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Sample records for hdo

  1. The isotopic dipole moment of HDO

    Energy Technology Data Exchange (ETDEWEB)

    Assafrao, Denise; Mohallem, Jose R [Laboratorio de Atomos e Moleculas Especiais, Departamento de Fisica, ICEx, Universidade Federal de Minas Gerais, CP 702, 30123-970, Belo Horizonte, MG (Brazil)

    2007-03-14

    An adiabatic variational approximation is used to study the monodeuterated water molecule, HDO, accounting for the isotopic effect. The isotopic dipole moment, pointing from D to H, is then calculated for the first time, yielding (1.5 {+-} 0.1) x 10{sup -3} Debye, being helpful in the interpretation of experiments. (fast track communication)

  2. Matrix Isolation Spectroscopy of H2O2, D2O, and HDO in Solid Parahydrogen

    National Research Council Canada - National Science Library

    Fajardo, Mario

    2003-01-01

    ...) solids doped with H2O, D2O and HDO molecules. Analysis of the rovibrational spectra of the isolated H20, D2O and HDO monomers reveals their existence as very slightly hindered rotors, typically showing only 2 to 5...

  3. Measurement of HDO Products Using GC-TCD: Towards Obtaining Reliable Analytical Data

    Directory of Open Access Journals (Sweden)

    Zuas Oman

    2018-03-01

    Full Text Available This paper reported the method development and validation of a gas chromatography with thermal conductivity detector (GC-TCD method for the measurement of the gaseous products of hydrodeoxygenation (HDO. The method validation parameters include selectivity, precision (repeatability and reproducibility, accuracy, linearity, limit of detection (LoD, limit of quantitation (LoQ, and robustness. The results showed that the developed method was able to separate the target components (H2, CO2, CH4 and CO from their mixtures without any special sample treatment. The validated method was selective, precise, accurate, and robust. Application of the developed and validated GC-TCD method to the measurement of by-product components of HDO of bio-oil revealed a good performance with relative standard deviation (RSD less than 1.0% for all target components, implying that the process of method development and validation provides a trustworthy way of obtaining reliable analytical data.

  4. Problemorienteret læring gennem udfordringer på jobbet - praksis på HDO Organisation

    DEFF Research Database (Denmark)

    Gjerding, Allan Næs

    2014-01-01

    Kapitlet belyser det taksonomiske grundlag for HDO på AAU og beskriver det som en kombination af Blooms taksonomi og Kolbs læringsteori. I den forbindelse introducerer kapitlet begrebet "cirkulær progression"......Kapitlet belyser det taksonomiske grundlag for HDO på AAU og beskriver det som en kombination af Blooms taksonomi og Kolbs læringsteori. I den forbindelse introducerer kapitlet begrebet "cirkulær progression"...

  5. AN INFRARED SEARCH FOR HDO IN COMET D/2012 S1 (ISON) AND IMPLICATIONS FOR iSHELL

    Energy Technology Data Exchange (ETDEWEB)

    Gibb, Erika L. [Department of Physics and Astronomy, University of Missouri—St Louis, 1 University Blvd, St Louis, MO 63121 (United States); Bonev, Boncho P.; Villanueva, Geronimo L.; Paganini, Lucas [Department of Physics, Catholic University of America, 620 Michigan Avenue NE, Washington, DC 20064 (United States); DiSanti, Michael A.; Mumma, Michael J., E-mail: gibbe@umsl.edu [Goddard Center for Astrobiology, NASA Goddard Space Flight Center, 8800 Greenbelt Road, Greenbelt, MD 20771 (United States)

    2016-01-10

    We performed a sensitive search for HDO in comet D/2012 S1 (ISON) on 2013 November 16, 17, and 22 using CSHELL and the NASA Infrared Telescope Facility. We constrained the HDO/H{sub 2}O ratio to <2.0 VSMOW (the terrestrial ocean value) at the 3σ uncertainty level from two independent measurements corresponding to different H{sub 2}O outgassing rates. This represents the best constrained HDO/H{sub 2}O ratio for a comet using a small (3 m) telescope and illustrates that when CSHELL is replaced with iSHELL, 3 m class telescopes are still strong contenders for detecting minor volatile species in moderately bright comets.

  6. HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect

    Directory of Open Access Journals (Sweden)

    Irina V. Deliy

    2017-10-01

    Full Text Available Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO2 and ((NH42HPO4 as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis, we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis.

  7. The HDO/H2O Ratio in Gas in the Inner Regions of a Low-mass Protostar

    DEFF Research Database (Denmark)

    Jørgensen, Jes Kristian; van Dishoeck, Ewine F.

    2010-01-01

    The HDO/H2O abundance ratio is thought to be a key diagnostic for the evolution of water during the star and planet formation process and thus for its origin on Earth. We here present millimeter-wavelength high angular resolution observations of the deeply embedded protostar NGC 1333-IRAS4B from...

  8. Semiclassical quantization of vibrational systems using fast-Fourier transform methods: Application to HDO stretches

    International Nuclear Information System (INIS)

    Pickett, T.J.; Shirts, R.B.

    1991-01-01

    Based on work by Martens and Ezra and partially developed independently by Eaker, we apply an improved method of approximating the quantum energy levels of a system of coupled oscillators using the fast-Fourier transform of classical coordinates and momenta to find quantizing trajectories. Application is made to a two-dimensional system modeling the stretching motions of the HDO molecule. The results are in excellent agreement with quantum calculations. This method is useful because: (1) it gives results which are independent of any separability of the Hamiltonian, (2) it is not limited in the number of degrees of freedom that can be handled, and (3) no zero-order approximation to the system is necessary. Results are equally valid inside and outside of resonance zones

  9. Upgrading pyrolysis bio-oil through hydrodeoxygenation (HDO) using non-sulfided Fe-Co/SiO2 catalyst

    International Nuclear Information System (INIS)

    Cheng, Shouyun; Wei, Lin; Julson, James; Rabnawaz, Muhammad

    2017-01-01

    Highlights: • Fe-Co/SiO 2 catalyst with medium acidity was more effective for bio-oil upgrading. • Co-loading of Fe and Co on SiO 2 support improved catalyst performance. • Catalyst showing the best catalytic activity had a Fe/Co mole ratio of 1. • Biofuel produced by Fe-Co(1)/SiO 2 had the higher hydrocarbons content at 22.44%. • The mechanism of bio-oil HDO on Fe-Co/SiO 2 catalysts is proposed. - Abstract: Hydrodeoxygenation (HDO) is an effective route to upgrade bio-oil to hydrocarbon bio-oil, but the development of efficient catalysts for bio-oil HDO still remains a challenge. In this study, non-sulfided Fe-Co/SiO 2 catalysts were used to upgrade bio-oil using HDO. A series of Fe-Co/SiO 2 catalysts with different Fe/Co mole ratios were prepared, characterized and evaluated. The Fe and/or Co loading did not change SiO 2 crystalline structure. The Fe and/or Co metals increased the amount and strength of Fe-Co/SiO 2 catalyst acidity. Physicochemical properties of upgraded bio-oils produced using Fe-Co/SiO 2 catalysts such as water content, total acid number, viscosity and higher heating values improved in comparison to raw bio-oil. Bimetallic Fe-Co/SiO 2 catalysts resulted in better HDO performance than monometallic Fe/SiO 2 or Co/SiO 2 catalysts. This was due to the synergistic effect of Fe and Co occurring on the SiO 2 support. Fe-Co/SiO 2 catalyst having medium amount of acidity was more effective for bio-oil upgrading. The highest hydrocarbons content produced using Fe-Co(1)/SiO 2 catalyst was 22.44%. The mechanism of bio-oil HDO on Fe-Co/SiO 2 catalysts is proposed.

  10. Deuterium in astrophysical ice analogues: Isotope exchange and IR detection sensitivity for HDO

    Science.gov (United States)

    Escribano, R. M.; Galvez, O.; Mate, B.; Herrero, V. J.

    2011-12-01

    Among D-bearing molecules, water is especially interesting from an astrophysical point of view. Although the deuterium content of water in astronomical environments is relatively small as compared with other molecules, it holds most valuable information, still largely undeciphered, on the dynamics of formation and evaporation of ice grain mantels in protostellar regions [1], and is crucial for the understanding of the formation of the Solar System and the Earth [2]. In this work, we have used the OD stretching bands of HDO and D2O molecules in various ice mixtures formed by vapor deposition on a cold substrate (see ref [3] for a description of the experimental set-up) to study the sensitivity of the IR technique for the detection of HDO in ice samples, and to monitor processes of H/D isotope exchange in these solids. It is found that the detection sensitivity is strongly dependent on the ice structure. The OD band is extremely broad and tends to disappear into the absorption continuum of H2O for low temperature amorphous samples. Detectable HDO/H2O ratios with this technique may range from a few per cent for amorphous samples to a few per thousand in crystalline ice. These relatively high upper limits and the appreciable dependence of the band shape on temperature, complicating the interpretation of data from many lines of sight, may question the usefulness of this technique. Isotopic H/D exchange in mixed ices of H2O/D2O is found to start at ~ 120 K and is greatly accelerated at 150 K, as crystallization proceeds in the ice. The process is mainly driven by proton transfer assisted by orientational defect mobility. Annealed amorphous samples are more favourable for isotope exchange than samples directly formed in the crystalline phase. The annealing process seems to lead to polycrystalline ice morphology with a higher defect activity. The present data emphasize the relevance of a depletion mechanism for D atoms in hydroxylic bonds in the solid state, recently

  11. Upgrading pine sawdust pyrolysis oil to green biofuels by HDO over zinc-assisted Pd/C catalyst

    International Nuclear Information System (INIS)

    Huang, Yinbin; Wei, Lin; Zhao, Xianhui; Cheng, Shouyun; Julson, James; Cao, Yuhe; Gu, Zhengrong

    2016-01-01

    Highlights: • The Pd/Zn synergistic catalysis was employed. • The true pyrolysis oil as substrate was used in HDO. • The products (gas and liquid) were analyzed. • The optimal reaction conditions were obtained. - Abstract: Upgrading pyrolysis oil by hydrodeoxygenation (HDO) is a promising route for the production of advanced biofuels. The proper reaction conditions and catalysts are important for the success of this process. Previously our research group investigated the ratio of Zn and Pd on the synergistic effect for HDO bio-oil upgrading. This present research focuses on determining the optimal reaction conditions for HDO conversion of pyrolysis oil produced from pine sawdust. Temperatures of 150, 200 and 250 °C and hydrogen pressures of 1.38, 2.76 and 4.14 MPa were evaluated. Syngas, liquids and coke were the primary products evaluated. Syngas was characterized using a Gas chromatography (GC). The liquids were characterized using a Gas chromatography–mass spectrometry (GC–MS). Increasing reaction temperature resulted in increased coke yields. Treatment at 250 °C and 1.38 MPa resulted in the highest hydrocarbon content (6.06%). The treatment at 200 °C and 1.38 MPa produced the largest amounts of hydrocarbons in C_6–C_1_2 range (5.07%). The physicochemical characterizations further support the GCMS results. Syngas analysis revealed that higher hydrogen pressure leads to increased hydrogen consumption and results in more oxy-compounds conversion to hydrocarbons. The syngas analysis also supports the liquid analysis result.

  12. Improved water vapour spectroscopy in the 4174–4300 cm−1 region and its impact on SCIAMACHY HDO/H2O measurements

    Directory of Open Access Journals (Sweden)

    R. A. Scheepmaker

    2013-04-01

    Full Text Available The relative abundance of the heavy water isotopologue HDO provides a deeper insight into the atmospheric hydrological cycle. The SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY allows for global retrievals of the ratio HDO/H2O in the 2.3 micron wavelength range. However, the spectroscopy of water lines in this region remains a large source of uncertainty for these retrievals. We therefore evaluate and improve the water spectroscopy in the range 4174–4300 cm−1 and test if this reduces systematic uncertainties in the SCIAMACHY retrievals of HDO/H2O. We use a laboratory spectrum of water vapour to fit line intensity, air broadening and wavelength shift parameters. The improved spectroscopy is tested on a series of ground-based high resolution FTS spectra as well as on SCIAMACHY retrievals of H2O and the ratio HDO/H2O. We find that the improved spectroscopy leads to lower residuals in the FTS spectra compared to HITRAN 2008 and Jenouvrier et al. (2007 spectroscopy, and the retrievals become more robust against changes in the retrieval window. For both the FTS and SCIAMACHY measurements, the retrieved total H2O columns decrease by 2–4% and we find a negative shift of the HDO/H2O ratio, which for SCIAMACHY is partly compensated by changes in the retrieval setup and calibration software. The updated SCIAMACHY HDO/H2O product shows somewhat steeper latitudinal and temporal gradients and a steeper Rayleigh distillation curve, strengthening previous conclusions that current isotope-enabled general circulation models underestimate the variability in the near-surface HDO/H2O ratio.

  13. Validation of SCIAMACHY HDO/H2O measurements using the TCCON and NDACC-MUSICA networks

    Science.gov (United States)

    Scheepmaker, R. A.; Frankenberg, C.; Deutscher, N. M.; Schneider, M.; Barthlott, S.; Blumenstock, T.; Garcia, O. E.; Hase, F.; Jones, N.; Mahieu, E.; Notholt, J.; Velazco, V.; Landgraf, J.; Aben, I.

    2015-04-01

    Measurements of the atmospheric HDO/H2O ratio help us to better understand the hydrological cycle and improve models to correctly simulate tropospheric humidity and therefore climate change. We present an updated version of the column-averaged HDO/H2O ratio data set from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The data set is extended with 2 additional years, now covering 2003-2007, and is validated against co-located ground-based total column δD measurements from Fourier transform spectrometers (FTS) of the Total Carbon Column Observing Network (TCCON) and the Network for the Detection of Atmospheric Composition Change (NDACC, produced within the framework of the MUSICA project). Even though the time overlap among the available data is not yet ideal, we determined a mean negative bias in SCIAMACHY δD of -35 ± 30‰ compared to TCCON and -69 ± 15‰ compared to MUSICA (the uncertainty indicating the station-to-station standard deviation). The bias shows a latitudinal dependency, being largest (∼ -60 to -80‰) at the highest latitudes and smallest (∼ -20 to -30‰) at the lowest latitudes. We have tested the impact of an offset correction to the SCIAMACHY HDO and H2O columns. This correction leads to a humidity- and latitude-dependent shift in δD and an improvement of the bias by 27‰, although it does not lead to an improved correlation with the FTS measurements nor to a strong reduction of the latitudinal dependency of the bias. The correction might be an improvement for dry, high-altitude areas, such as the Tibetan Plateau and the Andes region. For these areas, however, validation is currently impossible due to a lack of ground stations. The mean standard deviation of single-sounding SCIAMACHY-FTS differences is ∼ 115‰, which is reduced by a factor ∼ 2 when we consider monthly means. When we relax the strict matching of individual measurements and focus on the mean seasonalities using all available

  14. HDO of guaiacol over NiMo catalyst supported on activated carbon derived from castor de-oiled cake

    Directory of Open Access Journals (Sweden)

    Viviana Ospina

    2015-05-01

    Full Text Available Physical and chemical activation methods were used to prepare two different activated carbons (ACs from castor de-oiled cake. H2O/CO2 mixture was used as the physical activating agent, and for chemical activation potassium carbonate (K2CO3 was used. For both materials, textural and chemical properties were characterized by N2 adsorption–desorption isotherms, thermogravimetric analysis (TGA, Fourier Transform Infrared Spectroscopy (FTIR, thermal programmed reduction (TPR, X-ray fluorescence (XRF, and scanning electron microscopy (SEM. The ACs were used as supports for NiMo sulfide catalysts, which were prepared by wetness impregnation and in-situ sulfided for the hydrodeoxygenation (HDO of guaiacol (GUA as a model compound of bio-oil. The HDO reaction was carried out in a typical batch reactor at 5 MPa of H2 and 350 °C. Under the same test conditions, commercial catalysts were also tested in the reaction. Although the commercial catalysts displayed higher GUA conversion, the prepared catalysts showed higher activity and non-oxygenated and saturated products yield.

  15. Ground-based remote sensing of HDO/H2O ratio profiles: introduction and validation of an innovative retrieval approach

    Science.gov (United States)

    Schneider, M.; Hase, F.; Blumenstock, T.

    2006-10-01

    We propose an innovative approach for analysing ground-based FTIR spectra which allows us to detect variabilities of lower and middle/upper tropospheric HDO/H2O ratios. We show that the proposed method is superior to common approaches. We estimate that lower tropospheric HDO/H2O ratios can be detected with a noise to signal ratio of 15% and middle/upper tropospheric ratios with a noise to signal ratio of 50%. The method requires the inversion to be performed on a logarithmic scale and to introduce an inter-species constraint. While common methods calculate the isotope ratio posterior to an independent, optimal estimation of the HDO and H2O profile, the proposed approach is an optimal estimator for the ratio itself. We apply the innovative approach to spectra measured continuously during 15 months and present, for the first time, an annual cycle of tropospheric HDO/H2O ratio profiles as detected by ground-based measurements. Outliers in the detected middle/upper tropospheric ratios are interpreted by backward trajectories.

  16. Long-term series of tropospheric water vapour amounts and HDO/H2O ratio profiles above Jungfraujoch.

    Science.gov (United States)

    Lejeune, B.; Mahieu, E.; Schneider, M.; Hase, F.; Servais, C.; Demoulin, P.

    2012-04-01

    Water vapour is a crucial climate variable involved in many processes which widely determine the energy budget of our planet. In particular, water vapour is the dominant greenhouse gas in the Earth's atmosphere and its radiative forcing is maximum in the middle and upper troposphere. Because of the extremely high variability of water vapour concentration in time and space, it is challenging for the available relevant measurement techniques to provide a consistent data set useful for trend analyses and climate studies. Schneider et al. (2006a) showed that ground-based Fourier Transform Infrared (FTIR) spectroscopy, performed from mountain observatories, allows for the detection of H2O variabilities up to the tropopause. Furthermore, the FTIR measurements allow the retrieval of HDO amounts and therefore the monitoring of HDO/H2O ratio profiles whose variations act as markers for the source and history of the atmospheric water vapour. In the framework of the MUSICA European project (Multi-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water, http://www.imk-asf.kit.edu/english/musica.php), a new approach has been developed and optimized by M. Schneider and F. Hase, using the PROFFIT algorithm, to consistently retrieve tropospheric water vapour profiles from high-resolution ground-based infrared solar spectra and so taking benefit from available long-term data sets of ground-based observations. The retrieval of the water isotopologues is performed on a logarithmic scale from 14 micro-windows located in the 2600-3100 cm-1 region. Other important features of this new retrieval strategy are: a speed dependant Voigt line shape model, a joint temperature profile retrieval and an interspecies constraint for the HDO/H2O profiles. In this contribution, we will combine the quality of the MUSICA strategy and of our observations, which are recorded on a regular basis with FTIR spectrometers, under clear-sky conditions, at the NDACC site

  17. Profiles of CH4, HDO, H2O, and N2O with improved lower tropospheric vertical resolution from Aura TES radiances

    Directory of Open Access Journals (Sweden)

    D. Noone

    2012-02-01

    Full Text Available Thermal infrared (IR radiances measured near 8 microns contain information about the vertical distribution of water vapor (H2O, the water isotopologue HDO, and methane (CH4, key gases in the water and carbon cycles. Previous versions (Version 4 or less of the TES profile retrieval algorithm used a "spectral-window" approach to minimize uncertainty from interfering species at the expense of reduced vertical resolution and sensitivity. In this manuscript we document changes to the vertical resolution and uncertainties of the TES version 5 retrieval algorithm. In this version (Version 5, joint estimates of H2O, HDO, CH4 and nitrous oxide (N2O are made using radiances from almost the entire spectral region between 1100 cm−1 and 1330 cm−1. The TES retrieval constraints are also modified in order to better use this information. The new H2O estimates show improved vertical resolution in the lower troposphere and boundary layer, while the new HDO/H2O estimates can now profile the HDO/H2O ratio between 925 hPa and 450 hPa in the tropics and during summertime at high latitudes. The new retrievals are now sensitive to methane in the free troposphere between 800 and 150 mb with peak sensitivity near 500 hPa; whereas in previous versions the sensitivity peaked at 200 hPa. However, the upper troposphere methane concentrations are biased high relative to the lower troposphere by approximately 4% on average. This bias is likely related to temperature, calibration, and/or methane spectroscopy errors. This bias can be mitigated by normalizing the CH4 estimate by the ratio of the N2O estimate relative to the N2O prior, under the assumption that the same systematic error affects both the N2O and CH4 estimates. We demonstrate that applying this ratio theoretically reduces the CH4 estimate for non-retrieved parameters that jointly affect both the N2O and CH4 estimates. The relative upper troposphere to lower troposphere bias is approximately 2.8% after this bias

  18. Regular in situ measurements of HDO/H216O in the northern and southern hemispherical upper troposphere reveal tropospheric transport processes.

    Science.gov (United States)

    Christner, Emanuel; Dyroff, Christoph; Sanati, Shahrokh; Brenninkmeijer, Carl; Zahn, Andreas

    2013-04-01

    Atmospheric water in form of water vapor and clouds is an enormously crucial trace species. It is responsible for ~70 % of the natural greenhouse effect (Schmidt et al., JGR, 2010), carries huge amounts of latent heat, and is the major source of OH in the troposphere. The isotopic composition of water vapor is an elegant tracer for a better understanding and quantification of the extremely complex and variable hydrological cycle in Earth's atmosphere (evaporation, cloud condensation, rainout, re-evaporation, snow), which in turn is a prerequisite to improve climate modeling and predictions. In this context, water-isotopologues (here the isotope ratio HDO/H216O) can be used to study the atmospheric transport of water and in-cloud processes. As H216O and HDO differ in vapor pressure and molecular diffusion, fractionation occurs during condensation and rainout events. For that reason the ratio HDO/H216O preserves information about the transport and condensation history of an air mass. The tunable diode-laser absorption spectrometer ISOWAT was developed for airborne measurements of the water-isotopologue concentrations of H216O and HDO, probing fundamental rovibrational water-absorption lines at around 2.66 μm. Since April 2010 the spectrometer is regularly operated aboard the CARIBIC passenger aircraft (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container - Lufthansa, Airbus 340-600), which measures ~100 trace gases and aerosol components in the UTLS (9-12 km altitude) on four long-distance flights per month. During several flights across the equator (Africa) or close to the equator (Venezuela and Malaysia) an increase of HDO/H216O from the subtropics towards the tropics was measured (by more than 100 permil) at an altitude of ~12 km. This isotopic gradient can partly be attributed to differences in humidity. In addition there is a humidity independent latitudinal gradient (by more than 50 permil), revealing the strong

  19. Physical Properties and Seasonal Behavior of H2O, HDO, CO2 and Trace Gases on Mars: Quantitative Mapping from Earth-Based Observatories

    Science.gov (United States)

    Novak, Robert E.; Mumma, Michael J.

    2011-01-01

    Since 1997, we have used high-resolution (R greater than 40000) spectrometers on ground based-telescopes to study molecules that have astrobiological significance in Mars' atmosphere. We have used the NASA-IRTF, Keck II, and VLT telescopes in the 1.0-5.0 micron range. The spectrometer is set at a wavelength to detect specific molecules. Spectral/spatial images are produced. Extracts from these images provide column densities centered at latitude/longitude locations (resolution 400km at sub-Earth point). We have mapped the O2 singlet-Delta emission (a proxy for ozone), HDO, and H2O for seasonal dates throughout the Martian year. Previously undiscovered isotopic bands of CO2 have been identified along with isotopic forms of CO. We are searching for other molecules that have astrobiological importance and have successfully measured methane in Mars' atmosphere.

  20. A full-mission data set of H2O and HDO columns from SCIAMACHY 2.3 µm reflectance measurements

    Directory of Open Access Journals (Sweden)

    A. Schneider

    2018-06-01

    Full Text Available A new data set of vertical column densities of the water vapour isotopologues H2O and HDO from the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY instrument for the whole of the mission period from January 2003 to April 2012 is presented. The data are retrieved from reflectance measurements in the spectral range 2339 to 2383 nm with the Shortwave Infrared CO Retrieval (SICOR algorithm, ignoring atmospheric light scattering in the measurement simulation. The retrievals are validated with ground-based Fourier transform infrared measurements obtained within the Multi-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA project. A good agreement for low-altitude stations is found with an average bias of −3.6×1021 for H2O and −1.0×1018 molec cm−2 for HDO. The a posteriori computed δD shows an average bias of −8 ‰, even though polar stations have a larger negative bias. The latter is due to the large amount of sensor noise in SCIAMACHY in combination with low albedo and high solar zenith angles. To demonstrate the benefit of accounting for light scattering in the retrieval, the quality of the data product fitting effective cloud parameters simultaneously with trace gas columns is evaluated in a dedicated case study for measurements round high-altitude stations. Due to a large altitude difference between the satellite ground pixel and the mountain station, clear-sky scenes yield a large bias, resulting in a δD bias of 125 ‰. When selecting scenes with optically thick clouds within 1000 m above or below the station altitude, the bias in a posteriori δD is reduced from 125 to 44 ‰. The insights from the present study will also benefit the analysis of the data from the new Sentinel-5 Precursor mission.

  1. Analysis of the Rotational Spectrum of HDO in its v_2 = 0 and 1 Vibrational States up to 2.8 THz

    Science.gov (United States)

    Müller, Holger S. P.; Brünken, S.; Endres, C. P.; Lewen, F.; Pearson, J. C.; Yu, S.; Drouin, B. J.; Mäder, H.

    2011-06-01

    The rotational and rovibrational spectra of H_2O and its isotopologs, including HDO, are of great importance for atmospheric chemistry, astrophysics, and basic sciences. We recorded rotational spectra of HDO in the ground and first excited bending state from the microwave region up to 2.8 THz. Several spectrometers were employed in Kiel, Köln, and Pasadena. An up-to-date combined analysis with rovibrational data was presented, footnote{S. Brünken, PhD thesis, Universität zu Köln, July 2005, Cuvillier Verlag, Göttingen} in which a Hamiltonian based on Euler functions was used to overcome convergence difficulties of the conventional Watson Hamiltonian. The model had been employed previously, e. g., in a related analysis of D_2O spectra with v_2 ≤ 1. Recently, many more data have been obtained in Köln as well as in Pasadena. Including multiple measurements, these add up to about 230 and 100 new transition frequencies in v_2 = 0 and 1, respectively, reaching J = 17/13 and K_a = 9/5. In addition, a critically evaluated compilation of IR data was published very recently. Difficulties in reproducing the data within experimental uncertainties prompted a reanalysis of the data starting at small quantum numbers and extending the data set in small portions. At lower quantum numbers, difficulties were due to, e. g., few typographical errors and misassignments. At higher quantum numbers, interactions between v_2 = 0 and 1 as well as between these and higher states (e. g. v_2 = 2/v_1 = 1, which interact through Fermi resonance) are more important. The limitation of the present analysis to the lowest two vibrational states affords some transitions to be excluded from the analysis and causes a truncation of the data set at some values of J and K_a. S. Brünken, PhD thesis, Universität zu Köln, July 2005, Cuvillier Verlag, Göttingen H. M. Pickett, J. C. Pearson, C. P. Miller, J. Mol. Spectrosc. 233 (2005) 174. J. Tennyson et al., J. Quant. Spectrosc. Radiat. Transfer 111

  2. Measurements of CO2, CH4, H2O, and HDO over a 2-km Outdoor Path with Dual-Comb Spectroscopy

    Science.gov (United States)

    Rieker, G. B.; Giorgetta, F. R.; Coddington, I.; Swann, W. C.; Sinclair, L. C.; Cromer, C.; Baumann, E.; Newbury, N. R.; Kofler, J.; Petron, G.; Sweeney, C.; Tans, P. P.

    2013-12-01

    We demonstrate simultaneous sensing of CO2, CH4, H2O, and HDO over a 2-km outdoor open air path using dual-frequency-comb absorption spectroscopy (DCS). Our implementation of the DCS technique simultaneously offers broad spectral coverage (>8 THz, 267 cm-1) and fine spectral point spacing (100 MHz, 0.0033 cm-1) with a coherent eye-safe beam. The spectrometer, which is adapted from [Zolot et al., 2012], consists of two mutually coherent Erbium-doped fiber frequency-comb lasers which create a broad spectrum of perfectly spaced narrow linewidth frequency elements (';comb teeth') near 1.6 μm. The comb light is transmitted by a telescope and active steering mirrors from the roof of the NIST Boulder laboratory to a 50-cm flat mirror located 1 km away. The return light is received by a second telescope and carried via multimode fiber to a detector. The greenhouse gas absorption attenuates the teeth from the two combs that are coincident with the relevant molecular resonant frequencies. We purposefully offset the frequencies between the two frequency combs in a Vernier-like fashion so that each pair of comb teeth from the two combs results in a unique rf heterodyne beat frequency on the photodiode. The spectral spacing between subsequent comb teeth pairs is 100 MHz, far lower than the ~4 GHz linewidths of small molecule absorption features in the atmosphere. Because of the narrow comb linewidth, there is an essentially negligible instrument lineshape. The measured absorption spectrum can thus resolve neighboring absorption features of different species, and can be compared directly with HITRAN and recent greenhouse gas absorption models developed for satellite- and ground-based carbon observatories to determine the path-integrated concentrations of the absorbing species. Measurements covering the complete 30013←00001 absorption band of CO2 and absorption features of CH4, H2O and HDO between 1.6-1.67 μm were performed under a variety of atmospheric conditions. During

  3. Effect of temperature on the valency bands of HDO in water in the liquid and solid states. Effects on the analysis of heavy water using infra-red absorption; Effet de temperature sur les bandes de valence de HDO dans l'eau a l'etat liquide et a l'etat solide - consequences pour l'analyse de l'eau lourde par absorption infra-rouge

    Energy Technology Data Exchange (ETDEWEB)

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

    1964-07-01

    After, a description of the technique used, a qualitative examination is made of the influence of the temperature on the {nu}{sub OH}(3,400 cm{sup -1}) and {nu}{sub OD} (2,500 cm{sup -1}) valence bands of HDO in the liquid state and then during the passage to the solid state. Quantitative examination with two cells of different thickness makes it possible to define the influence of temperature on the residual absorption of the pure liquid (D{sub 2}O or H{sub 2}O and on the valency bands ({nu}{sub OH} and {nu}{sub OD} respectively). It is found that a similar change occurs in the two bands but that the changes in the background are very different. During the passage from the liquid to the solid state the shape of the bands varies considerably but little change occurs in the total intensity. It has been possible to express these results in a simple form which is directly applicable to analytical problems. (authors) [French] Apres un rappel de la technique utilisee, on examine qualitativement l'influence de la temperature sur les bandes de valence {nu}{sub OH} (3400 cm{sup -1}) et {nu}{sub OD} (2500 cm{sup -1}) de HDO a l'etat liquide puis le passage a l'etat solide. L'examen quantitatif, avec deux cuves d'epaisseurs differentes, permet de preciser l'influence de la temperature sur l'absorption residuelle du liquide pur (D{sub 2}O ou H{sub 2}O) et sur les bandes de valence ( {nu}{sub OH} et {nu}{sub OD} respectivement). On constate une evolution parallele de ces bandes mais un comportement tres different du fond continu. Lors du passage de l'etat liquide a l'etat solide, la forme des bandes varie considerablement mais non l'intensite totale. On a pu formuler ces resultats sous une forme simple applicable directement aux problemes analytiques. (auteurs)

  4. Understanding the Performance and Stability of Supported Ni-Co-Based Catalysts in Phenol HDO

    Directory of Open Access Journals (Sweden)

    Thuan M. Huynh

    2016-11-01

    Full Text Available Performances of bimetallic catalysts (Ni-Co supported on different acidic carriers (HZSM-5, HBeta, HY, ZrO2 and corresponding monometallic Ni catalysts in aqueous phase hydrodeoxygenation of phenol were compared in batch and continuous flow modes. The results revealed that the support acidity plays an important role in deoxygenation as it mainly controls the oxygen-removing steps in the reaction network. At the same time, sufficient hydrothermal stability of a solid catalyst is essential. Batch experiments revealed 10Ni10Co/HZSM-5 to be the best-performing catalyst in terms of conversion and cyclohexane yield. Complementary continuous runs provided more insights into the relationship between catalyst structure, efficiency and stability. After 24 h on-stream, the catalyst still reveals 100% conversion and a slight loss (from 100% to 90% in liquid hydrocarbon selectivity. The observed alloy of Co with Ni increased dispersion and stability of Ni-active sites, and combination with HZSM-5 resulted in a well-balanced ratio of metal and acid sites which promoted all necessary steps in preferred pathways. This was proved by studies of fresh and spent catalysts using various characterization techniques (N2 physisorption, X-ray diffraction (XRD, X-ray photoelectron spectroscopy (XPS, transmission electron microscopy (TEM and infrared spectroscopy of adsorbed pyridine (pyr-IR.

  5. Isotopic equilibrium constants of the deuterium exchange between HDO and H2S, H2Se and H2Te

    International Nuclear Information System (INIS)

    Marx, D.

    1959-11-01

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH 2 + OHD ↔ SHD + OH 2 ; SeH 2 + OHD ↔ SeHD + OH 2 ; TeH 2 + OHD ↔ TeHD + OH 2 . In gaseous phase, statistical thermodynamics leads to the expression: K (Z OHD x Z RH 2 )/(Z OH 2 x Z RHD ) x e W/T (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [fr

  6. Psychometric Assessment and Refinement of the Family Issues Scale of the Human Dimensions of Operations (HDO) Project

    National Research Council Canada - National Science Library

    Thompson, Megan

    2001-01-01

    The present report summarizes psychometric analyses and recommendations for item refinement of the Family Issues scale a measure included a predeployment survey of operational stress among Canadian Forces personnel...

  7. Airborne in situ vertical profiling of HDO / H216O in the subtropical troposphere during the MUSICA remote sensing validation campaign

    Science.gov (United States)

    Dyroff, C.; Sanati, S.; Christner, E.; Zahn, A.; Balzer, M.; Bouquet, H.; McManus, J. B.; Gonzalez-Ramos, Y.; Schneider, M.

    2015-05-01

    Vertical profiles of water vapor (H2O) and its isotope ratio D / H expressed as δD(H2O) were measured in situ by the ISOWAT II diode-laser spectrometer during the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA) airborne campaign. We present recent modifications of the instrument design. The instrument calibration on the ground as well as in flight is described. Based on the calibration measurements, the humidity-dependent uncertainty of our airborne data is determined. For the majority of the airborne data we achieved an accuracy (uncertainty of the mean) of Δ(δD) ≈10‰. Vertical profiles between 150 and ~7000 m were obtained during 7 days in July and August 2013 over the subtropical North Atlantic Ocean near Tenerife. The flights were coordinated with ground-based (Network for the Detection of Atmospheric Composition Change, NDACC) and space-based (Infrared Atmospheric Sounding Interferometer, IASI) FTIR remote sensing measurements of δD(H2O) as a means to validate the remote sensing humidity and δD(H2O) data products. The results of the validation are presented in detail in a separate paper (Schneider et al., 2014). The profiles were obtained with a high vertical resolution of around 3 m. By analyzing humidity and δD(H2O) correlations we were able to identify different layers of air masses with specific isotopic signatures. The results are discussed.

  8. Field Evaluation of All-Season Tactical Engine Oil OE/HDO-15/40 at Ft. Knox, Kentucky and Ft. Bliss, Texas

    Science.gov (United States)

    1986-07-01

    AND 13 oF PION ) I-. 0.50s0 £38T OIL ASILnSS LA•OlATO•T DATA BIL-L-21040 or/mOo ISO -60 Glass OIL fIiE IALIDATION PlOGI&l JAIOa•I-DIClI• E 1963 AND Jaiat...IGIl3 41013 , 3614. 6617, VII) TCODE*IBC25O 12S1 II0CIDIUI WAMIAiLI: 71 te0m Teal I stag SIO 0EW STD Isl33 mBIIUI AZINDOI VAIIAICES 1 Or Flog > I? 1980

  9. Catalytic hydroprocessing of coal-derived gasification residues to fuel blending stocks: effect of reaction variables and catalyst on hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), and hydrodesulfurization (HDS)

    Energy Technology Data Exchange (ETDEWEB)

    Dieter Leckel [Sasol Technology Research and Development, Sasolburg (South Africa). Fischer-Tropsch Refinery Catalysis

    2006-10-15

    Gas liquors, tar oils, and tar products resulting from the coal gasification of a high-temperature Fischer-Tropsch plant can be successfully refined to fuel blending components by the use of severe hydroprocessing conditions. High operating temperatures and pressures combined with low space velocities ensure the deep hydrogenation of refractory oxygen, sulfur, and nitrogen compounds. Hydrodeoxygenation, particularly the removal of phenolic components, hydrodesulfurization, and hydrodenitrogenation were obtained at greater than 99% levels using the NiMo and NiW on {gamma}-Al{sub 2}O{sub 3} catalysts. Maximum deoxygenation activity was achieved using the NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst having a maximum pore size distribution in the range of 110-220{angstrom}. The NiMo/{gamma}-Al{sub 2}O{sub 3} catalyst, which also has a relatively high proportion of smaller pore sizes (35-60 {angstrom}), displays lower hydrogenation activity. 30 refs., 1 fig. 8 tabs.

  10. Injection of deuterated water into the pulmonary/alveolar circulation; measurement of HDO in exhaled breath and implications to breath analysis

    Czech Academy of Sciences Publication Activity Database

    Tan, B. K.; Davies, S. J.; Španěl, Patrik; Smith, D.

    2012-01-01

    Roč. 6, č. 3 (2012), 036005 ISSN 1752-7155 Institutional support: RVO:61388955 Keywords : total body water * afterglow mass spectrometry * deuterium abundance Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.571, year: 2012

  11. THE HYPERFINE STRUCTURE OF THE ROTATIONAL SPECTRUM OF HDO AND ITS EXTENSION TO THE THz REGION: ACCURATE REST FREQUENCIES AND SPECTROSCOPIC PARAMETERS FOR ASTROPHYSICAL OBSERVATIONS

    Energy Technology Data Exchange (ETDEWEB)

    Cazzoli, Gabriele; Lattanzi, Valerio; Puzzarini, Cristina [Dipartimento di Chimica “Giacomo Ciamician”, Università di Bologna, Via Selmi 2, I-40126 Bologna (Italy); Alonso, José Luis [Grupo de Espectroscopía Molecular (GEM), Unidad Asociada CSIC, Edificio Quifima, Laboratorios de Espectroscopia y Bioespectroscopia, Parque Científico UVa, Universidad de Valladolid, E-47005 Valladolid (Spain); Gauss, Jürgen, E-mail: cristina.puzzarini@unibo.it [Institut für Physikalische Chemie, Universität Mainz, D-55099 Mainz (Germany)

    2015-06-10

    The rotational spectrum of the mono-deuterated isotopologue of water, HD{sup 16}O, has been investigated in the millimeter- and submillimeter-wave frequency regions, up to 1.6 THz. The Lamb-dip technique has been exploited to obtain sub-Doppler resolution and to resolve the hyperfine (hf) structure due to the deuterium and hydrogen nuclei, thus enabling the accurate determination of the corresponding hf parameters. Their experimental determination has been supported by high-level quantum-chemical calculations. The Lamb-dip measurements have been supplemented by Doppler-limited measurements (weak high-J and high-frequency transitions) in order to extend the predictive capability of the available spectroscopic constants. The possibility of resolving hf splittings in astronomical spectra has been discussed.

  12. Thermochemical and mechanistic aspects of removal of sulphur, nitrogen and oxygen from petroleum

    Energy Technology Data Exchange (ETDEWEB)

    Furimsky, E.

    1983-11-01

    The order of relative rates of hydrodesulphurization (HDS), hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO) depends on hydrogen pressure and may be estimated on the basis of chemical bond strengths. At near atmospheric pressure the rate of HDS is highest, followed by HDO and HDN. Under high pressures, the rate of HDS is again the highest followed by HDN and HDO.

  13. Upgrading Fast Pyrolysis Oil via Hydrodeoxygenation and Thermal Treatment: Effects of Catalytic Glycerol Pretreatment

    NARCIS (Netherlands)

    Reyhanitash, Ehsan; Tymchyshyn, M.; Yuan, Zhongshun; Albion, K.; van Rossum, G.; Xu, C.

    2014-01-01

    The effects of stabilizing fast pyrolysis oil (PO) with glycerol via catalytic glycerol pretreatment on upgrading via hydrodeoxygenation (HDO) or thermal treatment (TT) were studied. Nonstabilized (original) fast pyrolysis oil was also upgraded via HDO or TT to obtain benchmarks. Generally, HDO

  14. Review of the National Reduction Plan for NMVOM [Non-Methane Volatile Organic Materials]. Sectors industry, energy, TSG [trade, services and government] and building; Terugblik op het Nationaal Reductieplan NMVOS [Niet-Methaan Vluchtige Organische Stoffen]. Industrie, energie, HDO [handel, diensten en overheid] en bouw

    Energy Technology Data Exchange (ETDEWEB)

    Locht, G.

    2012-09-15

    The title project aims to reduce emissions of Volatile Organic Compounds (VOC) from several sectors in the period 2000-2010. This report is a review of the project and is based on the definitive data over these years in the Dutch Pollutant Release and Transfer Register (PRTR). Compared to the start of the NRP-NMVOS, there are now less instruments for environmental policy. There are more general binding environmental rules and less environmental permits. Furthermore, several agreements between governments and branches have ended. May 2012 the Gothenburg protocol was revised. It shows a VOC emission reduction for the Netherlands of 8% in 2020 compared to 2005. It is expected this will be achieved by means of the current policy and legislation [Dutch] Het titel project is opgesteld om de VOS-emissies van deze sectoren tereduceren. Het NRP-NMVOS heeft betrekking op de jaren 2000 tot en met 2010. Dit rapport is een terugblik op het project en gaat uit van de medio 2012 beschikbare definitieve emissiegegevens over al deze jaren. In vergelijking met de start van het NRP-NMVOS zijn er minder milieubeleidsinstrumenten. Er zijn meer algemene milieuregels en minder vergunningen en diverse convenanten tussen overheden en bedrijfsleven zijn afgelopen. In het herziene Gothenburg protocol van mei 2012 is voor Nederland voor 2020 en verder een NMVOS reductie van 8% ten opzichte van het 2005 niveau afgesproken. Het ligt in de verwachting dat dit gehaald gaat worden bij voortzetting van het huidige beleid en instrumentatie.

  15. Isotopic equilibrium constants of the deuterium exchange between HDO and H{sub 2}S, H{sub 2}Se and H{sub 2}Te; Etude des constantes des equilibres isotopiques du deuterium entre l'eau et les hydrures des metalloides de la deuxieme famille

    Energy Technology Data Exchange (ETDEWEB)

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

    1959-11-15

    We have determined experimentally the equilibrium constant K of each of the following isotope exchanges: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. In gaseous phase, statistical thermodynamics leads to the expression: K (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R being the elements S, Se or Te). Z, the partition functions, have been calculated and, through our experimental results, the constant W has been determined. Having obtained W, the equilibrium constant K has been calculated for a series of temperatures. (author) [French] Nous avons determine experimentalement la constante K de chacun des equilibres isotopiques suivants: SH{sub 2} + OHD {r_reversible} SHD + OH{sub 2}; SeH{sub 2} + OHD {r_reversible} SeHD + OH{sub 2}; TeH{sub 2} + OHD {r_reversible} TeHD + OH{sub 2}. En phase gazeuse, la thermodynamique donne l'expression: K = (Z{sub OHD} x Z{sub RH{sub 2}})/(Z{sub OH{sub 2}} x Z{sub RHD}) x e{sup W/T} (R representant un atome de soufre, selenium ou tellure). Les fonctions de partition Z de chacune des molecules ont ete calculees et, grace a nos resultats experimentaux, nous avons determine la constante W. Connaissant W, la constante d'equilibre K a pu etre tabulee en fonction de la temperature. (auteur)

  16. Production of advanced biofuels: co-processing of upgraded pyrolysis oil in standard refinery units

    NARCIS (Netherlands)

    De Miguel Mercader, F.; de Miguel Mercader, F.; Groeneveld, M.J.; Hogendoorn, Kees; Kersten, Sascha R.A.; Way, N.W.J.; Schaverien, C.J.

    2010-01-01

    One of the possible process options for the production of advanced biofuels is the co-processing of upgraded pyrolysis oil in standard refineries. The applicability of hydrodeoxygenation (HDO) was studied as a pyrolysis oil upgrading step to allow FCC co-processing. Different HDO reaction end

  17. Deuterium in atmospheric cycle

    International Nuclear Information System (INIS)

    Pontikis, M.C.

    Interest of the study concerning the deuterium content variation (HDO) in the atmospheric water. Standards and measurement methods. Molecule HDO cycle in the atmospheric water. Application to the study of hail-generating cumulus-nimbus and of the mantle of snow [fr

  18. Using polyfurfuryl alcohol to improve the hydrothermal stability of mesoporous oxides for reactions in the aqueous phase

    Science.gov (United States)

    Hydrodeoxygenation (HDO) of bio-oils derived from the pyrolysis of woody biomass is required to improve the stability and heating value of the liquid hydrocarbon products. Since pyrolysis produces bio-oils having up to 30 vol% water, HDO catalysts must not only be active and selective, but also sta...

  19. Competition Between Hydrotreating and Polymerization Reactions During Pyrolysis Oil Hydrodeoxygenation

    NARCIS (Netherlands)

    Mercader, F. De Miguel; Koehorst, P. J. J.; Heeres, H. J.; Kersten, S. R. A.; Hogendoorn, J. A.

    2011-01-01

    Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory-scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to

  20. A review of catalytic hydrodeoxygenation of lignin-derived phenols from biomass pyrolysis.

    Science.gov (United States)

    Bu, Quan; Lei, Hanwu; Zacher, Alan H; Wang, Lu; Ren, Shoujie; Liang, Jing; Wei, Yi; Liu, Yupeng; Tang, Juming; Zhang, Qin; Ruan, Roger

    2012-11-01

    Catalytic hydrodeoxygenation (HDO) of lignin-derived phenols which are the lowest reactive chemical compounds in biomass pyrolysis oils has been reviewed. The hydrodeoxygenation (HDO) catalysts have been discussed including traditional HDO catalysts such as CoMo/Al(2)O(3) and NiMo/Al(2)O(3) catalysts and transition metal catalysts (noble metals). The mechanism of HDO of lignin-derived phenols was analyzed on the basis of different model compounds. The kinetics of HDO of different lignin-derived model compounds has been investigated. The diversity of bio-oils leads to the complexities of HDO kinetics. The techno-economic analysis indicates that a series of major technical and economical efforts still have to be investigated in details before scaling up the HDO of lignin-derived phenols in existed refinery infrastructure. Examples of future investigation of HDO include significant challenges of improving catalysts and optimum operation conditions, further understanding of kinetics of complex bio-oils, and the availability of sustainable and cost-effective hydrogen source. Copyright © 2012 Elsevier Ltd. All rights reserved.

  1. Hydrodeoxygenation by deuterium gas--a powerful way to provide insight into the reaction mechanisms.

    Science.gov (United States)

    Ben, Haoxi; Ferguson, Glen A; Mu, Wei; Pu, Yunqiao; Huang, Fang; Jarvis, Mark; Biddy, Mary; Deng, Yulin; Ragauskas, Arthur J

    2013-11-28

    This study demonstrates the use of isotopic labelling and NMR to study the HDO process. As far as we know, this is the first reported effort to trace the incorporation of hydrogen in the HDO process of lignin pyrolysis oil thereby providing key fundamental insight into its reaction mechanism.

  2. Hydrodeoxygenation of pyrolysis oil fractions: process understanding and quality assessment through co-processing in refinery units

    NARCIS (Netherlands)

    De Miguel Mercader, F.; de Miguel Mercader, Ferran; Groeneveld, M.J.; Kersten, Sascha R.A.; Geantet, Christophe; Toussaint, Guy; Way, Nico W.J.; Schaverien, Colin J.; Hogendoorn, Kees

    2011-01-01

    Hydrodeoxygenation (HDO) of pyrolysis oil fractions was studied to better understand the HDO of whole pyrolysis oil and to assess the possibility to use individual upgrading routes for these fractions. By mixing pyrolysis oil and water in a 2:1 weight ratio, two fractions were obtained: an oil

  3. H2CAP - Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Stummann, Magnus Zingler; Høj, Martin; Gabrielsen, Jostein

    -oil by catalytic hydrodeoxygenation (HDO) is challenged by severe polymerization and coking upon heating the oil. Alternatively, performing fast pyrolysis in high-pressure hydrogen atmosphere in a fluid bed reactor with a HDO catalyst as bed medium could immediately stabilize reactive pyrolysis vapors [2...

  4. IR analyzer spots heavy water leaks

    International Nuclear Information System (INIS)

    Anon.

    1978-01-01

    A correlation spectrometer developed by Barringer Research Ltd. (in collaboration with Atomic Energy of Canada and Ontario Hydro) is used to measure HDO concentrations in DTO in the final (distillation) stage of heavy-water production. A unit has been installed at Bruce Heavy Water Plant. Previously, such spectrometers had been installed to detect heavy-water leaks in CANDU reactors. The principle on which the instrument works is explained, with illustrations. It works by comparing the absorption at 2.9 μm, due to HDO, with that at 2.6 μm, due to both HDO and D 2 O. (N.D.H.)

