELOPMENT OF THE HYBRID SULFUR PROCESS FOR HYDROGEN PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D.

    2010-07-22

    Thermochemical processes are being developed to provide global-scale quantities of hydrogen. A variant on sulfur-based thermochemical cycles is the Hybrid Sulfur (HyS) Process, which uses a sulfur dioxide depolarized electrolyzer (SDE) to produce the hydrogen. In the HyS Process, sulfur dioxide is oxidized in the presence of water at the electrolyzer anode to produce sulfuric acid and protons. The protons are transported through a cation-exchange membrane electrolyte to the cathode and are reduced to form hydrogen. In the second stage of the process, the sulfuric acid by-product from the electrolyzer is thermally decomposed at high temperature to produce sulfur dioxide and oxygen. The two gases are separated and the sulfur dioxide recycled to the electrolyzer for oxidation. The Savannah River National Laboratory (SRNL) has been exploring a fuel-cell design concept for the SDE using an anolyte feed comprised of concentrated sulfuric acid saturated with sulfur dioxide. The advantages of this design concept include high electrochemical efficiency and small footprint compared to a parallel-plate electrolyzer design. This paper will provide a summary of recent advances in the development of the SDE for the HyS process.

  14. Thermochemical hydrogen production via a cycle using barium and sulfur: reaction between barium sulfide and water

    Energy Technology Data Exchange (ETDEWEB)

    Ota, K.; Conger, W.L.

    1977-01-01

    The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653 to 866/sup 0/C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. The rate of formation of hydrogen can be expressed as: RH2 = 1.07 x 10/sup -2/ exp (-3180/RT) (mol H/sub 2//mol BaS s). Hydrogen sulfide was produced during the initial period of reaction and the quantity of hydrogen sulfide formed during this period decreased as the temperature of reaction was increased.

  15. HYBRID SULFUR ELECTROLYZER DEVELOPMENT FY09 SECOND QUARTER REPORT

    Energy Technology Data Exchange (ETDEWEB)

    Herman, D; David Hobbs, D; Hector Colon-Mercado, H; Timothy Steeper, T; John Steimke, J; Mark Elvington, M

    2009-04-15

    The primary objective of the DOE-NE Nuclear Hydrogen Initiative (NHI) is to develop the nuclear hydrogen production technologies necessary to produce hydrogen at a cost competitive with other alternative transportation fuels. The focus of the NHI is on thermochemical cycles and high temperature electrolysis that can be powered by heat from high temperature gas reactors. The Savannah River National Laboratory (SRNL) has been tasked with the primary responsibility to perform research and development in order to characterize, evaluate and develop the Hybrid Sulfur (HyS) thermochemical process. This report documents work during the first quarter of Fiscal Year 2009, for the period between January 1, 2009 and March 31, 2009. The HyS Process is a two-step hybrid thermochemical cycle that is part of the 'Sulfur Family' of cycles. As a sulfur cycle, it uses high temperature thermal decomposition of sulfuric acid to produce oxygen and to regenerate the sulfur dioxide reactant. The second step of the process uses a sulfur dioxide depolarized electrolyzer (SDE) to split water and produce hydrogen by electrochemically reacting sulfur dioxide with H{sub 2}O. The SDE produces sulfuric acid, which is then sent to the acid decomposer to complete the cycle. The DOE NHI program is developing the acid decomposer at Sandia National Laboratory for application to both the HyS Process and the Sulfur Iodine Cycle. The SDE is being developed at SRNL. During FY05 and FY06, SRNL designed and conducted proof-of-concept testing for a SDE using a low temperature, PEM fuel cell-type design concept. The advantages of this design concept include high electrochemical efficiency, small footprint and potential for low capital cost, characteristics that are crucial for successful implementation on a commercial scale. During FY07, SRNL extended the range of testing of the SDE to higher temperature and pressure, conducted a 100-hour longevity test with a 60-cm{sup 2} single cell electrolyzer

  16. Optimization of the Hybrid Sulfur Cycle for Nuclear Hydrogen Production Using UniSim Design

    Energy Technology Data Exchange (ETDEWEB)

    Jung, Yong Hun; Jeong, Yong Hoon [KAIST, Daejeon (Korea, Republic of)

    2009-05-15

    The sulfur-based thermochemical cycles are considered as the most promising methods to produce hydrogen. The Hybrid Sulfur (HyS) Cycle is a mixed thermochemical cycle with the sulfur-aided electrolysis as depicted in the Fig. 1. Hydrogen is produced from water by oxidizing sulfur dioxide in the low temperature electrolysis step and the sulfuric acid which is also produced in the electrolyzer proceeds to the high temperature thermochemical step. The sulfuric acid is concentrated in the concentrator first and then decomposed into steam and sulfur trioxide, which is further decomposed into sulfur dioxide and oxygen at high temperature (;1100 K) in the decomposer. After separated with oxygen in the separator, the sulfur dioxide is fed again to the electrolyzer to reduce the required electrode potential far below than that of the typical water electrolysis. Hydrogen is worth as a future energy carrier when it is produced cost effectively. In that sense, the energy efficiency of the hybrid sulfur cycle is needed to be improved as high as achievable. The flow sheet developed by Westinghouse, the first proposer of the cycle, is not optimized for the cycle efficiency. In the previous work, a detailed flow sheet model was developed and also the cycle efficiency of that was roughly estimated using the software CHEMKIN and CANARY based on the experimental data for the electrode potential and appropriate work of separation. The maximum efficiency was found to be 50.5% under the operating conditions of 10 bar and 1200K for decomposer and acid concentration of 60 mol% for decomposer, 60 wt. % for electrolyzer, respectively. In this study, more detailed flow sheet was developed and optimized by using software UniSim Design which is one of the most powerful process design and simulation tools.

  17. Development of a New Thermochemical and Electrolytic Hybrid Hydrogen Production System for Sodium Cooled FBR

    Science.gov (United States)

    Nakagiri, Toshio; Kase, Takeshi; Kato, Shoichi; Aoto, Kazumi

    A new thermo-chemical and electrolytic hybrid hydrogen production system in lower temperature range is newly proposed by the Japan Nuclear Cycle Development Institute (JAEA) to realize the hydrogen production from water by using the heat generation of sodium cooled Fast Breeder Reactor (FBR). The system is based on sulfuric acid (H2SO4) synthesis and decomposition process developed earlier (Westinghouse process), and sulfur trioxide (SO3) decomposition process is facilitated by electrolysis with ionic oxygen conductive solid electrolyte to reduce the operation temperature 200-300°C lower than Westinghouse process. SO3 decomposition with the voltage lower than 0.5V was confirmed in the temperature range of 500 to 600°C and theoretical thermal efficiency of the system evaluated based on chemical reactions was within the range of 35% to 55% under the influence of H2SO4 concentration and heat recovery. Furthermore, hydrogen production experiments to substantiate the whole process were performed. Stable hydrogen and oxygen production were observed in the experiments, and maximum duration of the experiments was about 5 hours.

  18. ENERGY EFFICIENCY LIMITS FOR A RECUPERATIVE BAYONET SULFURIC ACID DECOMPOSITION REACTOR FOR SULFUR CYCLE THERMOCHEMICAL HYDROGEN PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Gorensek, M.; Edwards, T.

    2009-06-11

    A recuperative bayonet reactor design for the high-temperature sulfuric acid decomposition step in sulfur-based thermochemical hydrogen cycles was evaluated using pinch analysis in conjunction with statistical methods. The objective was to establish the minimum energy requirement. Taking hydrogen production via alkaline electrolysis with nuclear power as the benchmark, the acid decomposition step can consume no more than 450 kJ/mol SO{sub 2} for sulfur cycles to be competitive. The lowest value of the minimum heating target, 320.9 kJ/mol SO{sub 2}, was found at the highest pressure (90 bar) and peak process temperature (900 C) considered, and at a feed concentration of 42.5 mol% H{sub 2}SO{sub 4}. This should be low enough for a practical water-splitting process, even including the additional energy required to concentrate the acid feed. Lower temperatures consistently gave higher minimum heating targets. The lowest peak process temperature that could meet the 450-kJ/mol SO{sub 2} benchmark was 750 C. If the decomposition reactor were to be heated indirectly by an advanced gas-cooled reactor heat source (50 C temperature difference between primary and secondary coolants, 25 C minimum temperature difference between the secondary coolant and the process), then sulfur cycles using this concept could be competitive with alkaline electrolysis provided the primary heat source temperature is at least 825 C. The bayonet design will not be practical if the (primary heat source) reactor outlet temperature is below 825 C.

  19. Contrasting effects of sulfur dioxide on cupric oxide and chloride during thermochemical formation of chlorinated aromatics.

    Science.gov (United States)

    Fujimori, Takashi; Nishimoto, Yoshihiro; Shiota, Kenji; Takaoka, Masaki

    2014-12-01

    Sulfur dioxide (SO2) gas has been reported to be an inhibitor of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs) formation in fly ash. However, other research has suggested little or no inhibitory effect of SO2 gas. Although these studies focused on reactions between SO2 gas and gas-phase chlorine (Cl) species, no attention was paid to thermochemical gas-solid reactions. In this study, we found contrasting effects of SO2 gas depending on the chemical form of copper (CuO vs CuCl2) with a solid-phase inorganic Cl source (KCl). Chlorinated aromatics (PCDD/Fs, polychlorinated biphenyls, and chlorobenzenes) increased and decreased in model fly ash containing CuO + KCl and CuCl2 + KCl, respectively, with increased SO2 injection. According to in situ Cu K-edge and S K-edge X-ray absorption spectroscopy, Cl gas and CuCl2 were generated and then promoted the formation of highly chlorinated aromatics after thermochemical reactions of SO2 gas with the solid-phase CuO + KCl system. In contrast, the decrease in aromatic-Cls in a CuCl2 + KCl system with SO2 gas was caused mainly by the partial sulfation of the Cu. The chemical form of Cu (especially the oxide/chloride ratio) may be a critical factor in controlling the formation of chlorinated aromatics using SO2 gas.

  20. Thermochemical destruction of asbestos-containing roofing slate and the feasibility of using recycled waste sulfuric acid.

    Science.gov (United States)

    Nam, Seong-Nam; Jeong, Seongkyeong; Lim, Hojoo

    2014-01-30

    In this study, we have investigated the feasibility of using a thermochemical technique on ∼17% chrysotile-containing roofing sheet or slate (ACS), in which 5N sulfuric acid-digestive destruction was incorporated with 10-24-h heating at 100°C. The X-ray diffraction (XRD) and the polarized light microscopy (PLM) results have clearly shown that raw chrysotile asbestos was converted to non-asbestiform material with no crystallinity by the low temperature thermochemical treatment. As an alternative to the use of pricey sulfuric acid, waste sulfuric acid discharged from a semiconductor manufacturing process was reused for the asbestos-fracturing purpose, and it was found that similar removals could be obtained under the same experimental conditions, promising the practical applicability of thermochemical treatment of ACWs. A thermodynamic understanding based on the extraction rates of magnesium and silica from a chrysotile structure has revealed that the destruction of chrysotile by acid-digestion is greatly influenced by the reaction temperatures, showing a 80.3-fold increase in the reaction rate by raising the temperature by 30-100°C. The overall destruction is dependent upon the breaking-up of the silicon-oxide layer - a rate-limiting step. This study is meaningful in showing that the low temperature thermochemical treatment is feasible as an ACW-treatment method.

  1. Occurrence of the Bunsen side reaction in the sulfur-iodine thermochemical cycle for hydrogen production

    Institute of Scientific and Technical Information of China (English)

    Qiao-qiao ZHU; Yan-wei ZHANG; Zhi YING; Jun-hu ZHOU; Zhi-hua WANG; Ke-fa CEN

    2013-01-01

    This study aimed to establish a closed-cycle operation technology with high thermal efficiency in the thermochemical sulfur-iodine cycle for large-scale hydrogen production.A series of experimental studies were performed to investigate the occurrence of side reactions in both the H2SO4 and HIx phases from the H2SO4/HI/I2/H2O quaternary system within a constant temperature range of 323-363 K.The effects of iodine content,water content and reaction temperature on the side reactions were evaluated.The results showed that an increase in the reaction temperature promoted the side reactions.However,they were prevented as the iodine or water content increased.The occurrence of side reactions was faster in kinetics and more intense in the H2SO4 phase than in the HIx phase.The sulfur or hydrogen sulfide formation reaction or the reverse Bunsen reaction was validated under certain conditions.

  2. Kinetics of uncatalyzed thermochemical sulfate reduction by sulfur-free paraffin

    Science.gov (United States)

    Zhang, Tongwei; Ellis, Geoffrey S.; Ma, Qisheng; Amrani, Alon; Tang, Yongchun

    2012-01-01

    To determine kinetic parameters of sulfate reduction by hydrocarbons (HC) without the initial presence of low valence sulfur, we carried out a series of isothermal gold-tube hydrous-pyrolysis experiments at 320, 340, and 360 °C under a constant confined pressure of 24.1 MPa. The reactants used consisted of saturated HC (sulfur-free) and CaSO4 in an aqueous solution buffered to three different pH conditions without the addition of elemental sulfur (S8) or H2S as initiators. H2S produced in the course of reaction was proportional to the extent of the reduction of CaSO4 that was initially the only sulfur-containing reactant. Our results show that the in situ pH of the aqueous solution (herein, in situ pH refers to the calculated pH value of the aqueous solution at certain experimental conditions) can significantly affect the rate of the thermochemical sulfate reduction (TSR) reaction. A substantial increase in the TSR reaction rate was observed with a decrease in the in situ pH. Our experimental results show that uncatalyzed TSR is a first-order reaction. The temperature dependence of experimentally measured H2S yields from sulfate reduction was fit with the Arrhenius equation. The determined activation energy for HC (sulfur-free) reacting with View the MathML sourceHSO4− in our experiments is 246.6 kJ/mol at pH values ranging from 3.0 to 3.5, which is slightly higher than the theoretical value of 227.0 kJ/mol using ab initio quantum chemical calculations on a similar reaction. Although the availability of reactive sulfate significantly affects the rate of reaction, a consistent rate constant was determined by accounting for the HSO4− ion concentration. Our experimental and theoretical approach to the determination of the kinetics of TSR is further validated by a reevaluation of several published experimental TSR datasets without the initial presence of native sulfur or H2S. When the effect of reactive sulfate concentration is appropriately accounted for, the

  3. Thermochemical destruction of asbestos-containing roofing slate and the feasibility of using recycled waste sulfuric acid

    Energy Technology Data Exchange (ETDEWEB)

    Nam, Seong-Nam, E-mail: namsn76@gmail.com [Engineering Research Institute, Seoul National University, Daehak-dong, Gwanak-gu 151-744 (Korea, Republic of); Jeong, Seongkyeong [Environmental Resource Recirculation Division, National Institute of Environmental Research, Environmental Research Complex, Kyeongseo-dong, Seo-gu, Incheon 404-708 (Korea, Republic of); Lim, Hojoo [Indoor Environment and Noise Division, National Institute of Environmental Research, Environmental Research Complex, Kyeongseo-dong, Seo-gu, Incheon 404-708 (Korea, Republic of)

    2014-01-30

    Highlights: • Asbestos-containing roofing slates (ACS) were thermochemically treated. • 5 N H{sub 2}SO{sub 4} with 100 °C heating for 10–24 h showed complete disappearance. • Asbestiform of ACS was changed to non-asbestiform after treatment. • Favorable destruction was occurred at the Mg(OH){sub 2} layer rather than SiO{sub 2} sheet. • Equivalent treatability of waste acid brightened the feasibility of this approach. -- Abstract: In this study, we have investigated the feasibility of using a thermochemical technique on ∼17% chrysotile-containing roofing sheet or slate (ACS), in which 5 N sulfuric acid-digestive destruction was incorporated with 10–24-h heating at 100 °C. The X-ray diffraction (XRD) and the polarized light microscopy (PLM) results have clearly shown that raw chrysotile asbestos was converted to non-asbestiform material with no crystallinity by the low temperature thermochemical treatment. As an alternative to the use of pricey sulfuric acid, waste sulfuric acid discharged from a semiconductor manufacturing process was reused for the asbestos-fracturing purpose, and it was found that similar removals could be obtained under the same experimental conditions, promising the practical applicability of thermochemical treatment of ACWs. A thermodynamic understanding based on the extraction rates of magnesium and silica from a chrysotile structure has revealed that the destruction of chrysotile by acid-digestion is greatly influenced by the reaction temperatures, showing a 80.3-fold increase in the reaction rate by raising the temperature by 30–100 °C. The overall destruction is dependent upon the breaking-up of the silicon-oxide layer – a rate-limiting step. This study is meaningful in showing that the low temperature thermochemical treatment is feasible as an ACW-treatment method.

  4. Study of thermochemical sulfate reduction mechanism using compound specific sulfur isotope analysis

    Science.gov (United States)

    Meshoulam, Alexander; Ellis, Geoffrey S.; Said Ahmad, Ward; Deev, Andrei; Sessions, Alex L.; Tang, Yongchun; Adkins, Jess F.; Liu, Jinzhong; Gilhooly, William P.; Aizenshtat, Zeev; Amrani, Alon

    2016-09-01

    The sulfur isotopic fractionation associated with the formation of organic sulfur compounds (OSCs) during thermochemical sulfate reduction (TSR) was studied using gold-tube pyrolysis experiments to simulate TSR. The reactants used included n-hexadecane (n-C16) as a model organic compound with sulfate, sulfite, or elemental sulfur as the sulfur source. At the end of each experiment, the S-isotopic composition and concentration of remaining sulfate, H2S, benzothiophene, dibenzothiophene, and 2-phenylthiophene (PT) were measured. The observed S-isotopic fractionations between sulfate and BT, DBT, and H2S in experimental simulations of TSR correlate well with a multi-stage model of the overall TSR process. Large kinetic isotope fractionations occur during the first, uncatalyzed stage of TSR, 12.4‰ for H2S and as much as 22.2‰ for BT. The fractionations decrease as the H2S concentration increases and the reaction enters the second, catalyzed stage. Once all of the oxidizable hydrocarbons have been consumed, sulfate reduction ceases and equilibrium partitioning then dictates the fractionation between H2S and sulfate (∼17‰). Experiments involving sparingly soluble CaSO4 show that during the second catalytic phase of TSR the rate of sulfate reduction exceeds that of sulfate dissolution. In this case, there is no apparent isotopic fractionation between source sulfate and generated H2S, as all of the available sulfate is effectively reduced at all reaction times. When CaSO4 is replaced with fully soluble Na2SO4, sulfate dissolution is no longer rate limiting and significant S-isotopic fractionation is observed. This supports the notion that CaSO4 dissolution can lead to the apparent lack of fractionation between H2S and sulfate produced by TSR in nature. The S-isotopic composition of individual OSCs record information related to geochemical reactions that cannot be discerned from the δ34S values obtained from bulk phases such as H2S, oil, and sulfate minerals, and

  5. Crystal Sinking Modeling for Designing Iodine Crystallizer in Thermochemical Sulfur-Iodine Hydrogen Production Process

    Energy Technology Data Exchange (ETDEWEB)

    Park, Byung Heung [Korea National University of Transportation, Chungju (Korea, Republic of); Jeong, Seong-Uk [Korea Institute of Energy Research, Daejeon (Korea, Republic of); Kang, Jeong Won [Korea University, Seoul (Korea, Republic of)

    2014-12-15

    SI process is a thermochemical process producing hydrogen by decomposing water while recycling sulfur and iodine. Various technologies have been developed to improve the efficiency on Section III of SI process, where iodine is separated and recycled. EED(electro-electrodialysis) could increase the efficiency of Section III without additional chemical compounds but a substantial amount of I{sub 2} from a process stream is loaded on EED. In order to reduce the load, a crystallization technology prior to EED is considered as an I{sub 2} removal process. In this work, I{sub 2} particle sinking behavior was modeled to secure basic data for designing an I{sub 2} crystallizer applied to I{sub 2}-saturated HI{sub x} solutions. The composition of HI{sub x} solution was determined by thermodynamic UVa model and correlation equations and pure properties were used to evaluate the solution properties. A multiphysics computational tool was utilized to calculate particle sinking velocity changes with respect to I{sub 2} particle radius and temperature. The terminal velocity of an I{sub 2} particle was estimated around 0.5 m/s under considered radius (1.0 to 2.5 mm) and temperature (10 to 50 .deg. C) ranges and it was analyzed that the velocity is more dependent on the solution density than the solution viscosity.

  6. Thermochemical Storage of Middle Temperature Wasted Heat by Functionalized C/Mg(OH2 Hybrid Materials

    Directory of Open Access Journals (Sweden)

    Emanuela Mastronardo

    2017-01-01

    Full Text Available For the thermochemical performance implementation of Mg(OH2 as a heat storage medium, several hybrid materials have been investigated. For this study, high-performance hybrid materials have been developed by exploiting the authors’ previous findings. Expanded graphite (EG/carbon nanotubes (CNTs-Mg(OH2 hybrid materials have been prepared through Mg(OH2 deposition-precipitation over functionalized, i.e., oxidized, or un-functionalized EG or CNTs. The heat storage performances of the carbon-based hybrid materials have been investigated through a laboratory-scale experimental simulation of the heat storage/release cycles, carried out by a thermogravimetric apparatus. This study offers a critical evaluation of the thermochemical performances of developed materials through their comparison in terms of heat storage and output capacities per mass and volume unit. It was demonstrated that both EG and CNTs improves the thermochemical performances of the storage medium in terms of reaction rate and conversion with respect to pure Mg(OH2. With functionalized EG/CNTs-Mg(OH2, (i the potential heat storage and output capacities per mass unit of Mg(OH2 have been completely exploited; and (ii higher heat storage and output capacities per volume unit were obtained. That means, for technological applications, as smaller volume at equal stored/released heat.

  7. Local hybrid functionals: an assessment for thermochemical kinetics.

    Science.gov (United States)

    Kaupp, Martin; Bahmann, Hilke; Arbuznikov, Alexei V

    2007-11-21

    Local hybrid functionals with position-dependent exact-exchange admixture are a new class of exchange-correlation functionals in density functional theory that promise to advance the available accuracy in many areas of application. Local hybrids with different local mixing functions (LMFs) governing the position dependence are validated for the heats of formation of the extended G3/99 set, and for two sets of barriers of hydrogen-transfer and heavy-atom transfer reactions (HTBH38 and NHTBH38 databases). A simple local hybrid Lh-SVWN with only Slater and exact exchange plus local correlation and a one-parameter LMF, g(r)=b(tau(W)(r)tau(r)), performs best and provides overall mean absolute errors for thermochemistry and kinetics that are a significant improvement over standard state-of-the-art global hybrid functionals. In particular, this local hybrid functional does not suffer from the systematic deterioration that standard functionals exhibit for larger molecules. In contrast, local hybrids based on generalized gradient approximation exchange tend to give rise to nonintuitive LMFs, and no improved functionals have been obtained along this route. The LMF is a real-space function and thus can be analyzed in detail. We use, in particular, graphical analyses to rationalize the performance of different local hybrids for thermochemistry and reaction barriers.

  8. A Carbon-Sulfur Hybrid with Pomegranate-like Structure for Lithium-Sulfur Batteries.

    Science.gov (United States)

    Shi, Yanting; Lv, Wei; Niu, Shuzhang; He, Yanbing; Zhou, Guangmin; Chen, Guohua; Li, Baohua; Yang, Quan-Hong; Kang, Feiyu

    2016-05-01

    A carbon-sulfur hybrid with pomegranate-like core-shell structure, which demonstrates a high rate performance and relatively high cyclic stability, is obtained through carbonization of a carbon precursor in the presence of a sulfur precursor (FeS2 ) and a following oxidation of FeS2 to sulfur by HNO3 . Such a structure effectively protects the sulfur and leaves enough buffer space after Fe(3+) removal and, at the same time, has an interconnected conductive network. The capacity of the obtained hybrid is 450 mA h g(-1) under the current density of 5 C. This work provides a simple strategy to design and prepare various high-performance carbon-sulfur hybrids for lithium-sulfur batteries.

  9. Entropy production and efficiency analysis of the Bunsen reaction in the General Atomic sulfur-iodine thermochemical hydrogen production cycle

    Energy Technology Data Exchange (ETDEWEB)

    Davis, M.E.; Conger, W.L.

    1980-01-01

    An entropy production and efficiency analysis of the first reaction in the General Atomic sulfur-iodine thermochemical hydrogen production cycle has been carried out by simulating the reaction including the mixing of reactants and separation of the resulting phases. The reaction: 2H/sub 2/O(L) + SO/sub 2/(g) + (excess) I/sub 2/(g) = H/sub 2/SO/sub 4/ (sol)(Phase I) + 2 HI core (Phase II) was simulated at 388 K, which is slightly above the melting point of I/sup 2/. Analysis of only this reaction shows that the reaction should be run at 15 to 25% I/sub 2/ reacted and the greatest excess of H/sub 2/O which will produce two product phases. Actual operating conditions are however dependent on the total processing scheme. An entropy production and efficiency analysis along with economic factors for the entire process is necessary to obtain these conditions.

  10. Fibrous hybrid of graphene and sulfur nanocrystals for high-performance lithium-sulfur batteries.

    Science.gov (United States)

    Zhou, Guangmin; Yin, Li-Chang; Wang, Da-Wei; Li, Lu; Pei, Songfeng; Gentle, Ian Ross; Li, Feng; Cheng, Hui-Ming

    2013-06-25

    Graphene-sulfur (G-S) hybrid materials with sulfur nanocrystals anchored on interconnected fibrous graphene are obtained by a facile one-pot strategy using a sulfur/carbon disulfide/alcohol mixed solution. The reduction of graphene oxide and the formation/binding of sulfur nanocrystals were integrated. The G-S hybrids exhibit a highly porous network structure constructed by fibrous graphene, many electrically conducting pathways, and easily tunable sulfur content, which can be cut and pressed into pellets to be directly used as lithium-sulfur battery cathodes without using a metal current-collector, binder, and conductive additive. The porous network and sulfur nanocrystals enable rapid ion transport and short Li(+) diffusion distance, the interconnected fibrous graphene provides highly conductive electron transport pathways, and the oxygen-containing (mainly hydroxyl/epoxide) groups show strong binding with polysulfides, preventing their dissolution into the electrolyte based on first-principles calculations. As a result, the G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles. These results demonstrate the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.

  11. Wet Chemistry Synthesis of Multidimensional Nanocarbon-Sulfur Hybrid Materials with Ultrahigh Sulfur Loading for Lithium-Sulfur Batteries.

    Science.gov (United States)

    Du, Wen-Cheng; Yin, Ya-Xia; Zeng, Xian-Xiang; Shi, Ji-Lei; Zhang, Shuai-Feng; Wan, Li-Jun; Guo, Yu-Guo

    2016-02-17

    An optimized nanocarbon-sulfur cathode material with ultrahigh sulfur loading of up to 90 wt % is realized in the form of sulfur nanolayer-coated three-dimensional (3D) conducting network. This 3D nanocarbon-sulfur network combines three different nanocarbons, as follows: zero-dimensional carbon nanoparticle, one-dimensional carbon nanotube, and two-dimensional graphene. This 3D nanocarbon-sulfur network is synthesized by using a method based on soluble chemistry of elemental sulfur and three types of nanocarbons in well-chosen solvents. The resultant sulfur-carbon material shows a high specific capacity of 1115 mA h g(-1) at 0.02C and good rate performance of 551 mA h g(-1) at 1C based on the mass of sulfur-carbon composite. Good battery performance can be attributed to the homogeneous compositing of sulfur with the 3D hierarchical hybrid nanocarbon networks at nanometer scale, which provides efficient multidimensional transport pathways for electrons and ions. Wet chemical method developed here provides an easy and cost-effective way to prepare sulfur-carbon cathode materials with high sulfur loading for application in high-energy Li-S batteries.

  12. Preliminary results from bench-scale testing of a sulfur-iodine thermochemical water-splitting cycle

    Energy Technology Data Exchange (ETDEWEB)

    O' Keefe, D.; Allen, C.; Besenbruch, G.; McCorkle, K.; Norman, J.; Sharp, R.

    1980-07-01

    Portions of a bench-scale model of a sulfur-iodine thermochemical water-splitting cycle have been operated at General Atomic Company as part of a comprehensive program to demonstrate the technology for hydrogen production from nonfossil sources. The hydrogen program is funded by the US Department of Energy, the Gas Research Institute, and General Atomic Company. The bench-scale model consists of three subunits which can be operated separately or together and is capable of producing as much as 4 std liters/min (6.7 x 10/sup -5/ m/sup 3//s at standard conditions) of gaseous hydrogen. One subunit (main solution reaction) reacts liquid water, liquid iodine (I/sub 2/) and gaseous sulfur dioxide (SO/sub 2/) to form two separable liquid phases: 50 wt % sulfuric acid (H/sub 2/SO/sub 4/) and a solution of iodine in hydriodic acid (HI/sub x/). Another subunit (H/sub 2/SO/sub 4/ concentration and decomposition) concentrates the H/sub 2/SO/sub 4/ phase to the azeotropic composition, then decomposes it at high temperature over a catalyst to form gaseous SO/sub 2/ and oxygen. The third subunit (HI separation and decomposition) separates the HI from water and I/sub 2/ by extractive distillation with phosphoric acid (H/sub 3/PO/sub 4/) and decomposes the HI in the vapor phase over a catalyst to form I/sub 2/ and product hydrogen. This paper presents the results of on-going parametric studies to determine the operating characteristics, performance, and capacity limitations of major components.

  13. Conceptual design model of the sulfur-iodine S-I thermochemical water splitting process for hydrogen production using nuclear heat source

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Rodriguez, Daniel; Parra, Lazaro Garcia, E-mail: dgr@instec.cu, E-mail: lgarcia@instec.cu [Departamento de Ingenieria Nuclear, Instituto Superior de Ciencias y Tecnologias Aplicadas, La Habana (Cuba)

    2011-07-01

    Hydrogen is the most indicated candidate for its implementation as energy carrier in a future sustainable scenario. The current hydrogen production is based on fossils fuels; they have a huge contribution to the atmosphere pollution. Thermochemical water-splitting cycles do not have this issue because they use solar or nuclear heat; their environment impact is smaller than conventional fuels. The software based on chemical process simulation (CPS) can be used to simulate the thermochemical water splitting cycle Sulfur-Iodine for hydrogen production. In the paper is developed a model for Sulfur-Iodine process in order to analyze his sensibility and calculate the efficiency and the influence of many parameters on this value. (author)

  14. Activated Carbon Catalysts for the Production of Hydrogen for the Sulfur-Iodine Thermochemical Water Splitting Cycle

    Energy Technology Data Exchange (ETDEWEB)

    Lucia M. Petkovic; Daniel M. Ginosar; Harry W. Rollins; Kyle C Burch; Cristina Deiana; Hugo S. Silva; Maria F. Sardella; Dolly Granados

    2009-05-01

    Seven activated carbon catalysts obtained from a variety of raw material sources and preparation methods were examined for their catalytic activity to decompose hydroiodic acid (HI) to produce hydrogen; a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. Within the group of ligno-cellulosic steam-activated carbon catalysts, activity increased with surface area. However, both a mineral-based steam-activated carbon and a ligno-cellulosic chemically-activated carbon displayed activities lower than expected based on their higher surface areas. In general, ash content was detrimental to catalytic activity while total acid sites, as determined by Bohem’s titrations, seemed to favor higher catalytic activity within the group of steam-activated carbons. These results suggest, one more time, that activated carbon raw materials and preparation methods may have played a significant role in the development of surface characteristics that eventually dictated catalyst activity and stability as well.

  15. Activated carbon catalysts for the production of hydrogen via the sulfur-iodine thermochemical water splitting cycle

    Energy Technology Data Exchange (ETDEWEB)

    Petkovic, Lucia M.; Ginosar, Daniel M.; Rollins, Harry W.; Burch, Kyle C. [Idaho National Laboratory, Interfacial Chemistry, P.O. Box 1625, Idaho Falls, ID 83415-2208 (United States); Deiana, Cristina; Silva, Hugo S.; Sardella, Maria F.; Granados, Dolly [Instituto de Ingenieria Quimica, Facultad de Ingenieria, Universidad Nacional de San Juan, Libertador 1109 (oeste) 5400 San Juan (Argentina)

    2009-05-15

    Seven activated carbon catalysts obtained from a variety of raw material sources and preparation methods were examined for their catalytic activity to decompose hydrogen iodide (HI) to produce hydrogen, a key reaction in the sulfur-iodine (S-I) thermochemical water splitting cycle. Activity was examined under a temperature ramp from 473 to 773 K. Within the group of lignocellulosic steam-activated carbon catalysts, activity increased with surface area. However, both a mineral-based steam-activated carbon and a lignocellulosic chemically activated carbon displayed activities lower than expected based on their higher surface areas. In general, ash content was detrimental to catalytic activity while total acid sites, as determined by Boehm's titrations, seemed to favor higher catalytic activity within the group of steam-activated carbons. These results suggest that activated carbon raw materials and preparation methods may have played a significant role in the development of surface characteristics that eventually dictated catalyst activity and stability as well. (author)

  16. HYBRID SULFUR RECOVERY PROCESS FOR NATURAL GAS UPGRADING

    Energy Technology Data Exchange (ETDEWEB)

    Girish Srinivas; Steven C. Gebhard; David W. DeBerry

    2001-05-01

    This first quarter report of 2001 describes progress on a project funded by the U.S. Department of Energy (DOE) to test a hybrid sulfur recovery process for natural gas upgrading. The process concept represents a low cost option for direct treatment of natural gas streams to remove H{sub 2}S in quantities equivalent to 0.2-25 metric tons (LT) of sulfur per day. This process is projected to have lower capital and operating costs than the competing technologies, amine/aqueous iron liquid redox and amine/Claus/tail gas treating, and have a smaller plant footprint, making it well suited to both on-shore and offshore applications. CrystaSulf{trademark} (service mark of Gas Research Institute) is a new nonaqueous sulfur recovery process that removes hydrogen sulfide (H{sub 2}S) from gas streams and converts it into elemental sulfur. CrystaSulf features high sulfur recovery similar to aqueous-iron liquid redox sulfur recovery processes, but differs from the aqueous processes in that CrystaSulf controls the location where elemental sulfur particles are formed. In the hybrid process, approximately 1/3 of the total H{sub 2}S in the natural gas is first oxidized to SO{sub 2} at low temperatures over a heterogeneous catalyst. Low temperature oxidation is done so that the H{sub 2}S can be oxidized in the presence of methane and other hydrocarbons without oxidation of the hydrocarbons. The project involves the development of a catalyst using laboratory/bench-scale catalyst testing, and then demonstration of the catalyst at CrystaTech's pilot plant in west Texas. During this reporting periods new catalyst formulations were tested. The experiments showed that the newest catalyst has slightly better performance, but catalyst TDA No.2 is still superior overall for use with the hybrid CrystaSulf process due to lower costs. Plans for catalyst pelletization and continued testing are described.

  17. HYBRID SULFUR PROCESS REFERENCE DESIGN AND COST ANALYSIS

    Energy Technology Data Exchange (ETDEWEB)

    Gorensek, M.; Summers, W.; Boltrunis, C.; Lahoda, E.; Allen, D.; Greyvenstein, R.

    2009-05-12

    PBMR (Pty.) Ltd. in the RSA, with the Hybrid Sulfur (HyS) Process, under development by the Savannah River National Laboratory (SRNL) in the US as part of the NHI. This work was performed by SRNL, Westinghouse Electric Company, Shaw, PBMR (Pty) Ltd., and Technology Insights under a Technical Consulting Agreement (TCA). Westinghouse Electric, serving as the lead for the PBMR process heat application team, established a cost-shared TCA with SRNL to prepare an updated HyS thermochemical water-splitting process flowsheet, a nuclear hydrogen plant preconceptual design and a cost estimate, including the cost of hydrogen production. SRNL was funded by DOE under the NHI program, and the Westinghouse team was self-funded. The results of this work are presented in this Final Report. Appendices have been attached to provide a detailed source of information in order to document the work under the TCA contract.

  18. FISCAL YEAR 2006 REPORT ON ELECTROLYZER COMPONENT DEVELOPMENT FOR THE HYBRID SULFUR PROJECT

    Energy Technology Data Exchange (ETDEWEB)

    Colon-Mercado, H; David Hobbs, D; Daryl Coleman, D; Amy Ekechukwu, A

    2006-08-03

    Thermochemical processes are being developed to provide global-scale quantities of hydrogen. A variant on sulfur-based thermochemical cycles is the Hybrid Sulfur (HyS) Process which uses a sulfur dioxide depolarized electrolyzer (SDE) to produce the hydrogen. In FY05, testing at the Savannah River National Laboratory (SRNL) explored a low temperature fuel cell design concept for the SDE. The advantages of this design concept include high electrochemical efficiency and small volumetric footprint that is crucial for successful implementation on a commercial scale. A key component of the SDE is the ion conductive membrane through which protons produced at anode migrate to the cathode and react to produce hydrogen. An ideal membrane for the SDE should have both low ionic resistivity and low sulfur dioxide transport. These features allow the electrolyzer to perform at high currents with low potentials, along with preventing contamination of both the hydrogen output and poisoning of the catalysts involved. Another key component is the electrocatalyst material used for the anode and cathode. Good electrocatalysts should be chemically stable and low overpotential for the desired electrochemical reactions. This report summarizes results from activities to evaluate different membrane and electrocatalyst materials for the SDE. Several different types of commercially-available membranes were analyzed for ionic resistance and sulfur dioxide transport including perfluorinated sulfonic acid, sulfonated poly-etherketone-ketone, and poly-benzimidazole membranes. Of these membrane types, the poly-benzimidazole (PBI) membrane, Celtec-L, exhibited the best combination of characteristics for use in an SDE. Testing examined the activity and stability of platinum and palladium as electrocatalyst for the SDE in sulfuric acid solutions. Cyclic and linear sweep voltammetry revealed that platinum provided better catalytic activity with much lower potentials and higher currents than palladium

  19. HYBRID SULFUR RECOVERY PROCESS FOR NATURAL GAS UPGRADING

    Energy Technology Data Exchange (ETDEWEB)

    Girish Srinivas; Steven C. Gebhard; David W. DeBerry

    2002-07-01

    This second quarter report of 2002 describes progress on a project funded by the U.S. Department of Energy (DOE) to test a hybrid sulfur recovery process for natural gas upgrading. The process concept represents a low cost option for direct treatment of natural gas streams to remove H{sub 2}S in quantities equivalent to 0.2-25 metric tons (LT) of sulfur per day. This process is projected to have lower capital and operating costs than the competing technologies, amine/aqueous iron liquid redox and amine/Claus/tail gas treating, and have a smaller plant footprint, making it well suited to both on-shore and offshore applications. CrystaSulf (service mark of CrystaTech, Inc.) is a new nonaqueous sulfur recovery process that removes hydrogen sulfide (H{sub 2}S) from gas streams and converts it into elemental sulfur. CrystaSulf features high sulfur recovery similar to aqueous-iron liquid redox sulfur recovery processes, but differs from the aqueous processes in that CrystaSulf controls the location where elemental sulfur particles are formed. In the hybrid process, approximately 1/3 of the total H{sub 2}S in the natural gas is first oxidized to SO{sub 2} at low temperatures over a heterogeneous catalyst. Low temperature oxidation is done so that the H{sub 2}S can be oxidized in the presence of methane and other hydrocarbons without oxidation of the hydrocarbons. The project involves the development of a catalyst using laboratory/bench-scale catalyst testing, and then demonstration of the catalyst at CrystaTech's pilot plant in west Texas. Previous reports described development of a catalyst with the required selectivity and efficiency for producing sulfur dioxide from H{sub 2}S. In the laboratory, the catalyst was shown to be robust and stable in the presence of several intentionally added contaminants, including condensate from the pilot plant site. This report describes testing using the laboratory apparatus but operated at the pilot plant using the actual pilot

  20. HYBRID SULFUR RECOVERY PROCESS FOR NATURAL GAS UPGRADING

    Energy Technology Data Exchange (ETDEWEB)

    Girish Srinivas; Steven C. Gebhard; David W. DeBerry

    2002-04-01

    This first quarter report of 2002 describes progress on a project funded by the U.S. Department of Energy (DOE) to test a hybrid sulfur recovery process for natural gas upgrading. The process concept represents a low cost option for direct treatment of natural gas streams to remove H{sub 2}S in quantities equivalent to 0.2-25 metric tons (LT) of sulfur per day. This process is projected to have lower capital and operating costs than the competing technologies, amine/aqueous iron liquid redox and amine/Claus/tail gas treating, and have a smaller plant footprint, making it well suited to both on-shore and offshore applications. CrystaSulf{sup SM} (service mark of CrystaTech, Inc.) is a new nonaqueous sulfur recovery process that removes hydrogen sulfide (H{sub 2}S) from gas streams and converts it into elemental sulfur. CrystaSulf features high sulfur recovery similar to aqueous-iron liquid redox sulfur recovery processes, but differs from the aqueous processes in that CrystaSulf controls the location where elemental sulfur particles are formed. In the hybrid process, approximately 1/3 of the total H{sub 2}S in the natural gas is first oxidized to SO{sub 2} at low temperatures over a heterogeneous catalyst. Low temperature oxidation is done so that the H{sub 2}S can be oxidized in the presence of methane and other hydrocarbons without oxidation of the hydrocarbons. The project involves the development of a catalyst using laboratory/bench-scale catalyst testing, and then demonstration of the catalyst at CrystaTech's pilot plant in west Texas. In a previous reporting period tests were done to determine the effect of hydrocarbons such as n-hexane on catalyst performance with and without H{sub 2}S present. The experiments showed that hexane oxidation is suppressed when H{sub 2}S is present. Hexane represents the most reactive of the C1 to C6 series of alkanes. Since hexane exhibits low reactivity under H{sub 2}S oxidation conditions, and more importantly, does not

  1. Graphene/sulfur hybrid nanosheets from a space-confined "sauna" reaction for high-performance lithium-sulfur batteries.

    Science.gov (United States)

    Fei, Linfeng; Li, Xiaogang; Bi, Wentuan; Zhuo, Zhiwen; Wei, Wenfei; Sun, Li; Lu, Wei; Wu, Xiaojun; Xie, Keyu; Wu, Changzheng; Chan, Helen L W; Wang, Yu

    2015-10-21

    A space-confined "sauna" reaction system is introduced for the simultaneous reduction and functionalization of graphene oxide to unique graphene-sulfur hybrid nanosheets, in which thin layers of amorphous sulfur are tightly anchored on the graphene sheet via strong chemical bonding. Upon being used as the cathode material in lithium-sulfur batteries, the as-synthesized composite shows an excellent electrochemical performance.

  2. HYBRID SULFUR RECOVERY PROCESS FOR NATURAL GAS UPGRADING

    Energy Technology Data Exchange (ETDEWEB)

    Dennis Dalrymple

    2004-06-01

    This final report describes the objectives, technical approach, results and conclusions for a project funded by the U.S. Department of Energy to test a hybrid sulfur recovery process for natural gas upgrading. The process concept is a configuration of CrystaTech, Inc.'s CrystaSulf{reg_sign} process which utilizes a direct oxidation catalyst upstream of the absorber tower to oxidize a portion of the inlet hydrogen sulfide (H{sub 2}S) to sulfur dioxide (SO{sub 2}) and elemental sulfur. This hybrid configuration of CrystaSulf has been named CrystaSulf-DO and represents a low-cost option for direct treatment of natural gas streams to remove H{sub 2}S in quantities equivalent to 0.2-25 metric tons (LT) of sulfur per day and more. This hybrid process is projected to have lower capital and operating costs than the competing technologies, amine/aqueous iron liquid redox and amine/Claus/tail gas treating, and have a smaller plant footprint, making it well suited to both onshore and offshore applications. CrystaSulf is a nonaqueous sulfur recovery process that removes H{sub 2}S from gas streams and converts it to elemental sulfur. In CrystaSulf, H{sub 2}S in the inlet gas is reacted with SO{sub 2} to make elemental sulfur according to the liquid phase Claus reaction: 2H{sub 2}S + SO{sub 2} {yields} 2H{sub 2}O + 3S. The SO{sub 2} for the reaction can be supplied from external sources by purchasing liquid SO{sub 2} and injecting it into the CrystaSulf solution, or produced internally by converting a portion of the inlet gas H{sub 2}S to SO{sub 2} or by burning a portion of the sulfur produced to make SO{sub 2}. CrystaSulf features high sulfur recovery similar to aqueous-iron liquid redox sulfur recovery processes, but differs from the aqueous processes in that CrystaSulf controls the location where elemental sulfur particles are formed. In the hybrid process, the needed SO{sub 2} is produced by placing a bed of direct oxidation catalyst in the inlet gas stream to oxidize

  3. A solar receiver-storage modular cascade based on porous ceramic structures for hybrid sensible/thermochemical solar energy storage

    Science.gov (United States)

    Agrafiotis, Christos; de Oliveira, Lamark; Roeb, Martin; Sattler, Christian

    2016-05-01

    The current state-of-the-art solar heat storage concept in air-operated Solar Tower Power Plants is to store the solar energy provided during on-sun operation as sensible heat in porous solid materials that operate as recuperators during off-sun operation. The technology is operationally simple; however its storage capacity is limited to 1.5 hours. An idea for extending this capacity is to render this storage concept from "purely" sensible to "hybrid" sensible/ thermochemical one, via coating the porous heat exchange modules with oxides of multivalent metals for which their reduction/oxidation reactions are accompanied by significant heat effects, or by manufacturing them entirely of such oxides. In this way solar heat produced during on-sun operation can be used (in addition to sensibly heating the porous solid) to power the endothermic reduction of the oxide from its state with the higher metal valence to that of the lower; the thermal energy can be entirely recovered by the reverse exothermic oxidation reaction (in addition to sensible heat) during off-sun operation. Such sensible and thermochemical storage concepts were tested on a solar-irradiated receiver- heat storage module cascade for the first time. Parametric studies performed so far involved the comparison of three different SiC-based receivers with respect to their capability of supplying solar-heated air at temperatures sufficient for the reduction of the oxides, the effect of air flow rate on the temperatures achieved within the storage module, as well as the comparison of different porous storage media made of cordierite with respect to their sensible storage capacity.

  4. HYBRID SULFUR ELECTROLYZER DEVELOPMENT, NHI WORK PACKAGE N-SR07TC0301, FY07 FIRST QUARTER REPORT

    Energy Technology Data Exchange (ETDEWEB)

    Summers, W

    2006-12-20

    The proof of concept of SO2 electrolysis for the hybrid sulfur (HyS) process is the second priority research target of the DOE Nuclear Hydrogen Initiative's thermochemical program for FY07. The proof of concept of the liquid-phase option must be demonstrated at the single cell level for an extended run times (>100 hours). The rate of development of HyS will depend on the identification of a promising membrane or an alternative means for controlling sulfur formation. Once successful long-duration operation has been demonstrated, SRNL will develop a multi-cell stack that can be connected to the H2SO4 decomposer being developed by SNL for the S-I ILS for a Hybrid Sulfur Integrated Laboratory-Scale Experiment during FY 2008. During the first quarter of FY07, SRNL continued the component development and membrane development activities with the goal of identifying and characterizing improved electrodes, electrocatalysts, membranes and MEA configurations which could then be tested at larger scale in the SDE test facility. A modified glass cell was fabricated to allow measurements of sulfur dioxide (SO2) transport across membrane samples at elevated temperatures (up to 70 C). This testing also includes evaluating SO2 transport in different sulfuric acid concentrations (30-70 wt%). A new potentiostat/frequency analyzer was installed for determining ionic conductivity of membranes. This instrument enhances our capabilities to characterize membrane, electrocatalyst and MEA properties and performance. Continuing work from FY06, evaluations were preformed on various commercial and experimental membranes and electrocatalyst materials for the SDE. Several different types of commercially-available membranes were analyzed for sulfur dioxide transport as a function of acid strength including perfluorinated sulfonic acid (PFSA), sulfonated polyetherketone-ketone, and poly-benzimidazole (PBI) membranes. Experimental membranes from the sulfonated diels-alder polyphenylenes (SDAPP

  5. Hydrogen production by water decomposition using a combined electrolytic-thermochemical cycle

    Science.gov (United States)

    Farbman, G. H.; Brecher, L. E.

    1976-01-01

    A proposed dual-purpose power plant generating nuclear power to provide energy for driving a water decomposition system is described. The entire system, dubbed Sulfur Cycle Water Decomposition System, works on sulfur compounds (sulfuric acid feedstock, sulfur oxides) in a hybrid electrolytic-thermochemical cycle; performance superior to either all-electrolysis systems or presently known all-thermochemical systems is claimed. The 3345 MW(th) graphite-moderated helium-cooled reactor (VHTR - Very High Temperature Reactor) generates both high-temperature heat and electric power for the process; the gas stream at core exit is heated to 1850 F. Reactor operation is described and reactor innards are illustrated. A cost assessment for on-stream performance in the 1990's is optimistic.

  6. Hierarchical nitrogen-doped porous graphene/reduced fluorographene/sulfur hybrids for high-performance lithium-sulfur batteries.

    Science.gov (United States)

    Liu, Zhixuan; Li, Jie; Xiang, Jingwei; Cheng, Shuai; Wu, Hao; Zhang, Na; Yuan, Lixia; Zhang, Wenfeng; Xie, Jia; Huang, Yunhui; Chang, Haixin

    2017-01-18

    It is a great challenge to obtain high performance cathodes with a high sulfur loading and good cycle performance due to the dissolution of intermediate lithium polysulfides in lithium-sulfur batteries. Herein, we report a novel hierarchical hybrid composed of nitrogen-doped porous graphene (NG), reduced fluorographene or graphene fluoride (RFG), and sulfur as a composite cathode in the Li-S batteries. In comparison with sulfur composites based on only either nitrogen-doped porous graphene or pure reduced fluorographene, the hierarchical hybrid of RFG, NG, and sulfur (NG-RFG/S) shows a better reversible capacity and rate capability performance due to a better confinement effect of lithium polysulfides and sulfur. The NG-RFG/S cathode with ∼63.2% S content exhibits a high discharge capacity of 1120 mA h g(-1) and retains 632 mA h g(-1) after 100 cycles at 0.1C. At the higher rate of 0.5C, the cell still maintains a discharge capacity of about 300 mA h g(-1) after 800 cycles, which reveals the great potential of this hybrid cathode for long-cycle-life, high energy density storage applications.

  7. Synergetic inhibition of thermochemical formation of chlorinated aromatics by sulfur and nitrogen derived from thiourea: Multielement characterizations.

    Science.gov (United States)

    Fujimori, Takashi; Nakamura, Madoka; Takaoka, Masaki; Shiota, Kenji; Kitajima, Yoshinori

    2016-07-01

    Nitrogen and sulfur (N/S)-containing compounds inhibit the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and furans (PCDFs) in thermal processes. However, few studies have examined the inhibition mechanisms of N/S-containing compounds. In the present study, we focused on thiourea [(NH2)2CS] as such a compound and investigated its inhibition effects and mechanisms. The production of PCDD/Fs, polychlorinated biphenyls (PCBs), and chlorobenzenes (CBzs) were inhibited by >99% in the model fly ash in the presence of 1.0% thiourea after heating at 300 °C. Experimental results using real fly ash series were indicative of the thermal destruction of these chlorinated aromatics by thiourea. Multielement characterization using K-edge X-ray absorption fine structures of copper, chlorine, sulfur, nitrogen, and carbon revealed three possible inhibition paths, namely, (a) sulfidization of the copper catalyst to CuS, Cu2S, and CuSO4; (b) blocking the chlorination of carbon via the reaction of chlorine with N-containing compounds to generate ammonium chloride and other minor compounds; and (c) changing the carbon frame involved in attacking the carbon matrix by sulfur and nitrogen. Thus, thiourea plays a role as a sulfur and nitrogen donor to achieve multiple and synergistic inhibition of chlorinated aromatics. Our results suggest that other N/S-containing inhibitors function based on similar mechanisms.

  8. Effects of thermal maturation and thermochemical sulfate reduction on compound-specific sulfur isotopic compositions of organosulfur compounds in Phosphoria oils from the Bighorn Basin, USA

    Science.gov (United States)

    Ellis, Geoffrey S.; Said-Ahamed, Ward; Lillis, Paul G.; Shawar, Lubna; Amrani, Alon

    2017-01-01

    Compound-specific sulfur isotope analysis was applied to a suite of 18 crude oils generated from the Permian Phosphoria Formation in the Bighorn Basin, western USA. These oils were generated at various levels of thermal maturity and some experienced thermochemical sulfate reduction (TSR). This is the first study to examine the effects of thermal maturation on stable sulfur isotopic compositions of individual organosulfur compounds (OSCs) in crude oil. A general trend of 34S enrichment in all of the studied compounds with increasing thermal maturity was observed, with the δ34S values of alkyl-benzothiophenes (BTs) tending to be enriched in 34S relative to those of the alkyl-dibenzothiophenes (DBTs) in lower-maturity oils. As thermal maturity increases, δ34S values of both BTs and DBTs become progressively heavier, but the difference in the average δ34S value of the BTs and DBTs (Δ34S BT-DBT) decreases. Differences in the isotopic response to thermal stress exhibited by these two compound classes are considered to be the result of relative differences in their thermal stabilities. TSR-altered Bighorn Basin oils have OSCs that are generally enriched in 34S relative to non-TSR-altered oils, with the BTs being enriched in 34S relative to the DBTs, similar to the findings of previous studies. However, several oils that were previously interpreted to have been exposed to minor TSR have Δ34S BT-DBT values that do not support this interpretation. The δ34S values of the BTs and DBTs in some of these oils suggest that they did not experience TSR, but were derived from a more thermally mature source. The heaviest δ34S values observed in the OSCs are enriched in 34S by up to 10‰ relative to that of Permian anhydrite in the Bighorn Basin, suggesting that there may be an alternate or additional source of sulfate in some parts of the basin. These results indicate that the sulfur isotopic composition of OSCs in oil provides a sensitive indicator for the extent of TSR

  9. HYBRID SULFUR ELECROLYZER DEVELOPMENT, NHI WORK PACKAGE N-SR07TC0301, FY08 FIRST QUARTER REPORT

    Energy Technology Data Exchange (ETDEWEB)

    Summers, W

    2007-12-20

    Hydrogen has been identified as a leading candidate to replace petroleum as part of the transition to a sustainable energy system, and major efforts are being conducted worldwide to develop the technologies and supporting activities required for this transition. In the United States, the federal research efforts are led by the U.S. Department of Energy (DOE). The U.S. DOE Hydrogen Program is an integrated inter-office program being conducted by the Office of Energy Efficiency and Renewable Energy, Office of Nuclear Energy (DOE-NE), Office of Fossil Energy and Office of Science. The primary objective of the DOE-NE Nuclear Hydrogen Initiative (NHI) is to develop the nuclear hydrogen production technologies necessary to produce hydrogen at a cost competitive with other alternative transportation fuels. The focus of the NHI is on thermochemical cycles and high temperature electrolysis. The Savannah River National Laboratory (SRNL) has been tasked with the primary responsibility to perform research and development in order to characterize, evaluate and develop the Hybrid Sulfur (HyS) thermochemical process. The HyS Process uses a sulfur dioxide depolarized electrolyzer (SDE) to split water and produce hydrogen. During FY05 and FY06, SRNL designed and conducted proof-of-concept testing for a SDE using a low temperature, PEM fuel cell-type design concept. The advantages of this design concept include high electrochemical efficiency and small footprint, characteristics that are crucial for successful implementation on a commercial scale. During FY07, SRNL extended the range of testing of the SDE to higher temperature and pressure, conducted a 100-hour longevity test, and designed and built a larger, multi-cell stack electrolyzer. The proof of concept of SO2 electrolysis for the HyS Process is a priority research target for the FY 2008 NHI Program. Technical options must be better defined and the challenges better understood. The current status of electrolyzer performance

  10. Hybrid nanostructured microporous carbon-mesoporous carbon doped titanium dioxide/sulfur composite positive electrode materials for rechargeable lithium-sulfur batteries

    Science.gov (United States)

    Zegeye, Tilahun Awoke; Kuo, Chung-Feng Jeffrey; Wotango, Aselefech Sorsa; Pan, Chun-Jern; Chen, Hung-Ming; Haregewoin, Atetegeb Meazah; Cheng, Ju-Hsiang; Su, Wei-Nien; Hwang, Bing-Joe

    2016-08-01

    Herein, we design hybrid nanostructured microporous carbon-mesoporous carbon doped titanium dioxide/sulfur composite (MC-Meso C-doped TiO2/S) as a positive electrode material for lithium-sulfur batteries. The hybrid MC-Meso C-doped TiO2 host material is produced by a low-cost, hydrothermal and annealing process. The resulting conductive material shows dual microporous and mesoporous behavior which enhances the effective trapping of sulfur and polysulfides. The hybrid MC-Meso C-doped TiO2/S composite material possesses rutile TiO2 nanotube structure with successful carbon doping while sulfur is uniformly distributed in the hybrid MC-Meso C-doped TiO2 composite materials after the melt-infusion process. The electrochemical measurement of the hybrid material also shows improved cycle stability and rate performance with high sulfur loading (61.04%). The material delivers an initial discharge capacity of 802 mAh g-1 and maintains it at 578 mAh g-1 with a columbic efficiency greater than 97.1% after 140 cycles at 0.1 C. This improvement is thought to be attributed to the unique hybrid nanostructure of the MC-Meso C-doped TiO2 host and the good dispersion of sulfur in the narrow pores of the MC spheres and the mesoporous C-doped TiO2 support.

  11. FY08 MEMBRANE CHARACTERIZATION REPORT FOR HYBRID SULFUR ELECTROLYZER

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D; Hector Colon-Mercado, H; Mark Elvington, M

    2008-09-01

    This report summarizes results from all of the membrane testing completed to date at the Savannah River National Laboratory (SRNL) for the sulfur dioxide-depolarized electrolyzer (SDE). Several types of commercially-available membranes have been analyzed for ionic resistance and sulfur dioxide transport including perfluorinated sulfonic acid (PFSA), sulfonated polyether-ketone-ketone (SPEKK), and polybenzimidazole membranes (PBI). Of these membrane types, the poly-benzimidazole membrane, Celtec-L, exhibited the best combination of characteristics for use in an SDE. Several experimental membranes have also been analyzed including hydrated sulfonated Diels-Alder polyphenylenes (SDAPP) membranes from Sandia National Laboratory, perfluorosulfonimide (PFSI) and sulfonated perfluorocyclobutyl aromatic ether (S-PFCB) prepared by Clemson University, hydrated platinum-treated PFSA prepared by Giner Electrochemical Systems (GES) and Pt-Nafion{reg_sign} 115 composites prepared at SRNL. The chemical stability, SO{sub 2} transport and ionic conductivity characteristics have been measured for several commercially available and experimental proton-conducting membranes. Commercially available PFSA membranes such as the Nafion{reg_sign} series exhibited excellent chemical stability and ionic conductivity in sulfur dioxide saturated sulfuric acid solutions. Sulfur dioxide transport in the Nafion{reg_sign} membranes varied proportionally with the thickness and equivalent weight of the membrane. Although the SO{sub 2} transport in the Nafion{reg_sign} membranes is higher than desired, the excellent chemical stability and conductivity makes this membrane the best commercially-available membrane at this time. Initial results indicated that a modified Nafion{reg_sign} membrane incorporating Pt nanoparticles exhibited significantly reduced SO{sub 2} transport. Reduced SO{sub 2} transport was also measured with commercially available PBI membrane and several experimental membranes produced

  12. Preparation of three-dimensional hybrid nanostructure-encapsulated sulfur cathode for high-rate lithium sulfur batteries

    Science.gov (United States)

    Xie, Jing; Yang, Juan; Zhou, Xiangyang; Zou, Youlan; Tang, Jingjing; Wang, Songcan; Chen, Feng

    2014-05-01

    A three-dimensional hybrid nanostructure incorporating the merits of the MWCNTs webs (MWCNTs-W) and the reduced graphene oxide (RGO) is designed to improve the high-rate cycling performance of the lithium-sulfur batteries. Owing to the excellent Li+ ion and electronic transport properties of the MWCNTs-W and the RGO, this unique structure can provide a three-dimensional conductive network and promote rapid charge-transfer reaction at the cathode. Furthermore, because of the rough surface and porous structure of the MWCNTs after activation with KOH, and the special adsorption ability of the RGO, the soluble polysulfide intermediates can be effectively trapped in the cathode. Therefore, when evaluating the electrochemical properties of the RGO@MWCNTs-W/S composite as the cathode material for lithium-sulfur batteries, it exhibits an excellent cyclical stability and high rate performance. In particular, even at an ultrahigh rate (5 C), a discharge capacity as high as 620 mAh g-1 is still retained for the RGO@MWCNTs-W/S composite with 68.93 wt% sulfur after 200 cycles, and the average coulombic efficiency is 96%.

  13. Development and Test Operation of a Demonstration Plant for Sulfuric Acid Splitting at the DLR Concentrating Solar Power Tower Facility

    OpenAIRE

    Thomey, Dennis; Streber, Hans-Peter; Guerra-Niehoff, Alejandro; Romero, Moises; Lapp, Justin; Roeb, Martin; Sattler, Christian

    2016-01-01

    Sulfuric acid splitting is a key step of the hybrid sulfur cycle (HyS) for solar thermochemical hydrogen production. This exothermal reaction can be divided into two steps: firstly, the evaporation of liquid sulfuric acid (H2SO4) at about 400 °C forming sulfur trioxide (SO3), and secondly, the decomposition of SO3 to sulfur dioxide (SO2) and oxygen (O2) at 800 – 1000 °C. While the first sub-reaction has fast kinetics, the second one is rather slow and requires the introduction of ...

  14. One-pot self-assembly of graphene/carbon nanotube/sulfur hybrid with three dimensionally interconnected structure for lithium-sulfur batteries

    Science.gov (United States)

    Niu, Shuzhang; Lv, Wei; Zhang, Chen; Shi, Yanting; Zhao, Jianfeng; Li, Baohua; Yang, Quan-Hong; Kang, Feiyu

    2015-11-01

    A graphene/carbon nanotube (CNT)/sulfur (denoted GCS) hybrid with interconnected structure is prepared through a one-pot self-assembly approach initiated by L-ascorbic acid reduction under a mild condition. In such a solution-based assembly process, the formation of an interconnected graphene/CNT conductive network is accompanied by the uniform loading of sulfur, whose fraction is as high as of 70 wt%. The as-prepared GCS hybrid delivers an initial capacity of 1008 mAh g-1 at 0.3C and maintains 704 mAh g-1 after 100 cycles. Remarkably, at a high rate of 1.0C, the cathode shows an excellent cyclic performance with a capacity of 657 mAh g-1 after 450 ycles and the capacity decay is only 0.04% per cycle. Moreover, the superior rate performance of GCS hybrid is attributed to the conductive network formed by interconnected graphene sheets and CNT, which supply an unimpeded and continuous path for electron and Li ion transfer and accommodate the volume variation of sulfur during charge/discharge cycling. In addition, the residual functional groups on GCS can retain intimate contact of the conducting matrix with sulfur and effectively confine the diffusion of polysulfides. This study gives an eco-friendly and highly effective solution-based approach for carbon-sulfur electrode for lithium-sulfur battery.

  15. Economic comparison of solar hydrogen generation by means of thermochemical cycles and electrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Graf, D.; Monnerie, N.; Roeb, M.; Schmitz, M.; Sattler, C. [German Aerospace Center, Institute of Technical Thermodynamics, Solar Research, Linder Hoehe, 51147 Cologne (Germany)

    2008-09-15

    Hydrogen is acclaimed to be an energy carrier of the future. Currently, it is mainly produced by fossil fuels, which release climate-changing emissions. Thermochemical cycles, represented here by the hybrid-sulfur cycle and a metal oxide based cycle, along with electrolysis of water are the most promising processes for 'clean' hydrogen mass production for the future. For this comparison study, both thermochemical cycles are operated by concentrated solar thermal power for multistage water splitting. The electricity required for the electrolysis is produced by a parabolic trough power plant. For each process investment, operating and hydrogen production costs were calculated on a 50 MW{sub th} scale. The goal is to point out the potential of sustainable hydrogen production using solar energy and thermochemical cycles compared to commercial electrolysis. A sensitivity analysis was carried out for three different cost scenarios. As a result, hydrogen production costs ranging from 3.9-5.6 EUR/kg for the hybrid-sulfur cycle, 3.5-12.8 EUR/kg for the metal oxide based cycle and 2.1-6.8 EUR/kg for electrolysis were obtained. (author)

  16. Hydrogen production by the solar-powered hybrid sulfur process: Analysis of the integration of the CSP and chemical plants in selected scenarios

    Science.gov (United States)

    Liberatore, Raffaele; Lanchi, Michela; Turchetti, Luca

    2016-05-01

    The Hybrid Sulfur (HyS) is a water splitting process for hydrogen production powered with high temperature nuclear heat and electric power; among the numerous thermo-chemical and thermo-electro-chemical cycles proposed in the literature, such cycle is considered to have a particularly high potential also if powered by renewable energy. SOL2HY2 (Solar to Hydrogen Hybrid Cycles) is a 3 year research project, co-funded by the Fuel Cells and Hydrogen Joint Undertaking (FCH JU). A significant part of the project activities are devoted to the analysis and optimization of the integration of the solar power plant with the chemical, hydrogen production plant. This work reports a part of the results obtained in such research activity. The analysis presented in this work builds on previous process simulations used to determine the energy requirements of the hydrogen production plant in terms of electric power, medium (550°C) temperature heat. For the supply of medium temperature (MT) heat, a parabolic trough CSP plant using molten salts as heat transfer and storage medium is considered. A central receiver CSP (Concentrated Solar Power) plant is considered to provide high temperature (HT) heat, which is only needed for sulfuric acid decomposition. Finally, electric power is provided by a power block included in the MT solar plant and/or drawn from the grid, depending on the scenario considered. In particular, the analysis presented here focuses on the medium temperature CSP plant, possibly combined with a power block. Different scenarios were analysed by considering plants with different combinations of geographical location and sizing criteria.