  5. Microbial degradation of a metal organic biocide in soils; Mikrobieller Abbau eines im Holzschutz verwendeten metallorganischen Biozids im Boden

    Energy Technology Data Exchange (ETDEWEB)

    Jakobs, Desiree

    2010-06-17

    The soil microbial community is able to degrade wood and variety of chemical wood-preservatives (WP) to generate energy by producing CO{sub 2} and as nutrition source to establish biomass. This work is focused on the characterisation of the microbial degradation of metal-organic WP including Copper-HDO (Cu-HDO) as biocide via {sup 13}C tracer experiments. Investigations with sterilized and non-sterilized soul incubated with Cu-HDO demonstrated that degradation of Cu-HDO was accelerated by the presence of the soil microbial community. Leaching of treated wood into the surrounding soil is characterized by low Cu-HDO concentrations (5 {mu}g - 20 {mu}g). Measurements of such biocide-concentrations by HPLC over time showed that Cu-HDO was degraded within a few days of soil incubation. Cu-HDO solely was degraded faster in soil compared to Cu-HDO as part of a WP. Presence of Cu-HDO significantly decreased the overall soil respiration compared to samples without Cu-HDO. Detailed information of the microbial metabolic pathways was achieved by comparison of {sup 12}C and {sup 13}C enriched Cu-HDO experiments and thereafter SIP-PLFA analysis. Monitoring of the {delta}{sup 13}C in PLFAs revealed that the carbon derived from the biocide was integrated nearly exclusively into the abundant PLFAs affiliated to gram negative bacteria. PLFAs indicative for fungi and other eukaryotic organism could be found only in low relative abundances and without {delta}{sup 13}C enrichment. This result suggests that eukaryotes were not involved in utilization of Copper-HADO based carbon. To characterise the impact of the co-biocide HDO on the microbial community the composition of the microbial community present at the surface of Copper-HDO, Copper-Amine treated specimens as well as of untreated specimens in soil contact was investigated. The bacterial community structure was characterized by the T-RFLP fingerprinting technique whereas the eukaryotic community structure was analyzed by the SSCP

  6. Directing Reaction Pathways through Controlled Reactant Binding at Pd-TiO2 Interfaces.

    Science.gov (United States)

    Zhang, Jing; Wang, Bingwen; Nikolla, Eranda; Medlin, J Will

    2017-06-01

    Recent efforts to design selective catalysts for multi-step reactions, such as hydrodeoxygenation (HDO), have emphasized the preparation of active sites at the interface between two materials having different properties. However, achieving precise control over interfacial properties, and thus reaction selectivity, has remained a challenge. Here, we encapsulated Pd nanoparticles (NPs) with TiO 2 films of regulated porosity to gain a new level of control over catalyst performance, resulting in essentially 100 % HDO selectivity for two biomass-derived alcohols. This catalyst also showed exceptional reaction specificity in HDO of furfural and m-cresol. In addition to improving HDO activity by maximizing the interfacial contact between the metal and metal oxide sites, encapsulation by the nanoporous oxide film provided a significant selectivity boost by restricting the accessible conformations of aromatics on the surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Hydrodeoxygenation of aliphatic and aromatic oxygenates on sulphided catalysts for production of second generation biofuels

    Energy Technology Data Exchange (ETDEWEB)

    Senol, O.I.

    2007-07-01

    Environmental concerns and diminishing petroleum reserves have increased the importance of biofuels for traffic fuel applications. Second generation biofuels produced from wood, vegetable oils and animal fats have been considered promising for delivering biofuels in large amount with low production cost. The abundance of oxygen in the form of various aliphatic and aromatic oxygenates decreases the quality of biofuels, however, and therefore the oxygen content of biofuels must be reduced. Upgrading of biofuels can be achieved by hydrodeoxygenation (HDO), which is similar to hydrodesulphurisation in oil refining. In HDO, oxygen-containing compounds are converted to hydrocarbons by eliminating oxygen in the form of water in the presence of hydrogen and a sulphided catalyst. Due to the low sulphur content of biofuels, a sulphiding agent is typically added to the HDO feed to maintain activity and stability of the catalyst. The aim of this work was to investigate HDO using aliphatic and aromatic oxygenates as model compounds on sulphided NiMo/gamma-Al{sub 2}O3 and CoMo/gamma-Al{sub 2}O3 catalysts. The effects of side product, water, and of sulphiding agents, H{sub 2}S and CS{sub 2}, on HDO were determined. The primary focus was on the HDO of aliphatic oxygenates, because a reasonable amount of data regarding the HDO of aromatic oxygenates already exists. The HDO of aliphatic esters produced hydrocarbons from intermediate alcohol, carboxylic acid, aldehyde and ether compounds. A few sulphur-containing compounds were also detected in trace amounts, and their formation caused desulphurisation of the catalysts. Hydrogenation reactions and acid-catalysed reactions (dehydration, hydrolysis, esterification, E{sub 2} elimination and SN{sub 2} nucleophilic substitution) played a major role in the HDO of aliphatic oxygenates. The NiMo catalyst showed a higher activity for HDO and hydrogenation reactions than the CoMo catalyst, but both catalysts became deactivated because of

  8. Hydrodeoxygenation of Pyrolysis Bio-Oil Over Ni Impregnated Mesoporous Materials.

    Science.gov (United States)

    Lee, In-Gu; Lee, Heejin; Kang, Bo Sung; Kim, Young-Min; Kim, Sang Chai; Jung, Sang-Chul; Ko, Chang Hyun; Park, Young-Kwon

    2018-02-01

    The catalytic hydrodeoxygenation (HDO) of bio-oil over Ni-supported mesoporous materials was performed using a high pressure autoclave reactor. The actual pyrolysis oil of cork oak wood was used as a sample, and Ni/Al-SBA-15 and Ni/Al-MSU-F were used as catalysts. In addition, supercritical ethanol was added as solvent. Both Ni-supported mesoporous catalysts showed efficient HDO reaction ability. A higher heating value and pH of bio-oil were achieved by the HDO reaction over both catalysts and upgraded bio-oil had a lower viscosity. Compared to Ni/Al-MSU-F, Ni/Al- SBA-15 produced more upgraded bio-oil with a lower oxygen content and higher heating value via a catalytic HDO process.

  9. Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach

    NARCIS (Netherlands)

    de Wild, P. J.; Huijgen, W.J.J.; Kloekhorst, A.; Chowdari, R. K.; Heeres, H. J.

    Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting

  10. Hydrodeoxygenation processes: advances on catalytic transformations of biomass-derived platform chemicals into hydrocarbon fuels.

    Science.gov (United States)

    De, Sudipta; Saha, Basudeb; Luque, Rafael

    2015-02-01

    Lignocellulosic biomass provides an attractive source of renewable carbon that can be sustainably converted into chemicals and fuels. Hydrodeoxygenation (HDO) processes have recently received considerable attention to upgrade biomass-derived feedstocks into liquid transportation fuels. The selection and design of HDO catalysts plays an important role to determine the success of the process. This review has been aimed to emphasize recent developments on HDO catalysts in effective transformations of biomass-derived platform molecules into hydrocarbon fuels with reduced oxygen content and improved H/C ratios. Liquid hydrocarbon fuels can be obtained by combining oxygen removal processes (e.g. dehydration, hydrogenation, hydrogenolysis, decarbonylation etc.) as well as by increasing the molecular weight via C-C coupling reactions (e.g. aldol condensation, ketonization, oligomerization, hydroxyalkylation etc.). Fundamentals and mechanistic aspects of the use of HDO catalysts in deoxygenation reactions will also be discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. Effective sextic superpotential and violation in NMSGUT

    Indian Academy of Sciences (India)

    C S Aulakh

    2017-10-05

    Oct 5, 2017 ... Indian Institute of Science Education and Research Mohali, Sector 81, Manauli PO,. Sahibzada ... able higher-dimensional operators (HDO) formed from the fields of ... Thus, an evaluation of the effective operators and their.

  12. Hydrodeoxygenation of mono- and dimeric lignin model compounds on noble metal catalysts

    NARCIS (Netherlands)

    Guvenatam, Burcu; Kursun, Osman; Heeres, Hero; Pidko, Evgeny A.; Hensen, Emiel J. M.

    2014-01-01

    The influence of reaction conditions (temperature, acidity) on the catalytic performance of supported Pt, Pd and Ru catalysts for the aqueous phase hydrodeoxygenation (HDO) of lignin model compounds was systematically investigated. Phenol conversion proceeds via hydrogenation of the aromatic ring

  13. Pyrolysis bio-oil upgrading to renewable fuels.

    Science.gov (United States)

    2014-01-01

    This study aims to upgrade woody biomass pyrolysis bio-oil into transportation fuels by catalytic hydrodeoxygenation : (HDO) using nanospring (NS) supported catalyst via the following research objectives: (1) develop nanospring-based : catalysts (nan...

  14. Use of promoters to enhance hydrodenitrogenation and hydrodeoxygenation catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Hirschon, A.S.; Ackerman, L.L.; Laine, R.M.; Wilson, R.B. Jr. (SRI International, Menlo Park, CA (USA). Inorganic and Organometallic Chemistry Program)

    1989-10-01

    Results demonstrate that addition of an active transalkylation catalyst such as ruthenium to a CoMo catalyst greatly increased the HDN activity and selectivity to aromatic products, using quinoline as a model compound. Although the non-promoted CoMo was a better HDO catalyst, in the presence of both nitrogen and oxygen containing models, the RuCoMo was the superior HDO in terms of both activity and selectivity. 5 refs., 4 tabs.

  15. Hydrodeoxygenation of Biomass Pyrolysis Vapor Model Compounds over MoS2 Based Catalysts: A Step in Understanding and Optimizing Fuel Production from Solid Biomass

    DEFF Research Database (Denmark)

    Dabros, Trine Marie Hartmann

    This thesis is dedicated to the investigation, development, and optimization of catalysts and operating conditions for catalytic hydropyrolysis and pyrolysis vapor hydrodeoxygenation (HDO) with the aim of producing liquid fuel from solid biomass.......This thesis is dedicated to the investigation, development, and optimization of catalysts and operating conditions for catalytic hydropyrolysis and pyrolysis vapor hydrodeoxygenation (HDO) with the aim of producing liquid fuel from solid biomass....

  16. Rapid and Sensitive Quantification of Isotopic Mixtures Using a Rapidly-Swept External Cavity Quantum Cascade Laser

    Directory of Open Access Journals (Sweden)

    Brian E. Brumfield

    2016-05-01

    Full Text Available A rapidly-swept external-cavity quantum cascade laser with an open-path Herriott cell is used to quantify gas-phase chemical mixtures of D2O and HDO at a rate of 40 Hz (25-ms measurement time. The chemical mixtures were generated by evaporating D2O liquid near the open-path Herriott cell, allowing the H/D exchange reaction with ambient H2O to produce HDO. Fluctuations in the ratio of D2O and HDO on timescales of <1 s due to the combined effects of plume transport and the H/D exchange chemical reaction are observed. Noise-equivalent concentrations (1σ (NEC of 147.0 ppbv and 151.6 ppbv in a 25-ms measurement time are determined for D2O and HDO, respectively, with a 127-m optical path. These NECs are improved to 23.0 and 24.0 ppbv with a 1-s averaging time for D2O and HDO, respectively. NECs <200 ppbv are also estimated for N2O, 1,1,1,2–tetrafluoroethane (F134A, CH4, acetone and SO2 for a 25-ms measurement time. The isotopic precision for measurement of the [D2O]/[HDO] concentration ratio of 33‰ and 5‰ is calculated for the current experimental conditions for measurement times of 25 ms and 1 s, respectively.

  17. Tritium ecovery from waste of fuel reprocessing, (1)

    International Nuclear Information System (INIS)

    Tsutsumi, Kenichi; Takeda, Hiroshi; Kohmoto, Harumi; Kon, Tetsuroh; Ayaki, Kazuo.

    1979-01-01

    For the Oldershaw distillation column, the effects of operating pressure, concentration of nitric acid and organic material on the separation of HTO or HDO were investigated, using 0.002 μCi/ml HTO and 1% HDO. In the total reflux and continuous distillation, the following facts were revealed: (1) High separation factor of HTO and HDO systems was obtained in the operating pressure of 100 mm Hg. (2) The overall column efficiency Eo of HDO system in the operating pressure of 760 mm Hg is large, although the effect of operating pressure in the HTO system of extremely low concentration is small. (3) The overall column efficiency Eo of HDO system is larger than that of HTO system. (4) The effect of the concentration of nitric acid and organic material is not significant in both systems. (5) The overall column efficiency E 0 of continuous distillation under the reflux ratios of 10 and 50 in HTO and 0.1 N HNO 3 system is the same as that of total reflux distillation. Thus, the distillation characteristics of HDO and HTO are not always identical. (J.P.N.)

  18. Wood-derived olefins by steam cracking of hydrodeoxygenated tall oils.

    Science.gov (United States)

    Pyl, Steven P; Dijkmans, Thomas; Antonykutty, Jinto M; Reyniers, Marie-Françoise; Harlin, Ali; Van Geem, Kevin M; Marin, Guy B

    2012-12-01

    Tall oil fractions obtained from Norwegian spruce pulping were hydrodeoxygenated (HDO) at pilot scale using a commercial NiMo hydrotreating catalyst. Comprehensive two dimensional gas chromatography (GC×GC) showed that HDO of both tall oil fatty acids (TOFA) and distilled tall oil (DTO) produced highly paraffinic hydrocarbon liquids. The hydrotreated fractions also contained fatty acid methyl esters and norabietane and norabietatriene isomers. Steam cracking of HDO-TOFA in a pilot plant revealed that high light olefin yields can be obtained, with 35.4 wt.% of ethene and 18.2 wt.% of propene at a coil outlet pressure (COP) of 1.7 bara, a dilution of 0.45 kg(steam)/kg(HDO-TOFA) and a coil outlet temperature (COT) of 820 °C. A pilot plant coking experiment indicated that cracking of HDO-TOFA at a COT of 850 °C results in limited fouling in the reactor. Co-cracking of HDO tall oil fractions with a typical fossil-based naphtha showed improved selectivity to desired light olefins, further demonstrating the potential of large scale olefin production from hydrotreated tall oil fractions in conventional crackers. Copyright © 2012 Elsevier Ltd. All rights reserved.

  19. Absorption spectra between 0.8 {mu} and 30 {mu} of mixtures of H{sub 2}O - D{sub 2}O in the liquid state; Le spectre d'absorption des melanges H{sub 2}O-D{sub 2}O a l'etat liquide entre 0,8 et 30 {mu}

    Energy Technology Data Exchange (ETDEWEB)

    Ceccaldi, M; Goldman, M; Roth, E [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1958-07-01

    There has been very little work carried out recently on the absorption bands of H{sub 2}O, HDO and D{sub 2}O in the liquid state. We have established the spectra of these molecules in between 0.8 and 30 p. The table of absorption bands of the molecules HDO and D{sub 2}O for which all the bands corresponding to those for H{sub 2}O had not been established has been completed. We have sought a convenient method of representing the variations in optical density of certain HDO bands as a function of the concentration of heavy water in the mixtures studied. (author) [French] Il y a peu de travaux recents sur les bandes d'absorption de H{sub 2}O, HDO et D{sub 2}O a l'etat liquide. Nous avons releve les spectres de ces molecules entre 0,8 et 30 p. Le tableau des bandes d'absorption des molecules HDO et D{sub 2}O, pour lesquelles le releve de toutes les bandes correspondantes a celles de H{sub 2}O n'etait pas encore effectue, a ete complete. Nous avons cherche des modes de representation commodes des variations de densite optique de certaines bandes de HDO en fonction de la teneur en eau lourde des melanges etudies. (auteur)

  20. Reaction pathways of furfural, furfuryl alcohol and 2-methylfuran on Cu(111) and NiCu bimetallic surfaces

    Science.gov (United States)

    Xiong, Ke; Wan, Weiming; Chen, Jingguang G.

    2016-10-01

    Hydrodeoxygenation (HDO) is an important reaction for converting biomass-derived furfural to value-added 2-methylfuran, which is a promising fuel additive. In this work, the HDO of furfural to produce 2-methylfuran occurred on the NiCu bimetallic surfaces prepared on either Ni(111) or Cu(111). The reaction pathways of furfural were investigated on Cu(111) and Ni/Cu(111) surfaces using density functional theory (DFT) calculations, temperature-programmed desorption (TPD) and high-resolution electron energy loss spectroscopy (HREELS) experiments. These studies provided mechanistic insights into the effects of bimetallic formation on enhancing the HDO activity. Specifically, furfural weakly adsorbed on Cu(111), while it strongly adsorbed on Ni/Cu(111) through an η2(C,O) configuration, which led to the HDO of furfural on Ni/Cu(111). The ability to dissociate H2 on Ni/Cu(111) is also an important factor for enhancing the HDO activity over Cu(111).

  1. Synergetic Effect of Ni2P/SiO2 and γ-Al2O3 Physical Mixture in Hydrodeoxygenation of Methyl Palmitate

    Directory of Open Access Journals (Sweden)

    Ivan V. Shamanaev

    2017-11-01

    Full Text Available The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2 or acidic (γ-Al2O3 material was studied in methyl palmitate hydrodeoxygenation (HDO. Methyl palmitate HDO was carried out at temperatures of 270–330 °C, H2/feed volume ratio of 600 Nm3/m3, and H2 pressure of 3.0 MPa. Ni2P/SiO2 catalyst, diluted with γ-Al2O3 showed a higher activity than Ni2P/SiO2 catalyst diluted with SiC or SiO2. The conversion of methyl palmitate increased significantly in the presence of γ-Al2O3 most probably due to the acceleration of the acid-catalyzed reaction of ester hydrolysis. The synergism of Ni2P/SiO2 and γ-Al2O3 in methyl palmitate HDO can be explained by the cooperation of the metal sites of Ni2P/SiO2 and the acid sites of γ-Al2O3 in consecutive metal-catalyzed and acid-catalyzed reactions of HDO. The obtained results let us conclude that the balancing of metal and acid sites plays an important role in the development of the efficient catalyst for the HDO of fatty acid esters over supported phosphide catalysts.

  2. Measurement of the deuterium concentration in water samples using a CW chemical deuterium fluoride laser

    International Nuclear Information System (INIS)

    Trautmann, M.

    1979-10-01

    In this study a new method for the determination of the deuterium content in water samples is described. The absorption of the radiation of a CW deuterium fluoride laser by the isotope HDO in the water vapor of the sample is measured by means of an optoacoustic detector (spectrophone). Thereby advantage is taken of the fact that H 2 O hardly absorbs the laser radiation and that D 2 O only exists in negligible concentrations. The isotope ratio of hydrogen can be calculated from the measured relative concentration of HDO. In the course of this investigation the relative absorption cross sections of HDO for the different laser lines were determined. It was thereby established that there exists a very good coincidence of an HDO absorption line with the 2P2 laser line. Using a very sensitive nonresonant spectrophone the relative concentration of HDO in natural water samples could be determined with an accuracy of about 10%. The experiments also demonstrated that with appropriate improvements made to the apparatus and using a second spectrophone as a reference it should be possible to increase this accuracy to 0,1%. (orig.)

  3. Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

    Energy Technology Data Exchange (ETDEWEB)

    Hensley, Alyssa J. R. [The; amp, Linda Voiland School of Chemical Engineering and Bioengineering, ∥Department of Physics; Institute for Integrated Catalysis and §Fundamental and; Wang, Yong [The; amp, Linda Voiland School of Chemical Engineering and Bioengineering, ∥Department of Physics; Institute for Integrated Catalysis and §Fundamental and; Mei, Donghai [The; amp, Linda Voiland School of Chemical Engineering and Bioengineering, ∥Department of Physics; Institute for Integrated Catalysis and §Fundamental and; McEwen, Jean-Sabin [The; amp, Linda Voiland School of Chemical Engineering and Bioengineering, ∥Department of Physics; Institute for Integrated Catalysis and §Fundamental and

    2018-01-30

    A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since water is ubiquitous in such reaction systems. Here, we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotes the direct through space tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.

  4. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts

    DEFF Research Database (Denmark)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard

    2018-01-01

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO2 in methanol at 220 °C and 50 bar H2 . A synergistic effect of Ni increased the yield of MP...... of the material. Interestingly, it was observed that Fe-Ni/ZrO2 also effectively catalyzed methanol reforming to produce H2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N2 instead of H2. Fe-Ni/ZrO2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl...

  5. Alkanes from Bioderived Furans by using Metal Triflates and Palladium-Catalyzed Hydrodeoxygenation of Cyclic Ethers.

    Science.gov (United States)

    Song, Hai-Jie; Deng, Jin; Cui, Min-Shu; Li, Xing-Long; Liu, Xin-Xin; Zhu, Rui; Wu, Wei-Peng; Fu, Yao

    2015-12-21

    Using a metal triflate and Pd/C as catalysts, alkanes were prepared from bioderived furans in a one-pot hydrodeoxygenation (HDO) process. During the reaction, the metal triflate plays a crucial role in the ring-opening HDO of furan compounds. The entire reaction process has goes through two major phases: at low temperatures, saturation of the exocyclic double bond and furan ring are catalyzed by Pd/C; at high temperatures, the HDO of saturated furan compounds is catalyzed by the metal triflate. The reaction mechanism was verified by analyzing the changes of the intermediates during the reaction. In addition, different metal triflates, solvents, and catalyst recycling were also investigated. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Study of hydrodeoxygenation of bio-oil from the fast pyrolysis of biomass

    Energy Technology Data Exchange (ETDEWEB)

    Su-ping, Z. [ECUST, Shanghai (China). Dept. of Chemical Engineering for Energy Resources

    2003-01-01

    The bio-oil obtained from the fast pyrolysis of biomass has a high oxygen content. Ketones and aldehydes, carboxylic acids and esters, aliphatic and aromatic alcohols, and ethers have been detected in significant quantities. Because of the reactivity of oxygenated groups, the main problems of the oil are instability. Therefore study of the deoxygenation of bio-oil is needed. In the present work the mechanism of hydrodeoxygenation (HDO) of bio-oil in the presence of a cobalt molybdate catalyst was studied. Particularly, the effects of reaction time, temperature, and hydrogen pressure on the HDO activity were examined. On the experimental results, a kinetic model for HDO of bio-oil was proposed. (author)

  7. Elucidation of reaction mechanism for m -cresol hydrodeoxygenation over Fe based catalysts: A kinetic study

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Yongchun; Wang, Yong

    2017-09-01

    Fe based catalysts are promising for hydrodeoxygenation (HDO) of lignin derived phenolics due to their high selectivity for aromatics. In this work, the reaction mechanism of m-cresol HDO on Fe catalysts and the kinetic consequence with Pd addition were elucidated by examining the effect of H2, H2O and m-cresol pressures on toluene formation rate on Fe and PdFe catalysts. A direct CO bond cleavage mechanism is proposed for HDO catalysis on both Fe and PdFe catalysts, while Pd provides a facilitated reaction pathway at the PdFe interface and therefore promotes the catalysis on Fe without changing the high selectivity towards aromatics.

  8. H2CAP - Hydrogen assisted catalytic biomass pyrolysis for green fuels

    DEFF Research Database (Denmark)

    Arndal, Trine Marie Hartmann; Høj, Martin; Jensen, Peter Arendt

    2014-01-01

    Pyrolysis of biomass produces a high yield of condensable oil at moderate temperature and low pressure.This bio-oil has adverse properties such as high oxygen and water contents, high acidity and immiscibility with fossil hydrocarbons. Catalytic hydrodeoxygenation (HDO) is a promising technology...... that can be used to upgrade the crude bio-oil to fuel-grade oil. The development of the HDO process is challenged by rapid catalyst deactivation, instability of the pyrolysis oil, poorly investigated reaction conditions and a high complexity and variability of the input oil composition. However, continuous...... catalytic hydropyrolysis coupled with downstream HDO of the pyrolysis vapors before condensation shows promise (Figure 1). A bench scale experimental setup will be constructed for the continuous conversion of solid biomass (100g /h) to low oxygen, fuel-grade bio-oil. The aim is to provide a proof...

  9. A new sensor for detection of coolant leakage in nuclear power plants using off-axis integrated cavity output spectroscopy

    International Nuclear Information System (INIS)

    Lee, Lim; Park, Hyunmin; Kim, Taek-Soo; Ko, Kwang-Hoon; Jeong, Do-Young

    2012-01-01

    A new sensor based on laser absorption spectroscopy was developed for the detection of coolant leakage which may happen in pressurized heavy water reactor (PHWR). Off-axis integrated output spectroscopy (OA-ICOS) technique was adopted for developing a simple and robust sensor with sufficient sensitivity. Leak events could be monitored by detecting a small change in semi-heavy water (HDO) concentration induced by the exchange reaction of leaked heavy water (D 2 O) with light water (H 2 O). From the results of feasibility tests, we have shown that the measured area of absorption features was linearly correlated with HDO concentration, and the minimum detectable change of HDO concentration with the developed sensor was evaluated as 3.2 ppm. This new sensor is expected to be a reliable and promising device for the detection of coolant leakage since it has some advantages on real-time monitoring and early detection for nuclear safety.

  10. Screening of Catalysts for Hydrodeoxygenation of Phenol as Model Compound for Bio-oil

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

    2013-01-01

    Four groups of catalysts have been tested for hydrodeoxygenation (HDO) of phenol as a model compound of bio-oil, including: oxide catalysts, methanol synthesis catalysts, reduced noble metal catalysts, and reduced non-noble metal catalysts. In total 23 different catalysts were tested at 100 bar H2...... and 275 °C in a batch reactor. The experiments showed that none of the tested oxides and methanol synthesis catalysts had any significant activity for phenol HDO at the given conditions, which were linked to their inability to hydrogenate the phenol. HDO of phenol over reduced metal catalysts could...... on a carbon support, but more active than the carbon supported noble metal catalysts when supported on ZrO2. This observation indicates that the nickel based catalysts require a metal oxide as carrier on which the activation of the phenol for the hydrogenation can take place through heterolytic dissociation...

  11. Comparison of high-definition oscillometry -- a non-invasive technology for arterial blood pressure measurement -- with a direct invasive method using radio-telemetry in awake healthy cats.

    Science.gov (United States)

    Martel, Eric; Egner, Beate; Brown, Scott A; King, Jonathan N; Laveissiere, Arnaud; Champeroux, Pascal; Richard, Serge

    2013-12-01

    This study compared indirect blood pressure measurements using a non-invasive method, high-definition oscillometry (HDO), with direct measurements using a radio-telemetry device in awake cats. Paired measurements partitioned to five sub-ranges were collected in six cats using both methods. The results were analysed for assessment of correlation and agreement between the two methods, taking into account all pressure ranges, and with data separated in three sub-groups, low, normal and high ranges of systolic (SBP) and diastolic (DBP) blood pressure. SBP data displayed a mean correlation coefficient of 0.92 ± 0.02 that was reduced for low SBP. The agreement level evaluated from the whole data set was high and slightly reduced for low SBP values. The mean correlation coefficient of DBP was lower than for SBP (ie, 0.81 ± 0.02). The bias for DBP between the two methods was 22.3 ± 1.6 mmHg, suggesting that HDO produced lower values than telemetry. These results suggest that HDO met the validation criteria defined by the American College of Veterinary Internal Medicine consensus panel and provided a faithful measurement of SBP in conscious cats. For DBP, results suggest that HDO tended to underestimate DBP. This finding is clearly inconsistent with the good agreement reported in dogs, but is similar to outcomes achieved in marmosets and cynomolgus monkeys, suggesting that this is not related to HDO but is species related. The data support that the HDO is the first and only validated non-invasive blood pressure device and, as such, it is the only non-invasive reference technique that should be used in future validation studies.

  12. Amino acid repletion does not decrease muscle protein catabolism during hemodialysis.

    Science.gov (United States)

    Raj, Dominic S C; Adeniyi, Oladipo; Dominic, Elizabeth A; Boivin, Michel A; McClelland, Sandra; Tzamaloukas, Antonios H; Morgan, Nancy; Gonzales, Lawrence; Wolfe, Robert; Ferrando, Arny

    2007-06-01

    Intradialytic protein catabolism is attributed to loss of amino acids in the dialysate. We investigated the effect of amino acid infusion during hemodialysis (HD) on muscle protein turnover and amino acid transport kinetics by using stable isotopes of phenylalanine, leucine, and lysine in eight patients with end-stage renal disease (ESRD). Subjects were studied at baseline (pre-HD), 2 h of HD without amino acid infusion (HD-O), and 2 h of HD with amino acid infusion (HD+AA). Amino acid depletion during HD-O augmented the outward transport of amino acids from muscle into the vein. Increased delivery of amino acids to the leg during HD+AA facilitated the transport of amino acids from the artery into the intracellular compartment. Increase in muscle protein breakdown was more than the increase in synthesis during HD-O (46.7 vs. 22.3%, P HD-O compared with pre-HD (-33.7 +/- 1.5 vs. -6.0 +/- 2.3, P acids, the net balance (-16.9 +/- 1.8) did not switch from net release to net uptake. HD+AA induced a proportional increase in muscle protein synthesis and catabolism. Branched chain amino acid catabolism increased significantly from baseline during HD-O and did not decrease during HD+AA. Protein synthesis efficiency, the fraction of amino acid in the intracellular pool that is utilized for muscle protein synthesis decreased from 42.1% pre-HD to 33.7 and 32.6% during HD-O and HD+AA, respectively (P acid repletion during HD increased muscle protein synthesis but did not decrease muscle protein breakdown.

  13. Laser spectroscopic visualization of hydrogen bond motions in liquid water

    Science.gov (United States)

    Bratos, S.; Leicknam, J.-Cl.; Pommeret, S.; Gallot, G.

    2004-12-01

    Ultrafast pump-probe experiments are described permitting a visualization of molecular motions in diluted HDO/D 2O solutions. The experiments were realized in the mid-infrared spectral region with a time resolution of 150 fs. They were interpreted by a careful theoretical analysis, based on the correlation function approach of statistical mechanics. Combining experiment and theory, stretching motions of the OH⋯O bonds as well as HDO rotations were 'filmed' in real time. It was found that molecular rotations are the principal agent of hydrogen bond breaking and making in water. Recent literatures covering the subject, including molecular dynamics simulations, are reviewed in detail.

  14. From biomass to fuels: Hydrotreating of oxygenated compounds

    Energy Technology Data Exchange (ETDEWEB)

    Gandarias, I.; Barrio, V.L.; Requies, J.; Arias, P.L.; Cambra, J.F.; Gueemez, M.B. [School of Engineering (UPV/EHU), c/ Alameda Urquijo s/n, 48013 Bilbao (Spain)

    2008-07-15

    Biomass is a renewable alternative to fossil raw materials in the production of liquid fuels and chemicals. Pyrolyzed biomass derived liquids contain oxygenated molecules that need to be removed to improve the stability of these liquids. A hydrotreating process, hydrodeoxygenation (HDO), is commonly used for this purpose. Thus, the aim of this work is to examine the role of advanced NiMo and NiW catalysts developed for HDS purposes in a HDO reaction. In addition, product distribution and catalyst stability are studied against changes in the feed composition, the solvent, and the catalyst pretreatment. (author)

  15. Mechanistic Investigation of Molybdate-Catalysed Transfer Hydrodeoxygenation

    DEFF Research Database (Denmark)

    Larsen, Daniel Bo; Petersen, Allan Robertson; Dethlefsen, Johannes Rytter

    2016-01-01

    The molybdate-catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the t......The molybdate-catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates...

  16. Selective hydrodeoxygenation of biomass-derived oxygenates to unsaturated hydrocarbons using molybdenum carbide catalysts.

    Science.gov (United States)

    Ren, Hui; Yu, Weiting; Salciccioli, Michael; Chen, Ying; Huang, Yulin; Xiong, Ke; Vlachos, Dionisios G; Chen, Jingguang G

    2013-05-01

    Which cleavage do you prefer? With a combination of density functional theory (DFT) calculations, surface science studies, and reactor evaluations, Mo(2)C is identified as a highly selective HDO catalyst to selectively convert biomass-derived oxygenates to unsaturated hydrocarbons through selective C-O bond scissions without C-C bond cleavage. This provides high-value HDO products for utilization as feedstocks for chemicals and fuels; this also reduces the overall consumption of H2 . Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Catalytic hydroconversion of tricaprylin and caprylic acid as model reaction for biofuel production from triglycerides

    Energy Technology Data Exchange (ETDEWEB)

    Boda, L.; Thernesz, A. [MOL Hungarian Oil and Gas Co. Plc., Szazhalombatta (Hungary); Onyestyak, G.; Solt, H.; Lonyi, F.; Valyon, J. [Hungarian Academy of Sciences, Budapest (Hungary). Inst. of Nanochemistry and Catalysis

    2010-07-01

    Palladium/activated carbon (Pd/C) and non-sulfided Ni,Mo/{gamma}-Al{sub 2}O{sub 3} catalysts were used. The hydroconversion was found to proceed in consecutive steps of tricaprylin (TC) hydrogenolysis (HYS) to caprylic acid (CA) and propane, and hydrodeoxygenation (HDO) of the acid intermediate to get hydrocarbon. Two HDO routes were distinguished: (i) over Pd/C the prevailing reaction route was the decarbonylation, whereas (ii) over molybdena-alumina catalysts the main reaction was the reduction of oxygen to get water. (orig.)

  18. Observations of Warm Water in Young Solar-System Analogs

    DEFF Research Database (Denmark)

    Persson, Magnus Vilhelm

    dioxide). The amount of warm water is deduced and its origin is observationally constrained. With both isotopologues observed, the HDO/H2O ratio is deduced. This ratio is then compared to other sources, e.g., comets and the Earth’s ocean, to gain understanding of the origin of the water in our own solar...... system. The emission line fluxes are modeled with radiative transfer tools and compared to other results of water abundances in the same source. The observed water emission, both H18(2 O and HDO is compact for all observed sources and traces the emission on R 150 AU scales or less. In one source...

  19. Influence on nickel particle size on the hydrodeoxygenation of phenol over Ni/SiO2

    DEFF Research Database (Denmark)

    Mortensen, Peter M.; Grunwaldt, Jan-Dierk; Jensen, Peter A.

    2016-01-01

    Hydrodeoxygenation (HDO) of phenol over nickel nano-particles of different size (5-22 nm) supported on SiO2 has been investigated in a batch reactor at 275 °C and 100 bar. Deoxygenation was only observed as a consecutive step of initial hydrogenation of phenol at the given conditions. Both the hy...

  20. Infrared photon-echo spectroscopy of water : The thermalization effects

    NARCIS (Netherlands)

    Pshenichnikov, Maxim S.; Yeremenko, Sergey; Wiersma, Douwe A.; Kobayashi, Takayoshi; Kobayashi, Tetsuro; Nelson, Keith A.; Okada, Tadashi; Silvestri, Sandro De

    2005-01-01

    The larger part of the nonlinear response in IR photon-echo and transient-grating spectroscopy on HDO-D2O mixtures at > 1-ps delays is found to originate from the D2O refractive index modulation due to local volume thermalization.

  1. Vibrational dynamics of ice in reverse micelles

    NARCIS (Netherlands)

    Dokter, A.M.; Petersen, C.; Woutersen, S.; Bakker, H.J.

    2008-01-01

    he ultrafast vibrational dynamics of HDO:D2O ice at 180 K in anionic reverse micelles is studied by midinfrared femtosecond pump-probe spectroscopy. Solutions containing reverse micelles are cooled to low temperatures by a fast-freezing procedure. The heating dynamics of the micellar solutions is

  2. Study of deuterated water in the low-mass protostar IRAS16293-2422

    Science.gov (United States)

    Coutens, A.; Vastel, C.; Caux, E.; Ceccarelli, C.; Herschel Chess Team

    2011-05-01

    Observations of deuterated water are an important complement for studies of H2O, since they give strong constraints on the formation processes: grain surfaces versus gas-phase chemistry through energetic process as shocks. The CHESS (Chemical HErschel Surveys of Star forming regions) Key Program has allowed to detect a lot of transitions of HDO (8) and H2O (16) as well as its isotopes H_218O and H_217O towards the low-mass protostar IRAS16293-2422 thanks to the unbiaised spectral survey carried out with the HIFI instrument on board the Herschel Space Observatory. Complementary data of HDO from the ground-based telescopes IRAM and JCMT are also available, allowing a precise determination of the abundance of deuterated water through the protostar envelope. In order to reproduce the observed line profiles, we have performed a modeling of HDO from the hot corino through the envelope using the physical structure of the protostar (Crimier et al. 2010) and the spherical Monte Carlo radiative transfer code RATRAN, which takes also into account radiative pumping by continuum emission from dust. We have used new HDO collision rates with H_2, recently computed by Wiesenfeld, Scribano and Faure (2011, PCCP). The same method has been applied to model H_2O and its isotopes H_218O and H_217O. We will present the results of this analysis and discuss the determined abundances.

  3. Upgrading biomass pyrolysis bio-oil to renewable fuels.

    Science.gov (United States)

    2015-01-01

    Fast pyrolysis is a process that can convert woody biomass to a crude bio-oil (pyrolysis oil). However, some of these compounds : contribute to bio-oil shelf life instability and difficulty in refining. Catalytic hydrodeoxygenation (HDO) of the bio-o...

  4. Mechanism of dehydration of phenols on nobel metals using first-principles micokinetic modeling

    Science.gov (United States)

    Phenolic compounds constitute a sizable fraction of depolymerized biomass and are an ideal feedstock for the production of chemicals such as benzene and toluene. However, these compounds require catalytic upgrade via hydrodeoxygenation (HDO), a process whereby oxygen is removed as water by adding hy...

  5. Carbon Nanofiber Supported Transition-Metal Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

    NARCIS (Netherlands)

    Jongerius, A.; Gosselink, R.W.; Dijkstra, J.; Bitter, J.H.; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2013-01-01

    Hydrodeoxygenation (HDO) studies over carbon nanofiber-supported (CNF) W2C and Mo2C catalysts were performed on guaiacol, a prototypical substrate to evaluate the potential of a catalyst for valorization of depolymerized lignin streams. Typical reactions were executed at 55 bar hydrogen pressure

  6. Hydrodeoxygenation of heavy oils derived from low-temperature coal gasification over NiW catalysts-effect of pore structure

    Energy Technology Data Exchange (ETDEWEB)

    Dieter Leckel [Sasol Technology Research and Development, Sasolburg (South Africa). Fischer-Tropsch Refinery Catalysis

    2008-01-15

    The effect of the pore structure on the hydroprocessing of heavy distillate oils derived from low-temperature coal gasification residues was studied using four NiW catalysts with different pore size distributions. The hydroprocessing was conducted at a pressure of 17.5 MPa, a temperature range of 370-410{sup o}C, and a 0.50 h{sup -1} space velocity. The degree of hydrodeoxygenation (HDO) in terms of phenolics removal was influenced by the catalyst pore structure, with the most preferable peak pore diameter for HDO ranging between 6.8 and 16 nm. The catalyst with the highest volume of pores in the 3.5-6 nm range showed the lowest HDO activity. The apparent activation energies for the HDO reaction varied between 59 and 87 kJ/mol, whereby the lowest values are obtained for the catalysts with a peak pore diameter of 11 and 16 nm. 30 refs., 5 figs., 6 tabs.

  7. From biomass to fuels: hydrotreating of oxygen-containing feeds on a CoMo/Al{sub 2}O{sub 3} hydrodesulfurization catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Viljava, T.-R.

    2001-07-01

    Biomass is a renewable alternative to fossil raw materials in the production of liquid fuels and chemicals. Liquefied biomass contains an abundance of oxygen-containing molecules that need to be removed to improve the stability of the liquids. A hydrotreating process, hydrodeoxygenation (HDO), is used for the purpose. Hydrodeoxygenation is similar to the hydrodesulfurization (HDS) process used in oil refining, relying upon a presulfided CoMo/{gamma}-Al{sub 2}O{sub 2}; catalyst. The stability of the sulfided catalyst is critical in HDO because biocrudes usually do not contain the sulfur compounds needed to maintain the sulfidation of the catalyst. The aim of this work was to examine the role of sulfur in maintaining the activity of the HDO catalyst. Sulfur was introduced as an organic sulfur-containing co-reactant or as a sulfur substituent in an oxygen-containing reactant molecule as a way of simulating mixed feeds composed of biocrudes and conventional crudes, or it was introduced as a low molecular weight sulfiding agent. In addition, the stability of the sulfided catalyst against changes in the feed composition was studied to find out whether the activity of the catalyst could be maintained by carrying out HDO alternately with HDS. Simultaneous HDO and HDS was studied in a batch reactor with model compounds having a sulfur-containing (inercapto or inethylmercapto) and an oxygen-containing (hydroxyl or inethoxy) substituent in the same molecule, and with binary mixtures of mono-substituted benzene compounds. In both cases, the reactions of the oxygencontaining substituents were strongly suppressed as long as a sulfur-containing functionality was present. HDS reactions of inercapto and inethylinercapto groups were either enhanced or retarded in the presence of oxygen-containing functionality. HDS was enhanced when the oxygen-containing substituent was located in Para-position to the sulfur substituent thereby increasing the electronegativity of the sulfur atom and

  8. Hydrotreating of compounds and mixtures of compounds having mercapto and hydroxyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Viljava, T.R.; Krause, A.O.I. [Helsinki University of Technology, Espoo (Finland)

    1997-07-01

    Simultaneous hydrodesulfurization (HDS) and hydrodeoxygenation (HDO) of mercapto and hydroxyl group containing benzenes was studied using a commercial presulfided CoMo/{gamma}- Al{sub 2}O{sub 3} catalyst under hydrotreating conditions (150-280 deg C, 7 MPa). Mercaptobenzene, phenol and 4-mercaptophenol were used as model compounds, and CS{sub 2} was used as precursor for H{sub 2}S. The HDS rate of a mercapto group in the presence of a hydroxyl substituent in the para position was higher than that for the molecule containing only a mercapto group. When the hydroxyl group was present as phenol, the HDS rate of the mercapto group was about 30% lower than that for mercaptobenzene without an oxygen-containing additive. The decrease in the HDS rate was independent of the initial molar ratio of sulfur and oxygen within the ratios studied (5:1-1:1). The HDO rate of a hydroxyl group was suppressed by the mercapto group present either in the same or in a separate molecule. HDO reactions did not start until HDS conversion was almost complete. CS{sub 2} also decreased the HDO rate of phenol. When compared to the reactions of phenol alone, the rate of the hydrogenolysis route to benzene was decreased in the presence of a sulfur additive more than the hydrogenolysis- hydrogenation route to cyclohexane. 19 refs.

  9. Catalytic Tandem Reaction for the Production of Jet and Diesel Fuel Range Alkanes

    DEFF Research Database (Denmark)

    Li, Hu; Gui, Zhenyou; Yang, Song

    2018-01-01

    Jet and diesel fuels are typically composed of C9-C14 and C12-C20 hydrocarbons, respectively, but the carbon-chain length of sugar-derived aldehydes and furanic compounds is no longer than C6. Here, a cascade catalytic process involving alkylation and hydrodeoxygenation (HDO) of 2-methylfuran (2-MF...

  10. CoMo sulphide-catalyzed hydrodeoxygenation of lignin model compounds: An extended reaction network for the conversion of monomeric and dimeric substrates

    NARCIS (Netherlands)

    Jongerius, A.L.; Jastrzebski, R; Bruijnincx, P.C.A.; Weckhuysen, B.M.

    2012-01-01

    In the present work, extensive hydrodeoxygenation (HDO) studies with a commercial sulfided CoMo/Al2O3 catalyst were performed on a library of ligninmodel compounds at 50 bar hydrogen pressure and 300 °C in dodecane, using a batch autoclave system. The catalyst was activated under hydrogen atmosphere

  11. Influence of H2O and H2S on the Composition, Activity, and Stability of Sulfided Mo, CoMo, and NiMo Supported on MgAl2O4 for Hydrodeoxygenation of Ethylene Glycol

    DEFF Research Database (Denmark)

    Dabros, Trine Marie Hartmann; Gaur, Abhijeet; Pintos, Delfina Garcia

    2018-01-01

    In this work, density functional theory (DFT), catalytic activity tests, and in-situ X-ray absorption spectroscopy (XAS) was performed to gain detailed insights into the activity and stability of MoS2, Ni-MoS2, and Co-MoS2 catalysts used for hydrodeoxygenation (HDO) of ethylene glycol upon...

  12. Catalytic cracking of fast and tail gas reactive pyrolysis bio-oils over HZSM-5

    Science.gov (United States)

    While hydrodeoxygenation (HDO) of pyrolysis oil is well understood as an upgrading method, the high processing pressures associated with it alone justify the exploration of alternative upgrading solutions, especially those that could adapt pyrolysis oils into the existing refinery infrastructure. Ca...

  13. Synergy in lignin upgrading by a combination of Cu-based mixed oxide and Ni-phosphide catalysts in supercritical ethanol

    NARCIS (Netherlands)

    Koranyi, T.I.; Huang, X.; Coumans, A.E.; Hensen, E.J.M.

    2017-01-01

    The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu–Mg–Al oxide (CuMgAlOx) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e.

  14. Calibration of personal dosemeters for extremities of fields of radiation gamma

    International Nuclear Information System (INIS)

    Papadopulos, S.; Gregori, S.; Moreno, B.; Guillen, J.

    1998-01-01

    In this work the conversion factors are presented obtained experimentally of kerma in free air in equivalent dose H(d,O o ) in finger and in arm for fields of radiation gamma of normal incidence dosemeters of extremities was irradiated, based on detecting TL of LIF 7 (TLD-700, Harshaw), placed on the surface of the finger phantom and arm

  15. Stability and resistance of nickel catalysts for hydrodeoxygenation

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Gardini, Diego; de Carvalho, Hudson W. P.

    2014-01-01

    The long term stability and resistance toward carbon deposition, sulfur, chlorine, and potassium of Ni/ZrO2 as a catalyst for the hydrodeoxygenation (HDO) of guaiacol in 1-octanol (as a model compound system for bio-oil) has been investigated at 250 degrees C and 100 bar in a trickle bed reactor...

  16. Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Gardini, Diego; Damsgaard, Christian Danvad

    2016-01-01

    The stability of Ni-MoS2/ZrO2 toward water, potassium, and chlorine containing compounds during hydrodeoxygenation (HDO) of a mixture of phenol and 1-octanol was investigated in a high pressure gas and liquid continuous flow fixed bed setup at 280 °C and 100 bar. To maintain the stability...

  17. Catalytic Hydrodeoxygenation of Biomass Pyrolysis Vapor Model Compounds over Molybdenum Sulfide Catalysts: Influence of Support, H2S and Water

    DEFF Research Database (Denmark)

    Arndal, Trine Marie Hartmann; Høj, Martin; Pintos, Delfina Garcia

    value, acidity and stability [1,2]. Upgrading ofcondensed pyrolysis oil is challenged by severe polymerization and coking upon heating. Instead, it is proposed toperform pyrolysis in the presence of hydrogen and an HDO catalyst for immediate stabilization and upgrading ofreactive pyrolysis products...

  18. Influence of Promotor, H2O and H2S on the Hydrodeoxygenation of Biomass Pyrolysis Vapor over MoS2 Catalysts

    DEFF Research Database (Denmark)

    Arndal, Trine M. H.; Høj, Martin; Gaur, Abhijeet

    Catalytic hydropyrolysis combines fast pyrolysis with catalytic upgrading by hydrodeoxygenation (HDO) in a single step for the production of fuel oil from biomass in which reactive pyrolysis vapors are upgraded before condensation. Catalyst activity and lifetime is challenged by carbon deposition...

  19. Identification and classification of components in flash pyrolysis oil and hydrodeoxygenated oils by two-dimensional gas chromatography and time-of-flight mass spectrometry

    NARCIS (Netherlands)

    Marsman, J. H.; Wildschut, J.; Evers, P.; Heeres, H. J.; Koning de, S.

    2008-01-01

    Hydrodeoxygenated pyrolysis oils (HDO) are considered promising renewable liquid energy carriers. To gain insights in the various reaction pathways taking place during the hydrodeoxygenation reaction of pyrolysis oil, two-dimensional gas chromatography with time-of-flight mass spectrometric analyses

  20. Water deuterium fractionation in the high-mass star-forming region G34.26+0.15 based on Herschel/HIFI data

    DEFF Research Database (Denmark)

    Coutens, Audrey; Vastel, C.; Hincelin, U.

    2014-01-01

    Understanding water deuterium fractionation is important for constraining the mechanisms of water formation in interstellar clouds. Observations of HDO and H_2^{18}O transitions were carried out towards the high-mass star-forming region G34.26+0.15 with the Heterodyne Instrument for the Far...... to an age of ˜105 yr after the infrared dark cloud stage....

  1. Ground-based Detection of Deuterated Water in Comet C/2014 Q2 (Lovejoy) at IR Wavelengths

    Energy Technology Data Exchange (ETDEWEB)

    Paganini, L.; Mumma, M. J.; Villanueva, G. L. [Goddard Center for Astrobiology, NASA Goddard Space Flight Center, Greenbelt, MD (United States); Gibb, E. L. [Department of Physics and Astronomy, University of Missouri, St. Louis, MO (United States)

    2017-02-20

    We conducted a deep search for deuterated water (HDO) in the Oort Cloud comet C/2014 Q2 (Lovejoy), through infrared (IR) spectroscopy with NIRSPEC at the Keck Observatory. In this Letter, we present our detections of HDO and water (H{sub 2}O) in comet Lovejoy on 2015 February 4 (post-perihelion) after 1 hr integration on source. The IR observations allowed simultaneous detection of H{sub 2}O and HDO, yielding production rates of 5.9 ± 0.13 × 10{sup 29} and 3.6 ± 1.0 × 10{sup 26} molecules s{sup −1}, respectively. The simultaneous detection permitted accurate determination of the isotopic ratio (D/H) in water of 3.02 ± 0.87 × 10{sup −4}, i.e., larger than the value for water in terrestrial oceans (or Vienna Standard Mean Ocean Water, VSMOW) by a factor of 1.94 ± 0.56. This D/H ratio in water exceeds the value obtained independently at millimeter wavelengths (0.89 ± 0.25 VSMOW; pre-perihelion). We discuss these parameters in the context of origins and emphasize the need for contemporaneous measurements of HDO and H{sub 2}O.