  17. Solar Thermochemical Hydrogen Production Plant Design

    OpenAIRE

    Littlefield, Jesse

    2012-01-01

    A plant was designed that uses a solar sulfur-ammonia thermochemical water-splitting cycle for the production of hydrogen. Hydrogen is useful as a fuel for stationary and mobile fuel cells. The chemical process simulator Aspen Plus® was used to model the plant and conduct simulations. The process utilizes the electrolytic oxidation of aqueous ammonium sulfite in the hydrogen production half cycle and the thermal decomposition of molten potassium pyrosulfate and gaseous sulfur trioxide in t...

  18. A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process for decentralized wastewater treatment.

    Science.gov (United States)

    Krayzelova, Lucie; Lynn, Thomas J; Banihani, Qais; Bartacek, Jan; Jenicek, Pavel; Ergas, Sarina J

    2014-09-15

    Nitrogen discharges from decentralized wastewater treatment (DWT) systems contribute to surface and groundwater contamination. However, the high variability in loading rates, long idle periods and lack of regular maintenance presents a challenge for biological nitrogen removal in DWT. A Tire-Sulfur Hybrid Adsorption Denitrification (T-SHAD) process was developed that combines nitrate (NO3(-)) adsorption to scrap tire chips with sulfur-oxidizing denitrification. This allows the tire chips to adsorb NO3(-) when the influent loading exceeds the denitrification capacity of the biofilm and release it when NO3(-) loading rates are low (e.g. at night). Three waste products, scrap tire chips, elemental sulfur pellets and crushed oyster shells, were used as a medium in adsorption, leaching, microcosm and up-flow packed bed bioreactor studies of NO3(-) removal from synthetic nitrified DWT wastewater. Adsorption isotherms showed that scrap tire chips have an adsorption capacity of 0.66 g NO3(-)-N kg(-1) of scrap tires. Leaching and microcosm studies showed that scrap tires leach bioavailable organic carbon that can support mixotrophic metabolism, resulting in lower effluent SO4(2-) concentrations than sulfur oxidizing denitrification alone. In column studies, the T-SHAD process achieved high NO3(-)-N removal efficiencies under steady state (90%), variable flow (89%) and variable concentration (94%) conditions.

  19. Membranes for the Sulfur-Iodine Integrated Laboratory Scale Demonstration

    Energy Technology Data Exchange (ETDEWEB)

    Frederick F. Stewart

    2007-08-01

    INL has developed polymeric membrane-based chemical separations to enable the thermochemical production of hydrogen. Major activities included studies of sulfuric acid concentration membranes, hydriodic acid concentration membranes, SO2/O2 separation membranes, potential applications of a catalyst reactor system for the decomposition of HI, and evaluation of the chemical separation needs for alternate thermochemical cycles. Membranes for the concentration of sulfuric acid were studied using pervaporation. The goal of this task was to offer the sulfur-iodine (S-I) and the hybrid sulfur (HyS) cycles a method to concentrate the sulfuric acid containing effluent from the decomposer without boiling. In this work, sulfuric acid decomposer effluent needs to be concentrated from ~50 % acid to 80 %. This task continued FY 2006 efforts to characterize water selective membranes for use in sulfuric acid concentration. In FY 2007, experiments were conducted to provide specific information, including transmembrane fluxes, separation factors, and membrane durability, necessary for proper decision making on the potential inclusion of this process into the S-I or HyS Integrated Laboratory Scale demonstration.

  20. HYBRID SULFUR FLOWSHEETS USING PEM ELECTROLYSIS AND A BAYONET DECOMPOSITION REACTOR

    Energy Technology Data Exchange (ETDEWEB)

    Gorensek, M; William Summers, W

    2008-05-30

    A conceptual design is presented for a Hybrid Sulfur process for the production of hydrogen using a high-temperature nuclear heat source to split water. The process combines proton exchange membrane-based SO{sub 2}-depolarized electrolyzer technology being developed at Savannah River National Laboratory with silicon carbide bayonet decomposition reactor technology being developed at Sandia National Laboratories. Both are part of the US DOE Nuclear Hydrogen Initiative. The flowsheet otherwise uses only proven chemical process components. Electrolyzer product is concentrated from 50 wt% sulfuric acid to 75 wt% via recuperative vacuum distillation. Pinch analysis is used to predict the high-temperature heat requirement for sulfuric acid decomposition. An Aspen Plus{trademark} model of the flowsheet indicates 340.3 kJ high-temperature heat, 75.5 kJ low-temperature heat, 1.31 kJ low-pressure steam, and 120.9 kJ electric power are consumed per mole of H{sub 2} product, giving an LHV efficiency of 35.3% (41.7% HHV efficiency) if electric power is available at a conversion efficiency of 45%.

  1. Ternary Hybrid Material for High-Performance Lithium-Sulfur Battery.

    Science.gov (United States)

    Fan, Qi; Liu, Wen; Weng, Zhe; Sun, Yueming; Wang, Hailiang

    2015-10-14

    The rechargeable lithium-sulfur battery is a promising option for energy storage applications because of its low cost and high energy density. The electrochemical performance of the sulfur cathode, however, is substantially compromised because of fast capacity decay caused by polysulfide dissolution/shuttling and low specific capacity caused by the poor electrical conductivities of the active materials. Herein we demonstrate a novel strategy to address these two problems by designing and synthesizing a carbon nanotube (CNT)/NiFe2O4-S ternary hybrid material structure. In this unique material architecture, each component synergistically serves a specific purpose: The porous CNT network provides fast electron conduction paths and structural stability. The NiFe2O4 nanosheets afford strong binding sites for trapping polysulfide intermediates. The fine S nanoparticles well-distributed on the CNT/NiFe2O4 scaffold facilitate fast Li(+) storage and release for energy delivery. The hybrid material exhibits balanced high performance with respect to specific capacity, rate capability, and cycling stability with outstandingly high Coulombic efficiency. Reversible specific capacities of 1350 and 900 mAh g(-1) are achieved at rates of 0.1 and 1 C respectively, together with an unprecedented cycling stability of ∼0.009% capacity decay per cycle over more than 500 cycles.

  2. Frequency Scale Factors for Some Double-Hybrid Density Functional Theory Procedures: Accurate Thermochemical Components for High-Level Composite Protocols.

    Science.gov (United States)

    Chan, Bun; Radom, Leo

    2016-08-09

    In the present study, we have obtained geometries and frequency scale factors for a number of double-hybrid density functional theory (DH-DFT) procedures. We have evaluated their performance for obtaining thermochemical quantities [zero-point vibrational energies (ZPVE) and thermal corrections for 298 K enthalpies (ΔH298) and 298 K entropies (S298)] to be used within high-level composite protocols (using the W2X procedure as a probe). We find that, in comparison with the previously prescribed protocol for optimization and frequency calculations (B3-LYP/cc-pVTZ+d), the use of contemporary DH-DFT methods such as DuT-D3 and DSD-type procedures leads to a slight overall improved performance compared with B3-LYP. A major strength of this approach, however, lies in the better robustness of the DH-DFT methods in that the largest deviations are notably smaller than those for B3-LYP. In general, the specific choices of the DH-DFT procedure and the associated basis set do not drastically change the performance. Nonetheless, we find that the DSD-PBE-P86/aug'-cc-pVTZ+d combination has a very slight edge over the others that we have examined, and we recommend its general use for geometry optimization and vibrational frequency calculations, in particular within high-level composite methods such as the higher-level members of the WnX series of protocols. The scale factors determined for DSD-PBE-P86/aug'-cc-pVTZ+d are 0.9830 (ZPVE), 0.9876 (ΔH298), and 0.9923 (S298).

  3. Corrosion Environments and Corrosion-resistant Materials for Iodine-sulfur Thermochemical Cycle%热化学碘硫循环的腐蚀环境与耐蚀材料

    Institute of Scientific and Technical Information of China (English)

    赵增华; 张平; 陈崧哲; 王来军; 徐景明

    2013-01-01

    利用核能经热化学碘硫循环制氢被认为是最有希望大规模应用的核能制氢技术.碘硫循环工艺简单、效率高,但由于反应体系为强腐蚀过程,设备材料的腐蚀问题是碘硫循环发展的一个难题.总结了碘硫循环中涉及的Bunsen反应、硫酸分解和氢碘酸分解部分的腐蚀环境;综述了金属材料、无机陶瓷材料和高分子材料在碘硫循环腐蚀环境中的耐腐蚀性能及可能的应用;并讨论了防腐蚀衬里技术应用的可能性;比较了陶瓷材料在硫酸分解设备中的应用.这些工作可为碘硫循环工程材料的选择与研发提供依据和理论参考.%The iodine-sulfur (IS) thermochemical cycle is one of the most promising,efficient,massive and CO2-free approaches for nuclear hydrogen production.One of the crucial issues for IS process is the corrosion-resistant performance of the construction materials since the strong corrosive environments are involved.The corrosion environments of Bunsen reaction,sulfuric acid decomposition and hydriodic acid decomposition reaction are discussed.The corrosion-resistant performance of the construction materials such as metals,ceramics and organic polymers used in IS process is reviewed.The potential of the anti-corrosion lining techniques in the process is discussed.The application of ceramic and polymer materials to sulfuric acid decomposition equipment manufacturers is compared.The results may offer basis and theoretical reference for the selection and development of corrosion-resistant materials for IS process.

  4. Process design and simulation of open-loop sulfur-iodine thermo-chemical cycle for hydrogen production%热化学硫碘开路循环制氢系统的设计与模拟

    Institute of Scientific and Technical Information of China (English)

    杨剑; 王智化; 张彦威; 陈云; 周俊虎; 岑可法

    2011-01-01

    In order to optimize the process and thermal efficiency of the open-loop sulfur-iodine (SI) thermo-chemical cycle for production of hydrogen, a flowsheet of open-loop SI thermo-chemical cycle was designed and simulated by Aspen Plus. The heat and mass balance as well as thermal efficiency were first calculated. The maximum thermal efficiency of the process was 66.2% considering waste heat recoveryand pumping power. Secondly, through sensitivity analysis, the effects of 5 operating parameters like: reflux ratio at HI distillation column, pressure in HI distillation column, flow rate of HI phase, conversion ratio of HI and mass fraction of H2 SO4 were evaluated to the thermal efficiency. Results show that the flow rate of HI phase and reflux ratio of the HI distillation column are the primary paramenters influence the total efficiency, while the other parameters are not so obviously. Through optimization of the Bunsen reactor operation condition, the flow rate of the HI phase can be reduced therefore improve the whole thermal efficiency. The simulation results agree well with published datas and can be used as reference for design and optimization of the large scale SI thermo-chemical cycle H2 production system.%为了对热化学硫碘开路循环制氢系统进行优化设计及热效率评估,利用大型化工流程模拟软件AspenPlus对硫碘开路循环联产氢气和硫酸系统进行设计和模拟,计算质量、能量平衡及热效率.在考虑泵功和废热回收的情况下,开路系统的最高计算热效率达到66.2%.其次,利用灵敏度分析,分别考察HI精馏塔同流比、精馏塔压力、HI相循环量、HI分解率和产品硫酸质量分数5个设计参数对系统效率的影响.结果显示,HI相循环量和精馏塔同流比是影响系统效率的主要因素,其他参数对效率影响较小.通过优化本生反应操作条件可显著减少HI相的循环量,提高系统效率.计算结果与文献参考值接近,为今后大

  5. Environmental, health, and safety issues of sodium-sulfur batteries for electric and hybrid vehicles

    Energy Technology Data Exchange (ETDEWEB)

    Mark, J

    1992-11-01

    This report is the last of four volumes that identify and assess the environmental, health, and safety issues that may affect the commercial-scale use of sodium-sulfur (Na/S) battery technology as the energy source in electric and hybrid vehicles. The reports are intended to help the Electric and Hybrid Propulsion Division of the Office of Transportation Technologies in the US Department of Energy (DOE/EHP) determine the direction of its research, development, and demonstration (RD D) program for Na/S battery technology. The reports review the status of Na/S battery RD D and identify potential hazards and risks that may require additional research or that may affect the design and use of Na/S batteries. This volume covers the in-vehicle safety issues of electric vehicles powered by Na/S batteries. The report is based on a review of the literature and on discussions with experts at DOE, national laboratories and agencies, and private industry. It has three major goals: (1) to identify the unique hazards associated with electric vehicle (EV) use; (2) to describe the existing standards, regulations, and guidelines that are or could be applicable to these hazards; and (3) to discuss the adequacy of the existing requirements in addressing the safety concerns of EVs.

  6. Three-Dimensional Sulfur/Graphene Multifunctional Hybrid Sponges for Lithium-Sulfur Batteries with Large Areal Mass Loading

    Science.gov (United States)

    Lu, Songtao; Chen, Yan; Wu, Xiaohong; Wang, Zhida; Li, Yang

    2014-04-01

    In this communication, we introduce the concept of three dimensional (3D) battery electrodes to enhance the capacity per footprint area for lithium-sulfur battery. In such a battery, 3D electrode of sulfur embedded into porous graphene sponges (S-GS) was directly used as the cathode with large areal mass loading of sulfur (12 mg cm-2), approximately 6-12 times larger than that of most reports. The graphene sponges (GS) worked as a framework that can provide high electronic conductive network, abilities to absorb the polysulfides intermediate, and meanwhile mechanical support to accommodate the volume changes during charge and discharge. As a result, the S-GS electrode with 80 wt.% sulfur can deliver an extremely high areal specific capacitance of 6.0 mAh cm-2 of the 11th cycle, and maintain 4.2 mAh cm-2 after 300 charge-discharge cycles at a rate of 0.1C, representing an extremely low decay rate (0.08% per cycle after 300 cycles), which could be the highest areal specific capacity with comparable cycle stability among the rechargeable Li/S batteries reported ever.

  7. 碘硫循环制氢中HI浓缩分离工艺的研究进展%Progress of HI concentration/separation in the iodine-sulfur thermochemical cycle for hydrogen production

    Institute of Scientific and Technical Information of China (English)

    王兆龙; 陈崧哲; 王少敏; 张平; 王来军; 徐景明

    2013-01-01

    综述了碘硫循环制氢中用于HI浓缩分离的3种主要技术路线,即磷酸萃取精馏、反应精馏以及电解电渗析预浓缩-精馏的研究进展,对各路线的过程原理、操作流程、能量利用效率等方面进行了讨论,在此基础上对比了其各自的优点和不足之处,并对其应用前景进行了展望。其中,磷酸萃取精馏开发最早,相对成熟,但操作流程复杂,运行效率需进一步提升;反应精馏流程有望以高集成度取得高效率,但所需条件非常苛刻,其设备开发、工艺实验等工作亟待展开;近年来发展较快的电解电渗析预浓缩-精馏工艺由于具有操作简单,条件温和,浓缩效率高等优点而具有较好的应用前景,其进一步工艺放大、模块化以及与精馏的高效协同等都是未来研究的重点和难点。%This paper reviewed the methods of phosphoric acid extractive distillation , reactive distillation and electro-electrodialysis pre-concentration for HI concentration and separation in iodine-sulfur thermochemical cycle. The mechanisms,energy efficiency,advantages,and prospects of these methods were discussed. Phosphoric acid extractive distillation was developed earlier than the other methods,however,its complicated operational conditions prevented the improvement of energy efficiency of this method. The high integrity level of reactive distillation could improve thermal efficiency dramatically,but experimental research concerning the practical application is very limited due to its rigorous operational conditions. Electro-electrodialysis for HI pre-concentration is a promising method because of its easy operation,mild conditions and high efficiency. Future research on this method should be focused on scale-up,modularization and the efficient cooperation with HI distillation.

  8. Thermochemical Process Development Unit

    Data.gov (United States)

    Federal Laboratory Consortium — This facility is used to demonstrate and evaluate the thermochemical conversion of biomass to produce syngas or pyrolysis oil that can be further converted to fuels...

  9. HYBRID SULFUR CYCLE FLOWSHEETS FOR HYDROGEN PRODUCTION USING HIGH-TEMPERATURE GAS-COOLED REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Gorensek, M.

    2011-07-06

    Two hybrid sulfur (HyS) cycle process flowsheets intended for use with high-temperature gas-cooled reactors (HTGRs) are presented. The flowsheets were developed for the Next Generation Nuclear Plant (NGNP) program, and couple a proton exchange membrane (PEM) electrolyzer for the SO2-depolarized electrolysis step with a silicon carbide bayonet reactor for the high-temperature decomposition step. One presumes an HTGR reactor outlet temperature (ROT) of 950 C, the other 750 C. Performance was improved (over earlier flowsheets) by assuming that use of a more acid-tolerant PEM, like acid-doped poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI), instead of Nafion{reg_sign}, would allow higher anolyte acid concentrations. Lower ROT was accommodated by adding a direct contact exchange/quench column upstream from the bayonet reactor and dropping the decomposition pressure. Aspen Plus was used to develop material and energy balances. A net thermal efficiency of 44.0% to 47.6%, higher heating value basis is projected for the 950 C case, dropping to 39.9% for the 750 C case.

  10. A Facile Bottom-Up Approach to Construct Hybrid Flexible Cathode Scaffold for High-Performance Lithium-Sulfur Batteries.

    Science.gov (United States)

    Ghosh, Arnab; Manjunatha, Revanasiddappa; Kumar, Rajat; Mitra, Sagar

    2016-12-14

    Lithium-sulfur batteries mostly suffer from the low utilization of sulfur, poor cycle life, and low rate performances. The prime factors that affect the performance are enormous volume change of the electrode, soluble intermediate product formation, poor electronic and ionic conductivity of S, and end discharge products (i.e., Li2S2 and Li2S). The attractive way to mitigate these challenges underlying in the fabrication of a sulfur nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic as well as electronic conductivity leading to a mechanically robust and mixed conductive (ionic and electronic conductive) sulfur electrode. Herein, we report a novel bottom-up approach to synthesize a unique freestanding, flexible cathode scaffold made of porous reduced graphene oxide, nanosized sulfur, and Mn3O4 nanoparticles, and all are three-dimensionally interconnected to each other by hybrid polyaniline/sodium alginate (PANI-SA) matrix to serve individual purposes. A capacity of 1098 mAh g(-1) is achieved against lithium after 200 cycles at a current rate of 2 A g(-1) with 97.6% of initial capacity at a same current rate, suggesting the extreme stability and cycling performance of such electrode. Interestingly, with the higher current density of 5 A g(-1), the composite electrode exhibited an initial capacity of 1015 mA h g(-1) and retained 71% of the original capacity after 500 cycles. The in situ Raman study confirms the polysulfide absorption capability of Mn3O4. This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance lithium-sulfur batteries and a strategy that can be used to develop flexible large power storage devices.

  11. A novel WS2 nanowire-nanoflake hybrid material synthesized from WO3 nanowires in sulfur vapor

    Science.gov (United States)

    Asres, Georgies Alene; Dombovari, Aron; Sipola, Teemu; Puskás, Robert; Kukovecz, Akos; Kónya, Zoltán; Popov, Alexey; Lin, Jhih-Fong; Lorite, Gabriela S.; Mohl, Melinda; Toth, Geza; Lloyd Spetz, Anita; Kordas, Krisztian

    2016-05-01

    In this work, WS2 nanowire-nanoflake hybrids are synthesized by the sulfurization of hydrothermally grown WO3 nanowires. The influence of temperature on the formation of products is optimized to grow WS2 nanowires covered with nanoflakes. Current-voltage and resistance-temperature measurements carried out on random networks of the nanostructures show nonlinear characteristics and negative temperature coefficient of resistance indicating that the hybrids are of semiconducting nature. Bottom gated field effect transistor structures based on random networks of the hybrids show only minor modulation of the channel conductance upon applied gate voltage, which indicates poor electrical transport between the nanowires in the random films. On the other hand, the photo response of channel current holds promise for cost-efficient solution process fabrication of photodetector devices working in the visible spectral range.

  12. Thermochemical surface engineering of steels

    DEFF Research Database (Denmark)

    Thermochemical Surface Engineering of Steels provides a comprehensive scientific overview of the principles and different techniques involved in thermochemical surface engineering, including thermodynamics, kinetics principles, process technologies and techniques for enhanced performance of steels...

  13. Quantitative analysis of the cell voltage of SO{sub 2}-depolarized electrolysis in hybrid sulfur process

    Energy Technology Data Exchange (ETDEWEB)

    Lulu, Xue; Ping, Zhang, E-mail: zhangping77@mail.tsinghua.edu.cn; Songzhe, Chen; Laijun, Wang

    2016-09-15

    SO{sub 2}-depolarized electrolysis (SDE) is the pivotal reaction in hybrid sulfur process. To date, the total cell potential for an SO{sub 2}-depolarized electrolyzer has been identified to be controlled dominantly by the sulfuric acid concentration of the anolyte and electrolysis temperature. Potential loss in SDE can be separated into four components, i.e., equilibrium potential, anodic polarization overpotential, cathodic polarization overpotential, and ohmic loss. In this work, the potential individual components of SDE were measured and calculated. Results showed that the anodic polarization overpotential exhibited the highest ratio in the cell voltage of SDE reaction, and the kinetics of the anodic reaction was controlled by a distinct reaction process under different cell potentials. This study increases understanding on SDE and provides assistance to improve its performance.

  14. Integration of photovoltaic and concentrated solar thermal technologies for H2 production by the hybrid sulfur cycle

    Science.gov (United States)

    Liberatore, Raffaele; Ferrara, Mariarosaria; Lanchi, Michela; Turchetti, Luca

    2017-06-01

    It is widely agreed that hydrogen used as energy carrier and/or storage media may significantly contribute in the reduction of emissions, especially if produced by renewable energy sources. The Hybrid Sulfur (HyS) cycle is considered as one of the most promising processes to produce hydrogen through the water-splitting process. The FP7 project SOL2HY2 (Solar to Hydrogen Hybrid Cycles) investigates innovative material and process solutions for the use of solar heat and power in the HyS process. A significant part of the SOL2HY2 project is devoted to the analysis and optimization of the integration of the solar and chemical (hydrogen production) plants. In this context, this work investigates the possibility to integrate different solar technologies, namely photovoltaic, solar central receiver and solar troughs, to optimize their use in the HyS cycle for a green hydrogen production, both in the open and closed process configurations. The analysis carried out accounts for different combinations of geographical location and plant sizing criteria. The use of a sulfur burner, which can serve both as thermal backup and SO2 source for the open cycle, is also considered.

  15. Thermochemical reactor systems and methods

    Energy Technology Data Exchange (ETDEWEB)

    Lipinski, Wojciech; Davidson, Jane Holloway; Chase, Thomas Richard

    2016-11-29

    Thermochemical reactor systems that may be used to produce a fuel, and methods of using the thermochemical reactor systems, utilizing a reactive cylindrical element, an optional energy transfer cylindrical element, an inlet gas management system, and an outlet gas management system.

  16. Thermochemical reactor systems and methods

    Science.gov (United States)

    Lipinski, Wojciech; Davidson, Jane Holloway; Chase, Thomas Richard

    2016-11-29

    Thermochemical reactor systems that may be used to produce a fuel, and methods of using the thermochemical reactor systems, utilizing a reactive cylindrical element, an optional energy transfer cylindrical element, an inlet gas management system, and an outlet gas management system.

  17. Polysulfide-Blocking Microporous Polymer Membrane Tailored for Hybrid Li-Sulfur Flow Batteries.

    Science.gov (United States)

    Li, Changyi; Ward, Ashleigh L; Doris, Sean E; Pascal, Tod A; Prendergast, David; Helms, Brett A

    2015-09-09

    Redox flow batteries (RFBs) present unique opportunities for multi-hour electrochemical energy storage (EES) at low cost. Too often, the barrier for implementing them in large-scale EES is the unfettered migration of redox active species across the membrane, which shortens battery life and reduces Coulombic efficiency. To advance RFBs for reliable EES, a new paradigm for controlling membrane transport selectivity is needed. We show here that size- and ion-selective transport can be achieved using membranes fabricated from polymers of intrinsic microporosity (PIMs). As a proof-of-concept demonstration, a first-generation PIM membrane dramatically reduced polysulfide crossover (and shuttling at the anode) in lithium-sulfur batteries, even when sulfur cathodes were prepared as flowable energy-dense fluids. The design of our membrane platform was informed by molecular dynamics simulations of the solvated structures of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) vs lithiated polysulfides (Li2Sx, where x = 8, 6, and 4) in glyme-based electrolytes of different oligomer length. These simulations suggested polymer films with pore dimensions less than 1.2-1.7 nm might incur the desired ion-selectivity. Indeed, the polysulfide blocking ability of the PIM-1 membrane (∼0.8 nm pores) was improved 500-fold over mesoporous Celgard separators (∼17 nm pores). As a result, significantly improved battery performance was demonstrated, even in the absence of LiNO3 anode-protecting additives.

  18. Integrating a Photocatalyst into a Hybrid Lithium-Sulfur Battery for Direct Storage of Solar Energy.

    Science.gov (United States)

    Li, Na; Wang, Yarong; Tang, Daiming; Zhou, Haoshen

    2015-08-03

    Direct capture and storage of abundant but intermittent solar energy in electrical energy-storage devices such as rechargeable lithium batteries is of great importance, and could provide a promising solution to the challenges of energy shortage and environment pollution. Here we report a new prototype of a solar-driven chargeable lithium-sulfur (Li-S) battery, in which the capture and storage of solar energy was realized by oxidizing S(2-) ions to polysulfide ions in aqueous solution with a Pt-modified CdS photocatalyst. The battery can deliver a specific capacity of 792 mAh g(-1) during 2 h photocharging process with a discharge potential of around 2.53 V versus Li(+)/Li. A specific capacity of 199 mAh g(-1), reaching the level of conventional lithium-ion batteries, can be achieved within 10 min photocharging. Moreover, the charging process of the battery can proceed under natural sunlight irradiation.

  19. A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

    Science.gov (United States)

    Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

    1980-01-01

    The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

  20. A thermochemical energy converter

    Energy Technology Data Exchange (ETDEWEB)

    Toyeguti, K.; Indzima, T.

    1982-08-09

    Mercury is used as the active mass of the anode in the converter and 0/sub 2/ is used as the active cathode material. The reaction of Mercury + 1/2 0/sub 2/-Hg0 occurs with a discharge. With heating to 500/sup 0/C the regeneration of the Mercury, Hg0 yields Mercury + 1/2 0/sub 2/, occurs. The device for performing the thermochenical conversion of energy contains an element body, an oxygen chamber, an oxygen electrode, a chamber with an alkaline liquid electrolyte, a separator, an auxiliary separator, an electrode and a chamber with the Mercury. The thermochemical reaction occurs in the reactor to which the Hg0 is transported along a pipe which has a refrigerator and a valve. The Mercury is fed into the element from a reservoir. The Mercury reduced in the reactor and in a reaction tower is fed into it through a closed cycle. The bellows is connected with the reactor by a pipe with a refrigerator. Through it the 0/sub 2/ goes in a closed cycle to the chamber. The current forming reactions are Hg + 20H-anion yields Hg0 + H/sub 2/0 + 2e and 1/2 0/sub 2/ + H/sub 2/0 + 2e yields 20H-anion. The voltage on the outleads of the element is approximately 0.3 volts.

  1. One-Pot Synthesis of Organic-Sulfur-Zinc Hybrid Materials via Polycondensation of a Zinc Salt and Thiols Generated in Situ from Cyclic Dithiocarbonates.

    Science.gov (United States)

    Ochiai, Bungo; Konta, Hirohisa

    2015-08-17

    Soluble organic-sulfur-zinc hybrid polymers were prepared via a one-pot reaction consisting of ring-opening addition and subsequent polycondensation. The first reaction is the nucleophilic ring-opening addition of 2-ethylhexylamine to multifunctional cyclic dithiocarbonates giving multiple thiols in situ. The sequential polycondensation of the in situ generated thiols with Zn(OAc)2 gave the target hybrid polymers. This one-pot method enabled the use of a shorter amine than the previous polycondensation of Zn(OAc)2 and purified thiols, which required octadecylamine to obtain a soluble product. The obtained hybrid polymers may be cast as composite films with polystyrene and poly(methyl methacrylate). Owing to the shorter alkyl chain, the calculated nD values of the products (1.60 or 1.61) are higher than that of the previous product bearing octadecyl chains (1.53).

  2. One-Pot Synthesis of Organic-Sulfur-Zinc Hybrid Materials via Polycondensation of a Zinc Salt and Thiols Generated in Situ from Cyclic Dithiocarbonates

    Directory of Open Access Journals (Sweden)

    Bungo Ochiai

    2015-08-01

    Full Text Available Soluble organic-sulfur-zinc hybrid polymers were prepared via a one-pot reaction consisting of ring-opening addition and subsequent polycondensation. The first reaction is the nucleophilic ring-opening addition of 2-ethylhexylamine to multifunctional cyclic dithiocarbonates giving multiple thiols in situ. The sequential polycondensation of the in situ generated thiols with Zn(OAc2 gave the target hybrid polymers. This one-pot method enabled the use of a shorter amine than the previous polycondensation of Zn(OAc2 and purified thiols, which required octadecylamine to obtain a soluble product. The obtained hybrid polymers may be cast as composite films with polystyrene and poly(methyl methacrylate. Owing to the shorter alkyl chain, the calculated nD values of the products (1.60 or 1.61 are higher than that of the previous product bearing octadecyl chains (1.53.

  3. Electrocatalytic activity of lithium polysulfides adsorbed into porous TiO2 coated MWCNTs hybrid structure for lithium-sulfur batteries

    Science.gov (United States)

    He, Xiulin; Hou, Huijie; Yuan, Xiqing; Huang, Long; Hu, Jingping; Liu, Bingchuan; Xu, Jingyi; Xie, Jia; Yang, Jiakuan; Liang, Sha; Wu, Xu

    2017-01-01

    Lithium-sulfur batteries have attracted great attention because of their high energy density, environmental friendliness, natural abundance and intrinsically low cost of sulfur. However, their commercial applications are greatly hindered by rapid capacity decay due to poor conductivity of electrode, fast dissolution of the intermediate polysulfides into the electrolyte, and the volume expansion of sulfur. Herein, we report a novel composite MWCNTs@TiO2-S nanostructure by grafting TiO2 onto the surface of MWCNTs, followed by incorporating sulfur into the composite. The inner MWCNTs improved the mechanical strength and conductivity of the electrode and the outer TiO2 provided the adsorption sites to immobilize polysulfides due to bonding interaction between TiO2 and polysulfides. The MWCNTs@TiO2-S composite with a mass ratio of 50% (MWCNTs in MWCNTs@TiO2) exhibited the highest electrochemistry performance among all compositing ratios of MWCNTs/TiO2. The performance improvement might be attributed to the downward shift of the apparent Fermi level to a more positive potential and electron rich space region at the interface of MWCNTs-TiO2 that facilitates the reduction of lithium polysulfide at a higher potential. Such a novel hybrid structure can be applicable for electrode design in other energy storage applications.

  4. Electrocatalytic activity of lithium polysulfides adsorbed into porous TiO2 coated MWCNTs hybrid structure for lithium-sulfur batteries

    Science.gov (United States)

    He, Xiulin; Hou, Huijie; Yuan, Xiqing; Huang, Long; Hu, Jingping; Liu, Bingchuan; Xu, Jingyi; Xie, Jia; Yang, Jiakuan; Liang, Sha; Wu, Xu

    2017-01-01

    Lithium-sulfur batteries have attracted great attention because of their high energy density, environmental friendliness, natural abundance and intrinsically low cost of sulfur. However, their commercial applications are greatly hindered by rapid capacity decay due to poor conductivity of electrode, fast dissolution of the intermediate polysulfides into the electrolyte, and the volume expansion of sulfur. Herein, we report a novel composite MWCNTs@TiO2-S nanostructure by grafting TiO2 onto the surface of MWCNTs, followed by incorporating sulfur into the composite. The inner MWCNTs improved the mechanical strength and conductivity of the electrode and the outer TiO2 provided the adsorption sites to immobilize polysulfides due to bonding interaction between TiO2 and polysulfides. The MWCNTs@TiO2-S composite with a mass ratio of 50% (MWCNTs in MWCNTs@TiO2) exhibited the highest electrochemistry performance among all compositing ratios of MWCNTs/TiO2. The performance improvement might be attributed to the downward shift of the apparent Fermi level to a more positive potential and electron rich space region at the interface of MWCNTs-TiO2 that facilitates the reduction of lithium polysulfide at a higher potential. Such a novel hybrid structure can be applicable for electrode design in other energy storage applications. PMID:28098167

  5. Electrocatalytic activity of lithium polysulfides adsorbed into porous TiO2 coated MWCNTs hybrid structure for lithium-sulfur batteries.

    Science.gov (United States)

    He, Xiulin; Hou, Huijie; Yuan, Xiqing; Huang, Long; Hu, Jingping; Liu, Bingchuan; Xu, Jingyi; Xie, Jia; Yang, Jiakuan; Liang, Sha; Wu, Xu

    2017-01-18

    Lithium-sulfur batteries have attracted great attention because of their high energy density, environmental friendliness, natural abundance and intrinsically low cost of sulfur. However, their commercial applications are greatly hindered by rapid capacity decay due to poor conductivity of electrode, fast dissolution of the intermediate polysulfides into the electrolyte, and the volume expansion of sulfur. Herein, we report a novel composite MWCNTs@TiO2-S nanostructure by grafting TiO2 onto the surface of MWCNTs, followed by incorporating sulfur into the composite. The inner MWCNTs improved the mechanical strength and conductivity of the electrode and the outer TiO2 provided the adsorption sites to immobilize polysulfides due to bonding interaction between TiO2 and polysulfides. The MWCNTs@TiO2-S composite with a mass ratio of 50% (MWCNTs in MWCNTs@TiO2) exhibited the highest electrochemistry performance among all compositing ratios of MWCNTs/TiO2. The performance improvement might be attributed to the downward shift of the apparent Fermi level to a more positive potential and electron rich space region at the interface of MWCNTs-TiO2 that facilitates the reduction of lithium polysulfide at a higher potential. Such a novel hybrid structure can be applicable for electrode design in other energy storage applications.

  6. Development of a new thermo-chemical and electrolytic hybrid hydrogen production process utilizing the heat from medium temperature heat source : development of the 1NL/h hydrogen production experimental apparatus

    Energy Technology Data Exchange (ETDEWEB)

    Takai, T.; Nakagiri, T.; Inagaki, Y. [Japan Atomic Energy Agency, O-arai, Ibaraki (Japan)

    2007-07-01

    A promising energy conversion system is a high efficiency hydrogen production system that uses nuclear heat. This paper presented the results of a study that developed a 1N/L hydrogen production experimental apparatus. The paper presented the results of an experiment that was conducted to evaluate the hydrogen production efficiency and clarify technical problems for development of a large-scale hydrogen production apparatus. The paper discussed the principals and characteristics of the hybrid hydrogen production in lower temperature range (HHLT) process and presented details on the hydrogen production apparatus and experiment. This included a discussion of the experimental conditions and experimental results. This was followed by a discussion that included an evaluation of hydrogen production efficiency and influence of efficiency of sulfur trioxide electrolysis. Last the paper presented technical problems from the experimental results. It was concluded that hydrogen production efficiency was evaluated about 2 per cent by trial evaluation. A 55 per cent efficiency was expected and therefore, the apparatus required improvement and optimization in order to obtain higher efficiency in the future. 6 refs., 2 tabs., 3 figs.

  7. High Performance Electrolyzers for Hybrid Thermochemical Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Dr. John W. Weidner

    2009-05-10

    Extensive electrolyzer testing was performed at the University of South Carolina (USC). Emphasis was given to understanding water transport under various operating (i.e., temperature, membrane pressure differential and current density) and design (i.e., membrane thickness) conditions when it became apparent that water transport plays a deciding role in cell voltage. A mathematical model was developed to further understand the mechanisms of water and SO2 transport, and to predict the effect of operating and design parameters on electrolyzer performance.

  8. Open-loop thermochemical cycles for the production of hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Conger, W.L.

    1979-01-01

    The concept of open-loop thermochemical cycles (cycles which have additional or other feedstocks than water and produce materials in addition to hydrogen and oxygen) is introduced. Preliminary analysis of possible feedstocks available indicates substantial quantities of hydrogen could possibly be produced through open-cycles. The advantages of open-cycles include the conversion of unwanted waste products to useful products while producing hydrogen. A compilation of open processes which would have SO/sub 2/ in addition to water as feedstock and which would produce sulfuric acid in addition to hydrogen and oxygen is given.

  9. Innovative solar thermochemical water splitting.

    Energy Technology Data Exchange (ETDEWEB)

    Hogan, Roy E. Jr.; Siegel, Nathan P.; Evans, Lindsey R.; Moss, Timothy A.; Stuecker, John Nicholas (Robocasting Enterprises, Albuquerque, NM); Diver, Richard B., Jr.; Miller, James Edward; Allendorf, Mark D. (Sandia National Laboratories, Livermore, CA); James, Darryl L. (Texas Tech University, Lubbock, TX)

    2008-02-01

    Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximity and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.

  10. Efficient Synthesis of Graphene Nanoscrolls for Fabricating Sulfur-Loaded Cathode and Flexible Hybrid Interlayer toward High-Performance Li-S Batteries.

    Science.gov (United States)

    Guo, Yi; Zhao, Gang; Wu, Naiteng; Zhang, Yun; Xiang, Mingwu; Wang, Bo; Liu, Heng; Wu, Hao

    2016-12-21

    A modified lyophilization approach is developed and used for highly efficient transformation of 2D graphene oxide sheet into 1D graphene nanoscroll (GNS) with high topological transforming efficiency (∼94%). Because of the unique open tubular structure and large specific surface area (545 m(2) g(-1)), GNS is utilized for the first time as a porous cathode scaffold for encapsulating sulfur with a high loading (81 wt %), and also as a conductive skeleton for assembling MnO2 nanowires into a flexible free-standing hybrid interlayer, both enabling high-rate and long-life Li-S battery.

  11. Experimental and computational thermochemical study of sulfur-containing amino acids: L-cysteine, L-cystine, and L-cysteine-derived radicals. S-S, S-H, and C-S bond dissociation enthalpies.

    Science.gov (United States)

    Roux, Maria Victoria; Foces-Foces, Concepción; Notario, Rafael; da Silva, Manuel A V Ribeiro; da Silva, Maria das Dores M C Ribeiro; Santos, Ana Filipa L O M; Juaristi, Eusebio

    2010-08-19

    This paper reports an experimental and theoretical study of the standard (p(degrees) = 0.1 MPa) molar enthalpies of formation at T = 298.15 K of the sulfur-containing amino acids l-cysteine [CAS 52-90-4] and l-cystine [CAS 56-89-3]. The standard (p(degrees) = 0.1 MPa) molar enthalpies of formation of crystalline l-cysteine and l-cystine were calculated from the standard molar energies of combustion, in oxygen, to yield CO2(g) and H2SO4.115H2O, measured by rotating-bomb combustion calorimetry at T = 298.15 K. The vapor pressures of l-cysteine were measured as function of temperature by the Knudsen effusion mass-loss technique. The standard molar enthalpy of sublimation, at T = 298.15 K, was derived from the Clausius-Clapeyron equation. The experimental values were used to calculate the standard (p(degrees) = 0.1 MPa) enthalpy of formation of l-cysteine in the gaseous phase, DeltafH(degrees)m(g) = -382.6 +/- 1.8 kJ x mol-1. Due to the low vapor pressures of l-cystine and since this compound decomposes at the temperature range required for a possible sublimation, it was not possible to determine its enthalpy of sublimation. Standard ab initio molecular orbital calculations at the G3(MP2)//B3LYP and/or G3 levels were performed. Enthalpies of formation, using atomization and isodesmic reactions, were calculated and compared with experimental data. A value of -755 +/- 10 kJ x mol-1 was estimated for the enthalpy of formation of cystine. Detailed inspections of the molecular and electronic structures of the compounds studied were carried out. Finally, bond dissociation enthalpies (BDE) of S-H, S-S, and C-S bonds, and enthalpies of formation of l-cysteine-derived radicals, were also computed.

  12. Synergistically Enhanced Polysulfide Chemisorption Using a Flexible Hybrid Separator with N and S Dual-Doped Mesoporous Carbon Coating for Advanced Lithium-Sulfur Batteries.

    Science.gov (United States)

    Balach, Juan; Singh, Harish K; Gomoll, Selina; Jaumann, Tony; Klose, Markus; Oswald, Steffen; Richter, Manuel; Eckert, Jürgen; Giebeler, Lars

    2016-06-15

    Because of the outstanding high theoretical specific energy density of 2600 Wh kg(-1), the lithium-sulfur (Li-S) battery is regarded as a promising candidate for post lithium-ion battery systems eligible to meet the forthcoming market requirements. However, its commercialization on large scale is thwarted by fast capacity fading caused by the Achilles' heel of Li-S systems: the polysulfide shuttle. Here, we merge the physical features of carbon-coated separators and the unique chemical properties of N and S codoped mesoporous carbon to create a functional hybrid separator with superior polysulfide affinity and electrochemical benefits. DFT calculations revealed that carbon materials with N and S codoping possess a strong binding energy to high-order polysulfide species, which is essential to keep the active material in the cathode side. As a result of the synergistic effect of N, S dual-doping, an advanced Li-S cell with high specific capacity and ultralow capacity degradation of 0.041% per cycle is achieved. Pushing our simple-designed and scalable cathode to a highly increased sulfur loading of 5.4 mg cm(-2), the Li-S cell with the functional hybrid separator can deliver a remarkable areal capacity of 5.9 mAh cm(-2), which is highly favorable for practical applications.

  13. 3D-hybrid material design with electron/lithium-ion dual-conductivity for high-performance Li-sulfur batteries

    Science.gov (United States)

    Zhao, Yan; Tan, Rui; Yang, Jie; Wang, Kai; Gao, Rongtan; Liu, Dong; Liu, Yidong; Yang, Jinlong; Pan, Feng

    2017-02-01

    We report a novel 3D-hybrid cathode material with three-dimensional (3D) N-GO/CNT framework to load sulfur (77.6 wt %), and sulfonated polyaniline (SPANI) of coating layer. Used as a cathode material, it possesses a high capacity (1196 mAh g-1@0.3 A g-1@1.6 mg cm-2), excellent charging-discharging rate (680 mAh g-1@7.5 A g-1) and long-life performance (maintaining 71.1% capacity over 450 cycles), which is mainly attributed to the benefits of excellent electronic/Li-ionic dual-conductivity and confinement effect of the 3D-hybrid N-GO/CNT framework coated by self-doping conducting polymer SPANI. Thus, a 3D sulfur cathode modified with electronic/Li-ionic dual-conduction network can significantly enhance the electrochemical performance and stability, and this novel type of material is very promising for commercial applications that require high energy and power density, long life, and excellent abuse tolerance.

  14. Research report for fiscal 1998. Research concerning studies for development of thermochemical solar hybrid fuel production system; 1998 nendo chosa hokokusho. Netsukagakuteki solar hybrid nenryo seisan system no kaihatsu kenkyu ni kakawaru chosa

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-03-01

    A solar heat-aided system is investigated, in which CO2 is recycled, with methanol, dimethyl ether, etc., serving as carriers of the solar heat energy. In the evaluation of validity of the system as a whole, the system scale and economy and technologies necessary for the system were studied, which was to find out whether solar methanol production was commercially feasible in the sun belt. It was concluded that solar methanol was capable of competing against LNG (liquefied natural gas) in cost, that Japan was able to establish its own technologies for developing coal gasification solar reactors using overseas technologies for information, and that therefore such a system was technologically and economically valid. In the study of related technologies as is, surveys were conducted on coal gasification, natural gas reforming furnaces, methanol synthesis, dimethyl ether synthesis, light condensing technology, current state and cost of solar reactors, etc. Also investigated were the marketability of solar hybrid fuel, CO2 reduction efficiency, and the construction cost at the assumed site of construction (Australia). (NEDO)

  15. OECD/NEA thermochemical database

    Energy Technology Data Exchange (ETDEWEB)

    Byeon, Kee Hoh; Song, Dae Yong; Shin, Hyun Kyoo; Park, Seong Won; Ro, Seung Gy

    1998-03-01

    This state of the art report is to introduce the contents of the Chemical Data-Service, OECD/NEA, and the results of survey by OECD/NEA for the thermodynamic and kinetic database currently in use. It is also to summarize the results of Thermochemical Database Projects of OECD/NEA. This report will be a guide book for the researchers easily to get the validate thermodynamic and kinetic data of all substances from the available OECD/NEA database. (author). 75 refs.

  16. Development of a seasonal thermochemical storage system

    NARCIS (Netherlands)

    Cuypers, R.; Maraz, N.; Eversdijk, J.; Finck, C.J.; Henquet, E.M.P.; Oversloot, H.P.; Spijker, J.C. van 't; Geus, A.C. de

    2012-01-01

    In our laboratories, a seasonal thermochemical storage system for dwellings and offices is being designed and developed. Based on a thermochemical sorption reaction, space heating, cooling and generation of domestic hot water will be achieved with up to 100% renewable energy, by using solar energy a

  17. CFD Studies on Biomass Thermochemical Conversion

    Directory of Open Access Journals (Sweden)

    Lifeng Yan

    2008-06-01

    Full Text Available Thermochemical conversion of biomass offers an efficient and economically process to provide gaseous, liquid and solid fuels and prepare chemicals derived from biomass. Computational fluid dynamic (CFD modeling applications on biomass thermochemical processes help to optimize the design and operation of thermochemical reactors. Recent progression in numerical techniques and computing efficacy has advanced CFD as a widely used approach to provide efficient design solutions in industry. This paper introduces the fundamentals involved in developing a CFD solution. Mathematical equations governing the fluid flow, heat and mass transfer and chemical reactions in thermochemical systems are described and sub-models for individual processes are presented. It provides a review of various applications of CFD in the biomass thermochemical process field.

  18. Combustion of thermochemically torrefied sugar cane bagasse.

    Science.gov (United States)

    Valix, M; Katyal, S; Cheung, W H

    2017-01-01

    This study compared the upgrading of sugar bagasse by thermochemical and dry torrefaction methods and their corresponding combustion behavior relative to raw bagasse. The combustion reactivities were examined by non-isothermal thermogravimetric analysis. Thermochemical torrefaction was carried out by chemical pre-treatment of bagasse with acid followed by heating at 160-300°C in nitrogen environment, while dry torrefaction followed the same heating treatment without the chemical pretreatment. The results showed thermochemical torrefaction generated chars with combustion properties that are closer to various ranks of coal, thus making it more suitable for co-firing applications. Thermochemical torrefaction also induced greater densification of bagasse with a 335% rise in bulk density to 340kg/m(3), increased HHVmass and HHVvolume, greater charring and aromatization and storage stability. These features demonstrate the potential of thermochemical torrefaction in addressing the practical challenges in using biomass such as bagasse as fuel.

  19. Recent review of thermochemical hydrogen production

    Science.gov (United States)

    Beghi, G. E.

    A survey is presented on the development to date of thermochemical water decomposition methods for the production of hydrogen. It is shown that: (1) both the technological feasibility of thermochemical processes and their competitiveness with water electrolysis have been demonstrated; (2) the scaling up of thermochemical methods to industrial production levels may proceed with existing technology; (3) the slowing down of programs concerned with the development of high temperature nuclear reactors could delay the scaling up of thermochemical hydrogen production to industrial levels; (4) this delay could, however, increase interest in such water decomposition processes as those employing photoreactions; and (5) the efficiency of thermochemical hydrogen production is highest in the case of systems with dedicated heat sources rated above 1000 MWth.

  20. Experimental and computational thermochemical study of oxindole

    Energy Technology Data Exchange (ETDEWEB)

    Miranda, Margarida S., E-mail: msmirand@fc.up.p [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Centro de Geologia da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Matos, M. Agostinha R., E-mail: marmatos@fc.up.p [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Morais, Victor M.F., E-mail: vmmorais@icbas.up.p [Centro de Investigacao em Quimica, Departamento de Quimica e Bioquimica, Faculdade de Ciencias da Universidade do Porto, Rua do Campo Alegre, 687, P-4169-007 Porto (Portugal); Instituto de Ciencias Biomedicas Abel Salazar, ICBAS, Universidade do Porto, P-4099-003 Porto (Portugal); Liebman, Joel F., E-mail: jliebman@umbc.ed [Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, Baltimore, MD 21250 (United States)

    2010-09-15

    An experimental and computational thermochemical study was performed for oxindole. The standard (p{sup 0}=0.1MPa) molar enthalpy of formation of solid oxindole was derived from the standard molar energy of combustion, in oxygen, at T = 298.15 K, measured by static bomb combustion calorimetry. The respective standard molar enthalpy of sublimation, at T = 298.15 K, was measured by Calvet microcalorimetry. The standard molar enthalpy of formation in the gas phase was derived as -(66.8 {+-} 3.2) kJ . mol{sup -1}. Density functional theory calculations with the B3LYP hybrid functional and the 6-31G* and 6-311G** sets have also been performed in order to obtain the most stable conformation of oxindole. A comparison has been made between the structure of oxindole and that of the related two-ring molecules: indoline and 2-indanone and the one-ring molecules: pyrrolidine and 2,3-dihydropyrrole. The G3(MP2)//B3LYP method and appropriate reactions were used to obtain estimates of the standard molar enthalpy of formation of oxindole in the gas phase, at T = 298.15 K. Computationally obtained estimates of the enthalpy of formation of oxindole are in very good agreement with the experimental gas phase value. The aromaticity of oxindole was evaluated through the analysis of the nucleus independent chemical shifts (NICS) obtained from the B3LYP/6-311G** wave functions.

  1. Thermochemical behavior of pretreated biomass

    Energy Technology Data Exchange (ETDEWEB)

    Biswas, Amit Kumar

    2011-07-01

    Mankind has to provide a sustainable alternative to its energy related problems. Bioenergy is considered as one of the potential renewable energy resources and as a result bioenergy market is also expected to grow dramatically in future. However, logistic issues are of serious concern while considering biomass as an alternative to fossil fuel. It can be improved by introducing pretreated wood pellet. The main objective of this thesis is to address thermochemical behaviour of steam exploded pretreated biomass. Additionally, process aspects of torrefaction were also considered in this thesis. Steam explosion (SE) was performed in a laboratory scale reactor using Salix wood chips. Afterwards, fuel and thermochemical aspects of SE residue were investigated. It was found that Steam explosion pretreatment improved both fuel and pellet quality. Pyrolysis of SE residue reveals that alerted biomass composition significantly affects its pyrolysis behaviour. Contribution from depolymerized components (hemicellulose, cellulose and lignin) of biomass was observed explicitly during pyrolysis. When devolatilization experiment was performed on pellet produced from SE residue, effect of those altered components was observed. In summary, pretreated biomass fuel characteristics is significantly different in comparison with untreated biomass. On the other hand, Process efficiency of torrefaction was found to be governed by the choice of appropriate operating conditions and the type of biomass.

  2. The Conceptual Design of an Integrated Nuclearhydrogen Production Plant Using the Sulfur Cycle Water Decomposition System

    Science.gov (United States)

    Farbman, G. H.

    1976-01-01

    A hydrogen production plant was designed based on a hybrid electrolytic-thermochemical process for decomposing water. The sulfur cycle water decomposition system is driven by a very high temperature nuclear reactor that provides 1,283 K helium working gas. The plant is sized to approximately ten million standard cubic meters per day of electrolytically pure hydrogen and has an overall thermal efficiently of 45.2 percent. The economics of the plant were evaluated using ground rules which include a 1974 cost basis without escalation, financing structure and other economic factors. Taking into account capital, operation, maintenance and nuclear fuel cycle costs, the cost of product hydrogen was calculated at $5.96/std cu m for utility financing. These values are significantly lower than hydrogen costs from conventional water electrolysis plants and competitive with hydrogen from coal gasification plants.

  3. Environmental, health, and safety issues of sodium-sulfur batteries for electric and hybrid vehicles. Volume 4, In-vehicle safety

    Energy Technology Data Exchange (ETDEWEB)

    Mark, J.

    1992-11-01

    This report is the last of four volumes that identify and assess the environmental, health, and safety issues that may affect the commercial-scale use of sodium-sulfur (Na/S) battery technology as the energy source in electric and hybrid vehicles. The reports are intended to help the Electric and Hybrid Propulsion Division of the Office of Transportation Technologies in the US Department of Energy (DOE/EHP) determine the direction of its research, development, and demonstration (RD&D) program for Na/S battery technology. The reports review the status of Na/S battery RD&D and identify potential hazards and risks that may require additional research or that may affect the design and use of Na/S batteries. This volume covers the in-vehicle safety issues of electric vehicles powered by Na/S batteries. The report is based on a review of the literature and on discussions with experts at DOE, national laboratories and agencies, and private industry. It has three major goals: (1) to identify the unique hazards associated with electric vehicle (EV) use; (2) to describe the existing standards, regulations, and guidelines that are or could be applicable to these hazards; and (3) to discuss the adequacy of the existing requirements in addressing the safety concerns of EVs.

  4. Biomass thermochemical conversion program. 1985 annual report

    Energy Technology Data Exchange (ETDEWEB)

    Schiefelbein, G.F.; Stevens, D.J.; Gerber, M.A.

    1986-01-01

    Wood and crop residues constitute a vast majority of the biomass feedstocks available for conversion, and thermochemical processes are well suited for conversion of these materials. The US Department of Energy (DOE) is sponsoring research on this conversion technology for renewable energy through its Biomass Thermochemical Conversion Program. The Program is part of DOE's Biofuels and Municipal Waste Technology Division, Office of Renewable Technologies. This report briefly describes the Thermochemical Conversion Program structure and summarizes the activities and major accomplishments during fiscal year 1985. 32 figs., 4 tabs.

  5. A Feasibility Study on Low Temperature Thermochemical Treatments of Austenitic Stainless Steel in Fluidized Bed Furnace

    Science.gov (United States)

    Haruman, Esa; Sun, Yong; Triwiyanto, Askar; Manurung, Yupiter H. P.; Adesta, Erry Y.

    2011-04-01

    In this work, the feasibility of using an industrial fluidized bed furnace to perform low temperature thermochemical treatments of austenitic stainless steels has been studied, with the aim to produce expanded austenite layers with combined wear and corrosion resistance, similar to those achievable by plasma and gaseous processes. Several low temperature thermochemical treatments were studied, including nitriding, carburizing, combined nitridingcarburizing (hybrid treatment), and sequential carburizing and nitriding. The results demonstrate that it is feasible to produce expanded austenite layers on the investigated austenitic stainless steel by the fluidized bed heat treatment technique, thus widening the application window for the novel low temperature processes. The results also demonstrate that the fluidized bed furnace is the most effective for performing the hybrid treatment, which involves the simultaneous incorporation of nitrogen and carbon together into the surface region of the component in nitrogen and carbon containing atmospheres. Such hybrid treatment produces a thicker and harder layer than the other three processes investigated.

  6. Incorporating Sulfur Inside the Pores of Carbons for Advanced Lithium-Sulfur Batteries: An Electrolysis Approach.

    Science.gov (United States)

    He, Bin; Li, Wen-Cui; Yang, Chao; Wang, Si-Qiong; Lu, An-Hui

    2016-01-26

    We have developed an electrolysis approach that allows effective and uniform incorporation of sulfur inside the micropores of carbon nanosheets for advanced lithium-sulfur batteries. The sulfur-carbon hybrid can be prepared with a 70 wt % sulfur loading, in which no nonconductive sulfur agglomerations are formed. Because the incorporated sulfur is electrically connected to the carbon matrix in nature, the hybrid cathode shows excellent electrochemical performance, including a high reversible capacity, good rate capability, and good cycling stability, as compared to one prepared using the popular melt-diffusion method.

  7. Potential heat exchange fluids for use in sulfuric acid vaporizers

    Science.gov (United States)

    Lawson, D. D.; Petersen, G. R.

    1981-01-01

    A series of liquids have been screened as candidate heat exchange fluids for service in thermochemical cycles that involve the vaporization of sulfuric acid. The required chemical and physical criteria of the liquids is described with the results of some preliminary high temperature test data presented.

  8. EVALUATION OF PROTON-CONDUCTING MEMBRANES FOR USE IN A SULFUR-DIOXIDE DEPOLARIZED ELECTROLYZER

    Energy Technology Data Exchange (ETDEWEB)

    Hobbs, D.; Elvington, M.; Colon-Mercado, H.

    2009-11-11

    The chemical stability, sulfur dioxide transport, ionic conductivity, and electrolyzer performance have been measured for several commercially available and experimental proton exchange membranes (PEMs) for use in a sulfur dioxide depolarized electrolyzer (SDE). The SDE's function is to produce hydrogen by using the Hybrid Sulfur (HyS) Process, a sulfur based electrochemical/thermochemical hybrid cycle. Membrane stability was evaluated using a screening process where each candidate PEM was heated at 80 C in 60 wt. % H{sub 2}SO{sub 4} for 24 hours. Following acid exposure, chemical stability for each membrane was evaluated by FTIR using the ATR sampling technique. Membrane SO{sub 2} transport was evaluated using a two-chamber permeation cell. SO{sub 2} was introduced into one chamber whereupon SO{sub 2} transported across the membrane into the other chamber and oxidized to H{sub 2}SO{sub 4} at an anode positioned immediately adjacent to the membrane. The resulting current was used to determine the SO{sub 2} flux and SO{sub 2} transport. Additionally, membrane electrode assemblies (MEAs) were prepared from candidate membranes to evaluate ionic conductivity and selectivity (ionic conductivity vs. SO{sub 2} transport) which can serve as a tool for selecting membranes. MEAs were also performance tested in a HyS electrolyzer measuring current density versus a constant cell voltage (1V, 80 C in SO{sub 2} saturated 30 wt% H2SO{sub 4}). Finally, candidate membranes were evaluated considering all measured parameters including SO{sub 2} flux, SO{sub 2} transport, ionic conductivity, HyS electrolyzer performance, and membrane stability. Candidate membranes included both PFSA and non-PFSA polymers and polymer blends of which the non-PFSA polymers, BPVE-6F and PBI, showed the best selectivity.

  9. Economic comparison of hydrogen production using sulfuric acid electrolysis and sulfur cycle water decomposition. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Farbman, G.H.; Krasicki, B.R.; Hardman, C.C.; Lin, S.S.; Parker, G.H.

    1978-06-01

    An evaluation of the relative economics of hydrogen production using two advanced techniques was performed. The hydrogen production systems considered were the Westinghouse Sulfur Cycle Water Decomposition System and a water electrolysis system employing a sulfuric acid electrolyte. The former is a hybrid system in which hydrogen is produced in an electrolyzer which uses sulfur dioxide to depolarize the anode. The electrolyte is sulfuric acid. Development and demonstration efforts have shown that extremely low cell voltages can be achieved. The second system uses a similar sulfuric acid electrolyte technology in water electrolysis cells. The comparative technoeconomics of hydrogen produced by the hybrid Sulfur Cycle and by water electrolysis using a sulfuric acid electrolyte were determined by assessing the performance and economics of 380 million SCFD plants, each energized by a very high temperature nuclear reactor (VHTR). The evaluation concluded that the overall efficiencies of hydrogen production, for operating parameters that appear reasonable for both systems, are approximately 41% for the sulfuric acid electrolysis and 47% for the hybrid Sulfur Cycle. The economic evaluation of hydrogen production, based on a 1976 cost basis and assuming a developed technology for both hydrogen production systems and the VHTRs, indicated that the hybrid Sulfur Cycle could generate hydrogen for a total cost approximately 6 to 7% less than the cost from the sulfuric acid electrolysis plant.

  10. Some Aspects of Thermochemical Decomposition of Peat

    Directory of Open Access Journals (Sweden)

    Y. A. Losiuk

    2008-01-01

    Full Text Available The paper considers peculiar features of thermochemical decomposition of peat as a result of quick pyrolysis. Evaluation of energy and economic expediency of the preliminary peat decomposition process for obtaining liquid and gaseous products has been made in the paper. The paper reveals prospects pertaining to application of the given technology while generating electric power and heat.

  11. Some Aspects of Thermochemical Decomposition of Peat

    OpenAIRE

    Y. A. Losiuk; S. V. Gibric; S. V. Korchinenko

    2008-01-01

    The paper considers peculiar features of thermochemical decomposition of peat as a result of quick pyrolysis. Evaluation of energy and economic expediency of the preliminary peat decomposition process for obtaining liquid and gaseous products has been made in the paper. The paper reveals prospects pertaining to application of the given technology while generating electric power and heat.

  12. 2009 Thermochemical Conversion Platform Review Report

    Energy Technology Data Exchange (ETDEWEB)

    Ferrell, John [Office of Energy Efficiency and Renewable Energy (EERE), Washington, DC (United States)

    2009-12-01

    This document summarizes the recommendations and evaluations provided by an independent external panel of experts at the U.S. Department of Energy Biomass Program’s Thermochemical Conversion platform review meeting, held on April 14-16, 2009, at the Sheraton Denver Downtown, Denver, Colorado.

  13. Thermochemical heat storage - system design issues

    NARCIS (Netherlands)

    Jong, A.J. de; Trausel, F.; Finck, C.J.; Vliet, L.D. van; Cuypers, R.

    2014-01-01

    Thermochemical materials (TCMs) are a promising solution for seasonal heat storage, providing the possibility to store excess solar energy from the warm season for later use during the cold season, and with that all year long sustainable energy. With our fixed bed, vacuum reactors using zeolite as T

  14. Thermochemical heat storage - system design issues

    NARCIS (Netherlands)

    Jong, A.J. de; Trausel, F.; Finck, C.J.; Vliet, L.D. van; Cuypers, R.

    2014-01-01

    Thermochemical materials (TCMs) are a promising solution for seasonal heat storage, providing the possibility to store excess solar energy from the warm season for later use during the cold season, and with that all year long sustainable energy. With our fixed bed, vacuum reactors using zeolite as

  15. Thermochemical characteristics of chitosan-polylactide copolymers

    Science.gov (United States)

    Goruynova, P. E.; Larina, V. N.; Smirnova, N. N.; Tsverova, N. E.; Smirnova, L. A.

    2016-05-01

    The energies of combustion of chitosan and its block-copolymers with different polylactide contents are determined in a static bomb calorimeter. Standard enthalpies of combustion and formation are calculated for these substances. The dependences of the thermochemical characteristics on block-copolymer composition are determined and discussed.

  16. Extension of a reactive distillation process design methodology: application to the hydrogen production through the Iodine-Sulfur thermochemical cycle; Generalisation d'une approche de conception de procedes de distillation reactive: application a la production d'hydrogene par le cycle thermochimique I-S

    Energy Technology Data Exchange (ETDEWEB)

    Belaissaoui, B

    2006-02-15

    Reactive distillation is a promising way to improve classical processes. This interest has been comforted by numerous successful applications involving reactive systems in liquid phase but never in vapour phase. In this context, general design tools have been developed for the analysis of reactive distillation processes whatever the reactive phase. A general model for open condensation and evaporation of vapour or liquid reactive systems in chemical equilibrium has been written and applied to extend the feasibility analysis, synthesis and design methods of the sequential design methodology of R. Thery (2002). The extended design methodology is applied to the industrial production of hydrogen through the iodine-sulphur thermochemical cycle by vapour phase reactive distillation. A column configuration is proposed with better performance formerly published configuration. (author)

  17. LASL thermochemical hydrogen status on September 30, 1979

    Energy Technology Data Exchange (ETDEWEB)

    Cox, K.E.

    1979-01-01

    The work described in this report was accomplished during the period October 1, 1978 to September 30, 1979. Most of the effort was applied to a study of the Los Alamos Scientific Laboratory (LASL) hybrid bismuth sulfate cycle. The work included a conceptual design of the cycle and experimental work to verify the design conditions. Key findings were: a 50.8% efficiency was obtained when an improved cycle design was coupled to a fusion energy source at 1500 K; experimental results showed an endothermic heat requirement of +172 kJ/mol for the decomposition of Bi/sub 2/O/sub 3/.2SO/sub 3/ to Bi/sub 2/O/sub 3/.SO/sub 3/, and SO/sub 3/; reaction times for bismuth sulfate decomposition were determined as a function of temperature. At 1240 K, < 1.5 min were required for the first two stages of decomposition from Bi/sub 2/O/sub 3/.3SO/sub 3/ to Bi/sub 2/O/sub 3/; tests made to determine the feasibility of decomposing Bi/sub 2/O/sub 3/.2SO/sub 3/ in a 1 inch diameter rotary kiln showed that Bi/sub 2/O/sub 3/.2SO/sub 3/ could be decomposed continuously. In related work, support was given to the DOE Thermochemical Cycle Evaluation Panel (Funk). The Second Annual International Energy Agency (IEA) Workshop on Thermochemical Hydrogen Production from Water met on September 24 to 27, 1979 at Los Alamos.

  18. Testing of an advanced thermochemical conversion reactor system

    Science.gov (United States)

    1990-01-01

    This report presents the results of work conducted by MTCI to verify and confirm experimentally the ability of the MTCI gasification process to effectively generate a high-quality, medium-Btu gas from a wider variety of feedstock and waste than that attainable in air-blown, direct gasification systems. The system's overall simplicity, due to the compact nature of the pulse combustor, and the high heat transfer rates attainable within the pulsating flow resonance tubes, provide a decided and near-term potential economic advantage for the MTCI indirect gasification system. The primary objective was the design, construction, and testing of a Process Design Verification System for an indirectly heated, thermochemical fluid-bed reactor and a pulse combustor an an integrated system that can process alternative renewable sources of energy such as biomass, black liquor, municipal solid waste and waste hydrocarbons, including heavy oils into a useful product gas. The test objectives for the biomass portion of this program were to establish definitive performance data on biomass feedstocks covering a wide range of feedstock qualities and characteristics. The test objectives for the black liquor portion of this program were to verify the operation of the indirect gasifier on commercial black liquor containing 65 percent solids at several temperature levels and to characterize the bed carbon content, bed solids particle size and sulfur distribution as a function of gasification conditions.

  19. Testing of an advanced thermochemical conversion reactor system

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    This report presents the results of work conducted by MTCI to verify and confirm experimentally the ability of the MTCI gasification process to effectively generate a high-quality, medium-Btu gas from a wider variety of feedstock and waste than that attainable in air-blown, direct gasification systems. The system's overall simplicity, due to the compact nature of the pulse combustor, and the high heat transfer rates attainable within the pulsating flow resonance tubes, provide a decided and near-term potential economic advantage for the MTCI indirect gasification system. The primary objective of this project was the design, construction, and testing of a Process Design Verification System for an indirectly heated, thermochemical fluid-bed reactor and a pulse combustor an an integrated system that can process alternative renewable sources of energy such as biomass, black liquor, municipal solid waste and waste hydrocarbons, including heavy oils into a useful product gas. The test objectives for the biomass portion of this program were to establish definitive performance data on biomass feedstocks covering a wide range of feedstock qualities and characteristics. The test objectives for the black liquor portion of this program were to verify the operation of the indirect gasifier on commercial black liquor containing 65 percent solids at several temperature levels and to characterize the bed carbon content, bed solids particle size and sulfur distribution as a function of gasification conditions. 6 refs., 59 figs., 29 tabs.

  20. Lunar sulfur

    Science.gov (United States)

    Kuck, David L.

    Ideas introduced by Vaniman, Pettit and Heiken in their 1988 Uses of Lunar Sulfur are expanded. Particular attention is given to uses of SO2 as a mineral-dressing fluid. Also introduced is the concept of using sulfide-based concrete as an alternative to the sulfur-based concretes proposed by Leonard and Johnson. Sulfur is abundant in high-Ti mare basalts, which range from 0.16 to 0.27 pct. by weight. Terrestrial basalts with 0.15 pct. S are rare. For oxygen recovery, sulfur must be driven off with other volatiles from ilmenite concentrates, before reduction. Troilite (FeS) may be oxidized to magnetite (Fe3O4) and SO2 gas, by burning concentrates in oxygen within a magnetic field, to further oxidize ilmenite before regrinding the magnetic reconcentration. SO2 is liquid at -20 C, the mean temperature underground on the Moon, at a minimum of 0.6 atm pressure. By using liquid SO2 as a mineral dressing fluid, all the techniques of terrestrial mineral separation become available for lunar ores and concentrates. Combination of sulfur and iron in an exothermic reaction, to form iron sulfides, may be used to cement grains of other minerals into an anhydrous iron-sulfide concrete. A sulfur-iron-aggregate mixture may be heated to the ignition temperature of iron with sulfur to make a concrete shape. The best iron, sulfur, and aggregate ratios need to be experimentally established. The iron and sulfur will be by-products of oxygen production from lunar minerals.

  1. Fundamental study of novel mid-and low-temperature solar thermochemical energy conversion

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A new approach to application of mid-and low-temperature solar thermochemical technology was in-troduced and investigated.Concentrated solar thermal energy in the range of 150―300℃ can be effi-ciently converted into high-grade solar fuel by integrating this technique with the endothermic reaction of hydrocarbons.The conversion mechanism of upgrading the low-grade solar thermal energy to high-grade chemical energy was examined based on the energy level.The new mechanism was used to integrate two novel solar thermal power systems:A solar/methanol fuel hybrid thermal power plant and a solar-hybrid combined cycle with inherent CO2 separation using chemical-looping combustion,for developing highly efficient solar energy use to generate electricity.An innovative prototype of a 5-kW solar receiver/reactor,as the key process for realizing the proposed system,was designed and manu-factured.Furthermore,experimental validation of energy conversion of the mid-and low-temperature solar thermochemical processes were conducted.In addition,a second practical and viable approach to the production of hydrogen,in combination with the novel mid-and low-temperature solar thermo-chemical process,was proposed and demonstrated experimentally in the manufactured solar re-ceiver/reactor prototype through methanol steam reforming.The results obtained here indicate that the development of mid-and low-temperature solar thermochemical technology may provide a promising and new direction to efficient utilization of low-grade solar thermal energy,and may enable step-wise approaches to cost-effective,globally scalable solar energy systems.

  2. Fundamental study of novel mid- and low-temperature solar thermochemical energy conversion

    Institute of Scientific and Technical Information of China (English)

    JIN HongGuang; HONG Hui; SUI Jun; LIU QiBin

    2009-01-01

    A new approach to application of mid- and low-temperature solar thermochemical technology was in-troduced and investigated. Concentrated solar thermal energy in the range of 150--300℃ can be effi-ciently converted into high-grade solar fuel by integrating this technique with the endothermic reaction of hydrocarbons. The conversion mechanism of upgrading the low-grade solar thermal energy to high-grade chemical energy was examined based on the energy level. The new mechanism was used to integrate two novel solar thermal power systems: A solar/methanol fuel hybrid thermal power plant and a solar-hybrid combined cycle with inherent CO2 separation using chemical-looping combustion, for developing highly efficient solar energy use to generate electricity. An innovative prototype of a 5-kW solar receiver/reactor, as the key process for realizing the proposed system, was designed and manu-factured. Furthermore, experimental validation of energy conversion of the mid- and low-temperature solar thermochemical processes were conducted. In addition, a second practical and viable approach to the production of hydrogen, in combination with the novel mid- and low-temperature solar thermo-chemical process, was proposed and demonstrated experimentally in the manufactured solar re-ceiver/reactor prototype through methanol steam reforming. The results obtained here indicate that the development of mid- and low-temperature solar thermochemical technology may provide a promising and new direction to efficient utilization of low-grade solar thermal energy, and may enable step-wise approaches to cost-effective, globally scalable solar energy systems.

  3. A web service infrastructure for thermochemical data.

    Science.gov (United States)

    Paolini, Christopher P; Bhattacharjee, Subrata

    2008-07-01

    W3C standardized Web Services are becoming an increasingly popular middleware technology used to facilitate the open exchange of chemical data. While several projects in existence use Web Services to wrap existing commercial and open-source tools that mine chemical structure data, no Web Service infrastructure has yet been developed to compute thermochemical properties of substances. This work presents an infrastructure of Web Services for thermochemical data retrieval. Several examples are presented to demonstrate how our Web Services can be called from Java, through JavaScript using an AJAX methodology, and within commonly used commercial applications such as Microsoft Excel and MATLAB for use in computational work. We illustrate how a JANAF table, widely used by chemists and engineers, can be quickly reproduced through our Web Service infrastructure.

  4. A Cable-Shaped Lithium Sulfur Battery.

    Science.gov (United States)

    Fang, Xin; Weng, Wei; Ren, Jing; Peng, Huisheng

    2016-01-20

    A carbon nanostructured hybrid fiber is developed by integrating mesoporous carbon and graphene oxide into aligned carbon nanotubes. This hybrid fiber is used as a 1D cathode to fabricate a new cable-shaped lithium-sulfur battery. The fiber cathode exhibits a decent specific capacity and lifespan, which makes the cable-shaped lithium-sulfur battery rank far ahead of other fiber-shaped batteries.

  5. Development of Efficient Flowsheet and Transient Modeling for Nuclear Heat Coupled Sulfur Iodine Cyclefor Hydrogen Production

    Energy Technology Data Exchange (ETDEWEB)

    Shripad T. Revankar; Nicholas R. Brown; Cheikhou Kane; Seungmin Oh

    2010-05-01

    The realization of the hydrogen as an energy carrier for future power sources relies on a practical method of producing hydrogen in large scale with no emission of green house gases. Hydrogen is an energy carrier which can be produced by a thermochemical water splitting process. The Sulfur-Iodine (SI) process is an example of a water splitting method using iodine and sulfur as recycling agents.

  6. Thermodynamic modeling of HIx part of the Iodine – Sulfur thermocycle

    OpenAIRE

    Hadj-Kali, Mohamed; Gerbaud, Vincent; Borgard, Jean-Marc; Floquet, Pascal; Joulia, Xavier; Carles, Philippe

    2007-01-01

    The thermochemical water splitting cycle is an environmentally attractive way to produce hydrogen without using fossil fuels. Among a hundreds possible cycles, the sulfur – iodine (IS) is a promising one, expected to become a major source of hydrogen production from nuclear or solar energy. The IS process cycle is divided into three sections; namely: (1) the Bunsen section whose purpose is to produce the two immiscible liquid acid phases: one containing mainly sulfuric acid and the other h...

  7. Membranes for H2 generation from nuclear powered thermochemical cycles.

    Energy Technology Data Exchange (ETDEWEB)

    Nenoff, Tina Maria; Ambrosini, Andrea; Garino, Terry J.; Gelbard, Fred; Leung, Kevin; Navrotsky, Alexandra (University of California, Davis, CA); Iyer, Ratnasabapathy G. (University of California, Davis, CA); Axness, Marlene

    2006-11-01

    In an effort to produce hydrogen without the unwanted greenhouse gas byproducts, high-temperature thermochemical cycles driven by heat from solar energy or next-generation nuclear power plants are being explored. The process being developed is the thermochemical production of Hydrogen. The Sulfur-Iodide (SI) cycle was deemed to be one of the most promising cycles to explore. The first step of the SI cycle involves the decomposition of H{sub 2}SO{sub 4} into O{sub 2}, SO{sub 2}, and H{sub 2}O at temperatures around 850 C. In-situ removal of O{sub 2} from this reaction pushes the equilibrium towards dissociation, thus increasing the overall efficiency of the decomposition reaction. A membrane is required for this oxygen separation step that is capable of withstanding the high temperatures and corrosive conditions inherent in this process. Mixed ionic-electronic perovskites and perovskite-related structures are potential materials for oxygen separation membranes owing to their robustness, ability to form dense ceramics, capacity to stabilize oxygen nonstoichiometry, and mixed ionic/electronic conductivity. Two oxide families with promising results were studied: the double-substituted perovskite A{sub x}Sr{sub 1-x}Co{sub 1-y}B{sub y}O{sub 3-{delta}} (A=La, Y; B=Cr-Ni), in particular the family La{sub x}Sr{sub 1-x}Co{sub 1-y}Mn{sub y}O{sub 3-{delta}} (LSCM), and doped La{sub 2}Ni{sub 1-x}M{sub x}O{sub 4} (M = Cu, Zn). Materials and membranes were synthesized by solid state methods and characterized by X-ray and neutron diffraction, SEM, thermal analyses, calorimetry and conductivity. Furthermore, we were able to leverage our program with a DOE/NE sponsored H{sub 2}SO{sub 4} decomposition reactor study (at Sandia), in which our membranes were tested in the actual H{sub 2}SO{sub 4} decomposition step.

  8. Thermochemical Process Development Unit: Researching Fuels from Biomass, Bioenergy Technologies (Fact Sheet)

    Energy Technology Data Exchange (ETDEWEB)

    2009-01-01

    The Thermochemical Process Development Unit (TCPDU) at the National Renewable Energy Laboratory (NREL) is a unique facility dedicated to researching thermochemical processes to produce fuels from biomass.

  9. Bioenergy II : Biomass Valorisation by a Hybrid Thermochemical Fractionation Approach

    NARCIS (Netherlands)

    de Wild, Paul J.; den Uil, Herman; Reith, Johannes H.; Lunshof, Anton; Hendriks, Carlijn; van Eck, Ernst R. H.; Heeres, Erik J.

    2009-01-01

    The need for green renewable sources is adamant because of the adverse effects of the increasing use of fossil fuels on our society. Biomass has been considered as a very attractive candidate for green energy carriers, chemicals and materials. The development of cheap and efficient fractionation tec

  10. Sulfur Earth

    Science.gov (United States)

    de Jong, B. H.

    2007-12-01

    Variations in surface tension affect the buoyancy of objects floating in a liquid. Thus an object floating in water will sink deeper in the presence of dishwater fluid. This is a very minor but measurable effect. It causes for instance ducks to drown in aqueous solutions with added surfactant. The surface tension of liquid iron is very strongly affected by the presence of sulfur which acts as a surfactant in this system varying between 1.9 and 0.4 N/m at 10 mass percent Sulfur (Lee & Morita (2002), This last value is inferred to be the maximum value for Sulfur inferred to be present in the liquid outer core. Venting of Sulfur from the liquid core manifests itself on the Earth surface by the 105 to 106 ton of sulfur vented into the atmosphere annually (Wedepohl, 1984). Inspection of surface Sulfur emission indicates that venting is non-homogeneously distributed over the Earth's surface. The implication of such large variation in surface tension in the liquid outer core are that at locally low Sulfur concentration, the liquid outer core does not wet the predominantly MgSiO3 matrix with which it is in contact. However at a local high in Sulfur, the liquid outer core wets this matrix which in the fluid state has a surface tension of 0.4 N/m (Bansal & Doremus, 1986), couples with it, and causes it to sink. This differential and diapiric movement is transmitted through the essentially brittle mantle (1024 Pa.s, Lambeck & Johnson, 1998; the maximum value for ice being about 1030 Pa.s at 0 K, in all likely hood representing an upper bound of viscosity for all materials) and manifests itself on the surface by the roughly 20 km differentiation, about 0.1 % of the total mantle thickness, between topographical heights and lows with concomitant lateral movement in the crust and upper mantle resulting in thin skin tectonics. The brittle nature of the medium though which this movement is transmitted suggests that the extremes in topography of the D" layer are similar in range to

  11. An Investigation on Low-Temperature Thermochemical Treatments of Austenitic Stainless Steel in Fluidized Bed Furnace

    Science.gov (United States)

    Haruman, E.; Sun, Y.; Triwiyanto, A.; Manurung, Y. H. P.; Adesta, E. Y.

    2012-03-01

    In this study, the feasibility of using an industrial fluidized bed furnace to perform low-temperature thermochemical treatments of austenitic stainless steels has been studied, with the aim to produce expanded austenite layers with combined wear and corrosion resistance, similar to those achievable by plasma and gaseous processes. Several low-temperature thermochemical treatments were studied, including nitriding, carburizing, combined nitriding-carburizing (hybrid treatment), and sequential carburizing and nitriding. The results demonstrate that it is feasible to produce expanded austenite layers on the investigated austenitic stainless steel by the fluidized bed heat treatment technique, thus widening the application window for the novel low-temperature processes. The results also demonstrate that the fluidized bed furnace is the most effective for performing the hybrid treatment, which involves the simultaneous incorporation of nitrogen and carbon together into the surface region of the component in nitrogen- and carbon-containing atmospheres. Such hybrid treatment produces a thicker and harder layer than the other three processes investigated.

  12. Screening analysis of solar thermochemical hydrogen concepts.

    Energy Technology Data Exchange (ETDEWEB)

    Diver, Richard B., Jr.; Kolb, Gregory J.

    2008-03-01

    A screening analysis was performed to identify concentrating solar power (CSP) concepts that produce hydrogen with the highest efficiency. Several CSP concepts were identified that have the potential to be much more efficient than today's low-temperature electrolysis technology. They combine a central receiver or dish with either a thermochemical cycle or high-temperature electrolyzer that operate at temperatures >600 C. The solar-to-hydrogen efficiencies of the best central receiver concepts exceed 20%, significantly better than the 14% value predicted for low-temperature electrolysis.

  13. Microencapsulation of salts for enhanced thermochemical storage materials

    NARCIS (Netherlands)

    Cuypers, R.; Jong, A.J. de; Eversdijk, J.; Spijker, J.C. van 't; Oversloot, H.P.; Ingenhut, B.L.J.; Cremers, R.K.H.; Papen-Botterhuis, N.E.

    2013-01-01

    Thermochemical storage is a new and emerging long-term thermal storage for residential use (cooling, heating & domestic hot water generation), offering high thermal storage density without the need for thermal insulation during storage (Fig. 1). However, existing materials for thermochemical storage

  14. Thermochemical water-splitting cycle, bench-scale investigations and process engineering. Annual report, October 1, 1978-September 30, 1979

    Energy Technology Data Exchange (ETDEWEB)

    Caprioglio, G.; McCorkle, K.H.; Besenbruch, G.E.; Rode, J.S.

    1980-03-01

    A program to investigate thermochemical water splitting has been under way at General Atomic Company (GA) since October 1972. This document is an annual progress report of Department of Energy (DOE) sponsored process development work on the GA sulfur-iodine thermochemical water splitting cycle. The work consisted of laboratory bench-scale investigations, demonstration of the process in a closed-loop cycle demonstrator, and process engineering design studies. A bench-scale system, consisting of three subunits, has been designed to study the cycle under continuous flow conditions. The designs of subunit I, which models the main solution reaction and product separation, and subunit II, which models the concentration and decomposition of sulfuric acid, were presented in an earlier annual report. The design of subunit III, which models the purification and decomposition of hydrogen iodide, is given in this report. Progress on the installation and operation of subunits I and II is described. A closed-loop cycle demonstrator was installed and operated based on a DOE request. Operation of the GA sulfur-iodine cycle was demonstrated in this system under recycle conditions. The process engineering addresses the flowsheet design of a large-scale production process consisting of four chemical sections (I through IV) and one helium heat supply section (V). The completed designs for sections I through V are presented. The thermal efficiency of the process calculated from the present flowsheet is 47%.

  15. Thermochemical sulfate reduction in deep petroleum reservoirs: a molecular approach; Thermoreduction des sulfates dans les reservoirs petroliers: approche moleculaire

    Energy Technology Data Exchange (ETDEWEB)

    Hanin, S.

    2002-11-01

    The thermochemical sulfate reduction (TSR) is a set of chemical reactions leading to hydrocarbon oxidation and production of carbon dioxide and sour gas (H{sub 2}S) which is observed in deep petroleum reservoirs enriched in anhydrites (calcium sulfate). Molecular and isotopic studies have been conducted on several crude oil samples to determine which types of compounds could have been produced during TSR. Actually, we have shown that the main molecules formed by TSR were organo-sulfur compounds. Indeed, sulfur isotopic measurements. of alkyl-di-benzothiophenes, di-aryl-disulfides and thia-diamondoids (identified by NMR or synthesis of standards) shows that they are formed during TSR as their value approach that of the sulfur of the anhydrite. Moreover, thia-diamondoids are apparently exclusively formed during this phenomenon and can thus be considered as true molecular markers of TSR. In a second part, we have investigated with laboratory experiments the formation mechanism of the molecules produced during TSR. A first model has shown that sulfur incorporation into the organic matter occurred with mineral sulfur species of low oxidation degree. The use of {sup 34}S allowed to show that the sulfates reduction occurred during these simulations. At least, some experiments on polycyclic hydrocarbons, sulfurized or not, allowed to establish that thia-diamondoids could be formed by acid-catalysed rearrangements at high temperatures in a similar way as the diamondoids. (author)

  16. TEA: A Code Calculating Thermochemical Equilibrium Abundances

    Science.gov (United States)

    Blecic, Jasmina; Harrington, Joseph; Bowman, M. Oliver

    2016-07-01

    We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. and Eriksson. It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp, the free thermochemical equilibrium code Chemical Equilibrium with Applications (CEA), and the example given by Burrows & Sharp. Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is available under a reproducible-research, open-source license via https://github.com/dzesmin/TEA.

  17. Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

    Science.gov (United States)

    Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.

    2008-01-01

    Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to

  18. Biomass thermochemical gasification: Experimental studies and modeling

    Science.gov (United States)

    Kumar, Ajay

    The overall goals of this research were to study the biomass thermochemical gasification using experimental and modeling techniques, and to evaluate the cost of industrial gas production and combined heat and power generation. This dissertation includes an extensive review of progresses in biomass thermochemical gasification. Product gases from biomass gasification can be converted to biopower, biofuels and chemicals. However, for its viable commercial applications, the study summarizes the technical challenges in the gasification and downstream processing of product gas. Corn stover and dried distillers grains with solubles (DDGS), a non-fermentable byproduct of ethanol production, were used as the biomass feedstocks. One of the objectives was to determine selected physical and chemical properties of corn stover related to thermochemical conversion. The parameters of the reaction kinetics for weight loss were obtained. The next objective was to investigate the effects of temperature, steam to biomass ratio and equivalence ratio on gas composition and efficiencies. DDGS gasification was performed on a lab-scale fluidized-bed gasifier with steam and air as fluidizing and oxidizing agents. Increasing the temperature resulted in increases in hydrogen and methane contents and efficiencies. A model was developed to simulate the performance of a lab-scale gasifier using Aspen Plus(TM) software. Mass balance, energy balance and minimization of Gibbs free energy were applied for the gasification to determine the product gas composition. The final objective was to optimize the process by maximizing the net energy efficiency, and to estimate the cost of industrial gas, and combined heat and power (CHP) at a biomass feedrate of 2000 kg/h. The selling price of gas was estimated to be 11.49/GJ for corn stover, and 13.08/GJ for DDGS. For CHP generation, the electrical and net efficiencies were 37 and 86%, respectively for corn stover, and 34 and 78%, respectively for DDGS. For

  19. Thermochemical Water Splitting for Hydrogen Production Utilizing Nuclear Heat from an HTGR

    Institute of Scientific and Technical Information of China (English)

    WU Xinxin; ONUKI Kaoru

    2005-01-01

    A very promising technology to achieve a carbon free energy system is to produce hydrogen from water, rather than from fossil fuels. Iodine-sulfur (IS) thermochemical water decomposition is one promising process. The IS process can be used to efficiently produce hydrogen using the high temperature gas-cooled reactor (HTGR) as the energy source supplying gas at 1000℃. This paper describes that demonstration experiment for hydrogen production was carried out by an IS process at a laboratory scale. The results confirmed the feasibility of the closed-loop operation for recycling all the reactants besides the water, H2, and O2. Then the membrane technology was developed to enhance the decomposition efficiency. The maximum attainable one-pass conversion rate of HI exceeds 90% by membrane technology, whereas the equilibrium rate is about 20%.

  20. Thermochemical factors affecting the dehalogenation of aromatics.

    Science.gov (United States)

    Sadowsky, Daniel; McNeill, Kristopher; Cramer, Christopher J

    2013-12-17

    Halogenated aromatics are one of the largest chemical classes of environmental contaminants, and dehalogenation remains one of the most important processes by which these compounds are degraded and detoxified. The thermodynamic constraints of aromatic dehalogenation reactions are thus important for understanding the feasibility of such reactions and the redox conditions necessary for promoting them. Accordingly, the thermochemical properties of the (poly)fluoro-, (poly)chloro-, and (poly)bromobenzenes, including standard enthalpies of formation, bond dissociation enthalpies, free energies of reaction, and the redox potentials of Ar-X/Ar-H couples, were investigated using a validated density functional protocol combined with continuum solvation calculations when appropriate. The results highlight the fact that fluorinated aromatics stand distinct from their chloro- and bromo- counterparts in terms of both their relative thermodynamic stability toward dehalogenation and how different substitution patterns give rise to relevant properties, such as bond strengths and reduction potentials.

  1. Solar Thermochemical Hydrogen Production Research (STCH)

    Energy Technology Data Exchange (ETDEWEB)

    Perret, Robert [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2011-05-01

    Eight cycles in a coordinated set of projects for Solar Thermochemical Cycles for Hydrogen production (STCH) were self-evaluated for the DOE-EERE Fuel Cell Technologies Program at a Working Group Meeting on October 8 and 9, 2008. This document reports the initial selection process for development investment in STCH projects, the evaluation process meant to reduce the number of projects as a means to focus resources on development of a few most-likely-to-succeed efforts, the obstacles encountered in project inventory reduction and the outcomes of the evaluation process. Summary technical status of the projects under evaluation is reported and recommendations identified to improve future project planning and selection activities.

  2. Biologically produced sulfur

    NARCIS (Netherlands)

    Kleinjan, W.E.; Keizer, de A.; Janssen, A.J.H.

    2003-01-01

    Sulfur compound oxidizing bacteria produce sulfur as an intermediate in the oxidation of hydrogen sulfide to sulfate. Sulfur produced by these microorganisms can be stored in sulfur globules, located either inside or outside the cell. Excreted sulfur globules are colloidal particles which are stabil

  3. 2011 Biomass Program Platform Peer Review. Thermochemical Conversion

    Energy Technology Data Exchange (ETDEWEB)

    Grabowski, Paul E. [Office of Energy Efficiency and Renewable Energy (EERE), Washington, DC (United States)

    2012-02-01

    This document summarizes the recommendations and evaluations provided by an independent external panel of experts at the 2011 U.S. Department of Energy Biomass Program’s Thermochemical Conversion Platform Review meeting.

  4. Method to prevent sulfur accumulation in membrane electrode assembly

    Science.gov (United States)

    Steimke, John L; Steeper, Timothy J; Herman, David T

    2014-04-29

    A method of operating a hybrid sulfur electrolyzer to generate hydrogen is provided that includes the steps of providing an anolyte with a concentration of sulfur dioxide, and applying a current. During steady state generation of hydrogen a plot of applied current density versus concentration of sulfur dioxide is below a boundary line. The boundary line may be linear and extend through the origin of the graph with a slope of 0.001 in which the current density is measured in mA/cm2 and the concentration of sulfur dioxide is measured in moles of sulfur dioxide per liter of anolyte.

  5. Sulfur and Nitrogen co-doped graphene quantum dot decorated ZnO nanorod/polymer hybrid flexible device for photosensing applications

    Energy Technology Data Exchange (ETDEWEB)

    Hmar, Jehova Jire L.; Majumder, Tanmoy; Dhar, Saurab; Mondal, Suvra Prakash, E-mail: suvraphy@gmail.com

    2016-08-01

    S and N co-doped graphene quantum dots (S,N-GQDs) have been synthesized by a hydrothermal process. S,N-GQDs are made up of 1–5 monolayer of graphene with average diameter 13.3 nm. The absorption peaks at 336 and 621 nm, are attributed to n → Π{sup ⁎} transitions of electrons in C=O and S=O bonds, respectively. S,N-GQDs are highly luminescent and showed excitation dependent emission behaviors. Hybrid photosensing device has been fabricated with S,N-GQD sensitized ZnO nanorods and a conjugated polymer poly(3-hexylthiophene) (P3HT). S,N-GQD decorated ZnO nanorod demonstrated higher photoresponse compared to pristine ZnO nanorod based device. S,N-GQD/ZnO nanorod hybrid device showed superior incident photon to electron conversion efficiency (IPCE), photoresponsivity and detectivity compared to the control samples. The flexibility study of the samples has been monitored by measuring current-voltage characteristics at different bending angles. - Highlights: • S and N co-doped graphene quantum dots (S,N-GQDs) were synthesized. • ZnO nanorods were grown on ITO coated flexible PET substrates. • S,N-GQDs were attached with ZnO nanorods and used as a green sensitizer. • Photosensing properties of S,N-GQD/ZnO and P3HT polymer hybrid device was studied.

  6. Sulfur metabolism in phototrophic sulfur bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2008-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

  7. Self-assembled sulfur/reduced graphene oxide nanoribbon paper as a free-standing electrode for high performance lithium-sulfur batteries.

    Science.gov (United States)

    Liu, Yang; Wang, Xuzhen; Dong, Yanfeng; Tang, Yongchao; Wang, Luxiang; Jia, Dianzeng; Zhao, Zongbin; Qiu, Jieshan

    2016-10-25

    Flexible, interconnected sulfur/reduced graphene oxide nanoribbon paper (S/RGONRP) is synthesized through S(2-) reduction and evaporation induced self-assembly processes. The in situ formed sulfur atoms chemically bonded with the surface of reduced graphene oxide nanoribbons and were physically trapped by the compact assembly, which make the hybrid a suitable cathode material for lithium-sulfur batteries.

  8. Inorganic-organic hybrid membranes with anhydrous proton conduction prepared from 3-aminopropyltriethoxysilane and sulfuric acid by the sol-gel method.

    Science.gov (United States)

    Tezuka, Teruaki; Tadanaga, Kiyoharu; Hayashi, Akitoshi; Tatsumisago, Masahiro

    2006-12-27

    Inorganic-organic hybrid membranes with anhydrous proton conduction were prepared from 3-aminopropyltriethoxysilane and H2SO4 by the sol-gel method. The membrane has a unique structure: a hexagonal phase formed by the stacking of rodlike polysiloxanes with ion complexes of ammonium groups and HSO4- extruded outside. The membranes showed high conductivity of 2 x 10-3 S cm-1 at 200 degrees C under dry atmosphere. In the membrane, protons probably migrate through the outside of the rodlike polysiloxanes along hydrogen-bond chains formed among HSO4- anions.

  9. Active Thermochemical Tables: thermochemistry for the 21st century

    Energy Technology Data Exchange (ETDEWEB)

    Ruscic, Branko [Chemistry Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Pinzon, Reinhardt E [Chemistry Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Laszewski, Gregor von [Mathematics and Computer Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Kodeboyina, Deepti [Mathematics and Computer Science Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Burcat, Alexander [Chemistry Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Leahy, David [Sandia National Laboratories, Livermore, CA 94551 (United States); Montoy, David [Chemistry Division, Argonne National Laboratory, Argonne, IL 60439 (United States); Los Alamos National Laboratory, Los Alamos, NM 87545 (United States); Wagner, Albert F [Chemistry Division, Argonne National Laboratory, Argonne, IL 60439 (United States)

    2005-01-01

    Active Thermochemical Tables (ATcT) are a good example of a significant breakthrough in chemical science that is directly enabled by the US DOE SciDAC initiative. ATcT is a new paradigm of how to obtain accurate, reliable, and internally consistent thermochemistry and overcome the limitations that are intrinsic to the traditional sequential approach to thermochemistry. The availability of high-quality consistent thermochemical values is critical in many areas of chemistry, including the development of realistic predictive models of complex chemical environments such as combustion or the atmosphere, or development and improvement of sophisticated high-fidelity electronic structure computational treatments. As opposed to the traditional sequential evolution of thermochemical values for the chemical species of interest, ATcT utilizes the Thermochemical Network (TN) approach. This approach explicitly exposes the maze of inherent interdependencies normally ignored by the conventional treatment, and allows, inter alia, a statistical analysis of the individual measurements that define the TN. The end result is the extraction of the best possible thermochemistry, based on optimal use of all the currently available knowledge, hence making conventional tabulations of thermochemical values obsolete. Moreover, ATcT offer a number of additional features that are neither present nor possible in the traditional approach. With ATcT, new knowledge can be painlessly propagated through all affected thermochemical values. ATcT also allows hypothesis testing and evaluation, as well as discovery of weak links in the TN. The latter provides pointers to new experimental or theoretical determinations that can most efficiently improve the underlying thermochemical body of knowledge.

  10. Electrochemical hydrogen production from thermochemical cycles using a proton exchange membrane electrolyzer

    Energy Technology Data Exchange (ETDEWEB)

    Sivasubramanian, PremKumar; Ramasamy, Ramaraja P.; Holland, Charles E.; Weidner, John W. [Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States); Freire, Francisco J. [Chlorine Recycle Consultants, Miami Beach, FL 33140 (United States)

    2007-03-15

    The electrochemical step in two thermochemical cycles for hydrogen production is reported. One cycle involves the electrochemical oxidation of sulfur dioxide to sulfuric acid (both water and SO{sub 2} are reactants). The other cycle involves the oxidation of anhydrous hydrogen bromide to bromine (anhydrous HBr is the only reactant). In both cycles, protons are reduced at the cathode to produce hydrogen. The novelty of this work is that both anode reactions are carried out in the gas phase of a proton exchange membrane (PEM) electrolyzer, which enhances the transport rate of reactants to the electrode surface. The HBr process achieved 2.0A/cm{sup 2} at 1.91 V. The SO{sub 2} process reached 0.4A/cm{sup 2}, but behind this current density the cell experienced mass transfer limitations of water across the membrane. However, the voltage required to achieve 0.4A/cm{sup 2} was 0.835 V, compared to 1.025 V for the HBr process at this current density. (author)

  11. Speciation of sulfur in biochar produced from pyrolysis and gasification of oak and corn stover.

    Science.gov (United States)

    Cheah, Singfoong; Malone, Shealyn C; Feik, Calvin J

    2014-01-01

    The effects of feedstock type and biomass conversion conditions on the speciation of sulfur in biochars are not well-known. In this study, the sulfur content and speciation in biochars generated from pyrolysis and gasification of oak and corn stover were determined. We found the primary determinant of the total sulfur content of biomass to be the feedstock from which the biochar is generated, with oak and corn stover biochars containing 160 and 600-800 ppm sulfur, respectively. In contrast, for sulfur speciation, we found the primary determinant to be the temperature combined with the thermochemical conversion method. The speciation of sulfur in biochars was determined using X-ray absorption near-edge structure (XANES), ASTM method D2492, and scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS). Biochars produced under pyrolysis conditions at 500-600 °C contain sulfate, organosulfur, and sulfide. In some cases, the sulfate contents are up to 77-100%. Biochars produced in gasification conditions at 850 °C contain 73-100% organosulfur. The increase of the organosulfur content as the temperature of biochar production increases suggests a similar sulfur transformation mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon and/or H2 to form organosulfur when the coal is heated. EDS mapping of a biochar produced from corn stover pyrolysis shows individual sulfur-containing mineral particles in addition to the sulfur that is distributed throughout the organic matrix.

  12. Speciation of Sulfur in Biochar Produced from Pyrolysis and Gasification of Oak and Corn Stover

    Science.gov (United States)

    2015-01-01

    The effects of feedstock type and biomass conversion conditions on the speciation of sulfur in biochars are not well-known. In this study, the sulfur content and speciation in biochars generated from pyrolysis and gasification of oak and corn stover were determined. We found the primary determinant of the total sulfur content of biomass to be the feedstock from which the biochar is generated, with oak and corn stover biochars containing 160 and 600–800 ppm sulfur, respectively. In contrast, for sulfur speciation, we found the primary determinant to be the temperature combined with the thermochemical conversion method. The speciation of sulfur in biochars was determined using X-ray absorption near-edge structure (XANES), ASTM method D2492, and scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS). Biochars produced under pyrolysis conditions at 500–600 °C contain sulfate, organosulfur, and sulfide. In some cases, the sulfate contents are up to 77–100%. Biochars produced in gasification conditions at 850 °C contain 73–100% organosulfur. The increase of the organosulfur content as the temperature of biochar production increases suggests a similar sulfur transformation mechanism as that in coal, where inorganic sulfur reacts with hydrocarbon and/or H2 to form organosulfur when the coal is heated. EDS mapping of a biochar produced from corn stover pyrolysis shows individual sulfur-containing mineral particles in addition to the sulfur that is distributed throughout the organic matrix. PMID:25003702

  13. Thermochemical energy storage : critical review and recent advances

    Energy Technology Data Exchange (ETDEWEB)

    Haji Abedin, A.; Rosen, M.A. [University of Ontario Inst. of Technology, Oshawa, ON (Canada). Faculty of Engineering and Applied Science

    2010-07-01

    The global increase in energy demand and environmental concerns are promoting the use of more efficient and cleaner energy technologies. Examples include advanced systems for waste energy recovery and energy integration. Thermochemical thermal energy storage (TES) is an emerging method with the potential for high energy density storage. It is not yet commercial and research and development is needed to better understand and design the technology and to resolve other practical aspects before commercial implementation can occur. TES is an advanced technology for storing thermal energy that can mitigate environmental impacts and facilitate more efficient and clean energy systems. This paper presented the principles of thermochemical TES and recent advances. Thermochemical TES was also critically assessed and compared with other TES types. The advantages and disadvantages of thermochemical TES were also considered as they relate to other TES types. It was concluded that thermochemical TES has the highest potential to achieve the required compact thermal energy storage where space is limited. 13 refs., 2 tabs., 1 fig.

  14. Thermochemical valorization and characterization of household biowaste.

    Science.gov (United States)

    Vakalis, S; Sotiropoulos, A; Moustakas, K; Malamis, D; Vekkos, K; Baratieri, M

    2016-04-15

    Valorization of municipal solid waste (MSW), by means of energy and material recovery, is considered to be a crucial step for sustainable waste management. A significant fraction of MSW is comprised from food waste, the treatment of which is still a challenge. Therefore, the conventional disposal of food waste in landfills is being gradually replaced by recycling aerobic treatment, anaerobic digestion and waste-to-energy. In principle, thermal processes like combustion and gasification are preferred for the recovery of energy due to the higher electrical efficiency and the significantly less time required for the process to be completed when compared to biological process, i.e. composting, anaerobic digestion and transesterification. Nonetheless, the high water content and the molecular structure of biowaste are constraining factors in regard to the application of thermal conversion pathways. Investigating alternative solutions for the pre-treatment and more energy efficient handling of this waste fraction may provide pathways for the optimization of the whole process. In this study, by means of utilizing drying/milling as an intermediate step, thermal treatment of household biowaste has become possible. Household biowaste has been thermally processed in a bench scale reactor by means of torrefaction, carbonization and high temperature pyrolysis. According to the operational conditions, fluctuating fractions of biochar, bio-oil (tar) and syngas were recovered. The thermochemical properties of the feedstock and products were analyzed by means of Simultaneous Thermal Analysis (STA), Ultimate and Proximate analysis and Attenuated Total Reflectance (ATR). The analysis of the products shows that torrefaction of dried household biowaste produces an energy dense fuel and high temperature pyrolysis produces a graphite-like material with relatively high yield.

  15. Thermochemical Conversion: Using Heat and Catalysts to Make Biofuels and Bioproducts

    Energy Technology Data Exchange (ETDEWEB)

    None

    2013-07-29

    This fact sheet discusses the Bioenergy Technologies Office's thermochemical conversion critical technology goal. And, how through the application of heat, robust thermochemical processes can efficiently convert a broad range of biomass.

  16. Capabilities to Support Thermochemical Hydrogen Production Technology Development

    Energy Technology Data Exchange (ETDEWEB)

    Daniel M. Ginosar

    2009-05-01

    This report presents the results of a study to determine if Idaho National Laboratory (INL) has the skilled staff, instrumentation, specialized equipment, and facilities required to take on work in thermochemical research, development, and demonstration currently being performed by the Nuclear Hydrogen Initiative (NHI). This study outlines the beneficial collaborations between INL and other national laboratories, universities, and industries to strengthen INL's thermochemical efforts, which should be developed to achieve the goals of the NHI in the most expeditious, cost effective manner. Taking on this work supports INL's long-term strategy to maintain leadership in thermochemical cycle development. This report suggests a logical path forward to accomplish this transition.

  17. New Developments in Thermo-Chemical Diffusion Processes

    Institute of Scientific and Technical Information of China (English)

    Bernd Edenhofer

    2004-01-01

    Thermo-chemical diffusion processes like carburising, nitriding and boronizing play an important part in modern manufacturing technologies. They exist in many varieties depending on the type of diffusing element used and the respective process procedure. The most important industrial heat treatment process is case-hardening, which consists of thermochemical diffusion process carburising or its variation carbonitriding, followed by a subsequent quench. The latest developments of using different gaseous carburising agents and increasing the carburising temperature are one main area of this paper. The other area is the evolvement of nitriding and especially the ferritic nitrocarburising process by improved process control and newly developed process variations using carbon, nitrogen and oxygen as diffusing elements in various process steps. Also boronizing and special thermo-chemical processes for stainless steels are discussed.

  18. Sulfur Iodine Process Summary for the Hydrogen Technology Down-Selection

    Energy Technology Data Exchange (ETDEWEB)

    Benjamin Russ

    2009-05-01

    This report summarizes the sulfur-iodine (SI) thermochemical water splitting process for the purpose of supporting the process for evaluating and recommending a hydrogen production technology to deploy with the Next Generation Nuclear Plant (NGNP). This package provides the baseline process description as well as a comparison with the process as it was implemented in the Integrated Lab Scale (ILS) experiment conducted at General Atomics from 2006-2009.

  19. A techno-economic review of thermochemical cellulosic biofuel pathways.

    Science.gov (United States)

    Brown, Tristan R

    2015-02-01

    Recent advances in the thermochemical processing of biomass have resulted in efforts to commercialize several cellulosic biofuel pathways. Until commercial-scale production is achieved, however, techno-economic analysis is a useful methodology for quantifying the economic competitiveness of these pathways with petroleum, providing one indication of their long-term feasibility under the U.S. revised Renewable Fuel Standard. This review paper covers techno-economic analyses of thermochemical cellulosic biofuel pathways in the open literature, discusses and compares their results, and recommends the adoption of additional analytical methodologies that will increase the value of future pathway analyses.

  20. Thermochemical production of hydrogen via multistage water splitting processes

    Science.gov (United States)

    Funk, J. E.

    1975-01-01

    This paper presents and reviews the fundamental thermodynamic principles underlying thermochemical water splitting processes. The overall system is considered first and the temperature limitation in process thermal efficiency is developed. The relationship to an ideal water electrolysis cell is described and the nature of efficient multistage reaction processes is discussed. The importance of the reaction entropy change and the relation of the reaction free energy change to the work of separation is described. A procedure for analyzing thermochemical water splitting processes is presented and its use to calculate individual stage efficiency is demonstrated. A number of processes are used to illustrate the concepts and procedures.

  1. Evaluation of wastewater treatment requirements for thermochemical biomass liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, D C [Pacific Northwest Lab., Richland, WA (United States)

    1992-04-01

    Biomass can provide a substantial energy source. Liquids are preferred for use as transportation fuels because of their high energy density and handling ease and safety. Liquid fuel production from biomass can be accomplished by any of several different processes including hydrolysis and fermentation of the carbohydrates to alcohol fuels, thermal gasification and synthesis of alcohol or hydrocarbon fuels, direct extraction of biologically produced hydrocarbons such as seed oils or algae lipids, or direct thermochemical conversion of the biomass to liquids and catalytic upgrading to hydrocarbon fuels. This report discusses direct thermochemical conversion to achieve biomass liquefaction and the requirements for wastewater treatment inherent in such processing. 21 refs.

  2. An Aerosol Condensation Model for Sulfur Trioxide

    Energy Technology Data Exchange (ETDEWEB)

    Grant, K E

    2008-02-07

    This document describes a model for condensation of sulfuric acid aerosol given an initial concentration and/or source of gaseous sulfur trioxide (e.g. fuming from oleum). The model includes the thermochemical effects on aerosol condensation and air parcel buoyancy. Condensation is assumed to occur heterogeneously onto a preexisting background aerosol distribution. The model development is both a revisiting of research initially presented at the Fall 2001 American Geophysical Union Meeting [1] and a further extension to provide new capabilities for current atmospheric dispersion modeling efforts [2]. Sulfuric acid is one of the most widely used of all industrial chemicals. In 1992, world consumption of sulfuric acid was 145 million metric tons, with 42.4 Mt (mega-tons) consumed in the United States [10]. In 2001, of 37.5 Mt consumed in the U.S., 74% went into producing phosphate fertilizers [11]. Another significant use is in mining industries. Lawuyi and Fingas [7] estimate that, in 1996, 68% of use was for fertilizers and 5.8% was for mining. They note that H{sub 2}SO{sub 4} use has been and should continue to be very stable. In the United States, the elimination of MTBE (methyl tertiary-butyl ether) and the use of ethanol for gasoline production are further increasing the demand for petroleum alkylate. Alkylate producers have a choice of either a hydrofluoric acid or sulfuric acid process. Both processes are widely used today. Concerns, however, over the safety or potential regulation of hydrofluoric acid are likely to result in most of the growth being for the sulfuric acid process, further increasing demand [11]. The implication of sulfuric acid being a pervasive industrial chemical is that transport is also pervasive. Often, this is in the form of oleum tankers, having around 30% free sulfur trioxide. Although sulfuric acid itself is not a volatile substance, fuming sulfuric acid (referred to as oleum) is [7], the volatile product being sulfur trioxide

  3. Solubility of Sulfur Dioxide in Sulfuric Acid

    Science.gov (United States)

    Chang, K. K.; Compton, L. E.; Lawson, D. D.

    1982-01-01

    The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.

  4. Critical Evaluation of Thermochemical Properties of C1-C4 Species: Updated Group-Contributions to Estimate Thermochemical Properties

    Science.gov (United States)

    Burke, S. M.; Simmie, J. M.; Curran, H. J.

    2015-03-01

    A review of literature on enthalpies of formation and molar entropies for alkanes, alkenes, alcohols, hydroperoxides, and their associated radicals has been compiled and critically evaluated. By comparing literature values, the overall uncertainty in thermochemical properties of small hydrocarbons and oxygenated hydrocarbons can be highlighted. In general, there is good agreement between heat of formation values in the literature for stable species; however, there is greater uncertainty in the values for radical species and for molar entropy values. Updated values for a group-additivity method for the estimation of thermochemical properties based on the evaluated literature data are proposed. The new values can be used to estimate thermochemical data for larger, combustion-relevant species for which no calculations or measurements currently exist, with increased confidence.

  5. Assessment of thermochemical data on steel deoxidation

    Directory of Open Access Journals (Sweden)

    Gómez, P.

    2009-08-01

    Full Text Available It is proposed to develop a method to judge the certainty on the information regarding to deoxidation equilibria of iron melts. To accomplish this objective, thermochemical data was collated and then evaluated. The basic knowledge on deoxidation conditions are framed by the non-ideal Henrian behaviour of diluted solutions of both deoxidizer and oxygen in liquid iron in equilibrium with a pure oxide. Conventional deoxidation reactions were considered at 1,873 K such that in their equilibrium constants, only first order interaction coefficients were considered. The criteria in selecting the most appropriated free energy equation was based on evaluating them under two critical composition points: 1 where they satisfy an oxygen to deoxidizer ratio dictated by its stoichiometry and 2 where oxygen contents at a given amount of deoxidizer reaches a minimum value. These data were plotted on logarithmic scales to appreciate the effects of deoxidizer’s valences. Once such information was classified, under restrictions 1 and 2, previous compositions were related to deoxidizer´s electronegativities.

    El presente artículo propone desarrollar un método para juzgar la certidumbre de la información pertinente al equilibrio de desoxidación de fundidos de hierro. Para lograr este objetivo, se recolectaron y evaluaron datos termoquímicos existentes. Las teorías sobre desoxidación se describen mediante el comportamiento Henriano de soluciones diluidas del agente desoxidante y el hierro fundido en equilibrio con un óxido. En este estudio, solo se consideran reacciones convencionales a 1.873 K, de forma tal que se consideraron las constantes de equilibrio y coeficientes de interacción de primer orden. El criterio empleado para utilizar la expresión más adecuada de la energía libre se basó en evaluar dos puntos críticos: uno, donde se satisface una relación oxígeno/desoxidante dictada por la estequiometría y dos,cuando el contenido de ox

  6. SUNgas: Thermochemical Approaches to Solar Fuels

    Science.gov (United States)

    Davidson, Jane

    2013-04-01

    Solar energy offers an intelligent solution to reduce anthropogenic emissions of greenhouse gases and to meet an expanding global demand for energy. A transformative change from fossil to solar energy requires collection, storage, and transport of the earth's most abundant but diffuse and intermittent source of energy. One intriguing approach for harvest and storage of solar energy is production of clean fuels via high temperature thermochemical processes. Concentrated solar energy is the heat source and biomass or water and carbon dioxide are the feedstocks. Two routes to produce fuels using concentrated solar energy and a renewable feed stock will be discussed: gasification of biomass or other carbonaceous materials and metal oxide cycles to produce synthesis gas. The first and most near term route to solar fuels is to gasify biomass. With conventional gasification, air or oxygen is supplied at fuel-rich levels to combust some of the feedstock and in this manner generate the energy required for conversion to H2 and CO. The partial-combustion consumes up to 40% of the energetic value of the feedstock. With air combustion, the product gas is diluted by high levels of CO2 and N2. Using oxygen reduces the product dilution, but at the expense of adding an oxygen plant. Supplying the required heat with concentrated solar radiation eliminates the need for partial combustion of the biomass feedstock. As a result, the product gas has an energetic value greater than that of the feedstock and it is not contaminated by the byproducts of combustion. The second promising route to solar fuels splits water and carbon dioxide. Two-step metal-oxide redox cycles hold out great potential because they the temperature required to achieve a reasonable degree of dissociation is lower than direct thermal dissociation and O2 and the fuel are produced in separate steps. The 1^st step is the endothermic thermal dissociation of the metal oxide to the metal or lower-valence metal oxide. The 2

  7. Probabilistic thermo-chemical analysis of a pultruded composite rod

    NARCIS (Netherlands)

    Baran, Ismet; Tutum, Cem C.; Hattel, Jesper H.

    2012-01-01

    In the present study the deterministic thermo-chemical pultrusion simulation of a composite rod taken from the literature [7] is used as a validation case. The predicted centerline temperature and cure degree profiles of the rod match well with those in the literature [7]. Following the validation c

  8. Probabilistic thermo-chemical analysis of a pultruded composite rod

    DEFF Research Database (Denmark)

    Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

    2012-01-01

    In the present study the deterministic thermo-chemical pultrusion simulation of a composite rod taken from the literature [7] is used as a validation case. The predicted centerline temperature and cure degree profiles of the rod match well with those in the literature [7]. Following the validation...

  9. Thermochemical conversion of waste tyres-a review.

    Science.gov (United States)

    Labaki, Madona; Jeguirim, Mejdi

    2016-10-27

    A review of the energy recovery from waste tyres is presented and focuses on the three thermochemical processes used to valorise waste tyres: pyrolysis, gasification, and combustion/incineration. After recalling the chemical composition of tyres, the thermogravimetric behaviours of tyres or their components under different atmospheres are described. Different kinetic studies on the thermochemical processes are treated. Then, the three processes were investigated, with a particular attention given to the gasification, due to the information unavailability on this process. Pyrolysis is a thermochemical conversion to produce a hydrocarbon rich gas mixture, condensable liquids or tars, and a carbon-rich solid residue. Gasification is a form of pyrolysis, carried out at higher temperatures and under given atmosphere (air, steam, oxygen, carbon dioxide, etc.) in order to yield mainly low molecular weight gaseous products. Combustion is a process that needs a fuel and an oxidizer with an ignition system to produce heat and/or steam. The effects of various process parameters such as temperature, heating rate, residence time, catalyst addition, etc. on the energy efficiency and the products yields and characteristics are mainly reviewed. These thermochemical processes are considered to be the more attractive and practicable methods for recovering energy and material from waste tyres. For the future, they are the main promising issue to treat and valorise used tyres. However, efforts should be done in developing more efficient technical systems.

  10. Biomass Program 2007 Program Peer Review - Thermochemical Conversion Platform Summary

    Energy Technology Data Exchange (ETDEWEB)

    none,

    2009-10-27

    This document discloses the comments provided by a review panel at the U.S. Department of Energy Office of the Biomass Program Peer Review held on November 15-16, 2007 in Baltimore, MD and the Biomass Program Peer Review for the Thermochemical Platform, held on July 9th and 10th in Golden, Colorado.

  11. Thermochemically Driven Gas-Dynamic Fracturing (TDGF)

    Energy Technology Data Exchange (ETDEWEB)

    Michael Goodwin

    2008-12-31

    This report concerns efforts to increase oil well productivity and efficiency via a method of heating the oil-bearing rock of the well, a technique known as Thermochemical Gas-Dynamic Fracturing (TGDF). The technique uses either a chemical reaction or a combustion event to raise the temperature of the rock of the well, thereby increasing oil velocity, and oil pumping rate. Such technology has shown promise for future application to both older wellheads and also new sites. The need for such technologies in the oil extraction field, along with the merits of the TGDF technology is examined in Chapter 1. The theoretical basis underpinning applications of TGDF is explained in Chapter 2. It is shown that productivity of depleted well can be increased by one order of magnitude after heating a reservoir region of radius 15-20 m around the well by 100 degrees 1-2 times per year. Two variants of thermal stimulation are considered: uniform heating and optimal temperature distribution in the formation region around the perforation zone. It is demonstrated that the well productivity attained by using equal amounts of thermal energy is higher by a factor of 3 to 4 in the case of optimal temperature distribution as compared to uniform distribution. Following this theoretical basis, two practical approaches to applying TDGF are considered. Chapter 3 looks at the use of chemical intiators to raise the rock temperature in the well via an exothermic chemical reaction. The requirements for such a delivery device are discussed, and several novel fuel-oxidizing mixtures (FOM) are investigated in conditions simulating those at oil-extracting depths. Such FOM mixtures, particularly ones containing nitric acid and a chemical initiator, are shown to dramatically increase the temperature of the oil-bearing rock, and thus the productivity of the well. Such tests are substantiated by preliminary fieldwork in Russian oil fields. A second, more cost effective approach to TGDF is considered in

  12. Thermochemical processes for water splitting - status and outlook

    Energy Technology Data Exchange (ETDEWEB)

    Weirich, W.; Behr, F. (Technische Hochschule Aachen (Germany, F.R.). Lehrstuhl fuer Reaktortechnik); Knoche, K.F. (Technische Hochschule Aachen (Germany, F.R.). Lehrstuhl fuer Technische Thermodynamik und Inst. fuer Thermodynamik); Barnert, H. (Kernforschungsanlage Juelich G.m.b.H. (Germany, F.R.). Inst. fuer Reaktorentwicklung)

    1984-04-01

    In this paper we discuss the proposals for processes which have already been realised in form of bench scale units or which have been planned, as well as those which have a high degree of development potential. A part of these cycles have in common the splitting of sulfuric acids which causes corrosion problems unsolved up to now. The essential part of the metal/metal hydride-processes is a hydrogen permeable membrane which separates the hydrogen acceptor from the water containing electrolyte melt. Actually we are intending to build up a lab cycle using a TiNi-basis membrane. The metal membranes offer a number of further interesting applications, such as (1) hydrogen production from gas mixtures at high temperatures, and (2) tritium separation from the helium of the HTR primary cooling circuit. A further promising process is the hydrocarbon hybrid cycle, in which the reduction of methanol to methane and oxygen is the key reaction. Till now we can detect a methane yield of up to 50%. An interesting combined procedure for the production of hydrogen and electricity is proposed, where sulphuric acid is decomposed by means of coal. The detailed mass and energy balance shows an efficiency of up to 57%. Thermodynamic analysis for the watersplitting cycles indicates efficiencies up to 50%. Further research and development work is necessary in order to solve material problems and to demonstrate the suitability and availability of the techniques using larger scale laboratory and prototype units.

  13. Sulfuric acid on Europa and the radiolytic sulfur cycle

    Science.gov (United States)

    Carlson, R. W.; Johnson, R. E.; Anderson, M. S.

    1999-01-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  14. THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER

    Energy Technology Data Exchange (ETDEWEB)

    PROJECT STAFF

    2011-10-31

    Thermal energy storage (TES) is an integral part of a concentrated solar power (CSP) system. It enables plant operators to generate electricity beyond on sun hours and supply power to the grid to meet peak demand. Current CSP sensible heat storage systems employ molten salts as both the heat transfer fluid and the heat storage media. These systems have an upper operating temperature limit of around 400 C. Future TES systems are expected to operate at temperatures between 600 C to 1000 C for higher thermal efficiencies which should result in lower electricity cost. To meet future operating temperature and electricity cost requirements, a TES concept utilizing thermochemical cycles (TCs) based on multivalent solid oxides was proposed. The system employs a pair of reduction and oxidation (REDOX) reactions to store and release heat. In the storage step, hot air from the solar receiver is used to reduce the oxidation state of an oxide cation, e.g. Fe3+ to Fe2+. Heat energy is thus stored as chemical bonds and the oxide is charged. To discharge the stored energy, the reduced oxide is re-oxidized in air and heat is released. Air is used as both the heat transfer fluid and reactant and no storage of fluid is needed. This project investigated the engineering and economic feasibility of this proposed TES concept. The DOE storage cost and LCOE targets are $15/kWh and $0.09/kWh respectively. Sixteen pure oxide cycles were identified through thermodynamic calculations and literature information. Data showed the kinetics of re-oxidation of the various oxides to be a key barrier to implementing the proposed concept. A down selection was carried out based on operating temperature, materials costs and preliminary laboratory measurements. Cobalt oxide, manganese oxide and barium oxide were selected for developmental studies to improve their REDOX reaction kinetics. A novel approach utilizing mixed oxides to improve the REDOX kinetics of the selected oxides was proposed. It partially

  15. THERMOCHEMICAL HEAT STORAGE FOR CONCENTRATED SOLAR POWER

    Energy Technology Data Exchange (ETDEWEB)

    PROJECT STAFF

    2011-10-31

    Thermal energy storage (TES) is an integral part of a concentrated solar power (CSP) system. It enables plant operators to generate electricity beyond on sun hours and supply power to the grid to meet peak demand. Current CSP sensible heat storage systems employ molten salts as both the heat transfer fluid and the heat storage media. These systems have an upper operating temperature limit of around 400 C. Future TES systems are expected to operate at temperatures between 600 C to 1000 C for higher thermal efficiencies which should result in lower electricity cost. To meet future operating temperature and electricity cost requirements, a TES concept utilizing thermochemical cycles (TCs) based on multivalent solid oxides was proposed. The system employs a pair of reduction and oxidation (REDOX) reactions to store and release heat. In the storage step, hot air from the solar receiver is used to reduce the oxidation state of an oxide cation, e.g. Fe3+ to Fe2+. Heat energy is thus stored as chemical bonds and the oxide is charged. To discharge the stored energy, the reduced oxide is re-oxidized in air and heat is released. Air is used as both the heat transfer fluid and reactant and no storage of fluid is needed. This project investigated the engineering and economic feasibility of this proposed TES concept. The DOE storage cost and LCOE targets are $15/kWh and $0.09/kWh respectively. Sixteen pure oxide cycles were identified through thermodynamic calculations and literature information. Data showed the kinetics of re-oxidation of the various oxides to be a key barrier to implementing the proposed concept. A down selection was carried out based on operating temperature, materials costs and preliminary laboratory measurements. Cobalt oxide, manganese oxide and barium oxide were selected for developmental studies to improve their REDOX reaction kinetics. A novel approach utilizing mixed oxides to improve the REDOX kinetics of the selected oxides was proposed. It partially

  16. Geochemical signatures of thermochemical sulfate reduction in controlled hydrous pyrolysis experiments

    Science.gov (United States)

    Zhang, T.; Ellis, G.S.; Walters, C.C.; Kelemen, S.R.; Wang, K.-s.; Tang, Y.

    2008-01-01

    A series of gold tube hydrous pyrolysis experiments was conducted in order to investigate the effect of thermochemical sulfate reduction (TSR) on gas generation, residual saturated hydrocarbon compositional alteration, and solid pyrobitumen formation. The intensity of TSR significantly depends on the H2O/MgSO4 mole ratio, the smaller the ratio, the stronger the oxidizing conditions. Under highly oxidizing conditions (MgSO4/hydrocarbon wt/wt 20/1 and hydrocarbon/H2O wt/wt 1/1), large amounts of H2S and CO2 are generated indicating that hydrocarbon oxidation coupled with sulfate reduction is the dominant reaction. Starting with a mixture of C21-C35 n-alkanes, these hydrocarbons are consumed totally at temperatures below the onset of hydrocarbon thermal cracking in the absence of TSR (400 ??C). Moreover, once the longer chain length hydrocarbons are oxidized, secondarily formed hydrocarbons, even methane, are oxidized to CO2. Using whole crude oils as the starting reactants, the TSR reaction dramatically lowers the stability of hydrocarbons leading to increases in gas dryness and gas/oil ratio. While their concentrations decrease, the relative distributions of n-alkanes do not change appreciably from the original composition, and consequently, are non-diagnostic for TSR. However, distinct molecular changes related to TSR are observed, Pr/n-C17 and Ph/n-C18 ratios decrease at a faster rate under TSR compared to thermal chemical alteration (TCA) alone. TSR promotes aromatization and the incorporation of sulfur and oxygen into hydrocarbons leading to a decrease in the saturate to aromatic ratio in the residual oil and in the generation of sulfur and oxygen rich pyrobitumen. These experimental findings could provide useful geochemical signatures to identify TSR in settings where TSR has occurred in natural systems. ?? 2008 Elsevier Ltd. All rights reserved.

  17. Quantitative Thermochemical Measurements in High-Pressure Gaseous Combustion

    Science.gov (United States)

    Kojima, Jun J.; Fischer, David G.

    2012-01-01

    We present our strategic experiment and thermochemical analyses on combustion flow using a subframe burst gating (SBG) Raman spectroscopy. This unconventional laser diagnostic technique has promising ability to enhance accuracy of the quantitative scalar measurements in a point-wise single-shot fashion. In the presentation, we briefly describe an experimental methodology that generates transferable calibration standard for the routine implementation of the diagnostics in hydrocarbon flames. The diagnostic technology was applied to simultaneous measurements of temperature and chemical species in a swirl-stabilized turbulent flame with gaseous methane fuel at elevated pressure (17 atm). Statistical analyses of the space-/time-resolved thermochemical data provide insights into the nature of the mixing process and it impact on the subsequent combustion process in the model combustor.

  18. Thermochemical water decomposition. [hydrogen separation for energy applications

    Science.gov (United States)

    Funk, J. E.

    1977-01-01

    At present, nearly all of the hydrogen consumed in the world is produced by reacting hydrocarbons with water. As the supply of hydrocarbons diminishes, the problem of producing hydrogen from water alone will become increasingly important. Furthermore, producing hydrogen from water is a means of energy conversion by which thermal energy from a primary source, such as solar or nuclear fusion of fission, can be changed into an easily transportable and ecologically acceptable fuel. The attraction of thermochemical processes is that they offer the potential for converting thermal energy to hydrogen more efficiently than by water electrolysis. A thermochemical hydrogen-production process is one which requires only water as material input and mainly thermal energy, or heat, as an energy input. Attention is given to a definition of process thermal efficiency, the thermodynamics of the overall process, the single-stage process, the two-stage process, multistage processes, the work of separation and a process evaluation.

  19. TEA: A Code for Calculating Thermochemical Equilibrium Abundances

    CERN Document Server

    Blecic, Jasmina; Bowman, M Oliver

    2015-01-01

    We present an open-source Thermochemical Equilibrium Abundances (TEA) code that calculates the abundances of gaseous molecular species. The code is based on the methodology of White et al. (1958) and Eriksson (1971). It applies Gibbs free-energy minimization using an iterative, Lagrangian optimization scheme. Given elemental abundances, TEA calculates molecular abundances for a particular temperature and pressure or a list of temperature-pressure pairs. We tested the code against the method of Burrows & Sharp (1999), the free thermochemical equilibrium code CEA (Chemical Equilibrium with Applications), and the example given by White et al. (1958). Using their thermodynamic data, TEA reproduces their final abundances, but with higher precision. We also applied the TEA abundance calculations to models of several hot-Jupiter exoplanets, producing expected results. TEA is written in Python in a modular format. There is a start guide, a user manual, and a code document in addition to this theory paper. TEA is ...