  2. Catalytic Conversion of Bio-oil to Fuel for Transportation

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard

    identied as a prospective route to bio-fuels. The upgrading is most favorably done by hydrodeoxygenation (HDO), producing bio-fuels at a quality equivalent to conventional fossil fuels. The topic of this Ph.D. thesis has been the development of active and stable catalysts for this reaction. In the search...

  3. Femtosecond spectroscopic study of the solvation of amphiphilic molecules by water

    NARCIS (Netherlands)

    Rezus, Y.L.A.; Bakker, H.J.

    2008-01-01

    We use polarization-resolved mid-infrared pump-probe spectroscopy to study the aqueous solvation of proline and N-methylacetamide. These molecules serve as models to study the solvation of proteins. We monitor the orientational dynamics of partly deuterated water molecules (HDO) that are present at

  4. Naval Postgraduate School Cost Center Financial Management Guide

    Science.gov (United States)

    1989-12-01

    Expenditures on Official Business 1. Advance registration fees for local workshops , seminars, classes, etc., of less than ten hours duration and...HCOOOHC999 0721-0730 63 Metorology Dept HD HDO0 -HD999 1 073 1-0740 Figure FA6 Sub-Cost Center OPTAR Document SerWa Numb~ers (con’t) Appendix F Page

  5. Ground-based Detection of Deuterated Water in Comet C/2014 Q2 (Lovejoy) at IR Wavelengths

    International Nuclear Information System (INIS)

    Paganini, L.; Mumma, M. J.; Villanueva, G. L.; Gibb, E. L.

    2017-01-01

    We conducted a deep search for deuterated water (HDO) in the Oort Cloud comet C/2014 Q2 (Lovejoy), through infrared (IR) spectroscopy with NIRSPEC at the Keck Observatory. In this Letter, we present our detections of HDO and water (H 2 O) in comet Lovejoy on 2015 February 4 (post-perihelion) after 1 hr integration on source. The IR observations allowed simultaneous detection of H 2 O and HDO, yielding production rates of 5.9 ± 0.13 × 10 29 and 3.6 ± 1.0 × 10 26 molecules s −1 , respectively. The simultaneous detection permitted accurate determination of the isotopic ratio (D/H) in water of 3.02 ± 0.87 × 10 −4 , i.e., larger than the value for water in terrestrial oceans (or Vienna Standard Mean Ocean Water, VSMOW) by a factor of 1.94 ± 0.56. This D/H ratio in water exceeds the value obtained independently at millimeter wavelengths (0.89 ± 0.25 VSMOW; pre-perihelion). We discuss these parameters in the context of origins and emphasize the need for contemporaneous measurements of HDO and H 2 O.

  6. Water deuteration in star-forming regions: Contribution of Herschel/HIFI spectroscopic data

    International Nuclear Information System (INIS)

    Coutens, Audrey

    2012-01-01

    Water (H_2O) is one of the most abundant molecules in the interstellar medium. In addition to being a primordial ingredient in the emergence of life, this species plays an essential role in the process of star formation through the cooling of warm gas. It also controls the chemistry for many species, either in the gas phase or on the grain surfaces. Studying its deuterated form HDO is a unique opportunity, through the estimation of the HDO/H_2O ratio, to constrain the mechanisms of water formation and to better understand the origin of water contained in terrestrial oceans. Indeed, recent results obtained with the Herschel satellite show that the HDO/H_2O ratio observed in comets is similar to the value measured in oceans (∼1.5 10"-"4), which suggests that comets could have brought a large fraction to Earth to form the oceans during heavy bombardments (Hartogh et al. 2011). In this thesis, I was interested in the study of deuterated water in the first stages of star formation, the Class 0 stage, which precede the formation of the protoplanetary disk leading to the birth of comets and planets. Through a 1D non-Local Thermodynamic Equilibrium radiative transfer modeling of the line profiles of the numerous HDO and H_2"1"8O transitions detected with the HIFI (Heterodyne Instrument for Far-Infrared) instrument onboard the Herschel Space Observatory and ground-based telescopes (IRAM, JCMT), I determined that the HDO/H_2O ratios of the solar-type protostar IRAS 16293-2422 was about 2% in the hot corino, the inner part of the protostellar envelope sufficiently warm (T ≥ 100 K) to desorb in gas phase the water molecules trapped in the icy grain mantles, and about 0.5% in the colder part of the envelope. This study (Coutens et al. 2012) also allowed me to show that an absorbing layer rich in water surrounds the protostar. This layer could be produced by the photo-desorption through the UV field of the water molecules frozen on the grains, on the edges of the molecular

  7. Vibrational and orientational dynamics of water in aqueous hydroxide solutions.

    Science.gov (United States)

    Hunger, Johannes; Liu, Liyuan; Tielrooij, Klaas-Jan; Bonn, Mischa; Bakker, Huib

    2011-09-28

    We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH(-) from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H(2)O. For the O-H vibration of HDO molecules outside the first hydration shell of OD(-), we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D(2)O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ~7 surrounding water molecules, considerably less than previously reported for the proton. © 2011 American Institute of Physics

  8. Agreement of high definition oscillometry with direct arterial blood pressure measurement at different blood pressure ranges in horses under general anaesthesia.

    Science.gov (United States)

    Tünsmeyer, Julia; Hopster, Klaus; Feige, Karsten; Kästner, Sabine Br

    2015-05-01

    To determine the agreement of high definition oscillometry (HDO) with direct arterial blood pressure measurements in normotensive, hypotensive and hypertensive horses during general anaesthesia. Experimental study. Seven healthy warmblood horses, aged 3-11 years, weighing 470-565 kg. Measurements from a HDO device with the cuff placed around the base of the tail were compared with pressures measured invasively from the facial artery. High blood pressures were induced by intravenous (IV) administration of dobutamine (5 μg kg(-1) minute(-1)) over ten minutes followed by norepinephrine (0.1 mg kg(-1) IV) and low pressures by increasing the inspired fraction of isoflurane and administration of nitroglycerine (0.05 mg kg(-1) IV). For analysis three pressure levels were determined: high (MAP>110 mmHg), normal (60 mmHgstandard deviation for SAP, MAP and DAP were 0.1 ± 19.4 mmHg, 0.5 ± 14.0, 4.7 ± 15.6, respectively. At high pressure levels bias and SD were 26.1 ± 37.3 (SAP), 4.2 ± 19.4 (MAP), 1.5 ± 16.8 (DAP) and at low pressures -20.0 ± 20.9 (SAP), -11.4 ± 19.6 (MAP), -4.7 ± 20.1 (DAP), with HDO measurements at a MAP <50 mmHg often failing. Good agreement with invasive arterial blood pressures was obtained with HDO at normotensive levels in horses. At high and low pressure ranges HDO was unreliable. Therefore, if haemodynamic instability is expected, invasive measurement remains preferable. © 2014 Association of Veterinary Anaesthetists and the American College of Veterinary Anesthesia and Analgesia.

  9. A GREAT search for Deuterium in Comets

    Science.gov (United States)

    Mumma, Michael

    2013-10-01

    Comets are understood to be the most pristine bodies in the Solar System. Their compositions reflect the chemical state of materials at the very earliest evolutionary stages of the protosolar nebula and, as such, they provide detailed insight into the physical and chemical processes operating in planet-forming disks. Isotopic fractionation ratios of the molecular ices in the nucleus are regarded as signatures of formation processes. These ratios provide unique information on the natal heritage of those ices, and can also test the proposal that Earth's water and other volatiles were delivered by cometary bombardment. Measurement of deuterium fractionation ratios is thus a major goal in contemporary cometary science and the D/H ratio of water - the dominant volatile in comets - holds great promise for testing the formation history of cometary matter. The D/H ratio in cometary water has been measured in only eight comets. Seven were from the Oort Cloud reservoir and the D/H ratio was about twice that of the Earth's oceans. However, the recent Herschel measurement of HDO/H2O in 103P/Hartley-2 (the first from the Kuiper Belt) was consistent with exogenous delivery of Earth's water by comets. Outstanding questions remain: are cometary HDO/H2O ratios consistent with current theories of nebular chemical evolution or with an interstellar origin? Does the HDO/H2O ratio vary substantially among comet populations? Hartley-2 is the only Kuiper Belt comet with measured HDO/H2O, are there comets with similar ratios in the Oort cloud? These questions can only be addressed by measuring HDO/H2O ratios in many more suitable bright comets. We therefore propose to measure the D/H ratio in water in a suitable target-of-opportunity comet by performing observations of HDO and OH with the GREAT spectrometer on SOFIA. A multi-wavelength, ground-based observing campaign will also be conducted in support of the airborne observations.

  10. Competitive reaction in hydrodenitrogenation and hydrodeoxygenation of coal-derived naphtha

    Energy Technology Data Exchange (ETDEWEB)

    Machida, M. (Idemitsu Kosan Co. Ltd., Tokyo (Japan). Central Research Lab.); Sakao, Y.; Ono, S. (Idemitsu Kosan Co. Ltd., Tokyo (Japan))

    1994-03-01

    The naphtha fraction derived from coal is expected to be one of the most suitable blending stocks for motor gasoline because of its high contents of cyclic hydrocarbons. However, since the contents of nitrogen and oxygen are high in the coal naphtha, the amounts of these elements must be reduced to acceptable levels. In this study, aiming to clarify the hydrodenitrogenation (HDN) and hydrodeoxygenation (HDO) performances of practical feed stocks, HDN and HDO of coal-derived naphtha and its model compounds were examined by using a catalyst Ni-Mo/Al2O3 group. There are tree types of nitrogen compounds, pyridine, pyrrole and aniline, in the coal-derived naphtha. Aniline type nitrogen compounds in the coal-derived naphtha are more resistant to HDN than pyridine type compounds, though aniline is more reactive than pyridine when the reaction is carried out individually. 14 refs., 7 figs., 3 tabs.

  11. Hydrodeoxygenation of Guaiacol Over Pt/Al-SBA-15 Catalysts.

    Science.gov (United States)

    Yu, Mi Jin; Park, Sung Hoon; Jeon, Jong-Ki; Ryu, Changkook; Sohn, Jung Min; Kim, Sang Chai; Park, Young-Kwon

    2015-01-01

    Upgrading of bio-oil through catalytic hydrodeoxygenation (HDO) reaction was investigated for guaiacol as a model compound. A batch reactor was used for the reaction condition of 40 bar and 250 degrees C. The target product was cyclohexane. Pt/Al-SBA-15 with the Si/Al ratios of 20, 40, and 80 and Pt/HZSM-5 were used as the catalyst. The SBA-15 catalysts were characterized by N2 adsorption-desorption, X-ray diffraction analysis, and temperature programmed desorption of ammonia. The order of cyclohexane yield was Pt/Al-SBA-15 (Si/Al = 20) > Pt/Al-SBA-15(40) > Pt/Al-SBA-15 (80), indicating that the quantity of acid sites plays an important role in the HDO reaction. On the other hand, Pt/HZSM-5 led to a very low cyclohexane yield, in spite of its abundant strong acid sites, due to its small pore size.

  12. Liquid-Phase Hydrodeoxygenation of Guaiacol over Mo2C Supported on Commercial CNF. Effects of Operating Conditions on Conversion and Product Selectivity

    Directory of Open Access Journals (Sweden)

    Rui Moreira

    2018-03-01

    Full Text Available In this work, a Mo2C catalyst that was supported on commercial carbon nanofibers (CNF was synthetized and tested in the hydrodeoxygenation (HDO of guaiacol. The effects of operating conditions (temperature and pressure and reaction time (2 and 4 h on the conversion of guaiacol and products selectivity were studied. The major reaction products were cresol and phenol, followed by xylenols and toluene. The use of more severe operating conditions during the HDO of guaiacol caused a diversification in the reaction pathways, and consequently in the selectivity to products. The formation of phenol may have occurred by demethylation of guaiacol, followed by dehydroxylation of catechol, together with other reaction pathways, including direct guaiacol demethoxylation, and demethylation of cresols. X-ray diffraction (XRD analysis of spent catalysts did not reveal any significant changes as compared to the fresh catalyst.

  13. High Selectively Catalytic Conversion of Lignin-Based Phenols into para-/m-Xylene over Pt/HZSM-5

    Directory of Open Access Journals (Sweden)

    Guozhu Liu

    2016-01-01

    Full Text Available High selectively catalytic conversion of lignin-based phenols (m-cresol, p-cresol, and guaiacol into para-/m-xylene was performed over Pt/HZSM-5 through hydrodeoxygenation and in situ methylation with methanol. It is found that the p-/m-xylene selectivity is uniformly higher than 21%, and even increase up to 33.5% for m-cresol (with phenols/methanol molar ratio of 1/8. The improved p-/m-xylene selectivity in presence of methanol is attributed to the combined reaction pathways: methylation of m-cresol into xylenols followed by HDO into p-/m-xylene, and HDO of m-cresol into toluene followed by methylation into p-/m-xylene. Comparison of the product distribution over a series of catalysts indicates that both metals and supporters have distinct effect on the p-/m-xylene selectivity.

  14. Hydrotreating catalyst deactivation by coke from SRC-II oil

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Y.; Kumata, F.; Massoth, F.E.

    1988-10-01

    Samples of a CoMo/Al/sub 2/O/sub 3/ catalyst were partially deactivated with SRC-II feed in an autoclave reactor to give coked samples of 5 to 18% C. The coked catalysts were analyzed for surface area, pore volume, coronene adsorption and diffusivity, and their catalytic activity determined for hydrodesulfurization (HDS), hydrodeoxygenation (HDO) and C-N hydrogenolysis (CNH) using model compounds. All of the above measurements decreased with increase in coke content. Property data indicate that some pores are blocked by coke and diffusivity results show narrowing of pore mouths with increasing coke content. Catalyst deactivation versus coke level was identical for HDS and HDO, but less for CNH. A simple model of coke deactivation was developed to relate activity to coke content. Coke is envisioned as forming wedge-like deposits in the catalyst pores. 11 refs., 5 figs., 3 tabs.

  15. Activity and selectivity of three molybdenum catalysts for coal liquefaction reactions

    Energy Technology Data Exchange (ETDEWEB)

    Curtis, C.W.; Pellegrino, J.L.

    The activity and selectivity of three different molybdenum catalysts for reactions occurring in coal liquefaction, specifically for hydrogenation (HYD), hydrodeoxygenation (HDO), hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrocracking (HYC), have been examined. The three molybdenum catalysts used were molybdenum napthenate, molybdenum on ..gamma..-alumina, and a precipitated, disordered MoS/sub 2/. Molybdenum naphthenate was most selective for HYD and HDN. All three catalysts exhibited approximately equal activity for HDS and HDO and little selectivity for HYC of alkyl bridge structures. The activity and selectivity of the three molybdenum catalysts for producing hydrocarbons and removing heteroatoms from coal during liquefaction were determined and compared. Molybdenum naphthenate was the most active catalyst for hydrocarbon production and removal of nitrogen- and oxygen-containing species during coal liquefaction. 31 refs., 4 figs., 7 tabs.

  16. Methyl Butanoate Adsorption on MoS2 Surface: A Density Functional Theory Investigation

    Directory of Open Access Journals (Sweden)

    Prabowo Wahyu Aji Eko

    2018-01-01

    Full Text Available Methyl butanoate is one of the compound which is obtained from triglyceride molecule. It has hydrocarbon components and hence may produce hydrocarbon through hydrodeoxygenation (HDO or decarbonylation (DCO processes. The first step to uncover the underlying mechanism of HDO or DCO is to find the active site of methyl butanoate adsorption over the catalyst. This study attempts to investigate the active site of methyl butanoate adsorption on MoS2 surface. Stable bonding configuration for methyl butanoate adsorption on MoS2 is investigated by using density functional theory (DFT. This investigation consists of geometry optimisation and adsorption energy calculations. The stable configuration of methyl butanoate adsorption on MoS2 surface is found to be on top of Mo atom in Mo-edge surface.

  17. Nano-catalysts for upgrading bio-oil: Catalytic decarboxylation and hydrodeoxygenation

    Science.gov (United States)

    Uemura, Yoshimitsu; Tran, Nga T. T.; Naqvi, Salman Raza; Nishiyama, Norikazu

    2017-09-01

    Bio-oil is a mixture of oxygenated chemicals produced by fast pyrolysis of lignocellulose, and has attracted much attention recently because the raw material is renewable. Primarily, bio-oil can be used as a replacement of heavy oil. But it is not highly recommended due to bio-oil's inferior properties: high acidity and short shelf life. Upgrading of bio-oil is therefore one of the important technologies nowadays, and is categorized into the two: (A) decrarboxylation/decarbonylation by solid acid catalysts and (B) hydrodeoxygenation (HDO) by metallic catalysts. In our research group, decarboxylation of bio-oil by zeolites and HDO of guaiacol (a model compound of bio-oil) have been investigated. In this paper, recent developments of these upgrading reactions in our research group will be introduced.

  18. Electron microscopy study of the deactivation of nickel based catalysts for bio oil hydrodeoxygenation

    DEFF Research Database (Denmark)

    Gardini, Diego; Mortensen, Peter Mølgaard; Carvalho, Hudson W. P.

    2014-01-01

    Hydrodeoxygenation (HDO) is proposed as an efficient way to remove oxygen in bio-oil, improving its quality as a more sustainable alternative to conventional fuels in terms of CO2 neutrality and relative short production cycle [1]. Ni and Ni-MoS2 nanoparticles supported on ZrO2 show potential...... as high-pressure (100 bar) catalysts for purification of bio-oil by HDO. However, the catalysts deactivate in presence of sulfur, chlorine and potassium species, which are all naturally occurring in real bio-oil. The deactivation mechanisms of the Ni/ZrO2 have been investigated through scanning...... transmission electron microscopy (STEM), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and X-ray diffraction (XRD). Catalytic testing has been performed using guaiacol in 1-octanol acting as a model compound for bio-oil. Addition of sulphur (0.3 vol% octanethiol) in the feed...

  19. Novel catalysts for upgrading coal-derived liquids. Final technical progress report

    Energy Technology Data Exchange (ETDEWEB)

    Thompson, L.T.; Savage, P.E.; Briggs, D.E.

    1995-03-31

    Research described in this report was aimed at synthesizing and evaluating supported Mo oxynitrides and oxycarbides for the selective removal of nitrogen, sulfur and oxygen from model and authentic coal-derived liquids. The Al{sub 2}O{sub 3}-supported oxynitrides and oxycarbides were synthesized via the temperature programmed reaction of supported molybdenum oxides or hydrogen bronzes with NH{sub 3} or an equimolar mixture of CH{sub 4} and H{sub 2}. Phase constituents and composition were determined by X-ray diffraction, CHN analysis, and neutron activation analysis. Oxygen chemisorption was used to probe the surface structure of the catalysts. The reaction rate data was collected using specially designed micro-batch reactors. The Al{sub 2}O{sub 3}-supported Mo oxynitrides and oxycarbides were competitively active for quinoline hydrodenitrogenation (HDN), benzothiophene hydrodesulfurization (HDS) and benzofuran hydrodeoxygenation (HDO). In fact, the HDN and HDO specific reaction rates for several of the oxynitrides and oxycarbides were higher than those of a commercial Ni-Mo/Al{sub 2}O{sub 3} hydrotreatment catalyst. Furthermore, the product distributions indicated that the oxynitrides and oxycarbides were more hydrogen efficient than the sulfide catalysts. For HDN and HDS the catalytic activity was a strong inverse function of the Mo loading. In contrast, the benzofuran hydrodeoxygenation (HDO) activities did not appear to be affected by the Mo loading but were affected by the heating rate employed during nitridation or carburization. This observation suggested that HDN and HDS occurred on the same active sites while HDO was catalyzed by a different type of site.

  20. Analysis of the Second Law of Thermodynamics applied to GS process in the primary production of heavy water

    International Nuclear Information System (INIS)

    Chavez, Rosa Hilda

    1991-01-01

    An evaluation of the entropic change, through the analysis of the Second Law of Thermodynamic of GS process, with the aim of determine the sections where the majors irreversibilities of the process are located, is presented in this work. This process consist in the first enrichment stage of GS, which operates bithermally at 305 D and 403 Kelvin degree and a pressure of 2 MPa, participating four chemical compounds: H 2 O, HDO, H 2 S and HDS (Author)

  1. Matrix isolation study of the interaction between water and the aromatic π-electron system

    International Nuclear Information System (INIS)

    Engdahl, A.; Nelander, B.

    1987-01-01

    The interaction of water (H 2 O, D 2 O, HDO) with toluene, the xylenes, pseudocumene, mesitylene, pentamethylbenzene, and hexamethylbenzene in argon matrices has been studied with infrared spectroscopy. Interaction energy estimates are given. The shapes of the observed absorption bands suggest that water executes a complicated motion relative to the ring plane of the aromatic hydrocarbon. The infrared spectrum of the benzene-water complex has been recorded as a function of temperature in argon, krypton, and nitrogen matrices

  2. History of the study of the telluric spectrum of the sun. II - 1900-1970

    Energy Technology Data Exchange (ETDEWEB)

    Melnikov, O.A.; Khilov, E.D.

    1981-01-01

    Studies of the telluric bands and lines in the solar spectrum are reviewed which were carried out between 1900 to 1970. Telluric features observed in the IR, visible, and UV regions are examined in detail. Special attention is given to telluric absorption bands due to H2O, O2, O3, CH4, N2O, CO2, C2H4, (O2)2, and HDO.

  3. Influence of oxalate ligand functionalization on Co/ZSM-5 activity in Fischer Tropsch synthesis and hydrodeoxygenation of oleic acid into hydrocarbon fuels.

    Science.gov (United States)

    Ayodele, Olumide Bolarinwa

    2017-08-30

    Achieving high degree of active metal dispersions at the highest possible metal loading and high reducibility of the metal remains a challenge in Fischer Tropsch synthesis (FTS) as well as in hydrogeoxygenation (HDO).This study therefore reports the influence of oxalic acid (OxA) functionalization on the metal dispersion, reducibility and activity of Co supported ZSM-5 catalyst in FTS and HDO of oleic acid into paraffin biofuel. The Brunauer-Emmett-Teller (BET) results showed that cobalt oxalate supported ZSM-5 catalyst (CoOx/ZSM-5) synthesized from the incorporation of freshly prepared cobalt oxalate complex into ZSM-5 displayed increase in surface area, pore volume and average pore size while the nonfunctionalized cobalt supported on ZSM-5 (Co/ZSM-5) catalyst showed reduction in those properties. Furthermore, both XRD and XPS confirmed the presence of Co° formed from the decomposition of CoOx during calcination of CoOx/ZSM-5 under inert atmosphere. The HRTEM showed that Co species average particle sizes were smaller in CoOx/ZSM-5 than in Co/ZSM-5, and in addition, CoOx/ZSM-5 shows a clear higher degree of active metal dispersion. The FTS result showed that at CO conversion over Co/ZSM-5 and CoOx/ZSM-5 catalysts were 74.28% and 94.23% and their selectivity to C 5+ HC production were 63.15% and 75.4%, respectively at 4 h TOS. The HDO result also showed that the CoOx/ZSM-5 has higher OA conversion of 92% compared to 59% over Co/ZSM-5. In addition CoOx/ZSM-5 showed higher HDO and isomerization activities compared to Co/ZSM-5.

  4. Improvement of hydrodenitrogenation (HDN) in co-refining of coal-derived liquid and petroleum fraction

    Energy Technology Data Exchange (ETDEWEB)

    Machida, M.; Ono, S. [Idemitsu Kosan Co. Ltd., Tokyo (Japan); Hattori, H. [Hokkaido University, Sapporo (Japan). Center for Advanced Research of Energy Technology

    1997-09-01

    The improvement in hydrodenitrogenation (HDN) of coal-derived liquids by co-refining with a petroleum fraction results principally from lowering the nitrogen content of the feedstock (coal-derived liquid) by blending with a nitrogen-free petroleum fraction. Effects of different fractions of coal-derived liquids on HDN and hydrodeoxygenation (HDO) were also examined. The HDN improvement by co-refining could be interpreted in terms of Langmuir-Hinshelwood mechanism. 38 refs., 3 figs., 3 tabs.

  5. Synthesis of jet fuel range branched cycloalkanes with mesityl oxide and 2-methylfuran from lignocellulose

    Science.gov (United States)

    Li, Shanshan; Li, Ning; Wang, Wentao; Li, Lin; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

    2016-09-01

    Jet fuel range branched cycloalkanes with high density (0.82 g mL-1) and low freezing point (217-219 K) was first prepared by the solvent-free intramolecular aldol condensation of the trione from the hydrolysis of the alkylation product of mesityl oxide and 2-methylfuran (or the one-pot reaction of mesityl oxide, 2-methylfuran and water), followed by hydrodeoxygenation (HDO).

  6. COMPARISON OF HIGH-DEFINITION OSCILLOMETRIC AND DIRECT ARTERIAL BLOOD PRESSURE MEASUREMENT IN ANESTHETIZED CHEETAHS (ACINONYX JUBATUS).

    Science.gov (United States)

    Sant Cassia, Emma V; Boswood, Adrian; Tordiffe, Adrian S W

    2015-09-01

    Blood pressure measurement reveals important insights into the health of conscious and anesthetized individuals. This is of particular interest in cheetahs (Acinonyx jubatus), which in captivity are known to suffer from chronic diseases that may be associated with hypertension and which often require immobilization for transport or veterinary treatment. Invasive testing methods are considered the gold standard but are not practical in many settings. Consequently, it is important to evaluate the use of noninvasive methods in this species. Measurements for systolic, diastolic, and mean arterial pressure obtained using high-definition oscillometry (HDO) at the coccygeal artery were compared to simultaneous direct measurements obtained via catheterization of the femoral or dorsal pedal artery in eight anesthetized captive cheetahs during nine anesthetic events. Overall, HDO and direct measurements agreed most closely for mean arterial pressure, and the poorest agreement was observed for systolic pressure. There was a tendency for low diastolic pressures to be underestimated and for high diastolic pressures to be overestimated. Across all three parameters, HDO measurements from the tail overestimated directly measured pressures in the femoral artery and underestimated those in the dorsal pedal artery. HDO agreed most closely with directly measured dorsal pedal pressures. Mean arterial pressure showed the greatest precision (standard deviation of 10.2 mm Hg) and lowest bias (-1.2 mm Hg), with 75.9% of readings within 10 mm Hg of the direct dorsal pedal pressure. Agreement with systolic pressure was hindered by a high bias (-10.4 mm Hg), but if a correction factor of +10 mm Hg was applied to all systolic measurements, agreement was improved and 65.7% of readings were within 10 mm Hg of the direct pressure. When compared to criteria defined by the American College of Veterinary Internal Medicine for validation of blood pressure devices, results were favorable, but a

  7. Stratospheric isotopic water profiles from a single submillimeter limb scan by TELIS

    Directory of Open Access Journals (Sweden)

    A. de Lange

    2009-08-01

    Full Text Available Around 490 GHz relatively strong HDO and H218O emission lines can be found in the submillimeter thermal-emission spectrum of the Earth's atmosphere, along with lines of the principal isotopologue of water vapour. These can be used for remote sensing of the rare/principal isotope ratio in the stratosphere. A sensitivity study has been performed for retrieval simulations of water isotopologues from balloon-borne measurements by the limb sounder TELIS (TErahertz and submillimeter LImb Sounder. The study demonstrates the capability of TELIS to determine, from a single limb scan, the profiles for H218O and HDO between 20 km and 37 km with a retrieval error of ≈3 and a spatial resolution of 1.5 km, as determined by the width of the averaging kernel. In addition HDO can be retrieved in the range of 10–20 km, albeit with a strongly deteriorated retrieval error. Expected uncertainties in instrumental parameters have only limited impact on the retrieval results.

  8. Refractive index calculation for analysis of aqueous solutions of heavy water

    International Nuclear Information System (INIS)

    Azuaga, N.S.; Marques, A.R.; Djega-Mariadassou, G.

    1978-01-01

    Refractive index measurements are used for analysis of aqueous solutions of D 2 O, particularly in the intermediate concentration range. The accuracy of titration is around 0.4% of atomic deuterium. Assuming that nsub(HDO)=(nsub(H 2 O)+nsub(D 2 O))/2, and that the refractive index of an initial mixture H 2 O-D 2 O is, in this case, an additive property of the molecular species, the refractive index n(t) of the ternary mixture (H 2 O-D 2 O-HDO) can be expressed by a relation. Using these two equations, it becomes possible to calculate the various types of calibration curves versus n, in the whole range of concentrations. To build these composition - n(t) curves, the only necessary data are the refractive index measurements of pure H 2 O and D 2 O and the value of equilibrium constant of the reaction H 2 O+D 2 O reversible 2HDO at the proper temperature [fr

  9. Heterogeneously catalyzed deuterium separation processes: Hydrogen-water exchange studies at elevated temperatures and pressures

    International Nuclear Information System (INIS)

    Halliday, J.D.; Rolston, J.H.; Au, J.C.; Den Hartog, J.; Tremblay, R.R.

    1985-01-01

    New processes for the separation of hydrogen isotopes are required to produce heavy water for CANDU nuclear reactors and to extract tritium formed in the moderator during reactor operation. Wetproofed platinum catalysts capable of promoting rapid exchange of isotopes between countercurrent flows of hydrogen and liquid water in packed columns have been developed at CRNL over the past 15 years. These catalysts provide a catalystic surface for the gas phase exchange reaction H/sub 2/O/sub (v)/ + HD/sub (g)/ ↔ HDO/sub (v)/ + H/sub 2(g)/ as well as a large liquid surface for the liquid phase isotope transfer reaction HDO/sub (v)/ + H/sub 2/O/sub (iota)/↔HDO/sub (iota)/+H/sub 2/O/sub (v)/. Any economic stand-alone heavy water separation process, based on bithermal hydrogen-water exchange over wetproofed platinum catalysts, requires rapid overall exchange of isotopes between two phases at two temperatures. Catalysts developed for cold tower operation at 25-60 0 C are now being tested in a laboratory scale stainless steel trickle bed reactor for performance and stability at simulated hot tower conditions, 150 0 C and 2.0 MPa pressure. Catalytically active layers containing platinum supported on carbon or crystalline silica and wetproofed with Teflon have been prepared on ceramic spheres and stainless steel screening and tested in both random and ordered bed columns

  10. Nitrogen-Doped Ordered Mesoporous Carbon Supported Bimetallic PtCo Nanoparticles for Upgrading of Biophenolics.

    Science.gov (United States)

    Wang, Guang-Hui; Cao, Zhengwen; Gu, Dong; Pfänder, Norbert; Swertz, Ann-Christin; Spliethoff, Bernd; Bongard, Hans-Josef; Weidenthaler, Claudia; Schmidt, Wolfgang; Rinaldi, Roberto; Schüth, Ferdi

    2016-07-25

    Hydrodeoxygenation (HDO) is an attractive route for the upgrading of bio-oils produced from lignocellulose. Current catalysts require harsh conditions to effect HDO, decreasing the process efficiency in terms of energy and carbon balance. Herein we report a novel and facile method for synthesizing bimetallic PtCo nanoparticle catalysts (ca. 1.5 nm) highly dispersed in the framework of nitrogen-doped ordered mesoporous carbon (NOMC) for this reaction. We demonstrate that NOMC with either 2D hexagonal (p6m) or 3D cubic (Im3‾ m) structure can be easily synthesized by simply adjusting the polymerization temperature. We also demonstrate that PtCo/NOMC (metal loading: Pt 9.90 wt %; Co 3.31 wt %) is a highly effective catalyst for HDO of phenolic compounds and "real-world" biomass-derived phenolic streams. In the presence of PtCo/NOMC, full deoxygenation of phenolic compounds and a biomass-derived phenolic stream is achieved under conditions of low severity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Production of bio-hydrogenated diesel by catalytic hydrotreating of palm oil over NiMoS2/γ-Al2O3 catalyst.

    Science.gov (United States)

    Srifa, Atthapon; Faungnawakij, Kajornsak; Itthibenchapong, Vorranutch; Viriya-Empikul, Nawin; Charinpanitkul, Tawatchai; Assabumrungrat, Suttichai

    2014-04-01

    Catalytic hydrotreating of palm oil (refined palm olein type) to produce bio-hydrogenated diesel (BHD) was carried out in a continuous-flow fixed-bed reactor over NiMoS2/γ-Al2O3 catalyst. Effects of dominant hydrotreating parameters: temperature: 270-420°C; H2 pressure: 15-80 bar; LHSV: 0.25-5.0 h(-1); and H2/oil ratio: 250-2000 N(cm(3)/cm(3)) on the conversion, product yield, and a contribution of hydrodeoxygenation (HDO) and decarbonylation/decarboxylation (DCO/DCO2) were investigated to find the optimal hydrotreating conditions. All calculations including product yield and the contribution of HDO and DCO/DCO2 were extremely estimated based on mole balance corresponding to the fatty acid composition in feed to fully understand deoxygenation behaviors at different conditions. These analyses demonstrated that HDO, DCO, and DCO2 reactions competitively occurred at each condition, and had different optimal and limiting conditions. The differences in the hydrotreating reactions, liquid product compositions, and gas product composition were also discussed. Copyright © 2014 Elsevier Ltd. All rights reserved.

  12. Mechanistic Investigation of Molybdate-Catalysed Transfer Hydrodeoxygenation.

    Science.gov (United States)

    Larsen, Daniel B; Petersen, Allan R; Dethlefsen, Johannes R; Teshome, Ayele; Fristrup, Peter

    2016-11-07

    The molybdate-catalysed transfer hydrodeoxygenation (HDO) of benzyl alcohol to toluene driven by oxidation of the solvent isopropyl alcohol to acetone has been investigated by using a combination of experimental and computational methods. A Hammett study that compared the relative rates for the transfer HDO of five para-substituted benzylic alcohols was carried out. Density-functional theory (DFT) calculations suggest a transition state with significant loss of aromaticity contributes to the lack of linearity observed in the Hammett study. The transfer HDO could also be carried out in neat PhCH 2 OH at 175 °C. Under these conditions, PhCH 2 OH underwent disproportionation to yield benzaldehyde, toluene, and significant amounts of bibenzyl. Isotopic-labelling experiments (using PhCH 2 OD and PhCD 2 OH) showed that incorporation of deuterium into the resultant toluene originated from the α position of benzyl alcohol, which is in line with the mechanism suggested by the DFT study. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Influence of Solvent on Liquid Phase Hydrodeoxygenation of Furfural-Acetone Condensation Adduct using Ni/Al2O3-ZrO2 Catalysts

    Science.gov (United States)

    Ulfa, S. M.; Mahfud, A.; Nabilah, S.; Rahman, M. F.

    2017-02-01

    Influence of water and acidic protic solvent on hydrodeoxygenation (HDO) of the furfural-acetone adduct (FAA) over Ni/Al2O3-ZrO2 (NiAZ) catalysts were investigated. The HDO of FAA was carried out in a batch reactor at 150°C for 8 hours. The NiAZ catalysts were home-made catalysts which were prepared by wet impregnation method with 10 and 20% nickel loading. The HDO reaction of FAA using 10NiAZ in water at 150°C gave alkane and oxygenated hydrocarbons at 31.41% with selectivity over tridecane (C13) in 6.67%. On the other hand, a reaction using acetic acid:water (1:19 v/v) in similar reaction condition gave only oxygenated compounds and hydrocracking product (C8-C10). The formation of tridecane (C13) was proposed by hydrogenation of C=O and C=C followed by decarboxylation without hydrocracking process. The presence of water facilitated decarboxylation mechanism by stabilized dehydrogenated derivatives of FAA.

  14. Activated Carbon, Carbon Nanofiber and Carbon Nanotube Supported Molybdenum Carbide Catalysts for the Hydrodeoxygenation of Guaiacol

    Directory of Open Access Journals (Sweden)

    Eduardo Santillan-Jimenez

    2015-03-01

    Full Text Available Molybdenum carbide was supported on three types of carbon support—activated carbon; multi-walled carbon nanotubes; and carbon nanofibers—using ammonium molybdate and molybdic acid as Mo precursors. The use of activated carbon as support afforded an X-ray amorphous Mo phase, whereas crystalline molybdenum carbide phases were obtained on carbon nanofibers and, in some cases, on carbon nanotubes. When the resulting catalysts were tested in the hydrodeoxygenation (HDO of guaiacol in dodecane, catechol and phenol were obtained as the main products, although in some instances significant amounts of cyclohexane were produced. The observation of catechol in all reaction mixtures suggests that guaiacol was converted into phenol via sequential demethylation and HDO, although the simultaneous occurrence of a direct demethoxylation pathway cannot be discounted. Catalysts based on carbon nanofibers generally afforded the highest yields of phenol; notably, the only crystalline phase detected in these samples was Mo2C or Mo2C-ζ, suggesting that crystalline Mo2C is particularly selective to phenol. At 350 °C, carbon nanofiber supported Mo2C afforded near quantitative guaiacol conversion, the selectivity to phenol approaching 50%. When guaiacol HDO was performed in the presence of acetic acid and furfural, guaiacol conversion decreased, although the selectivity to both catechol and phenol was increased.

  15. Hydrodeoxygenation of lignin-derived phenolic compounds to hydrocarbons over Ni/SiO2-ZrO2 catalysts.

    Science.gov (United States)

    Zhang, Xinghua; Zhang, Qi; Wang, Tiejun; Ma, Longlong; Yu, Yuxiao; Chen, Lungang

    2013-04-01

    Inexpensive non-sulfided Ni-based catalysts were evaluated for hydrodeoxygenation (HDO) using guaiacol as model compound. SiO2-ZrO2 (SZ), a complex oxide synthesized by precipitation method with different ratio of Si/Zr, was impregnated with Ni(NO3)2·6H2O and calcined at 500°C. Conversion rates and product distribution for guaiacol HDO at 200-340°C were determined. Guaiacol conversion reached the maximum at 300°C in the presence of Ni/SZ-3. When HDO reaction was carried out with real lignin-derived phenolic compounds under the optimal conditions determined for guaiacol, the total yield of hydrocarbons was 62.81%. These hydrocarbons were comprised of cyclohexane, alkyl-substituted cyclohexane and alkyl-substituted benzene. They have high octane number, would be the most desirable components for fungible liquid transportation fuel. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. Catalytic hydrotreatment of coal-derived naphtha using commercial catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Liaw, S.-J.; Keogh, R.A.; Thomas, G.A.; Davis, B.H. (University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research)

    Naphtha samples derived from the liquefaction of a bituminous Illinois No. 6 and a subbituminous Black Thunder coal were hydrotreated using commercial Co-Mo/Al[sub 2]O[sub 3], Ni-Mo/Al[sub 2]O[sub 3], and Ni-W/Al[sub 2]O[sub 3] catalysts. It was easier to remove the N, O and S heteroatoms from Illinois No. 6 naphtha than from the Black Thunder naphtha. Nitrogen and oxygen were more difficult to remove than sulfur in the temperature range 200-400[degree]C. Considerable differences in catalyst activity for the hydrodenitrogenation (HDN), hydrodeoxygenation (HDO), and hydrodesulfurization (HDS) reactions were observed. The Ni-Mo catalyst was found to be the most active catalyst for the HDN and HDO reactions and the least active catalyst for the HDS. The Co-Mo catalyst was the most active catalyst for the sulfur removal. For the Illinois No. 6 naphtha, a first-order reaction applies for the HDN and HDO reactions for all three catalysts. However, for the Black Thunder naphtha, the first-order reaction applies only at the lower space velocities; a large deviation is observed at higher space velocities. 11 refs., 15 figs., 4 tabs.

  17. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y.

    Science.gov (United States)

    Wang, Hongliang; Ruan, Hao; Feng, Maoqi; Qin, Yuling; Job, Heather; Luo, Langli; Wang, Chongmin; Engelhard, Mark H; Kuhn, Erik; Chen, Xiaowen; Tucker, Melvin P; Yang, Bin

    2017-04-22

    The synthesis of high-efficiency and low-cost catalysts for hydrodeoxygenation (HDO) of waste lignin to advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, and Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth-abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low-molecular-weight gaseous products. Among these catalysts, Ru-Cu/HY showed the best HDO performance, affording the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably a result of the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, and (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all bifunctional catalysts proved to be superior over the combination catalysts of Ru/Al 2 O 3 and HY zeolite. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Selective Hydrodeoxygenation of Alkyl Lactates to Alkyl Propionates with Fe-based Bimetallic Supported Catalysts.

    Science.gov (United States)

    Khokarale, Santosh Govind; He, Jian; Schill, Leonhard; Yang, Song; Riisager, Anders; Saravanamurugan, Shunmugavel

    2018-02-22

    Hydrodeoxygenation (HDO) of methyl lactate (ML) to methyl propionate (MP) was performed with various base-metal supported catalysts. A high yield of 77 % MP was obtained with bimetallic Fe-Ni/ZrO 2 in methanol at 220 °C and 50 bar H 2 . A synergistic effect of Ni increased the yield of MP significantly when using Fe-Ni/ZrO 2 instead of Fe/ZrO 2 alone. Moreover, the ZrO 2 support contributed to improve the yield as a phase transition of ZrO 2 from tetragonal to monoclinic occurred after metal doping giving rise to fine dispersion of the Fe and Ni on the ZrO 2 , resulting in a higher catalytic activity of the material. Interestingly, it was observed that Fe-Ni/ZrO 2 also effectively catalyzed methanol reforming to produce H 2 in situ, followed by HDO of ML, yielding 60 % MP at 220 °C with 50 bar N 2 instead of H 2 . Fe-Ni/ZrO 2 also catalyzed HDO of other short-chain alkyl lactates to the corresponding alkyl propionates in high yields around 70 %. No loss of activity of Fe-Ni/ZrO 2 occurred in five consecutive reaction runs demonstrating the high durability of the catalyst system. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Influence of convection on the diffusive transport and sieving of water and small solutes across the peritoneal membrane.

    Science.gov (United States)

    Asghar, Ramzana B; Diskin, Ann M; Spanel, Patrik; Smith, David; Davies, Simon J

    2005-02-01

    The three-pore model of peritoneal membrane physiology predicts sieving of small solutes as a result of the presence of a water-exclusive pathway. The purpose of this study was to measure the diffusive and convective components of small solute transport, including water, under differing convection. Triplicate studies were performed in eight stable individuals using 2-L exchanges of bicarbonate buffered 1.36 or 3.86% glucose and icodextrin. Diffusion of water was estimated by establishing an artificial gradient of deuterated water (HDO) between blood/body water and the dialysate. (125)RISA (radio-iodinated serum albumin) was used as an intraperitoneal volume marker to determine the net ultrafiltration and reabsorption of fluid. The mass transfer area coefficient (MTAC) for HDO and solutes was estimated using the Garred and Waniewski equations. The MTAC of HDO calculated for 1.36% glucose and icodextrin were similar (36.8 versus 39.7 ml/min; P = 0.3), whereas for other solutes, values obtained using icodextrin were consistently higher (P solutes is a reflection of their sieving. The increase in the MTAC of water and urea associated with an increase in convection is most likely due to increased mixing within the interstitium.

  20. Final Technical Report: Tandem and Bimetallic Catalysts for Oxidative Dehydrogenation of Light Hydrocarbon with Renewable Feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Abu-Omar, Mahdi [Purdue Univ., West Lafayette, IN (United States)

    2017-01-06

    An estimated 490 million metric tons of lignocellulosic biomass is available annually from U.S. agriculture and forestry. With continuing concerns over greenhouse gas emission, the development of efficient catalytic processes for conversion of biomass derived compounds is an important area of research. Since carbohydrates and polyols are rich in oxygen, approximately one oxygen atom per carbon, removal of hydroxyl groups via deoxygenation is needed. The necessary hydrogen required for hydrodeoxygenation (HDO) would either come from reforming biomass itself or from steam reforming of natural gas. Both processes contribute to global CO2 emission. The hope is that eventually renewable sources such as wind and solar for hydrogen production will become more viable and economic in the future. In the meantime, unconventional natural gas production in North America has boomed. As a result, light hydrocarbons present an opportunity when coupled with biomass derived oxygenates to generate valuable products from both streams without co-production of carbon dioxide. This concept is the focus of our current funding period. The objective of the project requires coupling two different types of catalysis, HDO and dehydrogenation. Our hypothesis was formulated around our success in establishing oxorhenium catalysts for polyol HDO reactions and known literature precedence for the use of iridium hydrides in alkane dehydrogenation. To examine our hypothesis we set out to investigate the reaction chemistry of binuclear complexes of oxorhenium and iridium hydride.

  1. Instrumentation and signal processing for the detection of heavy water using off axis-integrated cavity output spectroscopy technique

    Science.gov (United States)

    Gupta, A.; Singh, P. J.; Gaikwad, D. Y.; Udupa, D. V.; Topkar, A.; Sahoo, N. K.

    2018-02-01

    An experimental setup is developed for the trace level detection of heavy water (HDO) using the off axis-integrated cavity output spectroscopy technique. The absorption spectrum of water samples is recorded in the spectral range of 7190.7 cm-1-7191.5 cm-1 with the diode laser as the light source. From the recorded water vapor absorption spectrum, the heavy water concentration is determined from the HDO and water line. The effect of cavity gain nonlinearity with per pass absorption is studied. The signal processing and data fitting procedure is devised to obtain linear calibration curves by including nonlinear cavity gain effects into the calculation. Initial calibration of mirror reflectivity is performed by measurements on the natural water sample. The signal processing and data fitting method has been validated by the measurement of the HDO concentration in water samples over a wide range from 20 ppm to 2280 ppm showing a linear calibration curve. The average measurement time is about 30 s. The experimental technique presented in this paper could be applied for the development of a portable instrument for the fast measurement of water isotopic composition in heavy water plants and for the detection of heavy water leak in pressurized heavy water reactors.

  2. One-Pot Process for Hydrodeoxygenation of Lignin to Alkanes Using Ru-Based Bimetallic and Bifunctional Catalysts Supported on Zeolite Y

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Ruan, Hao [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Feng, Maoqi [Chemistry & Chemical Engineering Division, Southwest Research Institute, San Antonio TX 78238 USA; Qin, Yuling [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Job, Heather [Pacific Northwest National Laboratory, 902 Battelle Blvd Richland WA 99354 USA; Luo, Langli [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Wang, Chongmin [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Engelhard, Mark H. [Environmental Molecular Sciences Laboratory, 3335 Q Ave Richland WA 99354 USA; Kuhn, Erik [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Chen, Xiaowen [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO. 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-03-16

    The synthesis of high-efficiency and low-cost multifunctional catalysts for hydrodeoxygenation (HDO) of waste lignin into advanced biofuels is crucial for enhancing current biorefinery processes. Inexpensive transition metals, including Fe, Ni, Cu, Zn, were severally co-loaded with Ru on HY zeolite to form bimetallic and bifunctional catalysts. These catalysts were subsequently tested for HDO conversion of softwood lignin and several lignin model compounds. Results indicated that the inexpensive earth abundant metals could modulate the hydrogenolysis activity of Ru and decrease the yield of low molecular weight gaseous side-products. Among all the prepared catalysts, Ru-Cu/HY showed the best HDO performance, giving the highest selectivity to hydrocarbon products. The improved catalytic performance of Ru-Cu/HY was probably due to the following three factors: (1) high total and strong acid sites, (2) good dispersion of metal species and limited segregation, (3) high adsorption capacity for polar fractions, including hydroxyl groups and ether bonds. Moreover, all the bifunctional catalysts were proven to be superior over the combination catalysts of Ru/Al2O3 and HY zeolite, and this could be attributed to the “intimacy criterion”. The practical use of the designed catalysts would be promising in lignin valorization.

  3. Seasonal, synoptic and diurnal variation of atmospheric water-isotopologues in the boundary layer of Southwestern Germany caused by plant transpiration, cold-front passages and dewfall.

    Science.gov (United States)

    Christner, Emanuel; Dyroff, Christoph; Kohler, Martin; Zahn, Andreas; Gonzales, Yenny; Schneider, Matthias

    2013-04-01

    Atmospheric water is an enormously crucial trace gas. It is responsible for ~70 % of the natural greenhouse effect (Schmidt et al., JGR, 2010) and carries huge amounts of latent heat. The isotopic composition of water vapor is an elegant tracer for a better understanding and quantification of the extremely complex and variable hydrological cycle in Earth's atmosphere (evaporation, cloud condensation, rainout, re-evaporation, snow), which in turn is a prerequisite to improve climate modeling and predictions. As H216O, H218O and HDO differ in vapor pressure and mass, isotope fractionation occurs due to condensation, evaporation and diffusion processes. In contrast to that, plants are able to transpire water with almost no isotope fractionation. For that reason the ratio of isotopologue concentrations in the boundary layer (BL) provides, compared to humidity measurements alone, independent and additional constraints for quantifying the strength of evaporation and transpiration. Furthermore the isotope ratios contain information about transport history of an air mass and microphysical processes, that is not accessible by humidity measurements. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) a commercial Picarro Analyzer L2120-i is operated at Karlsruhe in Southwestern Germany, which is continuously measuring the isotopologues H216O, HDO and H218O of atmospheric water vapor since January 2012. A one year record of H216O, HDO and H218O shows clear seasonal, synoptic and diurnal characteristics and reveals the main driving processes affecting the isotopic composition of water vapor in the Middle European BL. Changes in continental plant transpiration and evaporation throughout the year lead to a slow seasonal HDO/H216O-variation, that cannot be explained by pure Rayleigh condensation. Furthermore, cold-front passages from NW lead to fast and pronounced depletion of the HDO/H216O-ratio within

  4. Hydrodeoxygenation of coal using organometallic catalyst precursors

    Science.gov (United States)

    Kirby, Stephen R.