  20. Thermochemical conversion of microalgal biomass into biofuels: a review.

    Science.gov (United States)

    Chen, Wei-Hsin; Lin, Bo-Jhih; Huang, Ming-Yueh; Chang, Jo-Shu

    2015-05-01

    Following first-generation and second-generation biofuels produced from food and non-food crops, respectively, algal biomass has become an important feedstock for the production of third-generation biofuels. Microalgal biomass is characterized by rapid growth and high carbon fixing efficiency when they grow. On account of potential of mass production and greenhouse gas uptake, microalgae are promising feedstocks for biofuels development. Thermochemical conversion is an effective process for biofuel production from biomass. The technology mainly includes torrefaction, liquefaction, pyrolysis, and gasification. Through these conversion technologies, solid, liquid, and gaseous biofuels are produced from microalgae for heat and power generation. The liquid bio-oils can further be upgraded for chemicals, while the synthesis gas can be synthesized into liquid fuels. This paper aims to provide a state-of-the-art review of the thermochemical conversion technologies of microalgal biomass into fuels. Detailed conversion processes and their outcome are also addressed.

  1. Thermochemical structure of the Earth's mantle and continental crust

    DEFF Research Database (Denmark)

    Guerri, Mattia

    A detailed knowledge of the Earth's thermal structure and chemical composition is fundamental in order to understand the processes driving the planet ormation and evolution. The inaccessibility of most of the Earth's interior makes the determination of its thermo-chemical conditions a challenging...... in determining crustal seismic discontinuities. In the second chapter, I deal about the possibility to disentangle the dynamic and isostatic contribution in shaping the Earth's surface topography. Dynamic topography is directly linked to mantle convection driven by mantle thermo-chemical anomalies, and can...... argue therefore that our understandings of the lithosphere density structure, needed to determine the isostatic topography, and of the mantle density and viscosity, required to compute the dynamic topography, are still too limited to allow a robust determination of mantle convection effects on the Earth...

  2. Observations of Circumstellar Thermochemical Equilibrium: The Case of Phosphorus

    Science.gov (United States)

    Milam, Stefanie N.; Charnley, Steven B.

    2011-01-01

    We will present observations of phosphorus-bearing species in circumstellar envelopes, including carbon- and oxygen-rich shells 1. New models of thermochemical equilibrium chemistry have been developed to interpret, and constrained by these data. These calculations will also be presented and compared to the numerous P-bearing species already observed in evolved stars. Predictions for other viable species will be made for observations with Herschel and ALMA.

  3. Thermochemical data for CVD modeling from ab initio calculations

    Energy Technology Data Exchange (ETDEWEB)

    Ho, P. [Sandia National Labs., Albuquerque, NM (United States); Melius, C.F. [Sandia National Labs., Livermore, CA (United States)

    1993-12-31

    Ab initio electronic-structure calculations are combined with empirical bond-additivity corrections to yield thermochemical properties of gas-phase molecules. A self-consistent set of heats of formation for molecules in the Si-H, Si-H-Cl, Si-H-F, Si-N-H and Si-N-H-F systems is presented, along with preliminary values for some Si-O-C-H species.

  4. Hydrogen peroxide thermochemical oscillator as driver for primordial RNA replication.

    Science.gov (United States)

    Ball, Rowena; Brindley, John

    2014-06-06

    This paper presents and tests a previously unrecognized mechanism for driving a replicating molecular system on the prebiotic earth. It is proposed that cell-free RNA replication in the primordial soup may have been driven by self-sustained oscillatory thermochemical reactions. To test this hypothesis, a well-characterized hydrogen peroxide oscillator was chosen as the driver and complementary RNA strands with known association and melting kinetics were used as the substrate. An open flow system model for the self-consistent, coupled evolution of the temperature and concentrations in a simple autocatalytic scheme is solved numerically, and it is shown that thermochemical cycling drives replication of the RNA strands. For the (justifiably realistic) values of parameters chosen for the simulated example system, the mean amount of replicant produced at steady state is 6.56 times the input amount, given a constant supply of substrate species. The spontaneous onset of sustained thermochemical oscillations via slowly drifting parameters is demonstrated, and a scheme is given for prebiotic production of complementary RNA strands on rock surfaces.

  5. PUMP DESIGN AND COMPUTATIONAL FLUID DYNAMIC ANALYSIS FOR HIGH TEMPERATURE SULFURIC ACID TRANSFER SYSTEM

    Directory of Open Access Journals (Sweden)

    JUNG-SIK CHOI

    2014-06-01

    Full Text Available In this study, we proposed a newly designed sulfuric acid transfer system for the sulfur-iodine (SI thermochemical cycle. The proposed sulfuric acid transfer system was evaluated using a computational fluid dynamics (CFD analysis for investigating thermodynamic/hydrodynamic characteristics and material properties. This analysis was conducted to obtain reliable continuous operation parameters; in particular, a thermal analysis was performed on the bellows box and bellows at amplitudes and various frequencies (0.1, 0.5, and 1.0 Hz. However, the high temperatures and strongly corrosive operating conditions of the current sulfuric acid system present challenges with respect to the structural materials of the transfer system. To resolve this issue, we designed a novel transfer system using polytetrafluoroethylene (PTFE, Teflon® as a bellows material for the transfer of sulfuric acid. We also carried out a CFD analysis of the design. The CFD results indicated that the maximum applicable temperature of PTFE is about 533 K (260 °C, even though its melting point is around 600 K. This result implies that the PTFE is a potential material for the sulfuric acid transfer system. The CFD simulations also confirmed that the sulfuric acid transfer system was designed properly for this particular investigation.

  6. Vertically Discontinuous Seismic Signatures From Continuous Thermochemical Plumes

    Science.gov (United States)

    Harris, A. C.; Kincaid, C.; Savage, B.

    2008-12-01

    To interpret seismic signatures associated with mantle upwellings, we must understand the distribution of thermochemical heterogeneities within mantle plumes. Thermochemical heterogeneities are expected to arise within plumes by the incorporation of subducted lithosphere (Eclogite and Harzburgite) that has reached the plume source region (thermal boundary layers in the mantle). We analyze laboratory experiments in conjunction with seismic velocity models to predict the seismic signature of thermochemical plumes. Laboratory experiments are fully three-dimensional and use glucose syrup (Rayleigh number: 106) to model the mantle and a two-layer subducted lithosphere, where composition (viscosity and density) is controlled by water content. Experiments show heterogeneous upwellings with variations in both temperature and composition that are more complex than predicted in previous plume models. Spatial distributions for temperature and composition in representative, repeatable types of thermochemical upwellings are tracked through time, scaled to mantle values and used to calculate predicted seismic velocities. Apparent seismic velocity signals are estimated for patterns in thermochemical heterogeneity with length scales ranging from 1 to 300 km and excess temperatures from 50 to 300°C. Results show that if plumes are purely thermal they can be identified in the usual way, by slow velocities. However, if plumes are a mixture of compositions, as predicted by laboratory models, their velocity structure is more complex. An Ecolgite lens within a plume at ~300km depth with an excess temperature of 250°C can have the same velocity as regular mantle with no excess temperature. A Harzburgite lobe of a plume head (up to half of the plume volume) at 300km depth with an excess temperature of 225°C can have the same Vs as regular mantle with no excess temperature, but can only mask up to 55°C in Vp. Spatial variations in temperature control velocity structure above 300km

  7. System and process for producing fuel with a methane thermochemical cycle

    Energy Technology Data Exchange (ETDEWEB)

    Diver, Richard B.

    2015-12-15

    A thermochemical process and system for producing fuel are provided. The thermochemical process includes reducing an oxygenated-hydrocarbon to form an alkane and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. Another thermochemical process includes reducing a metal oxide to form a reduced metal oxide, reducing an oxygenated-hydrocarbon with the reduced metal oxide to form an alkane, and using the alkane in a reforming reaction as a reducing agent for water, a reducing agent for carbon dioxide, or a combination thereof. The system includes a reformer configured to perform a thermochemical process.

  8. ADVANCED SULFUR CONTROL CONCEPTS

    Energy Technology Data Exchange (ETDEWEB)

    Apostolos A. Nikolopoulos; Santosh K. Gangwal; William J. McMichael; Jeffrey W. Portzer

    2003-01-01

    Conventional sulfur removal in integrated gasification combined cycle (IGCC) power plants involves numerous steps: COS (carbonyl sulfide) hydrolysis, amine scrubbing/regeneration, Claus process, and tail-gas treatment. Advanced sulfur removal in IGCC systems involves typically the use of zinc oxide-based sorbents. The sulfides sorbent is regenerated using dilute air to produce a dilute SO{sub 2} (sulfur dioxide) tail gas. Under previous contracts the highly effective first generation Direct Sulfur Recovery Process (DSRP) for catalytic reduction of this SO{sub 2} tail gas to elemental sulfur was developed. This process is currently undergoing field-testing. In this project, advanced concepts were evaluated to reduce the number of unit operations in sulfur removal and recovery. Substantial effort was directed towards developing sorbents that could be directly regenerated to elemental sulfur in an Advanced Hot Gas Process (AHGP). Development of this process has been described in detail in Appendices A-F. RTI began the development of the Single-step Sulfur Recovery Process (SSRP) to eliminate the use of sorbents and multiple reactors in sulfur removal and recovery. This process showed promising preliminary results and thus further process development of AHGP was abandoned in favor of SSRP. The SSRP is a direct Claus process that consists of injecting SO{sub 2} directly into the quenched coal gas from a coal gasifier, and reacting the H{sub 2}S-SO{sub 2} mixture over a selective catalyst to both remove and recover sulfur in a single step. The process is conducted at gasifier pressure and 125 to 160 C. The proposed commercial embodiment of the SSRP involves a liquid phase of molten sulfur with dispersed catalyst in a slurry bubble-column reactor (SBCR).

  9. Atmospheric Chemistry in Giant Planets, Brown Dwarfs, and Low-Mass Dwarf Stars II. Sulfur and Phosphorus

    CERN Document Server

    Visscher, C

    2005-01-01

    We use thermochemical equilibrium and kinetic calculations to model sulfur and phosphorus chemistry in the atmospheres of giant planets, brown dwarfs, low-mass stars, and extrasolar giant planets (EGPs). The chemical behavior of individual S- and P-bearing gases and condensates is determined as a function of pressure, temperature, and metallicity. Our results are independent of any particular model atmosphere and the behavior of different gases can be used to constrain atmospheric structure and metallicity. Hydrogen sulfide is the dominant sulfur gas in substellar atmospheres and approximately represents the atmospheric sulfur inventory. Depending on the prevailing S and C chemistry, the abundance of minor sulfur gases may constrain atmospheric temperatures or metallicity. Disequilibrium abundances of PH3 are expected in the observable atmospheres of substellar objects, and PH3 is representative of the total P abundance in giant planets and T dwarfs. A number of other phosphorus gases become relatively abunda...

  10. Sulfur recovery further improved

    Energy Technology Data Exchange (ETDEWEB)

    Borsboom, J.; Grinsven, M. van; Warners, A. van [Jacobs Nederland B.V., (Netherlands); Nisselrooy, P. van [Gastec N.V., (Netherlands)

    2002-04-01

    The original 100-year-old Claus process for producing sulfur from hydrogen sulfide in acid gas is described together with improvements which have been made over the years. The most recent modification, EUROCLAUS, achieves sulfur recoveries of 99-99.9 per cent. Five commercial units are being designed.

  11. Nanostructured sulfur cathodes

    KAUST Repository

    Yang, Yuan

    2013-01-01

    Rechargeable Li/S batteries have attracted significant attention lately due to their high specific energy and low cost. They are promising candidates for applications, including portable electronics, electric vehicles and grid-level energy storage. However, poor cycle life and low power capability are major technical obstacles. Various nanostructured sulfur cathodes have been developed to address these issues, as they provide greater resistance to pulverization, faster reaction kinetics and better trapping of soluble polysulfides. In this review, recent developments on nanostructured sulfur cathodes and mechanisms behind their operation are presented and discussed. Moreover, progress on novel characterization of sulfur cathodes is also summarized, as it has deepened the understanding of sulfur cathodes and will guide further rational design of sulfur electrodes. © 2013 The Royal Society of Chemistry.

  12. The world-class Howard's Pass SEDEX Zn-Pb district, Selwyn Basin, Yukon. Part II: the roles of thermochemical and bacterial sulfate reduction in metal fixation

    Science.gov (United States)

    Gadd, Michael G.; Layton-Matthews, Daniel; Peter, Jan M.; Paradis, Suzanne; Jonasson, Ian R.

    2017-03-01

    The Howard's Pass district of sedimentary exhalative (SEDEX) Zn-Pb deposits is located in Yukon Territory and comprises 14 Zn-Pb deposits that contain an estimated 400.7 Mt of sulfide mineralization grading 4.5 % Zn and 1.5 % Pb. Mineralization is hosted in carbonaceous and calcareous and, to a lesser extent, siliceous mudstones. Pyrite is a minor but ubiquitous mineral in the host rocks stratigraphically above, within, and below mineralization. Petrographic analyses reveal that pyrite has a complex and protracted growth history, preserving multiple generations of pyrite within single grains. Sulfur isotope analysis of paragenetically complex pyrite by secondary ion mass spectrometry (SIMS) reveals that sulfur isotope compositions vary with textural zonation. Within the Zn-Pb deposits, framboidal pyrite is the earliest pyrite generation recognized, and this exclusively has negative δ34S values (mean = -16.6 ± 4.1 ‰; n = 55), whereas paragenetically later pyrite and galena possess positive δ34S values (mean = 29.1 ± 7.5 and 22.4 ± 3.0 ‰, n = 13 and 13, respectively). Previous studies found that sphalerite and galena mineral separates have exclusively positive δ34S values (mean = 16.8 ± 3.3 and 12.7 ± 2.8 ‰, respectively; Goodfellow and Jonasson 1986). These distinct sulfur isotope values are interpreted to reflect varying contributions of bacterially reduced seawater sulfate (negative; framboidal pyrite) and thermochemically reduced seawater sulfate and/or hydrothermal sulfate (positive; galena, sphalerite, later forms of pyrite). Textural evidence indicates that framboidal pyrite predates galena and sphalerite deposition. Collectively, the in situ and bulk sulfur isotope data are much more complex than δ34S values permitted by prevailing genetic models that invoke only biogenically reduced sulfur and coeval deposition of galena, sphalerite, and framboidal pyrite within a euxinic water column, and we present several lines of evidence that argue

  13. The world-class Howard's Pass SEDEX Zn-Pb district, Selwyn Basin, Yukon. Part II: the roles of thermochemical and bacterial sulfate reduction in metal fixation

    Science.gov (United States)

    Gadd, Michael G.; Layton-Matthews, Daniel; Peter, Jan M.; Paradis, Suzanne; Jonasson, Ian R.

    2016-07-01

    The Howard's Pass district of sedimentary exhalative (SEDEX) Zn-Pb deposits is located in Yukon Territory and comprises 14 Zn-Pb deposits that contain an estimated 400.7 Mt of sulfide mineralization grading 4.5 % Zn and 1.5 % Pb. Mineralization is hosted in carbonaceous and calcareous and, to a lesser extent, siliceous mudstones. Pyrite is a minor but ubiquitous mineral in the host rocks stratigraphically above, within, and below mineralization. Petrographic analyses reveal that pyrite has a complex and protracted growth history, preserving multiple generations of pyrite within single grains. Sulfur isotope analysis of paragenetically complex pyrite by secondary ion mass spectrometry (SIMS) reveals that sulfur isotope compositions vary with textural zonation. Within the Zn-Pb deposits, framboidal pyrite is the earliest pyrite generation recognized, and this exclusively has negative δ34S values (mean = -16.6 ± 4.1 ‰; n = 55), whereas paragenetically later pyrite and galena possess positive δ34S values (mean = 29.1 ± 7.5 and 22.4 ± 3.0 ‰, n = 13 and 13, respectively). Previous studies found that sphalerite and galena mineral separates have exclusively positive δ34S values (mean = 16.8 ± 3.3 and 12.7 ± 2.8 ‰, respectively; Goodfellow and Jonasson 1986). These distinct sulfur isotope values are interpreted to reflect varying contributions of bacterially reduced seawater sulfate (negative; framboidal pyrite) and thermochemically reduced seawater sulfate and/or hydrothermal sulfate (positive; galena, sphalerite, later forms of pyrite). Textural evidence indicates that framboidal pyrite predates galena and sphalerite deposition. Collectively, the in situ and bulk sulfur isotope data are much more complex than δ34S values permitted by prevailing genetic models that invoke only biogenically reduced sulfur and coeval deposition of galena, sphalerite, and framboidal pyrite within a euxinic water column, and we present several lines of evidence that argue

  14. Advanced Electrochemical Technologies for Hydrogen Production by Alternative Thermochemical Cycles

    Energy Technology Data Exchange (ETDEWEB)

    Lvov, Serguei; Chung, Mike; Fedkin, Mark; Lewis, Michele; Balashov, Victor; Chalkova, Elena; Akinfiev, Nikolay; Stork, Carol; Davis, Thomas; Gadala-Maria, Francis; Stanford, Thomas; Weidner, John; Law, Victor; Prindle, John

    2011-01-06

    Hydrogen fuel is a potentially major solution to the problem of climate change, as well as addressing urban air pollution issues. But a key future challenge for hydrogen as a clean energy carrier is a sustainable, low-cost method of producing it in large capacities. Most of the world's hydrogen is currently derived from fossil fuels through some type of reforming processes. Nuclear hydrogen production is an emerging and promising alternative to the reforming processes for carbon-free hydrogen production in the future. This report presents the main results of a research program carried out by a NERI Consortium, which consisted of Penn State University (PSU) (lead), University of South Carolina (USC), Tulane University (TU), and Argonne National Laboratory (ANL). Thermochemical water decomposition is an emerging technology for large-scale production of hydrogen. Typically using two or more intermediate compounds, a sequence of chemical and physical processes split water into hydrogen and oxygen, without releasing any pollutants externally to the atmosphere. These intermediate compounds are recycled internally within a closed loop. While previous studies have identified over 200 possible thermochemical cycles, only a few have progressed beyond theoretical calculations to working experimental demonstrations that establish scientific and practical feasibility of the thermochemical processes. The Cu-Cl cycle has a significant advantage over other cycles due to lower temperature requirements – around 530 °C and below. As a result, it can be eventually linked with the Generation IV thermal power stations. Advantages of the Cu-Cl cycle over others include lower operating temperatures, ability to utilize low-grade waste heat to improve energy efficiency, and potentially lower cost materials. Another significant advantage is a relatively low voltage required for the electrochemical step (thus low electricity input). Other advantages include common chemical agents and

  15. New applications with time-dependent thermochemical simulation

    Energy Technology Data Exchange (ETDEWEB)

    Koukkari, P. [VTT Chemical Technology, Espoo (Finland); Laukkanen, L. [VTT Automation, Espoo (Finland); Penttilae, K. [Kemira Engineering Oy, Helsinki (Finland)

    1996-12-31

    A new method (RATEMIX) to calculate multicomponent chemical reaction mixtures as a series of sequential thermochemical states was recently introduced. The procedure combines multicomponent thermodynamics with chemical kinetics and may be used to simulate the multicomponent reactors as a thermochemical natural process. The method combines the desired reaction rates sequentially with constrained Gibbs energy minimization. The reactant concentrations are determined by the experimental (Arrhenius) rate laws. During the course of the given reaction the subsequent side reactions are supposed to occur reversibly. At every sequential stage of the given reaction the temperature and composition of the reaction mixture are calculated by a thermodynamic subroutine, which minimizes the Gibbs energy of the system and takes into account the heat transfer between the system and its surroundings. The extents of reaction are included as algorithmic constraints in the Gibbs energy minimization procedure. Initially, the reactants are introduced to the system as inert copies to match both the mass and energy balance of the reactive system. During the calculation the copies are sequentially interchanged to the actual reactants which allows one to simulate the time-dependent reaction route by using the thermochemical procedure. For each intermediate stage, the temperature and composition are calculated and as well numerical estimates of the thermodynamic functions are obtained. The method is applicable in processes where the core thermodynamic and kinetic data of the system are known and the time-dependent heat transfer data can either be measured or estimated by calculation. The method has been used to simulate e.g. high temperature flame reactions, zinc vapour oxidation and a counter-current rotary drum with chemical reactions. The procedure has today been tested with SOLGASMIX, CHEMSAGE and HSC programs. (author)

  16. Thermochemical heat storage. State-of-the-art report

    Energy Technology Data Exchange (ETDEWEB)

    Oelert, G.; Behret, H.; Friedel, W.; Hennemann, B.; Hodgett, D.; Purper, G.; Nelson, B.; Westermark, M.

    1982-01-01

    In practically all areas of energy conservation R and D (solar, waste heat, heat pumps, production processes) the storage of energy has been identified as a critical requirement in the optimization of systems. The energy storage densities theoretically achievable in thermochemical storage are much higher than those of sensible or latent heat storage and furthermore, thermochemical heat storage (TCHS), in contrast to the two former techniques, has been considered in the past to be theoretically free of heat losses. This project was designed to: characterize the major areas of possible TCHS use in Sweden; analyze the state of TCHS development worldwide; assess the prospects of TCHS in Sweden; and identify TCHS R and D needs as complementary efforts within energy conservation development. The approach, background, and the chemical, technical and social/economical investigations as well as the overall assessment of TCHS technology and the R and D recommendations are compiled in this report. The result of the study shows that the economy for long term thermochemical heat storage is not very favorable. However, this is true for any long term storage under the assumption that oil will be available at a reasonable price even at the end of this century. If by then oil is not available at all for heating of buildings, it is important to know what other systems can possibly be used. An important conclusion of the study is that practical design problems have often been underestimated. It is also clear that it could still be worthwhile to continue work on some systems.

  17. Estimating Equivalency of Explosives Through A Thermochemical Approach

    Energy Technology Data Exchange (ETDEWEB)

    Maienschein, J L

    2002-07-08

    The Cheetah thermochemical computer code provides an accurate method for estimating the TNT equivalency of any explosive, evaluated either with respect to peak pressure or the quasi-static pressure at long time in a confined volume. Cheetah calculates the detonation energy and heat of combustion for virtually any explosive (pure or formulation). Comparing the detonation energy for an explosive with that of TNT allows estimation of the TNT equivalency with respect to peak pressure, while comparison of the heat of combustion allows estimation of TNT equivalency with respect to quasi-static pressure. We discuss the methodology, present results for many explosives, and show comparisons with equivalency data from other sources.

  18. Non-equilibrium thermochemical heat storage in porous media

    DEFF Research Database (Denmark)

    Nagel, T.; Shao, H.; Singh, Ashok

    2013-01-01

    Thermochemical energy storage can play an important role in the establishment of a reliable renewable energy supply and can increase the efficiency of industrial processes. The application of directly permeated reactive beds leads to strongly coupled mass and heat transport processes that also...... compressible gas flow through a porous solid is presented along with its finite element implementation where solid-gas reactions occur and both phases have individual temperature fields. The model is embedded in the Theory of Porous Media and the derivation is based on the evaluation of the Clausius...

  19. High Efficiency Solar Thermochemical Reactor for Hydrogen Production.

    Energy Technology Data Exchange (ETDEWEB)

    McDaniel, Anthony H. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2017-09-30

    This research and development project is focused on the advancement of a technology that produces hydrogen at a cost that is competitive with fossil-based fuels for transportation. A twostep, solar-driven WS thermochemical cycle is theoretically capable of achieving an STH conversion ratio that exceeds the DOE target of 26% at a scale large enough to support an industrialized economy [1]. The challenge is to transition this technology from the laboratory to the marketplace and produce hydrogen at a cost that meets or exceeds DOE targets.

  20. Effects of thermo-chemical pre-treatment on anaerobic biodegradability and hydrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Fernandes, T.; Klaasse Bos, G.J.; Zeeman, G.; Sanders, J.P.M.; Lier, van J.B.

    2009-01-01

    The effects of different thermo-chemical pre-treatment methods were determined on the biodegradability and hydrolysis rate of lignocellulosic biomass. Three plant species, hay, straw and bracken were thermo-chemically pre-treated with calcium hydroxide, ammonium carbonate and maleic acid. After pre-

  1. Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment

    Science.gov (United States)

    Shishir P. S. Chundawat; Bryon S. Donohoe; Leonardo da Costa Sousa; Thomas Elder; Umesh P. Agarwal; Fachuang Lu; John Ralph; Michael E. Himmel; Venkatesh Balan; Bruce E. Dale

    2011-01-01

    Deconstruction of lignocellulosic plant cell walls to fermentable sugars by thermochemical and/or biological means is impeded by several poorly understood ultrastructural and chemical barriers. A promising thermochemical pretreatment called ammonia fiber expansion (AFEX) overcomes the native recalcitrance of cell walls through subtle morphological and physicochemical...

  2. Effect of thermal, chemical and thermo-chemical pre-treatments to enhance methane production

    DEFF Research Database (Denmark)

    Rafique, Rashad; Poulsen, Tjalfe; Nizami, Abdul-Sattar

    2010-01-01

    -treatments: thermal, thermo-chemical and chemical pre-treatments on the biogas and methane potential of dewatered pig manure. A laboratory scale batch digester is used for these pre-treatments at different temperature range (25 degrees C-150 degrees C). Results showed that thermo-chemical pretreatment has high effect...

  3. Effects of thermo-chemical pre-treatment on anaerobic biodegradability and hydrolysis of lignocellulosic biomass

    NARCIS (Netherlands)

    Fernandes, T.; Klaasse Bos, G.J.; Zeeman, G.; Sanders, J.P.M.; Lier, van J.B.

    2009-01-01

    The effects of different thermo-chemical pre-treatment methods were determined on the biodegradability and hydrolysis rate of lignocellulosic biomass. Three plant species, hay, straw and bracken were thermo-chemically pre-treated with calcium hydroxide, ammonium carbonate and maleic acid. After

  4. Low temperature thermochemical treatment of stainless steel; bridging from science to technology

    DEFF Research Database (Denmark)

    Christiansen, Thomas; Hummelshøj, Thomas Strabo; Somers, Marcel A. J.

    2010-01-01

    The present contribution gives an overview of some of the fundamental scientific aspects of low temperature thermochemical treatment of stainless steel, in particular the characterisation of socalled expanded austenite is addressed. Selected technological examples of thermochemical treatment...... of stainless steel are presented....

  5. Sulfuric Acid on Europa

    Science.gov (United States)

    1999-01-01

    Frozen sulfuric acid on Jupiter's moon Europa is depicted in this image produced from data gathered by NASA's Galileo spacecraft. The brightest areas, where the yellow is most intense, represent regions of high frozen sulfuric acid concentration. Sulfuric acid is found in battery acid and in Earth's acid rain. This image is based on data gathered by Galileo's near infrared mapping spectrometer.Europa's leading hemisphere is toward the bottom right, and there are enhanced concentrations of sulfuric acid in the trailing side of Europa (the upper left side of the image). This is the face of Europa that is struck by sulfur ions coming from Jupiter's innermost moon, Io. The long, narrow features that crisscross Europa also show sulfuric acid that may be from sulfurous material extruded in cracks. Galileo, launched in 1989, has been orbiting Jupiter and its moons since December 1995. JPL manages the Galileo mission for NASA's Office of Space Science, Washington DC. JPL is a division of the California Institute of Technology, Pasadena, CA.

  6. Cytoplasmic sulfur trafficking in sulfur-oxidizing prokaryotes.

    Science.gov (United States)

    Dahl, Christiane

    2015-04-01

    Persulfide groups are chemically versatile and participate in a wide array of biochemical pathways. Although it is well documented that persulfurated proteins supply a number of important and elaborate biosynthetic pathways with sulfane sulfur, it is far less acknowledged that the enzymatic generation of persulfidic sulfur, the successive transfer of sulfur as a persulfide between multiple proteins, and the oxidation of sulfane sulfur in protein-bound form are also essential steps during dissimilatory sulfur oxidation in bacteria and archaea. Here, the currently available information on sulfur trafficking in sulfur oxidizing prokaryotes is reviewed, and the idea is discussed that sulfur is always presented to cytoplasmic oxidizing enzymes in a protein-bound form, thus preventing the occurrence of free sulfide inside of the prokaryotic cell. Thus, sulfur trafficking emerges as a central element in sulfur-oxidizing pathways, and TusA homologous proteins appear to be central and common elements in these processes.

  7. Inorganic Polymer Nanocomposite Cathode for Long Cycle Life Lithium - Sulfur Batteries Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Physical Sciences Inc. (PSI) proposes to develop a hybrid composite structure of molybdenum disulfide (MoS2) with a class of polysulfide for lithium-sulfur...

  8. Bibliographic Review about Solar Hydrogen Production Through Thermochemical Cycles; Revision Bibliografica sobre la Produccion de Hidrogeno Solar Mediante Ciclos Termoquimicos

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez Saavedra, R.

    2007-12-28

    This report presents a summary of the different thermical processes used to obtain hydrogen through solar energy, paying more attention to the production of hydrogen from water through thermochemical cycles. In this aspect, it is briefly described the most interesting thermochemical cycles, focusing on thermochemical cycles based on oxides. (Author) 25 refs.

  9. Bibliographic Review about Solar Hydrogen Production Through Thermochemical Cycles; Revision Bibliografica sobre la Produccion de Hidrogeno Solar Mediante Ciclos Termoquimicos

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez Saavedra, R.

    2008-08-06

    This report presents a summary of the different thermical processes used to obtain hydrogen through solar energy, paying more attention to the production of hydrogen from water through thermochemical cycles. In this aspect, it is briefly y described the most interesting thermochemical cycles, focusing on thermochemical cycles based on oxides. (Author) 25 refs.

  10. Thermochemical processes for hydrogen production by water decomposition. Progress report, April 1--December 31, 1975

    Energy Technology Data Exchange (ETDEWEB)

    Perlmutter, D.D.; Myers, A.L.

    1975-12-01

    The interest in hydrogen as a chemical feedstock and as a possible non-polluting fuel has continued to be high, affected by recent estimates of 1980 prices for imported natural gas in the range of $3.00/MM Btu. Our exhaustive survey of multi-step thermochemical and hybrid cycles concluded that the most promising prospects to date are (1) a modification of Abraham's ANL-4 cycle, and (2) the Rohm and Haas multi-reaction, single reactor cycle. Both sequences utilize iodine-based oxidation-reduction chemistry and each ultimately produces hydrogen via an iodide vapor decomposition, in the first case from NH/sub 4/I, in the second from HI. Process feasibility depends on demonstration of separation steps of relatively low energy requirements. Further research is proposed along four lines: (1) modeling and computation focusing on selectivity in gas-solid reactions, (2) experimental studies of solids flow and mixing, as well as mass transfer and chemical reaction in rotating and/or oscillating kiln reactors, (3) kinetics of the crucial reactions in the ANL-4 and Rohm and Haas cycles, and gas separations associated with these processes, and (4) flow sheet evaluations and preliminary economics.

  11. Thermochemical Modeling of the Uranium-Cerium-Oxygen System

    Energy Technology Data Exchange (ETDEWEB)

    Voit, Stewart L [ORNL; Besmann, Theodore M [ORNL

    2010-10-01

    The objective of the Fuel Cycle R&D Program, Advanced Fuels campaign is to provide the research and development necessary to develop low loss, high quality nuclear fuels for ultra-high burnup reactor operation. Primary work in this area will be focused on the ceramic and metallic fuel systems. The goal of the current work is to enhance the understanding of ceramic nuclear fuel thermochemistry to support fuel research and development efforts. The thermochemical behavior of oxide nuclear fuel under irradiation is dependent on the oxygen to metal ratio (O:M). In fluorite-structured fuel, the actinide metal cation is bonded with {approx}2 oxygen atoms on a crystal lattice and as the metal atoms fission, fission fragments and free oxygen are created. The resulting fission fragments will contain some oxide forming elements, however these are insufficient to bind to all the liberated oxygen and therefore, there is an average increase in O:M with fuel burnup. Some of the fission products also form species that will migrate to and react with the cladding surface in a phenomenon known as Fuel Clad Chemical Interaction (FCCI). Cladding corrosion is life-limiting so it is desirable to understand influencing factors, such as oxide thermochemistry, which can be used to guide the design and fabrication of higher burn up fuel. A phased oxide fuel thermochemical model development effort is underway within the Advanced Fuels Campaign. First models of binary oxide systems are developed. For nuclear fuel system this means U-O and transuranic systems such as Pu-O, Np-O and Am-O. Next, the binary systems will be combined to form pseudobinary systems such as U-Pu-O, etc. The model development effort requires the use of data to allow optimization based on known thermochemical parameters as a function of composition and temperature. Available data is mined from the literature and supplemented by experimental work as needed. Due to the difficulty of performing fuel fabrication development

  12. Aircraft exhaust sulfur emissions

    Energy Technology Data Exchange (ETDEWEB)

    Brown, R.C.; Anderson, M.R.; Miake-Lye, R.C.; Kolb, C.E. [Aerodyne Research, Inc., Billerica, MA (United States). Center for Chemical and Environmental Physics; Sorokin, A.A.; Buriko, Y.I. [Scientific Research Center `Ecolen`, Moscow (Russian Federation)

    1997-12-31

    The extent to which fuel sulfur is converted to SO{sub 3} during combustion and the subsequent turbine flow in supersonic and subsonic aircraft engines is estimated numerically. The analysis is based on: a flamelet model with non-equilibrium sulfur chemistry for the combustor, and a one-dimensional, two-stream model with finite rate chemical kinetics for the turbine. The results indicate that between 2% and 10% of the fuel sulfur is emitted as SO{sub 3}. It is also shown that, for a high fuel sulfur mass loading, conversion in the turbine is limited by the level of atomic oxygen at the combustor exit, leading to higher SO{sub 2} oxidation efficiency at lower fuel sulfur loadings. While SO{sub 2} and SO{sub 3} are the primary oxidation products, the model results further indicate H{sub 2}SO{sub 4} levels on the order of 0.1 ppm for supersonic expansions through a divergent nozzle. This source of fully oxidized S(6) (SO{sub 3} + H{sub 2}SO{sub 4}) exceeds previously calculated S(6) levels due to oxidation of SO{sub 2} by OH in the exhaust plume outside the engine nozzle. (author) 26 refs.

  13. The Role of Nitrogen and Sulfur Interaction in Maize Quality(Zea mays L. )

    Institute of Scientific and Technical Information of China (English)

    XIE Rui-zhi; DONG Shu-ting; HU Chang-hao; WANG Kong-jun

    2003-01-01

    Two hybrids of maize with different responses to sulfur were used in the pool experiment. Theeffects of nitrogen and sulfur on the grain quality of maize were evaluated. The results indicated that grainquality changed with the nutrition supply. The contents of proteins, amino acids, soluble sugar, crude fat,But the effects of nitrogen and sulfur were not the same. Nitrogen increased starch content of the grain, but Sdecreased the content. Both N and S enhanced the proportion of amylopectin in starch. Sulfur nutrition signif-icantly improved the grain quality of maize when a large amount of nitrogen was used together. Both hybridshad similar response to N and S treatments.

  14. Interaction of stress and phase transformations during thermochemical surface engineering

    DEFF Research Database (Denmark)

    Jespersen, Freja Nygaard

    Low temperature nitriding of austenitic stainless steel causes a surface zone of expanded austenite, which improves the wear resistance of the stainless steel while preserving the stainless behavior. During nitriding huge residual stresses are introduced in the treated zone, arising from the volume...... expansion that accompanies the dissolution of high nitrogen contents in expanded austenite. An intriguing phenomenon during low-temperature nitriding, is that the residual stresses evoked by dissolution of nitrogen in the solid state, affect the thermodynamics and the diffusion kinetics of nitrogen...... dissolution. The present project is devoted to understanding the mutual interaction of stresses and phase transformations during thermochemical surface engineering by combining numerical modelling with experimental materials science. The modelling was done by combining solid mechanics with thermodynamics...

  15. Thermo-Chemical Convection in Europa's Icy Shell with Salinity

    Science.gov (United States)

    Han, L.; Showman, A. P.

    2005-01-01

    Europa's icy surface displays numerous pits, uplifts, and chaos terrains that have been suggested to result from solid-state thermal convection in the ice shell, perhaps aided by partial melting. However, numerical simulations of thermal convection show that plumes have insufficient buoyancy to produce surface deformation. Here we present numerical simulations of thermochemical convection to test the hypothesis that convection with salinity can produce Europa's pits and domes. Our simulations show that domes (200-300 m) and pits (300-400 m) comparable to the observations can be produced in an ice shell of 15 km thick with 5-10% compositional density variation if the maximum viscosity is less than 10(exp 18) Pa sec. Additional information is included in the original extended abstract.

  16. Characteristics of thermochemical treated EN10090 X50 steel

    Energy Technology Data Exchange (ETDEWEB)

    Schmitz, S.; Graf, K.; Scheid, A., E-mail: scheid@ufpr.br [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil); Moreno, A. [SDS Plasma, Sao Jose dos Pinhais, PR (Brazil)

    2014-07-01

    EN10090 X50 steel is commonly used for engine valves to withstand severe operation conditions involving high temperature and corrosion from fuel and combustion gas. Usually, to enhance wear performance, valves undergo nitriding thermochemical treatment by salt baths. The aim of this work is to produce diffusion layers at least 20μm thick with hardness higher than 700HV by plasma surface treatment with no continuous compounds layer using nitrogen and methane based atmospheres. Samples were characterized by laser Confocal and scanning electron microscopy, X-ray diffraction and Vickers hardness. Salt bath treatment induced formation of undesirable compounds layer at the surface and a diffusion layer thicker than 40μm, with hardness arising 1280HV{sub 0,010}. Plasma surface treatment produced diffusion layer thicker than 40μm with no continuous compounds layer and mean hardness varying from 750 to 960HV{sub 0,010}. (author)

  17. Moving bed reactor for solar thermochemical fuel production

    Science.gov (United States)

    Ermanoski, Ivan

    2013-04-16

    Reactors and methods for solar thermochemical reactions are disclosed. Embodiments of reactors include at least two distinct reactor chambers between which there is at least a pressure differential. In embodiments, reactive particles are exchanged between chambers during a reaction cycle to thermally reduce the particles at first conditions and oxidize the particles at second conditions to produce chemical work from heat. In embodiments, chambers of a reactor are coupled to a heat exchanger to pre-heat the reactive particles prior to direct exposure to thermal energy with heat transferred from reduced reactive particles as the particles are oppositely conveyed between the thermal reduction chamber and the fuel production chamber. In an embodiment, particle conveyance is in part provided by an elevator which may further function as a heat exchanger.

  18. Kinetics of Microstructure Evolution during Gaseous Thermochemical Surface Treatment

    DEFF Research Database (Denmark)

    Somers, Marcel A.J.; Christiansen, Thomas

    2005-01-01

    The incorporation of nitrogen or carbon in steel is widely applied to provide major improvements in materials performance with respect to fatigue, wear, tribology and atmospheric corrosion. These improvements rely on a modification of the surface adjacent region of the material, by the (internal......) precipitation of alloying element nitrides/carbides or by the development of a continuous layer of iron-based (carbo-) nitrides. The evolution of the microstructure during thermochemical treatments is not only determined by solid state diffusion, but in many cases also by the kinetics of the surface reactions...... and the interplay with mechanical stress. In the present article a few examples, covering research on the interaction of carbon and/or nitrogen with iron-based metals, are included to illustrate the various aspects of gas-metal interactions....

  19. Observations, Thermochemical Calculations, and Modeling of Exoplanetary Atmospheres

    CERN Document Server

    Blecic, Jasmina

    2016-01-01

    This dissertation as a whole aims to provide means to better understand hot-Jupiter planets through observing, performing thermochemical calculations, and modeling their atmospheres. We used Spitzer multi-wavelength secondary-eclipse observations and targets with high signal-to-noise ratios, as their deep eclipses allow us to detect signatures of spectral features and assess planetary atmospheric structure and composition with greater certainty. Chapter 1 gives a short introduction. Chapter 2 presents the Spitzer secondary-eclipse analysis and atmospheric characterization of WASP-14b. WASP-14b is a highly irradiated, transiting hot Jupiter. By applying a Bayesian approach in the atmospheric analysis, we found an absence of thermal inversion contrary to theoretical predictions. Chapter 3 describes the infrared observations of WASP-43b Spitzer secondary eclipses, data analysis, and atmospheric characterization. WASP-43b is one of the closest-orbiting hot Jupiters, orbiting one of the coolest stars with a hot Ju...

  20. An approach to thermochemical modeling of nuclear waste glass

    Energy Technology Data Exchange (ETDEWEB)

    Besmann, T.M.; Beahm, E.C. [Oak Ridge National Lab., TN (United States); Spear, K.E. [Pennsylvania State Univ., University Park, PA (United States)

    1998-11-01

    This initial work is aimed at developing a basic understanding of the phase equilibria and solid solution behavior of the constituents of waste glass. Current, experimentally determined values are less than desirable since they depend on measurement of the leach rate under non-realistic conditions designed to accelerate processes that occur on a geologic time scale. The often-used assumption that the activity of a species is either unity or equal to the overall concentration of the metal can also yield misleading results. The associate species model, a recent development in thermochemical modeling, will be applied to these systems to more accurately predict chemical activities in such complex systems as waste glasses.

  1. Non-equilibrium thermochemical heat storage in porous media

    DEFF Research Database (Denmark)

    Nagel, T.; Shao, H.; Singh, Ashok

    2013-01-01

    Thermochemical energy storage can play an important role in the establishment of a reliable renewable energy supply and can increase the efficiency of industrial processes. The application of directly permeated reactive beds leads to strongly coupled mass and heat transport processes that also...... compressible gas flow through a porous solid is presented along with its finite element implementation where solid-gas reactions occur and both phases have individual temperature fields. The model is embedded in the Theory of Porous Media and the derivation is based on the evaluation of the Clausius......-Duhem inequality. Special emphasis is placed on the interphase coupling via mass, momentum and energy interaction terms and their effects are partially illustrated using numerical examples. Novel features of the implementation of the described model are verified via comparisons to analytical solutions...

  2. Thermochemical Nonequilibrium Analysis of Oxygen in Shock Tube Flows

    Science.gov (United States)

    Neitzel, Kevin; Kim, Jae Gang; Boyd, Iain D.

    The successful development of hypersonic vehicles requires a detailed knowledge of the flow physics around the vehicle. The physics knowledge and modeling confidence drives the development of the major vehicle flight systems including the thermal protection system and flight control system. Specifically, an understanding of the thermochemical nonequilibrium behavior is crucial for this flight regime. The hypersonic flight regime involves an extremely high level of energy so a small error in the modeling of the energy processes can result in drastic changes in the vehicle design, including prohibitive design requirements. This emphasizes the need for a deep understanding of the underlying flow phenomena and molecular energy transfer processes in order to adequately design a hypersonic vehicle computationally.

  3. Thermochemical treatment of biogas digestate solids to produce organic fertilisers

    DEFF Research Database (Denmark)

    Pantelopoulos, Athanasios

    Anaerobic digestion of animal manures has been proposed as a process with twofold advantage. The production of biogas, a renewable source of energy, and the treatment of animal manures to increase their agronomic value and reduce their environmental impact. However, the residual of anaerobic...... velocity during thermal treatment influence the evaporation rate of water from the manure solids. At the same time, they also influence the ammonia emission rates, Lowering manure pH (controlling the NH4+ - NH3 equilibrium) can potentially reduce the loss rate. Furthermore, the changes occurring...... digestate nitrogen content (Paper I), ii) determine their C and N dynamics after soil incorporation (Paper II) and iii) assess the plant N and P uptake of ryegrass amended with different thermochemical treatments of the solids (Paper III). For a more mechanistic understanding of the processes involved...

  4. Thermochemical and thermophysical properties of alkaline-earth perovskites

    Energy Technology Data Exchange (ETDEWEB)

    Yamanaka, Shinsuke [Department of Nuclear Engineering, Graduate School of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871 (Japan)]. E-mail: yamanaka@nucl.eng.osaka-u.ac.jp; Kurosaki, Ken [Department of Nuclear Engineering, Graduate School of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871 (Japan); Maekawa, Takuji [Department of Nuclear Engineering, Graduate School of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871 (Japan); Matsuda, Tetsushi [Nuclear Fuel Industries, Ltd., Ohaza-Noda 950, Kumatori-cho, Sennan-gun, Osaka 590-0481 (Japan); Kobayashi, Shin-ichi [Nuclear Fuel Industries, Ltd., Ohaza-Noda 950, Kumatori-cho, Sennan-gun, Osaka 590-0481 (Japan); Uno, Masayoshi [Department of Nuclear Engineering, Graduate School of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871 (Japan)

    2005-09-01

    In order to contribute to safety evaluation of high burnup oxide fuels, we studied the thermochemical and thermophysical properties of alkaline-earth perovskites known as oxide inclusions. Polycrystalline samples of alkaline-earth perovskites, BaUO{sub 3}, BaZrO{sub 3}, BaCeO{sub 3}, BaMoO{sub 3}, SrTiO{sub 3}, SrZrO{sub 3}, SrCeO{sub 3}, SrMoO{sub 3}, SrHfO{sub 3} and SrRuO{sub 3}, were prepared and the thermal expansion coefficient, melting temperature, elastic moduli, Debye temperature, microhardness, heat capacity, and thermal conductivity were measured. The relationship between some physical properties was studied.

  5. Corrosion-resistant sulfur concretes

    Science.gov (United States)

    McBee, W. C.; Sullivan, T. A.; Jong, B. W.

    1983-04-01

    Sulfur concretes have been developed by the Bureau of Mines as construction materials with physical and mechanical properties that suit them for use in acid and salt corrosive environments where conventional concretes fail. Mixture design methods were established for preparing sulfur concretes using different types of aggregates and recently developed mixed-modified sulfur cements. Bench-scale testing of the sulfur concretes has shown their potential value. Corrosion resistance, strength, and durability of sulfur concrete are superior to those of conventional materials. Field in situ evaluation tests of the sulfur concretes as replacement for conventional concrete materials are in progress in corrosive areas of 24 commercial chemical, fertilizer, and metallurgical plants.

  6. Estimation of thermochemical behavior of spallation products in mercury target

    Energy Technology Data Exchange (ETDEWEB)

    Kobayashi, Kaoru; Kaminaga, Masanori; Haga, Katsuhiro; Kinoshita, Hidetaka; Aso, Tomokazu; Teshigawara, Makoto; Hino, Ryutaro [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

    2002-02-01

    In order to examine the radiation safety of a spallation mercury target system, especially source term evaluation, it is necessary to clarify the chemical forms of spallation products generated by spallation reaction with proton beam. As for the chemical forms of spallation products in mercury that involves large amounts of spallation products, these forms were estimated by using the binary phase diagrams and the thermochemical equilibrium calculation based on the amounts of spallation product. Calculation results showed that the mercury would dissolve Al, As, B, Be, Bi, C, Co, Cr, Fe, Ga, Ge, Ir, Mo, Nb, Os, Re, Ru, Sb, Si, Ta, Tc, V and W in the element state, and Ag, Au, Ba, Br, Ca, Cd, Ce, Cl, Cs, Cu, Dy, Er, Eu, F, Gd, Hf, Ho, I, In, K, La, Li, Lu, Mg, Mn, Na, Nd, Ni, O, Pb, Pd, Pr, Pt, Rb, Rh, S, Sc, Se, Sm, Sn, Sr, Tb, Te, Ti, Tl, Tm, Y, Yb, Zn and Zr in the form of inorganic mercury compounds. As for As, Be, Co, Cr, Fe, Ge, Ir, Mo, Nb, Os, Pt, Re, Ru, Se, Ta, V, W and Zr, precipitation could be occurred when increasing the amounts of spallation products with operation time of the spallation target system. On the other hand, beryllium-7 (Be-7), which is produced by spallation reaction of oxygen in the cooling water of a safety hull, becomes the main factor of the external exposure to maintain the cooling loop. Based on the thermochemical equilibrium calculation to Be-H{sub 2}O binary system, the chemical forms of Be in the cooling water were estimated. Then the Be could exist in the form of cations such as BeOH{sup +}, BeO{sup +} and Be{sup 2+} under the condition of less than 10{sup -8} of the Be mole fraction in the cooling water. (author)

  7. Mass-dependent sulfur isotope fractionation during reoxidative sulfur cycling

    DEFF Research Database (Denmark)

    Pellerin, André; Bui, Thi Hao; Rough, Mikaella

    2015-01-01

    of Mangrove Lake appears to include sulfide oxidation to elemental sulfur followed by the disproportionation of the elemental sulfur to sulfate and sulfide. This model also indicates that the reoxidative sulfur cycle of Mangrove Lake turns over from 50 to 80% of the sulfide produced by microbial sulfate...... that the two processes cannot be discriminated from each other....

  8. Third millenium ideal gas and condensed phase thermochemical database for combustion (with update from active thermochemical tables).

    Energy Technology Data Exchange (ETDEWEB)

    Burcat, A.; Ruscic, B.; Chemistry; Technion - Israel Inst. of Tech.

    2005-07-29

    The thermochemical database of species involved in combustion processes is and has been available for free use for over 25 years. It was first published in print in 1984, approximately 8 years after it was first assembled, and contained 215 species at the time. This is the 7th printed edition and most likely will be the last one in print in the present format, which involves substantial manual labor. The database currently contains more than 1300 species, specifically organic molecules and radicals, but also inorganic species connected to combustion and air pollution. Since 1991 this database is freely available on the internet, at the Technion-IIT ftp server, and it is continuously expanded and corrected. The database is mirrored daily at an official mirror site, and at random at about a dozen unofficial mirror and 'finger' sites. The present edition contains numerous corrections and many recalculations of data of provisory type by the G3//B3LYP method, a high-accuracy composite ab initio calculation. About 300 species are newly calculated and are not yet published elsewhere. In anticipation of the full coupling, which is under development, the database started incorporating the available (as yet unpublished) values from Active Thermochemical Tables. The electronic version now also contains an XML file of the main database to allow transfer to other formats and ease finding specific information of interest. The database is used by scientists, educators, engineers and students at all levels, dealing primarily with combustion and air pollution, jet engines, rocket propulsion, fireworks, but also by researchers involved in upper atmosphere kinetics, astrophysics, abrasion metallurgy, etc. This introductory article contains explanations of the database and the means to use it, its sources, ways of calculation, and assessments of the accuracy of data.

  9. Lunar Sulfur Capture System Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The Lunar Sulfur Capture System (LSCS) is an innovative method to recover sulfur compounds from lunar soil using sorbents derived primarily from in-situ resources....

  10. Lunar Sulfur Capture System Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The Lunar Sulfur Capture System (LSCS) is an innovative method to capture greater than 90 percent of sulfur gases evolved during thermal treatment of lunar soils....

  11. Radiation thermo-chemical models of protoplanetary disks I. Hydrostatic disk structure and inner rim

    NARCIS (Netherlands)

    Woitke, P.; Kamp, I.; Thi, W. -F.

    Context. Emission lines from protoplanetary disks originate mainly in the irradiated surface layers, where the gas is generally warmer than the dust. Therefore, interpreting emission lines requires detailed thermo-chemical models, which are essential to converting line observations into

  12. Synfuels from fusion: producing hydrogen with the Tandem Mirror Reactor and thermochemical cycles

    Energy Technology Data Exchange (ETDEWEB)

    Werner, R.W.; Ribe, F.L.

    1981-01-21

    This volume contains the following sections: (1) the Tandem Mirror fusion driver, (2) the Cauldron blanket module, (3) the flowing microsphere, (4) coupling the reactor to the process, (5) the thermochemical cycles, and (6) chemical reactors and process units. (MOW)

  13. Experimental investigation on thermochemical sulfate reduction by H2S initiation

    Science.gov (United States)

    Zhang, T.; Amrani, A.; Ellis, G.S.; Ma, Q.; Tang, Y.

    2008-01-01

    Hydrogen sulfide (H2S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 ??C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO4 in the presence of variable H2S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H2S occurred under acidic conditions (at pH ???3-3.5). However, sulfate reduction at pH ???5.0 was undetectable even at high initial H2S concentrations. To investigate whether the reaction of H2S(aq) and HSO4- occurs at pH ???3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO4 and variable H2S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO4 reduction was not measurable in the absence of paraffin even with high H2S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H2S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H2S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82, 1911-1916). Quantification of labile organosulfur compounds (LSC), such as thiols

  14. Zeolites Remove Sulfur From Fuels

    Science.gov (United States)

    Voecks, Gerald E.; Sharma, Pramod K.

    1991-01-01

    Zeolites remove substantial amounts of sulfur compounds from diesel fuel under relatively mild conditions - atmospheric pressure below 300 degrees C. Extracts up to 60 percent of sulfur content of high-sulfur fuel. Applicable to petroleum refineries, natural-gas processors, electric powerplants, and chemical-processing plants. Method simpler and uses considerably lower pressure than current industrial method, hydro-desulfurization. Yields cleaner emissions from combustion of petroleum fuels, and protects catalysts from poisoning by sulfur.

  15. Life cycle assessment of hydrogen production from S-I thermochemical process coupled to a high temperature gas reactor

    Energy Technology Data Exchange (ETDEWEB)

    Giraldi, M. R.; Francois, J. L.; Castro-Uriegas, D. [Departamento de Sistemas Energeticos, Facultad de Ingenieria, Universidad Nacional Autonoma de Mexico, Paseo Cuauhnahuac No. 8532, Col. Progreso, C.P. 62550, Jiutepec, Morelos (Mexico)

    2012-07-01

    The purpose of this paper is to quantify the greenhouse gas (GHG) emissions associated to the hydrogen produced by the sulfur-iodine thermochemical process, coupled to a high temperature nuclear reactor, and to compare the results with other life cycle analysis (LCA) studies on hydrogen production technologies, both conventional and emerging. The LCA tool was used to quantify the impacts associated with climate change. The product system was defined by the following steps: (i) extraction and manufacturing of raw materials (upstream flows), (U) external energy supplied to the system, (iii) nuclear power plant, and (iv) hydrogen production plant. Particular attention was focused to those processes where there was limited information from literature about inventory data, as the TRISO fuel manufacture, and the production of iodine. The results show that the electric power, supplied to the hydrogen plant, is a sensitive parameter for GHG emissions. When the nuclear power plant supplied the electrical power, low GHG emissions were obtained. These results improve those reported by conventional hydrogen production methods, such as steam reforming. (authors)

  16. Thermochemical Ablation Therapy of VX2 Tumor Using a Permeable Oil-Packed Liquid Alkali Metal

    OpenAIRE

    2015-01-01

    Objective Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors. Methods Permeable oil-packed sodium–potassium (NaK) was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluat...

  17. Structure of amorphous sulfur

    CSIR Research Space (South Africa)

    Eichinger, BE

    2001-06-01

    Full Text Available The lambda-transition of elemental sulfur occurring at about 159°C has long been associated with the conversion of cyclic S8 rings (c-S8) to amorphous polymer (a-S) via a ring opening polymerization. It is demonstrated, with the use of both density...

  18. Accidents with sulfuric acid

    Directory of Open Access Journals (Sweden)

    Rajković Miloš B.

    2006-01-01

    Full Text Available Sulfuric acid is an important industrial and strategic raw material, the production of which is developing on all continents, in many factories in the world and with an annual production of over 160 million tons. On the other hand, the production, transport and usage are very dangerous and demand measures of precaution because the consequences could be catastrophic, and not only at the local level where the accident would happen. Accidents that have been publicly recorded during the last eighteen years (from 1988 till the beginning of 2006 are analyzed in this paper. It is very alarming data that, according to all the recorded accidents, over 1.6 million tons of sulfuric acid were exuded. Although water transport is the safest (only 16.38% of the total amount of accidents in that way 98.88% of the total amount of sulfuric acid was exuded into the environment. Human factor was the common factor in all the accidents, whether there was enough control of the production process, of reservoirs or transportation tanks or the transport was done by inadequate (old tanks, or the accidents arose from human factor (inadequate speed, lock of caution etc. The fact is that huge energy, sacrifice and courage were involved in the recovery from accidents where rescue teams and fire brigades showed great courage to prevent real environmental catastrophes and very often they lost their lives during the events. So, the phrase that sulfuric acid is a real "environmental bomb" has become clearer.

  19. Enhanced Adhesion of Continuous Nanoporous Au Layers by Thermochemical Oxidation of Glassy Carbon

    Directory of Open Access Journals (Sweden)

    Lori Ana Bromberg

    2014-07-01

    Full Text Available The fabrication of a nanoporous gold (NPG-based catalyst on a glassy carbon (GC support results normally in large isolated and poorly adhering clusters that suffer considerable material loss upon durability testing. This work exploits thermochemical oxidation of GC, which, coupled with the utilization of some recent progress in fabricating continuous NPG layers using a Pd seed layer, aims to enhance the adhesion to the GC surface. Thermochemical oxidation causes interconnected pores within the GC structure to open and substantially improves the wettability of the GC surface, which are both beneficial toward the improvement of the overall quality of the NPG deposit. It is demonstrated that thermochemical oxidation neither affects the efficiency of the Au0.3Ag0.7 alloy (NPG precursor deposition nor hinders the achievement of continuity in the course of the NPG fabrication process. Furthermore, adhesion tests performed by a rotating disk electrode setup on deposits supported on thermochemically-oxidized and untreated GCs ascertain the enhanced adhesion on the thermochemically-oxidized samples. The best adhesion results are obtained on a continuous NPG layer fabricated on thermochemically-oxidized GC electrodes seeded with a dense network of Pd clusters.

  20. Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

    Science.gov (United States)

    Huang, Cunping (Inventor); T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor)

    2014-01-01

    Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

  1. Thermochemical Fragment Energy Method for Biomolecules: Application to a Collagen Model Peptide.

    Science.gov (United States)

    Suárez, Ernesto; Díaz, Natalia; Suárez, Dimas

    2009-06-09

    Herein, we first review different methodologies that have been proposed for computing the quantum mechanical (QM) energy and other molecular properties of large systems through a linear combination of subsystem (fragment) energies, which can be computed using conventional QM packages. Particularly, we emphasize the similarities among the different methods that can be considered as variants of the multibody expansion technique. Nevertheless, on the basis of thermochemical arguments, we propose yet another variant of the fragment energy methods, which could be useful for, and readily applicable to, biomolecules using either QM or hybrid quantum mechanical/molecular mechanics methods. The proposed computational scheme is applied to investigate the stability of a triple-helical collagen model peptide. To better address the actual applicability of the fragment QM method and to properly compare with experimental data, we compute average energies by carrying out single-point fragment QM calculations on structures generated by a classical molecular dynamics simulation. The QM calculations are done using a density functional level of theory combined with an implicit solvent model. Other free-energy terms such as attractive dispersion interactions or thermal contributions are included using molecular mechanics. The importance of correcting both the intermolecular and intramolecular basis set superposition error (BSSE) in the QM calculations is also discussed in detail. On the basis of the favorable comparison of our fragment-based energies with experimental data and former theoretical results, we conclude that the fragment QM energy strategy could be an interesting addition to the multimethod toolbox for biomolecular simulations in order to investigate those situations (e.g., interactions with metal clusters) that are beyond the range of applicability of common molecular mechanics methods.

  2. One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Hu, Pengfei [Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444 (China); Zhao, Bing, E-mail: bzhao@shu.edu.cn [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)

    2015-10-05

    Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g{sup −1} after 50 cycles at 100 mA g{sup −1}. • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g{sup −1} after 50 cycles at a current density of 100 mA g{sup −1} and reversible capacity of 517.9 mA h g{sup −1} at 1 A g{sup −1}. The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems.

  3. Structures, Hydration, and Electrical Mobilities of Bisulfate Ion-Sulfuric Acid-Ammonia/Dimethylamine Clusters: A Computational Study.

    Science.gov (United States)

    Tsona, Narcisse T; Henschel, Henning; Bork, Nicolai; Loukonen, Ville; Vehkamäki, Hanna

    2015-09-17

    Despite the well-established role of small molecular clusters in the very first steps of atmospheric particle formation, their thermochemical data are still not completely available due to limitation of the experimental techniques to treat such small clusters. We have investigated the structures and the thermochemistry of stepwise hydration of clusters containing one bisulfate ion, sulfuric acid, base (ammonia or dimethylamine), and water molecules using quantum chemical methods. We found that water facilitates proton transfer from sulfuric acid or the bisulfate ion to the base or water molecules, and depending on the hydration level, the sulfate ion was formed in most of the base-containing clusters. The calculated hydration energies indicate that water binds more strongly to ammonia-containing clusters than to dimethylamine-containing and base-free clusters, which results in a wider hydrate distribution for ammonia-containing clusters. The electrical mobilities of all clusters were calculated using a particle dynamics model. The results indicate that the effect of humidity is negligible on the electrical mobilities of molecular clusters formed in the very first steps of atmospheric particle formation. The combination of the results of this study with those previously published on the hydration of neutral clusters by our group provides a comprehensive set of thermochemical data on neutral and negatively charged clusters containing sulfuric acid, ammonia, or dimethylamine.

  4. Thermochemical scanning probe lithography of protein gradients at the nanoscale

    Science.gov (United States)

    Albisetti, E.; Carroll, K. M.; Lu, X.; Curtis, J. E.; Petti, D.; Bertacco, R.; Riedo, E.

    2016-08-01

    Patterning nanoscale protein gradients is crucial for studying a variety of cellular processes in vitro. Despite the recent development in nano-fabrication technology, combining nanometric resolution and fine control of protein concentrations is still an open challenge. Here, we demonstrate the use of thermochemical scanning probe lithography (tc-SPL) for defining micro- and nano-sized patterns with precisely controlled protein concentration. First, tc-SPL is performed by scanning a heatable atomic force microscopy tip on a polymeric substrate, for locally exposing reactive amino groups on the surface, then the substrate is functionalized with streptavidin and laminin proteins. We show, by fluorescence microscopy on the patterned gradients, that it is possible to precisely tune the concentration of the immobilized proteins by varying the patterning parameters during tc-SPL. This paves the way to the use of tc-SPL for defining protein gradients at the nanoscale, to be used as chemical cues e.g. for studying and regulating cellular processes in vitro.

  5. Solar Thermochemical Hydrogen Production via Terbium Oxide Based Redox Reactions

    Directory of Open Access Journals (Sweden)

    Rahul Bhosale

    2016-01-01

    Full Text Available The computational thermodynamic modeling of the terbium oxide based two-step solar thermochemical water splitting (Tb-WS cycle is reported. The 1st step of the Tb-WS cycle involves thermal reduction of TbO2 into Tb and O2, whereas the 2nd step corresponds to the production of H2 through Tb oxidation by water splitting reaction. Equilibrium compositions associated with the thermal reduction and water splitting steps were determined via HSC simulations. Influence of oxygen partial pressure in the inert gas on thermal reduction of TbO2 and effect of water splitting temperature (TL on Gibbs free energy related to the H2 production step were examined in detail. The cycle (ηcycle and solar-to-fuel energy conversion (ηsolar-to-fuel efficiency of the Tb-WS cycle were determined by performing the second-law thermodynamic analysis. Results obtained indicate that ηcycle and ηsolar-to-fuel increase with the decrease in oxygen partial pressure in the inert flushing gas and thermal reduction temperature (TH. It was also realized that the recuperation of the heat released by the water splitting reactor and quench unit further enhances the solar reactor efficiency. At TH=2280 K, by applying 60% heat recuperation, maximum ηcycle of 39.0% and ηsolar-to-fuel of 47.1% for the Tb-WS cycle can be attained.

  6. Thermochemical liquefaction characteristics of microalgae in sub- and supercritical ethanol

    Energy Technology Data Exchange (ETDEWEB)

    You, Qiao; Chen, Liang [College of Environmental Science and Engineering, Hunan University, Changsha (China); Key Laboratory of Environment Biology and Pollution Control, Ministry of Education, Changsha (China)

    2011-01-15

    Thermochemical liquefaction characteristics of Spirulina, a kind of high-protein microalgae, were investigated with the sub- and supercritical ethanol as solvent in a 1000 mL autoclave. The influences of various liquefaction parameters on the yields of products (bio-oil and residue) from the liquefaction of Spirulina were studied, such as the reaction temperature (T), the S/L ratio (R{sub 1}, solid: Spirulina, liquid: ethanol), the solvent filling ratio (R{sub 2}) and the type and dosage of catalyst. Without catalyst, the bio-oil yields were in the range of 35.4 wt.% and 45.3 wt.% depending on the changes of T, R{sub 1} and R{sub 2}. And the bio-oil yields increased generally with increasing T and R{sub 2}, while the bio-oil yields reduced with increasing R{sub 1}. The FeS catalyst was certified to be an ideal catalyst for the liquefaction of Spirulina microalgae for its advantages on promoting bio-oil production and suppressing the formation of residue. The optimal dosage of catalyst (FeS) was ranging from 5-7 wt.%. The elemental analyses and FT-IR and GC-MS measurements for the bio-oils revealed that the liquid products have much higher heating values than the crude Spirulina sample and fatty acid ethyl ester compounds were dominant in the bio-oils, irrespective of whether catalyst was used. (author)

  7. Environmental impacts of thermochemical biomass conversion. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Elliott, D.C.; Hart, T.R.; Neuenschwander, G.G.; McKinney, M.D.; Norton, M.V.; Abrams, C.W. [Pacific Northwest Lab., Richland, WA (United States)

    1995-06-01

    Thermochemical conversion in this study is limited to fast pyrolysis, upgrading of fast pyrolysis oils, and gasification. Environmental impacts of all types were considered within the project, but primary emphasis was on discharges to the land, air, and water during and after the conversion processes. The project discussed here is divided into five task areas: (1) pyrolysis oil analysis; (2) hydrotreating of pyrolysis oil; (3) gas treatment systems for effluent minimization; (4) strategic analysis of regulatory requirements; and (5) support of the IEA Environmental Systems Activity. The pyrolysis oil task was aimed at understanding the oil contaminants and potential means for their removal. The hydrotreating task was undertaken to better define one potential means for both improving the quality of the oil but also removing contaminants from the oil. Within Task 3, analyses were done to evaluate the results of gasification product treatment systems. Task 4 was a review and collection of regulatory requirements which would be applicable to the subject processes. The IEA support task included input to and participation in the IEA Bioenergy activity which directly relates to the project subject. Each of these tasks is described along with the results. Conclusions and recommendations from the overall project are given.

  8. Thermochemical Study of Lanthanum Complex Crystal with β-Alanine

    Institute of Scientific and Technical Information of China (English)

    陈平初; 屈松生; 詹正坤; 吴新明

    2002-01-01

    Lanthanum complex crystal with β-alanine (1∶3) was synthesized. Through the DTA,TG,chemistry analysis and comparison with literature, it shows that its form is {[La2(β-ala)6* (H2O)4](ClO4)6*H2O}n, and its purity is 98.86%. The dissolution enthalpy of the reactants and products in 2 mol*L-1 HCl solution (298.15K) was measured by using the isoperibol reaction calorimetry. ΔrHm was calculated by a designed thermochemical cycle of the coordination reaction. From the results and other auxiliary quantities, the standard molar enthalpy of formation of [La2(β-ala)6*(H2O)4](ClO4)6*H2O is obtained to be ΔfHm°{[La2(β-ala)6*(H2O)4](ClO4)6*H2O} = - 7062.911 kJ*mol-1.

  9. Thermochemical hydrogen generation of indium oxide thin films

    Directory of Open Access Journals (Sweden)

    Taekyung Lim

    2017-03-01

    Full Text Available Development of alternative energy resources is an urgent requirement to alleviate current energy constraints. As such, hydrogen gas is gaining attention as a future alternative energy source to address existing issues related to limited energy resources and air pollution. In this study, hydrogen generation by a thermochemical water-splitting process using two types of In2O3 thin films was investigated. The two In2O3 thin films prepared by chemical vapor deposition (CVD and sputtering deposition systems contained different numbers of oxygen vacancies, which were directly related to hydrogen generation. The as-grown In2O3 thin film prepared by CVD generated a large amount of hydrogen because of its abundant oxygen vacancies, while that prepared by sputtering had few oxygen vacancies, resulting in low hydrogen generation. Increasing the temperature of the In2O3 thin film in the reaction chamber caused an increase in hydrogen generation. The oxygen-vacancy-rich In2O3 thin film is expected to provide a highly effective production of hydrogen as a sustainable and efficient energy source.

  10. Thermochemical hydrogen generation of indium oxide thin films

    Science.gov (United States)

    Lim, Taekyung; Ju, Sanghyun

    2017-03-01

    Development of alternative energy resources is an urgent requirement to alleviate current energy constraints. As such, hydrogen gas is gaining attention as a future alternative energy source to address existing issues related to limited energy resources and air pollution. In this study, hydrogen generation by a thermochemical water-splitting process using two types of In2O3 thin films was investigated. The two In2O3 thin films prepared by chemical vapor deposition (CVD) and sputtering deposition systems contained different numbers of oxygen vacancies, which were directly related to hydrogen generation. The as-grown In2O3 thin film prepared by CVD generated a large amount of hydrogen because of its abundant oxygen vacancies, while that prepared by sputtering had few oxygen vacancies, resulting in low hydrogen generation. Increasing the temperature of the In2O3 thin film in the reaction chamber caused an increase in hydrogen generation. The oxygen-vacancy-rich In2O3 thin film is expected to provide a highly effective production of hydrogen as a sustainable and efficient energy source.

  11. Thermochemical Properties and Decomposition Kinetics of Ammonium Magnesium Phosphate Monohydrate

    Institute of Scientific and Technical Information of China (English)

    WU,Jian; YUAN,Ai-Qun; HUANG,Zai-Yin; TONG,Zhang-Fa; CHEN,Jie; LIANG,Rong-Lan

    2007-01-01

    Ammonium magnesium phosphate monohydrate NH4MgPO4·H2O was prepared via solid state reaction at room temperature and characterized by XRD, FT-IR and SEM. Thermochemical study was performed by an isoperibol solution calorimeter, non-isothermal measurement was used in a multivariate non-linear regression analysis to determine the kinetic reaction parameters. The results show that the molar enthalpy of reaction above is (28.795±0.182) kJ/mol (298.15 K), and the standard molar enthalpy of formation of the title complex is (-2185.43±13.80)kJ/mol (298.15 K). Kinetics analysis shows that the second decomposition of NH4MgPO4·H2O acts as a double-step reaction: an nth-order reaction (Fn) with n=4.28, E1=147.35 kJ/mol, A1=3.63×1013 s-1 is followed by a second-order reaction (F2) with E2=212.71 kJ/mol, A2= 1.82×1018 s-1.

  12. A Thermo-Chemical Reactor for analytical atomic spectrometry

    Science.gov (United States)

    Gilmutdinov, A. Kh.; Nagulin, K. Yu.

    2009-01-01

    A novel atomization/vaporization system for analytical atomic spectrometry is developed. It consists of two electrically and thermally separated parts that can be heated separately. Unlike conventional electrothermal atomizers in which atomization occurs immediately above the vaporization site and at the same instant of time, the proposed system allows analyte atomization via an intermediate stage of fractional condensation as a two stage process: Vaporization → Condensation → Atomization. The condensation step is selective since vaporized matrix constituents are mainly non-condensable gases and leave the system by diffusion while analyte species are trapped on the cold surface of a condenser. This kind of sample distillation keeps all the advantages of traditional electrothermal atomization and allows significant reduction of matrix interferences. Integration into one design a vaporizer, condenser and atomizer gives much more flexibility for in situ sample treatment and thus the system is called a Thermo-Chemical Reactor (TCR). Details of the design, temperature measurements, vaporization-condensation-atomization mechanisms of various elements in variety of matrices are investigated in the TCR with spectral, temporal and spatial resolution. The ability of the TCR to significantly reduce interferences and to conduct sample pyrolysis at much higher temperatures as compared to conventional electrothermal atomizers is demonstrated. The analytical potential of the system is shown when atomic absorption determination of Cd and Pb in citrus leaves and milk powder without the use of any chemical modification.

  13. Design Principles of Perovskites for Thermochemical Oxygen Separation.

    Science.gov (United States)

    Ezbiri, Miriam; Allen, Kyle M; Gàlvez, Maria E; Michalsky, Ronald; Steinfeld, Aldo

    2015-06-08

    Separation and concentration of O2 from gas mixtures is central to several sustainable energy technologies, such as solar-driven synthesis of liquid hydrocarbon fuels from CO2 , H2 O, and concentrated sunlight. We introduce a rationale for designing metal oxide redox materials for oxygen separation through "thermochemical pumping" of O2 against a pO2 gradient with low-grade process heat. Electronic structure calculations show that the activity of O vacancies in metal oxides pinpoints the ideal oxygen exchange capacity of perovskites. Thermogravimetric analysis and high-temperature X-ray diffraction for SrCoO3-δ , BaCoO3-δ and BaMnO3-δ perovskites and Ag2 O and Cu2 O references confirm the predicted performance of SrCoO3-δ , which surpasses the performance of state-of-the-art Cu2 O at these conditions with an oxygen exchange capacity of 44 mmol O 2 mol SrCoO 3-δ(-1) exchanged at 12.1 μmol O 2 min(-1)  g(-1) at 600-900 K. The redox trends are understood due to lattice expansion and electronic charge transfer.

  14. A thermochemically derived global reaction mechanism for detonation application

    Science.gov (United States)

    Zhu, Y.; Yang, J.; Sun, M.

    2012-07-01

    A 4-species 4-step global reaction mechanism for detonation calculations is derived from detailed chemistry through thermochemical approach. Reaction species involved in the mechanism and their corresponding molecular weight and enthalpy data are derived from the real equilibrium properties. By substituting these global species into the results of constant volume explosion and examining the evolution process of these global species under varied conditions, reaction paths and corresponding rates are summarized and formulated. The proposed mechanism is first validated to the original chemistry through calculations of the CJ detonation wave, adiabatic constant volume explosion, and the steady reaction structure after a strong shock wave. Good agreement in both reaction scales and averaged thermodynamic properties has been achieved. Two sets of reaction rates based on different detailed chemistry are then examined and applied for numerical simulations of two-dimensional cellular detonations. Preliminary results and a brief comparison between the two mechanisms are presented. The proposed global mechanism is found to be economic in computation and also competent in description of the overall characteristics of detonation wave. Though only stoichiometric acetylene-oxygen mixture is investigated in this study, the method to derive such a global reaction mechanism possesses a certain generality for premixed reactions of most lean hydrocarbon mixtures.

  15. Accidents with sulfuric acid

    OpenAIRE

    Rajković Miloš B.

    2006-01-01

    Sulfuric acid is an important industrial and strategic raw material, the production of which is developing on all continents, in many factories in the world and with an annual production of over 160 million tons. On the other hand, the production, transport and usage are very dangerous and demand measures of precaution because the consequences could be catastrophic, and not only at the local level where the accident would happen. Accidents that have been publicly recorded during the last eigh...

  16. Liquid fuel utilization in SOFC hybrid systems

    Energy Technology Data Exchange (ETDEWEB)

    Santin, Marco; Traverso, Alberto; Magistri, Loredana [TPG-DIMSET, University of Genoa, Via Montallegro 1, 16145 Genoa (Italy)

    2009-10-15

    The interest in solid oxide fuel cell systems comes from their capability of converting the chemical energy of traditional fuels into electricity, with high efficiency and low pollutant emissions. In this paper, a study of the design space of solid oxide fuel cell and gas turbine hybrids fed by methanol and kerosene is presented for stationary power generation in isolated areas (or transportation). A 500 kW class hybrid system was analysed using WTEMP original software developed by the Thermochemical Power Group of the University of Genoa. The choice of fuel-processing strategy and the influence of the main design parameters on the thermoeconomic characteristics of hybrid systems were investigated. The low capital and fuel cost of methanol systems make them the most attractive solutions among those investigated here. (author)

  17. Catalyst for the reduction of sulfur dioxide to elemental sulfur

    Science.gov (United States)

    Jin, Y.; Yu, Q.; Chang, S.G.

    1996-02-27

    The inventive catalysts allow for the reduction of sulfur dioxide to elemental sulfur in smokestack scrubber environments. The catalysts have a very high sulfur yield of over 90% and space velocity of 10,000 h{sup {minus}1}. They also have the capacity to convert waste gases generated during the initial conversion into elemental sulfur. The catalysts have inexpensive components, and are inexpensive to produce. The net impact of the invention is to make this technology practically available to industrial applications. 21 figs.

  18. Thermochemical Evolution of Earth's Core with Magnesium Precipitation

    Science.gov (United States)

    O'Rourke, J. G.; Stevenson, D. J.

    2014-12-01

    Vigorous convection within Earth's outer core drives a dynamo that has sustained a global magnetic field for at least 3.5 Gyr. Traditionally, people invoke three energy sources for the dynamo: thermal convection from cooling and freezing, compositional convection from light elements expelled by the growing inner core, and, perhaps, radiogenic heating from potassium-40. New theoretical and experimental work, however, indicates that the thermal and electrical conductivities of the outer core may be as much as three times higher than previously assumed. The implied increase in the adiabatic heat flux casts doubt on the ability of the usual mechanisms to explain the dynamo's longevity. Here, we present a quantitative model of the crystallization of magnesium-bearing minerals from the cooling core—a plausible candidate for the missing power source. Recent diamond-anvil cell experiments suggest that magnesium can partition into core material if thermodynamic equilibrium is achieved at high temperatures (>5000 K). We develop a model for core/mantle differentiation in which most of the core forms from material equilibrated at the base of a magma ocean as Earth slowly grows, but a small portion (~10%) equilibrated at extreme conditions in the aftermath of a giant impact. We calculate the posterior probability distribution for the original concentrations of magnesium and other light elements (chiefly oxygen and silicon) in the core, constrained by partitioning experiments and the observed depletion of siderophile elements in Earth's mantle. We then simulate the thermochemical evolution of cores with plausible compositions and thermal structures from the end of accretion to the present, focusing on the crystallization of a few percent of the initial core as ferropericlase and bridgmanite. Finally, we compute the associated energy release and verify that our final core compositions are consistent with the available seismological data.

  19. Biomass thermochemical conversion - overview of results; Biomassan jalostus - tutkimusalueen katsaus

    Energy Technology Data Exchange (ETDEWEB)

    Sipilae, K. [VTT Energy, Espoo (Finland). Energy Production Technologies

    1995-12-31

    In this Bioenergy research program the thermochemical conversion activities are mainly concentrated in three fields (1) flash pyrolysis and the use of wood oil in boilers and engines (2) biomass gasification for gas engine power plants and finally (3) conversion of black liquor and extractives in a pulp mill to various liquid fuels. Parallel to activities in Finland also significant work has been done in EU-Joule and Apas projects and in the IEA Bioenergy Agreement. In the area of flash pyrolysis technology, three new laboratory and PDU-units have been installed to VTT in order to produce various qualities of bio oils from wood and straw. The quality of pyrolysis oils have been characterized by physical and chemical methods supported by EU and IEA networks. Several companies are carrying out pyrolysis activities as well: Neste Oy is testing the wood oil in a 200 kW boiler, Waertsilae Diesel Oy is testing Canadian wood oil in a 1.5 MWe diesel power plant engine and Vapo Oy is carrying out investigations to produce pyrolysis oils in Finland. The biomass gasification coupled to a gas engine is an interesting alternative for small scale power production parallel to existing fluid bed boiler technology. VTT has installed a circulating fluid bed gasifier with advanced gas cleaning system to test various technologies in order to feed the gas to an engine. In order to produce liquid fuels at a pulp mill, the laboratory work has continued using crude soap as a raw material for high pressure liquid phase treatment and atmospheric pyrolysis process. The quality of the oil is like light fuel oil or diesel fuel, possibilities to use it as a lubricant will be investigated

  20. The computation of thermo-chemical nonequilibrium hypersonic flows

    Science.gov (United States)

    Candler, Graham

    1989-01-01

    Several conceptual designs for vehicles that would fly in the atmosphere at hypersonic speeds have been developed recently. For the proposed flight conditions the air in the shock layer that envelops the body is at a sufficiently high temperature to cause chemical reaction, vibrational excitation, and ionization. However, these processes occur at finite rates which, when coupled with large convection speeds, cause the gas to be removed from thermo-chemical equilibrium. This non-ideal behavior affects the aerothermal loading on the vehicle and has ramifications in its design. A numerical method to solve the equations that describe these types of flows in 2-D was developed. The state of the gas is represented with seven chemical species, a separate vibrational temperature for each diatomic species, an electron translational temperature, and a mass-average translational-rotational temperature for the heavy particles. The equations for this gas model are solved numerically in a fully coupled fashion using an implicit finite volume time-marching technique. Gauss-Seidel line-relaxation is used to reduce the cost of the solution and flux-dependent differencing is employed to maintain stability. The numerical method was tested against several experiments. The calculated bow shock wave detachment on a sphere and two cones was compared to those measured in ground testing facilities. The computed peak electron number density on a sphere-cone was compared to that measured in a flight test. In each case the results from the numerical method were in excellent agreement with experiment. The technique was used to predict the aerothermal loads on an Aeroassisted Orbital Transfer Vehicle including radiative heating. These results indicate that the current physical model of high temperature air is appropriate and that the numerical algorithm is capable of treating this class of flows.

  1. Effects of thermochemical pretreatment on the biodegradability of sludge from a biological wastewater treatment system

    Directory of Open Access Journals (Sweden)

    Ick-Tae Yeom

    2010-07-01

    Full Text Available The effects of thermochemical pretreatment on the sludge biodegradability were examined. Two types of tests were conducted: aerobic biodegradation and denitrification using thermochemically pretreated sludge as carbon source. In the aerobic biodegradation tests, the biodegradation efficiency for the sludge pretreated at 60, 70, 80 and 90oC (pH 11 was 1.4-2.2 times higher than that for the untreated sludge. The biodegradation efficiency for the supernatant was also about 1.9 times higher than that for the particulates. The biodegradation enhancement for the thermochemically pretreated sludge was demonstrated in denitrification tests. The supernatant showed its potential as a carbon source for the denitrification process.

  2. High-efficient thermochemical sorption refrigeration driven by low-grade thermal energy

    Institute of Scientific and Technical Information of China (English)

    LI TingXian; WANG RuZhu; WANG LiWei

    2009-01-01

    Thermochemical sorption refrigeration powered by low-grade thermal energy is one of the en ergy-saving and environment friendly green refrigeration technologies. The operation principle of sorption refrigeration system is based on the thermal effects of reversible physicochemical reaction processes between sorbents and refrigerants. This paper presents the developing study on the differ ent thermochemical sorption refrigeration cycles, and some representative high-efficient thermo chemical sorption refrigeration cycles were evaluated and analyzed based on the conventional single-effect sorption cycle. These advanced sorption refrigeration cycles mainly include the heat and mass recovery sorption cycle, double-effect sorption cycle, multi-effect sorption cycle, combined douhie-way sorption cycle, and double-effect and double-way sorption cycle with internal heat recovery.Moreover, the developing tendency of the thermochemical sorption refrigeration is also predicted in this paper.

  3. Efficiency maximization in solar-thermochemical fuel production: challenging the concept of isothermal water splitting.

    Science.gov (United States)

    Ermanoski, I; Miller, J E; Allendorf, M D

    2014-05-14

    Widespread adoption of solar-thermochemical fuel production depends on its economic viability, largely driven by the efficiency of use of the available solar resource. Herein, we analyze the efficiency of two-step cycles for thermochemical hydrogen production, with emphasis on efficiency. Owing to water thermodynamics, isothermal H2 production is shown to be impractical and inefficient, irrespective of reactor design or reactive oxide properties, but an optimal temperature difference between cycle steps, for which efficiency is the highest, can be determined for a wide range of other operating parameters. A combination of well-targeted pressure and temperature swing, rather than either individually, emerges as the most efficient mode of operation of a two-step thermochemical cycle for solar fuel production.

  4. RNA-Seq Analysis of Sulfur-Deprived Chlamydomonas Cells Reveals Aspects of Acclimation Critical for Cell Survival[W

    Science.gov (United States)

    González-Ballester, David; Casero, David; Cokus, Shawn; Pellegrini, Matteo; Merchant, Sabeeha S.; Grossman, Arthur R.

    2010-01-01

    The Chlamydomonas reinhardtii transcriptome was characterized from nutrient-replete and sulfur-depleted wild-type and snrk2.1 mutant cells. This mutant is null for the regulatory Ser-Thr kinase SNRK2.1, which is required for acclimation of the alga to sulfur deprivation. The transcriptome analyses used microarray hybridization and RNA-seq technology. Quantitative RT-PCR evaluation of the results obtained by these techniques showed that RNA-seq reports a larger dynamic range of expression levels than do microarray hybridizations. Transcripts responsive to sulfur deprivation included those encoding proteins involved in sulfur acquisition and assimilation, synthesis of sulfur-containing metabolites, Cys degradation, and sulfur recycling. Furthermore, we noted potential modifications of cellular structures during sulfur deprivation, including the cell wall and complexes associated with the photosynthetic apparatus. Moreover, the data suggest that sulfur-deprived cells accumulate proteins with fewer sulfur-containing amino acids. Most of the sulfur deprivation responses are controlled by the SNRK2.1 protein kinase. The snrk2.1 mutant exhibits a set of unique responses during both sulfur-replete and sulfur-depleted conditions that are not observed in wild-type cells; the inability of this mutant to acclimate to S deprivation probably leads to elevated levels of singlet oxygen and severe oxidative stress, which ultimately causes cell death. The transcriptome results for wild-type and mutant cells strongly suggest the occurrence of massive changes in cellular physiology and metabolism as cells become depleted for sulfur and reveal aspects of acclimation that are likely critical for cell survival. PMID:20587772

  5. Sulfur Encapsulated in Graphitic Carbon Nanocages for High-Rate and Long-Cycle Lithium-Sulfur Batteries.

    Science.gov (United States)

    Zhang, Juan; Yang, Chun-Peng; Yin, Ya-Xia; Wan, Li-Jun; Guo, Yu-Guo

    2016-11-01

    Hybrid sp(2) carbon with a graphene backbone and graphitic carbon nanocages (G-GCNs) is demonstrated as an ideal host for sulfur in Li-S batteries, because it serves as highly efficient electrochemical nanoreactors as well as polysulfides reservoirs. The as-obtained S/(G-GCNs) with high S content exhibits superior high-rate capability (765 mA h g(-1) at 5 C) and long-cycle life over 1000 cycles.

  6. Lithium sulfur batteries and electrolytes and sulfur cathodes thereof

    Energy Technology Data Exchange (ETDEWEB)

    Visco, Steven J.; Goncharenko, Nikolay; Nimon, Vitaliy; Petrov, Alexei; Nimon, Yevgeniy S.; De Jonghe, Lutgard C.; Katz, Bruce D.; Loginova, Valentina

    2017-05-23

    Lithium sulfur battery cells that use water as an electrolyte solvent provide significant cost reductions. Electrolytes for the battery cells may include water solvent for maintaining electroactive sulfur species in solution during cell discharge and a sufficient amount of a cycle life-enhancing compound that facilitates charging at the cathode. The combination of these two components enhances one or more of the following cell attributes: energy density, power density and cycle life. For instance, in applications where cost per Watt-Hour (Wh) is paramount, such as grid storage and traction applications, the use of an aqueous electrolyte in combination with inexpensive sulfur as the cathode active material can be a key enabler for the utility and automotive industries, for example, providing a cost effective and compact solution for load leveling, electric vehicles and renewable energy storage. Sulfur cathodes, and methods of fabricating lithium sulfur cells, in particular for loading lithium sulfide into the cathode structures, provide further advantages.

  7. Sulfur in Cometary Dust

    Science.gov (United States)

    Fomenkova, M. N.

    1997-01-01

    The computer-intensive project consisted of the analysis and synthesis of existing data on composition of comet Halley dust particles. The main objective was to obtain a complete inventory of sulfur containing compounds in the comet Halley dust by building upon the existing classification of organic and inorganic compounds and applying a variety of statistical techniques for cluster and cross-correlational analyses. A student hired for this project wrote and tested the software to perform cluster analysis. The following tasks were carried out: (1) selecting the data from existing database for the proposed project; (2) finding access to a standard library of statistical routines for cluster analysis; (3) reformatting the data as necessary for input into the library routines; (4) performing cluster analysis and constructing hierarchical cluster trees using three methods to define the proximity of clusters; (5) presenting the output results in different formats to facilitate the interpretation of the obtained cluster trees; (6) selecting groups of data points common for all three trees as stable clusters. We have also considered the chemistry of sulfur in inorganic compounds.

  8. Recent Canadian advances in nuclear-based hydrogen production and the thermochemical Cu-Cl cycle

    Energy Technology Data Exchange (ETDEWEB)

    Naterer, G. [Canada Research Chair Professor, University of Ontario Institute of Technology (UOIT), 2000 Simcoe Street, Oshawa, Ontario L1H 7K4 (Canada); Suppiah, S. [Manager, Hydrogen Isotopes Technology Branch, AECL, Chalk River, Ontario K0J 1J0 (Canada); Lewis, M. [Chemist, Chemical Engineering Division, Argonne National Laboratory, 9700 S. Cass Avenue, Argonne, Illinois 60439 (United States); Gabriel, K. [Associate Provost, Research, UOIT, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4 (Canada); Dincer, I.; Rosen, M.A. [Professor of Mechanical Engineering, UOIT, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4 (Canada); Fowler, M. [Assistant Professor of Chemical Engineering, University of Waterloo, 200 University Avenue, Waterloo, Ontario N2L 3G1 (Canada); Rizvi, G. [Assistant Professor of Mechanical Engineering, UOIT, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4 (Canada); Easton, E.B. [Assistant Professor of Chemistry, UOIT, 2000 Simcoe Street North, Oshawa, Ontario L1H 7K4 (Canada); Ikeda, B.M.; Pioro, I. [Associate Professor, Faculty of Energy Systems and Nuclear Science, UOIT, 2000 Simcoe St., Oshawa, ON L1H 7K4 (Canada); Kaye, M.H.; Lu, L. [Assistant Professor, Faculty of Energy Systems and Nuclear Science, UOIT, 2000 Simcoe Street, Oshawa, Ontario L1H 7K4 (Canada); Spekkens, P. [Vice President of Science and Technology Development, Ontario Power Generation, 889 Brock Road, Pickering, Ontario (Canada); Tremaine, P. [Professor of Chemistry, University of Guelph, 50 Stone Road East, Guelph, Ontario N1G 2W1 (Canada); Mostaghimi, J. [Canada Research Chair Professor, Mechanical Engineering, University of Toronto, Toronto, Ontario M5S 3E5 (Canada); Avsec, J. [Assistant Professor, Faculty of Energy Technology, Univ. of Maribor, Hocevarjev trg 1, 8270 Krsko (Slovenia); Jiang, J. [Professor and NSERC/UNENE Senior Industrial Research Chair, Electrical and Computer Engineering, Univ. of Western Ontario, London, Ontario N6A 5B9 (Canada)

    2009-04-15

    This paper presents recent Canadian advances in nuclear-based production of hydrogen by electrolysis and the thermochemical copper-chlorine (Cu-Cl) cycle. This includes individual process and reactor developments within the Cu-Cl cycle, thermochemical properties, advanced materials, controls, safety, reliability, economic analysis of electrolysis at off-peak hours, and integrating hydrogen plants with Canada's nuclear power plants. These enabling technologies are being developed by a Canadian consortium, as part of the Generation IV International Forum (GIF) for hydrogen production from the next generation of nuclear reactors. (author)

  9. THERMOCHEMICAL ENERGY STORAGE FOR SEASONAL BALANCE OF SURPLUS ELECTRICITY AND HEAT DEMAND IN DOMESTIC BUILDINGS

    OpenAIRE

    Schmidt, Matthias; Linder, Marc Philipp

    2016-01-01

    Thermochemical storage systems are predestined to store thermal energy for a long time since the storage principle itself is free of losses and allows for very high energy densities. Therefore we developed a new approach where electricity, p. e. from private PV-panels in the summer, is used to charge a thermochemical reaction system. The reaction product then can be stored in an inexpensive tank at room temperature. If there is heat demand during the winter part of the material can be supplie...

  10. Thermochemical pretreatments for enhancing succinic acid production from industrial hemp (Cannabis sativa L.)

    DEFF Research Database (Denmark)

    Gunnarsson, Ingólfur Bragi; Kuglarz, Mariusz; Karakashev, Dimitar Borisov

    2015-01-01

    The aim of this study was to develop an efficient thermochemical method for treatment of industrial hemp biomass, in order to increase its bioconversion to succinic acid. Industrial hemp was subjected to various thermochemical pretreatments using 0-3% H2SO4, NaOH or H2O2 at 121-180°C prior...... to enzymatic hydrolysis. The influence of the different pretreatments on hydrolysis and succinic acid production by Actinobacillus succinogenes 130Z was investigated in batch mode, using anaerobic bottles and bioreactors. Enzymatic hydrolysis and fermentation of hemp material pretreated with 3% H2O2 resulted...

  11. Importance of the ligand basis set in ab initio thermochemical calculations of transition metal species

    Science.gov (United States)

    Plascencia, Cesar; Wang, Jiaqi; Wilson, Angela K.

    2017-10-01

    The impact of basis set choice has been considered for a series of transition metal (TM) species. The need for higher level correlation consistent basis sets on both the metal and ligand has been investigated, and permutations in the pairings of basis set used for TM's and basis set used for ligands can lead to effective routes to complete basis set (CBS) limit extrapolations of thermochemical energetics with little change in thermochemical predictions as compared to those resulting from the use of traditional basis set pairings, while enabling computational cost savings. Basis set superposition errors (BSSE) that can arise have also been considered.

  12. Density functional investigation of the thermophysical and thermochemical properties of talc [Mg3Si4O10(OH)2

    Science.gov (United States)

    Ulian, Gianfranco; Valdrè, Giovanni

    2015-02-01

    The knowledge of the P, T behavior of talc is very important in mineralogical-petrological and geophysical research fields because talc can be considered a hydrous phase that can recycle water into the Earth's mantle and also an important mineral in both industrial and technological applications. However, very few works have been presented to fully characterize the thermodynamic properties of this mineral, especially at atomic scale. In a previous work, we modeled the structural and mechanical properties of talc using the B3LYP-D* hybrid density functional, which included a correction for the dispersive forces and all-electron Gaussian-type orbital basis sets. The results were in good agreement with single-crystal X-ray and neutron diffraction experimental data. Here, we extend the investigation to the thermochemical and thermophysical properties of talc using the same density functional approach and the quasi-harmonic approximation, providing the thermal equation of state, the heat capacity and the entropy of the mineral at different P, T conditions.

  13. Sulfur plant start-up

    Energy Technology Data Exchange (ETDEWEB)

    Hudson, Hank; Grigson, Susan [Ortloff Engineers Ltd. (United States)

    2002-02-01

    The authors discuss an Ortloff sulfur plant design concept using the Claus reaction that differs from accepted 'industry practice': cold reactor bed start-up. The process is designed to eliminate catalyst sulfation, heat damage and furnace overheating in sulfur recovery units. (UK)

  14. Renewable energy from corn residues by thermochemical conversion

    Science.gov (United States)

    Yu, Fei

    Declining fossil oil reserve, skyrocket price, unsecured supplies, and environment pollution are among the many energy problems we are facing today. It is our conviction that renewable energy is a solution to these problems. The long term goal of the proposed research is to develop commercially practical technologies to produce energy from renewable resources. The overall objective of my research is to study and develop thermochemical processes for converting bulky and low-energy-density biomass materials into bio-fuels and value-added bio-products. The rationale for the proposed research is that, once such processes are developed, processing facility can be set up on or near biomass product sites, reducing the costs associated with transport of bulky biomass which is a key technical barrier to biomass conversion. In my preliminary research, several conversion technologies including atmospheric pressure liquefaction, high pressure liquefaction, and microwave pyrolysis have been evaluated. Our data indicated that microwave pyrolysis had the potential to become a simple and economically viable biomass conversion technology. Microwave pyrolysis is an innovative process that provides efficient and uniform heating, and are robust to type, size and uniformity of feedstock and therefore suitable for almost any waste materials without needing to reduce the particle size. The proposed thesis focused on in-depth investigations of microwave pyrolysis of corn residues. My first specific aim was to examine the effects of processing parameters on product yields. The second specific research aim was to characterize the products (gases, bio-oils, and solid residues), which was critical to process optimization and product developments. Other research tasks included conducting kinetic modeling and preliminary mass and energy balance. This study demonstrated that microwave pyrolysis could be optimized to produce high value syngas, liquid fuels and pyrolytic carbons, and had a great

  15. Thermo-chemical Ice Penetrator for Icy Moons

    Science.gov (United States)

    Arenberg, J. W.; Lee, G.; Harpole, G.; Zamel, J.; Sen, B.; Ross, F.; Retherford, K. D.

    2016-12-01

    The ability to place sensors or to take samples below the ice surface enables a wide variety of potential scientific investigations. Penetrating an ice cap can be accomplished via a mechanical drill, laser drill, kinetic impactor, or heated penetrator. This poster reports on the development of technology for the latter most option, namely a self-heated probe driven by an exothermic chemical reaction: a Thermo-chemical ice penetrator (TChIP). Our penetrator design employs a eutectic mix of alkali metals that produce an exothermic reaction upon contact with an icy surface. This reaction increases once the ice starts melting, so no external power is required. This technology is inspired by a classified Cold-War era program developed at Northrop Grumman for the US Navy. Terrestrial demonstration of this technology took place in the Arctic; however, this device cannot be considered high TRL for application at the icy moons of the solar system due to the environmental differences between Earth's Arctic and the icy moons. These differences demand a TChIP design specific to these cold, low mass, airless worlds. It is expected that this model of TChIP performance will be complex, incorporating all of the forces on the penetrator, gravity, the thermo-chemistry at the interface between penetrator and ice, and multi-phase heat and mass transport, and hydrodynamics. Our initial efforts are aimed at the development of a validated set of tools and simulations to predict the performance of the penetrator for both the environment found on these icy moons and for a terrestrial environment. The purpose of the inclusion of the terrestrial environment is to aid in model validation. Once developed and validated, our models will allow us to design penetrators for a specific scientific application on a specific body. This poster discusses the range of scientific investigations that are enabled by TChIP. We also introduce the development plan to advance TChIP to the point where it can be

  16. Thermochemical properties for isooctane and carbon radicals: computational study.

    Science.gov (United States)

    Snitsiriwat, Suarwee; Bozzelli, Joseph W

    2013-01-17

    Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the isooctane parent and for the primary, secondary, and tertiary radicals in order to identify isomer energies. Intramolecular interactions are shown to have a significant effect on the enthalpy of formation of the isooctane parent and its radicals. The computed standard enthalpy of formation for the lowest energy conformers of isooctane from this study is -54.40 ± 1.60 kcal mol(-1), which is 0.8 kcal mol(-1) lower than the evaluated experimental value -53.54 ± 0.36 kcal mol(-1). The standard enthalpy of formation for the primary radical for a methyl on the quaternary carbon is -5.00 ± 1.69 kcal mol(-1), for the primary radical on the tertiary carbon is -5.18 ± 1.69 kcal mol(-1), for the secondary isooctane radical is -9.03 ± 1.84 kcal mol(-1), and for the tertiary isooctane radical is -12.30 ± 2.02 kcal mol(-1). Bond energy values for the isooctane radicals are 100.64 ± 1.73, 100.46 ± 1.73, 96.41 ± 1.88 and 93.14 ± 2.05 kcal mol(-1) for C3•CCCC2, C3CCCC2•, C3CC•CC2, and C3CCC•C2, respectively. Entropy and heat capacity values are reported for the lowest energy homologues.

  17. Thermo-chemical simulation of a composite offshore vertical axis wind turbine blade

    DEFF Research Database (Denmark)

    Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

    2012-01-01

    In the present study three dimensional steady state thermo-chemical simulation of a pultrusion process is investigated by using the finite element/nodal control volume (FE/NCV) technique. Pultrusion simulation of a composite having a C-shaped cross section is performed as a validation case...

  18. A new high-flux solar furnace for high-temperature thermochemical research

    Energy Technology Data Exchange (ETDEWEB)

    Haueter, P.; Seitz, T.; Steinfeld, A. [Paul Scherrer Inst., Villigen (Switzerland). Solar Process Technology Group

    1999-02-01

    A new high-flux solar furnace, capable of delivering up to 40 kW at peak concentration ratios exceeding 5000, is operational at PSI. Its optical design characteristics, main engineering features, and operating performance are described. This solar concentrating facility will be used principally for investigating the thermochemical processing of solar fuels at temperatures as high as 2500 K.

  19. Potential of summer legumes for thermochemical conversion to synthetic fuel in the southeast USA

    Science.gov (United States)

    Fallow periods during the summer in some crop rotations of the Southeast USA could potentially be used to grow feedstocks for energy production. The objective of this study was to evaluate Crotolaria juncea and cowpeas (Vigna unguiculata) as species to be used as feedstocks for thermochemical conver...

  20. A review on the properties of salt hydrates for thermochemical storage

    NARCIS (Netherlands)

    Trausel, F.; Jong, A.J. de; Cuypers, R.

    2014-01-01

    Solar energy is capable of supplying enough energy to answer the total demand of energy in dwellings. However, because of the discrepancy between energy supply and energy demand, an efficient way of storing thermal energy is crucial. Thermochemical storage of heat in salt hydrates provides an effici

  1. Neutralization and Acid Dissociation of Hydrogen Carbonate Ion: A Thermochemical Approach

    Science.gov (United States)

    Koga, Nobuyoshi; Shigedomi, Kana; Kimura, Tomoyasu; Tatsuoka, Tomoyuki; Mishima, Saki

    2013-01-01

    A laboratory inquiry into the thermochemical relationships in the reaction between aqueous solutions of NaHCO[subscript 3] and NaOH is described. The enthalpy change for this reaction, delta[subscript r]H, and that for neutralization of strong acid and NaOH(aq), delta[subscript n]H, are determined calorimetrically; the explanation for the…

  2. Experimental results of a 3 k Wh thermochemical heat storage module for space heating application

    NARCIS (Netherlands)

    Finck, C.J.; Henquet, E.M.R.; Soest, C.F.L. van; Oversloot, H.P.; Jong, A.J. de; Cuypers, R.; Spijker, J.C. van 't

    2014-01-01

    A 3 kWh thermochemical heat storage (TCS) module was built as part of an all-in house system implementation focusing on space heating application at a temperature level of 40 ºC and a temperature lift of 20 K. It has been tested and measurements showed a maximum water circuit temperature span (relea

  3. Thermochemical stability and nonstoichiometry of yttria-stabilized bismuth oxide solid solutions

    NARCIS (Netherlands)

    Kruidhof, H.; Vries, de K.J.; Burggraaf, A.J.

    1990-01-01

    The thermochemical stability of fast oxygen ion conducting yttria stabilized bismuthoxide (YSB) solid solutions containing 22.0–32.5 mol% of yttria was investigated. It was shown that in the temperature range between 650–740 C the stabilized cubic δ-phase containing less than 31.8 mol% of yttria is

  4. Radiation thermo-chemical models of protoplanetary disks I. Hydrostatic disk structure and inner rim

    NARCIS (Netherlands)

    Woitke, P.; Kamp, I.; Thi, W. -F.

    2009-01-01

    Context. Emission lines from protoplanetary disks originate mainly in the irradiated surface layers, where the gas is generally warmer than the dust. Therefore, interpreting emission lines requires detailed thermo-chemical models, which are essential to converting line observations into understandin

  5. Improving Students' Chemical Literacy Levels on Thermochemical and Thermodynamics Concepts through a Context-Based Approach

    Science.gov (United States)

    Cigdemoglu, Ceyhan; Geban, Omer

    2015-01-01

    The aim of this study was to delve into the effect of context-based approach (CBA) over traditional instruction (TI) on students' chemical literacy level related to thermochemical and thermodynamics concepts. Four eleventh-grade classes with 118 students in total taught by two teachers from a public high school in 2012 fall semester were enrolled…

  6. Improving Students' Chemical Literacy Levels on Thermochemical and Thermodynamics Concepts through a Context-Based Approach

    Science.gov (United States)

    Cigdemoglu, Ceyhan; Geban, Omer

    2015-01-01

    The aim of this study was to delve into the effect of context-based approach (CBA) over traditional instruction (TI) on students' chemical literacy level related to thermochemical and thermodynamics concepts. Four eleventh-grade classes with 118 students in total taught by two teachers from a public high school in 2012 fall semester were enrolled…

  7. Thermo-chemical simultion of a composite offshore vertical axis wind turbine blade

    NARCIS (Netherlands)

    Baran, Ismet; Tutum, Cem Celal; Hattel, Jesper Henri

    2012-01-01

    In the present study three dimensional steady state thermo-chemical simulation of a pultrusion process is investigated by using the finite element/nodal control volume (FE/NCV) technique. Pultrusion simulation of a composite having a C-shaped cross section is performed as a validation case. The

  8. 3D dual-confined sulfur encapsulated in porous carbon nanosheets and wrapped with graphene aerogels as a cathode for advanced lithium sulfur batteries

    Science.gov (United States)

    Hou, Yang; Li, Jianyang; Gao, Xianfeng; Wen, Zhenhai; Yuan, Chris; Chen, Junhong

    2016-04-01

    Although lithium-sulfur (Li-S) batteries have attracted much attention due to their high theoretical specific energy and low cost, their practical applications have been severely hindered by poor cycle life, inadequate sulfur utilization, and the insulating nature of sulfur. Here, we report a rationally designed Li-S cathode with a dual-confined configuration formed by confining sulfur in 2D carbon nanosheets with an abundant porous structure followed by 3D graphene aerogel wrapping. The porous carbon nanosheets act as the sulfur host and suppress the diffusion of polysulfide, while the graphene conductive networks anchor the sulfur-adsorbed carbon nanosheets, providing pathways for rapid electron/ion transport and preventing polysulfide dissolution. As a result, the hybrid electrode exhibits superior electrochemical performance, including a large reversible capacity of 1328 mA h g-1 in the first cycle, excellent cycling stability (maintaining a reversible capacity of 647 mA h g-1 at 0.2 C after 300 cycles) with nearly 100% Coulombic efficiency, and a high rate capability of 512 mA h g-1 at 8 C for 30 cycles, which is among the best reported rate capabilities.Although lithium-sulfur (Li-S) batteries have attracted much attention due to their high theoretical specific energy and low cost, their practical applications have been severely hindered by poor cycle life, inadequate sulfur utilization, and the insulating nature of sulfur. Here, we report a rationally designed Li-S cathode with a dual-confined configuration formed by confining sulfur in 2D carbon nanosheets with an abundant porous structure followed by 3D graphene aerogel wrapping. The porous carbon nanosheets act as the sulfur host and suppress the diffusion of polysulfide, while the graphene conductive networks anchor the sulfur-adsorbed carbon nanosheets, providing pathways for rapid electron/ion transport and preventing polysulfide dissolution. As a result, the hybrid electrode exhibits superior

  9. Fossilization of melanosomes via sulfurization.

    Science.gov (United States)

    McNamara, Maria E; van Dongen, Bart E; Lockyer, Nick P; Bull, Ian D; Orr, Patrick J

    2016-05-01

    Fossil melanin granules (melanosomes) are an important resource for inferring the evolutionary history of colour and its functions in animals. The taphonomy of melanin and melanosomes, however, is incompletely understood. In particular, the chemical processes responsible for melanosome preservation have not been investigated. As a result, the origins of sulfur-bearing compounds in fossil melanosomes are difficult to resolve. This has implications for interpretations of original colour in fossils based on potential sulfur-rich phaeomelanosomes. Here we use pyrolysis gas chromatography mass spectrometry (Py-GCMS), fourier transform infrared spectroscopy (FTIR) and time of flight secondary ion mass spectrometry (ToF-SIMS) to assess the mode of preservation of fossil microstructures, confirmed as melanosomes based on the presence of melanin, preserved in frogs from the Late Miocene Libros biota (NE Spain). Our results reveal a high abundance of organosulfur compounds and non-sulfurized fatty acid methyl esters in both the fossil tissues and host sediment; chemical signatures in the fossil tissues are inconsistent with preservation of phaeomelanin. Our results reflect preservation via the diagenetic incorporation of sulfur, i.e. sulfurization (natural vulcanization), and other polymerization processes. Organosulfur compounds and/or elevated concentrations of sulfur have been reported from melanosomes preserved in various invertebrate and vertebrate fossils and depositional settings, suggesting that preservation through sulfurization is likely to be widespread. Future studies of sulfur-rich fossil melanosomes require that the geochemistry of the host sediment is tested for evidence of sulfurization in order to constrain interpretations of potential phaeomelanosomes and thus of original integumentary colour in fossils.

  10. Sulfur cycling and metabolism of phototrophic and filamentous sulfur bacteria

    Science.gov (United States)

    Guerrero, R.; Brune, D.; Poplawski, R.; Schmidt, T. M.

    1985-01-01

    Phototrophic sulfur bacteria taken from different habitate (Alum Rock State Park, Palo Alto salt marsh, and Big Soda Lake) were grown on selective media, characterized by morphological and pigment analysis, and compared with bacteria maintained in pure culture. A study was made of the anaerobic reduction of intracellular sulfur globules by a phototrophic sulfur bacterium (Chromatium vinosum) and a filamentous aerobic sulfur bacterium (Beggiatoa alba). Buoyant densities of different bacteria were measured in Percoll gradients. This method was also used to separate different chlorobia in mixed cultures and to assess the relative homogeneity of cultures taken directly or enriched from natural samples (including the purple bacterial layer found at a depth of 20 meters at Big Soda Lake.) Interactions between sulfide oxidizing bacteria were studied.

  11. Numerical Modeling of Deep Mantle Flow: Thermochemical Convection and Entrainment

    Science.gov (United States)

    Mulyukova, Elvira; Steinberger, Bernhard; Dabrowski, Marcin; Sobolev, Stephan

    2013-04-01

    ) upwelling of the ambient material in the vicinity of the dense material (mechanism of selective withdrawal (Lister, 1989)), and (iii) cold downwellings sliding along the bottom boundary, and forcing the dense material upwards. The objective of this study is to compare the efficiency of entrainment by each of these mechanisms, and its dependence on the density and viscosity anomaly of the dense material with respect to the ambient mantle. To perform this study, we have developed a two-dimensional FEM code to model thermal convection in a hollow cylinder domain with presence of chemical heterogeneities, and using a realistic viscosity profile. We present the results of the simulations that demonstrate the entrainment mechanisms described above. In addition, we perfom numerical experiments in a Cartesian box domain, where the bottom right boundary of the box is deformed to resemble the geometry of an LLSVP edge. In some of the experiments, the bottom left part of the boundary is moving towards the right boundary, simulating a slab sliding along the core-mantle boundary towards an LLSVP. These experiments allow a detailed study of the process of entrainment, and its role in the thermochemical evolution of the Earth.

  12. Method of preparing graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuliang; Li, Xiaolin

    2015-04-07

    A method of preparing a graphene-sulfur nanocomposite for a cathode in a rechargeable lithium-sulfur battery comprising thermally expanding graphite oxide to yield graphene layers, mixing the graphene layers with a first solution comprising sulfur and carbon disulfide, evaporating the carbon disulfide to yield a solid nanocomposite, and grinding the solid nanocomposite to yield the graphene-sulfur nanocomposite. Rechargeable-lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter of less than 50 nm.

  13. Refined Sulfur Nanoparticles Immobilized in Metal-Organic Polyhedron as Stable Cathodes for Li-S Battery.

    Science.gov (United States)

    Bai, Linyi; Chao, Dongliang; Xing, Pengyao; Tou, Li Juan; Chen, Zhen; Jana, Avijit; Shen, Ze Xiang; Zhao, Yanli

    2016-06-15

    The lithium-sulfur (Li-S) battery presents a promising rechargeable energy storage technology for the increasing energy demand in a worldwide range. However, current main challenges in Li-S battery are structural degradation and instability of the solid-electrolyte interphase caused by the dissolution of polysulfides during cycling, resulting in the corrosion and loss of active materials. Herein, we developed novel hybrids by employing metal-organic polyhedron (MOP) encapsulated PVP-functionalized sulfur nanoparticles (S@MOP), where the active sulfur component was efficiently encapsulated within the core of MOP and PVP as a surfactant was helpful to stabilize the sulfur nanoparticles and control the size and shape of corresponding hybrids during their syntheses. The amount of sulfur embedded into MOP could be controlled according to requirements. By using the S@MOP hybrids as cathodes, an obvious enhancement in the performance of Li-S battery was achieved, including high specific capacity with good cycling stability. The MOP encapsulation could enhance the utilization efficiency of sulfur. Importantly, the structure of the S@MOP hybrids was very stable, and they could last for almost 1000 cycles as cathodes in Li-S battery. Such high performance has rarely been obtained using metal-organic framework systems. The present approach opens up a promising route for further applications of MOP as host materials in electrochemical and energy storage fields.

  14. Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

    Science.gov (United States)

    Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

    2014-06-17

    Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

  15. Hybrid Baryons

    CERN Document Server

    Page, P R

    2003-01-01

    We review the status of hybrid baryons. The only known way to study hybrids rigorously is via excited adiabatic potentials. Hybrids can be modelled by both the bag and flux-tube models. The low-lying hybrid baryon is N 1/2^+ with a mass of 1.5-1.8 GeV. Hybrid baryons can be produced in the glue-rich processes of diffractive gamma N and pi N production, Psi decays and p pbar annihilation.

  16. Dazhou Becomes China's Sulfur Base

    Institute of Scientific and Technical Information of China (English)

    Zhang He

    2008-01-01

    @@ Located at the juncture of Sichuan, Hubei, Shaanxi provinces and Chongqing municipality, Dazhou,which is a city in the eastem part of Southwest China's Sichuan Province and has convenient transport facilities, boasts natural gas reserves of 3.8 trillion cubic meters, of which 660 billion cubic meters have been found. It will make full use of its natural gas reserves to build Asia's largest sulfur producing base by 2010 when its annual sulfur output is expected to surpass 4 million tons.

  17. High-Flux Solar-Driven Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria

    National Research Council Canada - National Science Library

    William C. Chueh; Christoph Falter; Mandy Abbott; Danien Scipio; Philipp Furler; Sossina M. Haile; Aldo Steinfeld

    2010-01-01

    .... By using a solar cavity-receiver reactor, we combined the oxygen uptake and release capacity of cerium oxide and facile catalysis at elevated temperatures to thermochemically dissociate CO 2 and H 2...

  18. Optimizing stratospheric sulfur geoengineering by seasonally changing sulfur injections

    Science.gov (United States)

    Laakso, Anton; Partanen, Antti-Ilari; Kokkola, Harri; Lehtinen, Kari; Korhonen, Hannele

    2015-04-01

    Solar radiation management (SRM) by stratospheric sulfur injection has been shown to have potential in counteracting global warming if reducing of greenhouse gases has not been achieved fast enough and if climate warming will continue. Injecting large amounts of sulfate particles to the stratosphere would increase the reflectivity of the atmosphere and less sunlight would reach the surface. However, the effectivity (per injected sulphur mass unit) of this kind of geoengineering would decrease when amount of injected sulfur is increased. When sulfur concentration increases, stratospheric particles would grow to larger sizes which have larger gravitational settling velocity and which do not reflect radiation as efficiently as smaller particles. In many previous studies, sulfur has been assumed to be injected along the equator where yearly mean solar intensity is the highest and from where sulfur is spread equally to both hemispheres. However, the solar intensity will change locally during the year and sulfate has been assumed to be injected and spread to the hemisphere also during winter time, when the solar intensity is low. Thus sulfate injection could be expected to be more effective, if sulfur injection area is changed seasonally. Here we study effects of the different SRM injection scenarios by using two versions of the MPI climate models. First, aerosol spatial and temporal distributions as well as the resulting radiative properties from the SRM are defined by using the global aerosol-climate model ECHAM6.1-HAM2.2-SALSA. After that, the global and regional climate effects from different injection scenarios are predicted by using the Max Planck Institute's Earth System Model (MPI-ESM). We carried out simulations, where 8 Tg of sulfur is injected as SO2 to the stratosphere at height of 20-22 km in an area ranging over a 20 degree wide latitude band. Results show that changing the sulfur injection area seasonally would lead to similar global mean shortwave

  19. Nitrogen-doped MOF-derived micropores carbon as immobilizer for small sulfur molecules as a cathode for lithium sulfur batteries with excellent electrochemical performance.

    Science.gov (United States)

    Li, Zhaoqiang; Yin, Longwei

    2015-02-25

    Nitrogen-doped carbon (NDC) spheres with abundant 22 nm mesopores and 0.5 nm micropores are obtained by directly carbonization of nitrogen-contained metal organic framework (MOF) nanocrystals. Large S8 and small S2-4 molecules are successfully infiltrated into 22 nm mesopores and 0.5 nm micropores, respectively. We successfully investigate the effect of sulfur immobilization in mesopores and micropores on the electrochemical performance of lithium-sulfur (Li-S) battery based on NDC-sulfur hybrid cathodes. The large S8 molecules in 22 nm mesopores can be removed by a prolonged heat treatment, with only small molecules of S2-4 immobilized in micropores of NDC matrices. The NDC/S2-4 hybrid exhibits excellent cycling performance, high Coulombic efficiency, and good rate capability as cathode for Li-S batteries. The confinement of smaller S2-4 molecules in the micropores of NDS efficiently avoids the loss of active sulfur and formation of soluble high-order Li polysulfides. The porous carbon can buffer the volume expansion and contraction changes, promising a stable structure for cathode. Furthermore, N doping in MOF-derived carbon not only facilitates the fast charge transfer but also is helpful in building a stronger interaction between carbon and sulfur, strengthening immobilization ability of S2-4 in micropores. The NDS-sulfur hybrid cathode exhibits a reversible capacity of 936.5 mAh g(-1) at 100th cycle with a Coulombic efficiency of 100% under a current density of 335 mA g(-1). It displays a superior rate capability performance, delivering a capacity of 632 mAh g(-1) at a high rate of 5 A g(-1). This uniquely porous NDC derived from MOF nanocrystals could be applied in related high-energy storage devices.

  20. Sulfur-impregnated disordered carbon nanotubes cathode for lithium-sulfur batteries.

    Science.gov (United States)

    Guo, Juchen; Xu, Yunhua; Wang, Chunsheng

    2011-10-12

    The commercialization of lithium-sulfur batteries is hindered by low cycle stability and low efficiency, which are induced by sulfur active material loss and polysulfide shuttle reaction through dissolution into electrolyte. In this study, sulfur-impregnated disordered carbon nanotubes are synthesized as cathode material for the lithium-sulfur battery. The obtained sulfur-carbon tube cathodes demonstrate superior cyclability and Coulombic efficiency. More importantly, the electrochemical characterization indicates a new stabilization mechanism of sulfur in carbon induced by heat treatment.

  1. Thermochemical process for seasonal storage of solar energy: characterization and modeling of a high-density reactive bed

    OpenAIRE

    Michel, Benoit; Mazet, Nathalie; Mauran, Sylvain; Stitou, Driss; Jing XU

    2012-01-01

    International audience; This paper focuses on the characterization and modeling of a solid/gas thermochemical reaction between a porous reactive bed and moist air flowing through it. The aim is the optimization of both energy density and permeability of the reactive bed, in order to realize a high density thermochemical system for seasonal thermal storage for house heating application. Several samples with different implementation parameters (density, binder, diffuser, porous bed texture) hav...

  2. Spinel Metal Oxide-Alkali Carbonate-Based, Low-Temperature Thermochemical Cycles for Water Splitting and CO_2 Reduction

    OpenAIRE

    Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.

    2013-01-01

    A manganese oxide-based, thermochemical cycle for water splitting below 1000 °C has recently been reported. The cycle involves the shuttling of Na+ into and out of manganese oxides via the consumption and formation of sodium carbonate, respectively. Here, we explore the combinations of three spinel metal oxides and three alkali carbonates in thermochemical cycles for water splitting and CO_2 reduction. Hydrogen evolution and CO_2 reduction reactions of metal oxides with a given alkali carbona...

  3. Co3O4-Carbon Cloth free standing cathode for lithium sulfur battery

    Science.gov (United States)

    Xu, Jing; Su, Dawei; Wang, Guoxiu

    2017-07-01

    Lithium-sulfur (Li-S) battery has been considered to be one of the most promising next-generation electrochemical energy-storage systems due to its high theoretical energy of 2600 Wh kg-1 with low cost. The insulating nature of both sulfur and the dissolution of polysulfides are the two primary challenges for the application of lithium sulfur batteries. Here, we developed a binder-free cathode by chemisorption of Co3O4 to carbon cloth (CC), which was used as a 3D current collector to accommodate a large amount of sulfur, multiwall carbon nanofiber (MWCNF) and carbon black (CB) hybrids within the conductive scaffold, enabling the fabrication of ultrahigh sulfur loaded electrodes. The interconnected carbon fibers established a long-range conductive matrix for an efficient electron transport, the multiple conductive pathways guarantee high sulfur utilization. More importantly, the high electrolyte absorbability of the Co3O4-CC-S current collector facilitates well-localized polysulfides within the Co3O4-CC-S, meanwhile, the polar Co3O4 could also effectively entrapped the intermediated polysulfides preventing their free diffusion to the lithium anode, guaranteeing good cycling stability. Consequently, the Co3O4-CC-S electrodes exhibit excellent electrochemical performance with sulfur loading of 4.3 mg cm-2.

  4. Well-dispersed sulfur anchored on interconnected polypyrrole nanofiber network as high performance cathode for lithium-sulfur batteries

    Science.gov (United States)

    Yin, Fuxing; Liu, Xinyi; Zhang, Yongguang; Zhao, Yan; Menbayeva, Almagul; Bakenov, Zhumabay; Wang, Xin

    2017-04-01

    Preparation of novel sulfur/polypyrrole (S/PPy) composite consisting well-dispersed sulfur particles anchored on interconnected PPy nanowire network was demonstrated. In such hybrid structure, the as-prepared PPy clearly displays a three-dimensionally cross-linked and hierarchical porous structure, which was utilized in the composite cathode as a conductive network trapping soluble polysulfide intermediates and enhancing the overall electrochemical performance of the system. Benefiting from this unique structure, the S/PPy composite demonstrated excellent cycling stability, resulting in a discharge capacity of 931 mAh g-1 at the second cycle and retained about 54% of this value over 100 cycles at 0.1 C. Furthermore, the S/PPy composite cathode exhibits a good rate capability with a discharge capacity of 584 mAh g-1 at 1 C.

  5. Thermo-chemical, mechanical and resin flow integrated analysis in pultrusion

    Science.gov (United States)

    Carlone, Pierpaolo; Rubino, Felice; Palazzo, Gaetano S.

    2016-10-01

    The present work discusses some numerical outcomes provided by an integrated analysis of impregnation, thermo-chemical and stress/strain aspects in a conventional pultrusion process. The impregnation models describes resin flow and pressure distribution in the initial portion of the die, solving a non-homogeneous non-isothermal/reactive multiphase problem, using a finite volume scheme. The thermochemical model describes the heat transfer and degree of cure evolution of the processing resin. Finally, the stress/strain model computes the part distortion and in process stresses due to thermal, chemical, mechanical strains. An applicative case study is presented, simulating the impregnation step of the pultrusion process of a fiberglass-epoxy resin composite rod.

  6. A thermochemical calculation of the pyroxene saturation surface in the system diopside-albite-anorthite

    Science.gov (United States)

    Hon, R.; Henry, D. J.; Navrotsky, A.; Weill, D. F.

    1981-01-01

    The pyroxene saturation surface in the system diopside-albite-anorthite may be calculated to + or - 10 C from thermochemical data over most of its composition range. The thermochemical data used are the experimentally determined enthalpies of mixing of the ternary liquids and the enthalpy of fusion of diopside. These are combined with a mixing model for the configurational entropy in the melt and the activity of CaMgSi2O6 in the clinopyroxene, which is less than unity due to departures from CaMgSi2O6 stoichiometry. The two-lattice melt model appears to work satisfactorily throughout the pyroxene primary phase field but probably needs modification at more anorthite-rich compositions.

  7. Materials-Related Aspects of Thermochemical Water and Carbon Dioxide Splitting: A Review

    Directory of Open Access Journals (Sweden)

    Robert Pitz-Paal

    2012-10-01

    Full Text Available Thermochemical multistep water- and CO2-splitting processes are promising options to face future energy problems. Particularly, the possible incorporation of solar power makes these processes sustainable and environmentally attractive since only water, CO2 and solar power are used; the concentrated solar energy is converted into storable and transportable fuels. One of the major barriers to technological success is the identification of suitable active materials like catalysts and redox materials exhibiting satisfactory durability, reactivity and efficiencies. Moreover, materials play an important role in the construction of key components and for the implementation in commercial solar plants. The most promising thermochemical water- and CO2-splitting processes are being described and discussed with respect to further development and future potential. The main materials-related challenges of those processes are being analyzed. Technical approaches and development progress in terms of solving them are addressed and assessed in this review.

  8. Thermochemical ablation of carbon/carbon composites with non-linear thermal conductivity

    Directory of Open Access Journals (Sweden)

    Li Wei-Jie

    2014-01-01

    Full Text Available Carbon/carbon composites have been typically used to protect a rocket nozzle from high temperature oxidizing gas. Based on the Fourier’s law of heat conduction and the oxidizing ablation mechanism, the ablation model with non-linear thermal conductivity for a rocket nozzle is established in order to simulate the one-dimensional thermochemical ablation rate on the surface and the temperature distributions by using a written computer code. As the presented results indicate, the thermochemical ablation rate of a solid rocket nozzle calculated by using actual thermal conductivity, which is a function of temperature, is higher than that by a constant thermal conductivity, so the effect of thermal conductivity on the ablation rate of a solid rocket nozzle made of carbon/carbon composites cannot be neglected.

  9. Thermochemical sulphate reduction and Huayuan lead-zinc ore deposit in Hunan, China

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In recent years, some arguments with regard to the organicmineralization of MVT lead-zinc ore deposit are focused on the thermochemical sulphate reduction in the presence of organic matter. Based on the research into the organic geochemistry and C, O, S isotopes of mineralized host rocks, mineral gas fluid inclusion and solid bitumen from Huayuan (W. Hunan, China) lead-zinc ore deposit formed in the algal limestones of Qingxudong formation, Lower Cambrian, the authors consider that a lot of organic matter occurred and participated in mineralization. The organic matter from different sources participated in the mineralization with two main forms: thermochemical sul-phate reduction and thermal degradation which supplied abundant H2S for the precipitation.

  10. Properties of 15HN Steel after Various Thermo-Chemical Treatments

    Directory of Open Access Journals (Sweden)

    L. Klimek

    2007-07-01

    Full Text Available The aim of conducted research was to find universal steel that may serve to regenerate machine elements by MULTIPLEX method – or cladding of alloy steel and then subjecting to thermo-chemical treatment. This paper presents the results of metallographic examination, hardness distribution and selected tribological properties of vacuum carburized, sulphonitrided and vacuum nitrided layers obtained on 15HN steel. The results demonstrate that on 15HN steel (carburizing steel, nitrided and sulphonitrided layers show good durability and tribological properties. Therefore, it is possible to use it to regenerate machine elements by cladding method and then treat them by different thermo-chemical ways in order to obtain desired properties.

  11. Thermochemical energy storage with ammonia: Aiming for the sunshot cost target

    Science.gov (United States)

    Lavine, Adrienne S.; Lovegrove, Keith M.; Jordan, Joshua; Anleu, Gabriela Bran; Chen, Chen; Aryafar, Hamarz; Sepulveda, Abdon

    2016-05-01

    Thermochemical energy storage has the potential to reduce the cost of concentrating solar thermal power. This paper presents recent advances in ammonia-based thermochemical energy storage (TCES), supported by an award from the U.S. Dept. of Energy SunShot program. Advances have been made in three areas: identification of promising approaches for underground containment of the gaseous products of the dissociation reaction, demonstration that ammonia synthesis can be used to generate steam for a supercritical-steam Rankine cycle, and a preliminary design for integration of the endothermic reactors within a tower receiver. Based on these advances, ammonia-based TCES shows promise to meet the 15/kWht SunShot cost target.

  12. Thermochemical pretreatments for enhancing succinic acid production from industrial hemp (Cannabis sativa L.).

    Science.gov (United States)

    Gunnarsson, Ingólfur B; Kuglarz, Mariusz; Karakashev, Dimitar; Angelidaki, Irini

    2015-04-01

    The aim of this study was to develop an efficient thermochemical method for treatment of industrial hemp biomass, in order to increase its bioconversion to succinic acid. Industrial hemp was subjected to various thermochemical pretreatments using 0-3% H2SO4, NaOH or H2O2 at 121-180°C prior to enzymatic hydrolysis. The influence of the different pretreatments on hydrolysis and succinic acid production by Actinobacillus succinogenes 130Z was investigated in batch mode, using anaerobic bottles and bioreactors. Enzymatic hydrolysis and fermentation of hemp material pretreated with 3% H2O2 resulted in the highest overall sugar yield (73.5%), maximum succinic acid titer (21.9 g L(-1)), as well as the highest succinic acid yield (83%). Results obtained clearly demonstrated the impact of different pretreatments on the bioconversion efficiency of industrial hemp into succinic acid.

  13. Application of Thermochemical Modeling to Assessment/Evaluation of Nuclear Fuel Behavior

    Energy Technology Data Exchange (ETDEWEB)

    Besmann, Theodore M [University of South Carolina, Columbia; McMurray, Jake W [ORNL; Simunovic, Srdjan [ORNL

    2016-01-01

    The combination of new fuel compositions and higher burn-ups envisioned for the future means that representing fuel properties will be much more important, and yet more complex. Behavior within the oxide fuel rods will be difficult to model owing to the high temperatures, and the large number of elements generated and their significant concentrations that are a result of fuels taken to high burn-up. This unprecedented complexity offers an enormous challenge to the thermochemical understanding of these systems and opportunities to advance solid solution models to describe these materials. This paper attempts to model and simulate that behavior using an oxide fuels thermochemical description to compute the equilibrium phase state and oxygen potential of LWR fuel under irradiation.