    2002-04-01

    The objective of this dissertation was to determine the desirability of organometallic compounds for the hydrodeoxygenation (HDO) of coal during liquefaction. The primary focus of this study was the removal of phenol-like compounds from coal liquids for the production of a thermally stable jet fuel. Investigation of the HDO ability of an organometallic compound containing both cobalt and molybdenum (CoMo-T2) was achieved using a combination of model compound and coal experiments. Model compounds were chosen representing four oxygen functional groups present in a range of coals. Electron density and bond order calculations were performed for anthrone, dinaphthyl ether, xanthene, di-t-butylmethylphenol, and some of their derivatives to ascertain a potential order of hydrogenolysis and hydrogenation reactivity for these compounds. The four model compounds were then reacted with CoMo-T2, as well as ammonium tetrathiomolybdate (ATTM). Products of reaction were grouped as compounds that had undergone deoxygenation, those that had aromatic rings reduced, those that were products of both reaction pathways, and those produced through other routes. ATTM had an affinity for both reaction types. Its reaction order for the four model compounds with respect to deoxygenated compounds was the same as that estimated from electron density calculations for hydrogenolysis reactivity. CoMo-T2 appeared to show a preference toward hydrogenation, although deoxygenated products were still achieved in similar, or greater, yields, for almost all the model compounds. The reactivity order achieved for the four compounds with CoMo-T2 was similar to that estimated from bond order calculations for hydrogenation reactivity. Three coals were selected representing a range of coal ranks and oxygen contents. DECS-26 (Wyodak), DECS-24 (Illinois #6), and DECS-23 (Pittsburgh #8) were analyzed by CPMAS 13C NMR and pyrolysis-GC-MS to determine the functional groups comprising the oxygen content of these

  5. Upgrading pyrolysis bio-oil to biofuel over bifunctional Co-Zn/HZSM-5 catalyst in supercritical methanol

    International Nuclear Information System (INIS)

    Cheng, Shouyun; Wei, Lin; Julson, James; Muthukumarappan, Kasiviswanathan; Kharel, Parashu Ram

    2017-01-01

    Highlights: • Integration of Co-Zn/HZSM-5 and supercritical methanol was used for bio-oil hydrodeoxygenation. • Co-Zn/HZSM-5 exhibited higher effectiveness than Co/HZSM-5 or Zn/HZSM-5. • 15%Co5%Zn/HZSM-5 produced biofuel with the highest hydrocarbons content at 35.33%. • Loading of Co and/or Zn did not change crystalline structure of HZSM-5. • Hydrogenation and esterification are main reactions in bio-oil hydrodeoxygenation. - Abstract: The role of catalyst is essential in processes of upgrading biomass pyrolysis bio-oil into hydrocarbon biofuel. While the majority of heterogeneous catalytic processes are conducted in the presence of gas (nearly ideal) or liquid phase, a growing number of processes are utilizing supercritical fluids (SCFs) as reaction media. Although hydrodeoxygenation (HDO) is proven a promising process for pyrolysis bio-oil upgrading to hydrocarbon biofuel, catalyst efficiency remains a challenge. Integrating heterogeneous catalysts with SCFs in a bio-oil HDO process was investigated in this study. Bifunctional Co-Zn/HZSM-5 catalysts were firstly used to upgrade bio-oil to biofuel in supercritical methanol. The loading of Co and Zn did not change HZSM-5 crystalline structure. Physicochemical properties of biofuel produced by Co and/or Zn loaded HZSM-5 catalysts such as water content, total acid number, viscosity and higher heating value improved. Bimetallic Co-Zn/HZSM-5 catalysts showed enhanced reactions of decarboxylation and decarbonylation that resulted in higher yields of CO and CO 2 . Bimetallic Co-Zn/HZSM-5 catalysts were more effective for bio-oil HDO than monometallic Co/HZSM-5 or Zn/HZSM-5 catalyst , which was attributed to the synergistic effect of Co and Zn on HZSM-5 support. Bimetallic Co-Zn/HZSM-5 catalysts increased biofuel yields and hydrocarbons contents in biofuels in comparison with monometallic Co/HZSM-5 and Zn/HZSM-5 catalysts. 5%Co15%Zn/HZSM-5 catalyst generated the highest biofuel yield at 22.13 wt.%, and 15%Co5

  6. Development of Bio-Oil Commodity Fuel as a Refinery Feedstock from High Impact Algae Biomass

    Energy Technology Data Exchange (ETDEWEB)

    Kastner, James [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemical Engineering; Mani, Sudhagar [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemical Engineering; Das, K. C. [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemical Engineering; Hilten, Roger [Univ. of Georgia, Athens, GA (United States). Dept. of Biochemical Engineering; Jena, Umakanta [Desert Research Inst. (DRI), Reno, NV (United States)

    2014-11-30

    A two-stage hydrothermal liquefaction (HTL) process was developed to 1) reduce nitrogen levels in algal oil, 2) generate a nitrogen rich stream with limited inhibitors for recycle and algae cultivation, and 3) improve downstream catalytic hydrodenitrogenation and hydrodeoxygenation of the algal oil to refinery intermediates. In the first stage, low temperature HTL was conducted at 125, 175, and 225°C at holding times ranging from 1 to 30 min (time at reaction temperature). A consortium of three algal strains, namely Chlorella sorokiniana, Chlorella minutissima, and Scenedesmus bijuga were used to grow and harvest biomass in a raceway system – this consortium is called the UGA Raceway strain throughout the report. Subsequent analysis of the final harvested product indicated that only two strains predominated in the final harvest - Chlorella sorokiniana and Scenedesmus bijuga. Two additional strains representing a high protein (Spirulina platensis) and high lipid algae (Nannochloropsis) strains were also used in this study. These strains were purchased from suppliers. S. platensis biomass was provided by Earthrise Nutritionals LLC (Calipatria, CA) in dry powder form with defined properties, and was stored in airtight packages at 4°C prior to use. A Nannochloropsis paste from Reed Mariculture was purchased and used in the two-stage HTL/HDO experiments. The solids and liquids from this low temperature HTL pretreatment step were separated and analyzed, leading to the following conclusions. Overall, these results indicate that low temperature HTL (200-250°C) at short residence times (5-15 min) can be used to lyse algae cells and remove/separate protein and nitrogen before subsequent higher temperature HTL (for lipid and other polymer hydrolysis) and HDO. The significant reduction in nitrogen when coupled with low protein/high lipid algae cultivation methods at scale could significantly improve downstream catalytic HDO results. However, significant barriers and

  7. Hydrogenation and hydrodeoxygenation of difurfurylidene acetone to liquid alkanes over Raney Ni and the supported Pt catalysts

    International Nuclear Information System (INIS)

    Li, Yuping; Huang, Xiaoming; Zhang, Qian; Chen, Lungang; Zhang, Xinghua; Wang, Tiejun; Ma, Longlong

    2015-01-01

    Highlights: • The C_8−C_1_4 alkane yield of 82.9% was obtained in the two-step hydrogenation/HDO process. • Protonation effect from methanol solvent increased F_2A conversion in the two-step process. • The rate-determining step was acyl C=O bond hydrogenation in the first step of F_2A hydrogenation. • The acidic centers from SiO_2−ZrO_2 activated the acyl and oxygen atoms of intermediates. • Acidity of SiO_2−ZrO_2 and Pt active centers of 1 wt%Pt/SiO_2−ZrO_2 resulted stable HDO performance. - Abstract: Direct HDO process for difurfurylidene acetone dimer (F_2A) conversion to liquid alkanes (C_8−C_1_4) at 260 °C in a batch reactor was investigated over different material supported 1 wt%Pt catalysts, including SAPO-11, HZSM-5, SiO_2−Al_2O_3, MCM-22, and home-made SiO_2−ZrO_2. C_8−C_1_4 alkanes of 55.8% was obtained over the optimized 1 wt%Pt/SiO_2−ZrO_2 due to its proper pore size of 9.0 nm and moderate acidic centers, together with more than 10% carbon yield of the oxygenated hydrocarbons, including C_1_1−C_1_3 chain alcohols & ketones and the hydrogenated F_2A dimers with furan ring (H-F_2A dimers). To improve the liquid alkane yield, a two-step process for F_2A conversion was also investigated, which included low-temperature hydrogenation at 50 °C over Raney Ni catalyst in a batch reactor and the subsequent high-temperature hydrodeoxygenation (HDO) at 280 °C over 1 wt%Pt/SiO_2−ZrO_2 in a fixed-bed reactor. The selectivity of 1,5-di(tetrahydro-2-furanyl)-3-pentanol (II-c) was the highest of 83.0% among the hydrogenated intermediates of H-F_2A dimers due to the protonation effect of methanol as the solvent and the hydrogenation of C=C bonds by Ni active centers. In the same time, the high content of this saturated alcohol H-dimer of II-C increased the solubility and stability of the intermediates in methanol solvent. High carbon yield of C_8−C_1_4 alkanes of 82.9%(mol) was obtained after oxygen atom removal from H-F_2A dimers via

  8. Relation between frequency and H bond length in heavy water: Towards the understanding of the unusual properties of H bond dynamics in nanoporous media

    International Nuclear Information System (INIS)

    Pommeret, Stanislas; Leicknam, Jean-Claude; Bratos, Savo; Musat, Raluca; Renault, Jean Philippe

    2009-01-01

    The published work on H bond dynamics mainly refers to diluted solutions HDO/D 2 O rather than to normal water. The reasons for this choice are both theoretical and experimental. Mechanical isolation of the OH vibrator eliminating the resonant energy transfer makes it a better probe of the local H bond network, while the dilution in heavy water reduces the infrared absorption, which permits the use of thicker experimental cells. The isotopic substitution does not alter crucially the nature of the problem. The length r of an OH . . . O group is statistically distributed over a large interval comprised between 2.7 and 3.2 A with a mean value r 0 = 2.86 A. Liquid water may thus be viewed as a mixture of hydrogen bonds of different length. Two important characteristics of hydrogen bonding must be mentioned. (i) The OH stretching vibrations are strongly affected by this interaction. The shorter the length r of the hydrogen bond, the strongest the H bond link and the lower is its frequency ω: the covalent OH bond energy is lent to the OH. . .O bond and reinforces the latter. A number of useful relationships between ω and r were published to express this correlation. The one adopted in our previous work is the relationship due to Mikenda. (ii) Not only the OH vibrations, but also the HDO rotations are influenced noticeably by hydrogen bonding. This is due to steric forces that hinder the HDO rotations. As they are stronger in short than in long hydrogen bonds, rotations are slower in the first case than in the second. This effect was only recently discovered, but its existence is hardly to be contested. In the present contribution, we want to revisit the relationship between the frequency of the OH vibrator and the distance OH. . .O.

  9. Glucose- and Cellulose-Derived Ni/C-SO3H Catalysts for Liquid Phase Phenol Hydrodeoxygenation

    Energy Technology Data Exchange (ETDEWEB)

    Kasakov, Stanislav; Zhao, Chen; Barath, Eszter; Chase, Zizwe A.; Fulton, John L.; Camaioni, Donald M.; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A.

    2015-01-19

    Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalyzed the reduction of phenol to cyclohexanol in water. The state of 3 – 5 nm grafted Ni particles was analyzed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt.% C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support.

  10. A Novel Method for Pain Relief in Chronic Pancreatitis: an Old Drug in a New Pack: a Controlled Study.

    Science.gov (United States)

    Pujahari, Aswini Kumar

    2017-12-01

    Most of pain-relieving agents in chronic pancreatitis are nonspecific and unpredictable. Omeprazole induces hypergastrinemia due to reduced gastric acidity. Raised serum gastrin, in turn, modulates to reduce secretin level. Secretin is responsible for secretion of almost 80 % bicarbonate-rich pancreatic juice from the ductular epithelium without affecting enzyme output. It is a prospective randomized study in patients with CT-confirmed chronic pancreatitis. The control group got the standard care and 60 mg of omeprazole twice daily was added to the test group. Absence of pain relief at 14 days was considered as failure. Pain relief, weight gain and any toxic effect of omeprazole were reviewed at 12 months. One hundred thirty-seven cases were included, with an age range of 19 to 72 years. (mean 42.67). The majority of them were alcoholic males. At 2 weeks, pain relief was noted in 47/69(68.1 %) and 63/65(96.96 %) in the control and omeprazole group, respectively. At the end of 1 year, the omeprazole group had greater weight gain (95 %) than the control group (69.5 %). All the pseudocysts in the omeprazole group and most in the control group resolved. No side effect of omeprazole was seen. The high-dose omeprazole (HDO) group of patients had significantly better pain relief in chronic pancreatitis than those treated with conventional therapy. A high number of cases gained weight in the HDO group than the controlled group. No patient had clinical, endoscopic, biochemical, or haematological toxicity of HDO. More studies are necessary.

  11. OT1_ebergin_5: A Systematic Survery of the Water D to H Ratio in Hot Molecular Cores

    Science.gov (United States)

    Bergin, E.

    2010-07-01

    The D/H ratio of water and the enrichment of HDO relative to H2O in comets, oceans, and interstellar water vapor, has been posited as one of the primary links between chemistry in the cold (T = 10-20 K) dense interstellar medium (ISM) and chemistry in the Solar Nebula. However, there are only ~10 measurements of HDO/H2O, even in hot (T > 100 K) molecular cores, which have the most favorable chemistry (due to fossil evaporation of D-enriched ices) and excitation. In addition the existing measurements have a wide range of uncertainty, making it impossible to discern the presence of source-to-source variations, which could hint at the origin of deuterium enrichments in the dense ISM. We propose here to change this statistic with a systematic survey of HDO and H2O in a sample of 20 hot molecular cores spanning a two order of magnitude range in mass and luminosity. This will increase the number of known water D/H ratios by ~200%. This program is unique in scope for Herschel and requires the uniformity in calibration and high spectral resolution offered by the HIFI instrument. With the stability of HIFI we will be able to derive D/H ratios with significantly less uncertainty. Our observations will be combined with theoretical chemical models to explore the statistics offered by this sample. By looking at a large number of objects with a range of conditions we aim to unlock the secrets of water deuteration in the interstellar space.

  12. Deoxygenation of palm kernel oil to jet fuel-like hydrocarbons using Ni-MoS_2/γ-Al_2O_3 catalysts

    International Nuclear Information System (INIS)

    Itthibenchapong, Vorranutch; Srifa, Atthapon; Kaewmeesri, Rungnapa; Kidkhunthod, Pinit; Faungnawakij, Kajornsak

    2017-01-01

    Highlights: • The Ni-MoS_2/γ-Al_2O_3 catalysts synthesized using thiourea solution processing. • The Ni-MoS_2 showed semi-amorphous crystallinity with crystallite size of 5–10 nm. • The Ni K-edge XANES and EXAFS indicated the Ni substitution in MoS_2 structure. • A high yield of jet fuel-like hydrocarbon (>90%) from the palm kernel oil feedstock. • The HDO pathway was highly selective, while the DCO_2 and DCO pathways were minor. - Abstract: In the current study, palm kernel oil was used as a renewable feedstock for production of jet fuel-like hydrocarbons via the deoxygenation over the Ni-MoS_2/γ-Al_2O_3 catalyst. The dominant C12 fatty acid content in palm kernel oil makes it promising for jet fuel application. Synthesized by a liquid processing method with thiourea organosulfur agent, the catalyst revealed MoS_2 structure with low stacking, while Ni substitution in the MoS_2 structure and interaction with the Al_2O_3 support were determined based on the Ni K-edge XANES and EXAFS results. A high hydrodeoxygenation (HDO) activity, which as the major pathway in the deoxygenation, was observed upon application of a H_2 pressure of 30–50 bar over Ni-MoS_2/γ-Al_2O_3. The optimum product yield of approximately 92% was obtained mainly from the HDO pathway (∼60%) with 58% selectivity to C10–C12 jet fuel hydrocarbons. The flow property of the jet fuel-like hydrocarbons was more desirable than those obtained from palm olein oil-derived fuel.

  13. Catalytic upgrading of oleic acid into biofuel using Mo modified zeolite supported Ni oxalate catalyst functionalized with fluoride ion

    International Nuclear Information System (INIS)

    Ayodele, O.B.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

    2014-01-01

    Highlights: • Modification of zeolite with freshly prepared molybdenum oxalate. • Functionalization of Ni oxalate with HF and incorporation into Mo modified zeolite. • Characterization of synthesized Mo modified zeolite supported Ni oxalate catalyst. • Deoxygenation of oleic acid with the synthesized zeolite supported catalyst. • Reusability study on the synthesized zeolite supported catalyst. - Abstract: In this study, fluoride ion functionalized nickel oxalate supported on molybdenum modified zeolite (NiMoFOx/Zeol) catalyst was synthesized, characterized and tested on the hydrodeoxygenation (HDO) of oleic acid (OA) into paraffinic fuel. The NiMoFOx/Zeol characterization results confirmed the presence of both Ni and Mo as well as the formation of NiMoO 4 which is a highly HDO reactive specie at 2θ value of 43.6° according to the XRD result. NiMoFOx/Zeol also showed loss in crystallinity and reduction in the average particle size leading to increase in the pore volume and specific surface area due to the combined effects of fluoride ion presence, oxalic acid functionalization and calcination. The effect of temperature, pressure and NiMoFOx/Zeol loading studied showed that initial increase in their values increased the yield of the target fractions until some points where reduction was observed. The best observed experimental conditions to hydrodeoxygenate 40 g (∼45 mL) of OA into 75% n-C 18 and 23% i-C 18 were 360 °C, 30 mg NiMoFOx/Zeol loading and 20 bar using 100 mL H 2 /min. The presence of i-C 18 was due to the functionalization of the catalyst with fluoride ion. The catalyst reusability result displayed excellent qualities with marginal loss of only 2% in activity after third reuse due to the improved synthesis protocol that employed organometallic precursor. The results are strongly encouraging for further studies toward industrialization of HDO process

  14. Bifunctional Molybdenum Polyoxometalates for the Combined Hydrodeoxygenation and Alkylation of Lignin-Derived Model Phenolics.

    Science.gov (United States)

    Anderson, Eric; Crisci, Anthony; Murugappan, Karthick; Román-Leshkov, Yuriy

    2017-05-22

    Reductive catalytic fractionation of biomass has recently emerged as a powerful lignin extraction and depolymerization method to produce monomeric aromatic oxygenates in high yields. Here, bifunctional molybdenum-based polyoxometalates supported on titania (POM/TiO 2 ) are shown to promote tandem hydrodeoxygenation (HDO) and alkylation reactions, converting lignin-derived oxygenated aromatics into alkylated benzenes and alkylated phenols in high yields. In particular, anisole and 4-propylguaiacol were used as model compounds for this gas-phase study using a packed-bed flow reactor. For anisole, 30 % selectivity for alkylated aromatic compounds (54 % C-alkylation of the methoxy groups by methyl balance) with an overall 72 % selectivity for HDO at 82 % anisole conversion was observed over H 3 PMo 12 O 40 /TiO 2 at 7 h on stream. Under similar conditions, 4-propylguaiacol was mainly converted into 4-propylphenol and alkylated 4-propylphenols with a selectivity to alkylated 4-propylphenols of 42 % (77 % C-alkylation) with a total HDO selectivity to 4-propylbenzene and alkylated 4-propylbenzenes of 4 % at 92 % conversion (7 h on stream). Higher catalyst loadings pushed the 4-propylguaiacol conversion to 100 % and resulted in a higher selectivity to propylbenzene of 41 %, alkylated aromatics of 21 % and alkylated phenols of 17 % (51 % C-alkylation). The reactivity studies coupled with catalyst characterization revealed that Lewis acid sites act synergistically with neighboring Brønsted acid sites to simultaneously promote alkylation and hydrodeoxygenation activity. A reaction mechanism is proposed involving activation of the ether bond on a Lewis acid site, followed by methyl transfer and C-alkylation. Mo-based POMs represent a versatile catalytic platform to simultaneously upgrade lignin-derived oxygenated aromatics into alkylated arenes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Catalytic hydrodeoxygenation of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolites

    International Nuclear Information System (INIS)

    Lee, Hyung Won; Jun, Bo Ram; Kim, Hannah; Kim, Do Heui; Jeon, Jong-Ki; Park, Sung Hoon; Ko, Chang Hyun; Kim, Tae-Wan; Park, Young-Kwon

    2015-01-01

    The hydrodeoxygenation of 2-methoxy phenol and dibenzofuran, which are representative model compounds of bio-oil, was performed using two different Pt/mesoporous zeolite catalysts, Pt/mesoporous Y and Pt/mesoporous MFI. The reforming of 2-methoxy phenol and dibenzofuran via catalytic hydrodeoxygenation was investigated using a batch reactor at 40 bar and 250 °C. The characteristics of the catalysts were analyzed by N 2 adsorption-desorption, X-ray diffraction, and NH 3 temperature programmed desorption. Pt/mesoporous zeolite catalysts containing both strong acid sites and mesopores showed the higher conversion of 2-methoxy phenol than Pt/SiO 2 and Pt/Si-MCM-48 with no acid sites, Pt/γ-Al 2 O 3 , and a mixture of mesoporous Y and Pt/SiO 2 , indicating the importance of both Pt and strong acid sites for high catalytic activity. Among the two Pt/mesoporous zeolite catalysts tested, the conversion of 2-methoxy phenol to cyclohexane over Pt/mesoporous Y was much higher than that over the Pt/mesoporous MFI. This was attributed to the better textural properties, such as surface area, pore volume and micropore size, compared to those of Pt/mesoporous MFI. The catalytic conversions of dibenzofuran obtained using two Pt/mesoporous zeolite catalysts were similar and the main products were 1,1′-bicyclohexyl, cyclopentylmethyl-cyclohexane and cyclohexane. In addition, the reaction mechanisms of 2-methoxy phenol and dibenzofuran over Pt/mesoporous zeolite were suggested. - Highlights: • HDO of 2-methoxy phenol and dibenzofuran was performed over Pt/mesoporous zeolites. • Pt/mesoporous zeolites have mesopores and strong acid sites. • Main product of HDO of 2-methoxy phenol was cyclohexane. • Main products of HDO of dibenzofuran were bicyclohexyl (BCH), i-BCH, and cyclohexane

  16. Preparation and characterization of alumina supported nickel-oxalate catalyst for the hydrodeoxygenation of oleic acid into normal and iso-octadecane biofuel

    International Nuclear Information System (INIS)

    Ayodele, O.B.; Togunwa, Olayinka S.; Abbas, Hazzim F.; Daud, Wan Mohd Ashri Wan

    2014-01-01

    Highlights: • Preparation of nickel oxalate complex as catalyst precursor. • Incorporation of nickel oxalate complex into alumina support. • Characterization of the alumina supported nickel oxalate catalyst. • Hydrodeoxygenation of oleic acid with nickel oxalate catalyst. • Nickel oxalate catalyst reusability studies. - Abstract: In this study, nickel II oxalate complex (NiOx) was prepared by functionalization of nickel with oxalic acid (OxA) and incorporated into Al 2 O 3 to synthesize alumina supported nickel oxalate (NiOx/Al 2 O 3 ) catalyst for the hydrodeoxygenation (HDO) of oleic acid (OA) into biofuel. The synthesized NiOx/Al 2 O 3 was characterized and the X-ray fluorescence and elemental dispersive X-ray results showed that NiOx was successfully incorporated into the structure of Al 2 O 3 . The X-ray diffraction and Raman spectroscopy results confirmed that highly dispersed Ni species are present in the NiOx/Al 2 O 3 due to the functionalization with OxA. The catalytic activity of the NiOx/Al 2 O 3 on the HDO of OA produced a mixture of 21% iso-C18 and 72% n-C18 at a 360 °C, 20 bar, 30 mg NiOx/Al 2 O 3 loading pressure and gas flow rate of 100 mL/min. The presence of i-C 18 was ascribed to the OxA functionalization which increased the acidity of NiOx/Al 2 O 3 . The NiOx/Al 2 O 3 reusability study showed consistent HDO ability after 5 runs. These results are promising for further research into biofuel production for commercialization

  17. Glucose- and cellulose-derived Ni/C-SO3H catalysts for liquid phase phenol hydrodeoxygenation.

    Science.gov (United States)

    Kasakov, Stanislav; Zhao, Chen; Baráth, Eszter; Chase, Zizwe A; Fulton, John L; Camaioni, Donald M; Vjunov, Aleksei; Shi, Hui; Lercher, Johannes A

    2015-01-19

    Sulfonated carbons were explored as functionalized supports for Ni nanoparticles to hydrodeoxygenate (HDO) phenol. Both hexadecane and water were used as solvents. The dual-functional Ni catalysts supported on sulfonated carbon (Ni/C-SO3H) showed high rates for phenol hydrodeoxygenation in liquid hexadecane, but not in water. Glucose and cellulose were precursors to the carbon supports. Changes in the carbons resulting from sulfonation of the carbons resulted in variations of carbon sheet structures, morphologies and the surface concentrations of acid sites. While the C-SO3H supports were active for cyclohexanol dehydration in hexadecane and water, Ni/C-SO3H only catalysed the reduction of phenol to cyclohexanol in water. The state of 3-5 nm grafted Ni particles was analysed by in situ X-ray absorption spectroscopy. The results show that the metallic Ni was rapidly formed in situ without detectable leaching to the aqueous phase, suggesting that just the acid functions on Ni/C-SO3H are inhibited in the presence of water. Using in situ IR spectroscopy, it was shown that even in hexadecane, phenol HDO is limited by the dehydration step. Thus, phenol HDO catalysis was further improved by physically admixing C-SO3H with the Ni/C-SO3H catalyst to balance the two catalytic functions. The minimum addition of 7 wt % C-SO3H to the most active of the Ni/C-SO3H catalysts enabled nearly quantitative conversion of phenol and the highest selectivity (90%) towards cyclohexane in 6 h, at temperatures as low as 473 K, suggesting that the proximity to Ni limits the acid properties of the support. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Basic study of catalyst aging in the H-coal process

    Energy Technology Data Exchange (ETDEWEB)

    Cable, T.L.; Massoth, F.E.; Thomas, M.G.

    1985-04-01

    Samples of CoMo/Al/sub 2/O/sub 3/ catalysts used in an H-coal process demonstration run were studied to determine causes of catalyst deactivation. Physical and surface properties of the aged and regenerated catalysts were examined. Model compounds were used to assess four catalyst activity functions, viz., hydrodesulfurization (HDS), hydrogenation, cracking and hydrodeoxygenation (HDO). Other tests were performed to study the effects of coke and metals separately on the four catalyst activity functions. Catalyst coke content and metal deposits first increased rapidly, then more gradually with exposure time in the process run. Surface area and pore volume markedly decreased with exposure time. Catalyst activities of aged catalysts showed a rapid decline with exposure time. One-day exposure to coal resulted in significant losses in HDS and hydrogenation activities and nearly complete loss in cracking and HDO activities. Although metal deposits caused some permanent catalyst deactivation, coke had a much greater effect. Regenerated catalysts showed less recovery of catalytic activity as processing time increased. These results agreed well with product inspections from the process run. Oxygen chemisorption on aged-regenerated catalysts decreased with catalyst exposure time, indicating a significant loss of active sites. However, ESCA results showed no evidence of extensive sintering of the active MoS/sub 2/ phase. Permanent deactivation of the longer-time exposed catalysts can be ascribed, at least partly, to lateral growth of the active molybdenum sulfide phase. In addition, some loss in cobalt promotion occurred early in the process, which may account for the rapid loss in HDS and HDO activity in regenerated catalysts. 24 references.

  19. Hydrodeoxygenation of prairie cordgrass bio-oil over Ni based activated carbon synergistic catalysts combined with different metals.

    Science.gov (United States)

    Cheng, Shouyun; Wei, Lin; Zhao, Xianhui; Kadis, Ethan; Cao, Yuhe; Julson, James; Gu, Zhengrong

    2016-06-25

    Bio-oil can be upgraded through hydrodeoxygenation (HDO). Low-cost and effective catalysts are crucial for the HDO process. In this study, four inexpensive combinations of Ni based activated carbon synergistic catalysts including Ni/AC, Ni-Fe/AC, Ni-Mo/AC and Ni-Cu/AC were evaluated for HDO of prairie cordgrass (PCG) bio-oil. The tests were carried out in the autoclave under mild operating conditions with 500psig of H2 pressure and 350°C temperature. The catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) and transmission electron microscope (TEM). The results show that all synergistic catalysts had significant improvements on the physicochemical properties (water content, pH, oxygen content, higher heating value and chemical compositions) of the upgraded PCG bio-oil. The higher heating value of the upgraded bio-oil (ranging from 29.65MJ/kg to 31.61MJ/kg) improved significantly in comparison with the raw bio-oil (11.33MJ/kg), while the oxygen content reduced to only 21.70-25.88% from 68.81% of the raw bio-oil. Compared to raw bio-oil (8.78% hydrocarbons and no alkyl-phenols), the Ni/AC catalysts produced the highest content of gasoline range hydrocarbons (C6-C12) at 32.63% in the upgraded bio-oil, while Ni-Mo/AC generated the upgraded bio-oil with the highest content of gasoline blending alkyl-phenols at 38.41%. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Synergistic routes to liquid fuel for a petroleum-deprived future

    Energy Technology Data Exchange (ETDEWEB)

    Agrawal, R.; Singh, N.R. [Purdue University, West Lafayette, IN (United States). School of Chemical Engineering

    2009-07-15

    When compared with biomass gasification/Fischer-Tropsch synthesis, hydropyrolysis/hydrodeoxygenation (HDO)-based processes have a potential to achieve high biomass carbon conversion to liquid fuel with much lower amounts of supplementary H{sub 2}. On the basis of this observation, we suggest a Hydrogen Bio-oil (H{sub 2}Bioil) process using fast hydropyrolysis/HDO that has a potential to produce nearly double the amount of liquid fuel when compared with the existing biofuel processes while requiring only modest quantities of supplementary H{sub 2}. The optimal operating mode for the H{sub 2}Bioil process is suggested to be in an entrained bed mode in presence of H{sub 2} with gas phase HDO of hydropyrolyzed vapors. A remarkable result due to reduced need for the supplementary H{sub 2} is that it provides synergistic integration of the H(2)Bioil process with a coal gasification power plant or a small scale steam natural gas (NG) reformer leading to a dramatic increase in the liquid fuel production from biomass and coal or NG. Here, hot synthesis gas (T>500{sup o}C) from a coal gasifier or methane reformer supplies H{sub 2}/CO for hydropyrolysis and deoxygenation as well as heat for the process. This result is exciting, because it presents us with an option to build integrated H{sub 2}Bioil processes sooner rather than later when the cost effective H{sub 2}, becomes available from a carbon-free energy source such as solar or nuclear. The H{sub 2}Bioil process and its integrated version with a small scale NG reformer have strong potential to be attractive on a small scale while being more efficient than any current biomass to liquid fuel process in operation.

  1. Methane measurement by the Pioneer Venus large probe neutral mass spectrometer

    Science.gov (United States)

    Donahue, T. M.; Hodges, R. R., Jr.

    1992-12-01

    The Pioneer Venus Large Probe Mass Spectrometer detected a large quantity of methane as it descended below 20 km in the atmosphere of Venus. Terrestrial methane and Xe-136, both originating in the same container and flowing through the same plumbing, were deliberately released inside the mass spectrometer for instrumental reasons. However, the Xe-136 did not exhibit behavior similar to methane during Venus entry, nor did CH4 in laboratory simulations. The CH4 was deuterium poor compared to Venus water and hydrogen. While the inlet to the mass spectrometer was clogged with sulfuric acid droplets, significant deuteration of CH4 and its H2 progeny was observed. Since the only source of deuterium identifiable was water from sulfuric acid, we have concluded that we should correct the HDO/H2O ratio in Venus water from 3.2 x 10-2 to (5 plus or minus 0.7) x 10-2. When the probe was in the lower atmosphere, transfer of deuterium from Venus HDO and HD to CH4 can account quantitatively for the deficiencies recorded in HDO and HD below 10 km, and consequently, the mysterious gradients in water vapor and hydrogen mixing ratios we have reported. The revision in the D/H ratio reduces the mixing ratio of water vapor (and H2) reported previously by a factor of 3.2/5. We are not yet able to say whether the methane detected was atmospheric or an instrumental artifact. If it was atmospheric, its release must have been episodic and highly localized. Otherwise, the large D/H ratio in Venus water and hydrogen could not be maintained.

  2. Study on the hydrodeoxygenative upgrading of crude bio-oil produced from woody biomass by fast pyrolysis

    International Nuclear Information System (INIS)

    Kim, Tae-Seung; Oh, Shinyoung; Kim, Jae-Young; Choi, In-Gyu; Choi, Joon Weon

    2014-01-01

    Crude bio-oil produced from fast pyrolysis of yellow poplar wood was subjected to HDO (hydrodeoxygenation) for the purpose of reducing water content as well as increasing heating value. HDO was performed in an autoclave reactor at three different reaction factors: temperature (250–370 °C), reaction time (40–120 min), and Pd/C catalyst loading (0–6 wt%) under hydrogen atmosphere. After completion of HDO, gas, char, and two immiscible liquid products (light oil and heavy oil) were obtained. Liquid products were less acidic and contained less water than crude bio-oil. Water content of heavy oil was ranged between 0.4 wt% and 1.9 wt%. Heating values of heavy oil were estimated between 28.7 and 37.4 MJ/kg, which was about twice higher than that of crude bio-oil. Elemental analysis revealed that heavy oil had a lower O/C ratio (0.17–0.36) than crude bio-oil (0.71). H/C ratio of heavy oil decreased from 1.50 to 1.32 with an increase of temperature from 250 °C to 350 °C, respectively. - Highlights: • Bio-oil was subjected to hydrodeoxygenation with Pd/C catalyst in supercritical ethanol. • Gas, char and two immiscible liquids (light/heavy oil) were obtained as final products. • Ethanol addition reduced the char formation during hydrodeoxygenation. • The heavy oil was characteristic to less acidic and less water content than bio-oil. • Higher heating value of the heavy oil was measured to 28.7–37.4 MJ/kg

  3. Inconsistency in Reporting Abstention and Heavy Drinking Frequency: Associations with Sex and Socioeconomic Status, and Potential Impacts

    Science.gov (United States)

    Kydd, Robyn M.; Connor, Jennie

    2015-01-01

    Aims: To describe inconsistencies in reporting past-year drinking status and heavy drinking occasions (HDOs) on single questions from two different instruments, and to identify associated characteristics and impacts. Methods: We compared computer-presented Alcohol Use Disorder Identification Test-Consumption (AUDIT-C) with categorical response options, and mental health interview (MHI) with open-ended consumption questions, completed on the same day. Participants were 464 men and 459 women aged 38 (91.7% of surviving birth cohort members). Differences in dichotomous single-item measures of abstention and HDO frequency, associations of inconsistent reporting with sex, socioeconomic status (SES) and survey order, and impacts of instrument choice on associations of alcohol with sex and SES were examined. Results: The AUDIT-C drinking frequency question estimated higher past-year abstention prevalence (AUDIT = 7.6%, MHI = 5.4%), with one-third of AUDIT-C abstainers being MHI drinkers. Only AUDIT-C produced significant sex differences in abstainer prevalence. Inconsistencies in HDO classifications were bidirectional, but with fewer HDOs reported on the MHI than AUDIT-C question. Lower SES was associated with inconsistency in abstention and weekly+ HDOs. Abstention and higher HDO frequency were associated with lower SES overall, but sex-specific associations differed by instrument. Conclusions: In this context, data collection method affected findings, with inconsistencies in abstention reports having most impact. Future studies should: (a) confirm self-reported abstention; (b) consider piloting data collection methods in target populations; (c) expect impacts of sex and SES on measurements and analyses. PMID:25648932

  4. Widely tunable quantum cascade laser-based terahertz source.

    Science.gov (United States)

    Danylov, Andriy A; Light, Alexander R; Waldman, Jerry; Erickson, Neal; Qian, Xifeng

    2014-07-10

    A compact, tunable, ultranarrowband terahertz source, Δν∼1  MHz, is demonstrated by upconversion of a 2.324 THz, free-running quantum cascade laser with a THz Schottky-diode-balanced mixer using a swept, synthesized microwave source to drive the nonlinearity. Continuously tunable radiation of 1 μW power is demonstrated in two frequency regions: ν(Laser) ± 0 to 50 GHz and ν(Laser) ± 70 to 115 GHz. The sideband spectra were characterized with a Fourier-transform spectrometer, and the radiation was tuned through CO, HDO, and D2O rotational transitions.

  5. Mathematical simulation of water distillation column for decreasing volume of tritiated water

    International Nuclear Information System (INIS)

    Kinoshita, Masahiro; Naruse, Yuji

    1981-12-01

    Water distillation is an attractive method for decreasing volume of the tritiated water produced by operation of tritium facilities. The tritiated water is continuously fed to a column and it is separated into two streams. The top stream is discarded to the environment after addition of sufficient amount of uncontaminated water. The bottom stream is further treated for solidification and capsulation. The tridiagonal matrix method proved to provide surprisingly rapid convergences of the calculations. The concentration of deuterium naturally contained in the tritiated water is higher than the tritium concentration, but it was verified that presence of HDO can be ignored in the calculation. (author)

  6. Use of stable isotopes for estimating water and nitrogen transport in plants

    International Nuclear Information System (INIS)

    Grygoryuk, I.P.; Petrenko, N.I.; Shvedova, O.Yu.; Tkachev, V.I.; Yaroshenko, O.A.

    1998-01-01

    Peculiarities in the response of various wheat cultivars and maize hybrids to water deficiency were studied in laboratory and vegetation experiments. Their resistance to extemal environmental factors was estimated by changes in nitrogen ( 15 N) and water (HDO) accumulation, transport and distribution in plant organs. The water supply was maintained at 60% FWC (control) and was reduced to 30% FWC (experiment) in the absence of plant watering during different stages or with use of polyethylene glycol. Decrease in water potential of medium from -0.05 (control) to -0.5, -0.9 and -1.6 MPa resulted in inhibition of water absorption, transport and distribution in spring wheat organs. After 24-hour stress, root absorption of water of drought-resistant varieties as compared to non-drought resistant ones was more sensitive, during 5, 10 and 15 min intervals after HDO introduction in nutrition medium. Strong depression of water exchange was observed at weaker stress in non-resistant variety. HDO absorption of the low part of the stem at short exposure resembled that of roots. The 24-hour stress revealed the tendency to sharper inhibition of absorption of labelled water in leaves of resistant variety. At a more durable stress the intensity of leaf water-exchange resistant variety was stabilized, while in the non-resistant variety it was reduced considerably. The intensity of HDO and 15 N exchange under stress conditions depended on the lability of regulator mechanism of water transport. Genotypic specificity of N use by wheat and maize plants depending on water supply and inclusion of 15 N in total and protein N was found. The 15 N content in total N in spring wheat cultivars under optimum water supply and under drought made 3.65 to 6.20 and 1.69 to 3.47, respectively. The 15 N content in protein N under the above conditions was 3.03 to 5.96 and 2.36 to 2.93, respectively. At water stress the main mass of labelled N in plant roots and stems was localized, while its intake into

  7. Bibliography of electron and photon cross sections with atoms and molecules published in the 20th century. Water vapour

    International Nuclear Information System (INIS)

    Hayashi, Makoto

    2003-12-01

    Bibliographies of original and review reports of experiments or theories of electron and photon cross sections and also electron swarm data are presented for atomic or molecular species with specified targets. These works covered 17 atoms and 51 molecules. The present bibliography is only for water vapour (H 2 O, D 2 O and HDO). About 1200 papers were compiled. A comprehensive author index is included. The bibliography covers the period 1915 through 2000 for H 2 O. Finally, author's comments for electron collision cross sections and photodissociation processes of H 2 O are given. (author)

  8. A associação de haloperidol, dexametasona e ondansetrona reduz a intensidade de náusea, dor e consumo de morfina após gastrectomia vertical laparoscópica

    Directory of Open Access Journals (Sweden)

    Márcio Luiz Benevides

    2013-10-01

    Full Text Available JUSTIFICATIVA E OBJETIVOS: Náusea e vômito pós-operatório (NVPO ocorrem frequentemente após cirurgia bariátrica laparoscópica. A associação de haloperidol, dexametasona e ondansetrona pode reduzir esses eventos indesejáveis. O objetivo deste estudo foi avaliar a intensidade de náusea e dor, o número de episódios de vômito e o consumo de morfina no pós-operatório (PO de pacientes obesos submetidos à gastrectomia vertical laparoscópica (GVL. MÉTODO: Estudo clínico, aleatorizado, controlado e duplamente encoberto feito em 90 pacientes com índice de massa corporal > 35 kg.cm-2. Os pacientes foram distribuídos em três grupos de 30 para receberem no Grupo O: ondansetron 8 mg; no Grupo DO: ondansetron 8 mg e dexametasona 8 mg e no Grupo HDO: ondansetron 8 mg, dexametasona 8 mg e haloperidol 2 mg. Foram avaliados a intensidade de náusea e dor, por meio de escala numérica verbal, o número cumulativo de episódios de vômito e o consumo de morfina no período de 0-2, 2-12, 12-24 e 24-36 horas de PO. RESULTADOS: A intensidade de náusea foi menor no Grupo HDO comparado com o Grupo O (p = 0,001, a intensidade da dor foi menor no Grupo HDO comparado com o Grupo O (p = 0,046 e o consumo de morfina no Grupo HDO foi menor do que no Grupo O (p = 0,037. Não houve diferença do número de episódios de vômito entre os grupos (p = 0,052. CONCLUSÃO: A associação de haloperidol, dexametasona e ondansetron promoveu redução da intensidade de náusea, da dor e do consumo de morfina no PO de pacientes obesos submetidos à GVL.

  9. Co-Pyrolysis Behaviors of the Cotton Straw/PP Mixtures and Catalysis Hydrodeoxygenation of Co-Pyrolysis Products over Ni-Mo/Al2O3 Catalyst

    Directory of Open Access Journals (Sweden)

    Derun Hua

    2015-12-01

    Full Text Available The doping of PP (polypropylene with cotton straw improved the bio-oil yield, which showed there was a synergy in the co-pyrolysis of the cotton straw and PP at the range of 380–480 °C. In a fixed-bed reactor, model compounds and co-pyrolysis products were used for reactants of hydrodeoxygenation (HDO over Ni-Mo/Al2O3. The deoxygenation rate of model compounds decreased over Ni-Mo/Al2O3 in the following order: alcohol > aldehyde > acetic acid > ethyl acetate. The upgraded oil mainly consisted of C11 alkane.

  10. Upgrading including heteroatom removal from Victorian brown coal-derived liquids

    Energy Technology Data Exchange (ETDEWEB)

    Larkins, F.P.; Youings, J.C.; Jackson, W.R.; Park, D. (University of Tasmania, Hobart, Tasmania (Australia))

    1989-10-01

    It has been shown using model compounds that the hydrodeoxygenation performance of a catalyst is severely inhibited by the presence of nitrogen-containing compounds under conditions of moderate reaction severity. For a low molecular weight coal-derived liquid commercial catalysts were effective for HDO and HDN at 400{degree}C, 10 MPa H{sub 2} for 30 min reaction time. For a coal-derived liquid high in asphaltene commercial catalysts and others prepared and tested in this study were ineffective. Alternative catalysts and hydrotreating conditions of greater severity will be required for such materials to effect acceptable heteroatom removal. 3 refs., 2 figs., 2 tabs.

  11. Catalysts for petroleum desulfurization

    Energy Technology Data Exchange (ETDEWEB)

    Mueller, A.; Diemann, E.; Baumann, F.W.

    1988-01-01

    In order to obtain marketable products from low-quality oils, efficient hydrogenation processes are required for removing sulfur (hydrodesulfurization, HDS), nitrogen (hydrodenitrification, HDN), and oxygen (hydrodeoxygenation, HDO), which would poison the noble metal catalysts of the downstream petrochemical processes. Hydrogenation will produce low-sulfur, low-nitrogen fuels and thus contribute to the reduction of SO/sub 2/ and NO/sub x/ emissions which is long overdue from the ecological point of view (forest decline, acidification of surface bodies of water, etc.).

  12. Possible processes for origin of life and living matter in deuterium enriched hot mineral water

    OpenAIRE

    Ignatov, Ignat; Mosin, Oleg

    2013-01-01

    In the present paper the isotopic composition of water and its temperature in the process of evolution of life is analysed. It was proposed an assumption, that under conditions of the primary O 2 free atmosphere, under influence of short-wave solar radiation, geothermal energy and powerful spark discharges, deuterium in form of HDO could be collected in hydrosphere, which physical-chemical properties differ from those of H 2O. There were obtained adapted to the maximal concentration D 2O cell...

  13. Determining oil consumption of an I.C. engine

    International Nuclear Information System (INIS)

    Dale, B.W.

    1981-01-01

    A method of measuring the consumption of lubricating oil by an internal combustion engine comprising the operations of isotopically labelling representative fractions of oil with deuterium atoms, circulating the lubricating oil through an engine under test, and measuring the amount of deuterium emitted from the exhaust pipe of the engine. Apparatus comprising means for subjecting the exhaust gas to an oxidizing environment and an infra-red transmissive region in which the infrared spectrum of the gas can be observed for the determination of HDO from the O-D band stretch is also described. Preferably at least 10% of the hydrocarbons in the oil are deuterated. (author)

  14. Sector 7-8 powered up

    CERN Document Server

    2007-01-01

    1. Frédéric Gicquel from the Cryogenics for Accelerators Group (AT/ACR) and Anupama Kulkarni from the Magnets and Electrical Systems Group (AT/MEL) at the CERN Control Centre during the powering-up of Sector 7-8. 2. Frédérick Bordry, leader of the Power Converter Group (AB/PO), and Roberto Saban, responsible for coordinating the LHC commissioning (TS/HDO), celebrate the end of the first powering-up of an entire LHC sector: Sector 7-8.

  15. Effect of Blended Feedstock on Pyrolysis Oil Composition

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Kristin M [National Renewable Energy Laboratory (NREL), Golden, CO (United States); Gaston, Katherine R [National Renewable Energy Laboratory (NREL), Golden, CO (United States)

    2017-09-28

    Current techno-economic analysis results indicate biomass feedstock cost represents 27% of the overall minimum fuel selling price for biofuels produced from fast pyrolysis followed by hydrotreating (hydro-deoxygenation, HDO). As a result, blended feedstocks have been proposed as a way to both reduce cost as well as tailor key chemistry for improved fuel quality. For this study, two feedstocks were provided by Idaho National Laboratory (INL). Both were pyrolyzed and collected under the same conditions in the National Renewable Energy Laboratory's (NREL) Thermochemical Process Development Unit (TCPDU). The resulting oil properties were then analyzed and characterized for statistical differences.

  16. A Low-cost, High-yield Process for the Direct Productin of High Energy Density Liquid Fuel from Biomass

    Energy Technology Data Exchange (ETDEWEB)

    Agrawal, Rakesh [Purdue Univ., West Lafayette, IN (United States); Delgass, W. N. [Purdue Univ., West Lafayette, IN (United States); Ribeiro, F. [Purdue Univ., West Lafayette, IN (United States)

    2013-08-31

    The primary objective and outcome of this project was the development and validation of a novel, low-cost, high-pressure fast-hydropyrolysis/hydrodeoxygenation (HDO) process (H2Bioil) using supplementary hydrogen (H2) to produce liquid hydrocarbons from biomass. The research efforts under the various tasks of the project have culminated in the first experimental demonstration of the H2Bioil process, producing 100% deoxygenated >C4+ hydrocarbons containing 36-40% of the carbon in the feed of pyrolysis products from biomass. The demonstrated H{sub 2}Bioil process technology (i.e. reactor, catalyst, and downstream product recovery) is scalable to a commercial level and is estimated to be economically competitive for the cases when supplementary H2 is sourced from coal, natural gas, or nuclear. Additionally, energy systems modeling has revealed several process integration options based on the H2Bioilprocess for energy and carbon efficient liquid fuel production. All project tasks and milestones were completed or exceeded. Novel, commercially-scalable, high-pressure reactors for both fast-hydropyrolysis and hydrodeoxygenation were constructed, completing Task A. These reactors were capable of operation under a wide-range of conditions; enabling process studies that lead to identification of optimum process conditions. Model compounds representing biomass pyrolysis products were studied, completing Task B. These studies were critical in identifying and developing HDO catalysts to target specific oxygen functional groups. These process and model compound catalyst studies enabled identification of catalysts that achieved 100% deoxygenation of the real biomass feedstock, sorghum, to form hydrocarbons in high yields as part of Task C. The work completed during this grant has identified and validated the novel and commercially scalable H2Bioil process for production of hydrocarbon fuels from biomass. Studies on

  17. Hydrodeoxygenation of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts derived from hydrotalcite-like precursors

    Directory of Open Access Journals (Sweden)

    Natalia Andrea Pino

    2017-01-01

    Full Text Available The aqueous phase hydrodeoxygenation (HDO of furfuryl alcohol over Cu/MgAl and Cu/ZnAl catalysts with different Mg/Al and Zn/Al molar ratios, were investigated. Mg-Al and Zn-Al mixed oxides derived from hydrotalcites precursors were used as supports, which were impregnated with an aqueous solution of copper nitrate by incipient wetness impregnation. The HDO reaction was carried out in a typical batch reactor at 5 MPa of H2 and 200 °C for 4 h. Among the catalysts studied, the Cu/MgAl-0.5 catalyst exhibited the higher furfuryl alcohol conversion (86% and yield of cyclopentanol (35%, which is the reaction product with the highest hydrogen-carbon (H/C ratio. With the Cu/MgAl-3 catalyst a high cyclopentanone yield (67% was achieved. The results obtained, showed that copper supported on mixed oxides catalysts derived from hydrotalcite precursors are a promising alternative to improve the bio-oil quality.