  14. Experimental results of a 3 k Wh thermochemical heat storage module for space heating application

    OpenAIRE

    Finck, C.J.; Henquet, E.M.R.; Soest, C.F.L. van; Oversloot, H.P.; de Jong, A. J.; Cuypers, R.; Spijker, J.C. van 't

    2014-01-01

    A 3 kWh thermochemical heat storage (TCS) module was built as part of an all-in house system implementation focusing on space heating application at a temperature level of 40 ºC and a temperature lift of 20 K. It has been tested and measurements showed a maximum water circuit temperature span (released by adsorption) of 20 – 51 K which is by all means suitable for space heating.

  15. Implementation and application of adaptive mesh refinement for thermochemical mantle convection studies

    OpenAIRE

    Leng, Wei; Zhong, Shijie

    2011-01-01

    Numerical modeling of mantle convection is challenging. Owing to the multiscale nature of mantle dynamics, high resolution is often required in localized regions, with coarser resolution being sufficient elsewhere. When investigating thermochemical mantle convection, high resolution is required to resolve sharp and often discontinuous boundaries between distinct chemical components. In this paper, we present a 2-D finite element code with adaptive mesh refinement techniques for si...

  16. Thermochemical properties and contribution groups for ketene dimers and related structures from theoretical calculations.

    Science.gov (United States)

    Morales, Giovanni; Martínez, Ramiro

    2009-07-30

    This research's main goals were to analyze ketene dimers' relative stability and expand group additivity value (GAV) methodology for estimating the thermochemical properties of high-weight ketene polymers (up to tetramers). The CBS-Q multilevel procedure and statistical thermodynamics were used for calculating the thermochemical properties of 20 cyclic structures, such as diketenes, cyclobutane-1,3-diones, cyclobut-2-enones and pyran-4-ones, as well as 57 acyclic base compounds organized into five groups. According to theoretical heat of formation predictions, diketene was found to be thermodynamically favored over cyclobutane-1,3-dione and its enol-tautomeric form (3-hydroxycyclobut-2-enone). This result did not agree with old combustion experiments. 3-Hydroxycyclobut-2-enone was found to be the least stable dimer and its reported experimental detection in solution may have been due to solvent effects. Substituted diketenes had lower stability than substituted cyclobutane-1,3-diones with an increased number of methyl substituents, suggesting that cyclobutane-1,3-dione type dimers are the major products because of thermodynamic control of alkylketene dimerization. Missing GAVs for the ketene dimers and related structures were calculated through linear regression on the 57 acyclic base compounds. Corrections for non next neighbor interactions (such as gauche, eclipses, and internal hydrogen bond) were needed for obtaining a highly accurate and precise regression model. To the best of our knowledge, the hydrogen bond correction for GAV methodology is the first reported in the literature; this correction was correlated to MP2/6-31Gdagger and HF/6-31Gdagger derived geometries to facilitate its application. GAVs assessed by the linear regression model were able to reproduce acyclic compounds' theoretical thermochemical properties and experimental heat of formation for acetylacetone. Ring formation and substituent position corrections were calculated by consecutively

  17. Effect of thermochemical treatment on the surface morphology and hydrophobicity of heterogeneous ion-exchange membranes

    Science.gov (United States)

    Vasil'eva, V. I.; Pismenskaya, N. D.; Akberova, E. M.; Nebavskaya, K. A.

    2014-08-01

    A comparative analysis is performed on the effect thermochemical treatment in aqueous, alkali, and acid media has on the surface morphology and hydrophobicity of swelling heterogeneous ion-exchanged membranes. A correlation between changes in surface morphology and hydrophobicity is established. It is shown that under prolonged (50 h) membrane thermal treatment above room temperature, hydrophobicity is reduced due to substantial enlargement of cavities and cracks resulting from the partial destruction of inert binder (polyethylene) and reinforcing poly-ɛ-caproamide fabric (capron).

  18. Synfuels from fusion: using the tandem mirror reactor and a thermochemical cycle to produce hydrogen

    Energy Technology Data Exchange (ETDEWEB)

    Werner, R.W. (ed.)

    1982-11-01

    This study is concerned with the following area: (1) the tandem mirror reactor and its physics; (2) energy balance; (3) the lithium oxide canister blanket system; (4) high-temperature blanket; (5) energy transport system-reactor to process; (6) thermochemical hydrogen processes; (7) interfacing the GA cycle; (8) matching power and temperature demands; (9) preliminary cost estimates; (10) synfuels beyond hydrogen; and (11) thermodynamics of the H/sub 2/SO/sub 4/-H/sub 2/O system. (MOW)

  19. New developments of the CARTE thermochemical code: I-parameter optimization

    Science.gov (United States)

    Desbiens, N.; Dubois, V.

    We present the calibration of the CARTE thermochemical code that allows to compute the properties of a wide variety of CHON explosives. We have developed an optimization procedure to obtain an accurate multicomponents EOS (fluid phase and condensed phase of carbon). We show here that the results of CARTE code are in good agreement with the specific data of molecular systems and we extensively compare our calculations with measured detonation properties for several explosives.

  20. New developments of the CARTE thermochemical code: I-parameter optimization

    Directory of Open Access Journals (Sweden)

    Dubois V.

    2011-01-01

    Full Text Available We present the calibration of the CARTE thermochemical code that allows to compute the properties of a wide variety of CHON explosives. We have developed an optimization procedure to obtain an accurate multicomponents EOS (fluid phase and condensed phase of carbon. We show here that the results of CARTE code are in good agreement with the specific data of molecular systems and we extensively compare our calculations with measured detonation properties for several explosives.

  1. Comparative Life Cycle Assessment of Lignocellulosic Ethanol Production: Biochemical Versus Thermochemical Conversion

    Science.gov (United States)

    Mu, Dongyan; Seager, Thomas; Rao, P. Suresh; Zhao, Fu

    2010-10-01

    Lignocellulosic biomass can be converted into ethanol through either biochemical or thermochemical conversion processes. Biochemical conversion involves hydrolysis and fermentation while thermochemical conversion involves gasification and catalytic synthesis. Even though these routes produce comparable amounts of ethanol and have similar energy efficiency at the plant level, little is known about their relative environmental performance from a life cycle perspective. Especially, the indirect impacts, i.e. emissions and resource consumption associated with the production of various process inputs, are largely neglected in previous studies. This article compiles material and energy flow data from process simulation models to develop life cycle inventory and compares the fossil fuel consumption, greenhouse gas emissions, and water consumption of both biomass-to-ethanol production processes. The results are presented in terms of contributions from feedstock, direct, indirect, and co-product credits for four representative biomass feedstocks i.e., wood chips, corn stover, waste paper, and wheat straw. To explore the potentials of the two conversion pathways, different technological scenarios are modeled, including current, 2012 and 2020 technology targets, as well as different production/co-production configurations. The modeling results suggest that biochemical conversion has slightly better performance on greenhouse gas emission and fossil fuel consumption, but that thermochemical conversion has significantly less direct, indirect, and life cycle water consumption. Also, if the thermochemical plant operates as a biorefinery with mixed alcohol co-products separated for chemicals, it has the potential to achieve better performance than biochemical pathway across all environmental impact categories considered due to higher co-product credits associated with chemicals being displaced. The results from this work serve as a starting point for developing full life cycle

  2. Thermochemical ablation of carbon/carbon composites with non-linear thermal conductivity

    OpenAIRE

    2014-01-01

    Carbon/carbon composites have been typically used to protect a rocket nozzle from high temperature oxidizing gas. Based on the Fourier’s law of heat conduction and the oxidizing ablation mechanism, the ablation model with non-linear thermal conductivity for a rocket nozzle is established in order to simulate the one-dimensional thermochemical ablation rate on the surface and the temperature distributions by using a written computer code. As the presented re...

  3. Solar thermochemical reactor, methods of manufacture and use thereof and thermogravimeter

    Energy Technology Data Exchange (ETDEWEB)

    Klausner, James F.; Petrasch, Joerg

    2017-06-06

    A solar thermochemical reactor contains an outer member, an inner member disposed within an outer member, wherein the outer member surrounds the inner member and wherein the outer member has an aperture for receiving solar radiation. An inner cavity and an outer cavity are formed by the inner member and outer member and a reactive material that is capable of being magnetically stabilized is disposed in the outer cavity between the inner member and the outer member.

  4. Techniques for the estimation of Heats of Explosion (HEX) using thermochemical codes

    Science.gov (United States)

    Fifer, Robert A.; Morris, Jeffrey B.

    1993-09-01

    Procedures are outlined for calculating the heats of explosion (HEX) of neat energetic materials or propellant/explosive formulations using thermochemical codes. The 'exact' method and three approximate techniques are described; the approximate techniques either eliminate the need to sum the internal energies of the predicted products, or eliminate the need to specify a freeze-out temperature. The various techniques are illustrated for HMX and a nitrocellulose/nitroglycerine (NC/NG) mixture.

  5. Global thermochemical inversion of seismic waveforms, gravity satellite data, and topography

    Science.gov (United States)

    Fullea, J.; Lebedev, S.; Martinec, Z.

    2016-12-01

    Conventional methods of seismic tomography, topography, gravity and electromagnetic data analysis and geodynamic modelling constrain distributions of seismic velocity, density, electrical conductivity, and viscosity at depth, all depending on temperature and composition of Earth's rocks. However, modelling and interpretation of multiple data provide a multifaceted image of the true thermochemical structure of the Earth that needs to be consistently integrated. A simple combination of gravity, electromagnetic, geodynamics, petrological and seismic models alone is insufficient due to the non-uniqueness and different sensitivities of these models, and the internal consistency relationships that must connect all the intermediate parameters describing the Earth. In fact, global Earth models based on different observables often lead to rather different images of the Earth. A breakthrough in global and consistent imaging of the fine-scale thermochemical hydrous and rheological structure of the Earth's lithosphere and underlying mantle is needed. Thermodynamic and petrological links between seismic velocities, density, electrical conductivity, viscosity, melt, water, temperature, pressure and composition within the Earth can now be modelled accurately using new methods of computational petrology and data from laboratory experiments. The growth of very large terrestrial and satellite geophysical data over the last few years, together with the advancement of petrological and geophysical modelling techniques, now present an opportunity for global, thermochemical and deformation 3D imaging of the lithosphere and underlying upper mantle with unprecedented resolution. Here we present a method for self-consistent joint inversion of multiple data sets, including seismic, satellite gravity and surface topography data, applied to obtain a detailed and robust global thermochemical image of the lithosphere and underlying upper mantle. This project combines state-of-the-art seismic

  6. Thermo-chemical process with sewage sludge by using CO2.

    Science.gov (United States)

    Kwon, Eilhann E; Yi, Haakrho; Kwon, Hyun-Han

    2013-10-15

    This work proposed a novel methodology for energy recovery from sewage sludge via the thermo-chemical process. The impact of CO2 co-feed on the thermo-chemical process (pyrolysis and gasification) of sewage sludge was mainly investigated to enhance thermal efficiency and to modify the end products from the pyrolysis and gasification process. The CO2 injected into the pyrolysis and gasification process enhance the generation of CO. As compared to the thermo-chemical process in an inert atmosphere (i.e., N2), the generation of CO in the presence of CO2 was enhanced approximately 200% at the temperature regime from 600 to 900 °C. The introduction of CO2 into the pyrolysis and gasification process enabled the condensable hydrocarbons (tar) to be reduced considerably by expediting thermal cracking (i.e., approximately 30-40%); thus, exploiting CO2 as chemical feedstock and/or reaction medium for the pyrolysis and gasification process leads to higher thermal efficiency, which leads to environmental benefits. This work also showed that sewage sludge could be a very strong candidate for energy recovery and a raw material for chemical feedstock.

  7. Thermochemical recovery of heat contained in flue gases by means of bioethanol conversion

    Science.gov (United States)

    Pashchenko, D. I.

    2013-06-01

    In the present paper consideration is being given to the use of bioethanol in the schemes of thermochemical recovery of heat contained in exit flue gases. Schematic diagrams illustrate the realization of thermochemical heat recovery by implementing ethanol steam conversion and conversion of ethanol by means of products of its complete combustion. The feasibility of attaining a high degree of recovery of heat contained in flue gases at the moderate temperature (up to 450°C) of combustion components is demonstrated in the example of the energy balance of the system for thermochemical heat recovery. The simplified thermodynamic analysis of the process of ethanol steam conversion was carried out in order to determine possible ranges of variation of process variables (temperature, pressure, composition) of a reaction mixture providing the efficient heat utilization. It was found that at the temperature above 600 K the degree of ethanol conversion is near unity. The equilibrium composition of products of reaction of ethanol steam conversion has been identified for different temperatures at which the process occurs at the ratio H2O/EtOH = 1 and at the pressure of 0.1 MPa. The obtained results of calculation agree well with the experimental data.

  8. Application of program LAURA to thermochemical nonequilibrium flow through a nozzle

    Science.gov (United States)

    Gnoffo, Peter A.

    1991-01-01

    Program LAURA (Langley Aerothermodynamic Upwind Relaxation Algorithm) is an upwind-biased, point-implicit relaxation algorithm for obtaining the numerical solution to the governing equations for 3D viscous hypersonic flows in chemical and thermal nonequilibrium. The algorithm is derived using a finite-volume formulation in which the inviscid components of flux across cell walls are described with a modified Roe's averaging and with second-order corrections based on Yee's Symmetric Total Variation Diminishing scheme. The code has been applied to Problem 8.2 of this workshop for the case of thermochemical nonequilibrium flow through a nozzle. Chemical reaction rates are defined with the model of Park (1987). Thermal nonequilibrium is modeled using a two-temperature approximation in which the vibrational energies of all molecules are assumed to be in equilibrium at a single temperature which is generally different from the translational-rotational temperature. Two grids were used to define the flow for the original problem, with a stagnation temperature of 6500 K. A third case with a stagnation temperature of 10,000 K is also presented. The solution domain includes the converging nozzle, subsonic flow domain in which the gas is substantially in thermochemical equilibrium and the diverging nozzle, hypersonic flow domain in which the gas is substantially in thermochemical nonequilibrium.

  9. Recommended Ideal-Gas Thermochemical Functions for Heavy Water and its Substituent Isotopologues

    Science.gov (United States)

    Simkó, Irén; Furtenbacher, Tibor; Hrubý, Jan; Zobov, Nikolai F.; Polyansky, Oleg L.; Tennyson, Jonathan; Gamache, Robert R.; Szidarovszky, Tamás; Dénes, Nóra; Császár, Attila G.

    2017-06-01

    Accurate temperature-dependent ideal-gas internal partition functions, Qint(T), and several derived thermochemical functions are reported for heavy water, with an oxygen content corresponding to the isotopic composition of Vienna Standard Mean Ocean Water (VSMOW), and its constituent isotopologues, D216O, D217O, and D218O, for temperatures between 0 and 6000 K. The nuclear-spin-dependent partition functions are obtained by the direct summation technique, involving altogether about 16 000 measured and more than nine million computed bound rovibrational energy levels for the three molecules. Reliable standard uncertainties, as a function of temperature, are estimated for each thermochemical quantity determined, including the enthalpy, the entropy, and the isobaric heat capacity of the individual nuclear-spin-equilibrated isotopologues and of heavy water. The accuracy of the heavy-water ideal-gas Cp(T) is unprecedented, below 0.01% up to 1800 K. All the thermochemical functions are reported, in 1 K increments, in the supplementary material.

  10. Active Thermochemical Tables: Sequential Bond Dissociation Enthalpies of Methane, Ethane, and Methanol, and the Related Thermochemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ruscic, Branko

    2015-07-16

    Active Thermochemical Tables (ATcT) thermochemistry for the sequential bond dissociations of methane, ethane, and methanol systems were obtained by analyzing and solving a very large thermochemical network (TN). Values for all possible C–H, C–C, C–O, and O–H bond dissociation enthalpies at 298.15 K (BDE298) and bond dissociation energies at 0 K (D0) are presented. The corresponding ATcT standard gas-phase enthalpies of formation of the resulting CHn, n = 4–0 species (methane, methyl, methylene, methylidyne, and carbon atom), C2Hn, n = 6–0 species (ethane, ethyl, ethylene, ethylidene, vinyl, ethylidyne, acetylene, vinylidene, ethynyl, and ethynylene), and COHn, n = 4–0 species (methanol, hydroxymethyl, methoxy, formaldehyde, hydroxymethylene, formyl, isoformyl, and carbon monoxide) are also presented. The ATcT thermochemistry of carbon dioxide, water, hydroxyl, and carbon, oxygen, and hydrogen atoms is also included, together with the sequential BDEs of CO2 and H2O. The provenances of the ATcT enthalpies of formation, which are quite distributed and involve a large number of relevant determinations, are analyzed by variance decomposition and discussed in terms of principal contributions. The underlying reasons for periodic appearances of remarkably low and/or unusually high BDEs, alternating along the dissociation sequences, are analyzed and quantitatively rationalized. The present ATcT results are the most accurate thermochemical values currently available for these species.

  11. Benchmarking the DFT+U method for thermochemical calculations of uranium molecular compounds and solids.

    Science.gov (United States)

    Beridze, George; Kowalski, Piotr M

    2014-12-18

    Ability to perform a feasible and reliable computation of thermochemical properties of chemically complex actinide-bearing materials would be of great importance for nuclear engineering. Unfortunately, density functional theory (DFT), which on many instances is the only affordable ab initio method, often fails for actinides. Among various shortcomings, it leads to the wrong estimate of enthalpies of reactions between actinide-bearing compounds, putting the applicability of the DFT approach to the modeling of thermochemical properties of actinide-bearing materials into question. Here we test the performance of DFT+U method--a computationally affordable extension of DFT that explicitly accounts for the correlations between f-electrons - for prediction of the thermochemical properties of simple uranium-bearing molecular compounds and solids. We demonstrate that the DFT+U approach significantly improves the description of reaction enthalpies for the uranium-bearing gas-phase molecular compounds and solids and the deviations from the experimental values are comparable to those obtained with much more computationally demanding methods. Good results are obtained with the Hubbard U parameter values derived using the linear response method of Cococcioni and de Gironcoli. We found that the value of Coulomb on-site repulsion, represented by the Hubbard U parameter, strongly depends on the oxidation state of uranium atom. Last, but not least, we demonstrate that the thermochemistry data can be successfully used to estimate the value of the Hubbard U parameter needed for DFT+U calculations.

  12. Revisiting the BaO2/BaO redox cycle for solar thermochemical energy storage.

    Science.gov (United States)

    Carrillo, A J; Sastre, D; Serrano, D P; Pizarro, P; Coronado, J M

    2016-03-21

    The barium peroxide-based redox cycle was proposed in the late 1970s as a thermochemical energy storage system. Since then, very little attention has been paid to such redox couples. In this paper, we have revisited the use of reduction-oxidation reactions of the BaO2/BaO system for thermochemical heat storage at high temperatures. Using thermogravimetric analysis, reduction and oxidation reactions were studied in order to find the main limitations associated with each process. Furthermore, the system was evaluated through several charge-discharge stages in order to analyse its possible degradation after repeated cycling. Through differential scanning calorimetry the heat stored and released were also determined. Oxidation reaction, which was found to be slower than reduction, was studied in more detail using isothermal tests. It was observed that the rate-controlling step of BaO oxidation follows zero-order kinetics, although at high temperatures a deviation from Arrhenius behaviour was observed probably due to hindrances to anionic oxygen diffusion caused by the formation of an external layer of BaO2. This redox couple was able to withstand several redox cycles without deactivation, showing reaction conversions close to 100% provided that impurities are previously eliminated through thermal pre-treatment, demonstrating the feasibility of this system for solar thermochemical heat storage.

  13. Reuse of microalgae grown in full-scale wastewater treatment ponds: Thermochemical pretreatment and biogas production.

    Science.gov (United States)

    Passos, Fabiana; Felix, Leonardo; Rocha, Hemyle; Pereira, Jackson de Oliveira; de Aquino, Sérgio

    2016-06-01

    This study assessed thermochemical pretreatment of microalgae harvested from a full-scale wastewater treatment pond prior to its anaerobic digestion using acid and alkaline chemical doses combined with thermal pretreatment at 80°C. Results indicated that alkaline and thermal pretreatment contributed mostly to glycoprotein and pectin solubilisation; whilst acid pretreatment solubilised mostly hemicellulose, with lower effectiveness for proteins. Regarding the anaerobic biodegradability, biochemical methane potential (BMP) tests showed that final methane yield was enhanced after almost all pretreatment conditions when compared to non-pretreated microalgae, with the highest increase for thermochemical pretreatment at the lowest dose (0.5%), i.e. 82% and 86% increase for alkaline and acid, respectively. At higher doses, salt toxicity was revealed by K(+) concentrations over 5000mg/L. All BMP data from pretreated biomass was successfully described by the modified Gompertz model and optimal condition (thermochemical 0.5% HCl) showed an increase in final methane yield and the process kinetics. Copyright © 2016 Elsevier Ltd. All rights reserved.

  14. Deep Structures and Initiation of Plate Tectonics in Thermochemical Mantle Convection Models

    Science.gov (United States)

    Hansen, U.; Stein, C.

    2015-12-01

    Recently deep thermochemical structures have been studied intensively. The observed large anomalies with reduced seismic velocities (LLSVPs) beneath Africa and the Pacific are obtained in numerical models as an initial dense layer at the core-mantle boundary (CMB) is pushed up to piles by the convective flow (e.g., McNamara et al., EPSL 229, 1-9, 2010). Adding a dense CMB layer to a model featuring active plate tectonics, Trim et al. (EPSL 405, 1-14, 2014) find that surface mobility is strongly hindered by the dense material and can even vanish completely for a CMB layer that has a too high density or too large a volume.In a further study we employed a fully rheological model in which oceanic plates form self-consistently. We observe that an initial dense CMB layer strongly affects the formation of plates and therefore the onset time of plate tectonics. We present a systematic 2D parameter study exploring the time of plate initiation and discuss the resulting deep thermal and thermochemical structures in a self-consistent thermochemical mantle convection system.

  15. Biochemistry of Dissimilatory Sulfur Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Blake II, R.

    2003-05-30

    The long term goals of this research were to define the substrate oxidation pathways, the electron transport mechanisms, and the modes of energy conservation employed during the dissimilatory oxidation of sulfur practiced by various species of the thiobacilli. Specific adhesion of the thiobacilli to elemental sulfur was studied by electrical impedance, dynamic light scattering, laser Doppler velocimetry, and optical trapping methods. The conclusion is that the thiobacilli appear to express specific receptors that enable the bacteria to recognize and adhere to insoluble sulfur. The enzyme tetrathionate oxidase was purified from two species of the thiobacilli. Extensive structural and functional studies were conducted on adenosine 5'-phosphosulfate reductase purified from cell-free extracts of Thiobacillus denitrificans. The kinetic mechanism of rhodanese was studied.

  16. Hybrid vehicles

    Energy Technology Data Exchange (ETDEWEB)

    West, J.G.W. [Electrical Machines (United Kingdom)

    1997-07-01

    The reasons for adopting hybrid vehicles result mainly from the lack of adequate range from electric vehicles at an acceptable cost. Hybrids can offer significant improvements in emissions and fuel economy. Series and parallel hybrids are compared. A combination of series and parallel operation would be the ideal. This can be obtained using a planetary gearbox as a power split device allowing a small generator to transfer power to the propulsion motor giving the effect of a CVT. It allows the engine to run at semi-constant speed giving better fuel economy and reduced emissions. Hybrid car developments are described that show the wide range of possible hybrid systems. (author)

  17. Physiology of Haloalkaliphilic Sulfur-oxidizing Bacteria

    NARCIS (Netherlands)

    Banciu, H.L.

    2004-01-01

    The inorganic sulfur oxidation by obligate haloalkaliphilic chemolithoautotrophs was only recently discovered and investigated. These autotrophic sulfur oxidizing bacteria (SOB), capable of oxidation of inorganic sulfur compounds at moderate to high salt concentration and at high pH, can be divided

  18. Genetic engineering of sulfur-degrading Sulfolobus

    Energy Technology Data Exchange (ETDEWEB)

    Ho, N.W.Y.

    1991-01-01

    The objectives of the proposed research is to first establish a plasmid-mediated genetic transformation system for the sulfur degrading Sulfolobus, and then to clone and overexpress the genes encoding the organic-sulfur-degrading enzymes from Sulfolobus- as well as from other microorganisms, to develop a Sulfolobus-based microbial process for the removal of both organic and inorganic sulfur from coal.

  19. Sulfur: its clinical and toxicologic aspects.

    Science.gov (United States)

    Komarnisky, Lioudmila A; Christopherson, Robert J; Basu, Tapan K

    2003-01-01

    Although there is no known dietary requirement for inorganic sulfur, it is an essential element for all animal species in as much as they all require the sulfur-containing amino acid methionine. There are three predominate forms of organic sulfur in animals and humans: 1). the thiomethyl of methionine residues in protein; 2). the sulfhydryl disulfides of protein; and 3). the compounds containing ester or amide bound sulfates of glycosaminoglycans, steroids, and many xenobiotic metabolites. Thus, sulfur becomes an important constituent of amino acids, proteins, enzymes, vitamins and other biomolecules. Unlike mammalian species, plants can use inorganic sulfur and synthesize methionine from which are synthesized all the other important sulfur compounds. Hence, sulfur deficiency occurs mainly when plants are grown in sulfur-depleted soils and when humans and animals consume low-protein diets. In recent times, however, the increasing prevalence of refining petroleum and smelting sulfur compounds of metallic minerals into free metals are having a large impact on the balance of sulfur in the environment. Sulfur toxicity is associated mainly with high levels of the element and its toxic volatile substances in the environment. Sulfur dioxide (SO(2)), a major air pollutant, may adversely affect animal and human health by causing bronchitis, bronchoconstriction, and increased pulmonary resistance.

  20. Physiology of Haloalkaliphilic Sulfur-oxidizing Bacteria

    NARCIS (Netherlands)

    Banciu, H.L.

    2004-01-01

    The inorganic sulfur oxidation by obligate haloalkaliphilic chemolithoautotrophs was only recently discovered and investigated. These autotrophic sulfur oxidizing bacteria (SOB), capable of oxidation of inorganic sulfur compounds at moderate to high salt concentration and at high pH, can be divided

  1. Volatile earliest Triassic sulfur cycle

    DEFF Research Database (Denmark)

    Schobben, Martin; Stebbins, Alan; Algeo, Thomas J.

    2017-01-01

    Marine biodiversity decreases and ecosystem destruction during the end-Permian mass extinction (EPME) have been linked to widespread marine euxinic conditions. Changes in the biogeochemical sulfur cycle, microbial sulfate reduction (MSR), and marine dissolved sulfate concentrations during the Per...... of widespread euxinic conditions, posing a sustained threat to marine life during the Early Triassic....

  2. Insights into the iron and sulfur energetic metabolism of Acidithiobacillus ferrooxidans by microarray transcriptome profiling

    Energy Technology Data Exchange (ETDEWEB)

    R. Quatrini; C. Appia-Ayme; Y. Denis; J. Ratouchniak; F. Veloso; J. Valdes; C. Lefimil; S. Silver; F. Roberto; O. Orellana; F. Denizot; E. Jedlicki; D. Holmes; V. Bonnefoy

    2006-09-01

    Acidithiobacillus ferrooxidans is a well known acidophilic, chemolithoautotrophic, Gram negative, bacterium involved in bioleaching and acid mine drainage. In aerobic conditions, it gains energy mainly from the oxidation of ferrous iron and/or reduced sulfur compounds present in ores. After initial oxidation of the substrate, electrons from ferrous iron or sulfur enter respiratory chains and are transported through several redox proteins to oxygen. However, the oxidation of ferrous iron and reduced sulfur compounds has also to provide electrons for the reduction of NAD(P) that is subsequently required for many metabolic processes including CO2 fixation. To help to unravel the enzymatic pathways and the electron transfer chains involved in these processes, a genome-wide microarray transcript profiling analysis was carried out. Oligonucleotides corresponding to approximately 3000 genes of the A. ferrooxidans type strain ATCC23270 were spotted onto glass-slides and hybridized with cDNA retrotranscribed from RNA extracted from ferrous iron and sulfur grown cells. The genes which are preferentially transcribed in ferrous iron conditions and those preferentially transcribed in sulfur conditions were analyzed. The expression of a substantial number of these genes has been validated by real-time PCR, Northern blot hybridization and/or immunodetection analysis. Our results support and extend certain models of iron and sulfur oxidation and highlight previous observations regarding the possible presence of alternate electron pathways. Our findings also suggest ways in which iron and sulfur oxidation may be co-ordinately regulated. An accompanying paper (Appia-Ayme et al.) describes results pertaining to other metabolic functions.

  3. Sulfur-infiltrated graphene-backboned mesoporous carbon nanosheets with a conductive polymer coating for long-life lithium-sulfur batteries

    Science.gov (United States)

    Dong, Yanfeng; Liu, Shaohong; Wang, Zhiyu; Liu, Yang; Zhao, Zongbin; Qiu, Jieshan

    2015-04-01

    Sandwich-type, two-dimensional hybrid nanosheets were fabricated by the infiltration of nanosized sulfur into graphene-backboned mesoporous carbon with a PPy nanocoating. They exhibit a high reversible capacity for as long as 400 cycles with an ultra slow decay rate of 0.05% per cycle at the high rate of 1-3 C due to the efficient immobilization of polysulfides.Sandwich-type, two-dimensional hybrid nanosheets were fabricated by the infiltration of nanosized sulfur into graphene-backboned mesoporous carbon with a PPy nanocoating. They exhibit a high reversible capacity for as long as 400 cycles with an ultra slow decay rate of 0.05% per cycle at the high rate of 1-3 C due to the efficient immobilization of polysulfides. Electronic supplementary information (ESI) available: Experimental details, BET, SEM, XPS and more electrochemical data. See DOI: 10.1039/c5nr01015b

  4. Life cycle assessment of lithium sulfur battery for electric vehicles

    Science.gov (United States)

    Deng, Yelin; Li, Jianyang; Li, Tonghui; Gao, Xianfeng; Yuan, Chris

    2017-03-01

    Lithium-sulfur (Li-S) battery is widely recognized as the most promising battery technology for future electric vehicles (EV). To understand the environmental sustainability performance of Li-S battery on future EVs, here a novel life cycle assessment (LCA) model is developed for comprehensive environmental impact assessment of a Li-S battery pack using a graphene sulfur composite cathode and a lithium metal anode protected by a lithium-ion conductive layer, for actual EV applications. The Li-S battery pack is configured with a 61.3 kWh capacity to power a mid-size EV for 320 km range. The life cycle inventory model is developed with a hybrid approach, based on our lab-scale synthesis of the graphene sulfur composite, our lab fabrication of Li-S battery cell, and our industrial partner's battery production processes. The impacts of the Li-S battery are assessed using the ReCiPe method and benchmarked with those of a conventional Nickle-Cobalt-Manganese (NCM)-Graphite battery pack under the same driving distance per charge. The environmental impact assessment results illustrate that Li-S battery is more environmentally friendly than conventional NCM-Graphite battery, with 9%-90% lower impact. Finally, the improvement pathways for the Li-S battery to meet the USABC (U.S. Advanced Battery Consortium) targets are presented with the corresponding environmental impact changes.

  5. Rhodanese functions as sulfur supplier for key enzymes in sulfur energy metabolism.

    Science.gov (United States)

    Aussignargues, Clément; Giuliani, Marie-Cécile; Infossi, Pascale; Lojou, Elisabeth; Guiral, Marianne; Giudici-Orticoni, Marie-Thérèse; Ilbert, Marianne

    2012-06-08

    How microorganisms obtain energy is a challenging topic, and there have been numerous studies on the mechanisms involved. Here, we focus on the energy substrate traffic in the hyperthermophilic bacterium Aquifex aeolicus. This bacterium can use insoluble sulfur as an energy substrate and has an intricate sulfur energy metabolism involving several sulfur-reducing and -oxidizing supercomplexes and enzymes. We demonstrate that the cytoplasmic rhodanese SbdP participates in this sulfur energy metabolism. Rhodaneses are a widespread family of proteins known to transfer sulfur atoms. We show that SbdP has also some unusual characteristics compared with other rhodaneses; it can load a long sulfur chain, and it can interact with more than one partner. Its partners (sulfur reductase and sulfur oxygenase reductase) are key enzymes of the sulfur energy metabolism of A. aeolicus and share the capacity to use long sulfur chains as substrate. We demonstrate a positive effect of SbdP, once loaded with sulfur chains, on sulfur reductase activity, most likely by optimizing substrate uptake. Taken together, these results lead us to propose a physiological role for SbdP as a carrier and sulfur chain donor to these key enzymes, therefore enabling channeling of sulfur substrate in the cell as well as greater efficiency of the sulfur energy metabolism of A. aeolicus.

  6. Adsorption of 2-naphthalenesulfonic acid/sulfuric acid/sulfurous acid from aqueous solution by iron-impregnated weakly basic resin:Equilibrium and model

    Institute of Scientific and Technical Information of China (English)

    Changhai Li; Dongmei Jia

    2016-01-01

    Commercial grade weakly basic resin D301 was impregnated with iron through a simple method using ferric chloride. Experiments for single, bisolute and trinary competitive adsorption were carried out to investigate the adsorption behavior of 2-naphthalenesulfonic acid (NSA), sulfuric acid and sulfurous acid from their solution at 298K onto the novel hybrid iron impregnated D301(Fe-D301). Adsorption affinity of NSA on Fe-D301 was found to be much higher than that of sulfuric acid, while adsorption affinity of sulfuric acid was slightly higher than that of sulfurous acid. The data of single-solute adsorption were fitted to the Langmuir model and the Freundlich adsorption model. The non-ideal competitive adsorbed model coupled with the single-solute adsorp-tion models were used to predict the bisolute and trinary-solute competitive adsorption equilibria. The NICM coupled with the Langmuir model yields the favorable representation of the bisolute and trinary-solute compet-itive adsorption behavior.

  7. Use of detailed thermochemical databases to model chemical interactions in the Severe Accident codes

    Energy Technology Data Exchange (ETDEWEB)

    Barrachin, M. [IPSN/DRS, CEA Cadarache (France)

    2001-07-01

    For the prevention, mitigation and management of severe accidents, many problems related to core melt have to be solved: fuel degradation, melting and relocation, convection in the core melt(s), coolability of the core melt(s), fission product release, hydrogen production, behavior of the materials of the protective layers, ex-vessel spreading of the core melt(s).. To solve these problems such properties like thermal conductivity, heat capacity, density, viscosity, evaporation or sublimation of melts, the solidification behavior (solid/liquid fraction), the tendency to trap or to release the fission products, the stratification of melts notably metallic and oxide, must be known. However most of these properties are delicate to measure directly at high temperature and/or in the radio-active environment produced by the fission products. Therefore some of them must be derived by calculations from the physical-chemical description of the melt: number of phases, phase compositions, proportions of solids and liquids and their respective oxidation state, miscibility of the liquids, solubility of one phase in another, etc. This information is given by the phase diagrams of the materials in presence. Since more than ten years, IPSN has developed in collaboration with THERMODATA (Grenoble, France) a very detailed thermochemical database for the complex system U-O-Zr-Fe-Ni-La-Ba-Ru-Sr-Si-Mg-Ca-Al-(H-Ar). The direct coupling between the severe accident (SA) Codes and a thermochemical code with its database is not actually possible because of the computer time consuming and the size of the database. For this reason, most of the Severe Accident codes usually have a very simplified description for the phase diagrams which are not in agreement with the status of the art. In this presentation, alternative methodologies are detailed with their respective difficulties, the goal being to build an interface between a thermochemical database and a SA Code and to get a fast, accurate and

  8. Coupled thermochemical, isotopic evolution and heat transfer simulations in highly irradiated UO2 nuclear fuel

    Science.gov (United States)

    Piro, M. H. A.; Banfield, J.; Clarno, K. T.; Simunovic, S.; Besmann, T. M.; Lewis, B. J.; Thompson, W. T.

    2013-10-01

    Predictive capabilities for simulating irradiated nuclear fuel behavior are enhanced in the current work by coupling thermochemistry, isotopic evolution and heat transfer. Thermodynamic models that are incorporated into this framework not only predict the departure from stoichiometry of UO2, but also consider dissolved fission and activation products in the fluorite oxide phase, noble metal inclusions, secondary oxides including uranates, zirconates, molybdates and the gas phase. Thermochemical computations utilize the spatial and temporal evolution of the fission and activation product inventory in the pellet, which is typically neglected in nuclear fuel performance simulations. Isotopic computations encompass the depletion, decay and transmutation of more than 2000 isotopes that are calculated at every point in space and time. These computations take into consideration neutron flux depression and the increased production of fissile plutonium near the fuel pellet periphery (i.e., the so-called “rim effect”). Thermochemical and isotopic predictions are in very good agreement with reported experimental measurements of highly irradiated UO2 fuel with an average burnup of 102 GW d t(U)-1. Simulation results demonstrate that predictions are considerably enhanced when coupling thermochemical and isotopic computations in comparison to empirical correlations. Notice: This manuscript has been authored by UT-Battelle, LLC, under Contract No. DE-AC05-00OR22725 with the U.S. Department of Energy. The United States Government retains and the publisher, by accepting the article for publication, acknowledges that the United States Government retains a non-exclusive, paid-up, irrevocable, world-wide license to publish or reproduce the published form of this manuscript, or allow others to do so, for United States Government purposes.

  9. Thermochemical ablation therapy of VX2 tumor using a permeable oil-packed liquid alkali metal.

    Directory of Open Access Journals (Sweden)

    Ziyi Guo

    Full Text Available Alkali metal appears to be a promising tool in thermochemical ablation, but, it requires additional data on safety is required. The objective of this study was to explore the effectiveness of permeable oil-packed liquid alkali metal in the thermochemical ablation of tumors.Permeable oil-packed sodium-potassium (NaK was prepared using ultrasonic mixing of different ratios of metal to oil. The thermal effect of the mixture during ablation of muscle tissue ex vivo was evaluated using the Fluke Ti400 Thermal Imager. The thermochemical effect of the NaK-oil mixture on VX2 tumors was evaluated by performing perfusion CT scans both before and after treatment in 10 VX2 rabbit model tumors. VX2 tumors were harvested from two rabbits immediately after treatment to assess their viability using trypan blue and hematoxylin and eosin (H.E. staining.The injection of the NaK-oil mixture resulted in significantly higher heat in the ablation areas. The permeable oil controlled the rate of heat released during the NaK reaction with water in the living tissue. Perfusion computed tomography and its parameter map confirmed that the NaK-oil mixture had curative effects on VX2 tumors. Both trypan blue and H.E. staining showed partial necrosis of the VX2 tumors.The NaK-oil mixture may be used successfully to ablate tumor tissue in vivo. With reference to the controlled thermal and chemical lethal injury to tumors, using a liquid alkali in ablation is potentially an effective and safe method to treat malignant tumors.

  10. Thermochemical Properties of Hydrophilic Polymers from Cashew and Khaya Exudates and Their Implications on Drug Delivery.

    Science.gov (United States)

    Olorunsola, Emmanuel O; Bhatia, Partap G; Tytler, Babajide A; Adikwu, Michael U

    2016-01-01

    Characterization of a polymer is essential for determining its suitability for a particular purpose. Thermochemical properties of cashew gum (CSG) extracted from exudates of Anacardium occidentale L. and khaya gum (KYG) extracted from exudates of Khaya senegalensis were determined and compared with those of acacia gum BP (ACG). The polymers were subjected to different thermal and chemical analyses. Exudates of CSG contained higher amount of hydrophilic polymer. The pH of 2% w/v gum dispersions was in the order KYG application of cashew gum for formulation of basic and oxidizable drugs while using khaya gum for acidic drugs.

  11. New developments of the CARTE thermochemical code: Calculation of detonation properties of high explosives

    Science.gov (United States)

    Dubois, Vincent; Desbiens, Nicolas; Auroux, Eric

    2010-07-01

    We present the improvements of the CARTE thermochemical code which provides thermodynamic properties and chemical compositions of CHON systems over a large range of temperature and pressure with a very small computational cost. The detonation products are split in one or two fluid phase (s), treated with the MCRSR equation of state (EOS), and one condensed phase of carbon, modeled with a multiphase EOS which evolves with the chemical composition of the explosives. We have developed a new optimization procedure to obtain an accurate multicomponents EOS. We show here that the results of CARTE code are in good agreement with the specific data of molecular systems and measured detonation properties for several explosives.

  12. HYDRGN - a computerized technique for the analysis of thermochemical water-splitting cycles

    Energy Technology Data Exchange (ETDEWEB)

    Carty, R. H.; Conger, W. L.; Funk, J. E.; Barker, R.

    1977-06-01

    The HYDRGN computer program was designed to analyze closed thermochemical cycles for the production of hydrogen from water. This report includes the basic theory, assumptions, and methods of calculation used in this analysis along with a description of the program and its use. The source program and necessary data bank are available from the University of Kentucky. These may be obtained by sending a magnetic tape (minimum length 1200 ft) and a written request specifying the type of computer and recording characteristics of the tape. A small fee is charged for the recording and handling of the tape.

  13. Solar Hydrogen Production via a Samarium Oxide-Based Thermochemical Water Splitting Cycle

    OpenAIRE

    Rahul Bhosale; Anand Kumar; Fares AlMomani; Ujjal Ghosh; Mohammad Saad Anis; Konstantinos Kakosimos; Rajesh Shende; Marc A. Rosen

    2016-01-01

    The computational thermodynamic analysis of a samarium oxide-based two-step solar thermochemical water splitting cycle is reported. The analysis is performed using HSC chemistry software and databases. The first (solar-based) step drives the thermal reduction of Sm2O3 into Sm and O2. The second (non-solar) step corresponds to the production of H2 via a water splitting reaction and the oxidation of Sm to Sm2O3. The equilibrium thermodynamic compositions related to the thermal reduction and wat...

  14. Thermochemical characterization of pigeon pea stalk for its efficient utilization as an energy source

    Energy Technology Data Exchange (ETDEWEB)

    Katyal, S.K.; Iyer, P.V.R.

    2000-05-01

    Pigeon pea stalk is a widely available biomass species in India. In this article the potential use of pigeon pea stalk as a fuel source through thermochemical conversion methods such as combustion, gasification, and pyrolysis has been investigated through experimentation using a thermogravimetric analyzer and pilot-plant-scale equipment. It has been proposed that pigeon pea stalks can be effectively utilized in two ways. The first is to pyrolyze the material to produce value-added products such as char, tar, and fuel gas. The second alternative is to partially pyrolyze the material to remove tar-forming volatiles, followed by gasification of reactive char to generate producer gas.

  15. Thermochemical Biomass Gasification: A Review of the Current Status of the Technology

    Directory of Open Access Journals (Sweden)

    Ajay Kumar

    2009-07-01

    Full Text Available A review was conducted on the use of thermochemical biomass gasification for producing biofuels, biopower and chemicals. The upstream processes for gasification are similar to other biomass processing methods. However, challenges remain in the gasification and downstream processing for viable commercial applications. The challenges with gasification are to understand the effects of operating conditions on gasification reactions for reliably predicting and optimizing the product compositions, and for obtaining maximal efficiencies. Product gases can be converted to biofuels and chemicals such as Fischer-Tropsch fuels, green gasoline, hydrogen, dimethyl ether, ethanol, methanol, and higher alcohols. Processes and challenges for these conversions are also summarized.

  16. New developments of the CARTE thermochemical code: A two-phase equation of state for nanocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Dubois, Vincent, E-mail: vincent-jp.dubois@cea.fr; Pineau, Nicolas [CEA, DAM, DIF, F-91297 Arpajon (France)

    2016-01-07

    We developed a new equation of state (EOS) for nanocarbons in the thermodynamic range of high explosives detonation products (up to 50 GPa and 4000 K). This EOS was fitted to an extensive database of thermodynamic properties computed by molecular dynamics simulations of nanodiamonds and nano-onions with the LCBOPII potential. We reproduced the detonation properties of a variety of high explosives with the CARTE thermochemical code, including carbon-poor and carbon-rich explosives, with excellent accuracy.

  17. Interest of thermochemical data bases linked to complex equilibria calculation codes for practical applications

    Energy Technology Data Exchange (ETDEWEB)

    Cenerino, G. [CEA Centre d`Etudes de Fontenay-aux-Roses, 92 (France). Dept. de Protection de l`Environnement et des Installations; Chevalier, P.Y.; Fischer, E. [Thermodata, 38 -Saint-Martin-d`Heres (France); Marbeuf, A. [Centre National de la Recherche Scientifique (CNRS), 92 - Meudon-Bellevue (France). Lab. de Magnetisme et de Physique du Solide; Frenk, A. [Ecole Polytechnique Federale, Lausanne (Switzerland); Vahlas, C. [Laboratoire Marcel Mathieu, Centre Helioparc, 64 - Pau (France)

    1992-12-31

    Since 1974, Thermodata has been working on developing an Integrated Information System in Inorganic Chemistry. A major effort was carried on the thermochemical data assessment of both pure substances and multicomponent solution phases. The available data bases are connected to powerful calculation codes (GEMINI = Gibbs Energy Minimizer), which allow to determine the thermodynamical equilibrium state in multicomponent systems. The high interest of such an approach is illustrated by recent applications in as various fields as semi-conductors, chemical vapor deposition, hard alloys and nuclear safety. (author). 26 refs., 6 figs.

  18. Design and construction of a cascading pressure reactor prototype for solar-thermochemical hydrogen production

    Science.gov (United States)

    Ermanoski, Ivan; Grobbel, Johannes; Singh, Abhishek; Lapp, Justin; Brendelberger, Stefan; Roeb, Martin; Sattler, Christian; Whaley, Josh; McDaniel, Anthony; Siegel, Nathan P.

    2016-05-01

    Recent work regarding the efficiency maximization for solar thermochemical fuel production in two step cycles has led to the design of a new type of reactor—the cascading pressure reactor—in which the thermal reduction step of the cycle is completed in multiple stages, at successively lower pressures. This approach enables lower thermal reduction pressures than in single-staged reactors, and decreases required pump work, leading to increased solar to fuel efficiencies. Here we report on the design and construction of a prototype cascading pressure reactor and testing of some of the key components. We especially focus on the technical challenges particular to the design, and their solutions.

  19. Synthesis and design of optimal biorefinery using an expanded network with thermochemical and biochemical biomass conversion platforms

    DEFF Research Database (Denmark)

    Cheali, Peam; Gernaey, Krist; Sin, Gürkan

    2013-01-01

    This study presents the development of an expanded biorefinery processing network for producing biofuels that combines biochemical and thermochemical conversion platforms. The expanded network is coupled to a framework that uses a superstructure based optimization approach to generate and compare...... of 72 processing intervals . This superstructure was integrated with an earlier developed superstructure for biochemical conversion routes thereby forming a formidable number of biorefinery alternatives. The expanded network was demonstrated to be versatile and useful as a decision support tool...... of a large number of alternatives at their optimal points. In this study the superstructure for thermochemical conversion route is formulated by using NREL studies of thermochemical conversion of biomass considering 3 biomass feedstocks, 2 products, 3 by-products and 18 processing intervals with combination...

  20. Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power

    Energy Technology Data Exchange (ETDEWEB)

    Brown, L.C.; Funk, J.F.; Showalter, S.K.

    1999-12-15

    OAK B188 Initial Screening of Thermochemical Water-Splitting Cycles for High Efficiency Generation of Hydrogen Fuels Using Nuclear Power There is currently no large scale, cost-effective, environmentally attractive hydrogen production process, nor is such a process available for commercialization. Hydrogen is a promising energy carrier, which potentially could replace the fossil fuels used in the transportation sector of our economy. Fossil fuels are polluting and carbon dioxide emissions from their combustion are thought to be responsible for global warming. The purpose of this work is to determine the potential for efficient, cost-effective, large-scale production of hydrogen utilizing high temperature heat from an advanced nuclear power station. Almost 800 literature references were located which pertain to thermochemical production of hydrogen from water and over 100 thermochemical watersplitting cycles were examined. Using defined criteria and quantifiable metrics, 25 cycles have been selected for more detailed study.

  1. Upper mantle compositional variations and discontinuity topography imaged beneath Australia from Bayesian inversion of surface-wave phase velocities and thermochemical modeling

    DEFF Research Database (Denmark)

    Khan, A.; Zunino, Andrea; Deschamps, F.

    2013-01-01

    models of the thermochemical and anisotropic structure of the mantle to 450 km depth. Dispersion data are linked to thermochemical parameters through a thermodynamic formalism for computing mantle mineral phase equilibria and physical properties. The inverse problem is solved using a probabilistic...

  2. Transporters in plant sulfur metabolism

    Directory of Open Access Journals (Sweden)

    Tamara eGigolashvili

    2014-09-01

    Full Text Available Sulfur is an essential nutrient, necessary for synthesis of many metabolites. The uptake of sulfate, primary and secondary assimilation, the biosynthesis, storage and final utilisation of sulfur (S containing compounds requires a lot of movement between organs, cells, and organelles. Efficient transport systems of S-containing compounds across the internal barriers or the plasma membrane and organellar membranes are therefore required. Here, we review a current state of knowledge of the transport of a range of S-containing metabolites within and between the cells as well as of their long distance transport. An improved understanding of mechanisms and regulation of transport will facilitate successful engineering of the respective pathways, to improve the plant yield, biotic interaction and nutritional properties of crops.

  3. Disproportionation and thermochemical sulfate reduction reactions in S-H20-Ch4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

    Science.gov (United States)

    Yuan, Shunda; Chou, I-Ming; Burruss, Robert A.

    2013-01-01

    Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

  4. Sulfur globule oxidation in green sulfur bacteria is dependent on the dissimilatory sulfite reductase system

    DEFF Research Database (Denmark)

    Holkenbrink, Carina; Ocón Barbas, Santiago; Mellerup, Anders;

    2011-01-01

    Green sulfur bacteria oxidize sulfide and thiosulfate to sulfate with extracellular globules of elemental sulfur as intermediate. Here we investigated which genes are involved in the formation and consumption of these sulfur globules in the green sulfur bacterium Chlorobaculum tepidum. We show...... that sulfur globule oxidation is strictly dependent on the dissimilatory sulfite reductase (DSR) system. Deletion of dsrM/CT2244 or dsrT/CT2245 or the two dsrCABL clusters (CT0851-CT0854, CT2247-2250) abolished sulfur globule oxidation and prevented formation of sulfate from sulfide, whereas deletion of dsr...

  5. Acid-base thermochemistry of gaseous oxygen and sulfur substituted amino acids (Ser, Thr, Cys, Met).

    Science.gov (United States)

    Riffet, Vanessa; Frison, Gilles; Bouchoux, Guy

    2011-11-07

    Acid-base thermochemistry of isolated amino acids containing oxygen or sulfur in their side chain (serine, threonine, cysteine and methionine) have been examined by quantum chemical computations. Density functional theory (DFT) was used, with B3LYP, B97-D and M06-2X functionals using the 6-31+G(d,p) basis set for geometry optimizations and the larger 6-311++G(3df,2p) basis set for energy computations. Composite methods CBS-QB3, G3B3, G4MP2 and G4 were applied to large sets of neutral, protonated and deprotonated conformers. Conformational analysis of these species, based on chemical approach and AMOEBA force field calculations, has been used to identify the lowest energy conformers and to estimate the population of conformers expected to be present at thermal equilibrium at 298 K. It is observed that G4, G4MP2, G3B3, CBS-QB3 composite methods and M06-2X DFT lead to similar conformer energies. Thermochemical parameters have been computed using either the most stable conformers or equilibrium populations of conformers. Comparison of experimental and theoretical proton affinities and Δ(acid)H shows that the G4 method provides the better agreement with deviations of less than 1.5 kJ mol(-1). From this point of view, a set of evaluated thermochemical quantities for serine, threonine, cysteine and methionine may be proposed: PA = 912, 919, 903, 938; GB = 878, 886, 870, 899; Δ(acid)H = 1393, 1391, 1396, 1411; Δ(acid)G = 1363, 1362, 1367, 1382 kJ mol(-1). This study also confirms that a non-negligible ΔpS° is associated with protonation of methionine and that the most acidic hydrogen of cysteine in the gas phase is that of the SH group. In several instances new conformers were identified thus suggesting a re-examination of several IRMPD spectra.

  6. Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

    Science.gov (United States)

    Loeffler, M. J.; Hudson, R. L.; Moore, M. H.; Carlson, R. W.

    2011-01-01

    We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

  7. Seismic evidence for a chemically distinct thermochemical reservoir in Earth's deep mantle beneath Hawaii

    Science.gov (United States)

    Zhao, Chunpeng; Garnero, Edward J.; McNamara, Allen K.; Schmerr, Nicholas; Carlson, Richard W.

    2015-09-01

    Nearly antipodal continent-sized zones of reduced seismic shear wave velocities exist at the base of Earth's mantle, one beneath the Pacific Ocean, the other beneath the South Atlantic Ocean and Africa. Geophysicists have attributed the low velocity zones to elevated temperatures associated with large-scale mantle convection processes, specifically, hot mantle upwelling in response to cooler subduction-related downwelling currents. Hypotheses have included superplumes, isochemical heterogeneity, and stable as well as metastable basal thermochemical piles. Here we analyze waveform broadening and travel times of S waves from 11 deep focus earthquakes in the southwest Pacific recorded in North America, resulting in 8500 seismograms studied that sample the deep mantle beneath the Pacific. Waveform broadening is referenced to a mean S-wave shape constructed for each event, to define a relative "misfit". Large misfits are consistent with multipathing that can broaden wave pulses. Misfits of deep mantle sampling S-waves infer that the structure in the northeast part of the low velocity province beneath the Pacific has a sharp side as well as a sloping sharp top to the feature. This sharp boundary morphology is consistent with geodynamic predictions for a stable thermochemical reservoir. The peak of the imaged pile is below Hawaii, supporting the hypothesis of a whole mantle plume beneath the hotspot.

  8. Heavy metal removal from sewage sludge ash by thermochemical treatment with gaseous hydrochloric acid.

    Science.gov (United States)

    Vogel, Christian; Adam, Christian

    2011-09-01

    Sewage sludge ash (SSA) is a suitable raw material for fertilizers due to its high phosphorus (P) content. However, heavy metals must be removed before agricultural application and P should be transferred into a bioavailable form. The utilization of gaseous hydrochloric acid for thermochemical heavy metal removal from SSA at approximately 1000 °C was investigated and compared to the utilization of alkaline earth metal chlorides. The heavy metal removal efficiency increased as expected with higher gas concentration, longer retention time and higher temperature. Equivalent heavy metal removal efficiency were achieved with these different Cl-donors under comparable conditions (150 g Cl/kg SSA, 1000 °C). In contrast, the bioavailability of the P-bearing compounds present in the SSA after thermal treatment with gaseous HCl was not as good as the bioavailability of the P-bearing compounds formed by the utilization of magnesium chloride. This disadvantage was overcome by mixing MgCO(3) as an Mg-donor to the SSA before thermochemical treatment with the gaseous Cl-donor. A test series under systematic variation of the operational parameters showed that copper removal is more depending on the retention time than the removal of zinc. Zn-removal was declined by a decreasing ratio of the partial pressures of ZnCl(2) and water.

  9. Characterisation of agroindustrial solid residues as biofuels and potential application in thermochemical processes.

    Science.gov (United States)

    Virmond, Elaine; De Sena, Rennio F; Albrecht, Waldir; Althoff, Christine A; Moreira, Regina F P M; José, Humberto J

    2012-10-01

    In the present work, selected agroindustrial solid residues from Brazil - biosolids from meat processing wastewater treatment and mixture of sawdust with these biosolids; residues from apple and orange juice industries; sugarcane bagasse; açaí kernels (Euterpe oleracea) and rice husk - were characterised as solid fuels and an evaluation of their properties, including proximate and ultimate composition, energy content, thermal behaviour, composition and fusibility of the ashes was performed. The lower heating value of the biomasses ranged from 14.31 MJkg(-1) to 29.14 MJkg(-1), on a dry and ash free basis (daf), all presenting high volatile matter content, varying between 70.57 wt.% and 85.36 wt.% (daf) what improves the thermochemical conversion of the solids. The fouling and slagging tendency of the ashes was predicted based on the fuel ash composition and on the ash fusibility correlations proposed in the literature, which is important to the project and operation of biomass conversion systems. The potential for application of the Brazilian agroindustrial solid residues studied as alternative energy sources in thermochemical processes has been identified, especially concerning direct combustion for steam generation.

  10. Surface Cleaning or Activation?Control of Surface Condition Prior to Thermo-Chemical Heat Treatment

    Institute of Scientific and Technical Information of China (English)

    Brigitte Haase; Juan Dong; Jens Heinlein

    2004-01-01

    Actual heat treatment processes must face increasing specifications with reference to process quality, safety and results in terms of reproducibility and repeatability. They can be met only if the parts' surface condition is controlled during manufacturing and, especially, prior to the treatment. An electrochemical method for the detection of a steel part's surface condition is presented, together with results, consequences, and mechanisms concerning surface pre-treatment before the thermochemical process. A steel surface's activity or passivity can be detected electrochemically, independently from the chemical background. The selected method was the recording of potential vs. time curves at small constant currents, using a miniaturized electrochemical cell, a (nearly) non-destructive electrolyte and a potentio-galvanostatic setup. The method enables to distinguish types of surface contamination which do not interfere with the thermochemical process, from passive layers which do and must be removed. Whereas some types of passive layers can be removed using conventional cleaning processes and agents, others are so stable that their effects can only be overcome by applying an additional activation pre-treatment, e.g. oxynitriding.

  11. Thermochemical nanolithography fabrication and atomic force microscopy characterization of functional nanostructures

    Science.gov (United States)

    Wang, Debin

    This thesis presents the development of a novel atomic force microscope (AFM) based nanofabrication technique termed as thermochemical nanolithography (TCNL). TCNL uses a resistively heated AFM cantilever to thermally activate chemical reactions on a surface with nanometer resolution. This technique can be used for fabrication of functional nanostructures that are appealing for various applications in nanofluidics, nanoelectronics, nanophotonics, and biosensing devices. This thesis research is focused on three main objectives. The first objective is to study the fundamentals of TCNL writing aspects. We have conducted a systematic study of the heat transfer mechanism using finite element analysis modeling, Raman spectroscopy, and local glass transition measurement. In addition, based on thermal kinetics analysis, we have identified several key factors to achieve high resolution fabrication of nanostructures during the TCNL writing process. The second objective is to demonstrate the use of TCNL on a variety of systems and thermochemical reactions. We show that TCNL can be employed to (1) modify the wettability of a polymer surface at the nanoscale, (2) fabricate nanoscale templates on polymer films for assembling nano-objects, such as proteins and DNA, (3) fabricate conjugated polymer semiconducting nanowires, and (4) reduce graphene oxide with nanometer resolution. The last objective is to characterize the TCNL nanostructures using AFM based methods, such as friction force microscopy, phase imaging, electric force microscopy, and conductive AFM. We show that they are useful for in situ characterization of nanostructures, which is particularly challenging for conventional macroscopic analytical tools, such as Raman spectroscopy, IR spectroscopy, and fluorescence microscopy.

  12. Systematic validation of non-equilibrium thermochemical models using Bayesian inference

    KAUST Repository

    Miki, Kenji

    2015-10-01

    © 2015 Elsevier Inc. The validation process proposed by Babuška et al. [1] is applied to thermochemical models describing post-shock flow conditions. In this validation approach, experimental data is involved only in the calibration of the models, and the decision process is based on quantities of interest (QoIs) predicted on scenarios that are not necessarily amenable experimentally. Moreover, uncertainties present in the experimental data, as well as those resulting from an incomplete physical model description, are propagated to the QoIs. We investigate four commonly used thermochemical models: a one-temperature model (which assumes thermal equilibrium among all inner modes), and two-temperature models developed by Macheret et al. [2], Marrone and Treanor [3], and Park [4]. Up to 16 uncertain parameters are estimated using Bayesian updating based on the latest absolute volumetric radiance data collected at the Electric Arc Shock Tube (EAST) installed inside the NASA Ames Research Center. Following the solution of the inverse problems, the forward problems are solved in order to predict the radiative heat flux, QoI, and examine the validity of these models. Our results show that all four models are invalid, but for different reasons: the one-temperature model simply fails to reproduce the data while the two-temperature models exhibit unacceptably large uncertainties in the QoI predictions.

  13. Thermochemical hydrolysis of macroalgae Ulva for biorefinery: Taguchi robust design method

    Science.gov (United States)

    Jiang, Rui; Linzon, Yoav; Vitkin, Edward; Yakhini, Zohar; Chudnovsky, Alexandra; Golberg, Alexander

    2016-06-01

    Understanding the impact of all process parameters on the efficiency of biomass hydrolysis and on the final yield of products is critical to biorefinery design. Using Taguchi orthogonal arrays experimental design and Partial Least Square Regression, we investigated the impact of change and the comparative significance of thermochemical process temperature, treatment time, %Acid and %Solid load on carbohydrates release from green macroalgae from Ulva genus, a promising biorefinery feedstock. The average density of hydrolysate was determined using a new microelectromechanical optical resonator mass sensor. In addition, using Flux Balance Analysis techniques, we compared the potential fermentation yields of these hydrolysate products using metabolic models of Escherichia coli, Saccharomyces cerevisiae wild type, Saccharomyces cerevisiae RN1016 with xylose isomerase and Clostridium acetobutylicum. We found that %Acid plays the most significant role and treatment time the least significant role in affecting the monosaccharaides released from Ulva biomass. We also found that within the tested range of parameters, hydrolysis with 121 °C, 30 min 2% Acid, 15% Solids could lead to the highest yields of conversion: 54.134–57.500 gr ethanol kg‑1 Ulva dry weight by S. cerevisiae RN1016 with xylose isomerase. Our results support optimized marine algae utilization process design and will enable smart energy harvesting by thermochemical hydrolysis.

  14. Evaluation energy efficiency of bioconversion knot rejects to ethanol in comparison to other thermochemically pretreated biomass.

    Science.gov (United States)

    Wang, Zhaojiang; Qin, Menghua; Zhu, J Y; Tian, Guoyu; Li, Zongquan

    2013-02-01

    Rejects from sulfite pulp mill that otherwise would be disposed of by incineration were converted to ethanol by a combined physical-biological process that was comprised of physical refining and simultaneous saccharification and fermentation (SSF). The energy efficiency was evaluated with comparison to thermochemically pretreated biomass, such as those pretreated by dilute acid (DA) and sulfite pretreatment to overcome recalcitrance of lignocelluloses (SPORL). It was observed that the structure deconstruction of rejects by physical refining was indispensable to effective bioconversion but more energy intensive than that of thermochemically pretreated biomass. Fortunately, the energy consumption was compensated by the reduced enzyme dosage and the elevated ethanol yield. Furthermore, adjustment of disk-plates gap led to reduction in energy consumption with negligible influence on ethanol yield. In this context, energy efficiency up to 717.7% was achieved for rejects, much higher than that of SPORL sample (283.7%) and DA sample (152.8%). Copyright © 2012 Elsevier Ltd. All rights reserved.

  15. Chemical and thermochemical aspects of the ozonolysis of ethyl oleate: decomposition enthalpy of ethyl oleate ozonide.

    Science.gov (United States)

    Cataldo, Franco

    2013-01-01

    Neat ethyl oleate was ozonized in a bubble reactor and the progress of the ozonolysis was followed by infrared (FT-IR) spectroscopy and by the differential scanning calorimetry (DSC). The ozonolysis was conducted till a molar ratio O3/C=C≈1 when the exothermal reaction spontaneously went to completion. A specific thermochemical calculation on ethyl oleate ozonation has been made to determine the theoretical heat of the ozonization reaction using the group increment approach. A linear relationship was found both in the integrated absorptivity of the ozonide infrared band at 1110 cm(-1) and the ozonolysis time as well as the thermal decomposition enthalpy of the ozonides and peroxides formed as a result of the ozonation. The DSC decomposition temperature of ozonated ethyl oleate occurs with an exothermal peak at about 150-155 °C with a decomposition enthalpy of 243.0 kJ/mol at molar ratio O3/C=C≈1. It is shown that the decomposition enthalpy of ozonized ethyl oleate is a constant value (≈243 kJ/mol) at any stage of the O3/C=C once an adequate normalization of the decomposition enthalpy for the amount of the adsorbed ozone is taken into consideration. The decomposition enthalpy of ozonized ethyl oleate was also calculated using a simplified thermochemical model, obtaining a result in reasonable agreement with the experimental value.