  18. Hydration of amino acids: FTIR spectra and molecular dynamics studies.

    Science.gov (United States)

    Panuszko, Aneta; Adamczak, Beata; Czub, Jacek; Gojło, Emilia; Stangret, Janusz

    2015-11-01

    The hydration of selected amino acids, alanine, glycine, proline, valine, isoleucine and phenylalanine, has been studied in aqueous solutions by means of FTIR spectra of HDO isotopically diluted in H2O. The difference spectra procedure and the chemometric method have been applied to remove the contribution of bulk water and thus to separate the spectra of solute-affected HDO. To support interpretation of obtained spectral results, molecular dynamics simulations of amino acids were performed. The structural-energetic characteristic of these solute-affected water molecules shows that, on average, water affected by amino acids forms stronger and shorter H-bonds than those in pure water. Differences in the influence of amino acids on water structure have been noticed. The effect of the hydrophobic side chain of an amino acid on the solvent interactions seems to be enhanced because of the specific cooperative coupling of water strong H-bond chain, connecting the carboxyl and amino groups, with the clathrate-like H-bond network surrounding the hydrocarbon side chain. The parameter derived from the spectral data, which corresponds to the contributions of the population of weak hydrogen bonds of water molecules which have been substituted by the stronger ones in the hydration sphere of amino acids, correlated well with the amino acid hydrophobicity indexes.

  19. Complex formation in aqueous trimethylamine-N-oxide (TMAO) solutions.

    Science.gov (United States)

    Hunger, Johannes; Tielrooij, Klaas-Jan; Buchner, Richard; Bonn, Mischa; Bakker, Huib J

    2012-04-26

    We study aqueous solutions of the amphiphilic osmolyte trimethylamine-N-oxide (TMAO) using broadband dielectric spectroscopy and femtosecond mid-infrared spectroscopy. Both experiments provide strong evidence for distinctively slower rotation dynamics for water molecules interacting with the hydrophobic part of the TMAO molecules. Further, water is found to interact more strongly at the hydrophilic site of the TMAO molecules: we find evidence for the formation of stable, TMAO·2H2O and/or TMAO·3H2O complexes. While this coordination structure seems obvious, the lifetime of these complexes is found to be extraordinarily long (>50 ps). The existence of these long-lived complexes leads to pronounced parallel dipole correlations between water and TMAO, reflected in enhanced amplitudes in the dielectric spectra. The strong interaction between water and TMAO also results in a red-shifted band for the O-D stretching vibration of HDO molecules in an isotopically diluted aqueous TMAO solution. This O-D stretching vibration has a vibrational lifetime of 670 fs, which is significantly shorter than the lifetime of the O-D stretch vibration of bulk-like HDO molecules, presumably due to efficient coupling to vibrational modes of TMAO. The rotational dynamics of these O-D groups are slowed down dramatically, and are limited by the rotation of the whole complex, while the O-D vector oriented away from TMAO probably shows an accelerated reorientation.

  20. Atmospheric Hydrodeoxygenation of Biomass Fast Pyrolysis Vapor by MoO3

    DEFF Research Database (Denmark)

    Zhou, Guofeng; Jensen, Peter Arendt; Le, Duy Michael

    2016-01-01

    was not significant at temperatures below 400 °C. At 450 °C catalyst temperature and 93 vol % H2 concentration, the wood pyrolysis vapor was more active toward cracking forming gas species instead of performing the desired HDO forming hydrocarbons. The lignin pyrolysis vapor was more resistant to cracking and yielded...... 16.2 wt %daf organic liquid, while achieving 52% degree of deoxygenation at 450 °C catalyst temperature under 89 vol % H2 concentration. The corresponding energy recovery in the liquid phase was 23.5%. The spent catalyst showed two deactivation routes, coke formation and reduction of MoO3 to MoO2......, which is inactive in HDO. The catalyst experienced severe reduction at temperatures higher than 400 °C. The yields of coke relative to the fed biomass were in the range of 3–4 wt %daf for lignin and 5–6 wt %daf for wood. Compared to untreated bio-oil the upgraded lignin organic liquid showed improved...

  1. Dynamics of a bistable Miura-origami structure

    Science.gov (United States)

    Fang, Hongbin; Li, Suyi; Ji, Huimin; Wang, K. W.

    2017-05-01

    Origami-inspired structures and materials have shown extraordinary properties and performances originating from the intricate geometries of folding. However, current state of the art studies have mostly focused on static and quasistatic characteristics. This research performs a comprehensive experimental and analytical study on the dynamics of origami folding through investigating a stacked Miura-Ori (SMO) structure with intrinsic bistability. We fabricate and experimentally investigated a bistable SMO prototype with rigid facets and flexible crease lines. Under harmonic base excitation, the SMO exhibits both intrawell and interwell oscillations. Spectrum analyses reveal that the dominant nonlinearities of SMO are quadratic and cubic, which generate rich dynamics including subharmonic and chaotic oscillations. The identified nonlinearities indicate that a third-order polynomial can be employed to approximate the measured force-displacement relationship. Such an approximation is validated via numerical study by qualitatively reproducing the phenomena observed in the experiments. The dynamic characteristics of the bistable SMO resemble those of a Helmholtz-Duffing oscillator (HDO); this suggests the possibility of applying the established tools and insights of HDO to predict origami dynamics. We also show that the bistability of SMO can be programmed within a large design space via tailoring the crease stiffness and initial stress-free configurations. The results of this research offer a wealth of fundamental insights into the dynamics of origami folding, and provide a solid foundation for developing foldable and deployable structures and materials with embedded dynamic functionalities.

  2. High-pressure vapor-phase hydrodeoxygenation of lignin-derived oxygenates to hydrocarbons by a PtMo bimetallic catalyst: Product selectivity, reaction pathway, and structural characterization

    Energy Technology Data Exchange (ETDEWEB)

    Yohe, Sara L.; Choudhari, Harshavardhan J.; Mehta, Dhairya D.; Dietrich, Paul J.; Detwiler, Michael D.; Akatay, Cem M.; Stach, Eric A.; Miller, Jeffrey T.; Delgass, W. Nicholas; Agrawal, Rakesh; Ribeiro, Fabio H.

    2016-12-01

    High-pressure, vapor-phase, hydrodeoxygenation (HDO) reactions of dihydroeugenol (2-methoxy-4-propylphenol), as well as other phenolic, lignin-derived compounds, were investigated over a bimetallic platinum and molybdenum catalyst supported on multi-walled carbon nanotubes (5%Pt2.5%Mo/MWCNT). Hydrocarbons were obtained in 100% yield from dihydroeugenol, including 98% yield of the hydrocarbon propylcyclohexane. The final hydrocarbon distribution was shown to be a strong function of hydrogen partial pressure. Kinetic analysis showed three main dihydroeugenol reaction pathways: HDO, hydrogenation, and alkylation. The major pathway occurred via Pt catalyzed hydrogenation of the aromatic ring and methoxy group cleavage to form 4-propylcyclohexanol, then Mo catalyzed removal of the hydroxyl group by dehydration to form propylcyclohexene, followed by hydrogenation of propylcyclohexene on either the Pt or Mo to form the propylcyclohexane. Transalkylation by the methoxy group occurred as a minor side reaction. Catalyst characterization techniques including chemisorption, scanning transmission electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy were employed to characterize the catalyst structure. Catalyst components identified were Pt particles, bimetallic PtMo particles, a Mo carbide-like phase, and Mo oxide phases.

  3. Diagnosing the Role of Transpiration in the Transition from Dry to Wet Season Over the Amazon Using Satellite Observations

    Science.gov (United States)

    Wright, J. S.; Fu, R.; Yin, L.; Chae, J.

    2013-12-01

    Reanalysis data indicates that land surface evapotranspiration plays a key role in determining the timing of wet season onset over the Amazon. Here, we use satellite observations of water vapor and its stable isotopes, carbon dioxide, leaf area index, and precipitation together with reanalysis data to explore the importance of transpiration in initiating the transition from dry season to wet season over the Amazon. The growth of vegetation in this region is primarily limited by the availability of sunlight rather than the availability of soil moisture, so that the increase of solar radiation during the dry season coincides with dramatic increases in leaf area index within forested ecosystems. This period of plant growth is accompanied by uptake of carbon dioxide and enrichment of heavy isotopes in water vapor, particularly near the land surface. Reanalysis data indicate that this pre-wet season enrichment of HDO is accompanied by sharp increases in the surface latent heat flux, which eventually triggers sporadic moist convection. The transport of transpiration-enriched near-surface air by this convection causes a dramatic increase in free-tropospheric HDO in late August and September. September also marks transition points in the annual cycles of leaf area index (maximum) and carbon dioxide (minimum). The increase in convective activity during this period creates convergence, enhancing moisture transport into the region and initiating the wet season.

  4. Synthesis of high density aviation fuel with cyclopentanol derived from lignocellulose

    Science.gov (United States)

    Sheng, Xueru; Li, Ning; Li, Guangyi; Wang, Wentao; Yang, Jinfan; Cong, Yu; Wang, Aiqin; Wang, Xiaodong; Zhang, Tao

    2015-03-01

    For the first time, renewable high density aviation fuels were synthesized at high overall yield (95.6%) by the Guerbet reaction of cyclopentanol which can be derived from lignocellulose, followed by the hydrodeoxygenation (HDO). The solvent-free Guerbet reaction of cyclopentanol was carried out under the co-catalysis of solid bases and Raney metals. Among the investigated catalyst systems, the combinations of magnesium-aluminium hydrotalcite (MgAl-HT) and Raney Ni (or Raney Co) exhibited the best performances. Over them, high carbon yield (96.7%) of C10 and C15 oxygenates was achieved. The Guerbet reaction products were further hydrodeoxygenated to bi(cyclopentane) and tri(cyclopentane) over a series of Ni catalysts. These alkanes have high densities (0.86 g mL-1 and 0.91 g mL-1) and can be used as high density aviation fuels or additives to bio-jet fuel. Among the investigated HDO catalysts, the 35 wt.% Ni-SiO2-DP prepared by deposition-precipitation method exhibited the highest activity.

  5. Preparation, Characterization, and Catalytic Activity of MoCo/USY Catalyst on Hydrodeoxygenation Reaction of Anisole

    Science.gov (United States)

    Nugrahaningtyas, K. D.; Suharbiansah, R. S. R.; Rahmawati, F.

    2018-03-01

    This research aims to prepare, characterize, and study the catalytic activity of Molybdenum (Mo) and Cobalt (Co) metal with supporting material Ultra Stable Y-Zeolite (USY), to produce catalysts with activity in hydrotreatment reaction and in order to eliminate impurities compounds that containing unwanted groups heteroatoms. The bimetallic catalysts MoCo/USY were prepared by wet impregnation method with weight variation of Co metal 0%, 2%, 4%, 6%, 8%, and Mo metal 8% (w/w), respectively. Activation method of the catalyst included calcination, oxidation, reduction and the crystallinity was characterized using X-ray diffraction (XRD), the acidity of the catalyst was analyzed using Fourier Transform Infrared Spectroscopy (FT-IR) and gravimetry method, minerals present in the catalyst was analyzed using X-Ray Fluorescence (XRF), and surface of the catalyst was analyzed using Surface Area Analyzer (SAA). Catalytic activity test (benzene yield product) of MoCo/USY on hydrodeoxigenation reaction of anisole aimed to determine the effect of Mo-Co/USY for catalytic activity in the reaction hydrodeoxigenation (HDO) anisole. Based on characterization and test of catalytic activity, it is known that catalytic of MoCo/USY 2% (catalyst B) shows best activities with acidity of 10.209 mmol/g, specific area of catalyst of 426.295 m2/g, pore average of 14.135 Å, total pore volume 0.318 cc/g, and total yield of HDO products 6.06%.

  6. Deoxygenation of glycolaldehyde and furfural on Mo2C/Mo(100)

    Science.gov (United States)

    McManus, Jesse R.; Vohs, John M.

    2014-12-01

    The desire to produce fuels and chemicals in an energy conscious, environmentally sympathetic approach has motivated considerable research on the use of cellulosic biomass feedstocks. One of the major challenges facing the utilization of biomass is finding effective catalysts for the efficient and selective removal of oxygen from the highly-oxygenated, biomass-derived platform molecules. Herein, a study of the reaction pathways for the biomass-derived platform molecule furfural and biomass-derived sugar model compound glycolaldehyde provides insight into the mechanisms of hydrodeoxygenation (HDO) on a model molybdenum carbide catalyst, Mo2C/Mo(100). Using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS), it was found that the Mo2C/Mo(100) catalyst was active for selective deoxygenation of the aldehyde carbonyl by facilitating adsorption of the aldehyde in an η2(C,O) bonding configuration. Furthermore, the catalyst showed no appreciable activity for furanic ring hydrogenation, highlighting the promise of relatively inexpensive Mo2C catalysts for selective HDO chemistry.

  7. Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran.

    Science.gov (United States)

    Saha, Basudeb; Bohn, Christine M; Abu-Omar, Mahdi M

    2014-11-01

    2,5-Dimethylfuran (DMF), a promising cellulosic biofuel candidate from biomass derived intermediates, has received significant attention because of its low oxygen content, high energy density, and high octane value. A bimetallic catalyst combination containing a Lewis-acidic Zn(II) and Pd/C components is effective for 5-hydroxymethylfurfural (HMF) hydrodeoxygenation (HDO) to DMF with high conversion (99%) and selectivity (85% DMF). Control experiments for evaluating the roles of zinc and palladium revealed that ZnCl2 alone did not catalyze the reaction, whereas Pd/C produced 60% less DMF than the combination of both metals. The presence of Lewis acidic component (Zn) was also found to be beneficial for HMF HDO with Ru/C catalyst, but the synergistic effect between the two metal components is more pronounced for the Pd/Zn system than the Ru/Zn. A comparative analysis of the Pd/Zn/C catalyst to previously reported catalytic systems show that the Pd/Zn system containing at least four times less precious metal than the reported catalysts gives comparable or better DMF yields. The catalyst shows excellent recyclability up to 4 cycles, followed by a deactivation, which could be due to coke formation on the catalyst surface. The effectiveness of this combined bimetallic catalyst has also been tested for one-pot conversion of fructose to DMF. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Synergy in Lignin Upgrading by a Combination of Cu-Based Mixed Oxide and Ni-Phosphide Catalysts in Supercritical Ethanol.

    Science.gov (United States)

    Korányi, Tamás I; Huang, Xiaoming; Coumans, Alessandro E; Hensen, Emiel J M

    2017-04-03

    The depolymerization of lignin to bioaromatics usually requires a hydrodeoxygenation (HDO) step to lower the oxygen content. A mixed Cu-Mg-Al oxide (CuMgAlO x ) is an effective catalyst for the depolymerization of lignin in supercritical ethanol. We explored the use of Ni-based cocatalysts, i.e. Ni/SiO 2 , Ni 2 P/SiO 2 , and Ni/ASA (ASA = amorphous silica alumina), with the aim of combining lignin depolymerization and HDO in a single reaction step. While the silica-supported catalysts were themselves hardly active in lignin upgrading, Ni/ASA displayed comparable lignin monomer yield as CuMgAlO x . A drawback of using an acidic support is extensive dehydration of the ethanol solvent. Instead, combining CuMgAlO x with Ni/SiO 2 and especially Ni 2 P/SiO 2 proved to be effective in increasing the lignin monomer yield, while at the same time reducing the oxygen content of the products. With Ni 2 P/SiO 2 , the lignin monomer yield was 53 wt %, leading to nearly complete deoxygenation of the aromatic products.

  9. Hydrotreatment activities of supported molybdenum nitrides and carbides

    Energy Technology Data Exchange (ETDEWEB)

    Dolce, G.M.; Savage, P.E.; Thompson, L.T. [University of Michigan, Ann Arbor, MI (United States). Dept. of Chemical Engineering

    1997-05-01

    The growing need for alternative sources of transportation fuels encourages the development of new hydrotreatment catalysts. These catalysts must be active and more hydrogen efficient than the current commercial hydrotreatment catalysts. Molybdenum nitrides and carbides are attractive candidate materials possessing properties that are comparable or superior to those of commercial sulfide catalysts. This research investigated the catalytic properties of {gamma}-Al{sub 2}O{sub 3}-supported molybdenum nitrides and carbides. These catalysts were synthesized via temperature-programmed reaction of supported molybdenum oxides with ammonia or methane/hydrogen mixtures. Phase constituents and compositions were determined by X-ray diffraction, elemental analysis, and neutral activation analysis. Oxygen chemisorption was used to probe the surface properties of the catalysts. Specific activities of the molybdenum nitrides and carbides were competitive with those of a commercial sulfide catalyst for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). For HDN and HDS, the catalytic activity on a molybdenum basis was a strong inverse function of the molybdenum loading. Product distributions of the HDN, HDO and HDS of a variety of heteroatom compounds indicated that several of the nitrides and carbides were more hydrogen efficient than the sulfide catalyst. 35 refs., 8 figs., 7 tabs.

  10. Second row transition metal sulfides for the hydrotreatment of coal-derived naphtha. 1. Catalyst preparation, characterization and comparison of rate of simultaneous removal of total sulfur, nitrogen and oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Raje, A.P.; Liaw, S.-J.; Srinivasan, R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

    1997-03-13

    Naphtha derived from an Illinois No. 6 coal contains appreciable quantities of sulfur-, nitrogen- and oxygen-containing compounds. The hydrotreatment of this naphtha was evaluated over unsupported transition metal sulfide catalysts (Ru, Rh, Mo, Pd, Zr, Mb). The catalysts were prepared by a room temperature precipitation reaction. Surface areas, crystalline phase and particle size distributions were determined by Brunauer-Emmet-Teller (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM), respectively. A comparison of average particle sizes calculated from these three techniques has enable the understanding of the morphology of the transition metal sulfides. The catalysts exhibit a so-called volcano plot for the HDS of dibenzothiophene. Similar so-called volcano plots are also exhibited for the simultaneous hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and the hydrodeoxygenation (HDO) of the coal-derived naphtha containing a mixture of heteroatoms. The order of reactivity of the transition metal catalysts is the same for all three of the processes. Ruthenium sulfide is the most active catalyst for HDS, HDN and HDO of the coal-derived naphtha. 22 refs., 3 figs., 4 tabs.

  11. Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations.

    Science.gov (United States)

    Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A; Boateng, Akwasi A; Vlachos, Dionisios G

    2015-01-01

    Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted-Evans-Polanyi (BEP) correlations for small open-chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon-dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential-energy surface of guaiacol-HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx (x<3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon-ring hydrogenation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Bio-oil from fast pyrolysis of lignin: Effects of process and upgrading parameters.

    Science.gov (United States)

    Fan, Liangliang; Zhang, Yaning; Liu, Shiyu; Zhou, Nan; Chen, Paul; Cheng, Yanling; Addy, Min; Lu, Qian; Omar, Muhammad Mubashar; Liu, Yuhuan; Wang, Yunpu; Dai, Leilei; Anderson, Erik; Peng, Peng; Lei, Hanwu; Ruan, Roger

    2017-10-01

    Effects of process parameters on the yield and chemical profile of bio-oil from fast pyrolysis of lignin and the processes for lignin-derived bio-oil upgrading were reviewed. Various process parameters including pyrolysis temperature, reactor types, lignin characteristics, residence time, and feeding rate were discussed and the optimal parameter conditions for improved bio-oil yield and quality were concluded. In terms of lignin-derived bio-oil upgrading, three routes including pretreatment of lignin, catalytic upgrading, and co-pyrolysis of hydrogen-rich materials have been investigated. Zeolite cracking and hydrodeoxygenation (HDO) treatment are two main methods for catalytic upgrading of lignin-derived bio-oil. Factors affecting zeolite activity and the main zeolite catalytic mechanisms for lignin conversion were analyzed. Noble metal-based catalysts and metal sulfide catalysts are normally used as the HDO catalysts and the conversion mechanisms associated with a series of reactions have been proposed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  13. Biobased alkylphenols from lignins via a two-step pyrolysis - Hydrodeoxygenation approach.

    Science.gov (United States)

    de Wild, P J; Huijgen, W J J; Kloekhorst, A; Chowdari, R K; Heeres, H J

    2017-04-01

    Five technical lignins (three organosolv, Kraft and soda lignin) were depolymerised to produce monomeric biobased aromatics, particularly alkylphenols, by a new two-stage thermochemical approach consisting of dedicated pyrolysis followed by catalytic hydrodeoxygenation (HDO) of the resulting pyrolysis oils. Pyrolysis yielded a mixture of guaiacols, catechols and, optionally, syringols in addition to alkylphenols. HDO with heterogeneous catalysts (Ru/C, CoMo/alumina, phosphided NiMO/C) effectively directed the product mixture towards alkylphenols by, among others, demethoxylation. Up to 15wt% monomeric aromatics of which 11wt% alkylphenols was obtained (on the lignin intake) with limited solid formation (<3wt% on lignin oil intake). For comparison, solid Kraft lignin was also directly hydrotreated for simultaneous depolymerisation and deoxygenation resulting in two times more alkylphenols. However, the alkylphenols concentration in the product oil is higher for the two-stage approach. Future research should compare direct hydrotreatment and the two-stage approach in more detail by techno-economic assessments. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Studies on catalytic hydrotreating of recycled solvents from coal liquefaction process. Part 1. Characteristics changes of recycled solvents during hydrotreating

    Energy Technology Data Exchange (ETDEWEB)

    Morimura, Y.; Nakata, S.; Yokota, Y.; Shirota, Y.; Nakamura, M. [Chiyoda Corp., Tokyo (Japan); Mitarai, Y. [Sumitomo Metal Mining Co. Ltd., Tokyo (Japan); Inoue, Y. [Nippon Ketjen Co. Ltd., Tokyo (Japan)

    1995-07-01

    A bituminous coal liquefaction process, called the NEDOL process, is under development by the New Energy and Industrial Technology Development Organization (NEDO). Important features of this process include the capacity to produce hydrogen-donatable solvents, obtained by hydrogenation of middle distillates of coal derived oils, and to recycle these solvents to a liquefaction stage as hydrogen donor solvents. These recycled solvents, obtained by liquefaction of Wandoan coal, and their catalytic hydrotreated oils, have been extensively characterized, using a variety of analytical methods. The following items have been examined and are discussed in this study: (1) Influence of chemical hydrogen consumption on the reactivities of hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodeoxygenation (HDO) and hydrogenation of aromatic-rings, during hydrotreating; (2) Changes in composition of hydrocarbon types, nitrogen- and oxygen-containing compounds, as a function of chemical hydrogen consumption; (3) Changes of average molecular weights; (4) Characteristics changes of oxygen- and nitrogen-containing compounds, and reactivities of HDO and HDN; (5) Characteristics changes of donatable hydrogen as a function of a degree of hydrogenation ({delta}fa). 14 refs., 14 figs., 3 tabs.

  15. Bond rearrangement caused by sudden single and multiple ionization of water molecules

    International Nuclear Information System (INIS)

    Ben-Itzhak, I.; Sayler, A. Max; Leonard, M.; Maseberg, J.W.; Hathiramani, D.; Wells, E.; Smith, M.A.; Xia, Jiangfan; Wang, Pengqian; Carnes, K.D.; Esry, B.D.

    2005-01-01

    Bond rearrangement, namely the dissociation of water into H 2 + +O q+ following ionization by fast proton and highly charged ion impact, was investigated. Single ionization by fast proton impact exhibits a strong isotopic effect, the dissociation of H 2 O + ->H 2 + +O being about twice as likely as D 2 O + ->D 2 + +O, with HDO + ->HD + +O in between. This suggests that the bond rearrangement does not happen during the slow dissociation, but rather during the very fast ionization, and thus H 2 + should also be produced when the water molecule is multiply ionized. We observed that the H 2 + +O + and H 2 + +O 2+ production in 1MeV/amu F 7+ +H 2 O collisions are 0.209+/-0.006% and 0.0665+/-0.003%, respectively, of the main double-ionization dissociation product, H 2 O 2+ ->H + +OH + . This ratio is similar to the triple to double ionization ratio in similar collisions with atomic targets thus suggesting that the bond-rearrangement fraction out of each ionization level is approximately constant. Similar dissociation channels in the heavier water isotopes, which are expected to be smaller, are under study. Finally, the fragmentation of HDO exhibits very strong isotopic preference for breaking the OH bond over the OD bond

  16. Dynamics of a bistable Miura-origami structure.

    Science.gov (United States)

    Fang, Hongbin; Li, Suyi; Ji, Huimin; Wang, K W

    2017-05-01

    Origami-inspired structures and materials have shown extraordinary properties and performances originating from the intricate geometries of folding. However, current state of the art studies have mostly focused on static and quasistatic characteristics. This research performs a comprehensive experimental and analytical study on the dynamics of origami folding through investigating a stacked Miura-Ori (SMO) structure with intrinsic bistability. We fabricate and experimentally investigated a bistable SMO prototype with rigid facets and flexible crease lines. Under harmonic base excitation, the SMO exhibits both intrawell and interwell oscillations. Spectrum analyses reveal that the dominant nonlinearities of SMO are quadratic and cubic, which generate rich dynamics including subharmonic and chaotic oscillations. The identified nonlinearities indicate that a third-order polynomial can be employed to approximate the measured force-displacement relationship. Such an approximation is validated via numerical study by qualitatively reproducing the phenomena observed in the experiments. The dynamic characteristics of the bistable SMO resemble those of a Helmholtz-Duffing oscillator (HDO); this suggests the possibility of applying the established tools and insights of HDO to predict origami dynamics. We also show that the bistability of SMO can be programmed within a large design space via tailoring the crease stiffness and initial stress-free configurations. The results of this research offer a wealth of fundamental insights into the dynamics of origami folding, and provide a solid foundation for developing foldable and deployable structures and materials with embedded dynamic functionalities.

  17. Novel Fast Pyrolysis/Catalytic Technology for the Production of Stable Upgraded Liquids

    Energy Technology Data Exchange (ETDEWEB)

    Oyama, Ted; Agblevor, Foster; Battaglia, Francine; Klein, Michael

    2013-01-18

    The objective of the proposed research is the demonstration and development of a novel biomass pyrolysis technology for the production of a stable bio-oil. The approach is to carry out catalytic hydrodeoxygenation (HDO) and upgrading together with pyrolysis in a single fluidized bed reactor with a unique two-level design that permits the physical separation of the two processes. The hydrogen required for the HDO will be generated in the catalytic section by the water-gas shift reaction employing recycled CO produced from the pyrolysis reaction itself. Thus, the use of a reactive recycle stream is another innovation in this technology. The catalysts will be designed in collaboration with BASF Catalysts LLC (formerly Engelhard Corporation), a leader in the manufacture of attrition-resistant cracking catalysts. The proposed work will include reactor modeling with state-of-the-art computational fluid dynamics in a supercomputer, and advanced kinetic analysis for optimization of bio-oil production. The stability of the bio-oil will be determined by viscosity, oxygen content, and acidity determinations in real and accelerated measurements. A multi-faceted team has been assembled to handle laboratory demonstration studies and computational analysis for optimization and scaleup.

  18. Physical inversion of the full IASI spectra: Assessment of atmospheric parameters retrievals, consistency of spectroscopy and forward modelling

    International Nuclear Information System (INIS)

    Liuzzi, G.; Masiello, G.; Serio, C.; Venafra, S.; Camy-Peyret, C.

    2016-01-01

    Spectra observed by the Infrared Atmospheric Sounder Interferometer (IASI) have been used to assess both retrievals and the spectral quality and consistency of current forward models and spectroscopic databases for atmospheric gas line and continuum absorption. The analysis has been performed with thousands of observed spectra over sea surface in the Pacific Ocean close to the Mauna Loa (Hawaii) validation station. A simultaneous retrieval for surface temperature, atmospheric temperature, H_2O, HDO, O_3 profiles and gas average column abundance of CO_2, CO, CH_4, SO_2, N_2O, HNO_3, NH_3, OCS and CF_4 has been performed and compared to in situ observations. The retrieval system considers the full IASI spectrum (all 8461 spectral channels on the range 645–2760 cm"−"1). We have found that the average column amount of atmospheric greenhouse gases can be retrieved with a precision better than 1% in most cases. The analysis of spectral residuals shows that, after inversion, they are generally reduced to within the IASI radiometric noise. However, larger residuals still appear for many of the most abundant gases, namely H_2O, CH_4 and CO_2. The H_2O ν_2 spectral region is in general warmer (higher radiance) than observations. The CO_2ν_2 and N_2O/CO_2ν_3 spectral regions now show a consistent behavior for channels, which are probing the troposphere. Updates in CH_4 spectroscopy do not seem to improve the residuals. The effect of isotopic fractionation of HDO is evident in the 2500–2760 cm"−"1 region and in the atmospheric window around 1200 cm"−"1. - Highlights: • This is the first work that uses the full IASI spectrum. This aspect is new and unique. • Simultaneous retrieval of the average amount of CO_2, N_2O, CO, CH_4, SO_2, HNO_3, NH_3, OCS and CF_4, T, H_2O, HDO, O_3 profiles, and T_s. • Assessment of spectroscopy consistency over the full IASI spectrum (645 to 2760 cm"−"1). • Two-year record of IASI retrievals are available on request, compared

  19. Procedure for obtaining visas for Switzerland and France - Signature rights

    CERN Multimedia

    2015-01-01

    In accordance with the Status Agreements with CERN, Switzerland and France facilitate the entry of members of the Organization’s personnel on to their territories. Where relevant, detailed procedures for obtaining visas apply.   Within the framework of those procedures, only the following individuals are authorised to initiate the Note verbale procedure as well as to sign the Official Invitation Letters and the Conventions d’accueil. 1.     Kirsti ASPOLA (PH – CMO) 2.     Catherine BRANDT (DG – IR) 3.     Oliver BRÜNING (BE – HDO) 4.     Michelle CONNOR (PH – DI) 5.     Gaëlle DUPERRIER (PH – DI) 6.     Patrick FASSNACHT (PH – ADO) 7.     Fernando FERN...

  20. A HERSCHEL STUDY OF D/H IN WATER IN THE JUPITER-FAMILY COMET 45P/HONDA-MRKOS-PAJDUŠÁKOVÁ AND PROSPECTS FOR D/H MEASUREMENTS WITH CCAT

    International Nuclear Information System (INIS)

    Lis, D. C.; Blake, G. A.; Biver, N.; Bockelée-Morvan, D.; Crovisier, J.; Moreno, R.

    2013-01-01

    We present Herschel observations of water isotopologues in the atmosphere of the Jupiter-family comet 45P/Honda-Mrkos-Pajdušáková. No HDO emission is detected, with a 3σ upper limit of 2.0 × 10 –4 for the D/H ratio. This value is consistent with the earlier Herschel measurement in the Jupiter-family comet 103P/Hartley 2. The canonical value of 3 × 10 –4 measured pre-Herschel in a sample of Oort-cloud comets can be excluded at a 4.5σ level. The observations presented here further confirm that a diversity of D/H ratios exists in the comet population and emphasize the need for additional measurements with future ground-based facilities, such as CCAT, in the post-Herschel era

  1. A Herschel Study of D/H in Water in the Jupiter-family Comet 45P/Honda-Mrkos-Pajdušáková and Prospects for D/H Measurements with CCAT

    Science.gov (United States)

    Lis, D. C.; Biver, N.; Bockelée-Morvan, D.; Hartogh, P.; Bergin, E. A.; Blake, G. A.; Crovisier, J.; de Val-Borro, M.; Jehin, E.; Küppers, M.; Manfroid, J.; Moreno, R.; Rengel, M.; Szutowicz, S.

    2013-09-01

    We present Herschel observations of water isotopologues in the atmosphere of the Jupiter-family comet 45P/Honda-Mrkos-Pajdušáková. No HDO emission is detected, with a 3σ upper limit of 2.0 × 10-4 for the D/H ratio. This value is consistent with the earlier Herschel measurement in the Jupiter-family comet 103P/Hartley 2. The canonical value of 3 × 10-4 measured pre-Herschel in a sample of Oort-cloud comets can be excluded at a 4.5σ level. The observations presented here further confirm that a diversity of D/H ratios exists in the comet population and emphasize the need for additional measurements with future ground-based facilities, such as CCAT, in the post-Herschel era.

  2. Deuterium exchange between hydrogen and water in a trickle bed reactor

    International Nuclear Information System (INIS)

    Enright, J.T.; Chuang, T.T.

    1978-01-01

    The catalyzed exchange of deuterium between hydrogen and liquid water has been studied as the basis for a heavy water production process. Platinum catalyst which had been waterproofed with Teflon was tested in a 0.2 m diameter trickle bed reactor at pressures and temperatures up to 6 MPa and 440 K. Extensive experimental data were used to test a model of the system which was developed from fundamental principles. It was found that mass transfer plays a very important role in the overall exchange and the conventional theory of vapour/liquid mass transfer does not adequately describe the absorption process. Modelling of the data has resulted in the postulation of a second method of mass transfer whereby HDO transfers directly from the catalyst to the bulk liquid phase. (author)

  3. Deactivation of Ni-MoS2 by bio-oil impurities during hydrodeoxygenation of phenol and octanol

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Gardini, Diego; Damsgaard, Christian Danvad

    2016-01-01

    The stability of Ni-MoS2/ZrO2 toward water, potassium, and chlorine containing compounds during hydrodeoxygenation (HDO) of a mixture of phenol and 1-octanol was investigated in a high pressure gas and liquid continuous flow fixed bed setup at 280 °C and 100 bar. To maintain the stability...... of the catalyst, sufficient co-feeding of a sulfur source was necessary to avoid oxidation of the sulfide phase by oxygen replacement of the edge sulfur atoms in the MoS2 structure. However, the addition of sulfur to the feed gas resulted in the formation of sulfur containing compounds, mainly thiols, in the oil...... impregnated on the catalyst in a stoichiometric ratio relative to the active metal. This deactivation was a result of adsorption of potassium on the edge vacancy sites of the MoS2 slabs....

  4. Application, Deactivation, and Regeneration of Heterogeneous Catalysts in Bio-Oil Upgrading

    Directory of Open Access Journals (Sweden)

    Shouyun Cheng

    2016-12-01

    Full Text Available The massive consumption of fossil fuels and associated environmental issues are leading to an increased interest in alternative resources such as biofuels. The renewable biofuels can be upgraded from bio-oils that are derived from biomass pyrolysis. Catalytic cracking and hydrodeoxygenation (HDO are two of the most promising bio-oil upgrading processes for biofuel production. Heterogeneous catalysts are essential for upgrading bio-oil into hydrocarbon biofuel. Although advances have been achieved, the deactivation and regeneration of catalysts still remains a challenge. This review focuses on the current progress and challenges of heterogeneous catalyst application, deactivation, and regeneration. The technologies of catalysts deactivation, reduction, and regeneration for improving catalyst activity and stability are discussed. Some suggestions for future research including catalyst mechanism, catalyst development, process integration, and biomass modification for the production of hydrocarbon biofuels are provided.

  5. Catalytic hydrotreatment of Illinois No. 6 coal-derived naphtha: comparison of molybdenum nitride and molybdenum sulfide for heteroatom removal

    Energy Technology Data Exchange (ETDEWEB)

    Raje, A.; Liaw, S.J.; Chary, K.V.R.; Davis, B.H. [University of Kentucky, Lexington, KY (United States). Center for Applied Energy Research

    1995-03-16

    The hydrotreatment of naphtha derived from Illinois No. 6 coal was investigated using molybdenum sulfide and nitride catalysts. The two catalysts are compared on the basis of total catalyst weight. Molybdenum sulfide is more active than molybdenum nitride for hydrodesulfurization (HDS) of a coal-derived naphtha. The rate of hydrodeoxygenation (HDO) of the naphtha over both catalysts are comparable. For hydrodenitrogenation (HDN), the sulfide is more active than the nitride only at higher temperatures ({gt}325{degree}C). Based upon conversion data, the naphtha can be lumped into a reactive and a less reactive fraction with each following first-order kinetics for heteroatom removal. The HDS and HDN rates and activation energies of the less reactive lump are smaller for the nitride than for the sulfide catalyst.

  6. A review of catalytic upgrading of bio-oil to engine fuels

    DEFF Research Database (Denmark)

    Mortensen, Peter Mølgaard; Grunwaldt, Jan-Dierk; Jensen, Peter Arendt

    2011-01-01

    As the oil reserves are depleting the need of an alternative fuel source is becoming increasingly apparent. One prospective method for producing fuels in the future is conversion of biomass into bio-oil and then upgrading the bio-oil over a catalyst, this method is the focus of this review article...... are traditional hydrodesulphurization (HDS) catalysts, such as Co–MoS2/Al2O3, or metal catalysts, as for example Pd/C. However, catalyst lifetimes of much more than 200h have not been achieved with any current catalyst due to carbon deposition. Zeolite cracking is an alternative path, where zeolites, e.g. HZSM-5...... produce fuels of acceptable grade for the current infrastructure. HDO is evaluated as being a path to fuels in a grade and at a price equivalent to present fossil fuels, but several tasks still have to be addressed within this process. Catalyst development, understanding of the carbon forming mechanisms...

  7. Biofuel Production from Jatropha Bio-Oil Derived Fast Pyrolysis: Effect and Mechanism of CoMoS Supported on Al2O3

    Science.gov (United States)

    Rodseanglung, T.; Ratana, T.; Phongaksorn, M.; Tungkamani, S.

    2018-03-01

    The aims of this research was to understand the CoMo/Al2O3 sulfide catalyst effect to remove oxygen-containing and nitrogen-containing molecules from Jatropha bio-oil derived fast pyrolysis converted to biofuels via hydrotreating process. The activity and selectivity of CoMo/γ-Al2O3 sulfided catalysts in hydrodeoxygenation (HDO) of Jatropha bio-oil derived fast pyrolysis was evaluated in a Parr batch reactor under 50 bar of H2 atmosphere for 2 h at 300 320 and 340 °C. It appeared that the CoMo/Al2O3 sulfide catalyst have high performance in activity for promoting the fatty acid, fatty ester, fatty amide and fatty nitrile compounds were converted to paraffin/olefin (Diesel range), this could be the CUS site on supported Al2O3 catalyst. The difference in selectivity products allowed us to propose a reaction scheme.

  8. Selective One-Pot Production of High-Grade Diesel-Range Alkanes from Furfural and 2-Methylfuran over Pd/NbOPO4.

    Science.gov (United States)

    Xia, Qineng; Xia, Yinjiang; Xi, Jinxu; Liu, Xiaohui; Zhang, Yongguang; Guo, Yong; Wang, Yanqin

    2017-02-22

    A one-pot method for the selective production of high-grade diesel-range alkanes from biomass-derived furfural and 2-methylfuran (2-MF) was developed by combining the hydroxyalkylation/alkylation (HAA) condensation of furfural with 2-MF and the subsequent hydrodeoxygenation (HDO) over a multifunctional Pd/NbOPO 4 catalyst. The effects of various reaction conditions as well as a variety of solid-acid catalysts and metal-loaded NbOPO 4 catalysts were systematically investigated to optimize the reaction conditions for both reactions. Under the optimal reaction conditions up to 89.1 % total yield of diesel-range alkanes was obtained from furfural and 2-MF by this one-pot method. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Communication: Disorder-suppressed vibrational relaxation in vapor-deposited high-density amorphous ice

    Science.gov (United States)

    Shalit, Andrey; Perakis, Fivos; Hamm, Peter

    2014-04-01

    We apply two-dimensional infrared spectroscopy to differentiate between the two polyamorphous forms of glassy water, low-density (LDA) and high-density (HDA) amorphous ices, that were obtained by slow vapor deposition at 80 and 11 K, respectively. Both the vibrational lifetime and the bandwidth of the 1-2 transition of the isolated OD stretch vibration of HDO in H2O exhibit characteristic differences when comparing hexagonal (Ih), LDA, and HDA ices, which we attribute to the different local structures - in particular the presence of interstitial waters in HDA ice - that cause different delocalization lengths of intermolecular phonon degrees of freedom. Moreover, temperature dependent measurements show that the vibrational lifetime closely follows the structural transition between HDA and LDA phases.

  10. Bio-aviation fuel production from hydroprocessing castor oil promoted by the nickel-based bifunctional catalysts.

    Science.gov (United States)

    Liu, Siyang; Zhu, Qingqing; Guan, Qingxin; He, Liangnian; Li, Wei

    2015-05-01

    Bio-aviation fuel was firstly synthesized by hydroprocessing castor oil in a continuous-flow fixed-bed microreactor with the main objective to obtain the high yield of aviation fuel and determine the elemental compositions of the product phases as well as the reaction mechanism. Highest aviation range alkane yields (91.6 wt%) were achieved with high isomer/n-alkane ratio (i/n) 4.4-7.2 over Ni supported on acidic zeolites. In addition, different fuel range alkanes can be obtained by adjusting the degree of hydrodeoxygenation (HDO) and hydrocracking. And the observations are rationalized by a set of reaction pathways for the various product phases. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. First results of the observations of trace gases in the Martian atmosphere by the Planetary Fourier Spectrometer onboard the Mars Express

    Science.gov (United States)

    Titov, D. V.; Ignatiev, N.; Formisano, V.; Grassi, D.; Giuranna, M.; Maturilli, A.; Piccioni, G.; Moroz, V. I.; Lellouch, E.; Encrenaz, T.; Pfs Team

    High spectral resolution observations of Mars by the PFS/Mars Express provide new insight into the atmospheric composition. Spectral features of atmospheric CO2 and its isotopes at 15, 4.3, 2.7, 1.4 μ m, CO at 4.7 and 2.35 μ m, and H2O at 40, 2.56, and 1.38 μ m as well as solar spectral features are clearly identified in the PFS spectra. HDO spectral details at 3.7 μ m were also tentatively detected. The paper will present qualitative and quantitative analysis of the PFS spectra in the regions of spectral bands of trace gases. Abundance of minor constituents will be determined using complete radiative transfer modeling including possible non-LTE effects. We will also present results of search for other minor species with emphasis on the limb observations that provide higher air mass factor.

  12. The Unexpectedly Bright Comet C-2012 F6 (Lemmon) Unveiled at Near-Infrared Wavelengths

    Science.gov (United States)

    Paganini, Lucas; Disanti, Michael A.; Mumma, Michael J.; Villanueva, Geronimo L.; Bonev, Boncho P.; Keane, Jacqueline V.; Gibb, Erika L.; Boehnhardt, Hermann; Meech, Karen J.

    2013-01-01

    We acquired near-infrared spectra of the Oort cloud comet C/2012 F6 (Lemmon) at three different heliocentric distances (R h) during the comet's 2013 perihelion passage, providing a comprehensive measure of the outgassing behavior of parent volatiles and cosmogonic indicators. Our observations were performed pre-perihelion at R h = 1.2 AU with CRIRES (on 2013 February 2 and 4), and post-perihelion at R h = 0.75 AU with CSHELL (on March 31 and April 1) and R h = 1.74 AU with NIRSPEC (on June 20). We detected 10 volatile species (H2O, OH* prompt emission, C2H6, CH3OH, H2CO, HCN, CO, CH4, NH3, and NH2), and obtained upper limits for two others (C2H2 and HDO). One-dimensional spatial profiles displayed different distributions for some volatiles, confirming either the existence of polar and apolar ices, or of chemically distinct active vents in the nucleus. The ortho-para ratio for water was 3.31 +/- 0.33 (weighted mean of CRIRES and NIRSPEC results), implying a spin temperature >37 K at the 95% confidence limit. Our (3s) upper limit for HDO corresponds to D/H comet C/2012 F6 as rather depleted in C2H6 and CH3OH, while HCN, CH4, and CO displayed abundances close to their median values found among comets. H2CO was the only volatile showing a relative enhancement. The relative paucity of C2H6 and CH3OH (with respect to H2O) suggests formation within warm regions of the nebula. However, the normal abundance of HCN and hypervolatiles CH4 and CO, and the enhancement of H2CO, may indicate a possible heterogeneous nucleus of comet C/2012 F6 (Lemmon), possibly as a result of radial mixing within the protoplanetary disk

  13. Analysis and removal of heteroatom containing species in coal liquid distillate over NiMo catalysts

    Energy Technology Data Exchange (ETDEWEB)

    S.D. Sumbogo Murtia; Ki-Hyouk Choi; Kinya Sakanishi; Osamu Okuma; Yozo Korai; Isao Mochida [Kyushu University, Fukuoka (Japan). Institute for Materials Chemistry and Engineering

    2005-02-01

    Heteroatom containing molecules in South Banko coal liquid (SBCL) distillate were identified with a gas chromatograph equipped with an atomic emission detector (GC-AED). Thiophenes and benzothiophenes were found to be the major sulfur compounds. Pyridines, anilines, and phenols were the major nitrogen and oxygen compounds, respectively. Reactivities of heteroatom containing species in hydrotreatment over conventional NiMoS/Al{sub 2}O{sub 3}, NiMoS/Al{sub 2}O{sub 3}-SiO{sub 2} catalysts were very different according to their cyclic structure as well as the kind of heteroatom in the species. The sulfur species were completely desulfurized over the catalysts examined in the present study by 60 min at 360{degree}C under initial hydrogen pressure of 5 MPa. However, hydrodenitrogenation was more difficult than hydrodesulfurization even at 450{degree}C. Anilines were found the most refractory ones among the nitrogen species. Hydrodeoxygenation of SBCL was also difficult in the hydrotreatment conditions examined in the present study. Dibenzofuran was the most refractory molecule among the oxygen species. A two-stage reaction configuration at 340 and 360{degree}C improved HDN and HDO reactivities, although the conversions were still insufficient. Increasing the acidity of the support as well as the loading of the metals on the NiMoS/Al{sub 2}O{sub 3} catalysts improved very much the heteroatom reduction to achieve complete removal of nitrogen by two-stage reaction configuration at 340-360{degree}C and oxygen at 360{degree}C, respectively. The addition of H{sub 2}S in the reaction atmosphere inhibited the HDN reaction but increased markedly the HDO conversion. The acidic support increased the activity in hydrotreatment through enhancing the hydrogenation activity, while H{sub 2}S maintained the catalyst in a sufficiently sulfided state. 19 refs., 4 figs., 8 tabs.

  14. The roles of convection, extratropical mixing, and in-situ freeze-drying in the Tropical Tropopause Layer

    Directory of Open Access Journals (Sweden)

    W. G. Read

    2008-10-01

    Full Text Available Mechanisms for transporting and dehydrating air across the tropical tropopause layer (TTL are investigated with a conceptual two dimensional (2-D model. The 2-D TTL model combines the Holton and Gettelman cold trap dehydration mechanism (Holton and Gettelman, 2001 with the two column convection model of Folkins and Martin (2005. We investigate 3 possible transport scenarios through the TTL: 1 slow uniform ascent across the level of zero radiative heating without direct convective mixing, 2 convective mixing of H2O vapor at 100% relative humidity with respect to ice (RHi with no ice retention, and 3 convective mixing of extremely subsaturated air (100% RHi following the moist adiabatic temperature above the level of neutral buoyancy with sufficient ice retention such that total H2O is 100%RHi. The three mechanisms produce similar seasonal cycles for H2O that are in good quantitative agreement with the Aura Microwave Limb Sounder (MLS measurements. We use Aura MLS measurement of CO and Atmospheric Chemistry Experiment-Fourier Transform Spectrometer measurement of HDO to distinguish among the transport mechanisms. Model comparisons with the observations support the view that H2O is predominantly controlled by regions having the lowest cold point tropopause temperature but the trace species CO and HDO support the convective mixing of dry air and lofted ice. The model provides some insight into the processes affecting the long term trends observed in stratospheric H2O.

  15. Performance of the Chicago Water Isotope Spectrometer in the UTLS during the Asian Monsoon

    Science.gov (United States)

    Gaeta, D. C.; Clouser, B.; Sarkozy, L.; Singer, C. E.; Moyer, E. J.

    2017-12-01

    The preferential condensation of water vapor isotopologues makes the isotopic composition of water vapor a useful tracer of the processes responsible for the distribution of water in the UTLS, but the UTLS also offers particular challenges for its measurement. We report here on the field performance of a new instrument designed for measurement of HDO and H2O in the UTLS region: the Chicago Water Isotope Spectrometer (Chi-WIS). Chi-WIS is a laser-based infrared absorption spectrometer at 2.65 μm that uses a high-reflectivity optical cavity to obtain 6 km of effective path length, allowing sensitive measurements of scarce molecules. During the 2017 StratoClim aircraft campaign in Kathmandu, Nepal, Chi-WIS flew aboard the M-55 Geophysica high-altitude research aircraft in a series of flights to probe the Asian Monsoon. Preliminary results show in-flight performance consistent with laboratory performance and the achievement of design targets necessary to reach UTLS science goals. Residual noise on spectra is stable across flights at 4-5x10-4 with 1 second averaging (i.e. absorption depth of .04-.05%); the instrument is robust in terms of alignment and shows no evidence of optical resonances. The resulting measurement precision is as expected from these characteristics. Because we use a relatively strong water line, the water vapor measurement is extremely precise: constant-altitude flight legs in the stratosphere at 4 ppm H2O show 1 s standard deviation 0.03 ppmv for 1 s averaging, and 0.08 ppbv for HDO with 10 s averaging. We show comparisons with other StratoClim instruments and examples of how these measurements resolve scientifically relevant atmospheric features.

  16. Stable Water Isotopologues in the Stratosphere Retrieved from Odin/SMR Measurements

    Directory of Open Access Journals (Sweden)

    Tongmei Wang

    2018-01-01

    Full Text Available Stable Water Isotopologues (SWIs are important diagnostic tracers for understanding processes in the atmosphere and the global hydrological cycle. Using eight years (2002–2009 of retrievals from Odin/SMR (Sub-Millimetre Radiometer, the global climatological features of three SWIs, H216O, HDO and H218O, the isotopic composition δD and δ18O in the stratosphere are analysed for the first time. Spatially, SWIs are found to increase with altitude due to stratospheric methane oxidation. In the tropics, highly depleted SWIs in the lower stratosphere indicate the effect of dehydration when the air comes through the cold tropopause, while, at higher latitudes, more enriched SWIs in the upper stratosphere during summer are produced and transported to the other hemisphere via the Brewer–Dobson circulation. Furthermore, we found that more H216O is produced over summer Northern Hemisphere and more HDO is produced over summer Southern Hemisphere. Temporally, a tape recorder in H216O is observed in the lower tropical stratosphere, in addition to a pronounced downward propagating seasonal signal in SWIs from the upper to the lower stratosphere over the polar regions. These observed features in SWIs are further compared to SWI-enabled model outputs. This helped to identify possible causes of model deficiencies in reproducing main stratospheric features. For instance, choosing a better advection scheme and including methane oxidation process in a specific model immediately capture the main features of stratospheric water vapor. The representation of other features, such as the observed inter-hemispheric difference of isotopic component, is also discussed.

  17. Mild Biomass Liquefaction Process for Economic Production of Stabilized Refinery-Ready Bio-oil

    Energy Technology Data Exchange (ETDEWEB)

    Gangwal, Santosh [Southern Research, Durham, NC (United States); Meng, Jiajia [Southern Research, Durham, NC (United States); McCabe, Kevin [Southern Research, Durham, NC (United States); Larson, Eric [Princeton Univ., NJ (United States). Princeton Environmental Inst.; Mastro, Kelly [Southern Research, Durham, NC (United States)

    2016-04-25

    Southern Research (SR) in cooperation with U.S. Department of Energy (DOE), Bioenergy Technology Office (BETO), investigated a biomass liquefaction process for economic production of stabilized refinery-ready bio-oil. The project was awarded by DOE under a Funding Opportunity Announcement (DE-FOA-0000686) for Bio-oil Stabilization and Commoditization that intended to evaluate the feasibility of using bio-oil as a potential feedstock in an existing petroleum refinery. SR investigated Topic Area 1 of the FOA at Technology Readiness Level 2-3 to develop thermochemical liquefaction technologies for producing a bio-oil feedstock from high-impact biomass that can be utilized within a petroleum refinery. Bio-oil obtained from fast pyrolysis of biomass is a green intermediate that can be further upgraded into a biofuel for blending in a petroleum refinery using a hydro-deoxygenation (HDO) route. Co-processing pyrolysis bio-oil in a petroleum refinery is an attractive approach to leverage the refinery’s existing capital. However, the petroleum industry is reluctant to accept pyrolysis bio-oil because of a lack of a standard definition for an acceptable bio-oil feedstock in existing refinery processes. Also per BETO’s multiyear program plan, fast pyrolysis-based bio-fuel is presently not cost competitive with petroleum-based transportation fuels. SR aims to develop and demonstrate a cost-effective low-severity thermal liquefaction and hydrodeoxygenation (HDO) process to convert woody biomass to stabilized bio-oils that can be directly blended with hydrotreater input streams in a petroleum refinery for production of gasoline and/or diesel range hydrocarbons. The specific project objectives are to demonstrate the processes at laboratory scale, characterize the bio-oil product and develop a plan in partnership with a refinery company to move the technology towards commercialization.

  18. Pt-based Bi-metallic Monolith Catalysts for Partial Upgrading of Microalgae Oil

    Energy Technology Data Exchange (ETDEWEB)

    Lawal, Adeniyi [Stevens Inst. of Technology, Hoboken, NJ (United States); Manganaro, James [Anasyn LLC, Princeton, NJ (United States); Goodall, Brian [Valicor Renewables LLC, Dexter, MI (United States); Farrauto, Robert [Columbia Univ., New York, NY (United States)

    2015-03-24

    Valicor’s proprietary wet extraction process in conjunction with thermochemical pre-treatment was performed on algal biomass from two different algae strains, Nannochloropsis Salina (N.S.) and Chlorella to produce algae oils. Polar lipids such as phospholipids were hydrolyzed, and metals and metalloids, known catalyst poisons, were separated into the aqueous phase, creating an attractive “pre-refined” oil for hydrodeoxygenation (HDO) upgrading by Stevens. Oil content and oil extraction efficiency of approximately 30 and 90% respectively were achieved. At Stevens, we formulated a Pt-based bi-metallic catalyst which was demonstrated to be effective in the hydro-treating of the algae oils to produce ‘green’ diesel. The bi-metallic catalyst was wash-coated on a monolith, and in conjunction with a high throughput high pressure (pilot plant) reactor system, was used in hydrotreating algae oils from N.S. and Chlorella. Mixtures of these algae oils and refinery light atmospheric gas oil (LAGO) supplied by our petroleum refiner partner, Marathon Petroleum Corporation, were co-processed in the pilot plant reactor system using the Pt-based bi-metallic monolith catalyst. A 26 wt% N.S. algae oil/74 wt % LAGO mixture hydrotreated in the reactor system was subjected to the ASTM D975 Diesel Fuel Specification Test and it met all the important requirements, including a cetane index of 50.5. An elemental oxygen analysis performed by an independent and reputable lab reported an oxygen content of trace to none found. The successful co-processing of a mixture of algae oil and LAGO will enable integration of algae oil as a refinery feedstock which is one of the goals of DOE-BETO. We have presented experimental data that show that our precious metal-based catalysts consume less hydrogen than the conventional hydrotreating catalyst NiMo Precious metal catalysts favor the hydrodecarbonylation/hydrodecarboxylation route of HDO over the dehydration route preferred by base metal

  19. Evaluating climate model performance in the tropics with retrievals of water isotopic composition from Aura TES

    Science.gov (United States)

    Field, Robert; Kim, Daehyun; Kelley, Max; LeGrande, Allegra; Worden, John; Schmidt, Gavin

    2014-05-01

    Observational and theoretical arguments suggest that satellite retrievals of the stable isotope composition of water vapor could be useful for climate model evaluation. The isotopic composition of water vapor is controlled by the same processes that control water vapor amount, but the observed distribution of isotopic composition is distinct from amount itself . This is due to the fractionation that occurs between the abundant H216O isotopes (isotopologues) and the rare and heavy H218O and HDO isotopes during evaporation and condensation. The fractionation physics are much simpler than the underlying moist physics; discrepancies between observed and modeled isotopic fields are more likely due to problems in the latter. Isotopic measurements therefore have the potential for identifying problems that might not be apparent from more conventional measurements. Isotopic tracers have existed in climate models since the 1980s but it is only since the mid 2000s that there have been enough data for meaningful model evaluation in this sense, in the troposphere at least. We have evaluated the NASA GISS ModelE2 general circulation model over the tropics against water isotope (HDO/H2O) retrievals from the Aura Tropospheric Emission Spectrometer (TES), alongside more conventional measurements. A small ensemble of experiments was performed with physics perturbations to the cumulus and planetary boundary layer schemes, done in the context of the normal model development process. We examined the degree to which model-data agreement could be used to constrain a select group of internal processes in the model, namely condensate evaporation, entrainment strength, and moist convective air mass flux. All are difficult to parameterize, but exert strong influence over model performance. We found that the water isotope composition was significantly more sensitive to physics changes than precipitation, temperature or relative humidity through the depth of the tropical troposphere. Among the

  20. Immersion Gratings for Infrared High-resolution Spectroscopy

    Science.gov (United States)

    Sarugaku, Yuki; Ikeda, Yuji; Kobayashi, Naoto; Kaji, Sayumi; Sukegawa, Takashi; Sugiyama, Shigeru; Nakagawa, Takao; Arasaki, Takayuki; Kondo, Sohei; Nakanishi, Kenshi; Yasui, Chikako; Kawakita, Hideyo

    2016-10-01

    High-resolution spectroscopy in the infrared wavelength range is essential for observations of minor isotopologues, such as HDO for water, and prebiotic organic molecules like hydrocarbons/P-bearing molecules because numerous vibrational molecular bands (including non-polar molecules) are located in this wavelength range. High spectral resolution enables us to detect weak lines without spectral line confusion. This technique has been widely used in planetary sciences, e.g., cometary coma (H2O, CO, and organic molecules), the martian atmosphere (CH4, CO2, H2O and HDO), and the upper atmosphere of gas giants (H3+ and organic molecules such as C2H6). Spectrographs with higher resolution (and higher sensitivity) still have a potential to provide a plenty of findings. However, because the size of spectrographs scales with the spectral resolution, it is difficult to realize it.Immersion grating (IG), which is a diffraction grating wherein the diffraction surface is immersed in a material with a high refractive index (n > 2), provides n times higher spectral resolution compared to a reflective grating of the same size. Because IG reduces the size of spectrograph to 1/n compared to the spectrograph with the same spectral resolution using a conventional reflective grating, it is widely acknowledged as a key optical device to realize compact spectrographs with high spectral resolution.Recently, we succeeded in fabricating a CdZnTe immersion grating with the theoretically predicted diffraction efficiency by machining process using an ultrahigh-precision five-axis processing machine developed by Canon Inc. Using the same technique, we completed a practical germanium (Ge) immersion grating with both a reflection coating on the grating surface and the an AR coating on the entrance surface. It is noteworthy that the wide wavelength range from 2 to 20 um can be covered by the two immersion gratings.In this paper, we present the performances and the applications of the immersion

  1. Detections and Sensitive Upper Limits for Methane and Related Trace Gases on Mars during 2003-2014, and planned extensions in 2016

    Science.gov (United States)

    Mumma, Michael J.; Villanueva, Geronimo L.; Novak, Robert E.

    2015-11-01

    Five groups report methane detections on Mars; all results suggest local release and high temporal variability [1-7]. Our team searched for CH4 on many dates and seasons and detected it on several dates [1, 9, 10]. TLS (Curiosity rover) reported methane upper limits [6], and then detections [7] that were consistent in size with earlier reports and that also showed rapid modulation of CH4 abundance.[8] argued that absorption features assigned to Mars 12CH4 by [1] might instead be weak lines of terrestrial 13CH4. If not properly removed, terrestrial 13CH4 signatures would appear on the blue wing of terrestrial 12CH4 even when Mars is red-shifted - but they do not (Fig. S6 of [1]), demonstrating that terrestrial signatures were correctly removed. [9] demonstrated that including the dependence of δ13CH4 with altitude did not affect the residual features, nor did taking δ13CH4 as zero. Were δ13CH4 important, its omission would have overemphasized the depth of 13CH4 terrestrial absorption, introducing emission features in the residual spectra [1]. However, the residual features are seen in absorption, establishing their origin as non-terrestrial - [8] now agrees with this view.We later reported results for multiple organic gases (CH4, CH3OH, H2CO, C2H6, C2H2, C2H4), hydroperoxyl (HO2), three nitriles (N2O, NH3, HCN) and two chlorinated species (HCl, CH3Cl) [9]. Most of these species cannot be detected with current space assets, owing to instrumental limitations (e.g., spectral resolving power). However, the high resolution infrared spectrometers (NOMAD, ACS) on ExoMars 2016 (Trace Gas Orbiter) will begin measurements in late 2016. In solar occultation, TGO sensitivities will far exceed prior capabilities.We published detailed hemispheric maps of H2O and HDO on Mars, inferring the size of a lost early ocean [10]. In 2016, we plan to acquire 3-D spatial maps of HDO and H2O with ALMA, and improved maps of organics with iSHELL/NASA-IRTF.References: [1] Mumma et al. Sci09

  2. Global distributions of water vapour isotopologues retrieved from IMG/ADEOS data

    Directory of Open Access Journals (Sweden)

    H. Herbin

    2007-07-01

    Full Text Available The isotopologic composition of water vapour in the atmosphere provides valuable information on many climate, chemical and dynamical processes. The accurate measurements of the water isotopologues by remote-sensing techniques remains a challenge, due to the large spatial and temporal variations. Simultaneous profile retrievals of the main water isotopologues (i.e. H216O, H218O and HDO and their ratios are presented here for the first time, along their retrieved global distributions. The results are obtained by exploiting the high resolution infrared spectra recorded by the Interferometric Monitor for Greenhouse gases (IMG instrument, which has operated in the nadir geometry onboard the ADEOS satellite between 1996 and 1997. The retrievals are performed on cloud-free radiances, measured during ten days of April 1997, considering two atmospheric windows (1205–1228 cm−1; 2004–2032 cm−1 and using a line-by-line radiative transfer model and an inversion procedure based on the Optimal Estimation Method (OEM. Characterizations in terms of vertical sensitivity and error budget are provided. We show that a relatively high vertical resolution is achieved for H216O (~4–5 km, and that the retrieved profiles are in fair agreement with local sonde measurements, at different latitudes. The retrieved global distributions of H216O, H218O, HDO and their ratios are presented and found to be consistent with previous experimental studies and models. The Ocean-Continent difference, the latitudinal and vertical dependence of the water vapour amount and the isotopologic depletion are notably well reproduced. Others trends, possibly related to small-scale variations in the vertical profiles are also discussed. Despite the difficulties encountered for computing accurately the isotopologic ratios, our results demonstrate the ability

  3. Analysing the origin of rain- and subsurface water in seasonal wetlands of north-central Namibia

    Science.gov (United States)

    Hiyama, Tetsuya; Kanamori, Hironari; Kambatuku, Jack R.; Kotani, Ayumi; Asai, Kazuyoshi; Mizuochi, Hiroki; Fujioka, Yuichiro; Iijima, Morio

    2017-03-01

    We investigated the origins of rain- and subsurface waters of north-central Namibia’s seasonal wetlands, which are critical to the region’s water and food security. The region includes the southern part of the Cuvelai system seasonal wetlands (CSSWs) of the Cuvelai Basin, a transboundary river basin covering southern Angola and northern Namibia. We analysed stable water isotopes (SWIs) of hydrogen (HDO) and oxygen (H2 18O) in rainwater, surface water and shallow groundwater. Rainwater samples were collected during every rainfall event of the rainy season from October 2013 to April 2014. The isotopic ratios of HDO (δD) and oxygen H2 18O (δ 18O) were analysed in each rainwater sample and then used to derive the annual mean value of (δD, δ 18O) in precipitation weighted by each rainfall volume. Using delta diagrams (plotting δD vs. δ 18O), we showed that the annual mean value was a good indicator for determining the origins of subsurface waters in the CSSWs. To confirm the origins of rainwater and to explain the variations in isotopic ratios, we conducted atmospheric water budget analysis using Tropical Rainfall Measuring Mission (TRMM) multi-satellite precipitation analysis (TMPA) data and ERA-Interim atmospheric reanalysis data. The results showed that around three-fourths of rainwater was derived from recycled water at local-regional scales. Satellite-observed outgoing longwave radiation (OLR) and complementary satellite data from MODerate-resolution Imaging Spectroradiometer (MODIS) and Advanced Microwave Scanning Radiometer (AMSR) series implied that the isotopic ratios in rainwater were affected by evaporation of raindrops falling from convective clouds. Consequently, integrated SWI analysis of rain-, surface and subsurface waters, together with the atmospheric water budget analysis, revealed that shallow groundwater of small wetlands in this region was very likely to be recharged from surface waters originating from local rainfall, which was

  4. Gene expression analysis of the biocontrol fungus Trichoderma harzianum in the presence of tomato plants, chitin, or glucose using a high-density oligonucleotide microarray.

    Science.gov (United States)

    Samolski, Ilanit; de Luis, Alberto; Vizcaíno, Juan Antonio; Monte, Enrique; Suárez, M Belén

    2009-10-13

    It has recently been shown that the Trichoderma fungal species used for biocontrol of plant diseases are capable of interacting with plant roots directly, behaving as symbiotic microorganisms. With a view to providing further information at transcriptomic level about the early response of Trichoderma to a host plant, we developed a high-density oligonucleotide (HDO) microarray encompassing 14,081 Expressed Sequence Tag (EST)-based transcripts from eight Trichoderma spp. and 9,121 genome-derived transcripts of T. reesei, and we have used this microarray to examine the gene expression of T. harzianum either alone or in the presence of tomato plants, chitin, or glucose. Global microarray analysis revealed 1,617 probe sets showing differential expression in T. harzianum mycelia under at least one of the culture conditions tested as compared with one another. Hierarchical clustering and heat map representation showed that the expression patterns obtained in glucose medium clustered separately from the expression patterns observed in the presence of tomato plants and chitin. Annotations using the Blast2GO suite identified 85 of the 257 transcripts whose probe sets afforded up-regulated expression in response to tomato plants. Some of these transcripts were predicted to encode proteins related to Trichoderma-host (fungus or plant) associations, such as Sm1/Elp1 protein, proteases P6281 and PRA1, enchochitinase CHIT42, or QID74 protein, although previously uncharacterized genes were also identified, including those responsible for the possible biosynthesis of nitric oxide, xenobiotic detoxification, mycelium development, or those related to the formation of infection structures in plant tissues. The effectiveness of the Trichoderma HDO microarray to detect different gene responses under different growth conditions in the fungus T. harzianum strongly indicates that this tool should be useful for further assays that include different stages of plant colonization, as well as

  5. Continuous infra-red measurement using an interference filter, dosage of H{sub 2}O - D{sub 2}O mixtures; Doseur continu infra-rouge a filtre interferentiel dosage des melanges H{sub 2}O - D{sub 2}O

    Energy Technology Data Exchange (ETDEWEB)

    Ceccaldi, M; Goujon, P [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1964-07-01

    In this report is described original work leading to the construction of an apparatus for the continuous measurement of the isotopic content of H{sub 2}O - D{sub 2}O mixtures. The measurement is based on an application of the Beer-Lambert law to the {gamma}{sub OH} band of HDO (3400 cm{sup -1}). The conditions of measurement are given. The apparatus is a double-beam device in which the wave length selection is obtained with an interference filter together with a modulator acting as a pass-band filter. The large-surface pneumatic detector using capacity changes has made it possible to obtain a simple optical set-up. Various results are presented. If sufficient precautions are taken to maintain the apparatus and the water at a constant temperature it is possible to carry out measurements with a precision of {+-} 0.002, or else to detect concentration differences of 0.001 per cent in the case of heavy waters containing more than 99.5 per cent of D{sub 2}O. (authors) [French] Dans ce memoire original il est decrit la realisation d'un appareil destine a mesurer en continu la teneur isotopique des melanges H{sub 2}O-D{sub 2}O. La mesure est basee sur l'application de la loi de Beer-Lambert a la bande {gamma}{sub OH} de HDO (3400 cm{sup -1}). Les conditions de mesure sont precisees. L'appareil est un dispositif 'double-faisceau' dans lequel la selection des longueurs d'onde est obtenue par un filtre interferentiel associe a un modulateur travaillant en filtre passe-bande. Le detecteur pneumatique, de grande surface, a variation de capacite, a permis un montage optique simple. Divers resultats sont presentes. En prenant la precaution de maintenir constante la temperature de l'appareil et de l'eau on peut effectuer des mesures a {+-} 0,002 pour cent pres, ou mettre en evidence des ecarts de teneur de 0,001 pour cent pour des eaux lourdes de titre superieur a 99,5 pour cent. (auteurs)

  6. Aplicación de Gestión Total Eficiente de Energía en el Centro Internacional de Salud “La Pradera” ; Application of Total Management Techniques of Energy Efficiency at the International Health Centre "La Pradera”

    Directory of Open Access Journals (Sweden)

    Leyat Fernández Velázquez

    2014-06-01

    Full Text Available En este artículo se presentan los primeros resultados obtenidos de la aplicación de la Metodología de las Técnicas de Gestión Total Eficiente de la Energía en el Centro Internacional de Salud “La Pradera”. Se realizó una caracterización energética del Centro, determinándose la estructura de consumo de los portadores energéticos. Se efectuó una investigación estadística de los datos del Centro durante los años 2010 y 2011, obteniéndose que el portador energético más influyente en el consumo de la instalación es la energía eléctrica. Se analizó la relación entre el índice de consumo kilowatt hora vs habitación-día-ocupada (kWh/HDO para evaluar correctamente la eficiencia energética del centro, determinándose que la temperatura ambiente es un factor significativo en los consumos de electricidad, lo cual conllevó a la obtención de un nuevo índice de consumo que refleja acertadamente el comportamiento del consumo de energía eléctrica en función de los servicios prestados por esta entidad. This article presents the first results of the application of the Methodology for Total Management Techniques of Energy Efficiency at the International Health Centre "La Pradera". It was realized an energetic characterization of the Centre, determining the structure of energy carriers consumption. It was conducted a statistical investigation of the data Centre during the years 2010 and 2011, giving the electricity as the more influential energy consumption of the facility. It was analyzed the relationship between kilowatt hour consumption rate vs day-occupied-room (kWh / HDO to assess correctly the energy efficiency of the Centre concluding that the room temperature is a significant factor in the consumption of electricity, which led to the award of a new index that accurately reflects the consumption behaviour of electric energy consumption based on the services provided by this entity.

  7. Solid deuterated water in space: detection constraints from laboratory experiments

    Science.gov (United States)

    Urso, R. G.; Palumbo, M. E.; Baratta, G. A.; Scirè, C.; Strazzulla, G.

    2018-06-01

    The comparison between astronomical spectra and laboratory experiments is fundamental to spread light on the structure and composition of ices found in interstellar dense molecular clouds and in Solar System bodies. Water is among the most abundant solid-phase species observed in these environments, and several attempts have been made to investigate the presence of its solid-phase isotopologues. In particular, the detection of the O-D stretching mode band at 4.1 μm due to both D2O and HDO within icy grain mantles is still under debate, and no detection have been reported about the presence of these species within icy bodies in the Solar System yet. In the near future, an important contribution could derive from the data acquired in the O-D stretching mode spectral range by the sensitive instruments on board the James Webb Space Telescope. With this in mind, we performed several laboratory experiments to study the O-D stretching mode band in solid mixtures containing water and deuterated water deposited in the temperature range between 17 and 155 K, in order to simulate astrophysical relevant conditions. Furthermore, samples have been studied at various temperature and irradiated with energetic ions (200 keV H+) in order to study the effects induced by both thermal and energetic processing. Our results provide some constraints on the detection of the 4.1 μm band in astronomical environments.

  8. Hot water in the Inner 100 AU of the Class 0 protostar NGC 1333 IRAS2A

    DEFF Research Database (Denmark)

    Visser, Ruud; Jørgensen, Jes Kristian; Kristensen, Lars E.

    2013-01-01

    -303 lines of H_2^{16}O and H_2^{18}O (1097 GHz, E u/k = 249 K) in the low-mass Class 0 protostar NGC 1333 IRAS2A. A spherical radiative transfer model with a power-law density profile is unable to reproduce both the HIFI data and existing interferometric data on the H_2^{18}O 313-220 line (203 GHz, E u....../k = 204 K). Instead, the HIFI spectra likely show optically thick emission from a hot core with a radius of about 100 AU. The mass of the hot core is estimated from the C18O J = 9-8 and 10-9 lines. We derive a lower limit to the hot water abundance of 2 × 10-5, consistent with the theoretical predictions...... of ~10-4. The revised HDO/H2O abundance ratio is 1 × 10-3, an order of magnitude lower than previously estimated. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA....

  9. Synthesis of Green Diesel From Waste Cooking Oil Through Hydrodeoxygenation Technology With NiMo/γ-Al2O3 Catalysts

    Directory of Open Access Journals (Sweden)

    Heriyanto Heri

    2018-01-01

    Full Text Available Hydrodeoxygenation (HDO of waste cooking oil (WCO and trapped grease over sulfide catalysts was examined to produce high quality transportation fuel from low-grade resources. The hydrodeoxygenation of waste cooking oils was carried out in a high pressure of 30 and 60 bar and high temperature of 300 – 400 °C in a batch reactor autoclave. NiMo/γ-Al2O3 catalyst was prepared and for the first time tested in hydroprocessing of waste cooking oil. The content of NiMo/γ-Al2O3 in each catalyst was about wCo 5 wt.%. A maximum of 77,97 % green diesel yield was achieved at nearly complete conversion of waste cooking oil using NiMo/γ-Al2O3 at temperature of 400°C, pressure 60 bar and 4 hours of reaction time. The oxygen content was decreased from 14,25 wt.% to 13,35 wt.%, at temperature of 400°C, pressure of 30 bar and 1 hour of reaction time. The Hydrodeoxygenation process was much influenced by temperature, pressure, and time.

  10. Conceptual Study of A Hetrodyne Receiver for the Origins Space Telescope

    Science.gov (United States)

    Wiedner, Martina

    2018-01-01

    The Origins Space Telescope (OST) is a mission concept of an extremely versatile observatory with 5 science instruments, of which the HEterodyne Receivers for OST (HERO) is one. HERO's main targets are high spectral resolution observations (Δλ/λ up to 107 or Δv = 0.03km/s) of water to follow its trail from cores to YSOs as well as H2O and HDO observations on comets. HERO will probe all neutral ISM phases using cooling lines ([CII], [OI]) and hydrides as probes of CO-dark H2 (CH, HF). HERO will reveal how molecular clouds and filaments form in the local ISM up to nearby galaxies. In order to achieve these observational goals, HERO will cover an extremely wide frequency range from 468 to 2700 GHz and a window around the OI line at 4563 to 4752GHz. It will consist of very large focal plane arrays of 128 pixels between 900 - 2700 GHz and at 4.7 THz, and 32 pixels for the 468 to 900 GHz range. The instrument is exploiting Herschel/HIFI heritage. HERO's large arrays require low dissipation and low power components. The HERO concept makes use of the latest cryogenic SiGe amplifier technology, as well as CMOS technology for the backends with 2 orders of magnitude lower power.

  11. The effect of pressure on the near-neighbor distance in water

    International Nuclear Information System (INIS)

    Whalley, E.

    1975-01-01

    When liquid water is compressed, the O--O hydrogen bonds tend to contract because of the direct effect of the pressure, and the O--O--O angles tend to deviate more from the tetrahedral. The coupling between the O--O stretching and O--O--O angle bending is such that the change of the angles tends to increase the bond lengths. The net effect of pressure is the resultant of the direct contraction and the indirect expansion. It is suggested that the actual contraction can be measured by the effect of pressure on the O--H or O--D stretching frequencies of HDO in dilute solution in D 2 O or H 2 O. The application of this suggestion to literature data shows that the bond contracts only about 0.3 of the rate that the hydrogen bond in ice contracts. No doubt the contraction due to the direct effect of pressure is largely compensated by the expansion due to the distortion of the O--O--O angles

  12. A hollow-waveguide gas correlation radiometer for ultra-precise column measurements of formaldehyde on Mars

    International Nuclear Information System (INIS)

    Wilson, Emily L; Riris, Haris; Heaps, William S; Neveu, Marc; Georgieva, Elena M

    2011-01-01

    We present preliminary results in the development of a miniaturized gas correlation radiometer that implements a hollow-core optical fiber (hollow-waveguide) gas correlation cell. The substantial reduction in mass and volume of the gas correlation cell makes this technology appropriate for an orbital mission—capable of pinpointing sources of trace gases in the Martian atmosphere. Here, we demonstrate a formaldehyde (H 2 CO) sensor and report a detection limit equivalent to ∼30 ppb in the Martian atmosphere. The relative simplicity of the technique allows it to be expanded to measure a range of atmospheric trace gases of interest on Mars such as methane (CH 4 ), water vapor (H 2 O), deuterated water vapor (HDO), and methanol (CH 3 OH). Performance of a formaldehyde instrument in a Mars orbit has been simulated assuming a 3 m long, 1000 µm inner diameter hollow-core fiber gas correlation cell, a 92.8° sun-synchronous orbit from 400 km with a horizontal sampling scale of 10 km × 10 km. Initial results indicate that for 1 s of averaging, a detection limit of 1 ppb is possible

  13. Coherent cavity-enhanced dual-comb spectroscopy.

    Science.gov (United States)

    Fleisher, Adam J; Long, David A; Reed, Zachary D; Hodges, Joseph T; Plusquellic, David F

    2016-05-16

    Dual-comb spectroscopy allows for the rapid, multiplexed acquisition of high-resolution spectra without the need for moving parts or low-resolution dispersive optics. This method of broadband spectroscopy is most often accomplished via tight phase locking of two mode-locked lasers or via sophisticated signal processing algorithms, and therefore, long integration times of phase coherent signals are difficult to achieve. Here we demonstrate an alternative approach to dual-comb spectroscopy using two phase modulator combs originating from a single continuous-wave laser capable of > 2 hours of coherent real-time averaging. The dual combs were generated by driving the phase modulators with step-recovery diodes where each comb consisted of > 250 teeth with 203 MHz spacing and spanned > 50 GHz region in the near-infrared. The step-recovery diodes are passive devices that provide low-phase-noise harmonics for efficient coupling into an enhancement cavity at picowatt optical powers. With this approach, we demonstrate the sensitivity to simultaneously monitor ambient levels of CO2, CO, HDO, and H2O in a single spectral region at a maximum acquisition rate of 150 kHz. Robust, compact, low-cost and widely tunable dual-comb systems could enable a network of distributed multiplexed optical sensors.

  14. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts.

    Science.gov (United States)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P; Yang, Bin

    2018-01-10

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al 2 O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf) 4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote deoxygenation reactions catalyzed by super Lewis acids. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    International Nuclear Information System (INIS)

    Wang, Hongliang; Wang, Huamin; Kuhn, Eric; Tucker, Melvin P.; Yang, Bin

    2017-01-01

    Super Lewis acids containing the triflate anion [e.g., Hf(OTf) 4 , Ln(OTf) 3 , In(OTf) 3 , Al(OTf) 3 ] and noble metal catalysts (e.g., Ru/C, Ru/Al2O 3 ) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage through selective bonding to etheric oxygens while the noble metal catalyzed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt % of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates by protonating hydroxyl groups and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalyzed by super Lewis acids.

  16. Efficient Hydrogenolysis of Guaiacol over Highly Dispersed Ni/MCM-41 Catalyst Combined with HZSM-5

    Directory of Open Access Journals (Sweden)

    Songbai Qiu

    2016-09-01

    Full Text Available A series of MCM-41 supported Ni catalysts with high metal dispersion was successfully synthesized by simple co-impregnation using proper ethylene glycol (EG. The acquired Ni-based catalysts performed the outstanding hydrogenolysis activity of guaiacol. The effects of the synthesis parameters including drying temperature, calcination temperature, and metal loading on the physical properties of NiO nanoparticles were investigated through the use of X-ray diffraction (XRD. The drying temperature was found to significantly influence the particle sizes of NiO supported on MCM-41, but the calcination temperature and metal loading had less influence. Interestingly, the small particle size (≤3.3 nm and the high dispersion of NiO particles were also obtained for co-impregnation on the mixed support (MCM-41:HZSM-5 = 1:1, similar to that on the single MCM-41 support, leading to excellent hydrogenation activity at low temperature. The guaiacol conversion could reach 97.9% at 150 °C, and the catalytic activity was comparative with that of noble metal catalysts. The hydrodeoxygenation (HDO performance was also promoted by the introduction of acidic HZSM-5 zeolite and an 84.1% yield of cyclohexane at 240 °C was achieved. These findings demonstrate potential applications for the future in promoting and improving industrial catalyst performance.

  17. Synthesis of α-MoC1-x Nanoparticles with a Surface-Modified SBA-15 Hard Template: Determination of Structure-Function Relationships in Acetic Acid Deoxygenation.

    Science.gov (United States)

    Baddour, Frederick G; Nash, Connor P; Schaidle, Joshua A; Ruddy, Daniel A

    2016-07-25

    Surface modification of mesoporous SBA-15 silica generated a hydrophobic environment for a molybdenum diamine (Mo-diamine) precursor solution, enabling direct growth of isolated 1.9±0.4 nm α-MoC1-x nanoparticles (NPs) inside the pores of the support. The resulting NP catalysts are bifunctional, and compared to bulk α-MoC1-x and β-Mo2 C, the NPs exhibit a greater acid-site:H-site ratio and a fraction of stronger acid sites. The greater acid-site:H-site ratio results in higher decarbonylation (DCO) selectivity during acetic acid hydrodeoxygenation (HDO) reactions, and the stronger acid sites lead to higher activity and ketonization (KET) selectivity at high temperatures. The hard-templating synthetic method could be a versatile route toward carbide NPs of varying size, composition, and phase, on a range of mesoporous oxide supports. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Production of Jet Fuel-Range Hydrocarbons from Hydrodeoxygenation of Lignin over Super Lewis Acid Combined with Metal Catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Hongliang [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA; Current address: Center of Biomass Engineering/College of Agronomy and Biotechnology, China Agricultural University, Beijing 100193 PR China; Wang, Huamin [Pacific Northwest National Laboratory, 902 Battelle Boulevard Richland WA 99354 USA; Kuhn, Eric [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Tucker, Melvin P. [National Bioenergy Center, National Renewable Energy Laboratory, 15013 Denver West Parkway Golden CO 80401 USA; Yang, Bin [Department of Biological Systems Engineering, Washington State University, Richland WA 99354 USA

    2017-11-14

    Super Lewis acids containing the triflate anion (e.g. Hf(OTf)4, Ln(OTf)3, Al(OTf)3) and noble metal catalysts (e.g. Ru/C, Ru/Al2O3) formed efficient catalytic systems to generate saturated hydrocarbons from lignin in high yields. In such catalytic systems, the metal triflates mediated rapid ether bond cleavage via selective bonding to etheric oxygens while the noble metal catalysed subsequent hydrodeoxygenation (HDO) reactions. Near theoretical yields of hydrocarbons were produced from lignin model compounds by the combined catalysis of Hf(OTf)4 and ruthenium-based catalysts. When a technical lignin derived from a pilot-scale biorefinery was used, more than 30 wt% of the hydrocarbons produced with this catalytic system were cyclohexane and alkylcyclohexanes in the jet fuel range. Super Lewis acids are postulated to strongly interact with lignin substrates via protonating hydroxyls and ether linkages, forming intermediate species that enhance hydrogenation catalysis by supported noble metal catalysts. Meanwhile, the hydrogenation of aromatic rings by the noble metal catalysts can promote oxygenation reactions catalysed by super Lewis acids.

  19. Deuterium trapping in the carbon-silicon co-deposition layers prepared by RF sputtering in D2 atmosphere

    Science.gov (United States)

    Zhang, Hongliang; Zhang, Weiyuan; Su, Ranran; Tu, Hanjun; Shi, Liqun; Hu, Jiansheng

    2018-04-01

    Deuterated carbon-silicon layers co-deposited on graphite and silicon substrates by radio frequency magnetron sputtering in pure D2 plasma were produced to study deuterium trapping and characteristics of the C-Si layers. The C-Si co-deposited layers were examined by ion beam analysis (IBA), Raman spectroscopy (RS), infrared absorption (IR) spectroscopy, thermal desorption spectroscopy (TDS) and scanning electron microscopy (SEM). It was found that the growth rate of the C-Si co-deposition layer decreased with increasing temperature from 350 K to 800 K, the D concentration and C/Si ratios increased differently on graphite and silicon substrates. TDS shows that D desorption is mainly as D2, HD, HDO, CD4, and C2D4 and release peaks occurred at temperatures of less than 900 K. RS and IR analysis reveal that the structure of the C-Si layers became more disordered with increasing temperatures. Rounded areas of peeling with 1-2 μm diameters were observed on the surface.

  20. Spatially-Scanned Dual Comb Spectroscopy for Atmospheric Measurements

    Science.gov (United States)

    Cossel, K.; Waxman, E.; Giorgetta, F.; Cermak, M.; Coddington, I.; Hesselius, D.; Ruben, S.; Swann, W.; Rieker, G. B.; Newbury, N.

    2017-12-01

    Measuring trace gas emissions from sources that are spatially complex and temporally variable, such as leaking natural gas infrastructure, is challenging with current measurement systems. Here, we present a new technique that provides the path-integrated concentrations of multiple gas species between a ground station and a retroreflector mounted on a small quadcopter. Such a system could provide the ability to quantify small area emissions sources as well measure vertical mixing within the boundary layer. The system is based on a near-infrared dual frequency-comb spectroscopy system (DCS) covering 1.58-1.7 microns, which enables rapid, accurate measurements of CO2, CH4, H2O, and HDO. The eye-safe laser light is launched from a telescope on a fast azimuth, elevation gimbal to a small quadcopter carrying a lightweight retroreflector as well as a high-precision real-time kinematic GPS receiver (for real-time cm-level path length measurements) and pressure, temperature and humidity sensors. Here, we show the results of test measurements from controlled releases of CH4 as well as from test vertical profiles.

  1. Functional Analysis of the Trichoderma harzianum nox1 Gene, Encoding an NADPH Oxidase, Relates Production of Reactive Oxygen Species to Specific Biocontrol Activity against Pythium ultimum▿†

    Science.gov (United States)

    Montero-Barrientos, M.; Hermosa, R.; Cardoza, R. E.; Gutiérrez, S.; Monte, E.

    2011-01-01

    The synthesis of reactive oxygen species (ROS) is one of the first events following pathogenic interactions in eukaryotic cells, and NADPH oxidases are involved in the formation of such ROS. The nox1 gene of Trichoderma harzianum was cloned, and its role in antagonism against phytopathogens was analyzed in nox1-overexpressed transformants. The increased levels of nox1 expression in these transformants were accompanied by an increase in ROS production during their direct confrontation with Pythium ultimum. The transformants displayed an increased hydrolytic pattern, as determined by comparing protease, cellulase, and chitinase activities with those for the wild type. In confrontation assays against P. ultimum the nox1-overexpressed transformants were more effective than the wild type, but not in assays against Botrytis cinerea or Rhizoctonia solani. A transcriptomic analysis using a Trichoderma high-density oligonucleotide (HDO) microarray also showed that, compared to gene expression for the interaction of wild-type T. harzianum and P. ultimum, genes related to protease, cellulase, and chitinase activities were differentially upregulated in the interaction of a nox1-overexpressed transformant with this pathogen. Our results show that nox1 is involved in T. harzianum ROS production and antagonism against P. ultimum. PMID:21421791

  2. Method for enriching and separating heavy hydrogen isotopes from substance streams containing such isotopes by means of isotope exchange

    International Nuclear Information System (INIS)

    Knochel, A.; Eggers, I.; Klatte, B.; Wilken, R. D.

    1985-01-01

    A process for enriching and separating heavy hydrogen isotopes having a heavy hydrogen cation (deuterium and/or tritium) from substance streams containing them, wherein the respectively present hydrogen isotopes are exchanged in chemical equilibria. A protic, acid solution containing deuterium and/or tritium is brought into contact with a value material from the group of open-chained polyethers or aminopolyethers, macro-monocyclic or macro-polycyclic polyethers, macro-monocyclic or macro-polycyclic amino polyethers, and mixtures of these values, in their free or proton salt form to form a reaction product of the heavy hydrogen cation with the value or value salt and bring about enrichment of deuterium and/or tritium in the reaction product. The reaction product containing the value or value salt is separated from the solution. The separated reaction product is treated to release the hydrogen isotope(s) to be enriched in the form of deuterium oxide (HDO) and/or tritium oxide (HTO) by regenerating the value or its salt, respectively. The regenerated value is returned for reuse

  3. Laser-based sensor for a coolant leak detection in a nuclear reactor

    Science.gov (United States)

    Kim, T.-S.; Park, H.; Ko, K.; Lim, G.; Cha, Y.-H.; Han, J.; Jeong, D.-Y.

    2010-08-01

    Currently, the nuclear industry needs strongly a reliable detection system to continuously monitor a coolant leak during a normal operation of reactors for the ensurance of nuclear safety. In this work, we propose a new device for the coolant leak detection based on tunable diode laser spectroscopy (TDLS) by using a compact diode laser. For the feasibility experiment, we established an experimental setup consisted of a near-IR diode laser with a wavelength of about 1392 nm, a home-made multi-pass cell and a sample injection system. The feasibility test was performed for the detection of the heavy water (D2O) leaks which can happen in a pressurized heavy water reactor (PWHR). As a result, the device based on the TDLS is shown to be operated successfully in detecting a HDO molecule, which is generated from the leaked heavy water by an isotope exchange reaction between D2O and H2O. Additionally, it is suggested that the performance of the new device, such as sensitivity and stability, can be improved by adapting a cavity enhanced absorption spectroscopy and a compact DFB diode laser. We presume that this laser-based leak detector has several advantages over the conventional techniques currently employed in the nuclear power plant, such as radiation monitoring, humidity monitoring and FT-IR spectroscopy.

  4. Economic analysis of novel synergistic biofuel (H2Bioil) processes

    International Nuclear Information System (INIS)

    Singh, Navneet R.; Mallapragada, Dharik S.; Agrawal, Rakesh; Tyner, Wallace E.

    2012-01-01

    Fast-pyrolysis based processes can be built on small-scale and have higher process carbon and energy efficiency as compared to other options. H 2 Bioil is a novel process based on biomass fast-hydropyrolysis and subsequent hydrodeoxygenation (HDO) and can potentially provide high yields of high energy density liquid fuel at relatively low hydrogen consumption. This paper contains a comprehensive financial analysis of the H 2 Bioil process with hydrogen derived from different sources. Three different carbon tax scenarios are analyzed: no carbon tax, $55/metric ton carbon tax and $110/metric ton carbon tax. The break-even crude oil price for a delivered biomass cost of $94/metric ton when hydrogen is derived from coal, natural gas or nuclear energy ranges from $103 to $116/bbl for no carbon tax and even lower ($99-$111/bbl) for the carbon tax scenarios. This break-even crude oil price compares favorably with the literature estimated prices of fuels from alternate biochemical and thermochemical routes. The impact of the chosen carbon tax is found to be limited relative to the impact of the H 2 source on the H 2 Bioil break-even price. The economic robustness of the processes for hydrogen derived from coal, natural gas, or nuclear energy is seen by an estimated break-even crude oil price of $114-$126/bbl when biomass cost is increased to $121/metric ton. (orig.)

  5. Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase; Spectroscopie infrarouge resolue en temps pour l'etude de la dynamique femtoseconde du proton en phase liquide

    Energy Technology Data Exchange (ETDEWEB)

    Amir, W

    2003-12-15

    This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D{sub 2}O for reasons of experimental and theoretical suitability. However this is not water. Pure water H{sub 2}O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

  6. Economic analysis of novel synergistic biofuel (H{sub 2}Bioil) processes

    Energy Technology Data Exchange (ETDEWEB)

    Singh, Navneet R.; Mallapragada, Dharik S.; Agrawal, Rakesh [Purdue University, School of Chemical Engineering, West Lafayette, IN (United States); Tyner, Wallace E. [Purdue University, Department of Agricultural Economics, West Lafayette, IN (United States)

    2012-06-15

    Fast-pyrolysis based processes can be built on small-scale and have higher process carbon and energy efficiency as compared to other options. H{sub 2}Bioil is a novel process based on biomass fast-hydropyrolysis and subsequent hydrodeoxygenation (HDO) and can potentially provide high yields of high energy density liquid fuel at relatively low hydrogen consumption. This paper contains a comprehensive financial analysis of the H{sub 2}Bioil process with hydrogen derived from different sources. Three different carbon tax scenarios are analyzed: no carbon tax, $55/metric ton carbon tax and $110/metric ton carbon tax. The break-even crude oil price for a delivered biomass cost of $94/metric ton when hydrogen is derived from coal, natural gas or nuclear energy ranges from $103 to $116/bbl for no carbon tax and even lower ($99-$111/bbl) for the carbon tax scenarios. This break-even crude oil price compares favorably with the literature estimated prices of fuels from alternate biochemical and thermochemical routes. The impact of the chosen carbon tax is found to be limited relative to the impact of the H{sub 2} source on the H{sub 2}Bioil break-even price. The economic robustness of the processes for hydrogen derived from coal, natural gas, or nuclear energy is seen by an estimated break-even crude oil price of $114-$126/bbl when biomass cost is increased to $121/metric ton. (orig.)

  7. Hydrogen assisted catalytic biomass pyrolysis. Effect of temperature and pressure

    DEFF Research Database (Denmark)

    Stummann, M.Z.; Høj, M.; Schandel, C. B.

    2018-01-01

    fraction of 17 and 22% daf, corresponding to an energy recovery of between 40 and 53% in the organic product. The yield of the non-condensable gases varied between a mass fraction of 24 and 32% daf and the char yield varied between 9.6 and 18% daf. The condensed organics contained a mass fraction of 42....... The effect of varying the temperature (365–511 °C) and hydrogen pressure (1.6–3.6 MPa) on the product yield and organic composition was studied. The mass balance closed by a mass fraction between 90 and 101% dry ash free basis (daf). The yield of the combined condensed organics and C4+ varied between a mass......–75% aromatics, based on GC × GC-FID chromatographic peak area, and the remainder was primarily naphthenes with minor amounts of paraffins. The condensed organics were essentially oxygen free (mass fraction below 0.001%) when both reactors were used. Bypassing the HDO reactor increased the oxygen concentration...

  8. Trapping of deuterium dissolved in fluidized Li by Y

    Energy Technology Data Exchange (ETDEWEB)

    Fukada, Satoshi, E-mail: sfukada@nucl.kyushu-u.ac.jp [Kyushu University, Fukuoka 816-8580 (Japan); Hiromoto, Tetsushi; Shigeharu, Satoshi; Sugie, Kunihiro [Kyushu University, Fukuoka 816-8580 (Japan); Edao, Yuki [Japan Atomic Energy Agency, Tokai 319-1195 (Japan)

    2014-10-15

    Highlights: • Recovery of deuterium is experimentally proved in liquid Li forced convection flow by Y metal trap. • 10 ppm D as the target concentration is successfully removed from Li flow. • H{sub 2}O or HNO{sub 3} dissolution technique is developed to analyze D concentration in Li or Y. - Abstract: Recovery of D dissolved in a liquid Li flow at low D concentration is experimentally investigated using a Y metal absorber under the two fluidized conditions: (a) in a vertical cylindrical tube and (b) in an agitated vessel. The target concentration is 1 appm in Li around at 300 °C. The two concentrations of D remaining in Li and recovered by Y are detected by a dissolution method using H{sub 2}O with depleted-D and HNO{sub 3}. The main released species is HD. A small amount of HDO released is reduced to HD by a Mg particle bed. It is found that HF-treated Y can absorb H isotopes at the target temperature and concentration. The chemical dissolution technique is found to be useful to specify the two absolute concentrations of D recovered by Y and D remaining in Li.

  9. Trapping of deuterium dissolved in fluidized Li by Y

    International Nuclear Information System (INIS)

    Fukada, Satoshi; Hiromoto, Tetsushi; Shigeharu, Satoshi; Sugie, Kunihiro; Edao, Yuki

    2014-01-01

    Highlights: • Recovery of deuterium is experimentally proved in liquid Li forced convection flow by Y metal trap. • 10 ppm D as the target concentration is successfully removed from Li flow. • H 2 O or HNO 3 dissolution technique is developed to analyze D concentration in Li or Y. - Abstract: Recovery of D dissolved in a liquid Li flow at low D concentration is experimentally investigated using a Y metal absorber under the two fluidized conditions: (a) in a vertical cylindrical tube and (b) in an agitated vessel. The target concentration is 1 appm in Li around at 300 °C. The two concentrations of D remaining in Li and recovered by Y are detected by a dissolution method using H 2 O with depleted-D and HNO 3 . The main released species is HD. A small amount of HDO released is reduced to HD by a Mg particle bed. It is found that HF-treated Y can absorb H isotopes at the target temperature and concentration. The chemical dissolution technique is found to be useful to specify the two absolute concentrations of D recovered by Y and D remaining in Li

  10. New measurements of D/H on Mars using EXES aboard SOFIA

    Science.gov (United States)

    Encrenaz, T.; DeWitt, C.; Richter, M. J.; Greathouse, T. K.; Fouchet, T.; Montmessin, F.; Lefèvre, F.; Bézard, B.; Atreya, S. K.; Aoki, S.; Sagawa, H.

    2018-05-01

    The global D/H ratio on Mars is an important measurement for understanding the past history of water on Mars; locally, through condensation and sublimation processes, it is a possible tracer of the sources and sinks of water vapor on Mars. Measuring D/H as a function of longitude, latitude and season is necessary for determining the present averaged value of D/H on Mars. Following an earlier measurement in April 2014, we used the Echelon Cross Echelle Spectrograph (EXES) instrument on board the Stratospheric Observatory for Infrared Astronomy (SOFIA) facility to map D/H on Mars on two occasions, on March 24, 2016 (Ls = 127°), and January 24, 2017 (Ls = 304°), by measuring simultaneously the abundances of H2O and HDO in the 1383-1391 cm-1 range (7.2 μm). The D/H disk-integrated values are 4.0 (+0.8, -0.6) × Vienna Standard Mean Ocean Water (VSMOW) and 4.5 (+0.7, -0.6) × VSMOW, respectively, in agreement with our earlier result. The main result of this study is that there is no evidence of strong local variations in the D/H ratio nor for seasonal variations in the global D/H ratio between northern summer and southern summer.

  11. Time resolved infrared spectroscopy of femtosecond proton dynamics in the liquid phase

    International Nuclear Information System (INIS)

    Amir, W.