  16. A thermochemical pathway for controlled synthesis of AlN nanoparticles in non-isothermal conditions

    Energy Technology Data Exchange (ETDEWEB)

    Nersisyan, Hayk H. [Department of Nanomaterials Engineering, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); RASOM, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Yoo, Bung Uk [Graduate School of Energy Science and Technology, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Lee, Kab Ho [Department of Nanomaterials Engineering, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Lee, Jong Hyeon, E-mail: jonglee@cnu.ac.kr [Department of Nanomaterials Engineering, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); Graduate School of Energy Science and Technology, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of); RASOM, Chungnam National University, 79 Daehak-ro, Yuseong-gu, Daejeon 305-764 (Korea, Republic of)

    2015-03-20

    Highlights: • A non-isothermal combustion process was developed for synthesizing AlN nanoparticles. • Temperature-time profiles and combustion parameters were recorded and discussed. • AlN nanoparticles (50–200 nm) with a specific surface of 7.9–20.8 m{sup 2}/g were prepared. • The thermochemical mechanism of AlN formation in the combustion wave was clarified. - Abstract: The synthesis of AlN nanoparticles in non-isothermal high-temperature conditions was developed. The process involved Al{sub 2}O{sub 3}–Mg–NH{sub 4}Cl mixtures preparation and combustion in nitrogen atmosphere. Temperature profiles in the combustion waves were recorded by thermocouples, and the values of combustion temperature and wave velocity were determined from the recorded profiles. The existence of two independed combustion regimes with maximum temperatures of about 850 °C and 1400–1600 °C were revealed based on concentrations of NH{sub 4}Cl. AlN nanocrystals were obtained and investigated by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller surface area. AlN nanocrystals prepared under non-isothermal combustion process were comprised well distributed multi-faceted particles with an average size of 50–200 nm. The chemical reactions in the combustion wave were discussed and a possible thermochemical pathway for the synthesis of AlN nanoparticles was proposed.

  17. Systematic validation of non-equilibrium thermochemical models using Bayesian inference

    Energy Technology Data Exchange (ETDEWEB)

    Miki, Kenji [NASA Glenn Research Center, OAI, 22800 Cedar Point Rd, Cleveland, OH 44142 (United States); Panesi, Marco, E-mail: mpanesi@illinois.edu [Department of Aerospace Engineering, University of Illinois at Urbana-Champaign, 306 Talbot Lab, 104 S. Wright St., Urbana, IL 61801 (United States); Prudhomme, Serge [Département de mathématiques et de génie industriel, Ecole Polytechnique de Montréal, C.P. 6079, succ. Centre-ville, Montréal, QC, H3C 3A7 (Canada)

    2015-10-01

    The validation process proposed by Babuška et al. [1] is applied to thermochemical models describing post-shock flow conditions. In this validation approach, experimental data is involved only in the calibration of the models, and the decision process is based on quantities of interest (QoIs) predicted on scenarios that are not necessarily amenable experimentally. Moreover, uncertainties present in the experimental data, as well as those resulting from an incomplete physical model description, are propagated to the QoIs. We investigate four commonly used thermochemical models: a one-temperature model (which assumes thermal equilibrium among all inner modes), and two-temperature models developed by Macheret et al. [2], Marrone and Treanor [3], and Park [4]. Up to 16 uncertain parameters are estimated using Bayesian updating based on the latest absolute volumetric radiance data collected at the Electric Arc Shock Tube (EAST) installed inside the NASA Ames Research Center. Following the solution of the inverse problems, the forward problems are solved in order to predict the radiative heat flux, QoI, and examine the validity of these models. Our results show that all four models are invalid, but for different reasons: the one-temperature model simply fails to reproduce the data while the two-temperature models exhibit unacceptably large uncertainties in the QoI predictions.

  18. Climate Impact and Economic Feasibility of Solar Thermochemical Jet Fuel Production.

    Science.gov (United States)

    Falter, Christoph; Batteiger, Valentin; Sizmann, Andreas

    2016-01-05

    Solar thermochemistry presents a promising option for the efficient conversion of H2O and CO2 into liquid hydrocarbon fuels using concentrated solar energy. To explore the potential of this fuel production pathway, the climate impact and economic performance are analyzed. Key drivers for the economic and ecological performance are thermochemical energy conversion efficiency, the level of solar irradiation, operation and maintenance, and the initial investment in the fuel production plant. For the baseline case of a solar tower concentrator with CO2 capture from air, jet fuel production costs of 2.23 €/L and life cycle greenhouse gas (LC GHG) emissions of 0.49 kgCO2-equiv/L are estimated. Capturing CO2 from a natural gas combined cycle power plant instead of the air reduces the production costs by 15% but leads to LC GHG emissions higher than that of conventional jet fuel. Favorable assumptions for all involved process steps (30% thermochemical energy conversion efficiency, 3000 kWh/(m(2) a) solar irradiation, low CO2 and heliostat costs) result in jet fuel production costs of 1.28 €/L at LC GHG emissions close to zero. Even lower production costs may be achieved if the commercial value of oxygen as a byproduct is considered.

  19. Biochar potential evaluation of palm oil wastes through slow pyrolysis: Thermochemical characterization and pyrolytic kinetic studies.

    Science.gov (United States)

    Lee, Xin Jiat; Lee, Lai Yee; Gan, Suyin; Thangalazhy-Gopakumar, Suchithra; Ng, Hoon Kiat

    2017-03-22

    This research investigated the potential of palm kernel shell (PKS), empty fruit bunch (EFB) and palm oil sludge (POS), abundantly available agricultural wastes, as feedstock for biochar production by slow pyrolysis (50mLmin(-1) N2 at 500°C). Various characterization tests were performed to establish the thermochemical properties of the feedstocks and obtained biochars. PKS and EFB had higher lignin, volatiles, carbon and HHV, and lower ash than POS. The thermochemical conversion had enhanced the biofuel quality of PKS-char and EFB-char exhibiting increased HHV (26.18-27.50MJkg(-1)) and fixed carbon (53.78-59.92%), and decreased moisture (1.03-2.26%). The kinetics of pyrolysis were evaluated by thermogravimetry at different heating rates (10-40°C). The activation energies determined by Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa models were similar, and comparable with literature data. The findings implied that PKS and EFB are very promising sources for biochars synthesis, and the obtained chars possessed significant biofuel potential.

  20. Production of activated carbon by waste tire thermochemical degradation with CO2.

    Science.gov (United States)

    Betancur, Mariluz; Martínez, Juan Daniel; Murillo, Ramón

    2009-09-15

    The thermochemical degradation of waste tires in a CO(2) atmosphere without previous treatment of devolatilization (pyrolysis) in order to obtain activated carbons with good textural properties such as surface area and porosity was studied. The operating variables studied were CO(2) flow rate (50 and 150 mL/min), temperature (800 and 900 degrees C) and reaction time (1, 1.5, 2, 2.5 and 3h). Results show a considerable effect of the temperature and the reaction time in the porosity development. Kinetic measurements showed that the reactions involved in the thermochemical degradation of waste tire with CO(2), are similar to those developed in the pyrolysis process carried out under N(2) atmosphere and temperatures below 760 degrees C, for particles sizes of 500 microm and heating rate of 5 degrees C/min. For temperatures higher than 760 degrees C the CO(2) starts to oxidize the remaining carbon black. Activated carbon with a 414-m(2)/g surface area at 900 degrees C of temperature, 150 mL/min of CO(2) volumetric flow and 180 min of reaction time was obtained. In this work it is considering the no reactivity of CO(2) for devolatilization of the tires (up to 760 degrees C), and also the partial oxidation of residual char at high temperature for activation (>760 degrees C). It is confirmed that there are two consecutive stages (devolatilization and activation) developed from the same process.

  1. Effect of thermal, chemical and thermo-chemical pre-treatments to enhance methane production

    Energy Technology Data Exchange (ETDEWEB)

    Rafique, Rashad; Nizami, Abdul-Sattar; Murphy, Jerry D.; Kiely, Gerard [Department of Civil and Environmental Engineering, University College Cork (Ireland); Poulsen, Tjalfe Gorm [Department of Biotechnology, Chemistry and Environmental Engineering, Aalborg University (Denmark); Asam, Zaki-ul-Zaman [Department of Civil Engineering, National University of Ireland Galway (Ireland)

    2010-12-15

    The rise in oil price triggered the exploration and enhancement of various renewable energy sources. Producing biogas from organic waste is not only providing a clean sustainable indigenous fuel to the number of on-farm digesters in Europe, but also reducing the ecological and environmental deterioration. The lignocellulosic substrates are not completely biodegraded in anaerobic digesters operating at commercial scale due to their complex physical and chemical structure, which result in meager energy recovery in terms of methane yield. The focus of this study is to investigate the effect of pre-treatments: thermal, thermo-chemical and chemical pre-treatments on the biogas and methane potential of dewatered pig manure. A laboratory scale batch digester is used for these pre-treatments at different temperature range (25 C-150 C). Results showed that thermo-chemical pretreatment has high effect on biogas and methane potential in the temperature range (25-100 C). Maximum enhancement is observed at 70 C with increase of 78% biogas and 60% methane production. Thermal pretreatment also showed enhancement in the temperature range (50-10 C), with maximum enhancement at 100 C having 28% biogas and 25% methane increase. (author)

  2. Directly irradiated fluidized bed reactors for thermochemical processing and energy storage: Application to calcium looping

    Science.gov (United States)

    Tregambi, Claudio; Montagnaro, Fabio; Salatino, Piero; Solimene, Roberto

    2017-06-01

    Directly irradiated fluidized bed reactors are very promising in the context of concentrated solar power applications, as they can be operated at process temperatures high enough to perform thermochemical storage reactions with high energy density. Limestone calcination-carbonation is an appealing reaction for thermochemical storage applications due to the cheapness of the raw material, and the interesting value of the reaction enthalpy at fairly high process temperatures. Moreover, limestone calcination-carbonation is intensively studied in Calcium Looping (CaL) application for post combustion CO2 capture and sequestration. In this work, the dynamics of a directly irradiated 0.1 m ID fluidized bed reactor exposed to a 12 kWel simulated solar furnace is analyzed with specific reference to temperature distribution at the surface and in the bulk of the bed. Simulation of the solar radiation was performed through an array of three short arc Xe-lamps coupled with elliptical reflectors, yielding a peak flux of nearly 3000 kW m-2 and a total power of nearly 3 kW incident on the bed surface. Moreover, the directly irradiated fluidized bed reactor has been used to perform CaL tests by alternating solar-driven limestone calcination and autothermal recarbonation of lime. CaL has been investigated with the twofold perspective of: a) accomplishing energy storage by solar-driven calcination of limestone; b) perform solar-aided CO2 capture from flue gas to be embodied in carbon capture and sequestration schemes.

  3. The Deep Water Abundance on Jupiter: New Constraints from Thermochemical Kinetics and Diffusion Modeling

    CERN Document Server

    Visscher, Channon; Saslow, Sarah A

    2010-01-01

    We have developed a one-dimensional thermochemical kinetics and diffusion model for Jupiter's atmosphere that accurately describes the transition from the thermochemical regime in the deep troposphere (where chemical equilibrium is established) to the quenched regime in the upper troposphere (where chemical equilibrium is disrupted). The model is used to calculate chemical abundances of tropospheric constituents and to identify important chemical pathways for CO-CH4 interconversion in hydrogen-dominated atmospheres. In particular, the observed mole fraction and chemical behavior of CO is used to indirectly constrain the Jovian water inventory. Our model can reproduce the observed tropospheric CO abundance provided that the water mole fraction lies in the range (0.25-6.0) x 10^-3 in Jupiter's deep troposphere, corresponding to an enrichment of 0.3 to 7.3 times the protosolar abundance (assumed to be H2O/H2 = 9.61 x 10^-4). Our results suggest that Jupiter's oxygen enrichment is roughly similar to that for carb...

  4. Benchmark Study of the Structural and Thermochemical Properties of a Dihydroazulene/Vinylheptafulvene Photoswitch

    DEFF Research Database (Denmark)

    Koerstz, Mads; Elm, Jonas; Mikkelsen, Kurt Valentin

    2017-01-01

    We investigate the performance of four different density functional theory (DFT) functionals (M06-2X, ωB97X-D, PBE0, and B3LYP-D3BJ) for calculating the structural and thermochemical properties of the dihydroazulene/vinylheptafulvene photoswitch (DHA/VHF). We find that all the tested DFT function......We investigate the performance of four different density functional theory (DFT) functionals (M06-2X, ωB97X-D, PBE0, and B3LYP-D3BJ) for calculating the structural and thermochemical properties of the dihydroazulene/vinylheptafulvene photoswitch (DHA/VHF). We find that all the tested DFT......, indicating that the largest source of error when calculating storage free energies originates from errors in the calculated single point energies. It was found that ωB97X-D and M06-2X performed decently for predicting storage energies. While B3LYP-D3BJ and PBE0 generally underestimated the storage energy...

  5. Hybrid Metaheuristics

    CERN Document Server

    2013-01-01

    The main goal of this book is to provide a state of the art of hybrid metaheuristics. The book provides a complete background that enables readers to design and implement hybrid metaheuristics to solve complex optimization problems (continuous/discrete, mono-objective/multi-objective, optimization under uncertainty) in a diverse range of application domains. Readers learn to solve large scale problems quickly and efficiently combining metaheuristics with complementary metaheuristics, mathematical programming, constraint programming and machine learning. Numerous real-world examples of problems and solutions demonstrate how hybrid metaheuristics are applied in such fields as networks, logistics and transportation, bio-medical, engineering design, scheduling.

  6. Cytochromes and iron sulfur proteins in sulfur metabolism of phototrophic bacteria

    Science.gov (United States)

    Fischer, U.

    1985-01-01

    Dissimilatory sulfur metabolism in phototrophic sulfur bacteria provides the bacteria with electrons for photosynthetic electron transport chain and, with energy. Assimilatory sulfate reduction is necessary for the biosynthesis of sulfur-containing cell components. Sulfide, thiosulfate, and elemental sulfur are the sulfur compounds most commonly used by phototrophic bacteria as electron donors for anoxygenic photosynthesis. Cytochromes or other electron transfer proteins, like high-potential-iron-sulfur protein (HIPIP) function as electron acceptors or donors for most enzymatic steps during the oxidation pathways of sulfide or thiosulfate. Yet, heme- or siroheme-containing proteins themselves undergo enzymatic activities in sulfur metabolism. Sirohemes comprise a porphyrin-like prosthetic group of sulfate reductase. eenzymatic reactions involve electron transfer. Electron donors or acceptors are necessary for each reaction. Cytochromes and iron sulfur problems, are able to transfer electrons.

  7. HYDROCARBON AND SULFUR SENSORS FOR SOFC SYSTEMS

    Energy Technology Data Exchange (ETDEWEB)

    A.M. Azad; Chris Holt; Todd Lesousky; Scott Swartz

    2003-11-01

    The following report summarizes work conducted during the Phase I program Hydrocarbon and Sulfur Sensors for SOFC Systems under contract No. DE-FC26-02NT41576. For the SOFC application, sensors are required to monitor hydrocarbons and sulfur in order to increase the operation life of SOFC components. This report discusses the development of two such sensors, one based on thick film approach for sulfur monitoring and the second galvanic based for hydrocarbon monitoring.

  8. Thiophenic Sulfur Compounds Released During Coal Pyrolysis

    Science.gov (United States)

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-01-01

    Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  9. Physiology of Haloalkaliphilic Sulfur-oxidizing Bacteria

    OpenAIRE

    Banciu, H.L.

    2004-01-01

    The inorganic sulfur oxidation by obligate haloalkaliphilic chemolithoautotrophs was only recently discovered and investigated. These autotrophic sulfur oxidizing bacteria (SOB), capable of oxidation of inorganic sulfur compounds at moderate to high salt concentration and at high pH, can be divided into three genera belonging to the γ subdivision of the Proteobacteria: Thioalkalimicrobium, Thioalkalivibrio and Thioalkalispira. Their taxonomy, metabolic diversity and the potential application...

  10. Characterization of Chemosynthetic Microbial Mats Associated with Intertidal Hydrothermal Sulfur Vents in White Point, San Pedro, CA, USA

    Science.gov (United States)

    Miranda, Priscilla J.; McLain, Nathan K.; Hatzenpichler, Roland; Orphan, Victoria J.; Dillon, Jesse G.

    2016-01-01

    The shallow-sea hydrothermal vents at White Point (WP) in Palos Verdes on the southern California coast support microbial mats and provide easily accessed settings in which to study chemolithoautotrophic sulfur cycling. Previous studies have cultured sulfur-oxidizing bacteria from the WP mats; however, almost nothing is known about the in situ diversity and activity of the microorganisms in these habitats. We studied the diversity, micron-scale spatial associations and metabolic activity of the mat community via sequence analysis of 16S rRNA and aprA genes, fluorescence in situ hybridization (FISH) microscopy and sulfate reduction rate (SRR) measurements. Sequence analysis revealed a diverse group of bacteria, dominated by sulfur cycling gamma-, epsilon-, and deltaproteobacterial lineages such as Marithrix, Sulfurovum, and Desulfuromusa. FISH microscopy suggests a close physical association between sulfur-oxidizing and sulfur-reducing genotypes, while radiotracer studies showed low, but detectable, SRR. Comparative 16S rRNA gene sequence analyses indicate the WP sulfur vent microbial mat community is similar, but distinct from other hydrothermal vent communities representing a range of biotopes and lithologic settings. These findings suggest a complete biological sulfur cycle is operating in the WP mat ecosystem mediated by diverse bacterial lineages, with some similarity with deep-sea hydrothermal vent communities. PMID:27512390

  11. Mesoporous TiO2 Nanocrystals/Graphene as an Efficient Sulfur Host Material for High-Performance Lithium-Sulfur Batteries.

    Science.gov (United States)

    Li, Yuanyuan; Cai, Qifa; Wang, Lei; Li, Qingwei; Peng, Xiang; Gao, Biao; Huo, Kaifu; Chu, Paul K

    2016-09-14

    Rechargeable lithium-sulfur (Li-S) batteries are promising in high-energy storage due to the large specific energy density of about 2600 W h kg(-1). However, the low conductivity of sulfur and discharge products as well as polysulfide-shuttle effect between the cathode and anode hamper applications of Li-S batteries. Herein, we describe a novel and efficient S host material consisting of mesoporous TiO2 nanocrystals (NCs) fabricated in situ on reduced graphene oxide (rGO) for Li-S batteries. The TiO2@rGO hybrid can be loaded with 72 wt % sulfur. The strong chemisorption ability of the TiO2 NCs toward polysulfide combined with high electrical conductivity of rGO effectively localize the soluble polysulfide species within the cathode and facilitate electron and Li ions transport to/from the cathode materials. The sulfur-incorporated TiO2@rGO hybrid (S/TiO2@rGO) shows large capacities of 1116 and 917 mA h g(-1) at the current densities of 0.2 and 1 C (1 C = 1675 mA g(-1)) after 100 cycles, respectively. When the current density is increased 20 times from 0.2 to 4 C, 60% capacity is retained, thereby demonstrating good cycling stability and rate capability. The synergistic effects of TiO2 NCs toward effective chemisorption of polysulfides and conductive rGO with high electron mobility make a promising application of S/TiO2@rGO hybrid in high-performance Li-S batteries.

  12. Characterization of sulfur oxidizing bacteria related to biogenic sulfuric acid corrosion in sludge digesters

    OpenAIRE

    Huber, Bettina;Herzog, Bastian;Drewes, Jörg E.;Koch, Konrad;Müller, Elisabeth

    2017-01-01

    Background Biogenic sulfuric acid (BSA) corrosion damages sewerage and wastewater treatment facilities but is not well investigated in sludge digesters. Sulfur/sulfide oxidizing bacteria (SOB) oxidize sulfur compounds to sulfuric acid, inducing BSA corrosion. To obtain more information on BSA corrosion in sludge digesters, microbial communities from six different, BSA-damaged, digesters were analyzed using culture dependent methods and subsequent polymerase chain reaction denaturing gradient ...

  13. Active microbial sulfur disproportionation in the Mesoproterozoic.

    Science.gov (United States)

    Johnston, David T; Wing, Boswell A; Farquhar, James; Kaufman, Alan J; Strauss, Harald; Lyons, Timothy W; Kah, Linda C; Canfield, Donald E

    2005-12-02

    The environmental expression of sulfur compound disproportionation has been placed between 640 and 1050 million years ago (Ma) and linked to increases in atmospheric oxygen. These arguments have their basis in temporal changes in the magnitude of 34S/32S fractionations between sulfate and sulfide. Here, we present a Proterozoic seawater sulfate isotope record that includes the less abundant sulfur isotope 33S. These measurements imply that sulfur compound disproportionation was an active part of the sulfur cycle by 1300 Ma and that progressive Earth surface oxygenation may have characterized the Mesoproterozoic.

  14. Hybrid intermediaries

    OpenAIRE

    Cetorelli, Nicola

    2014-01-01

    I introduce the concept of hybrid intermediaries: financial conglomerates that control a multiplicity of entity types active in the "assembly line" process of modern financial intermediation, a system that has become known as shadow banking. The complex bank holding companies of today are the best example of hybrid intermediaries, but I argue that financial firms from the "nonbank" space can just as easily evolve into conglomerates with similar organizational structure, thus acquiring the cap...

  15. Hybrid composites

    CSIR Research Space (South Africa)

    Jacob John, Maya

    2009-04-01

    Full Text Available effect was observed for the elongation at break of the hybrid composites. The impact strength of the hybrid composites increased with the addition of glass fibres. The tensile and impact properties of thermoplastic natural rubber reinforced short... panels made from conventional structural materials. Figure 3 illustrates the performance of cellular biocomposite panels against conventional systems used for building and residential construction, namely a pre- cast pre-stressed hollow core concrete...

  16. Microbial Sulfur Geochemistry in Mine Systems (Invited)

    Science.gov (United States)

    Warren, L. A.; Norlund, K. L.; Hitchcock, A.

    2010-12-01

    Acid mine drainage (AMD), metal laden, acidic water, is the most pressing mining environmental issue on a global scale. While it is well recognized that the activity of autotrophic Fe and S bacteria amplify the oxidation of the sulfidic wastes, thereby generating acidity and leaching metals; the underlying microbial geochemistry is not well described. This talk will highlight results revealing the importance of microbial cooperation associated with a novel sulfur-metabolizing consortium enriched from mine waters. Results generated by an integrated approach, combining field characterization, geochemical experimentation, scanning transmission X-ray microscopy (STXM), and fluorescence in situ hybridization (FISH) [1]describing the underlying ecological drivers, the functionally relevant biogeochemical architecture of the consortial macrostructure as well as the identities of this environmental sulphur redox cycling consortium will be presented. The two common mine bacterial strains involved in this consortium, Acidithiobacillus ferroxidans and Acidiphilium sp., are specifically spatially segregated within a macrostructure (pod) of extracellular polymeric substance (EPS) that enables coupled sulphur oxidation and reduction reactions despite bulk, oxygenated conditions. Identical pod formation by type culture strains was induced and linked to ecological conditions. The proposed sulphur geochemistry associated with this bacterial consortium produces 40-90% less acid than expected based on abiotic AMD models, with implications for both AMD mitigation and AMD carbon flux modeling. We are currently investigating the implications of these sulphur-processing pods for metal dynamics in mine systems. These results demonstrate how microbes can orchestrate their geochemical environment to facilitate metabolism, and underscore the need to consider microbial interactions and ecology in constraining their geochemical impacts. [1] Norlund, Southam, Tyliszcczak, Hu, Karunakaran, Obst

  17. Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

    Science.gov (United States)

    Journal of Chemical Education, 2015

    2015-01-01

    This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

  18. Using a Laboratory Inquiry with High School Students to Determine the Reaction Stoichiometry of Neutralization by a Thermochemical Approach

    Science.gov (United States)

    Journal of Chemical Education, 2015

    2015-01-01

    This paper presents the design and practical application of a laboratory inquiry at high school chemistry level for systematic chemistry learning, as exemplified by a thermochemical approach to the reaction stoichiometry of neutralization using Job's method of continuous variation. In the laboratory inquiry, students are requested to propose the…

  19. Fuels production by the thermochemical transformation of the biomass; La production de carburants par transformation thermochimique de la biomasse

    Energy Technology Data Exchange (ETDEWEB)

    Claudet, G. [CEA, 75 - Paris (France)

    2005-07-01

    The biomass is a local and renewable energy source, presenting many advantages. This paper proposes to examine the biomass potential in France, the energy valorization channels (thermochemical chains of thermolysis and gasification) with a special interest for the hydrogen production and the research programs oriented towards the agriculture and the forest. (A.L.B.)

  20. Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium-sulfur batteries

    Science.gov (United States)

    Liu, Ya; Guo, Jinxin; Zhang, Jun; Su, Qingmei; Du, Gaohui

    2015-01-01

    Lithium-sulfur (Li-S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li-S battery. The sulfur nanospheres with diameter of 400-500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g-1 and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li-S batteries.

  1. Copper chloride electrolyzer for the production of hydrogen via the copper-chlorine thermochemical cycle

    Science.gov (United States)

    Roy, Rahul Dev

    Hydrogen is considered a key element in solving the upcoming energy crisis, it is not the primary fuel source but an "energy carrier" similar to electricity and has to be produced using some other hydrogen rich source. Thermochemical water decomposition is a promising alternative to steam-methane reforming and electrolytic water splitting for a sustainable method of large-scale hydrogen production. The Copper-Chlorine thermochemical cycle is one of prime contenders among all the other thermochemical cycles being studied because of its low energy requirements compared to others and mild operating conditions, therefore making it available to be readily integrated to the available nuclear reactors or solar energy installations. This present work focuses on the study and development of a proton exchange membrane (PEM) electrolyzer cell for the Copper-Chlorine thermo chemical cycle to obtain a better understanding through experiments and models of this process. Different operating and design parameters such as temperature, flow rate, current density, membranes and gas diffusion layers were considered to reduce the voltage and hence increase the efficiency of the electrolyzer. The effects of catalyst and mass transfer were studied on the thin film electrode using a rotating disk electrode (RDE) setup. A mathematical model was also developed to monitor the performance of the electrolyzer by predicting the change in concentration of copper chloride in the system with respect to time. It is observed that flow rate and temperature plays a major role in decreasing the voltage drop. There was no effect of catalyst in the anode when compared to a bare anode at lower flow rates; but at higher flow rates there was significant decrease in voltage drop when a carbon cloth was placed at the anode end. High surface area carbon black has comparable activity towards CuCl oxidation with conventional catalyst like Platinum or Ruthenium oxide. It is also seen that mass transfers possess a

  2. Geodynamically Consistent Interpretation of Seismic Tomography for Thermal and Thermochemical Mantle Plumes

    Science.gov (United States)

    Samuel, H.; Bercovici, D.

    2006-05-01

    Recent theoretical developments as well as increased data quality and coverage have allowed seismic tomographic imaging to better resolve narrower structures at both shallow and deep mantle depths. However, despite these improvements, the interpretation of tomographic images remains problematic mainly because of: (1) the trade off between temperature and composition and their different influence on mantle flow; (2) the difficulty in determining the extent and continuity of structures revealed by seismic tomography. We present two geodynamic studies on mantle plumes which illustrate the need to consider both geodynamic and mineral physics for a consistent interpretation of tomographic images in terms of temperature composition and flow. The first study aims to investigate the coupled effect of pressure and composition on thermochemical plumes. Using both high resolution 2D numerical modeling and simple analytical theory we show that the coupled effect of composition and pressure have a first order impact on the dynamics of mantle thermochemical plumes in the lower mantle: (1) For low Si enrichment of the plume relative to a reference pyrolitic mantle, an oscillatory behavior of the plume head is observed; (2) For Si-enriched plume compositions, the chemical density excess of the plume increases with height, leading to stagnation of large plume heads at various depths in the lower mantle. As a consequence, these thermochemical plumes may display broad (~ 1200 km wide and more) negative seismic velocity anomalies at various lower mantle depths, which may not necessarily be associated with upwelling currents. The second study focuses on the identification of thermal mantle plumes by seismic tomography beneath the Hawaiian hot spot: we performed a set of 3D numerical experiments in a spherical shell to model a rising plume beneath a moving plate. The thermal structure obtained is converted into P and S wave seismic velocities using mineral physics considerations. We

  3. Global thermochemical imaging of the lithosphere using satellite and terrestrial observations

    Science.gov (United States)

    Fullea, Javier; Lebedev, Sergei; Martinec, Zdenek; Celli, Nicolas

    2017-04-01

    Conventional methods of seismic tomography, topography, gravity and electromagnetic data analysis and geodynamic modelling constrain distributions of seismic velocity, density, electrical conductivity, and viscosity at depth, all depending on temperature and composition of the rocks within the Earth. However, modelling and interpretation of multiple data sets provide a multifaceted image of the true thermochemical structure of the Earth that needs to be appropriately and consistently integrated. A simple combination of gravity, electromagnetic, geodynamics, petrological and seismic models alone is insufficient due to the non-uniqueness and different sensitivities of these models, and the internal consistency relationships that must connect all the intermediate parameters describing the Earth involved. Thermodynamic and petrological links between seismic velocities, density, electrical conductivity, viscosity, melt, water, temperature, pressure and composition within the Earth can now be modelled accurately using new methods of computational petrology and data from laboratory experiments. The growth of very large terrestrial and satellite (e.g., Swarm and GOCE ESA missions) geophysical data sets over the last few years, together with the advancement of petrological and geophysical modelling techniques, now present an opportunity for global, thermochemical and deformation 3D imaging of the lithosphere and underlying upper mantle with unprecedented resolution. This project combines state-of-the-art seismic waveform tomography (using both surface and body waves), newly available global gravity satellite data (geoid and gravity anomalies and new gradiometric measurements from ESA's GOCE mission) and surface heat flow and elevation within a self-consistent thermodynamic framework. The aim is to develop a method for detailed and robust global thermochemical image of the lithosphere and underlying upper mantle. In a preliminary study, we convert a state-of-the-art global

  4. Sulfur Dioxide Analyzer Instrument Handbook

    Energy Technology Data Exchange (ETDEWEB)

    Springston, Stephen R [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2016-05-01

    The Sulfur Dioxide Analyzer measures sulfur dioxide based on absorbance of UV light at one wavelength by SO2 molecules which then decay to a lower energy state by emitting UV light at a longer wavelength. Specifically, SO2 + hυ1 →SO2 *→SO2 + hυ2 The emitted light is proportional to the concentration of SO2 in the optical cell. External communication with the analyzer is available through an Ethernet port configured through the instrument network of the AOS systems. The Model 43i-TLE is part of the i-series of Thermo Scientific instruments. The i-series instruments are designed to interface with external computers through the proprietary Thermo Scientific iPort Software. However, this software is somewhat cumbersome and inflexible. Brookhaven National Laboratory (BNL) has written an interface program in National Instruments LabView that both controls the Model 43i-TLE Analyzer AND queries the unit for all measurement and housekeeping data. The LabView vi (the software program written by BNL) ingests all raw data from the instrument and outputs raw data files in a uniform data format similar to other instruments in the AOS and described more fully in Section 6.0 below.

  5. Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

    2015-01-01

    Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

  6. Sulfur-carbon nanocomposites and their application as cathode materials in lithium-sulfur batteries

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Chengdu; Dudney, Nancy J.; Howe, Jane Y.

    2017-08-01

    The invention is directed in a first aspect to a sulfur-carbon composite material comprising: (i) a bimodal porous carbon component containing therein a first mode of pores which are mesopores, and a second mode of pores which are micropores; and (ii) elemental sulfur contained in at least a portion of said micropores. The invention is also directed to the aforesaid sulfur-carbon composite as a layer on a current collector material; a lithium ion battery containing the sulfur-carbon composite in a cathode therein; as well as a method for preparing the sulfur-composite material.

  7. Sulfur Reduction in Acid Rock Drainage Environments

    NARCIS (Netherlands)

    Florentino, A.P.; Weijma, J.; Stams, A.J.M.; Sanchez Andrea, I.

    2015-01-01

    Microbiological suitability of acidophilic sulfur reduction for metal recovery was explored by enriching sulfur reducers from acidic sediments at low pH (from 2 to 5) with hydrogen, glycerol, methanol and acetate as electron donors at 30°C. The highest levels of sulfide in the enrichments were detec

  8. Ambient Air Monitoring for Sulfur Compounds

    Science.gov (United States)

    Forrest, Joseph; Newman, Leonard

    1973-01-01

    A literature review of analytical techniques available for the study of compounds at low concentrations points up some of the areas where further research is needed. Compounds reviewed are sulfur dioxide, sulfuric acid, ammonium sulfate and bisulfate, metal sulfates, hydrogen sulfide, and organic sulfides. (BL)

  9. Comparative Genomics of Green Sulfur Bacteria

    DEFF Research Database (Denmark)

    Ussery, David; Davenport, C; Tümmler, B

    2010-01-01

    Eleven completely sequenced Chlorobi genomes were compared in oligonucleotide usage, gene contents, and synteny. The green sulfur bacteria (GSB) are equipped with a core genome that sustains their anoxygenic phototrophic lifestyle by photosynthesis, sulfur oxidation, and CO(2) fixation. Whole...... weight of 10(6), and are probably instrumental for the bacteria to generate their own intimate (micro)environment....

  10. Heterogeneous photocatalytic reactions of sulfur aromatic compounds.

    Science.gov (United States)

    Samokhvalov, Alexander

    2011-11-18

    Sulfur aromatic compounds, such as mono-, di-, tri-, and tetraalkyl-substituted thiophene, benzothiophenes, dibenzothiophenes, are the molecular components of many fossils (petroleum, oil shale, tar sands, bitumen). Structural units of natural, cross-linked heteroaromatic polymers present in brown coals, turf, and soil are similar to those of sulfur aromatic compounds. Many sulfur aromatic compounds are found in the streams of petroleum refining and upgrading (naphthas, gas oils) and in the consumer products (gasoline, diesel, jet fuels, heating fuels). Besides fossils, the structural fragments of sulfur aromatic compounds are present in molecules of certain organic semiconductors, pesticides, small molecule drugs, and in certain biomolecules present in human body (pheomelanin pigments). Photocatalysis is the frontier area of physical chemistry that studies chemical reactions initiated by absorption of photons by photocatalysts, that is, upon electronic rather than thermal activation, under "green" ambient conditions. This review provides systematization and critical review of the fundamental chemical and physicochemical information on heterogeneous photocatalysis of sulfur aromatic compounds accumulated in the last 20-30 years. Specifically, the following topics are covered: physicochemical properties of sulfur aromatic compounds, major classes of heterogeneous photocatalysts, mechanisms and reactive intermediates of photocatalytic reactions of sulfur aromatic compounds, and the selectivity of these reactions. Quantum chemical calculations of properties and structures of sulfur aromatic compounds, their reactive intermediates, and the structure of adsorption complexes formed on the surface of the photocatalysts are also discussed.

  11. Sulfur Reduction in Acid Rock Drainage Environments

    NARCIS (Netherlands)

    Florentino, A.P.; Weijma, J.; Stams, A.J.M.; Sanchez Andrea, I.

    2015-01-01

    Microbiological suitability of acidophilic sulfur reduction for metal recovery was explored by enriching sulfur reducers from acidic sediments at low pH (from 2 to 5) with hydrogen, glycerol, methanol and acetate as electron donors at 30°C. The highest levels of sulfide in the enrichments were detec

  12. Halophilic and haloalkaliphilic sulfur-oxidizing bacteria

    NARCIS (Netherlands)

    Sorokin, D.Y.; Banciu, H.; Robertson, L.A.; Kuenen, J.G.; Muntyan, M.S.; Muyzer, G.; Rosenberg, E.; DeLong, F.; Delong, E.; Lory, S.; Stackebrandt, E.; Thompson, F.

    2013-01-01

    Chemotrophic sulfur-oxidizing bacteria (SOB) represent an important functional group of microorganisms responsible for the dark oxidation of reduced sulfur compounds generated by sulfidogens. Until recently, only a single genus of halophilic SOB (Halothiobacillus) has been described, and nothing was

  13. Halophilic and haloalkaliphilic sulfur-oxidizing bacteria

    NARCIS (Netherlands)

    Sorokin, D.Y.; Banciu, H.; Robertson, L.A.; Kuenen, J.G.; Muntyan, M.S.; Muyzer, G.; Rosenberg, E.; DeLong, F.; Delong, E.; Lory, S.; Stackebrandt, E.; Thompson, F.

    2013-01-01

    Chemotrophic sulfur-oxidizing bacteria (SOB) represent an important functional group of microorganisms responsible for the dark oxidation of reduced sulfur compounds generated by sulfidogens. Until recently, only a single genus of halophilic SOB (Halothiobacillus) has been described, and nothing was

  14. The adsorption of sulfur by microporous materials

    NARCIS (Netherlands)

    Steijns, M.; Mars, P.

    1976-01-01

    The sorption of sulfur by the zeolites NaX (= 13X) and CaA (= 5A) and an activated charcoal prepared from sugar was investigated at temperatures between 150 and 350°C and relative sulfur pressures between 10−4 and 10−1. The adsorbate-adsorbate interaction indicated by the S-shaped isotherm for the z

  15. New candidate for biofuel feedstock beyond terrestrial biomass for thermo-chemical process (pyrolysis/gasification) enhanced by carbon dioxide (CO2).

    Science.gov (United States)

    Kwon, Eilhann E; Jeon, Young Jae; Yi, Haakrho

    2012-11-01

    The enhanced thermo-chemical process (i.e., pyrolysis/gasification) of various macroalgae using carbon dioxide (CO(2)) as a reaction medium was mainly investigated. The enhanced thermo-chemical process was achieved by expediting the thermal cracking of volatile chemical species derived from the thermal degradation of the macroalgae. This process enables the modification of the end products from the thermo-chemical process and significant reduction of the amount of condensable hydrocarbons (i.e., tar, ∼50%), thereby directly increasing the efficiency of the gasification process.

  16. Effect of Additive on Sulfur-fixation Process of Sulfur-fixation Agent

    Institute of Scientific and Technical Information of China (English)

    XIE Jun-lin; QIU Jian-rong; ZHAO Gai-ju; LOU Jin-ping; HAN Chun-hua

    2003-01-01

    The crystallization behavior of desulfurization product is directly related to its high-temperatureresistant ability. Effects of the additive on the sulfur-fixation efficiency of the Ba-sulfur-fixation agent and also on the crystallization behavior of the sulfur-fixation product were studied when CaCO3 and BaCO3 were used as the desulfurization agent and MgO and SrCO3 used as the assistant sulfur-fixation agent. The result shows that increase of sulfur-fixation capability for the additive is not owe to their directly react to form sulfate or interact with CaCO3 and BaCO3 to form composite mineral heat-resistant in high temperature, but owe to their activation to sulfur-fixation reaction of the sulfur-fixation agent.

  17. Techno-economic Analysis for the Thermochemical Conversion of Biomass to Liquid Fuels

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yunhua; Tjokro Rahardjo, Sandra A.; Valkenburt, Corinne; Snowden-Swan, Lesley J.; Jones, Susanne B.; Machinal, Michelle A.

    2011-06-01

    ). This study is part of an ongoing effort within the Department of Energy to meet the renewable energy goals for liquid transportation fuels. The objective of this report is to present a techno-economic evaluation of the performance and cost of various biomass based thermochemical fuel production. This report also documents the economics that were originally developed for the report entitled “Biofuels in Oregon and Washington: A Business Case Analysis of Opportunities and Challenges” (Stiles et al. 2008). Although the resource assessments were specific to the Pacific Northwest, the production economics presented in this report are not regionally limited. This study uses a consistent technical and economic analysis approach and assumptions to gasification and liquefaction based fuel production technologies. The end fuels studied are methanol, ethanol, DME, SNG, gasoline and diesel.

  18. Thermo-chemical pretreatment and enzymatic hydrolysis for enhancing saccharification of catalpa sawdust.

    Science.gov (United States)

    Jin, Shuguang; Zhang, Guangming; Zhang, Panyue; Li, Fan; Fan, Shiyang; Li, Juan

    2016-04-01

    To improve the reducing sugar production from catalpa sawdust, thermo-chemical pretreatments were examined and the chemicals used including NaOH, Ca(OH)2, H2SO4, and HCl. The hemicellulose solubilization and cellulose crystallinity index (CrI) were significantly increased after thermo-alkaline pretreatments, and the thermo-Ca(OH)2 pretreatment showed the best improvement for reducing sugar production comparing to other three pretreatments. The conditions of thermo-Ca(OH)2 pretreatment and enzymatic hydrolysis were systematically optimized. Under the optimal conditions, the reducing sugar yield increased by 1185.7% comparing to the control. This study indicates that the thermo-Ca(OH)2 pretreatment is ideal for the saccharification of catalpa sawdust and that catalpa sawdust is a promising raw material for biofuel.

  19. 3D Thermochemical Numerical Model of a Convergent Zone With an Overriding Plate

    Science.gov (United States)

    Mason, W. G.; Moresi, L.; Betts, P. G.

    2008-12-01

    We have created a new three dimensional thermochemical numerical model of a convergent zone, in which a viscoplastic oceanic plate subducts beneath a viscous overriding plate, using the finite element Geoscience research code Underworld. Subduction is initiated by mantle flow induced by the gravitational instability of a slab tip, and buoyancy of the overriding plate. A cold thermal boundary layer envelopes both plates, and is partially dragged into the mantle along with the subducting slab. The trench rolls back as the slab subducts, and the overriding plate follows the retreating trench without being entrained into the upper mantle. The model is repeated with the overriding plate excluded, to analyse the influence of the overriding plate. The overriding plate retards the rate of subduction. Maximum strain rates, evident along the trench in the absence of an overriding plate, extend to a greater depth within the subducted portion of the slab in the presence of an overriding plate.

  20. Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation

    Directory of Open Access Journals (Sweden)

    Sophia Haussener

    2012-01-01

    Full Text Available High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium.

  1. Effective Heat and Mass Transport Properties of Anisotropic Porous Ceria for Solar Thermochemical Fuel Generation.

    Science.gov (United States)

    Haussener, Sophia; Steinfeld, Aldo

    2012-01-19

    High-resolution X-ray computed tomography is employed to obtain the exact 3D geometrical configuration of porous anisotropic ceria applied in solar-driven thermochemical cycles for splitting H2O and CO2. The tomography data are, in turn, used in direct pore-level numerical simulations for determining the morphological and effective heat/mass transport properties of porous ceria, namely: porosity, specific surface area, pore size distribution, extinction coefficient, thermal conductivity, convective heat transfer coefficient, permeability, Dupuit-Forchheimer coefficient, and tortuosity and residence time distributions. Tailored foam designs for enhanced transport properties are examined by means of adjusting morphologies of artificial ceria samples composed of bimodal distributed overlapping transparent spheres in an opaque medium.

  2. Comparative study of thermochemical processes for hydrogen production from biomass fuels.

    Science.gov (United States)

    Biagini, Enrico; Masoni, Lorenzo; Tognotti, Leonardo

    2010-08-01

    Different thermochemical configurations (gasification, combustion, electrolysis and syngas separation) are studied for producing hydrogen from biomass fuels. The aim is to provide data for the production unit and the following optimization of the "hydrogen chain" (from energy source selection to hydrogen utilization) in the frame of the Italian project "Filiera Idrogeno". The project focuses on a regional scale (Tuscany, Italy), renewable energies and automotive hydrogen. Decentred and small production plants are required to solve the logistic problems of biomass supply and meet the limited hydrogen infrastructures. Different options (gasification with air, oxygen or steam/oxygen mixtures, combustion, electrolysis) and conditions (varying the ratios of biomass and gas input) are studied by developing process models with uniform hypothesis to compare the results. Results obtained in this work concern the operating parameters, process efficiencies, material and energetic needs and are fundamental to optimize the entire hydrogen chain.

  3. Entropy Analysis of Solar Two-Step Thermochemical Cycles for Water and Carbon Dioxide Splitting

    Directory of Open Access Journals (Sweden)

    Matthias Lange

    2016-01-01

    Full Text Available The present study provides a thermodynamic analysis of solar thermochemical cycles for splitting of H2O or CO2. Such cycles, powered by concentrated solar energy, have the potential to produce fuels in a sustainable way. We extend a previous study on the thermodynamics of water splitting by also taking into account CO2 splitting and the influence of the solar absorption efficiency. Based on this purely thermodynamic approach, efficiency trends are discussed. The comprehensive and vivid representation in T-S diagrams provides researchers in this field with the required theoretical background to improve process development. Furthermore, results about the required entropy change in the used redox materials can be used as a guideline for material developers. The results show that CO2 splitting is advantageous at higher temperature levels, while water splitting is more feasible at lower temperature levels, as it benefits from a great entropy change during the splitting step.

  4. Thermochemical studies on complex of [Sm(o-NBA)_3phen]_2

    Institute of Scientific and Technical Information of China (English)

    肖圣雄; 张建军; 李旭; 李强国; 任宁; 李环

    2010-01-01

    A ternary complex [Sm(o-NBA)3phen]2 (o-NBA: o-Nitrobenzoate; phen: 1,10-phenanthroline) was synthesized and characterized by elemental analysis, IR, molar conductance, and thermogravimetric analysis. The dissolution enthalpies of SmCl3·6H2O(s), o-HNBA(s) and phen·H2O(s) in mixed solvent (VHCl :VDMF :VDMSO=2:2:1) were determined by calorimetry at 298.15 K. The enthalpy change of the reaction was determined to be rHmΔθ=252.49±1.60 kJ/mol. Using the relevant data in the literature and a thermochemical recycle ...

  5. A Study of the Theoretical Potential of Thermochemical Exhaust Heat Recuperation for Internal Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Chakravarthy, Veerathu K [ORNL; Daw, C Stuart [ORNL; Pihl, Josh A [ORNL; Conklin, Jim [ORNL

    2010-01-01

    We present a detailed thermodynamic analysis of thermochemical recuperation (TCR) applied to an idealized internal combustion engine with single-stage work extraction. Results for several different fuels are included. For a stoichiometric mixture of methanol and air, TCR can increase the estimated ideal engine Second Law efficiency by about 3% for constant pressure reforming and over 5% for constant volume reforming. For ethanol and isooctane the estimated Second Law efficiency increases for constant volume reforming are 9% and 11%, respectively. The Second Law efficiency improvements from TCR result primarily from the higher intrinsic exergy of the reformed fuel and pressure boost associated with gas mole increase. Reduced combustion irreversibility may also yield benefits for future implementations of combined cycle work extraction.

  6. A Study of the Theoretical Potential of Thermochemical Exhaust Heat Recuperation in Internal Combustion Engines

    Energy Technology Data Exchange (ETDEWEB)

    Daw, C Stuart [ORNL; Pihl, Josh A [ORNL; Chakravarthy, Veerathu K [ORNL; Conklin, Jim [ORNL

    2010-01-01

    A detailed thermodynamic analysis of thermochemical recuperation (TCR) applied to an idealized internal combustion engine with single-stage work extraction is presented. Results for several different fuels are included. For a stoichiometric mixture of methanol and air, TCR can increase the estimated ideal engine second law efficiency by about 3% for constant pressure reforming and over 5% for constant volume reforming. For ethanol and isooctane, the estimated second law efficiency increases for constant volume reforming are 9 and 11%, respectively. The second law efficiency improvements from TCR result primarily from the higher intrinsic exergy of the reformed fuel and pressure boost associated with the gas mole increase. Reduced combustion irreversibility may also yield benefits for future implementations of combined cycle work extraction.

  7. Thermochemical recycling of mixture of scrap tyres and waste lubricating oil into high caloric value products

    Energy Technology Data Exchange (ETDEWEB)

    Abdul-Raouf, Manar E.; Maysour, Nermine E.; Abdul-Azim, Abdul-Azim A. [Egyptian Petroleum Research Institute, Nasr City, Cairo (Egypt); Amin, Mahasen S. [Faculty of Science, Benha University, Benha (Egypt)

    2010-06-15

    Scrap tyres and used lubricating oils represent together growing environmental problem because they are not biodegradable and their components cannot readily be recovered. In the present investigation, the thermochemical recycling of mixture of old tyres with waste lubricating oil by pyrolysis and the value of the products obtained have been studied. First, thermobalance experiments were carried out, studying the influence of the following variables: temperature, type of catalyst and catalyst concentration on the pyrolysis reaction of a mixture of 1/1 wt./wt. oil/tyre ratio. These thermobalance results were thoroughly investigated to study the effect of the main process variables on yields of derived products: oils, gases and solid residue. (author)

  8. Onboard Hydrogen Generation for a Spark Ignition Engine via Thermochemical Recuperation

    Science.gov (United States)

    Silva, Isaac Alexander

    A method of exhaust heat recovery from a spark-ignition internal combustion engine was explored, utilizing a steam reforming thermochemical reactor to produce a hydrogen-rich effluent, which was then consumed in the engine. The effects of hydrogen in the combustion process have been studied extensively, and it has been shown that an extension of the lean stability limit is possible through hydrogen enrichment. The system efficiency and the extension of the operational range of an internal combustion engine were explored through the use of a methane fueled naturally aspirated single cylinder engine co-fueled with syngas produced with an on board methane steam reformer. It was demonstrated that an extension of the lean stability limit is possible using this system.

  9. Thermochemical prediction of chemical form distributions of fission products in LWR mixed oxide fuels

    Energy Technology Data Exchange (ETDEWEB)

    Moriyama, Kouki; Furuya, Hirotaka [Kyushu Univ., Fukuoka (Japan). Faculty of Engineering

    1998-06-01

    Radial distribution of chemical forms of fission products (FPs) in LWR mixed oxide (MOX) fuel pins was theoretically predicted by a thermochemical computer code SOLGASMIX-PV. The amounts of fission products generated in the fuel were calculated by ORIGEN-2 code, and the radial distributions of temperature and oxygen potential were calculated by taking the neutron depression and oxygen redistribution in the fuel into account. A fuel pellet was radially divided into 51 sections and chemical forms of FPs were calculated in each section. The effects of linear heat rating (LHR) and average O/U ratio on radial distribution of chemical form were evaluated. It was found that the radial distribution of chemical forms depends strongly on the LHR and the O/M ratio, and is not proportional to that of burnup. (author)

  10. A Perspective on Thermochemical and Electrochemical Processes for Titanium Metal Production

    Science.gov (United States)

    Zhang, Ying; Fang, Zhigang Zak; Sun, Pei; Zheng, Shili; Xia, Yang; Free, Michael

    2017-10-01

    Titanium metal is produced commercially by the costly and energy-intensive Kroll process, which is highly matured and optimized. In the last several decades, many new methods have been proposed to reduce the production cost of Ti metal and thus widen its applications. These new methods can be categorized into two main groups: thermochemical and electrochemical methods. Even though detailed operations for different processes vary, the various processes in each category share the same principles. This article outlines the differences and the challenges between different processes on the basis of these shared principles, with an emphasis on the developmental processes. Although several of these new processes are at the laboratory or pilot-plant development stage, it is recognized that systematic fundamental research and open scientific exchanges are still sorely needed in this area to improve the new technologies.

  11. Vertical distribution of water in the atmosphere of Venus - A simple thermochemical explanation

    Science.gov (United States)

    Lewis, John S.; Grinspoon, David H.

    1990-01-01

    Several lines of evidence concerning the vertical abundance profile of water in the atmosphere of Venus lead to strikingly unusual distributions (the water vapor abundance decreases sharply in the immediate vicinity of the surface) or to serious conflicts in the profiles (different IR bands suggest water abundances that are discrepant by a factor of 2.5 to 10). These data sets can be reconciled if (1) water molecules associate with carbon dioxide and sulfur trioxide to make gaseous carbonic acid and sulfuric acid in the lower atmosphere, and (2) the discrepant 0.94-micrometer water measurements are due to gaseous sulfuric acid, requiring it to be a somewhat stronger absorber than water vapor in this wavelength region. A mean total water abundance of 50 + or - 20 parts/million and a near-surface free water vapor abundance of 10 + or - 4 parts/million are derived.

  12. Thermochemical flows couple the Earth's inner core growth to mantle heterogeneity.

    Science.gov (United States)

    Aubert, Julien; Amit, Hagay; Hulot, Gauthier; Olson, Peter

    2008-08-07

    Seismic waves sampling the top 100 km of the Earth's inner core reveal that the eastern hemisphere (40 degrees E-180 degrees E) is seismically faster, more isotropic and more attenuating than the western hemisphere. The origin of this hemispherical dichotomy is a challenging problem for our understanding of the Earth as a system of dynamically coupled layers. Previously, laboratory experiments have established that thermal control from the lower mantle can drastically affect fluid flow in the outer core, which in turn can induce textural heterogeneity on the inner core solidification front. The resulting texture should be consistent with other expected manifestations of thermal mantle control on the geodynamo, specifically magnetic flux concentrations in the time-average palaeomagnetic field over the past 5 Myr, and preferred eddy locations in flows imaged below the core-mantle boundary by the analysis of historical geomagnetic secular variation. Here we show that a single model of thermochemical convection and dynamo action can account for all these effects by producing a large-scale, long-term outer core flow that couples the heterogeneity of the inner core with that of the lower mantle. The main feature of this thermochemical 'wind' is a cyclonic circulation below Asia, which concentrates magnetic field on the core-mantle boundary at the observed location and locally agrees with core flow images. This wind also causes anomalously high rates of light element release in the eastern hemisphere of the inner core boundary, suggesting that lateral seismic anomalies at the top of the inner core result from mantle-induced variations in its freezing rate.

  13. Thermochemical analysis of laterite ore alkali roasting: Comparison of sodium carbonate, sodium sulfate, and sodium hydroxide

    Science.gov (United States)

    Samadhi, Tjokorde Walmiki

    2017-01-01

    The abundance of global nickel reserve is in fact dominated by low grade laterite ores containing only approximately 1.0-1.8 %-Ni. Indonesia is a major limonite and saprolite ores source, particularly in the Sulawesi, northern Maluku, and Papua islands. Production of nickel from laterites typically requires a pre-concentration step which breaks down the mineral crystalline structure, thereby facilitating the subsequent extraction of the valuable metals. This work discusses the thermochemical analysis of the alkali roasting of an Indonesian saprolite ore using Na2CO3, Na2SO4, and NaOH. These alkali compounds are selected due to their relatively low cost. The Factsage thermochemical computation package is used to predict thermodynamically stable gaseous, solution, pure liquid, and pure solid phases present in the roasting process at temperatures from 100 to 1200°C at ambient pressure, in inert atmosphere. The formation of a liquid solution (or slag) phase is interpreted as a major indicator of mineral structure breakdown. The computed slag formation temperatures are 373.2, 1041.4, and 792.0°C when using Na2CO3, Na2SO4, and NaOH, respectively. The masses of volatilized alkali at 1200°C with a total feed mass of 100 gram are 0.49, 3.24, and 3.25 mg for Na2CO3, Na2SO4, and NaOH, respectively. It is therefore hypothesized that Na2CO3 is the most competitive sodium-based alkali for saprolite ore roasting.

  14. A thermochemical model for shock-induced reactions (heat detonations) in solids

    Energy Technology Data Exchange (ETDEWEB)

    Boslough, M.B. (Sandia National Laboratories, Albuquerque, New Mexico 87185 (US))

    1990-02-01

    Recent advances in studies of shock-induced chemistry in reactive solids have led to the recognition of a new class of energetic materials which are unique in their response to shock waves. Experimental work has shown that chemical energy can be released on a time scale shorter than shock-transit times in laboratory samples. However, for many compositions, the reaction products remain in the condensed state upon release from high pressure, and no sudden expansion takes place. Nevertheless, if such a reaction is sufficiently rapid, it can be modeled as a type of detonation, termed heat detonation'' in the present paper. It is shown that unlike an explosive detonation, an unsupported heat detonation will decay to zero unless certain conditions are met. An example of such a reaction is Fe{sub 2}O{sub 3} +2Al+shock{r arrow}Al{sub 2} O{sub 3} +2Fe (the standard thermite reaction). A shock-wave equation of state is determined from a mixture theory for reacted and unreacted porous thermite. The calculated shock temperatures are compared to experimentally measured shock temperatures, demonstrating that a shock-induced reaction takes place. Interpretation of the measured temperature history in the context of the thermochemical model implies that the principal rate-controlling kinetic mechanism is dynamic mixing at the shock front. Despite the similarity in thermochemical modeling of heat detonations to explosive detonations, the two processes are qualitatively very different in reaction mechanism as well as in the form the energy takes upon release, with explosives producing mostly work and heat detonations producing mostly heat.

  15. Ceramic carbon electrode-based anodes for use in the copper-chlorine thermochemical cycle

    Energy Technology Data Exchange (ETDEWEB)

    Ranganathan, S.; Easton, E.B. [Univ. of Ontario Inst. of Technology, Oshawa, ON (Canada). Faculty of Science

    2009-07-01

    A thermochemical cycle is a process by which water is decomposed into hydrogen and oxygen through a series of chemical reactions. The chemicals that are used in these reactions are regenerated and recycled during the process. Sol-gel chemistry is becoming more common for the synthesis of electrode materials. The sol-gel reaction can be conducted in the presence of a carbon black to form a ceramic carbon electrode (CCE). The resultant CCE structure contains electronically conductive carbon particle pathways that are bound together through the ceramic binder, which can also promote ion transport. The CCE structure also has a high active surface area and is chemically and thermally robust. This paper presented an investigation of CCE materials prepared using 3-aminopropyl trimethoxysilane. Several electrochemical experiments including cyclic voltammetry and electrochemical impedance spectroscopy were performed to characterize their suitability as anode electrode materials for use in the electrochemical step of the copper-chlorine thermochemical cycle. Subsequent experiments included the manipulation of the relative ratio of organosilane carbon precursors to gauge its impact on electrode properties and performance. An overview of the materials characterization and electrochemical measurements were also presented. Specifically, the paper presented the experiment with particular reference to the CCE preparation; electrochemical experiments; thermal analysis; and scanning electron microscopy. Results were also provided. These included TGA analysis; scanning electron microscopy analysis; electrochemical characterization; and anodic polarization. Characterization of these CCE material demonstrated that they had good thermal stability, could be used at high temperatures, and were therefore, very promising anode materials. 15 refs., 7 figs.

  16. In vitro thermal profile suitability assessment of acids and bases for thermochemical ablation: underlying principles.

    Science.gov (United States)

    Freeman, Laura A; Anwer, Bilal; Brady, Ryan P; Smith, Benjamin C; Edelman, Theresa L; Misselt, Andrew J; Cressman, Erik N K

    2010-03-01

    To measure and compare temperature changes in a recently developed gel phantom for thermochemical ablation as a function of reagent strength and concentration with several acids and bases. Aliquots (0.5-1 mL) of hydrochloric acid or acetic acid and sodium hydroxide or aqueous ammonia were injected for 5 seconds into a hydrophobic gel phantom. Stepwise increments in concentration were used to survey the temperature changes caused by these reactions. Injections were performed in triplicate, measured with a thermocouple probe, and plotted as functions of concentration and time. Maximum temperatures were reached almost immediately in all cases, reaching 75 degrees C-110 degrees C at the higher concentrations. The highest temperatures were seen with hydrochloric acid and either base. More concentrated solutions of sodium hydroxide tended to mix incompletely, such that experiments at 9 M and higher were difficult to perform consistently. Higher concentrations for any reagent resulted in higher temperatures. Stronger acid and base combinations resulted in higher temperatures versus weak acid and base combinations at the same concentration. Maximum temperatures obtained are in a range known to cause tissue coagulation, and all combinations tested therefore appeared suitable for further investigation in thermochemical ablation. Because of the loss of the reaction chamber shape at higher concentrations of stronger agents, the phantom does not allow complete characterization under these circumstances. Adequate mixing of reagents to maximize heating potential and avoid systemic exposure to unreacted acid and base must be addressed if the method is to be safely employed in tissues. In addition, understanding factors that control lesion shape in a more realistic tissue model will be critical. Copyright 2010 SIR. Published by Elsevier Inc. All rights reserved.

  17. Thermochemical storage for CSP via redox structured reactors/heat exchangers: The RESTRUCTURE project

    Science.gov (United States)

    Karagiannakis, George; Pagkoura, Chrysoula; Konstandopoulos, Athanasios G.; Tescari, Stefania; Singh, Abhishek; Roeb, Martin; Lange, Matthias; Marcher, Johnny; Jové, Aleix; Prieto, Cristina; Rattenbury, Michael; Chasiotis, Andreas

    2017-06-01

    The present work provides an overview of activities performed in the framework of the EU-funded collaborative project RESTRUCTURE, the main goal of which was to develop and validate a compact structured reactor/heat exchanger for thermochemical storage driven by 2-step high temperature redox metal oxide cycles. The starting point of development path included redox materials qualification via both theoretical and lab-scale experimental studies. Most favorable compositions were cobalt oxide/alumina composites. Preparation of small-scale structured bodies included various approaches, ranging from perforated pellets to more sophisticated honeycomb geometries, fabricated by extrusion and coating. Proof-of-concept of the proposed novel reactor/heat exchanger was successfully validated in small-scale structures and the next step included scaling up of redox honeycombs production. Significant challenges were identified for the case of extruded full-size bodies and the final qualified approach related to preparation of cordierite substrates coated with cobalt oxide. The successful experimental evaluation of the pilot reactor/heat exchanger system constructed motivated the preliminary techno-economic evaluation of the proposed novel thermochemical energy storage concept. Taking into account experimental results, available technologies and standard design aspects a model for a 70.5 MWe CSP plant was defined. Estimated LCOE costs were calculated to be in the range of reference values for Combined Cycle Power Plants operated by natural gas. One of main cost contributors was the storage system itself, partially due to relatively high cost of cobalt oxide. This highlighted the need to identify less costly and equally efficient to cobalt oxide redox materials.

  18. Review and analysis of the 1980-1989 biomass thermochemical conversion program

    Energy Technology Data Exchange (ETDEWEB)

    Stevens, D.J.

    1994-09-01

    In the period between 1980 and 1989, the U.S. Department of Energy (DOE) sponsored research and development projects through its Biomass Thermochemical Conversion (BTC) Program. Thermochemical conversion technologies use elevated temperatures to convert biomass into more useful forms of energy such as fuel gases or transportation fuels. The BTC Program included a wide range of biomass conversion projects in the areas of gasification, pyrolysis, liquefaction, and combustion. This work formed the basis of the present DOE research and development efforts on advanced liquid fuel and power generation systems. At the beginning of Fiscal Year 1989, the management of the BTC Program was transferred from Pacific Northwest Laboratory (PNL) to National Renewable Energy Laboratory (NREL, formerly Solar Energy Research Institute). This document presents a summary of the research which was performed under the BTC Program during the 1981-1989 time frame. The document consists of an analysis of the research projects which were funded by the BTC Program and a bibliography of published documents. This work will help ensure that information from PNL`s BTC Program is available to those interested in biomass conversion technologies. The background of the BTC Program is discussed in the first chapter of this report. In addition, a brief summary of other related biomass research and development programs funded by the U.S. Department of Energy and others is presented with references where additional information can be found. The remaining chapters of the report present a detailed summary of the research projects which were funded by the BTC Program. The progress which was made on each project is summarized, the overall impact on biomass conversion is discussed, and selected references are provided.

  19. Vapor-liquid phase behavior of the iodine-sulfur water-splitting process : LDRD final report for FY03.

    Energy Technology Data Exchange (ETDEWEB)

    Bradshaw, Robert W.; Larson, Richard S.; Lutz, Andrew E.

    2004-01-01

    This report summarizes the results of a one-year LDRD project that was undertaken to better understand the equilibrium behavior of the iodine-water-hydriodic acid system at elevated temperature and pressure. We attempted to extend the phase equilibrium database for this system in order to facilitate development of the iodine-sulfur water-splitting process to produce hydrogen to a commercial scale. The iodine-sulfur cycle for thermochemical splitting of water is recognized as the most efficient such process and is particularly well suited to coupling to a high-temperature source of process heat. This study intended to combine experimental measurements of vapor-liquid-liquid equilibrium and equation-of-state modeling of equilibrium solutions using Sandia's Chernkin software. Vapor-liquid equilibrium experiments were conducted to a limited extent. The Liquid Chernkin software that was developed as part of an earlier LDRD project was enhanced and applied to model the non-ideal behavior of the liquid phases.