    2003-12-01

    This work of thesis aims to understand the strong mobility of protons in water. Water is fundamental to life and mediates many chemical and biological processes. However this liquid is poorly understood at the molecular level. The richness of interdisciplinary sciences allows us to study the properties which make it so unique. The technique used for this study was the femtosecond time resolved vibrational spectroscopy. Several experiments were carried out to characterize the femtosecond proton dynamics in water. The visualization of the rotation of water molecules obtained by anisotropy measurements will be presented. This experiment is carried out in isotopic water HDO/D 2 O for reasons of experimental and theoretical suitability. However this is not water. Pure water H 2 O was also studied without thermal effects across vibrations modes. An intermolecular energy resonant transfer was observed. Finally the localized structure of the proton in water (called Eigen form) was clearly experimentally observed. This molecule is implicated in the abnormal mobility of the proton in water (Grotthuss mechanism). (author)

  12. Fourier transform measurements of water vapor line parameters in the 4200-6600 cm{sup -1} region

    Energy Technology Data Exchange (ETDEWEB)

    Jenouvrier, Alain [Groupe de Spectrometrie Moleculaire et Atmospherique, UMR CNRS 6089, UFR Sciences, Moulin de la Housse, B.P. 1039, 51067 Reims Cedex 2 (France)]. E-mail: alain.jenouvrier@univ-reims.fr; Daumont, Ludovic [Groupe de Spectrometrie Moleculaire et Atmospherique, UMR CNRS 6089, UFR Sciences, Moulin de la Housse, B.P. 1039, 51067 Reims Cedex 2 (France); Regalia-Jarlot, Laurence [Groupe de Spectrometrie Moleculaire et Atmospherique, UMR CNRS 6089, UFR Sciences, Moulin de la Housse, B.P. 1039, 51067 Reims Cedex 2 (France); Tyuterev, Vladimir G. [Groupe de Spectrometrie Moleculaire et Atmospherique, UMR CNRS 6089, UFR Sciences, Moulin de la Housse, B.P. 1039, 51067 Reims Cedex 2 (France); Carleer, Michel [Service de Chimie Quantique et de Photophysique, CP 160/09, Universite Libre de Bruxelles, 50 Av. F.D. Roosevelt, B-1050 Brussels (Belgium); Vandaele, Ann Carine [Institut d' Aeronomie Spatiale de Belgique, Av. Circulaire 3, B-1180 Brussels (Belgium); Mikhailenko, Semen [Laboratory of Theoretical Spectroscopy, Institute of Atmospheric Optics, Russian Academy of Sciences, 1, Av. Akademichesskii, 634055 Tomsk (Russian Federation); Fally, Sophie [Service de Chimie Quantique et de Photophysique, CP 160/09, Universite Libre de Bruxelles, 50 Av. F.D. Roosevelt, B-1050 Brussels (Belgium)

    2007-06-15

    New high-resolution water vapor absorption spectra were obtained at room temperature in the 4200-6600 cm{sup -1} spectral region by combining Fourier transform spectrometers (FTS) with single and multiple reflection cells. With absorption paths from 0.3 to 1800 m in pure and air diluted water vapor, accurate measurements of about 10400 lines in an intensity range from 10{sup -29} to 10{sup -19} cm/molecule have been performed. Positions, intensities, self- and air-broadening coefficients and air-induced shifts were determined for the H{sub 2} {sup 16}O, H{sub 2} {sup 17}O, H{sub 2} {sup 18}O and HDO isotopologues. The rovibrational assignment of the observed lines was performed with the use of global variational predictions and allowed the identification of several new energy levels. One major contribution of this work consists of the identification of 3280 new weak lines. A very close agreement between the new measured parameters and those listed in the database is reported as well as between the observations and the most recent variational calculations for the positions and the intensities. The present parameters provide an extended and homogeneous data set for water vapor, which is shown to significantly improve the databases for atmospheric applications, especially in the transmission windows on both sides of the band centered at 5400 cm{sup -1}.

  13. Air exposure and sample storage time influence on hydrogen release from tungsten

    Energy Technology Data Exchange (ETDEWEB)

    Moshkunov, K.A., E-mail: moshkunov@gmail.co [National Research Nuclear University ' MEPhI' , Kashirskoe sh. 31, 115409 Moscow (Russian Federation); Schmid, K.; Mayer, M. [Max-Planck-Institut fuer Plasmaphysik, EURATOM Association, Boltzmannstrasse 2, D-85748 Garching (Germany); Kurnaev, V.A.; Gasparyan, Yu.M. [National Research Nuclear University ' MEPhI' , Kashirskoe sh. 31, 115409 Moscow (Russian Federation)

    2010-09-30

    In investigations of hydrogen retention in first wall components the influence of the conditions of the implanted target storage prior to analysis and the storage time is often neglected. Therefore we have performed a dedicated set of experiments. The release of hydrogen from samples exposed to ambient air after irradiation was compared to samples kept in vacuum. For air exposed samples significant amounts of HDO and D{sub 2}O are detected during TDS. Additional experiments have shown that heavy water is formed by recombination of releasing D and H atoms with O on the W surface. This water formation can alter hydrogen retention results significantly, in particular - for low retention cases. In addition to the influence of ambient air exposure also the influence of storage time in vacuum was investigated. After implantation at 300 K the samples were stored in vacuum for up to 1 week during which the retained amount decreased significantly. The subsequently measured TDS spectra showed that D was lost from both the high and low energy peaks during storage at ambient temperature of {approx}300 K. An attempt to simulate this release from both peaks during room temperature storage by TMAP 7 calculations showed that this effect cannot be explained by conventional diffusion/trapping models.

  14. Air exposure and sample storage time influence on hydrogen release from tungsten

    International Nuclear Information System (INIS)

    Moshkunov, K.A.; Schmid, K.; Mayer, M.; Kurnaev, V.A.; Gasparyan, Yu.M.

    2010-01-01

    In investigations of hydrogen retention in first wall components the influence of the conditions of the implanted target storage prior to analysis and the storage time is often neglected. Therefore we have performed a dedicated set of experiments. The release of hydrogen from samples exposed to ambient air after irradiation was compared to samples kept in vacuum. For air exposed samples significant amounts of HDO and D 2 O are detected during TDS. Additional experiments have shown that heavy water is formed by recombination of releasing D and H atoms with O on the W surface. This water formation can alter hydrogen retention results significantly, in particular - for low retention cases. In addition to the influence of ambient air exposure also the influence of storage time in vacuum was investigated. After implantation at 300 K the samples were stored in vacuum for up to 1 week during which the retained amount decreased significantly. The subsequently measured TDS spectra showed that D was lost from both the high and low energy peaks during storage at ambient temperature of ∼300 K. An attempt to simulate this release from both peaks during room temperature storage by TMAP 7 calculations showed that this effect cannot be explained by conventional diffusion/trapping models.

  15. Air exposure and sample storage time influence on hydrogen release from tungsten

    Science.gov (United States)

    Moshkunov, K. A.; Schmid, K.; Mayer, M.; Kurnaev, V. A.; Gasparyan, Yu. M.

    2010-09-01

    In investigations of hydrogen retention in first wall components the influence of the conditions of the implanted target storage prior to analysis and the storage time is often neglected. Therefore we have performed a dedicated set of experiments. The release of hydrogen from samples exposed to ambient air after irradiation was compared to samples kept in vacuum. For air exposed samples significant amounts of HDO and D 2O are detected during TDS. Additional experiments have shown that heavy water is formed by recombination of releasing D and H atoms with O on the W surface. This water formation can alter hydrogen retention results significantly, in particular - for low retention cases. In addition to the influence of ambient air exposure also the influence of storage time in vacuum was investigated. After implantation at 300 K the samples were stored in vacuum for up to 1 week during which the retained amount decreased significantly. The subsequently measured TDS spectra showed that D was lost from both the high and low energy peaks during storage at ambient temperature of ˜300 K. An attempt to simulate this release from both peaks during room temperature storage by TMAP 7 calculations showed that this effect cannot be explained by conventional diffusion/trapping models.

  16. Nanoporous Cu–Al–Co Alloys for Selective Furfural Hydrodeoxygenation to 2-Methylfuran

    Energy Technology Data Exchange (ETDEWEB)

    Hutchings, Gregory S.; Luc, Wesley; Lu, Qi; Zhou, Yang; Vlachos, Dionisios G.; Jiao, Feng (Delaware)

    2017-03-17

    By finding new catalysts for selective and efficient conversion of biomass-derived products to industrially relevant chemicals and fuels, a transition from fossil fuel feedstocks may be achieved. Furfural (C5H4O2) is a platform chemical which may be converted to multiple heterocyclic and ring-opening products, but to date there have been few catalysts which enable selective hydrodeoxygenation to 2-methylfuran (2-MF, C5H6O). Here, we present a self-supported nanoporous Cu–Al–Co ternary alloy catalyst with high furfural HDO activity toward 2-MF, achieving up to 66.0% selectivity and 98.2% overall conversion at 513 K with only a ~5 atomic % Co composition. Some further analysis over multiple temperature conditions and nominal Co concentrations was performed to examine optimal conditions and tune catalyst performance, and operando X-ray absorption spectroscopy experiments were conducted to elucidate the structure of the catalyst in the reaction environment.

  17. Acquisition system of analysis and control data for the catalytic isotopic exchange module of the cryogenic pilot plant with mathematical modeling

    International Nuclear Information System (INIS)

    Retevoi, Carmen Maria; Cristescu, Ioana; Bornea, Anisia; Cristescu, Ion

    2000-01-01

    The main problem of the isotope exchange is the catalytic action of the reaction. In order to increase the economic efficiency it is suggested using the hydrophobic catalysts. The 'virtual instrument' which we design is made for monitoring the constant temperature of column, analysis and power supply commands for electrical heat exchangers. With the most popular signal conditioning product line, SCXI 1100 and DAQ hardware AT-MIO-16-XE-10 from National Instruments, we perform the multi-channel acquisition at DAQ boards rates. We chose signal conditioning owing to the following advantages: electrically isolation, transducer interfacing, signal amplification, filtering and high-speed channel multiplexing. The mathematical modeling allows us the equilibrium graphical representation of operating curve for system with equation H 2 O+HD -> HDO+H 2 . With Mc. Cobe-Thicle diagram there are determined the numbers of theoretical taller for different configurations of hydrophilic package / catalyst bed. Also, it is easy to monitor the operating parameter variation (L/G-liquid/gas, temperature, etc.) and feeding concentration on gaseous and liquid phase for separation performances. (authors)

  18. Chemistry and catalysis of coal liquefaction, catalytic and thermal upgrading of coal liquid and hydrogenation of CO to produce fuels. Quarterly progress report, April-June 1980

    Energy Technology Data Exchange (ETDEWEB)

    Wiser, W.H.

    1980-01-01

    Systematic hydrodeoxygenation (HDO) studies of polycyclic ketones, e.g., 1-tetralone (1) and 2-tetralone (2) were carried out. The change in product composition as a function of sulfided catalyst type, reaction temperature, and contact time were investigated and feasible mechanistic schemes were developed. The hydrodenitrogenation (HDN) of acridine, a compound representative of linear N-containing polycyclics with a middle pyridine ring, was investigated. Results obtained show that at least two aromatic rings in the acridine system must be saturated before removal of the nitrogen atom from the middle ring could be effected. The catalytic cracking of 9,10-dihydronaphthalene was systematically investigated and a feasible mechanistic scheme for the reactions involved was developed. The study demonstrates that conventional zeolite-containing catalysts are ineffective for cracking of a middle hydroaromatic ring, flanked by two aromatic rings. Cracking of a middle hydroaromatic ring with such catalysts is effected only if the ring is flanked by at least another hydroaromatic ring, as in 1,2,3,4,9,10,11,12-octahydrophenanthrene. Studies on the effect of deactivation of commercial CoMo/Al/sub 2/O/sub 3/ catalysts by pyridine poisoning and by coke showed that the remaining active sites were essentially identical in character to those on the fresh catalyst. Thus, deactivation causes loss of some sites, but does not affect the activity of the remaining sites. Pyridine was much more effective in deactivating the catalyst than coke on a weight basis.

  19. Strategy for high-accuracy-and-precision retrieval of atmospheric methane from the mid-infrared FTIR network

    Directory of Open Access Journals (Sweden)

    R. Sussmann

    2011-09-01

    Full Text Available We present a strategy (MIR-GBM v1.0 for the retrieval of column-averaged dry-air mole fractions of methane (XCH4 with a precision <0.3% (1-σ diurnal variation, 7-min integration and a seasonal bias <0.14% from mid-infrared ground-based solar FTIR measurements of the Network for the Detection of Atmospheric Composition Change (NDACC, comprising 22 FTIR stations. This makes NDACC methane data useful for satellite validation and for the inversion of regional-scale sources and sinks in addition to long-term trend analysis. Such retrievals complement the high accuracy and precision near-infrared observations of the younger Total Carbon Column Observing Network (TCCON with time series dating back 15 years or so before TCCON operations began.

    MIR-GBM v1.0 is using HITRAN 2000 (including the 2001 update release and 3 spectral micro windows (2613.70–2615.40 cm−1, 2835.50–2835.80 cm−1, 2921.00–2921.60 cm−1. A first-order Tikhonov constraint is applied to the state vector given in units of per cent of volume mixing ratio. It is tuned to achieve minimum diurnal variation without damping seasonality. Final quality selection of the retrievals uses a threshold for the goodness of fit (χ2 < 1 as well as for the ratio of root-mean-square spectral noise and information content (<0.15%. Column-averaged dry-air mole fractions are calculated using the retrieved methane profiles and four-times-daily pressure-temperature-humidity profiles from National Center for Environmental Prediction (NCEP interpolated to the time of measurement.

    MIR-GBM v1.0 is the optimum of 24 tested retrieval strategies (8 different spectral micro-window selections, 3 spectroscopic line lists: HITRAN 2000, 2004, 2008. Dominant errors of the non-optimum retrieval strategies are systematic HDO/H2O-CH4 interference errors leading to a seasonal bias up to ≈5%. Therefore interference

  20. Cold guided beams of polar molecules

    International Nuclear Information System (INIS)

    Motsch, Michael

    2010-01-01

    This thesis reports on experiments characterizing cold guided beams of polar molecules which are produced by electrostatic velocity filtering. This filtering method exploits the interaction between the polar molecules and the electric field provided by an electrostatic quadrupole guide to extract efficiently the slow molecules from a thermal reservoir. For molecules with large and linear Stark shifts such as deuterated ammonia (ND 3 ) or formaldehyde (H 2 CO), fluxes of guided molecules of 10 10 -10 11 molecules/s are produced. The velocities of the molecules in these beams are in the range of 10-200 m/s and correspond to typical translational temperatures of a few Kelvin. The maximum velocity of the guided molecules depends on the Stark shift, the molecular mass, the geometry of the guide, and the applied electrode voltage. Although the source is operated in the near-effusive regime, the number density of the slowest molecules is sensitive to collisions. A theoretical model, taking into account this velocity-dependent collisional loss of molecules in the vicinity of the nozzle, reproduces the density of the guided molecules over a wide pressure range. A careful adjustment of pressure allows an increase in the total number of molecules, whilst yet minimizing losses due to collisions of the sought-for slow molecules. This is an important issue for future applications. Electrostatic velocity filtering is suited for different molecular species. This is demonstrated by producing cold guided beams of the water isotopologs H 2 O, D 2 O, and HDO. Although these are chemically similar, they show linear and quadratic Stark shifts, respectively, when exposed to external electric fields. As a result, the flux of HDO is larger by one order of magnitude, and the flux of the individual isotopologs shows a characteristic dependence on the guiding electric field. The internal-state distribution of guided molecules is studied with a newly developed diagnostic method: depletion

  1. The structure and function of supported molybdenum nitride and molybdenum carbide hydrotreating catalysts

    Science.gov (United States)

    Dolce, Gregory Martin

    1997-11-01

    A series of gamma-Alsb2Osb3 supported molybdenum nitrides and carbides were prepared by the temperature programmed reaction of supported molybdates with ammonia and methane/hydrogen mixtures, respectively. In the first part of this research, the effects of synthesis heating rates and molybdenum loading on the catalytic properties of the materials were examined. A significant amount of excess carbon was deposited on the surface of the carbides during synthesis. The materials consisted of small particles which were very highly dispersed. Oxygen chemisorption indicated that the nitride particles may have been two-dimensional. The dispersion of the carbides, however, appeared to decrease as the loading increased. The catalysts were evaluated for hydrodenitrogenation (HDN), hydrodesulfurization (HDS), and hydrodeoxygenation (HDO). The molybdenum loading had the largest effect on the activity of the materials. For the nitrides, the HDN and HDS activities were inverse functions of the loading. This suggested that the most active HDN and HDS sites were located at the perimeter of the two-dimensional particles. The HDN and HDS activities of the carbides followed the same trend as the oxygen uptake. This result suggested that oxygen titrated the active sites on the supported carbides. Selected catalysts were evaluated for methylcarbazole HDN, dibenzothiophene HDS, and dibenzofuran HDO. The activity and selectivity of the nitrides and carbides were competitive with a presulfided commercial catalyst. In the second part of this work, a series of supported nitrides and carbides were prepared using a wider range of loadings (5-30 wt% Mo). Thermogravimetric analysis was used to determine the temperature at which excess carbon was deposited on the carbides. By modifying the synthesis parameters, the deposition of excess carbon was effectively inhibited. The dispersions of the supported nitrides and carbides were constant and suggested that the materials consisted of two

  2. Comet 67P Through the Lens of Art

    Science.gov (United States)

    Smirnova, Ekaterina

    2017-04-01

    My proposal is to share my artistic exploration of a comet through the bodily senses, while finding inspiration in scientific data. I will present my artwork as a slideshow, showcasing: large scale paintings, ceramic sculptures, music and interactive augmented reality. The Rosetta mission of the European Space Agency (ESA) to comet 67P/ Churyumov-Gerasimenko is remarkable. The scientific investigation of the comet's composition, atmosphere, dust, vapor, surface and internal structure are crucial to help researchers understand the origin of the solar system and our own planet. Sight: Paintings Rosetta mission discovered that the water on the comet is different from the water on Earth; as measured with the ROSINA-DFMS instrument on Rosetta, water on 67P contains approximately 3 times more hydrogen­deuterium oxide - HDO, than found in Earth's oceans. In the art studio I re-create water that is close in composition to the water on the comet, by concentrating the level of HDO. With this water I paint large scale watermedia paintings, based on the photographs by Rosetta (OSIRIS, Nav. Cam.). Touch: Sculptures While exploring the comet's three-dimensional form, I focus more deeply on the composition of the comet. Stoneware clay and my choice of a glaze both include iron oxide, a common constituent of meteorites and comets. Hearing: Music An audio piece "A Singing Comet", by Manuel Senfft, based on the Rosetta Plasma Consortium data, inspired me to make a musical piece. In collaboration with clarinetist Lee Mottram (Wales) and composer Takuto Fukuda (Japan) we created an electro­acoustic composition in which we tell the story of comets visiting our Solar System, repeating their cycle, curving around the sun and releasing water, carrying away dust to form their tails. Smell In collaboration with The Open University, UK, postcards with a smell of the comet were created, introducing the chemical components of the comet. The smell was recreated by combining several molecules

  3. The unexpectedly bright comet C/2012 F6 (Lemmon) unveiled at near-infrared wavelengths

    Energy Technology Data Exchange (ETDEWEB)

    Paganini, Lucas; DiSanti, Michael A.; Mumma, Michael J.; Villanueva, Geronimo L.; Bonev, Boncho P. [Goddard Center for Astrobiology, NASA GSFC, MS 690, Greenbelt, MD 20771 (United States); Keane, Jacqueline V.; Meech, Karen J. [Institute for Astronomy, University of Hawaii, Honolulu, HI 96822 (United States); Gibb, Erika L. [Department of Physics and Astronomy, University of Missouri, St. Louis, MO 63121 (United States); Boehnhardt, Hermann, E-mail: lucas.paganini@nasa.gov [Max-Planck-Institut für Sonnensystemforschung, D-37191, Katlenburg-Lindau (Germany)

    2014-01-01

    We acquired near-infrared spectra of the Oort cloud comet C/2012 F6 (Lemmon) at three different heliocentric distances (R {sub h}) during the comet's 2013 perihelion passage, providing a comprehensive measure of the outgassing behavior of parent volatiles and cosmogonic indicators. Our observations were performed pre-perihelion at R {sub h} = 1.2 AU with CRIRES (on 2013 February 2 and 4), and post-perihelion at R {sub h} = 0.75 AU with CSHELL (on March 31 and April 1) and R {sub h} = 1.74 AU with NIRSPEC (on June 20). We detected 10 volatile species (H{sub 2}O, OH* prompt emission, C{sub 2}H{sub 6}, CH{sub 3}OH, H{sub 2}CO, HCN, CO, CH{sub 4}, NH{sub 3}, and NH{sub 2}), and obtained upper limits for two others (C{sub 2}H{sub 2} and HDO). One-dimensional spatial profiles displayed different distributions for some volatiles, confirming either the existence of polar and apolar ices, or of chemically distinct active vents in the nucleus. The ortho-para ratio for water was 3.31 ± 0.33 (weighted mean of CRIRES and NIRSPEC results), implying a spin temperature >37 K at the 95% confidence limit. Our (3σ) upper limit for HDO corresponds to D/H < 2.45 × 10{sup –3} (i.e., <16 Vienna Standard Mean Ocean Water, VSMOW). At R {sub h} = 1.2 AU (CRIRES), the production rate for water was Q(H{sub 2}O) = 1.9 ± 0.1 × 10{sup 29} s{sup –1} and its rotational temperature was T {sub rot} ∼ 69 K. At R {sub h} = 0.75 AU (CSHELL), we measured Q(H{sub 2}O) = 4.6 ± 0.6 × 10{sup 29} s{sup –1} and T {sub rot} = 80 K on March 31, and 6.6 ± 0.9 × 10{sup 29} s{sup –1} and T {sub rot} = 100 K on April 1. At R {sub h} = 1.74 AU (NIRSPEC), we obtained Q(H{sub 2}O) = 1.1 ± 0.1 × 10{sup 29} s{sup –1} and T {sub rot} ∼ 50 K. The measured volatile abundance ratios classify comet C/2012 F6 as rather depleted in C{sub 2}H{sub 6} and CH{sub 3}OH, while HCN, CH{sub 4}, and CO displayed abundances close to their median values found among comets. H{sub 2}CO was the only volatile

  4. Chemodynamical deuterium fractionation in the early solar nebula: The origin of water on earth and in asteroids and comets

    International Nuclear Information System (INIS)

    Albertsson, T.; Semenov, D.; Henning, Th.

    2014-01-01

    Formation and evolution of water in the solar system and the origin of water on Earth constitute one of the most interesting questions in astronomy. The prevailing hypothesis for the origin of water on Earth is by delivery through water-rich small solar system bodies. In this paper, the isotopic and chemical evolution of water during the early history of the solar nebula, before the onset of planetesimal formation, is studied. A gas-grain chemical model that includes multiply deuterated species and nuclear spin-states is combined with a steady-state solar nebula model. To calculate initial abundances, we simulated 1 Myr of evolution of a cold and dark TMC-1-like prestellar core. Two time-dependent chemical models of the solar nebula are calculated over 1 Myr: (1) a laminar model and (2) a model with two-dimensional (2D) turbulent mixing. We find that the radial outward increase of the H 2 O D/H ratio is shallower in the chemodynamical nebular model than in the laminar model. This is related to more efficient defractionation of HDO via rapid gas-phase processes because the 2D mixing model allows the water ice to be transported either inward and thermally evaporated or upward and photodesorbed. The laminar model shows the Earth water D/H ratio at r ≲ 2.5 AU, whereas for the 2D chemodynamical model this zone is larger, r ≲ 9 AU. Similarly, the water D/H ratios representative of the Oort-family comets, ∼2.5-10 × 10 –4 , are achieved within ∼2-6 AU and ∼2-20 AU in the laminar and the 2D model, respectively. We find that with regards to the water isotopic composition and the origin of the comets, the mixing model seems to be favored over the laminar model.

  5. Distributions of δD observations from IASI/MetOp across the globe and intercomparison with other instruments/measurements

    Science.gov (United States)

    Lacour, Jean-Lionel; Clarisse, Lieven; Hurtmans, Daniel; Clerbaux, Cathy; Worden, John; Schneider, Matthias; Risi, Camille; Coheur, Pierre-François

    2014-05-01

    The Infrared Atmospheric Sounding Interferometer (IASI) onboard MetOp, through its observations of the water isotopologues, has great potential to support research on hydrological processes responsible for the moistening/drying of the atmosphere. The instrumental characteristics of the spectrometer (low radiometric noise and good spectral resolution) combined with its high sampling (global coverage twice a day) make it particularly suitable for providing numerous observations of the isotopologues ratio (δD) of water vapour in the troposphere. Retrieving isotopologues ratios at the required accuracy is, however, a challenging task. To get meaningful results, the retrieval needs to be well constrained. This can be achieved, with the optimal estimation method, by using an a priori probability density function containing correlation information between HDO and H2O. In this presentation, first, we will show that the measurements are mainly sensitive to δD in the troposphere between 3 and 6 km. We will illustrate the capabilities of IASI to provide δD observations at high spatio-temporal resolution with some distributions across the globe and we will discuss their added values to constrain hydrological processes. Second, we will document how IASI observations compare to other remote sounding observations of δD in the troposphere. Comparisons of IASI observations with the TES sounder and with three ground-based NDACC FTIR (Izaña, Kalsruhe and Kiruna, data generated within the project MUSICA) will be presented. The differences between the instruments as well as the methodology to compare them will be exposed. We will show that the different instruments agree within their own uncertainties and vertical sensitivities, asserting the use of IASI δD observations for scientific purposes.

  6. Intercomparison of TCCON and MUSICA Water Vapour Products

    Science.gov (United States)

    Weaver, D.; Strong, K.; Deutscher, N. M.; Schneider, M.; Blumenstock, T.; Robinson, J.; Notholt, J.; Sherlock, V.; Griffith, D. W. T.; Barthlott, S.; García, O. E.; Smale, D.; Palm, M.; Jones, N. B.; Hase, F.; Kivi, R.; Ramos, Y. G.; Yoshimura, K.; Sepúlveda, E.; Gómez-Peláez, Á. J.; Gisi, M.; Kohlhepp, R.; Warneke, T.; Dohe, S.; Wiegele, A.; Christner, E.; Lejeune, B.; Demoulin, P.

    2014-12-01

    We present an intercomparison between the water vapour products from the Total Carbon Column Observing Network (TCCON) and the MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water (MUSICA), two datasets from ground-based Fourier Transform InfraRed (FTIR) spectrometers with good global representation. Where possible, comparisons to radiosondes are also included. The near-infrared TCCON measurements are optimized to provide precise monitoring of greenhouse gases for carbon cycle studies; however, TCCON's retrievals also produce water vapour products. The mid-infrared MUSICA products result from retrievals optimized to give precise and accurate information about H2O, HDO, and δD. The MUSICA water vapour products have been validated by extensive intercomparisons with H2O and δD in-situ measurements made from ground, radiosonde, and aircraft (Schneider et al. 2012, 2014), as well as by intercomparisons with satellite-based H2O and δD remote sensing measurements (Wiegele et al., 2014). This dataset provides a valuable reference point for other measurements of water vapour. This study is motivated by the limited intercomparisons performed for TCCON water vapour products and limited characterisation of their uncertainties. We compare MUSICA and TCCON products to assess the potential for TCCON measurements to contribute to studies of the water cycle, water vapour's role in climate and use as a tracer for atmospheric dynamics, and to evaluate the performance of climate models. The TCCON and MUSICA products result from measurements taken using the same FTIR instruments, enabling a comparison with constant instrumentation. The retrieval techniques differ, however, in their method and a priori information. We assess the impact of these differences and characterize the comparability of the TCCON and MUSICA datasets.

  7. Alcohol Involvement in Sexual Behaviour and Adverse Sexual Health Outcomes from 26 to 38 Years of Age.

    Directory of Open Access Journals (Sweden)

    Jennie L Connor

    Full Text Available Research on alcohol and sexual behaviour has focused on young adults or high-risk groups, showing alcohol use contributing to riskier sexual choices. Adults now in their late thirties have been exposed to heavier drinking norms than previously, raising questions about effects on sexual wellbeing. We examined self-reported use and consequences of alcohol in sexual contexts, and its association with usual drinking pattern at age 38, and also associations of heavy drinking occasion (HDO frequency with number of sexual partners, sexually transmitted infections (STIs, and terminations of pregnancy (TOPs, from 26-32 and 32-38 years of age.Members of the Dunedin Study birth cohort answered computer-presented questions about sexual behaviour and outcomes, and interviewer-administered alcohol consumption questions, at age 26, 32 and 38 years.Response level was >90% at each assessment. At 38, drinking before or during sex in the previous year was common (8.2% of men; 14.6% of women reported "usually/always", and unwanted consequences were reported by 13.5% of men and 11.9% of women, including regretted sex or failure to use contraception or condoms. Frequent heavy drinkers were more likely to "use alcohol to make it easier to have sex" and regret partner choice, particularly women. Heavy drinking frequency was strongly associated with partner numbers for men and women at 32, but only for women at 38. Significantly higher odds of STIs amongst the heaviest drinking men, and TOPs amongst the heaviest drinking women were seen at 32-38.Alcohol involvement in sex continues beyond young adulthood where it has been well documented, and is common at 38. Women appear to be more affected than men, and heavy drinking is associated with poorer outcomes for both. Improving sexual health and wellbeing throughout the life course needs to take account of the role of alcohol in sexual behaviour.

  8. The SPICAV-SOIR instrument probing the atmosphere of Venus: an overview

    Science.gov (United States)

    Trompet, Loïc; Mahieux, Arnaud; Wilquet, Valérie; Robert, Séverine; Chamberlain, Sarah; Thomas, Ian; Carine Vandaele, Ann; Bertaux, Jean-Loup

    2016-04-01

    The Solar Occultation in the Infrared (SOIR) channel mounted on top of the SPICAV instrument of the ESA's Venus Express mission has observed the atmosphere of Venus during more than eight years. This IR spectrometer (2.2-4.3 μm) with a high spectral resolution (0.12 cm-1) combined an echelle grating with an acousto-optic tunable filter for order selection. SOIR performed more than 1500 solar occultation measurements leading to about two millions spectra. The Royal Belgian Institute for Space Aeronomy (BIRA-IASB) was in charge of SOIR's development and operations as well as its data pipeline. BIRA-IASB carried out several studies on the composition of Venus mesosphere and lower thermosphere: carbon dioxide, carbon monoxide, hydrogen halide (HF, HCl, DF, DCl), sulfur dioxide, water (H2O, HDO) as well as sulphuric acid aerosols in the upper haze of Venus. Density and temperature profiles of the upper atmosphere of Venus (60 km to 170 km) at the terminator have been retrieved from SOIR's spectra using different assumptions, wherein the hydrostatic equilibrium and the local thermodynamical equilibrium in the radiative transfer calculations. These results allow us to produce an Atmospheric model of Venus called Venus Atmosphere from SOIR measurements at the Terminator (VAST). Data obtained by SOIR will also contribute to update the Venus International Reference Atmosphere (VIRA). Recently, the treatment of the raw data to transmittance has been optimized, and a new dataset of spectra has been produced. All raw spectra (PSA level 2) as well as calibrated spectra (PSA level 3) have been delivered to ESA's Planetary Science Archive (PDSPSA). Consequently the re-analysis of all spectra has been undergone. We will briefly present the improvements implemented in the data pipeline. We will also show a compilation of results obtained by the instrument considering the complete mission duration.

  9. Do birds of like feather flock together? The use of a novel 13C+D combustion isotope analyzer to track bird migration

    Science.gov (United States)

    Saad, N.

    2011-12-01

    Information on spring migration routes, geographic linkages among winter, spring, and breeding locations, and potential geographic effects on arrival body condition of a variety of avian species is so far little known. Stable isotope ratios are exquisitely sensitive to the biochemistry of living organisms and the nutrients available to them. Isotope ratios provide detailed knowledge useful in a variety of fields, including birds migration, through a combination of stable-isotope measurements of carbon (13C/12C) and hydrogen (D/H) isotopes of flight feathers and breast feathers of tissues representing different periods of dietary integration and body composition analyses. Associations among specific geographic areas, habitat use, and arrival condition can be elucidated through the measurement of these dual isotopes. We report here on the development of a novel laser spectroscopy based system for the simultaneous analysis of the stable isotope ratios of carbon (13C/12C) and hydrogen (D/H) that is robust, easy-to-use, and is the first stable isotope ratio analysis system to combine the measurement of 13C/12C and D/H in one simple analysis from a bulk organic sample with an application to bird migration. The system comprises a combustion module to convert the organic sample into CO2 and H2O and a Cavity Ring-Down Spectrometer (CRDS) that analyzes the combustion species inside an optical cavity based on the molecular absorption of individual isotopomers. This CRDS uses dual lasers to target the four isotpomers of interest: 12CO2, 13CO2, H2O and HDO. The system delivers a typical precision of 0.1 permil for δ13C and 1.5 permil for δD that parallels that achieved by IRMS, but with an unprecedented simplicity that allows ecologists to leverage the science and elucidate the avian migration patterns.

  10. Stable water isotopes in the coupled atmosphere–land surface model ECHAM5-JSBACH

    Directory of Open Access Journals (Sweden)

    B. Haese

    2013-09-01

    Full Text Available In this study we present first results of a new model development, ECHAM5-JSBACH-wiso, where we have incorporated the stable water isotopes H218O and HDO as tracers in the hydrological cycle of the coupled atmosphere–land surface model ECHAM5-JSBACH. The ECHAM5-JSBACH-wiso model was run under present-day climate conditions at two different resolutions (T31L19, T63L31. A comparison between ECHAM5-JSBACH-wiso and ECHAM5-wiso shows that the coupling has a strong impact on the simulated temperature and soil wetness. Caused by these changes of temperature and the hydrological cycle, the δ18O in precipitation also shows variations from −4‰ up to 4‰. One of the strongest anomalies is shown over northeast Asia where, due to an increase of temperature, the δ18O in precipitation increases as well. In order to analyze the sensitivity of the fractionation processes over land, we compare a set of simulations with various implementations of these processes over the land surface. The simulations allow us to distinguish between no fractionation, fractionation included in the evaporation flux (from bare soil and also fractionation included in both evaporation and transpiration (from water transport through plants fluxes. While the isotopic composition of the soil water may change for δ18O by up to +8&permil:, the simulated δ18O in precipitation shows only slight differences on the order of ±1‰. The simulated isotopic composition of precipitation fits well with the available observations from the GNIP (Global Network of Isotopes in Precipitation database.

  11. Chemodynamical deuterium fractionation in the early solar nebula: The origin of water on earth and in asteroids and comets

    Energy Technology Data Exchange (ETDEWEB)

    Albertsson, T.; Semenov, D.; Henning, Th., E-mail: albertsson@mpia.de [Max-Planck-Institut für Astronomie, Königstuhl 17, D-69117 Heidelberg (Germany)

    2014-03-20

    Formation and evolution of water in the solar system and the origin of water on Earth constitute one of the most interesting questions in astronomy. The prevailing hypothesis for the origin of water on Earth is by delivery through water-rich small solar system bodies. In this paper, the isotopic and chemical evolution of water during the early history of the solar nebula, before the onset of planetesimal formation, is studied. A gas-grain chemical model that includes multiply deuterated species and nuclear spin-states is combined with a steady-state solar nebula model. To calculate initial abundances, we simulated 1 Myr of evolution of a cold and dark TMC-1-like prestellar core. Two time-dependent chemical models of the solar nebula are calculated over 1 Myr: (1) a laminar model and (2) a model with two-dimensional (2D) turbulent mixing. We find that the radial outward increase of the H{sub 2}O D/H ratio is shallower in the chemodynamical nebular model than in the laminar model. This is related to more efficient defractionation of HDO via rapid gas-phase processes because the 2D mixing model allows the water ice to be transported either inward and thermally evaporated or upward and photodesorbed. The laminar model shows the Earth water D/H ratio at r ≲ 2.5 AU, whereas for the 2D chemodynamical model this zone is larger, r ≲ 9 AU. Similarly, the water D/H ratios representative of the Oort-family comets, ∼2.5-10 × 10{sup –4}, are achieved within ∼2-6 AU and ∼2-20 AU in the laminar and the 2D model, respectively. We find that with regards to the water isotopic composition and the origin of the comets, the mixing model seems to be favored over the laminar model.

  12. Lamellar zirconium phosphates to host metals for catalytic purposes.

    Science.gov (United States)

    Ballesteros-Plata, Daniel; Infantes-Molina, Antonia; Rodríguez-Aguado, Elena; Braos-García, Pilar; Rodríguez-Castellón, Enrique

    2018-02-27

    In the present study a porous lamellar zirconium phosphate heterostructure (PPH) formed from zirconium(iv) phosphate expanded with silica galleries (P/Zr molar ratio equal to 2 and (Si + Zr)/P equal to 3) was prepared to host noble metals. Textural and structural characterization of PPH-noble metal materials was carried out in order to elucidate the location and dispersion of the metallic particles and the properties of the resulting material to be used in catalytic processes. In the present paper, their activity in the catalytic hydrodeoxygenation (HDO) reaction of dibenzofuran (DBF) was evaluated. X-ray diffraction (XRD), solid state nuclear magnetic resonance (NMR) and X-ray photoelectron spectroscopy (XPS) evidenced that the structure of the pillared zirconium phosphate material was not modified by the incorporation of Pt and Pd. Moreover, transmission electron microscopy (TEM) showed a different dispersion of the noble metal. The acidity of the resulting PPH-noble metal materials also changed, although in all cases the acidity was of weak nature, and the incorporation of noble metals affected Brønsted acid sites as observed from 31 P NMR spectra. In general, the textural, structural and acidic properties of the resulting materials suggest that PPH can be considered a good candidate to be used as a catalytic support. Thus, the catalytic results of the PPH-noble metal samples indicated that the Pd sample showed a stable behavior probably ascribed to a high dispersion of the active phase. However, the Pt sample suffered from fast deactivation. The selectivity to the reaction products was strongly dependent on the noble metal employed.

  13. Hydrotreatment of solvolytically liquefied lignocellulosic biomass over NiMo/Al2O3 catalyst: Reaction mechanism, hydrodeoxygenation kinetics and mass transfer model based on FTIR

    International Nuclear Information System (INIS)

    Grilc, M.; Likozar, B.; Levec, J.

    2014-01-01

    Raw residual wood biomass, containing cellulose, hemicellulose and lignin, was liquefied at low temperature by ultrasound-assisted solvolysis and acidolysis by glycerol, diethylene glycol and p-toluenesulfonic acid. Liquefied biomass was consequently upgraded by hydrotreatment utilizing heterogeneous catalysis over NiMo/Al 2 O 3 bifunctional catalyst. Effects of temperature (200−350 °C), heating rate (2.5–10.0 K min −1 ), hydrogen/nitrogen pressure (2−8 MPa), mixing (250−1000 min −1 ), hydrogen donor solvent (tetralin) and catalyst contents on deoxygenation were established. Reactions of liquefaction products, such as levulinic acid, were quantified based on their functional groups by Fourier transform infrared spectroscopy, whereas catalyst was examined by scanning electron microscopy, energy-dispersive X-ray spectroscopy (EDX) and X-ray diffraction analysis (XRD). Chemical kinetics of hydrodeoxygenation (HDO), decarbonylation and decarboxylation were determined by originally developed lumped model, based on reaction mechanisms and pathways, while the external mass transfer resistance proved to be negligible under the applied hydrodynamic conditions. The presence of hydrocracking reactions was confirmed by a decrease in product viscosity, and the upgrade for energetic or fuel applications by measurements of calorific value. - Highlights: • Liquefaction of waste lignocellulosic biomass with glycerol at low temperature. • Hydrotreatment, hydrocracking and hydrodeoxygenation of liquefied waste biomass. • Deoxygenation using heterogeneous catalysis over NiMo/Al 2 O 3 bifunctional catalyst. • Proposal of reaction mechanism; chemical kinetics and mass transfer considerations. • Effect of temperature, heating rate, pressure, mixing, solvent and catalyst content

  14. Spray pyrolysis synthesis of γ-Al_2O_3 supported metal and metal phosphide catalysts and their activity in the hydrodeoxygenation of a bio-oil model compound

    International Nuclear Information System (INIS)

    Ly, Hoang Vu; Im, Kyungmin; Go, Youngchae; Galiwango, Emmanuel; Kim, Seung-Soo; Kim, Jinsoo; Choi, Jae Hyung; Woo, Hee Chul

    2016-01-01

    Highlights: • Spherical γ-Al_2O_3 supported metal and metal phosphide catalysts were synthesized by spray pyrolysis method. • Hydrodeoxygenation (HDO) of 2-furyl methyl ketone (FMK) was conducted using metal/metal phosphide catalysts. • FMK was converted into 2-allyl furan and methyl cyclohexane. • The highest FMK conversion of 83% was achieved over 10 wt% Ni/γ-Al_2O_3 catalysts at reaction temperature of 400 °C. - Abstract: In this study, spherical γ-Al_2O_3 supported metal and metal phosphide (Ni, Co, Ni_2P and CoP) catalysts were successfully prepared by combining sol-gel and spray pyrolysis methods. First boehmite sol was prepared based on the Yoldas process and then the corresponding metal salts were added to the sol at the desired concentration, followed by spray pyrolysis of the mixed solution. As the well-mixed solution was transformed to spherical γ-Al_2O_3 supported metal and metal phosphide catalysts during spray pyrolysis process, the metal species were uniformly distributed in the mesoporous γ-Al_2O_3 supports. The product catalysts were investigated under different conditions for hydrodeoxygenation of bio-oil model compound, 2-furyl methyl ketone (FMK), which is the main component of the bio-oil product from pyrolysis of Saccharina japonica. Among the investigated catalysts, the 10 wt% Ni/γ-Al_2O_3 catalyst after calcination at 800 °C showed the highest FMK conversion of 83.02% at the reaction temperature of 400 °C. The gas and liquid products were analyzed by gas chromatography (GC) with TCD/FID detectors and GC–MS, respectively, to determine the product compositions.

  15. THE HERSCHEL AND IRAM CHESS SPECTRAL SURVEYS OF THE PROTOSTELLAR SHOCK L1157-B1: FOSSIL DEUTERATION

    International Nuclear Information System (INIS)

    Codella, C.; Fontani, F.; Vasta, M.; Ceccarelli, C.; Lefloch, B.; Kahane, C.; Taquet, V.; Wiesenfeld, L.; Busquet, G.; Caselli, P.; Lis, D.; Viti, S.

    2012-01-01

    We present the first study of deuteration toward the protostellar shock L1157-B1, based on spectral surveys performed with the Herschel-HIFI and IRAM 30 m telescopes. The L1157 outflow is driven by a low-mass Class 0 protostar and is considered the prototype of the so-called chemically active outflows. The young (2000 yr), bright blueshifted bow shock, B1, is an ideal laboratory for studying the gas chemically enriched by the release of dust mantles due to the passage of a shock. A total of 12 emission lines (up to E u = 63 K) of CH 2 DOH, HDCO, and DCN are detected. In addition, two lines of NH 2 D and HDO are tentatively reported. To estimate the deuteration, we also extracted from our spectral survey emission lines of non-deuterated isotopologues ( 13 CH 3 OH, H 2 13 CO, H 13 CN, H 2 13 CO, and NH 3 ). We infer higher deuteration fractions for CH 3 OH (D/H = 0.2-2 × 10 –2 ) and H 2 CO (5-8 × 10 –3 ) than for H 2 O (0.4-2 × 10 –3 ), HCN (∼10 –3 ), and ammonia (≤3 × 10 –2 ). The measurement of deuteration of water, formaldehyde, and methanol in L1157-B1 provides a fossil record of the gas before it was shocked by the jet driven by the protostar. A comparison with gas-grain models indicates that the gas passed through a low-density (≤10 3 cm –3 ) phase, during which the bulk of water ices formed, followed by a phase of increasing density, up to 3 × 10 4 cm –3 , during which formaldehyde and methanol ices formed.

  16. One-pot aqueous phase catalytic conversion of sorbitol to gasoline over nickel catalyst

    International Nuclear Information System (INIS)

    Weng, Yujing; Qiu, Songbai; Xu, Ying; Ding, Mingyue; Chen, Lungang; Zhang, Qi; Ma, Longlong; Wang, Tiejun

    2015-01-01

    Highlights: • Directly production gasoline (C5–C12 alkanes) from biomass-derived sugar alcohol sorbitol. • Temperature of STG (553–593 K) was lower than that of traditional methanol to gasoline (MTG) (623–773 K). • Gasoline yield of 46.9% and C7–C12 hydrocarbons reached up to 45.5% in the gasoline products. - Abstract: The carbon chain extension and hydrodeoxygenation steps play critical roles in the high-energy-density hydrocarbons production. In this paper, a systematic study had been carried out to investigate one-pot aqueous phase catalytic conversion of sorbitol to gasoline (STG) over bifunctional Ni-based catalysts. Characterization technologies of N 2 physisorption, X-ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NH 3 temperature-programmed desorption (NH 3 -TPD) were used to study the textural properties, phase compositions, acid behavior and morphologies of the catalysts. The catalytic performances were tested in a fixed bed reactor. It was found that the physically mixed Ni/HZSM-5 and Ni/silica-gel (mesoporous SG) catalyst realized the carbon chain extension and exhibited excellent performances on hydrodeoxygenation (HDO) reaction (46.9% of gasoline (C5–C12) yield and 45.5% of C7–C12 hydrocarbons in the gasoline products). Especially, the temperature of STG (553–593 K) was lower obviously than that of the traditional methanol to gasoline (MTG) process (623–773 K). It provided a novel transformation of sorbitol to long-chain alkanes by one-pot process over the bifunctional catalyst (Ni@HZSM-5/SG), wherein hydrodeoxygenation, ketonization and aldol condensation steps were integrated

  17. DYNAMIC DEUTERIUM ENRICHMENT IN COMETARY WATER VIA ELEY–RIDEAL REACTIONS

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yunxi; Giapis, Konstantinos P., E-mail: giapis@cheme.caltech.edu [Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125 (United States)

    2017-01-20

    The deuterium-to-hydrogen ratio (D/H) in water found in the coma of Jupiter family comet (JFC) 67P/Churyumov–Gerasimenko was reported to be (5.3 ± 0.7) × 10{sup −4}, the highest among comets and three times the value for other JFCs with an ocean-like ratio. This discrepancy suggests the diverse origins of JFCs and clouds the issue of the origin of Earth’s oceanic water. Here we demonstrate that Eley–Rideal reactions between accelerated water ions and deuterated cometary surface analogs can lead to instantaneous deuterium enrichment in water scattered from the surface. The reaction proceeds with H{sub 2}O{sup +} abstracting adsorbed D atoms, forming an excited H{sub 2}DO* state, which dissociates subsequently to produce energetic HDO. Hydronium ions are also produced readily by the abstraction of H atoms, consistent with H{sub 3}O{sup +} detection and abundance in various comets. Experiments with water isotopologs and kinematic analysis on deuterated platinum surfaces confirmed the dynamic abstraction mechanism. The instantaneous fractionation process is independent of the surface temperature and may operate on the surface of cometary nuclei or dust grains, composed of deuterium-rich silicates and carbonaceous chondrites. The requisite energetic water ions have been detected in the coma of 67P in two populations. This dynamic fractionation process may temporarily increase the water D/H ratio, especially as the comet gets closer to the Sun. The magnitude of the effect depends on the water ion energy-flux and the deuterium content of the exposed cometary surfaces.

  18. Gas And Ice Spectrometer/Radar (GAISR): a new instrument for close-up comet activity observations

    Science.gov (United States)

    Cooper, Ken; Monje, Raquel; Cochrane, Corey; Tang, Adrian; Alonso, Maria; Dengler, Robert; Durden, Stephen; Choukroun, Mathieu

    2017-10-01

    The Rosetta mission at 67P/Churyumov-Gerasimenko enabled the first detailed and long-term survey of cometary activity, which occurs primarily through water outgassing and emission of dust. Its highly-capable instrument suite improved our understanding of the outgassing and the dust emission and size distribution separately, however the coupling between the two remains poorly understood. GAISR consists of a dual-channel submillimeter-wave spectrometer inspired from MIRO/Rosetta, coupled to a small-particle Doppler radar for simultaneous observations of outgassing and emission of the large dust particles (comprising most of the mass emitted) in cometary jets and plumes of outer solar system satellites. GAISR’s medium-range W-band (95 GHz) radar will operate in a frequency-modulated continuous-wave (FMCW) mode with 1 Watt of transmit power to achieve high sensitivity detection of the range and velocity distribution of 0.1-10 mm sized ice and dust particles released by jets and plumes. The radar’s primary aperture also functions as an antenna for two passive heterodyne spectrometer channels at 270 and 560 GHz for detecting the abundance, temperature, and velocity of water vapor and its isotopes (including HDO), as well other major cometary volatiles such as CO, NH3, CH3OH. GAISR has been designed with a priority placed on low mass and power needs, to facilitate its infusion in future planetary missions. This is accomplished by leveraging recent innovations in W-band signal generation using low power silicon integrated circuits, state-of-the art III-V semiconductor devices for signal amplification and detection, and compact quasioptical duplexing. A new signal processing algorithm for FMCW Doppler radar detection out to the maximum range ambiguity limit has also been developed. GAISR’s performance testing has begun, and this poster will summarize its proven capabilities and plans for validation in relevant environments.

  19. Measurement of concentration of heavy water

    International Nuclear Information System (INIS)

    Tsukamoto, Yuichi; Kondo, Mitsuo; Sakurai, Naoyuki

    1979-01-01

    The concentration of heavy water is measured as one of the technical management in the Fugen plant. The heavy water is used as the moderator in the reactor. The measuring method depends on the theory of light absorption. The light absorption range of heavy water spreads from near infrared to infrared zone. The near infrared absorption was adopted for the purpose, as the absorption is much larger in infrared zone, and the measurement has to be conducted, limiting the apparent absorption. This measuring method is available to determine the concentration of heavy water in the broad range exactly. The preparation of heavy water sample and the measurement of the absorption spectra of near infrared ray are explained, as the experimental procedure. The sample cell was made of quartz, and the spectroscope was the Hitachi 323 type. The resolving power is 100 nm and 27 nm for the wave length of 1000 nm and 2500 nm, respectively. Concerning the measured results, the absorption was recorded in the wave length range from 600 nm to 2600 nm, and for the heavy water concentration range from 0 to 99.77 wt. %. The peaks of absorption were located at the wave length of 1450, 1660, 1920, 1970, 2020 and 2600 nm. The three kinds of fundamental vibration mode of the molecules of both light and heavy water are shown, and the peaks belong to H 2 O, HDO and D 2 O, respectively. The relation between the absorption and the heavy water concentration, and that between the transmissivity and the wave length are shown, when the cell thickness was varied to 5 mm and 20 mm, and the heavy water concentration to 21%, 62% and 99.85%. (Nakai, Y.)

  20. Thermoneutral isotope exchange reactions of cations in the gas phase

    International Nuclear Information System (INIS)

    Ausloos, P.; Lias, S.G.