  20. Sulfur nanocrystals anchored graphene composite with highly improved electrochemical performance for lithium-sulfur batteries

    Science.gov (United States)

    Zhang, Jun; Dong, Zimin; Wang, Xiuli; Zhao, Xuyang; Tu, Jiangping; Su, Qingmei; Du, Gaohui

    2014-12-01

    Two kinds of graphene-sulfur composites with 50 wt% of sulfur are prepared using hydrothermal method and thermal mixing, respectively. Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectra mapping show that sulfur nanocrystals with size of ∼5 nm dispersed on graphene sheets homogeneously for the sample prepared by hydrothermal method (NanoS@G). While for the thermal mixed graphene-sulfur composite (S-G mixture), sulfur shows larger and uneven size (50-200 nm). X-ray Photoelectron Spectra (XPS) reveals the strong chemical bonding between the sulfur nanocrystals and graphene. Comparing with the S-G mixture, the NanoS@G composite shows highly improved electrochemical performance as cathode for lithium-sulfur (Li-S) battery. The NanoS@G composite delivers an initial capacity of 1400 mAh g-1 with the sulfur utilization of 83.7% at a current density of 335 mA g-1. The capacity keeps above 720 mAh g-1 over 100 cycles. The strong adherence of the sulfur nanocrystals on graphene immobilizes sulfur and polysulfides species and suppressed the "shuttle effect", resulting higher coulombic efficiency and better capacity retention. Electrochemical impedance also suggests that the strong bonding enabled rapid electronic/ionic transport and improved electrochemical kinetics, therefore good rate capability is obtained. These results demonstrate that the NanoS@G composite is a very promising candidate for high-performance Li-S batteries.

  1. Magnesiothermic synthesis of sulfur-doped graphene as an efficient metal-free electrocatalyst for oxygen reduction

    Science.gov (United States)

    Wang, Jiacheng; Ma, Ruguang; Zhou, Zhenzhen; Liu, Guanghui; Liu, Qian

    2015-01-01

    Efficient metal-free electrocatalysts for oxygen reduction reaction (ORR) are highly expected in future low-cost energy systems. We have successfully prepared crumpled, sheet-like, sulfur-doped graphene by magnesiothermic reduction of easily available, low-cost, nontoxic CO2 (in the form of Na2CO3) and Na2SO4 as the carbon and sulfur sources, respectively. At high temperature, Mg can reduce not only carbon in the oxidation state of +4 in CO32− to form graphene, but also sulfur in SO42− from its highest (+6) to lowest valence which was hybridized into the carbon sp2 framework. Various characterization results show that sulfur-doped graphene with only few layers has an appropriate sulfur content, hierarchically robust porous structure, large surface area/pore volume, and highly graphitized textures. The S-doped graphene samples exhibit not only a high activity for ORR with a four-electron pathway, but also superior durability and tolerance to MeOH crossover to 40% Pt/C. This is mainly ascribed to the combination of sulfur-related active sites and hierarchical porous textures, facilitating fast diffusion of oxygen molecules and electrolyte to catalytic sites and release of products from the sites. PMID:25790856

  2. Effect of the glassy carbon structure on the aspect ratio of micropoints of matrix field-emission cathodes prepared by thermochemical etching

    Science.gov (United States)

    Pleshkova, L. S.; Shesterkin, V. I.

    2016-11-01

    The application of thermochemical etching technology makes it possible to reveal and investigate the structure of SU-2000 glassy carbon using electron microscopy. The glassy carbon structure at the microscopic and nanoscopic levels is inhomogeneous and consists of pockets with an irregular cross section separated by partitions. This structure sets the limits on the aspect ratio of geometrical sizes and micropoint packing density in the matrix prepared by thermochemical etching.

  3. Solid State Thermochemical Decomposition of Neat 1,3,5,5-Tetranitrohexahydropyrimidine (DNNC) and its DNNC-d6 Perdeuterio-Labeled Analogue

    Science.gov (United States)

    2006-01-01

    SUPPLEMENTARY NOTES As published in Thermochimica Acta 440 (2006) 146-155. 14. ABSTRACT The solid state thermochemical decomposition kinetics and...Prescribed by ANSI Std. 239.18 Thermochimica Acta 440 (2006) 146–155 Solid state thermochemical decomposition of neat 1,3,5,5... Thermochimica Acta 440 (2006) 146–155 147 solid state, describe reactions occurring within a thin zone of reactant–product contact that advance into the

  4. Concentration of HI in Iodine–Sulfur cycle using EED stack

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Songzhe, E-mail: chenszh@mail.tsinghua.edu.cn [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Wang, Renling [Department of Chemical Engineering, China University of Petroleum, Beijing 102249 (China); Zhang, Ping; Wang, Laijun; Xu, Jingming [Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Ke, Yangchuan [Department of Chemical Engineering, China University of Petroleum, Beijing 102249 (China)

    2014-05-01

    Concentration and separation of HI is very important for the efficient hydrogen production of Iodine–Sulfur thermochemical cycle, because of the presence of HI–H{sub 2}O azeotropy at HI:H{sub 2}O = ∼1:5 (molar ratio). Electro-electrodialysis (EED) has been proved to be very promising in concentrating HI, while the researches on stacked EED cells, which are essential for large scale application of EED process, has not been reported. In this study, EED stacks including 1, 2 and 4 cell units (50 mm × 50 mm effective membrane area) were designed and applied for the concentration of HI in HIx solution (HI–H{sub 2}O–I{sub 2} mixture), using Nafion membrane and graphite electrodes. At 60 °C and 0.10 A/cm{sup 2}, the performance of the stacks was evaluated, and the effects of initial composition of HIx and EED unit quantity on the HI concentrating capacity and cell voltage were discussed.

  5. Amylopectin wrapped graphene oxide/sulfur for improved cyclability of lithium-sulfur battery.

    Science.gov (United States)

    Zhou, Weidong; Chen, Hao; Yu, Yingchao; Wang, Deli; Cui, Zhiming; Disalvo, Francis J; Abruña, Héctor D

    2013-10-22

    An amylopectin wrapped graphene oxide-sulfur composite was prepared to construct a 3-dimensionally cross-linked structure through the interaction between amylopectin and graphene oxide, for stabilizing lithium sulfur batteries. With the help of this cross-linked structure, the sulfur particles could be confined much better among the layers of graphene oxide and exhibited significantly improved cyclability, compared with the unwrapped graphene oxide-sulfur composite. The effect of the electrode mass loading on electrochemical performance was investigated as well. In the lower sulfur mass loading cells, such as 2 mg cm(-2), both the capacity and the efficiency were obviously better than those of the higher sulfur mass loading cells, such as 6 mg cm(-2).

  6. Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

    2017-06-06

    The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

  7. Sulfur Isotopic Characteristics of Coal in China and Sulfur Isotopic Fractionation during Coal—burning Process

    Institute of Scientific and Technical Information of China (English)

    洪业汤; 张鸿斌; 等

    1993-01-01

    The determined results of the sulfur contents and isotopic composition of coal samples from major coal mines in 15 provinces and regions of China show that the coal mined in the north of China is characterized by higher 34S and lower sulfur content, but that in the south of China has lower 34S and higher sulfur content.During the coal-burning process in both indrstrial and daily use of coal as fuel the released sulfur dioxide is always enriched in lighter sulfur isotope relative to the corresponding coal;the particles are always enriched in heavier sulfur isotope.The discussion on the environmental geochemical significance of the above-mentioned results also has been made.

  8. Dual-Confined Sulfur Nanoparticles Encapsulated in Hollow TiO2 Spheres Wrapped with Graphene for Lithium-Sulfur Batteries.

    Science.gov (United States)

    Fan, Haining; Tang, Qunli; Chen, Xiaohua; Fan, Binbin; Chen, Shanliang; Hu, Aiping

    2016-10-20

    Lithium-sulfur (Li-S) batteries are attractive owing to their higher energy density and lower cost compared with the universally used lithium-ion batteries (LIBs), but there are some problems that stop their practical use, such as low utilization and rapid capacity-fading of the sulfur cathode, which is mainly caused by the shuttle effect, and the uncontrollable deposition of lithium sulfide species. Herein, we report the design and fabrication of dual-confined sulfur nanoparticles that were encapsulated inside hollow TiO2 spheres; the encapsulated nanoparticles were prepared by a facile hydrolysis process combined with acid etching, followed by "wrapping" with graphene (G-TiO2 @S). In this unique composite architecture, the hollow TiO2 spheres acted as effective sulfur carriers by confining the polysulfides and buffering volume changes during the charge-discharge processes by means of physical force from the hollow spheres and chemical binding between TiO2 and the polysulfides. Moreover, the graphene-wrapped skin provided an effective 3D conductive network to improve the electronic conductivity of the sulfur cathode and, at the same time, to further suppress the dissolution of the polysulfides. As results, the G-TiO2 @S hybrids exhibited a high and stable discharge capacity of up to 853.4 mA h g(-1) over 200 cycles at 0.5 C (1 C=1675 mA g(-1) ) and an excellent rate capability of 675 mA h g(-1) at a current rate of 2 C; thus, G-TiO2 @S holds great promise as a cathode material for Li-S batteries.

  9. Improvements in the manufacture of sulfur from hydrogen sulfide

    Energy Technology Data Exchange (ETDEWEB)

    Azoulay, A.

    1968-12-23

    In this process for the manufacture of sulfur from hydrogen sulfide and sulfur dioxide, the sulfur is separated from the gas after reaction by direct contact by cooling with a cooling liquid. The sulfur is carried away by the cooling liquid.

  10. Comparative studies on thermochemical characterization of corn stover pretreated by white-rot and brown-rot fungi.

    Science.gov (United States)

    Zeng, Yelin; Yang, Xuewei; Yu, Hongbo; Zhang, Xiaoyu; Ma, Fuying

    2011-09-28

    The effects of white-rot and brown-rot fungal pretreatment on the chemical composition and thermochemical conversion of corn stover were investigated. Fungus-pretreated corn stover was analyzed by Fourier transform infrared spectroscopy and X-ray diffraction analysis to characterize the changes in chemical composition. Differences in thermochemical conversion of corn stover after fungal pretreatment were investigated using thermogravimetric and pyrolysis analysis. The results indicated that the white-rot fungus Irpex lacteus CD2 has great lignin-degrading ability, whereas the brown-rot fungus Fomitopsis sp. IMER2 preferentially degrades the amorphous regions of the cellulose. The biopretreatment favors thermal decomposition of corn stover. The weight loss of IMER2-treated acid detergent fiber became greater, and the oil yield increased from 32.7 to 50.8%. After CD2 biopretreatment, 58% weight loss of acid detergent lignin was achieved and the oil yield increased from 16.8 to 26.8%.

  11. Influence of steel composition and plastic deformation on the surface properties induced by low temperature thermochemical processing

    DEFF Research Database (Denmark)

    Bottoli, Federico

    “PressPerfect” Project was to create a methodology to predict the performance of high quality stainless steels after forming and finishing treatments. The Ph.D. Project focused on the optimization of low-temperature thermochemical processes on severalstainless steel classes used for the surface treatment of industrial......Low-temperature thermochemical surface hardening by nitriding, carburizing and nitrocarburizing is used to improve the performance of stainless steels with respect to wear, fatigue and corrosion resistance.The dissolution of nitrogen and/or carbon atoms in the materials surface leads...... to the formation of a supersaturated solid solution known as expanded austenite, or S-Phase. Expanded austenite is characterized by high hardness, up to 1400 Vickers, and high compressive stresses in the surface region, which result in improved wear and fatigue resistance of the components. Along...

  12. Mass-independent sulfur of inclusions in diamond and sulfur recycling on early Earth.

    Science.gov (United States)

    Farquhar, J; Wing, B A; McKeegan, K D; Harris, J W; Cartigny, P; Thiemens, M H

    2002-12-20

    Populations of sulfide inclusions in diamonds from the Orapa kimberlite pipe in the Kaapvaal-Zimbabwe craton, Botswana, preserve mass-independent sulfur isotope fractionations. The data indicate that material was transferred from the atmosphere to the mantle in the Archean. The data also imply that sulfur is not well mixed in the diamond source regions, allowing for reconstruction of the Archean sulfur cycle and possibly offering insight into the nature of mantle convection through time.

  13. Ab Initio Computations and Active Thermochemical Tables Hand in Hand: Heats of Formation of Core Combustion Species.

    Science.gov (United States)

    Klippenstein, Stephen J; Harding, Lawrence B; Ruscic, Branko

    2017-09-07

    The fidelity of combustion simulations is strongly dependent on the accuracy of the underlying thermochemical properties for the core combustion species that arise as intermediates and products in the chemical conversion of most fuels. High level theoretical evaluations are coupled with a wide-ranging implementation of the Active Thermochemical Tables (ATcT) approach to obtain well-validated high fidelity predictions for the 0 K heat of formation for a large set of core combustion species. In particular, high level ab initio electronic structure based predictions are obtained for a set of 348 C, N, O, and H containing species, which corresponds to essentially all core combustion species with 34 or fewer electrons. The theoretical analyses incorporate various high level corrections to base CCSD(T)/cc-pVnZ analyses (n = T or Q) using H2, CH4, H2O, and NH3 as references. Corrections for the complete-basis-set limit, higher-order excitations, anharmonic zero-point energy, core-valence, relativistic, and diagonal Born-Oppenheimer effects are ordered in decreasing importance. Independent ATcT values are presented for a subset of 150 species. The accuracy of the theoretical predictions is explored through (i) examination of the magnitude of the various corrections, (ii) comparisons with other high level calculations, and (iii) through comparison with the ATcT values. The estimated 2σ uncertainties of the three methods devised here, ANL0, ANL0-F12, and ANL1, are in the range of ±1.0-1.5 kJ/mol for single-reference and moderately multireference species, for which the calculated higher order excitations are 5 kJ/mol or less. In addition to providing valuable references for combustion simulations, the subsequent inclusion of the current theoretical results into the ATcT thermochemical network is expected to significantly improve the thermochemical knowledge base for less-well studied species.

  14. Ceria based inverse opals for thermochemical fuel production: Quantification and prediction of high temperature behavior

    Science.gov (United States)

    Casillas, Danielle Courtney

    Solar energy has the potential to supply more than enough energy to meet humanity's energy demands. Here, a method for thermochemical solar energy storage through fuel production is presented. A porous non-stoichiometric oxide, ceria, undergoes partial thermal reduction and oxidation with concentrated solar energy as a heat source, and water as an oxidant. The resulting yields for hydrogen fuel and oxygen are produced in two discrete steps, while the starting material maintains its original phase. Ordered porosity has been shown superior to random porosity for thermochemical fuel production applications, but stability limits for these structures are currently undefined. Ceria-based inverse opals are currently being investigated to assess the architectural influence on thermochemical hydrogen production. Low tortuosity and continuous interconnected pore network allow for facile gas transport and improved reaction kinetics. Ceria-based ordered materials have recently been shown to increase maximum hydrogen production over non-ordered porous ceria. Thermal stability of ordered porosity was quantified using quantitative image analysis. Fourier analysis was applied to SEM images of the material. The algorithm results in an order parameter gamma that describes the degree of long range order maintained by these structures, where gamma>4 signifies ordered porosity. According to this metric, a minimum zirconium content of 20 atomic percent (at%) is necessary for these architectures to survive aggressive annealing up to 1000°C. Zirconium substituted ceria (ZSC) with Zr loadings in excess of 20at% developed undesired tetragonal phases. Through gamma, we were able to find a balance between the benefit of zirconium additions on structural stability and its negative impact on phase. This work demonstrates the stability of seemingly delicate architectures, and the operational limit for ceria based inverse opals to be 1000°C for 1microm pore size. Inverse opals having sub

  15. Double layering of a thermochemical plume in the upper mantle beneath Hawaii

    Science.gov (United States)

    Ballmer, M. D.; Ito, G.; Wolfe, C. J.; Cadio, C.; Solomon, S. C.

    2012-04-01

    Volcanism far from plate boundaries has traditionally been explained by "classical" plume theory. Classical plumes are typically described as narrow thermal upwellings that rise through the entire mantle to be deflected into a thin (Iceland, are indeed well explained by near-classical thermal plumes. High-resolution seismic velocity images obtained from the PLUME project support the concept of a deep-rooted mantle plume beneath the Hawaiian hotspot. However, in detail these images challenge traditional concepts inasmuch as they indicate a low-velocity body in the upper mantle that is too thick (~400 km) and asymmetric to be interpreted as a classical pancake. Classical plume theory is, moreover, inconsistent with several geochemical characteristics of Hawaiian magmas, which point to a heterogeneous mantle source involving mafic lithologies such as eclogite and not an exclusively thermal (i.e., isochemical) origin¹. To explore the dynamical and melting behavior of plumes containing a substantial fraction (~15%) of eclogite, we performed three-dimensional numerical simulations of thermochemical convection. Relative to ambient-mantle peridotite, eclogite is intrinsically dense. This density contrast is sensitive to phase changes in the upper mantle; the contrast peaks at 410-300 km and lessens at about 250-190 km depth, where eclogite is subsequently removed by melting. For a plume core with an eclogite content >12%, these effects locally increase the density beyond that of the ambient mantle. Therefore, the upwelling column forms a broad and thick pool at depths of 450-300 km (which we term the deep eclogite pool, or DEP). As the DEP is well supported by the deeper stem of the plume and its non-eclogitic outskirts, it inflates to release a shallow thermal plume. This latter plume sustains hotspot volcanism and feeds a hot shallow pancake that compensates the seafloor swell. Our model predictions reconcile a range of characteristics for Hawaiian volcanism. We find

  16. Analysis of sulfur in deposited aerosols by thermal decomposition and sulfur dioxide analyzer.

    Science.gov (United States)

    Yamamoto, Masatoshi

    2005-07-15

    A thermal decomposition method that measures aerosol sulfur at the nanogram level directly from the collection substrate is described. A thermal decomposition apparatus was designed. A stainless steel strip was used as the aerosol collection substrate. A 0.1 mol/L MnCl2 solution was added as the thermal decomposition catalyst. Currents were passed through the strip where aerosol particles had been deposited. In this way, the strip was heated at 780 +/- 10 degrees C, and particulate sulfur was evaporated. A sulfur dioxide analyzer (SDA) with flame photometric detector (FPD) was used to detect gaseous sulfur. High sulfur recoveries from (NH4)2SO4 and other inorganic sulfates, such as NH4HSO4, K2SO4, MgSO4, and CaSO4, were obtained. From the sulfur blank and the calibration, a lower limited detection of 0.2 ng of sulfur and the determination range of 3.3-167 ng of sulfur were estimated. The method is effective for measuring the sulfate size distributions of urban aerosols in a small sample air volume of 50-60 L. The method is applicable to measuring the sulfur in aqueous extracts of size-segregated urban aerosols collected by impactor and comparing the results with the sulfate data measured by ion chromatography.

  17. Mechanisms and evolution of oxidative sulfur metabolism in green sulfur bacteria

    DEFF Research Database (Denmark)

    Gregersen, Lea Haarup; Bryant, Donald A.; Frigaard, Niels-Ulrik

    2011-01-01

    Green sulfur bacteria (GSB) constitute a closely related group of photoautotrophic and thiotrophic bacteria with limited phenotypic variation. They typically oxidize sulfide and thiosulfate to sulfate with sulfur globules as an intermediate. Based on genome sequence information from 15 strains......, the distribution and phylogeny of enzymes involved in their oxidative sulfur metabolism was investigated. At least one homolog of sulfide:quinone oxidoreductase (SQR) is present in all strains. In all sulfur-oxidizing GSB strains except the earliest diverging Chloroherpeton thalassium, the sulfide oxidation...... and SOX systems. Finally, based upon structural, biochemical, and phylogenetic analyses, a uniform nomenclature is suggested for sqr genes in prokaryotes....

  18. Sulfur-centered reactive intermediates derived from the oxidation of sulfur compounds of biological interest

    Energy Technology Data Exchange (ETDEWEB)

    Abedinzadeh, Z. [Lab. de Chimie Physique, UMR, Univ. Rene Descartes, Paris (France)

    2001-02-01

    Sulphur compounds play a central role in the structure and activity of many vital systems. In the living cell, sulfur constitutes an essential part of the defense against oxidative damage and is transformed into a variety of sulfur free radical species. Many studies of the chemistry of sulfur-centered radicals using pulse radiolysis and photolysis techniques to detect and measure the kinetics of these radicals have been published and reviewed. This paper discusses the present state of research on the formation and reactivity of certain sulfur-centered radicals [RS{sup .}, RSS{sup .}, RS{sup .+}, (RSSR){sup .+}] and their implications for biological systems. (author)

  19. Linking neutral and charged sulfuric acid-ammonia and sulfuric acid-dimethylamine clusters

    Science.gov (United States)

    Ortega, Ismael K.; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Kurtén, Theo; Vehkamäki, Hanna

    2013-05-01

    We have used a quantum chemical method to calculate the formation free energies of negatively charged sulfuric acid - ammonia and sulfuric acid - dimethylamine clusters. Using the calculated formation free energies we have estimated the evaporation rates of the clusters. We have compared the evaporation rate of the charged clusters with the corresponding neutral clusters. We found that, although small clusters of sulfuric acid with ammonia and dimethylamine are stable and should be present in the atmosphere, they can not be detected using mass spectroscopy techniques. Charging the cluster will result in the fast evaporation of the base molecules, and they will be detected as pure sulfuric acid cluster.

  20. Dual protection of sulfur by carbon nanospheres and graphene sheets for lithium-sulfur batteries.

    Science.gov (United States)

    Wang, Bei; Wen, Yanfen; Ye, Delai; Yu, Hua; Sun, Bing; Wang, Guoxiu; Hulicova-Jurcakova, Denisa; Wang, Lianzhou

    2014-04-25

    Well-confined elemental sulfur was implanted into a stacked block of carbon nanospheres and graphene sheets through a simple solution process to create a new type of composite cathode material for lithium-sulfur batteries. Transmission electron microscopy and elemental mapping analysis confirm that the as-prepared composite material consists of graphene-wrapped carbon nanospheres with sulfur uniformly distributed in between, where the carbon nanospheres act as the sulfur carriers. With this structural design, the graphene contributes to direct coverage of sulfur to inhibit the mobility of polysulfides, whereas the carbon nanospheres undertake the role of carrying the sulfur into the carbon network. This composite achieves a high loading of sulfur (64.2 wt %) and gives a stable electrochemical performance with a maximum discharge capacity of 1394 mAh g(-1) at a current rate of 0.1 C as well as excellent rate capability at 1 C and 2 C. The improved electrochemical properties of this composite material are attributed to the dual functions of the carbon components, which effectively restrain the sulfur inside the carbon nano-network for use in lithium-sulfur rechargeable batteries.

  1. Corrosion pathways in liquid sulfur run-down pits and other liquid sulfur handling facilities

    Energy Technology Data Exchange (ETDEWEB)

    Clark, P.D.; Dowling, N.I.; Huang, M.

    2010-01-15

    This poster presentation explained why sulfur pits deteriorate over time and provided the detailed chemistry of the mechanisms for the deterioration of concrete in sulfur pits. Liquid and solid sulfur may build up in the pore structure of the concrete, which is followed by chemical reactions. The sulfur formation inside the concrete pore structure is catalyzed by concrete constituents. The sulfate formation in sulfur pit concrete was described. The chemical process that produces the corrosion of re-enforcing steel rods used in the construction of sulfur pits was also described. The consequence of such corrosion is the loss of structural integrity. The secondary corrosion processes at concrete pit reinforcing steel were also presented. To limit the deterioration of sulfur pit concrete, high-density silica facing should be used on the concrete to prevent the ingress of gases into the concrete. Silica does not catalyze the conversion of hydrogen disulfide and sulfur dioxide to sulfur, so there is no formation of stable sulfates and acidic intermediates. 8 figs.

  2. Protected Sulfur Cathode with Mixed Conductive Coating Layer for Lithium Sulfur Battery

    Science.gov (United States)

    Jin, Jun; Wen, Zhaoyin; Wang, Qingsong; Gu, Sui; Huang, Xiao; Chen, Chunhua

    2016-10-01

    A mixed conductive coating layer composed of lithium ion conductive ceramic powder, carbon and binder was introduced on the surface of a sulfur electrode. This coating layer is designed to suppress the migration of lithium polysulfides from the sulfur electrode, and improve the cycling capacity of a lithium sulfur battery. The protected sulfur cathode with a mixed conductive coating layer delivered an initial specific capacity of 1236 mAh g-1 at 0.5C and maintained a capacity of 842 mAh g-1 after 100 cycles. In particular, a soft package battery with protected cathode exhibits improved cycling capacity and excellent rate performance.

  3. Mesoporous hollow carbon spheres for lithium–sulfur batteries: distribution of sulfur and electrochemical performance

    Directory of Open Access Journals (Sweden)

    Anika C. Juhl

    2016-08-01

    Full Text Available Hollow carbon spheres (HCS with a nanoporous shell are promising for the use in lithium–sulfur batteries because of the large internal void offering space for sulfur and polysulfide storage and confinement. However, there is an ongoing discussion whether the cavity is accessible for sulfur. Yet no valid proof of cavity filling has been presented, mostly due to application of unsuitable high-vacuum methods for the analysis of sulfur distribution. Here we describe the distribution of sulfur in hollow carbon spheres by powder X-ray diffraction and Raman spectroscopy along with results from scanning electron microscopy and nitrogen physisorption. The results of these methods lead to the conclusion that the cavity is not accessible for sulfur infiltration. Nevertheless, HCS/sulfur composite cathodes with areal sulfur loadings of 2.0 mg·cm−2 were investigated electrochemically, showing stable cycling performance with specific capacities of about 500 mAh·g−1 based on the mass of sulfur over 500 cycles.

  4. ROE Total Sulfur Deposition 1989-1991

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset identifies the amount of wet, dry, and total deposition of sulfur in kilograms per hectare from 1989 to 1991 at a set of point locations across the...

  5. ROE Total Sulfur Deposition 2011-2013

    Data.gov (United States)

    U.S. Environmental Protection Agency — This dataset identifies the amount of wet, dry, and total deposition of sulfur in kilograms per hectare from 2011 to 2013 at a set of point locations across the...

  6. Environmental behavior and analysis of agricultural sulfur.

    Science.gov (United States)

    Griffith, Corey M; Woodrow, James E; Seiber, James N

    2015-11-01

    Sulfur has been widely used for centuries as a staple for pest and disease management in agriculture. Presently, it is the largest-volume pesticide in use worldwide. This review describes the sources and recovery methods for sulfur, its allotropic forms and properties and its agricultural uses, including development and potential advantages of nanosulfur as a fungicide. Chemical and microbial reactivity, interactions in soil and water and analytical methods for determination in environmental samples and foodstuffs, including inexpensive analytical methods for sulfur residues in wine, beer and other food/beverage substrates, will be reviewed. The toxicology of sulfur towards humans and agriculturally important fungi is included, with some restrictions on use to promote safety. The review concludes with areas for which more research is warranted.

  7. Atmospheric influence of Earth's earliest sulfur cycle

    Science.gov (United States)

    Farquhar; Bao; Thiemens

    2000-08-01

    Mass-independent isotopic signatures for delta(33)S, delta(34)S, and delta(36)S from sulfide and sulfate in Precambrian rocks indicate that a change occurred in the sulfur cycle between 2090 and 2450 million years ago (Ma). Before 2450 Ma, the cycle was influenced by gas-phase atmospheric reactions. These atmospheric reactions also played a role in determining the oxidation state of sulfur, implying that atmospheric oxygen partial pressures were low and that the roles of oxidative weathering and of microbial oxidation and reduction of sulfur were minimal. Atmospheric fractionation processes should be considered in the use of sulfur isotopes to study the onset and consequences of microbial fractionation processes in Earth's early history.

  8. Efficient Electrolytes for Lithium-Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Natarajan eAngulakshmi

    2015-05-01

    Full Text Available This review article mainly encompasses on the state-of-the-art electrolytes for lithium–sulfur batteries. Different strategies have been employed to address the issues of lithium-sulfur batteries across the world. One among them is identification of electrolytes and optimization of their properties for the applications in lithium-sulfur batteries. The electrolytes for lithium-sulfur batteries are broadly classified as (i non-aqueous liquid electrolytes, (ii ionic liquids, (iii solid polymer and (iv glass-ceramic electrolytes. This article presents the properties, advantages and limitations of each type of electrolytes. Also the importance of electrolyte additives on the electrochemical performance of Li-S cells is discussed.

  9. Amine reactivity with charged sulfuric acid clusters

    OpenAIRE

    Bzdek, B. R.; D. P. Ridge; Johnston, M. V.

    2011-01-01

    The distribution of ionic species produced by electrospray of an ammonium sulfate solution in both positive and negative polarities is examined using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Positively-charged ammonium bisulfate cluster composition differs significantly from negatively-charged cluster composition. For positively-charged clusters all sulfuric acid is neutralized to bisulfate, whereas for negatively-charged clusters the degree of sulfuric acid neu...

  10. Amine reactivity with charged sulfuric acid clusters

    OpenAIRE

    Bzdek, B. R.; D. P. Ridge; Johnston, M. V.

    2011-01-01

    The distribution of charged species produced by electrospray of an ammonium sulfate solution in both positive and negative polarities is examined using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). Positively-charged ammonium bisulfate cluster composition differs significantly from negatively-charged cluster composition. For positively-charged clusters all sulfuric acid is neutralized to bisulfate, whereas for negatively-charged clusters the degree of sulfuric acid n...

  11. Biologically produced sulfur particles and polysulfide ions

    OpenAIRE

    Kleinjan, W. E.

    2005-01-01

    This thesis deals with the effects of particles of biologically produced sulfur (or 'biosulfur') on a biotechnological process for the removal of hydrogen sulfide from gas streams. Particular emphasis is given to the role of polysulfide ions in such a process. These polysulfide ions are formed from reaction of sulfide with biologically produced sulfur. The basic concepts of this H 2 S removal process were developed at the department of Environmental Technology of Wageningen University and the...

  12. Attachment of Thiobacillus thiooxidans to sulfur crystals.

    Science.gov (United States)

    SCHAEFFER, W I; HOLBERT, P E; UMBREIT, W W

    1963-01-01

    Schaeffer, W. I. (Rutgers, The State University, New Brunswick, N.J.), P. E. Holbert, and W. W. Umbreit. Attachment of Thiobacillus thiooxidans to sulfur crystals. J. Bacteriol. 85:137-140. 1963.-Electron micrographs of replicas of sulfur crystals before and after attack by Thiobacillus thiooxidans show that the microorganisms erode the crystal in the area immediately adjacent to the cell. When there are many cells, the entire crystal surface appears eroded.

  13. Polymer Electrolytes for Lithium/Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    The Nam Long Doan

    2012-08-01

    Full Text Available This review evaluates the characteristics and advantages of employing polymer electrolytes in lithium/sulfur (Li/S batteries. The main highlights of this study constitute detailed information on the advanced developments for solid polymer electrolytes and gel polymer electrolytes, used in the lithium/sulfur battery. This includes an in-depth analysis conducted on the preparation and electrochemical characteristics of the Li/S batteries based on these polymer electrolytes.

  14. Mixed Population Screening for Sulfur Isotopes

    Institute of Scientific and Technical Information of China (English)

    CUI Bin; ZHAO Lei; ZHAN Zhaoyang; HE Zhijun

    2004-01-01

    Quantitative research of the origin of sulfur isotopes is a difficult problem that has puzzled geochemists all along. In the study of the middle and lower reaches of the Yangtze River and the Dongpo orefield in Hunan Province,the authors successfully applied the mathematical model of mixed population screening to quantitatively resolving the problem on the origin of sulfur isotopes, which is significant in finding out the source of mineralizing matter and metallogenic mechanisms.

  15. Evaluation of the performance of MP4-based procedures for a wide range of thermochemical and kinetic properties

    Science.gov (United States)

    Yu, Li-Juan; Wan, Wenchao; Karton, Amir

    2016-11-01

    We evaluate the performance of standard and modified MPn procedures for a wide set of thermochemical and kinetic properties, including atomization energies, structural isomerization energies, conformational energies, and reaction barrier heights. The reference data are obtained at the CCSD(T)/CBS level by means of the Wn thermochemical protocols. We find that none of the MPn-based procedures show acceptable performance for the challenging W4-11 and BH76 databases. For the other thermochemical/kinetic databases, the MP2.5 and MP3.5 procedures provide the most attractive accuracy-to-computational cost ratios. The MP2.5 procedure results in a weighted-total-root-mean-square deviation (WTRMSD) of 3.4 kJ/mol, whilst the computationally more expensive MP3.5 procedure results in a WTRMSD of 1.9 kJ/mol (the same WTRMSD obtained for the CCSD(T) method in conjunction with a triple-zeta basis set). We also assess the performance of the computationally economical CCSD(T)/CBS(MP2) method, which provides the best overall performance for all the considered databases, including W4-11 and BH76.

  16. Thermochemical properties of some alkaline-earth silicates and zirconates. Fission product behaviour during molten core-concrete interactions

    Energy Technology Data Exchange (ETDEWEB)

    Huntelaar, M.E.

    1996-06-19

    This thesis aims to make a contribution to a better understanding of the chemical processes occurring during an ex-vessel MCCI accident with a western-type of nuclear reactor. Chosen is for a detailed thermochemical study of the silicates and zirconates of barium and strontium. In Chapter one a short introduction in the history of (research in) nuclear safety is given, followed by the state-of-the-art of molten core-concrete interactions in Chapter two. In both Chapters the role of chemical thermodynamics on this particular subject is dealt with. The experimental work on the silicates and zirconates of barium and strontium performed for this thesis, is described in the Chapters three, four, five, six, and parts of eight. In Chapter three the basis for all thermochemical measurements, the sample preparation is given. Because the sample preparation effects the accuracy of the thermodynamic measurements, a great deal of effort is spent in optimizing the synthesis of the silicates which resulted in the TEOS-method widely employed here. In the next Chapters the different thermochemical techniques used, are described: The low-temperature heat capacity measurements and the enthalpy increment measurements in Chapter four, the enthalpy-of-solution measurements in Chapter five, and measurements to determine the crystal structures in Chapter six. (orig.).

  17. High Efficiency Generation of Hydrogen Fuels Using Solar Thermochemical Splitting of Water

    Energy Technology Data Exchange (ETDEWEB)

    Heske, Clemens; Moujaes, Samir; Weimer, Alan; Wong, Bunsen; Siegal, Nathan; McFarland, Eric; Miller, Eric; Lewis, Michele; Bingham, Carl; Roth, Kurth; Sabacky, Bruce; Steinfeld, Aldo

    2011-09-29

    The objective of this work is to identify economically feasible concepts for the production of hydrogen from water using solar energy. The ultimate project objective was to select one or more competitive concepts for pilot-scale demonstration using concentrated solar energy. Results of pilot scale plant performance would be used as foundation for seeking public and private resources for full-scale plant development and testing. Economical success in this venture would afford the public with a renewable and limitless source of energy carrier for use in electric power load-leveling and as a carbon-free transportation fuel. The Solar Hydrogen Generation Research (SHGR) project embraces technologies relevant to hydrogen research under the Office of Hydrogen Fuel Cells and Infrastructure Technology (HFCIT) as well as concentrated solar power under the Office of Solar Energy Technologies (SET). Although the photoelectrochemical work is aligned with HFCIT, some of the technologies in this effort are also consistent with the skills and technologies found in concentrated solar power and photovoltaic technology under the Office of Solar Energy Technologies (SET). Hydrogen production by thermo-chemical water-splitting is a chemical process that accomplishes the decomposition of water into hydrogen and oxygen using only heat or a combination of heat and electrolysis instead of pure electrolysis and meets the goals for hydrogen production using only water and renewable solar energy as feed-stocks. Photoelectrochemical hydrogen production also meets these goals by implementing photo-electrolysis at the surface of a semiconductor in contact with an electrolyte with bias provided by a photovoltaic source. Here, water splitting is a photo-electrolytic process in which hydrogen is produced using only solar photons and water as feed-stocks. The thermochemical hydrogen task engendered formal collaborations among two universities, three national laboratories and two private sector

  18. Simulating the Thermochemical Magmatic and Tectonic Evolution of Venus's Mantle and Lithosphere: Intrusive vs. Extrusive Magmatism

    Science.gov (United States)

    Tackley, Paul; Armann, Marina

    2013-04-01

    Here we extend the models of [1]. Numerical convection models of the thermochemical evolution of Venus are compared to present-day topography and geoid, recent resurfacing history and surface deformation. The models include melting, magmatism, decaying heat-producing elements, core cooling, realistic temperature-dependent viscosity and either stagnant lid or episodic lithospheric overturn. In [1] it was found that in stagnant lid convection the dominant mode of heat loss is magmatic heat pipe, which requires massive magmatism and produces very thick crust, inconsistent with observations. Partitioning of heat-producing elements into the crust helps but does not help enough. Episodic lid overturn interspersed by periods of quiescence effectively loses Venus's heat while giving lower rates of volcanism and a thinner crust. Calculations predict 5-8 overturn events over Venus's history, each lasting ~150 Myr, initiating in one place and then spreading globally. During quiescent periods convection keeps the lithosphere thin. Magmatism keeps the mantle temperature constant over Venus's history. Crustal recycling occurs by entrainment in stagnant lid convection, and by lid overturn in episodic mode. Venus-like amplitudes of topography and geoid can be produced in either stagnant or episodic modes, with a viscosity profile that is Earth-like but shifted to higher values. The basalt density inversion below the olivine-perovskite transition causes compositional stratification around 730 km; breakdown of this layering increases episodicity but far less than episodic lid overturn. The classical stagnant lid mode with interior temperature rheological temperature scale lower than TCMB is not reached because mantle temperature is controlled by magmatism while the core cools slowly from a superheated start. Core heat flow decreases with time, possibly shutting off the dynamo, particularly in episodic cases. Here we extend [1] by considering intrusive magmatism as an alternative to

  19. An experimental test plan for the characterization of molten salt thermochemical properties in heat transport systems

    Energy Technology Data Exchange (ETDEWEB)

    Pattrick Calderoni

    2010-09-01

    Molten salts are considered within the Very High Temperature Reactor program as heat transfer media because of their intrinsically favorable thermo-physical properties at temperatures starting from 300 C and extending up to 1200 C. In this context two main applications of molten salt are considered, both involving fluoride-based materials: as primary coolants for a heterogeneous fuel reactor core and as secondary heat transport medium to a helium power cycle for electricity generation or other processing plants, such as hydrogen production. The reference design concept here considered is the Advanced High Temperature Reactor (AHTR), which is a large passively safe reactor that uses solid graphite-matrix coated-particle fuel (similar to that used in gas-cooled reactors) and a molten salt primary and secondary coolant with peak temperatures between 700 and 1000 C, depending upon the application. However, the considerations included in this report apply to any high temperature system employing fluoride salts as heat transfer fluid, including intermediate heat exchangers for gas-cooled reactor concepts and homogenous molten salt concepts, and extending also to fast reactors, accelerator-driven systems and fusion energy systems. The purpose of this report is to identify the technical issues related to the thermo-physical and thermo-chemical properties of the molten salts that would require experimental characterization in order to proceed with a credible design of heat transfer systems and their subsequent safety evaluation and licensing. In particular, the report outlines an experimental R&D test plan that would have to be incorporated as part of the design and operation of an engineering scaled facility aimed at validating molten salt heat transfer components, such as Intermediate Heat Exchangers. This report builds on a previous review of thermo-physical properties and thermo-chemical characteristics of candidate molten salt coolants that was generated as part of the

  20. Improving the performance of lithium-sulfur batteries by graphene coating

    Science.gov (United States)

    Zhou, Xiangyang; Xie, Jing; Yang, Juan; Zou, Youlan; Tang, Jingjing; Wang, Songcan; Ma, Lulu; Liao, Qunchao

    2013-12-01

    A graphene coating mesoporous carbon/sulfur (RGO@CMK-3/S) composite, which is characteristic of a hybrid structure by incorporating the merits of CMK-3 matrix and graphene (RGO) skin, is synthesized by a facile and scalable route. The CMK-3/S composite is synthesized via a simple melt-diffusion strategy, and then a thin RGO skin is absorbed on the CMK-3/S composite surface in aqueous solution. When evaluating the electrochemical properties of as-prepared RGO wrapped nanostructures as cathode materials in lithium-sulfur batteries, it exhibits much improved cyclical stability and high rate performance. The RGO@CMK-3/S composite with 53.14 wt.% sulfur presents a reversible discharge capacity of about 734 mA h g-1 after 100 cycles at 0.5 C. The improved performance is attributed to the unique structure of RGO@CMK-3/S composite. CMK-3 with extensively mesopores can offer buffering space for the volume change of sulfur and efficient diffusion channel for lithium ions during the charge/discharge process. Meanwhile, the conductive RGO coating skin physically and chemically prevents the dissolution of polysulfides from the cathode, both of which contribute to the reduced capacity fade and improved electrochemical properties.

  1. Ocular Effects of Sulfur Mustard

    Directory of Open Access Journals (Sweden)

    Yunes Panahi

    2013-06-01

    Full Text Available Purpose: To review current knowledge about ocular effects of sulfur mustard (SM and the associated histopathologic findings and clinical manifestationsMethods: Literature review of medical articles (human and animal studies was accomplished using PubMed, Scopus and ISI databases. A total of 274 relevant articles in English were retrieved and reviewed thoroughly.Results: Eyes are the most sensitive organs to local toxic effects of mustard gas. Ocular injuries are mediated through different toxic mechanisms including: biochemical damages, biomolecular and gene expression modification, induction of immunologic and inflammatory reactions, disturbing ultrastructural architecture of the cornea, and long-lasting corneal denervation. The resulting ocular injuries can roughly be categorized into acute or chronic complications. Most of the patients recover from acute injuries, but a minority of victims will suffer from chronic ocular complications. Mustard gas keratopathy (MGK is a devastating late complication of SM intoxication that proceeds from limbal stem cell deficiency (LSCD.Conclusion: SM induces several different damaging changes in case of ocular exposure; hence leading to a broad spectrum of ocular manifestations in terms of severity, timing and form. Unfortunately, no effective strategy has been introduced yet to inhibit or restore these damaging changes.

  2. Sulfur nutrition of deciduous trees

    Science.gov (United States)

    Herschbach, Cornelia; Rennenberg, Heinz

    2001-01-01

    Sulfur in its reduced form (-II) is an essential nutrient for growth and development, but is mainly available to plants in its oxidised form as sulfate. Deciduous trees take up sulfate by the roots from the soil solution and reduce sulfate to sulfide via assimilatory sulfate reduction in both roots and leaves. For reduction in the leaves, sulfate is loaded into the xylem and transported to the shoot. The surplus of sulfate not reduced in the chloroplast or stored in the vacuole and the surplus of reduced S not used for protein synthesis in the leaves is loaded into the phloem and transported back to the roots. Along the transport path, sulfate and glutathione (GSH) is unloaded from the phloem for storage in xylem and phloem parenchyma as well as in pit and ray cells. Re-mobilised S from storage tissues is loaded into the xylem during spring, but a phloem to xylem exchange does not appear to exist later in the season. As a consequence, a cycling pool of S was only found during the change of the seasons. The sulfate:glutathione ratio in the phloem seems to be involved in the regulation of S nutrition. This picture of S nutrition is discussed in relation to the different growth patterns of deciduous trees from the temperate climate zone, i.e. (1) terminated, (2) periodic and (3) indeterminate growth patterns, and in relation to environmental changes.

  3. Genetic engineering of sulfur-degrading Sulfolobus

    Energy Technology Data Exchange (ETDEWEB)

    Ho, N.W.Y. (Purdue Univ., Lafayette, IN (USA). Lab. of Renewable Resources Engineering)

    1990-01-01

    Recent studies have shown that some microorganisms can play a significant role in removing the sulfur compounds from coal. Sulfolobus acidocaldarius is one such microorganism. Some microorganisms can remove only organic sulfur from coal, other can remove only inorganic sulfur from coal, but S. acidocaldarius seems to be able to remove both the organic and the inorganic sulfur from coal. Furthermore, S. acidocaldarius has been shown to be able to use the sulfur and carbon derived from coal as its sole carbon and energy source for growth. These properties make this microorganism unique for coal desulfurization. This project is aimed at applying recombinant DNA techniques to improve the capability of S. acidocaldarius for coal desulfurization, which includes making it the host for housing foreign genes that encode the most effective enzymes for coal desulfurization. Since there is no established vectors and procedures for introducing vectors into S. acidocaldarius and related microorganisms, the immediate goal is to establish a gene cloning system for this species. During the present quarter, the authors have studied a few systems which can be used as the potential selection mechanism for the selection of the desired transformants. In addition, they also analyzed the extracellular proteins from S. acidocaldarius as well as other potential organic sulfur removing species and also managed to obtain most strains and plasmids that are needed for this work. Results to date are given. 1 tab.

  4. Microphysical simulations of sulfur burdens from stratospheric sulfur geoengineering

    Directory of Open Access Journals (Sweden)

    J. M. English

    2012-01-01

    Full Text Available Recent microphysical studies suggest that geoengineering by continuous stratospheric injection of SO2 gas may be limited by the growth of the aerosols. We study the efficacy of SO2, H2SO4 and aerosol injections on aerosol mass and optical depth using a three-dimensional general circulation model with sulfur chemistry and sectional aerosol microphysics (WACCM/CARMA. We find increasing injection rates of SO2 in a narrow band around the equator to have limited efficacy while broadening the injecting zone as well as injecting particles instead of SO2 gas increases the sulfate burden for a given injection rate, in agreement with previous work. We find that injecting H2SO4 gas instead of SO2 does not discernibly alter sulfate size or mass, in contrast with a previous study using a plume model with a microphysical model. However, the physics and chemistry in aircraft plumes, which are smaller than climate model grid cells, need to be more carefully considered. We find equatorial injections increase aerosol optical depth in the Northern Hemisphere more than the Southern Hemisphere, potentially inducing regional climate changes. We also find significant perturbations to tropospheric aerosol for all injections studied, particularly in the upper troposphere and near the poles, where sulfate burden increases by up to 100 times. This enhanced burden could have implications for tropospheric radiative forcing and chemistry. These results highlight the need to mitigate greenhouse gas emissions through means other than geoengineering, and to further study geoengineering before it can be seriously considered as a climate intervention option.

  5. Microphysical simulations of sulfur burdens from stratospheric sulfur geoengineering

    Directory of Open Access Journals (Sweden)

    J. M. English

    2012-05-01

    Full Text Available Recent microphysical studies suggest that geoengineering by continuous stratospheric injection of SO2 gas may be limited by the growth of the aerosols. We study the efficacy of SO2, H2SO4 and aerosol injections on aerosol mass and optical depth using a three-dimensional general circulation model with sulfur chemistry and sectional aerosol microphysics (WACCM/CARMA. We find increasing injection rates of SO2 in a narrow band around the equator to have limited efficacy while broadening the injecting zone as well as injecting particles instead of SO2 gas increases the sulfate burden for a given injection rate, in agreement with previous work. We find that injecting H2SO4 gas instead of SO2 does not discernibly alter sulfate size or mass, in contrast with a previous study using a plume model with a microphysical model. However, the physics and chemistry in aircraft plumes, which are smaller than climate model grid cells, need to be more carefully considered. We also find significant perturbations to tropospheric aerosol for all injections studied, particularly in the upper troposphere and near the poles, where sulfate burden increases by up to 100 times. This enhanced burden could have implications for tropospheric radiative forcing and chemistry. These results highlight the need to mitigate greenhouse gas emissions rather than attempt to cool the planet through geoengineering, and to further study geoengineering before it can be seriously considered as a climate intervention option.

  6. Hybrid microelectronic technology

    Science.gov (United States)

    Moran, P.

    Various areas of hybrid microelectronic technology are discussed. The topics addressed include: basic thick film processing, thick film pastes and substrates, add-on components and attachment methods, thin film processing, and design of thick film hybrid circuits. Also considered are: packaging hybrid circuits, automating the production of hybrid circuits, application of hybrid techniques, customer's view of hybrid technology, and quality control and assurance in hybrid circuit production.

  7. Possible thermochemical disequilibrium in the atmosphere of the exoplanet GJ 436b

    CERN Document Server

    Stevenson, Kevin B; Nymeyer, Sarah; Madhusudhan, Nikku; Seager, Sara; Bowman, William C; Hardy, Ryan A; Deming, Drake; Rauscher, Emily; Lust, Nate B

    2010-01-01

    The nearby extrasolar planet GJ 436b--which has been labelled as a 'hot Neptune'--reveals itself by the dimming of light as it crosses in front of and behind its parent star as seen from Earth. Respectively known as the primary transit and secondary eclipse, the former constrains the planet's radius and mass, and the latter constrains the planet's temperature and, with measurements at multiple wavelengths, its atmospheric composition. Previous work using transmission spectroscopy failed to detect the 1.4-\\mu m water vapour band, leaving the planet's atmospheric composition poorly constrained. Here we report the detection of planetary thermal emission from the dayside of GJ 436b at multiple infrared wavelengths during the secondary eclipse. The best-fit compositional models contain a high CO abundance and a substantial methane (CH4) deficiency relative to thermochemical equilibrium models for the predicted hydrogen-dominated atmosphere. Moreover, we report the presence of some H2O and traces of CO2. Because CH...

  8. Single-domain chemical, thermochemical and thermal remanences in a basaltic rock

    CERN Document Server

    Draeger, U; Poidras, T; Riisager, J; Draeger, Ulrike; Pr\\'{e}vot, Michel; Poidras, Thierry; Riisager, Janna

    2005-01-01

    Tiny basaltic samples containing finely grained titanomagnetite with Curie temperature less than 100 C were heated in air in weak field (25 to 100microT) at temperatures between 400 and 560 C for times as long as 32 hours. Oxyexsolution of titanomagnetite resulted in the crystallization of interacting single domain particles with Curie point close to 540 C and the concomitant development of one of two types chemical remanence, depending upon thermal treatment: isothermal chemical remanence (CRM) or thermochemical remanence (TCRM), the latter acquired under the combined effects of chemical change and temperature decrease. CRM and TCRM acquired under various conditions were subjected to Thellier-type experiments. The CRM/TRM ratio is found to be less than one and increases rapidly with acquisition temperature (0.35 at 400 C, 0.65 at 450 C, and 0.90 at 500 C). Thus, very large underestimate of geomagnetic field paleostrength can occur when a natural CRM is not recognized as such and is believed to be a natural T...

  9. Thermochemical plots using JCZS2i piece-wise curve fits.

    Energy Technology Data Exchange (ETDEWEB)

    Miller, David L.; Schoof, Justin C.; Hobbs, Michael L.

    2013-10-01

    This report presents plots of specific heat, enthalpy, entropy, and Gibbs free energy for 1439 species in the JCZS2i database. Included in this set of species are 496 condensed-phase species and 943 gas-phase species. The gas phase species contain 80 anions and 112 cations for a total of 192 ions. The JCZS2i database is used in conjunction with the TIGER thermochemical code to predict thermodynamic states from ambient conditions to high temperatures and pressures. Predictions from the TIGER code using the JCZS2i database can be used in shock physics codes where temperatures may be as high as 20,000 K and ions may be present. Such high temperatures were not considered in the original JCZS database, and extrapolations made for these temperatures were unrealistic. For example, specific heat would sometimes go negative at high temperatures which fails the definition of specific heat. The JCZS2i database is a new version of the JCZS database that is being created to address these inaccuracies. The purpose of the current report is to visualize the high temperature extrapolations to insure that the specific heat, enthalpy, entropy, and Gibbs free energy predictions are reasonable up to 20,000 K.

  10. Computational study on thermochemical properties for perhalogenated methanols (CX3OH) (X = F, Cl, Br).

    Science.gov (United States)

    Alrawashdeh, Ahmad I; Poirier, Raymond A

    2015-04-16

    The perhalogenated methanols (CX3OH; X = F, Cl, and Br) are found in the atmosphere as products of the degradation of halocarbons. The thermochemical properties for these molecules have been calculated at the HF, MP2, and B3LYP levels of theories in conjunction with six different basis sets as well as at G3MP2 and CBS-QB3. Calculated properties include the gas-phase enthalpies of formation (ΔfH(0)), gas-phase acidities (ΔacidG(0)), gas-phase proton affinity, and bond dissociation energies of the C-O and O-H bonds of CX3OH. Excellent agreement is found between the results obtained using G3MP2 and CBS-QB3 methods and the available experimental data. The results obtained using MP2 are more consistent with the experimental, G3MP2, and CBS-QB3 values than those computed at B3LYP. In general, the 6-311+G(d,p) basis set when combined with the HF or MP2 level of theory produced better results than other basis sets considered in this study.

  11. Controlled Chemical Patterns with ThermoChemical NanoLithography (TCNL)

    Science.gov (United States)

    Carroll, Keith; Giordano, Anthony; Wang, Debin; Kodali, Vamsi; King, W. P.; Marder, S. R.; Riedo, E.; Curtis, J. E.

    2012-02-01

    Many research areas, both fundamental and applied, rely upon the ability to organize non-trivial assemblies of molecules on surfaces. In this work, we introduce a significant extension of ThermoChemical NanoLithography (TCNL), a high throughput chemical patterning technique that uses temperature-driven chemical reactions localized near the tip of a thermal cantilever. By combining a chemical kinetics based model with experiments, we have developed a protocol for varying the concentration of surface bound molecules. The result is an unprecedented ability to fabricate extremely complex patterns comprised of varying chemical concentrations, as demonstrated by sinusoidal patterns of amine groups with varying pitches (˜5-15 μm) and the replication of Leonardo da Vinci's Mona Lisa with dimensions of ˜30 x 40 μm^2. Programmed control of the chemical reaction rate should have widespread applications for a technique which has already been shown to nanopattern various substrates including graphene nanowires, piezoelectric crystals, and optoelectronic materials.

  12. Dynamic/Thermochemical Balance Drives Unusual Alkyl/F Exchange Reactions in Siloxides and Analogs.

    Science.gov (United States)

    Correra, Thiago C; Fernandes, André S; Riveros, José M

    2016-03-17

    A recent report has shown that siloxides can undergo an unusual Me/F exchange reaction promoted by NF3 in the gas phase ( Angew. Chem. Int. Ed. 2012, 51, 8632-8635). A more extensive study of this kind of exchange has been carried out using mass spectrometry techniques (FT-ICR), DFT calculations, natural bond orbital (NBO) analysis, and Born-Oppenheimer molecular dynamics simulations (BOMD), using NF3, SO2F2, and CF4 as fluorine donors and evaluating the effect of replacing the Si center by Ge and C. This comprehensive approach shows that NF3 is crucial for the exchange reaction, as SO2F2 forms SO3F(-) via a pentacoordinated channel whereas no reaction is observed for CF4. The uniqueness of NF3 is caused by favorable thermochemical consideration and by dynamic effects that preclude the formation of the ubiquitous Si-F pentacoordinated species. Me3GeO(-) was shown to be as reactive as siloxides toward NF3, whereas C analogs showed no reactions under our experimental conditions. The exchange reaction was also shown to take place for triethylsiloxides. These exchange reactions are examples of reaction systems that avoid the lower energy pathway and are driven by dynamic effects that cannot be explained by the potential energy surface.

  13. Chemical characterization of sulphur-iodine thermochemical cycle flowstreams by Raman spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liberatore, Raffaele; Falconieri, Mauro; Lanchi, Michela; Spadoni, Annarita [ENEA CR, Casaccia (Italy)

    2010-07-01

    The Sulphur-Iodine (S-I) thermochemical cycle for hydrogen production from water is one of the widest investigated cycles in the world. Considered the complexity of the S-I process scheme, the focus on chemical characterization of the flowstreams in the loop plant is crucial in order to fully understand chemical equilibriums involved at varying hydriodic acid: (HI:I{sub 2}) ratio in the mixtures and to determine HI and I{sub 2} contents as well. Raman spectroscopy has been widely used to investigate iodine solutions, however few works deals with I{sub 2} in HI aqueous mixtures. The aim of the present study is to use Raman spectroscopy for a rapid qualitative and quantitative characterization of the HI-H{sub 2}O-I{sub 2} mixtures involved in the S-I process. At this purpose, Raman spectra of solutions with known HI and I{sub 2} concentration have been recorded at varying I{sub 2} and HI compositions. It has been found that the chemistry of these solutions is highly dependant on HI:I{sub 2} molar ratio. For ratio up to 1:1, the dominant iodine compounds are I{sub 3}{sup -} and its corresponding ion pair HI{sub 3}. At higher values, close to those of the hydriodic phase HIx of the Bunsen reaction, there is experimental evidence of the formation of higher polyiodine and polyiodides compounds. (orig.)

  14. Thermochemical Equilibrium Model of Synthetic Natural Gas Production from Coal Gasification Using Aspen Plus

    Directory of Open Access Journals (Sweden)

    Rolando Barrera

    2014-01-01

    Full Text Available The production of synthetic or substitute natural gas (SNG from coal is a process of interest in Colombia where the reserves-to-production ratio (R/P for natural gas is expected to be between 7 and 10 years, while the R/P for coal is forecasted to be around 90 years. In this work, the process to produce SNG by means of coal-entrained flow gasifiers is modeled under thermochemical equilibrium with the Gibbs free energy approach. The model was developed using a complete and comprehensive Aspen Plus model. Two typical technologies used in entrained flow gasifiers such as coal dry and coal slurry are modeled and simulated. Emphasis is put on interactions between the fuel feeding technology and selected energy output parameters of coal-SNG process, that is, energy efficiencies, power, and SNG quality. It was found that coal rank does not significantly affect energy indicators such as cold gas, process, and global efficiencies. However, feeding technology clearly has an effect on the process due to the gasifying agent. Simulations results are compared against available technical data with good accuracy. Thus, the proposed model is considered as a versatile and useful computational tool to study and optimize the coal to SNG process.

  15. Thermochemical cycles for energy storage: Thermal decomposition of ZnCO sub 4 systems

    Energy Technology Data Exchange (ETDEWEB)

    Wentworth, W.E. (Houston Univ., TX (United States))

    1992-04-01

    The overall objective of our research has been to develop thermochemical cycles that can be used for energy storage. A specific cycle involving ammonium hydrogen sulfate (NH{sub 4}HSO{sub 4}) has been proposed. Each reaction in the proposed cycle has been examined experimentally. Emphasis has been placed on the basic chemistry of these reactions. In the concluding phase of this research, reported herein, we have shown that when NH{sub 4}HSO{sub 4} is mixed with ZnO and decomposed, the resulting products can be released stepwise (H{sub 2}A{sub (g)} at {approximately}163{degrees}C, NH{sub 3(g)} at 365--418{degrees}C, and a mixture of SO{sub 2(g)} and SO{sub 3(g)} at {approximately}900{degrees}C) and separated by controlling the reaction temperature. Side reactions do not appear to be significant and the respective yields are high as would be required for the successful use of this energy storage reaction in the proposed cycle. Thermodynamic, kinetic, and other reaction parameters have been measured for the various steps of the reaction. Finally we have completed a detailed investigation of one particular reaction: the thermal decomposition of zinc sulfate (ZnSO{sub 4}). We have demonstrated that this reaction can be accelerated and the temperature required reduced by the addition of excess ZnO, V{sub 2}A{sub 5} and possibly other metal oxides.

  16. The flammability limits of lean fuel-air mixtures: thermochemical and kinetic criteria for explosion hazards.

    Science.gov (United States)

    Burgess, D; Hertzberg, M

    1975-01-01

    The present state of knowledge is reviewed concisely in terms of the experimental methods used, the effect of apparatus size, accuracy of data, methods of data presentation, and the sensitivity of the limits to initial temperature and pressure. The heat of combustion per mole of gas mixture at the lean limit is a reliable thermochemical criterion for the flammability of organic fuels with comparable reactivities. The limit calorific value for the heavy paraffins is 11.5 +/- 0.1 kcal mole -1. However, kinetic effects strongly influence this value. Highly reactive fuels (hydrogen, acetylene) require lower energy contents, whereas less reactive fuels (ammonia) require higher values. Hydrogen-starved fuels (carbon monoxide, cyanogen) show marked anomalies and are sensitive to impurities that can provide H-atom chain carriers. These kinetic effects are reflected in the experimentally measurable burning velocity of the fuel. This parameter is a key ingredient in the theory of flammable limits, which is briefly sketched. Five competing processes dissipate power from the combustion wave and quench it at some characteristic limit velocity. The prevalent consensus that the limits are controlled by natural convection is clearly demonstrated, and the complex interplay of kinetics and thermochemistry follows logically therefrom.

  17. Thermochemical pretreatments of organic fraction of municipal solid waste from a mechanical-biological treatment plant.

    Science.gov (United States)

    Álvarez-Gallego, Carlos José; Fdez-Güelfo, Luis Alberto; de los Ángeles Romero Aguilar, María; Romero García, Luis Isidoro

    2015-02-09

    The organic fraction of municipal solid waste (OFMSW) usually contains high lignocellulosic and fatty fractions. These fractions are well-known to be a hard biodegradable substrate for biological treatments and its presence involves limitations on the performance of anaerobic processes. To avoid this, thermochemical pretreatments have been applied on the OFMSW coming from a full-scale mechanical-biological treatment (MBT) plant, in order to pre-hydrolyze the waste and improve the organic matter solubilisation. To study the solubilisation yield, the increments of soluble organic matter have been measured in terms of dissolved organic carbon (DOC), soluble chemical oxygen demand (sCOD), total volatile fatty acids (TVFA) and acidogenic substrate as carbon (ASC). The process variables analyzed were temperature, pressure and NaOH dosage. The levels of work for each variable were three: 160-180-200 °C, 3.5-5.0-6.5 bar and 2-3-4 g NaOH/L. In addition, the pretreatment time was also modified among 15 and 120 min. The best conditions for organic matter solubilisation were 160 °C, 3 g NaOH/L, 6.5 bar and 30 min, with yields in terms of DOC, sCOD, TVFA and ASC of 176%, 123%, 119% and 178% respectively. Thus, predictably the application of this pretreatment in these optimum conditions could improve the H2 production during the subsequent Dark Fermentation process.

  18. Evaluation of thermochemical pretreatment and continuous thermophilic condition in rice straw composting process enhancement.

    Science.gov (United States)

    Hosseini, Seyed Mohammad; Abdul Aziz, Hamidi

    2013-04-01

    The effects of thermochemical pretreatment and continuous thermophilic conditions on the composting of a mixture of rice straw residue and cattle manure were investigated using a laboratory-scale composting reactor. Results indicate that the composting period of rice straw can be shortened to less than 10 days by applying alkali pre-treatment and continuous thermophilic composting conditions. The parameters obtained on day 9 of this study are similar to the criteria level published by the Canadian Council of Ministers of the Environment. The moisture content, organic matter reduction, pH level, electrical conductivity, total organic carbon reduction, soluble chemical oxygen demand reduction, total Kjeldahl nitrogen, carbon-to-nitrogen ratio, and germination index were 62.07%, 16.99%, 7.30%, 1058 μS/cm, 17.00%, 83.43%, 2.06%, 16.75%, and 90.33%, respectively. The results of this study suggest that the application of chemical-biological integrated processes under thermophilic conditions is a novel method for the rapid degradation and maturation of rice straw residue.

  19. Thermochemical pretreatment of lignocellulose to enhance methane fermentation: II. Evaluation and application of pretreatment model.

    Science.gov (United States)

    Baugh, K D; Levy, J A; McCarty, P L

    1988-01-01

    A model was developed and evaluated as a tool for predicting the formation of soluble products from staged thermochemical treatment of lignocellulosic materials under acidic conditions typical of autohydrolysis. The model was used to predict the general trend of hemi-cellulose and cellulose hydrolysis between pH 2 and 4 and temperatures of 170-230 degrees C, and results were compared with experimental data. When the model was evaluated for this range of temperatures and pH values, results indicated: (1) a relatively low temperature (175 degrees C) during the first stage allows hydrolysis of the hemi-cellulose polysaccharides without significant mono-saccharide decomposition, (2) subsequent stages at higher temperatures (equal or greater than 200 degrees C) are needed for significant cellulose hydrolysis, but glucose decomposition will also occur, and, (3) a pH in the range of 2-2.5 will enhance polysaccharide hydrolysis while limiting monosaccharide decomposition. The model's predictions, indicating that the formation of biodegradable products could be optimized using Pretreatments at pH 2-2.5 for the pH range evaluated, were confirmed in experiments with white fir as a representative lig nocellulose.

  20. Thermochemical pretreatment and anaerobic digestion of dairy cow manure: Experimental and economic evaluation.

    Science.gov (United States)

    Passos, Fabiana; Ortega, Valentina; Donoso-Bravo, Andrés

    2017-03-01

    The aim of this study was to assess technically and economically the application thermochemical pretreatment in the anaerobic digestion of dairy cow manure. After selecting the optimum substrate to inoculum (S/I) ratio in a preliminary BMP test, the following tests compared 20 different pretreatment conditions varying temperature (100 and 37°C), exposure time (5 and 30min and 12 and 24h) and chemical doses (0.5, 2, 6 and 10% of HCl or NaOH). The highest value of maximum production rate was achieved at an S/I ratio of 0.25gVSsgVSi(-1). The major improvements of the methane potential were 23.6% with 10% of NaOH at 100°C for 5min and 20.6% with 2% of HCl at 37°C. The technical-economic analysis showed that the implementation of neither thermal alkali nor thermal-acid pretreatment would be feasible and the conventional one-step anaerobic digestion outperforms both alternatives.