    1981-01-01

    Rate constants have been measured for reactions of the type AD 2 + + MH → MD + ADH + , where AD 2 + is CD 3 CND + , CD 3 CDOD + , (CD 3 COCD 3 )D + , or (C 2 D 5 ) 2 OD + and the MH molecules are alcohols, acids, mercaptans, H 2 S, AsH 3 , PH 3 , or aromatic molecules. Rate constants are also presented for the reactions Ar/sub H/D + + D 2 O → Ar/sub d/D + + HDO, where Ar/sub H/D + is a deuteronated aromatic molecule and Ar/sub D/D + is the same species with a D atom incorporated on the ring. In all but two cases, the competing deuteron transfer is sufficiently endothermic that it cannot be observed under the conditions of the ICR experiments at 320 to 420 K. The efficiencies of the isotope exchange reactions are interpreted in terms of estimated potential surface cross sections for the reactions AD 2 + + MH → [AD 2 + MH] → [ADMHD + ] → [ADH + MD] → ADH + + MD. When the formation of the [ADMHD + ] complex is estimated to be thermoneutral or slightly endothermic, the isotope exchange process is inefficient (probability of a reactive collision 2 + MH] → [ADMHD + ] is exothermic. For most of the systems, trends in reaction efficiency appear to be related to factors such as dipole moments of reactant species (or for aromatic compounds, the electron-donating or -withdrawing properties of ring substituents) which influence the relative orientation of the two reactant species in the complex

  1. Effect of polyunsaturated fatty acids and their metabolites on bleomycin-induced cytotoxic action on human neuroblastoma cells in vitro.

    Directory of Open Access Journals (Sweden)

    Sailaja Polavarapu

    Full Text Available In the present study, we noted that bleomycin induced growth inhibitory action was augmented by all the polyunsaturated fatty acids (PUFAs tested on human neuroblastoma IMR-32 (0.5 × 10(4 cells/100 µl of IMR cells (EPA > DHA > ALA = GLA = AA > DGLA = LA: ∼ 60, 40, 30, 10-20% respectively at the maximum doses used. Of all the prostaglandins (PGE1, PGE2, PGF2α, and PGI2 and leukotrienes (LTD4 and LTE4 tested; PGE1, PGE2 and LTD4 inhibited the growth of IMR-32 cells to a significant degree at the highest doses used. Lipoxin A4 (LXA4, 19,20-dihydroxydocosapentaenoate (19, 20 DiHDPA and 10(S,17(S-dihydroxy-4Z,7Z,11E,13Z,15E,19Z-docosahexaenoic acid (protectin: 10(S,17(SDiHDoHE, metabolites of DHA, significantly inhibited the growth of IMR-32 cells. Pre-treatment with AA, GLA, DGLA and EPA and simultaneous treatment with all PUFAs used in the study augmented growth inhibitory action of bleomycin. Surprisingly, both indomethacin and nordihydroguaiaretic acid (NDGA at 60 and 20 µg/ml respectively enhanced the growth of IMR-32 cells even in the presence of bleomycin. AA enhanced oxidant stress in IMR-32 cells as evidenced by an increase in lipid peroxides, superoxide dismutase levels and glutathione peroxidase activity. These results suggest that PUFAs suppress growth of human neuroblastoma cells, augment growth inhibitory action of bleomycin by enhancing formation of lipid peroxides and altering the status of anti-oxidants and, in all probability, increase the formation of lipoxins, resolvins and protectins from their respective precursors that possess growth inhibitory actions.

  2. The isotopic composition of precipitation from a winter storm – a case study with the limited-area model COSMOiso

    Directory of Open Access Journals (Sweden)

    K. Yoshimura

    2012-02-01

    Full Text Available Stable water isotopes are valuable tracers of the atmospheric water cycle, and potentially provide useful information also on weather-related processes. In order to further explore this potential, the water isotopes H218O and HDO are incorporated into the limited-area model COSMO. In a first case study, the new COSMOiso model is used for simulating a winter storm event in January 1986 over the eastern United States associated with intense frontal precipitation. The modelled isotope ratios in precipitation and water vapour are compared to spatially distributed δ18O observations. COSMOiso very accurately reproduces the statistical distribution of δ18O in precipitation, and also the synoptic-scale spatial pattern and temporal evolution agree well with the measurements. Perpendicular to the front that triggers most of the rainfall during the event, the model simulates a gradient in the isotopic composition of the precipitation, with high δ18O values in the warm air and lower values in the cold sector behind the front. This spatial pattern is created through an interplay of large scale air mass advection, removal of heavy isotopes by precipitation at the front and microphysical interactions between rain drops and water vapour beneath the cloud base. This investigation illustrates the usefulness of high resolution, event-based model simulations for understanding the complex processes that cause synoptic-scale variability of the isotopic composition of atmospheric waters. In future research, this will be particularly beneficial in combination with laser spectrometric isotope observations with high temporal resolution.

  3. Water vapor stable isotope observations from tropical Australia

    KAUST Repository

    Parkes, Stephen

    2015-04-01

    The response of the tropical hydrological cycle to anthropogenically induced changes in radiative forcing is one of the largest discrepancies between climate models. Paleoclimate archives of the stable isotopic composition of precipitation in the tropics indicate a relationship with precipitation amount that could be exploited to study past hydroclimate and improve our knowledge of how this region responds to changes in climate forcing. Recently modelling studies of convective parameterizations fitted with water isotopes and remote sensing of water vapor isotopes in the tropics have illustrated uncertainty in the assumed relationship with rainfall amount. Therefore there is a need to collect water isotope data in the tropics that can be used to evaluate these models and help identify the relationships between the isotopic composition of meteoric waters and rainfall intensity. However, data in this region is almost non-existent. Here we present in-situ water vapor isotopic measurements and the HDO retrievals from the co-located Total Column Carbon Observing Network (TCCON) site at Darwin in Tropical Australia. The Darwin site is interestingly placed within the tropical western pacific region and is impacted upon by a clear monsoonal climate, and key climate cycles including ENSO and Madden Julian Oscillations. The analysis of the data illustrated relationships between water vapor isotopes and humidity which demonstrated the role of precipitation processes in the wet season and air mass mixing during the dry season. Further the wet season observations show complex relationships between humidity and isotopes. A simple Rayleigh distillation model was not obeyed, instead the importance of rainfall re-evaporation in generating the highly depleted signatures was demonstrated. These data potentially provide a useful tool for evaluating model parameterizations in monsoonal regions as they demonstrate relationships with precipitation processes that cannot be observed with

  4. No Photon Left Behind: How Billions of Spectral Lines are Transforming Planetary Sciences

    Science.gov (United States)

    Villanueva, Geronimo L.

    2014-06-01

    With the advent of realistic potential energy surface (PES) and dipole moment surface (DMS) descriptions, theoretically computed linelists can now synthesize accurate spectral parameters for billions of spectral lines sampling the untamed high-energy molecular domain. Being the initial driver for these databases the characterization of stellar spectra, these theoretical databases, in combination with decades of precise experimental studies (nicely compiled in community databases such as HITRAN and GEISA), are leading to unprecedented precisions in the characterization of planetary atmospheres. Cometary sciences are among the most affected by this spectroscopic revolution. Even though comets are relatively cold bodies (T˜100 K), their infrared molecular emission is mainly defined by non-LTE solar fluorescence induced by a high-energy source (Sun, T˜5600 K). In order to interpret high-resolution spectra of comets acquired with extremely powerful telescopes (e.g., Keck, VLT, NASA-IRTF), we have developed advanced non-LTE fluorescence models that integrate the high-energy dynamic range of ab-initio databases (e.g., BT2, VTT, HPT2, BYTe, TROVE) and the precision of laboratory and semi-empirical compilations (e.g., HITRAN, GEISA, CDMS, WKMC, SELP, IUPAC). These new models allow us to calculate realistic non-LTE pumps, cascades, branching-ratios, and emission rates for a broad range of excitation regimes for H2O, HDO, HCN, HNC and NH3. We have implemented elements of these compilations to the study of Mars spectra, and we are now exploring its application to modeling non-LTE emission in exoplanets. In this presentation, we present application of these advanced models to interpret highresolution spectra of comets, Mars and exoplanets.

  5. Growth and differentiation on a trypanosome of the subgenus Schizotrypanum from the bat Phyllostomus hastatus

    Directory of Open Access Journals (Sweden)

    Sônia I. Hamanaka

    1993-12-01

    Full Text Available The effects of temperature, pH, osmolarity and aeration on the growth and differentiation of a trypanosome ofthe subgenus Schizotrypanum isolatedfrom the bat Phyllostomus hastatus were studied. In general, the growth characteristics ofthe flagellate were similar to those of Trypanosoma (Schizotrypanum cruzi. However, the parasite did not growth at 33 or 37C. Increase in the osmolarity and aeration promoted growth at 33C. Significant metacyclogenesis was detected only in the growth condition where maximal growth occured (28C, pH 7.3, 380m0s/kg, in tissue cullure flasks, at the end ofthe exponential growth phase. The begining of the metacyclogenesis process was coincident with most glucose utilization and lowest pH. During metacyclogenesis both culture medium pH and osmolarity increased steadly.Foram estudados os efeitos da temperatura, do pH, da osmolaridade e da areaçâo sobre o crescimento e a diferenciação de um tripanosoma do subgenêro Schizotrypanum, isolado do morcego Phyllostomus hastatus. Em geral, as características do crescimento do flagelado foram semelhantes àquelas do Trypanosoma (Schizotrypanum cruzi. Entretanto, o parasita não de desenvolveu a 33 ou 37°C. O aumento na osmolaridade e areaçâo estimulou o crescimento a 33°C. Metaciclogênese sifhificativa foi detectada somente na condição de crescimento, onde ocorreu desenvolvimento máximo (28°C, pH 7.3, 320m0/kg H20, em frascos de cultura de tecido, no final da fase do crescimento exponencial. O início do processo de metaciclogênese coincidiu com maior utilização de glucose e menor pH. Durante a metaciclogênese, o pHdo meio de cultura e a osmolaridade aumentaram constantemente.

  6. A cohesion/tension mechanism explains the gating of water channels (aquaporins) in Chara internodes by high concentration.

    Science.gov (United States)

    Ye, Qing; Wiera, Boguslaw; Steudle, Ernst

    2004-02-01

    Isolated internodes of Chara corallina have been used to study the gating of aquaporins (water channels) in the presence of high concentrations of osmotic solutes of different size (molecular weight). Osmolytes were acetone and three glycol ethers: ethylene glycol monomethyl ether (EGMME), diethylene glycol monomethyl ether (DEGMME), and triethylene glycol monoethyl ether (TEGMEE). The 'osmotic efficiency' of osmolytes was quite different. Their reflection coefficients ranged between 0.15 (acetone), 0.59 (EGMME), 0.78 (DEGMME), and 0.80 (TEGMEE). Bulk water permeability (Lp) and diffusive permeabilities (Ps) of heavy water (HDO), hydrogen peroxide (H2O2), acetone, and glycol ethers (EGMME, DEGMME, and TEGMEE) were measured using a cell pressure probe. Cells were treated with different concentrations of osmotic solutes of up to 800 mM ( approximately 2.0 MPa of osmotic pressure). Inhibition of aquaporin activity increased with both increasing concentration and size of solutes (reflection coefficients). As cell Lp decreased, Ps increased, indicating that water and solutes used different passages across the plasma membrane. Similar to earlier findings of an osmotic gating of ion channels, a cohesion/tension model of the gating of water channels in Chara internodes by high concentration is proposed. According to the model, tensions (negative pressures) within water channels affected the open/closed state by changing the free energy between states and favoured a distorted/collapsed rather than the open state. They should have differed depending on the concentration and size of solutes that are more or less excluded from aquaporins. The bigger the solute, the lower was the concentration required to induce a reversible closure of aquaporins, as predicted by the model.

  7. Effect of omega-3 fatty acid ethyl esters on the oxylipin composition of lipoproteins in hypertriglyceridemic, statin-treated subjects.

    Science.gov (United States)

    Newman, John W; Pedersen, Theresa L; Brandenburg, Verdayne R; Harris, William S; Shearer, Gregory C

    2014-01-01

    Oxylipins mediate inflammation, vascular tension, and more. Their presence in lipoproteins could explain why lipoproteins mediate nearly identical activities. To determine how oxylipins are distributed in the lipoproteins of hypertriglyceridemic subjects, and whether omega-3 fatty acids alter them in a manner consistent with improved cardiovascular health, we recruited 15 dyslipidemic subjects whose levels of low density lipoprotein cholesterol (LDL-C) were at goal but who remained hypertriglyceridemic (200-499 mg/dL). They were treated them with the indicated dose of 4 g/d omega-3 acid ethyl esters (P-OM3) for 8 weeks. Measured oxylipins included mid-chain alcohols (HETEs, HEPEs and HDoHEs), ketones (KETEs), epoxides (as EpETrEs, EpETEs, and EpDPEs). At baseline, arachidonate-oxylipins (HETEs, KETEs, and EpETrEs) were most abundant in plasma with the greatest fraction of total abundance (mean |95% CI|) being carried in high density lipoproteins (HDL); 42% |31, 57| followed by very low density lipoproteins (VLDL); 27% |20, 36|; and LDL 21% |16, 28|. EPA- and DHA-derived oxylipins constituted less than 11% of total. HDL carried alcohols and epoxides but VLDL was also rich in ketones. Treatment decreased AA-derived oxylipins across lipoprotein classes (-23% |-33, -12|, p = 0.0003), and expanded EPA-(322% |241, 422|, plipoprotein class carries a unique oxylipin complement. P-OM3 treatment alters the oxylipin content of all classes, reducing pro-inflammatory and increasing anti-inflammatory species, consistent with the improved inflammatory and vascular status associated with the treatment. ClinicalTrials.gov NCT00959842.

  8. SMA OBSERVATIONS OF THE W3(OH) COMPLEX: PHYSICAL AND CHEMICAL DIFFERENTIATION BETWEEN W3(H{sub 2}O) AND W3(OH)

    Energy Technology Data Exchange (ETDEWEB)

    Qin, Sheng-Li [Department of Astronomy, Yunnan University, and Key Laboratory of Astroparticle Physics of Yunnan Province, Kunming, 650091 (China); Schilke, Peter; Sánchez-Monge, Álvaro [Physikalisches Institut, Universität zu Köln, Zülpicher Str. 77, D-50937 Köln (Germany); Wu, Jingwen [Department of Physics and Astronomy, University of California, Los Angeles, CA 90095 (United States); Wu, Yuefang [Department of Astronomy, Peking University, Beijing, 100871 (China); Liu, Tie [Korea Astronomy and Space Science Institute 776, Daedeokdaero, Yuseong-gu, Daejeon, Korea 305-348 (Korea, Republic of); Liu, Ying, E-mail: slqin@bao.ac.cn [Department of Physics and Hebei Advanced Thin Film Laboratory, Hebei Normal University, Shijiazhuang 050024 (China)

    2015-04-10

    We report on the Submillimeter Array (SMA) observations of molecular lines at 270 GHz toward the W3(OH) and W3(H{sub 2}O) complex. Although previous observations already resolved the W3(H{sub 2}O) into two or three sub-components, the physical and chemical properties of the two sources are not well constrained. Our SMA observations clearly resolved the W3(OH) and W3(H{sub 2}O) continuum cores. Taking advantage of the line fitting tool XCLASS, we identified and modeled a rich molecular spectrum in this complex, including multiple CH{sub 3}CN and CH{sub 3}OH transitions in both cores. HDO, C{sub 2}H{sub 5}CN, O{sup 13}CS, and vibrationally excited lines of HCN, CH{sub 3}CN, and CH{sub 3}OCHO were only detected in W3(H{sub 2}O). We calculate gas temperatures and column densities for both cores. The results show that W3(H{sub 2}O) has higher gas temperatures and larger column densities than W3(OH) as previously observed, suggesting physical and chemical differences between the two cores. We compare the molecular abundances in W3(H{sub 2}O) to those in the Sgr B2(N) hot core, the Orion KL hot core, and the Orion Compact Ridge, and discuss the chemical origin of specific species. An east–west velocity gradient is seen in W3(H{sub 2}O), and the extension is consistent with the bipolar outflow orientation traced by water masers and radio jets. A north–south velocity gradient across W3(OH) is also observed. However, with current observations we cannot be assured whether the velocity gradients are caused by rotation, outflow, or radial velocity differences of the sub-components of W3(OH)

  9. Essential fatty acids and lipid mediators. Endocannabinoids

    Directory of Open Access Journals (Sweden)

    G. Caramia

    2012-03-01

    Full Text Available In 1929 Burr and Burr discovered the essential fatty acids omega-6 and omega-3. Since then, researchers have shown a growing interest in polyunsaturated fatty acids (PUFA as precursors of “lipid mediator” molecules, often with opposing effects, prostaglandins, prostacyclins, thromboxanes, leukotrienes, lipossines, resolvines, protectines, maresins that regulate immunity, platelet aggregation, inflammation, etc. They showed that the balance between omega-3 and omega-6 acids has a profound influence on all the body’s inflammatory responses and a raised level of PUFA omega-3 in tissue correlate with a reduced incidence of degenerative cardiovascular disease, some mental illnesses such as depression, and neuro-degenerative diseases such as Alzheimer’s. The CYP-catalyzed epoxidation and hydroxylation of arachidonic acid (AA were established recently as the so-called third branch of AGE cascade. Cytochrome P450 (CYP epoxygenases convert AA to four epoxyeicosatrienoic acid (EET regioisomers, that produce vascular relaxation anti-inflammatory effects on blood vessels and in the kidney, promote angiogenesis, and protect ischemic myocardium and brain. Eicosapentaenoic acid (EPA and docosahexaenoic acid (DHA are accessible to CYP enzymes in the same way as AA. Metabolites derived from EPA include epoxyeicosatetraenoic acids (EETR and hydroxyeicosapentaenoic acids (19- and 20-HEPE, whereas DHA include epoxydocosapentaenoic acids (EDPs hydroxydocosahexaenoic acids (21- and 22-HDoHE. For many of the CYP isoforms, the n-3 PUFAs are the preferred substrates and the available data suggest that some of the vasculo- and cardioprotective effects attributed to dietary n-3 PUFAs may be mediated by CYP-dependent metabolites of EPA and DHA. From AA derives also endocannabinoids like anandamide (N-arachidonoylethanolamine and 2-arachidonoylglycerol, capable of mimicking the pharmacological actions of the active principle of Cannabis sativa preparations such as

  10. Cross-validation of IASI/MetOp derived tropospheric δD with TES and ground-based FTIR observations

    Science.gov (United States)

    Lacour, J.-L.; Clarisse, L.; Worden, J.; Schneider, M.; Barthlott, S.; Hase, F.; Risi, C.; Clerbaux, C.; Hurtmans, D.; Coheur, P.-F.

    2015-03-01

    The Infrared Atmospheric Sounding Interferometer (IASI) flying onboard MetOpA and MetOpB is able to capture fine isotopic variations of the HDO to H2O ratio (δD) in the troposphere. Such observations at the high spatio-temporal resolution of the sounder are of great interest to improve our understanding of the mechanisms controlling humidity in the troposphere. In this study we aim to empirically assess the validity of our error estimation previously evaluated theoretically. To achieve this, we compare IASI δD retrieved profiles with other available profiles of δD, from the TES infrared sounder onboard AURA and from three ground-based FTIR stations produced within the MUSICA project: the NDACC (Network for the Detection of Atmospheric Composition Change) sites Kiruna and Izaña, and the TCCON site Karlsruhe, which in addition to near-infrared TCCON spectra also records mid-infrared spectra. We describe the achievable level of agreement between the different retrievals and show that these theoretical errors are in good agreement with empirical differences. The comparisons are made at different locations from tropical to Arctic latitudes, above sea and above land. Generally IASI and TES are similarly sensitive to δD in the free troposphere which allows one to compare their measurements directly. At tropical latitudes where IASI's sensitivity is lower than that of TES, we show that the agreement improves when taking into account the sensitivity of IASI in the TES retrieval. For the comparison IASI-FTIR only direct comparisons are performed because the sensitivity profiles of the two observing systems do not allow to take into account their differences of sensitivity. We identify a quasi negligible bias in the free troposphere (-3‰) between IASI retrieved δD with the TES, which are bias corrected, but important with the ground-based FTIR reaching -47‰. We also suggest that model-satellite observation comparisons could be optimized with IASI thanks to its high

  11. A Portable FTIR Analyser for Field Measurements of Trace Gases and their Isotopologues: CO2, CH4, N2O, CO, del13C in CO2 and delD in water vapour

    Science.gov (United States)

    Griffith, D. W.; Bryant, G. R.; Deutscher, N. M.; Wilson, S. R.; Kettlewell, G.; Riggenbach, M.

    2007-12-01

    We describe a portable Fourier Transform InfraRed (FTIR) analyser capable of simultaneous high precision analysis of CO2, CH4, N2O and CO in air, as well as δ13C in CO2 and δD in water vapour. The instrument is based on a commercial 1 cm-1 resolution FTIR spectrometer fitted with a mid-IR globar source, 26 m multipass White cell and thermoelectrically-cooled MCT detector operating between 2000 and 7500 cm-1. Air is passed through the cell and analysed in real time without any pre-treatment except for (optional) drying. An inlet selection manifold allows automated sequential analysis of samples from one or more inlet lines, with typical measurement times of 1-10 minutes per sample. The spectrometer, inlet sampling sequence, real-time quantitative spectrum analysis, data logging and display are all under the control of a single program running on a laptop PC, and can be left unattended for continuous measurements over periods of weeks to months. Selected spectral regions of typically 100-200 cm-1 width are analysed by a least squares fitting technique to retrieve concentrations of trace gases, 13CO2 and HDO. Typical precision is better than 0.1% without the need for calibration gases. Accuracy is similar if measurements are referenced to calibration standard gases. δ13C precision is typically around 0.1‰, and for δD it is 1‰. Applications of the analyser include clean and polluted air monitoring, tower-based flux measurements such as flux gradient or integrated horizontal flux measurements, automated soil chambers, and field-based measurements of isotopic fractionation in soil-plant-atmosphere systems. The simultaneous multi-component advantages can be exploited in tracer-type emission measurements, for example of CH4 from livestock using a co-released tracer gas and downwind measurement. We have also developed an open path variant especially suited to tracer release studies and measurements of NH3 emissions from agricultural sources. An illustrative

  12. Comparison of the hanging-drop technique and running-drip method for identifying the epidural space in dogs.

    Science.gov (United States)

    Martinez-Taboada, Fernando; Redondo, José I

    2017-03-01

    To compare the running-drip and hanging-drop techniques for locating the epidural space in dogs. Prospective, randomized, clinical trial. Forty-five healthy dogs requiring epidural anaesthesia. Dogs were randomized into four groups and administered epidural anaesthesia in sternal (S) or lateral (L) recumbency. All blocks were performed by the same person using Tuohy needles with either a fluid-prefilled hub (HDo) or connected to a drip set attached to a fluid bag elevated 60 cm (RDi). The number of attempts, 'pop' sensation, clear drop aspiration or fluid dripping, time to locate the epidural space (TTLES) and presence of cerebrospinal fluid (CSF) were recorded. A morphine-bupivacaine combination was injected after positive identification. The success of the block was assessed by experienced observers based on perioperative usage of rescue analgesia. Data were checked for normality. Binomial variables were analysed with the chi-squared or Fisher's exact test as appropriate. Non-parametric data were analysed using Kruskal-Wallis and Mann-Whitney tests. Normal data were studied with an anova followed by a Tukey's means comparison for groups of the same size. A p-value of Drop aspiration was observed more often in SHDo (nine of 11 dogs) than in LHDo (two of 11 dogs) (p = 0.045). Mean (range) TTLES was longer in LHDo [47 (18-82) seconds] than in SHDo [20 (14-79) seconds] (p = 0.006) and SRDi [(34 (17-53) seconds] (p = 0.038). There were no differences in 'pop' sensation, presence of CSF, rescue analgesia or pain scores between the groups. The running-drip method is a useful and fast alternative technique for identifying the epidural space in dogs. The hanging-drop technique in lateral recumbency was more difficult to perform than the other methods, requiring more time and attempts. Copyright © 2017 Association of Veterinary Anaesthetists and American College of Veterinary Anesthesia and Analgesia. Published by Elsevier Ltd. All rights reserved.

  13. Isotope composition of winter precipitation and snow cover in the foothills of the Altai

    Directory of Open Access Journals (Sweden)

    N. S. Malygina

    2017-01-01

    Full Text Available Over the past three decades, several general circulation models of the atmosphere and ocean (atmospheric and oceanic general circulation models  – GCMs have been improved by modeling the hydrological cycle with the use of isotopologues (isotopes of water HDO and H2 18O. Input parameters for the GCM models taking into account changes in the isotope composition of atmospheric precipitation were, above all, the results obtained by the network GNIP – Global Network of Isotopes in Precipitation. At different times, on the vast territory of Russia there were only about 40 simultaneously functioning stations where the sampling of atmospheric precipitation was performed. In this study we present the results of the isotope composition of samples taken on the foothills of the Altai during two winter seasons of 2014/15 and 2015/16. Values of the isotope composition of precipitation changed in a wide range and their maximum fluctuations were 25, 202 and 18‰ for δ18О, dexc and δD, respectively. The weighted-mean values of δ18О and δD of the precipitation analyzed for the above two seasons were close to each other (−21.1 and −158.1‰ for the first season and −21.1 and −161.9‰ for the second one, while dexc values differed significantly. The comparison of the results of isotope analysis of the snow cover integral samples with the corresponding in the time interval the weighted-mean values of precipitation showed high consistency. However, despite the similarity of values of δ18О and δD, calculated for precipitation and snow cover, and the results, interpolated in IsoMAP (from data of the GNIP stations for 1960–2010, the dexc values were close to mean annual values of IsoMAP for only the second winter season. According to the trajectory analysis (the HYSPLIT model, the revealed differences between both, the seasons, and the long-term average values of IsoMAP, were associated with a change of main regions where the air masses

  14. THE HERSCHEL AND IRAM CHESS SPECTRAL SURVEYS OF THE PROTOSTELLAR SHOCK L1157-B1: FOSSIL DEUTERATION

    Energy Technology Data Exchange (ETDEWEB)

    Codella, C.; Fontani, F.; Vasta, M. [INAF, Osservatorio Astrofisico di Arcetri, Largo Enrico Fermi 5, I-50125 Firenze (Italy); Ceccarelli, C.; Lefloch, B.; Kahane, C.; Taquet, V.; Wiesenfeld, L. [UJF-Grenoble 1/CNRS-INSU, Institut de Planetologie et d' Astrophysique de Grenoble (IPAG) UMR 5274, Grenoble, F-38041 (France); Busquet, G. [INAF - Istituto di Astrofisica e Planetologia Spaziali, via Fosso del Cavaliere 100, I-00133, Roma (Italy); Caselli, P. [School of Physics and Astronomy, University of Leeds, Leeds LS2 9JT (United Kingdom); Lis, D. [California Institute of Technology, Cahill Center for Astronomy and Astrophysics 301-17, Pasadena, CA 91125 (United States); Viti, S., E-mail: codella@rcetri.astro.it [Department of Physics and Astronomy, University College London, London (United Kingdom)

    2012-09-20

    We present the first study of deuteration toward the protostellar shock L1157-B1, based on spectral surveys performed with the Herschel-HIFI and IRAM 30 m telescopes. The L1157 outflow is driven by a low-mass Class 0 protostar and is considered the prototype of the so-called chemically active outflows. The young (2000 yr), bright blueshifted bow shock, B1, is an ideal laboratory for studying the gas chemically enriched by the release of dust mantles due to the passage of a shock. A total of 12 emission lines (up to E{sub u} = 63 K) of CH{sub 2}DOH, HDCO, and DCN are detected. In addition, two lines of NH{sub 2}D and HDO are tentatively reported. To estimate the deuteration, we also extracted from our spectral survey emission lines of non-deuterated isotopologues ({sup 13}CH{sub 3}OH, H{sub 2} {sup 13}CO, H{sup 13}CN, H{sub 2} {sup 13}CO, and NH{sub 3}). We infer higher deuteration fractions for CH{sub 3}OH (D/H = 0.2-2 Multiplication-Sign 10{sup -2}) and H{sub 2}CO (5-8 Multiplication-Sign 10{sup -3}) than for H{sub 2}O (0.4-2 Multiplication-Sign 10{sup -3}), HCN ({approx}10{sup -3}), and ammonia ({<=}3 Multiplication-Sign 10{sup -2}). The measurement of deuteration of water, formaldehyde, and methanol in L1157-B1 provides a fossil record of the gas before it was shocked by the jet driven by the protostar. A comparison with gas-grain models indicates that the gas passed through a low-density ({<=}10{sup 3} cm{sup -3}) phase, during which the bulk of water ices formed, followed by a phase of increasing density, up to 3 Multiplication-Sign 10{sup 4} cm{sup -3}, during which formaldehyde and methanol ices formed.

  15. Aluminum and Other Coatings for the Passivation of Tritium Storage Vessels

    Energy Technology Data Exchange (ETDEWEB)

    Spencer, W. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Korinko, P. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

    2016-11-16

    Using a highly sensitive residual gas analyzer, the off-gassing of hydrogen, water, and hydrocarbons from surface-treated storage vessels containing deuterium was measured. The experimental storage vessels were compared to a low-off-gassing, electro-polished 304L canister. Alternative vessels were made out of aluminum, or were coatings on 304L steel. Coatings included powder pack aluminide, electro-plated aluminum, powder pack chromide, dense electro-plated chromium, copper plated, and copper plated with 25 and 50 percent nano-diamond. Vessels were loaded with low pressure deuterium to observe exchange with protium or hydrogen as observed with formation of HD and HDO. Off gas of D2O or possible CD4 was observed at mass 20. The main off-gas in all of the studies was H2. The studies indicated that coatings required significant post-coating treatment to reduce off-gas and enhance the permeation barrier from gases likely added during the coating process. Dense packed aluminum coatings needed heating to drive off water. Electro-plated aluminum, chromium and copper coatings appeared to trap hydrogen from the plating process. Nano-diamond appeared to enhance the exchange rate with hydrogen off gas, and its coating process trapped significant amounts of hydrogen. Aluminum caused more protium exchange than chromium-treated surfaces. Aluminum coatings released more water, but pure aluminum vessels released small amounts of hydrogen, little water, and generally performed well. Chromium coating had residual hydrogen that was difficult to totally outgas but otherwise gave low residuals for water and hydrocarbons. Our studies indicated that simple coating of as received 304L metal will not adequately block hydrogen. The base vessel needs to be carefully out-gassed before applying a coating, and the coating process will likely add additional hydrogen that must be removed. Initial simple bake-out and leak checks up to 350° C for a few hours was

  16. Atmospheric influences on infrared-laser signals used for occultation measurements between Low Earth Orbit satellites

    Directory of Open Access Journals (Sweden)

    S. Schweitzer

    2011-10-01

    conclude that the set of SWIR channels proposed for implementing the LMIO method (Kirchengast and Schweitzer, 2011 provides adequate sensitivity to accurately retrieve eight trace species of key importance to climate and atmospheric chemistry (H2O, CO2, 13CO2, C18OO, CH4, N2O, O3, CO in the upper troposphere/lower stratosphere region outside clouds under all atmospheric conditions. Two further species (HDO, H218O can be retrieved in the upper troposphere.

  17. Can we determine what controls the spatio-temporal distribution of d-excess and 17O-excess in precipitation using the LMDZ general circulation model?

    Directory of Open Access Journals (Sweden)

    C. Risi

    2013-09-01

    Full Text Available Combined measurements of the H218O and HDO isotopic ratios in precipitation, leading to second-order parameter D-excess, have provided additional constraints on past climates compared to the H218O isotopic ratio alone. More recently, measurements of H217O have led to another second-order parameter: 17O-excess. Recent studies suggest that 17O-excess in polar ice may provide information on evaporative conditions at the moisture source. However, the processes controlling the spatio-temporal distribution of 17O-excess are still far from being fully understood. We use the isotopic general circulation model (GCM LMDZ to better understand what controls d-excess and 17O-excess in precipitation at present-day (PD and during the last glacial maximum (LGM. The simulation of D-excess and 17O-excess is evaluated against measurements in meteoric water, water vapor and polar ice cores. A set of sensitivity tests and diagnostics are used to quantify the relative effects of evaporative conditions (sea surface temperature and relative humidity, Rayleigh distillation, mixing between vapors from different origins, precipitation re-evaporation and supersaturation during condensation at low temperature. In LMDZ, simulations suggest that in the tropics convective processes and rain re-evaporation are important controls on precipitation D-excess and 17O-excess. In higher latitudes, the effect of distillation, mixing between vapors from different origins and supersaturation are the most important controls. For example, the lower d-excess and 17O-excess at LGM simulated at LGM are mainly due to the supersaturation effect. The effect of supersaturation is however very sensitive to a parameter whose tuning would require more measurements and laboratory experiments. Evaporative conditions had previously been suggested to be key controlling factors of d-excess and 17O-excess, but LMDZ underestimates their role. More generally, some shortcomings in the simulation of 17O

  18. Studying the Mars atmosphere using a SOIR Instrument

    Science.gov (United States)

    Drummond, R.; Vandaele, A.; Daerden, F.; Neefs, E.; Mahieux, A.; Wilquet, V.; Montmessin, F.; Bertaux, J.; McConnell, J. C.; Kaminski, J. W.

    2009-05-01

    SOIR (Solar Occultation InfraRed spectrometer) is currently part of the SPICAV/SOIR instrument on board the Venus Express orbiter (VEX). SOIR, an Echelle infrared spectrometer using an acousto-optic tunable filter (AOTF) for the order selection, is probing the atmosphere by solar occultation, operating between 2.2 and 4.3 μm, with a resolution of 0.15 cm-1. This spectral range is suitable for the detection of several key components of planetary atmospheres, including H2O and its isotopologue HDO, CH4 and other trace species. The SOIR instrument was designed to have a minimum of moving parts, to be light and compact in order to fit on top of the SPICAV instrument. The AOTF allows a narrow range of wavelengths to pass, according to the radio frequency applied to the TeO2 crystal; this selects the order. The advantage of the AOTF is that different orders can be observed quickly and easily during one occultation. To obtain a compact optical scheme, a Littrow configuration was implemented in which the usual collimating and imaging lenses are merged into a single off-axis parabolic mirror. The light is diffracted on the echelle grating, where orders overlap and addition occurs, and finally is recorded by the detector. The detector is 320x256 pixels and is cooled to 88K during an occultation measurement, to maximise the signal to noise ratio. SOIR on VEX has been in orbit around Venus since April 2006, allowing us to characterise the instrument and study its performance. These data have allowed the engineering team to devise several instrumental improvements. The next step in further improving the readiness for Martian atmospheric studies comes in close collaboration with the Mars Atmospheric Modelling group at BIRA-IASB. A General Circulation Model is used to simulate the Martian atmosphere. Currently work is underway with SPICAM data to verify the GCM inputs and outputs. Later the GCM output will be used as feedback for instrumental design of both an improved version

  19. Long open-path measurements of greenhouse gases in air using near-infrared Fourier transform spectroscopy

    Directory of Open Access Journals (Sweden)

    D. W. T. Griffith

    2018-03-01

    Full Text Available In complex and urban environments, atmospheric trace gas composition is highly variable in time and space. Point measurement techniques for trace gases with in situ instruments are well established and accurate, but do not provide spatial averaging to compare against developing high-resolution atmospheric models of composition and meteorology with resolutions of the order of a kilometre. Open-path measurement techniques provide path average concentrations and spatial averaging which, if sufficiently accurate, may be better suited to assessment and interpretation with such models. Open-path Fourier transform spectroscopy (FTS in the mid-infrared region, and differential optical absorption spectroscopy (DOAS in the UV and visible, have been used for many years for open-path spectroscopic measurements of selected species in both clean air and in polluted environments. Near infrared instrumentation allows measurements over longer paths than mid-infrared FTS for species such as greenhouse gases which are not easily accessible to DOAS.In this pilot study we present the first open-path near-infrared (4000–10 000 cm−1, 1.0–2.5 µm FTS measurements of CO2, CH4, O2, H2O and HDO over a 1.5 km path in urban Heidelberg, Germany. We describe the construction of the open-path FTS system, the analysis of the collected spectra, several measures of precision and accuracy of the measurements, and the results a four-month trial measurement period in July–November 2014. The open-path measurements are compared to calibrated in situ measurements made at one end of the open path. We observe significant differences of the order of a few ppm for CO2 and a few tens of ppb for CH4 between the open-path and point measurements which are 2 to 4 times the measurement repeatability, but we cannot unequivocally assign the differences to specific local sources or sinks. We conclude that open-path FTS may provide a valuable new tool for investigations of

  20. Implementation of a Novel Laser System for Simultaneous Measurement of 13C/12C and D/H to Food Provenance

    Science.gov (United States)

    Saad, N.; Hoffnagle, J.

    2012-04-01

    Olive oil samples were analyzed using the world's first simultaneous δ13C + δD instrument, the 13C+D Combustion Module-Cavity Ringdown Spectroscopy (CM-CRDS) Isotope Analyzer. Simultaneous measurements of δ13C and δD of the whole oil have been performed on commercially available olive oils produced in Greece, Spain, Italy, California, Lebanon, Israel, Australia and Turkey. Together, the measurements of isotopic ratios of carbon (13C/12C) and hydrogen (D/H) produce statistically significant differentiation between olive oils from different locations around the globe. Stable isotope ratios are exquisitely sensitive to the biochemistry of plant species and the nutrients available to them in a particular geographical location. Isotope ratios provide detailed knowledge useful for forensic applications through a combination of stable-isotope measurements of carbon (13C/12C) and hydrogen (D/H) isotopes of organic matter and can help the associations among specific geographic areas through the measurement of these dual isotopes. We report here on the development of a novel laser spectroscopy based system for the simultaneous analysis of the stable isotope ratios of carbon (13C/12C) and hydrogen (D/H) that is robust, easy-to-use, and is the first stable isotope ratio analysis system to combine the measurement of 13C/12C and D/H in one simple analysis from a bulk organic sample. The system comprises a combustion module to convert the organic sample into CO2 and H2O and a Cavity Ring-Down Spectrometer (CRDS) that analyzes the combustion species inside an optical cavity based on the molecular absorption of individual isotopomers. The CRDS uses dual lasers to target the four isotpomers of interest: 12CO2, 13CO2, H2O and HDO. The system delivers a typical precision of 0.1permil for δ13C and 1.5 permil for δD that parallels that achieved by IRMS, but with an unprecedented simplicity that allows scientists to leverage the science and map out the provenance of the analyzed

  1. Transition Metal Phosphide Nanoparticles Supported on SBA-15 as Highly Selective Hydrodeoxygenation Catalysts for the Production of Advanced Biofuels.

    Science.gov (United States)

    Yang, Yongxing; Ochoa-Hernández, Cristina; de la Peña O'Shea, Víctor A; Pizarro, Patricia; Coronado, Juan M; Serrano, David P

    2015-09-01

    A series of catalysts constituted by nanoparticles of transition metal (M = Fe, Co, Ni and Mo) phosphides (TMP) dispersed on SBA-15 were synthesized by reduction of the corresponding metal phosphate precursors previously impregnated on the mesostructured support. All the samples contained a metal-loading of 20 wt% and with an initial M/P mole ratio of 1, and they were characterized by X-ray diffraction (XRD), N2 sorption, H2-TPR and transmission electron microscopy (TEM). Metal phosphide nanocatalysts were tested in a high pressure continuous flow reactor for the hydrodeoxygenation (HDO) of a methyl ester blend containing methyl oleate (C17H33-COO-CH3) as main component (70%). This mixture constitutes a convenient surrogate of triglycerides present in vegetable oils, and following catalytic hydrotreating yields mainly n-alkanes. The results of the catalytic assays indicate that Ni2P/SBA-15 catalyst presents the highest ester conversion, whereas the transformation rate is about 20% lower for MoP/SBA-15. In contrast, catalysts based on Fe and Co phosphides show a rather limited activity. Hydrocarbon distribution in the liquid product suggests that both hydrodeoxygenation and decarboxylation/decarbonylation reactions occur simultaneously over the different catalysts, although MoP/SBA-15 possess a selectivity towards hydrodeoxygenation exceeding 90%. Accordingly, the catalyst based on MoP affords the highest yield of n-octadecane, which is the preferred product in terms of carbon atom economy. Subsequently, in order to conjugate the advantages of both Ni and Mo phosphides, a series of catalysts containing variable proportions of both metals were prepared. The obtained results reveal that the mixed phosphides catalysts present a catalytic behavior intermediate between those of the monometallic phosphides. Accordingly, only marginal enhancement of the yield of n-octadecane is obtained for the catalysts with a Mo/Ni ratio of 3. Nevertheless, owing to this high selectivity

  2. Effects of P/Ni ratio and Ni content on performance of γ-Al_2O_3-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons

    International Nuclear Information System (INIS)

    Zhang, Zhena; Tang, Mingxiao; Chen, Jixiang

    2016-01-01

    Graphical abstract: - Highlights: • The formation of AlPO_4 was unfavorable for that of nickel phosphides. • The phase compositions of nickel phosphide depended on the amount of reduced P. • Catalytic activity was determined by surface Ni site density and catalyst acidity. • HDO pathway was promoted by increasing P/Ni ratio and Ni content. • Nickel phosphide gave much higher carbon yield and lower H_2 consumption than Ni. - Abstract: γ-Al_2O_3-supported nickel phosphides (mNi-Pn) were prepared by the TPR method and tested for the deoxygenation of methyl laurate to hydrocarbons. The effects of the P/Ni ratio (n = 1.0–2.5) and Ni content (m = 5–15 wt.%) in the precursors on their structure and performance were investigated. Ni/γ-Al_2O_3 was also studied for comparison. It was found that the formation of AlPO_4 in the precursor inhibited the reduction of phosphate and so the formation of nickel phosphides. With increasing the P/Ni ratio and Ni content, the Ni, Ni_3P, Ni_1_2P_5 and Ni_2P phases orderly formed, accompanying with the increases of their particle size and the amount of weak acid sites (mainly due to P-OH group), while the CO uptake and the amount of medium strong acid sites (mainly related to Ni sites) reached maximum on 10%Ni-P1.5. In the deoxygenation reaction, compared with Ni/γ-Al_2O_3, the mNi-Pn catalysts showed much lower activities for decarbonylation, C−C hydrogenolysis and methanation due to the ligand and ensemble effects of P. The conversion and the selectivity to n-C11 and n-C12 hydrocarbons achieved maximum on 10%Ni-P 2.0 for the 10%Ni-Pn catalysts and on 8%Ni-P2.0 for the mNi-P2.0 catalysts, while the turnover frequency (TOF) of methyl laurate mainly increased with the P/Ni ratio and Ni content. We propose that TOF was influenced by the nickel phosphide phases, the catalyst acidity and the particle size as well as the synergetic effect between the Ni site and acid site. Again, the hydrodeoxygenation pathway of methyl

  3. Synthesis and characterization of catalysts for the selective transformation of biomass-derived materials

    Science.gov (United States)

    Ghampson, Isaac Tyrone

    The experimental work in this thesis focuses on generating catalysts for two intermediate processes related to the thermal conversion of lignocellulosic biomass: the synthesis and characterization of mesoporous silica supported cobalt catalysts for the Fischer-Tropsch reaction, and an exploration of the reactivity of bulk and supported molybdenum-based nitride catalysts for the hydrodeoxygenation (HDO) of guaiacol, a lignin model compound. The first section of the work details the synthesis of a series of silica-supported cobalt Fischer-Tropsch catalysts with pore diameters ranging from 2-23 nm. Detailed X-ray diffraction measurements were used to determine the composition and particle diameters of the metal fraction, analyzed as a three-phase system containing Cofcc, Cohcp and CoO particles. Catalyst properties were determined at three stages in catalyst history: (1) after the initial calcination step to thermally decompose the catalyst precursor into Co3O4, (2) after the hydrogen reduction step to activate the catalyst to Co and (3) after the FT reaction. From the study, it was observed that larger pore diameters supported higher turnover frequency; smaller pore diameters yielded larger mole fraction of CoO; XRD on post-reduction and post-FTS catalyst samples indicated significant changes in dispersivity after reduction. In the next section, the catalytic behaviors of unsupported, activated carbon-, alumina-, and SBA-15 mesoporous silica-supported molybdenum nitride catalysts were evaluated for the hydrodeoxygenation of guaiacol (2-methoxy phenol) at 300°C and 5 MPa. The nitride catalysts were prepared by thermal decomposition of bulk and supported ammonium heptamolybdate to form MoO 3 followed by nitridation in either flowing ammonia or a nitrogen/hydrogen mixture. The catalytic properties were strongly affected by the nitriding and purging treatment as well as the physical and chemical properties of support. The overall reaction was influenced by the

  4. The dependence of entrainment and drizzle in marine stratiform clouds on biomass burning aerosols derived from stable isotope and thermodynamic profiles

    Science.gov (United States)

    Henze, D.; Noone, D.

    2017-12-01

    A third of the world's biomass burning aerosol (BBA) particles are generated in southern Africa, and these particles are swept into the midlevel troposphere over the southeast Atlantic Ocean. The presence of these aerosols over the marine environment of the south east Atlantic offers a unique natural laboratory for studying aerosol effects on climate, and specifically a modification to the hydrologic cycle and microphysical characteristics of clouds. Different rates of condensation with high aerosol numbers change the precipitation rates in drizzling stratiform clouds, while the mixing of aerosols into the cloud layer is synonymous with entrainment from above cloud top near the top of the subtropical inversion. To better understanding the magnitude of the aerosol influence on southeast Atlantic boundary layer clouds we analyze the cloud-top entrainment and drizzle as a function of aerosol loading to determine the impact of BBA. Entrainment was determined from mixing line analysis based on profile measurements of moist static energy, total water, and the two most common heavy isotopes of water - HDO and H218O. Data was collected on the P-3 Orion aircraft during the NASA 2017 ORACLES campaign. Using these measurements, a box model was constructed using the combined conservation laws associated with all four of these quantities to estimate the entrainment and rainout of cloud liquid. The population of profiles sampled by the aircraft over the course of the 30 day mission spans varying concentrations of BBA. Initial plots of the water isotope mixing lines show where and to what degree the BBA air mass has mixed into the boundary layer air mass from above. This is demonstrated by the fact that the mixing end-members are the same for the different areas sampled, but the rate at which the various mixing lines are traversed as a function of altitude varies. Further, the mixing lines as a function of height traverse back and forth between end members multiple times over one

  5. Origins Space Telescope: HEterodyne Receiver for OST (HERO)

    Science.gov (United States)

    Bergin, Edwin; Wiedner, Martina; Laurens, Andre; Gerin, Maryvonne; HERO team, Origins Space Telescope Science and Technology Definition Team

    2018-01-01

    The Origins Space Telescope (OST) is a mission concept for the Far-Infrared Surveyor, one of the four science and technology definition studies selected by NASA HQ for the 2020 Astronomy and Astrophysics Decadal survey. The OST study will encompass two mission concepts (poster by A. Cooray). Concept 1 is an extremely versatile observatory with 5 science instruments, of which the HEterodyne Receivers for OST (HERO) is one.HERO’s main targets are high spectral resolution observations (Dl/l up to 107 or Dv = 0.03km/s) of water to follow its trail from cores to YSOs as well as H2O and HDO observations on comets to explore the origins of water. HERO will probe all neutral ISM phases using cooling lines ([CII], [OI]) and hydrides as probes of CO-dark H2 (CH, HF). HERO will reveal how molecular clouds and filaments form in the local ISM up to nearby galaxies. HERO will enable detailed understanding of feedback mechanisms : shocks, cosmic rays, UV induced feedback and will provide a map of the cosmic ray ionization rate in the Galaxy and nearby galaxies using molecular ions (ArH+, OH+, H3O+).In order to achieve these observational goals, HERO will cover an extremely wide frequency range from 468 to 2700 GHz (641 to 111microns) and a window around the OI line at 4563 to 4752GHz (66 to 63 microns). It will consist of very large focal plane arrays of 128 pixels between 900 - 2700 GHz and at 4.7 THz, and 32 pixels for the 468 to 900 GHz range. The instrument is exploiting Herschel/HIFI heritage, but will go well beyond HIFIs capacities. HERO’s large arrays require low dissipation and low power components. The HERO concept makes use of the latest cryogenic SiGe amplifier technology, as well as CMOS technology for the backends with 2 orders of magnitude lower power. Advances in Local Oscillator technology have also been taken into account and ambitious, but realistic assumptions have been made for future amplifier multiplier chains going up to 4.7 THz.Origins will enable

  6. Effects of the gas-liquid ratio on the optimal quantity of the catalyst for the CECE process with a homogeneously packed LPCE column

    International Nuclear Information System (INIS)

    Ushida, A.; Sugiyama, T.; Yamamoto, I.

    2007-01-01

    concentrations of HD or HDO in gas and liquid samples were measured using a stable isotope ratio mass spectrometer (MAT252, Thermo Finnigan) with a relative accuracy to 1 %. In the present paper we report experimental and/or analytical results for the effects of the gas-liquid ratio on the optimal quantity of the catalyst. (orig.)

  7. Greenhouse Observations of the Stratosphere and Troposphere (GHOST): a novel shortwave infrared spectrometer developed for the Global Hawk unmanned aerial vehicle

    Science.gov (United States)

    Humpage, Neil; Boesch, Hartmut; Palmer, Paul; Parr-Burman, Phil; Vick, Andy; Bezawada, Naidu; Black, Martin; Born, Andy; Pearson, David; Strachan, Jonathan; Wells, Martyn

    2014-05-01

    The tropospheric distribution of greenhouse gases (GHGs) is dependent on surface flux variations, atmospheric chemistry and transport processes over a wide range of spatial and temporal scales. Errors in assumed atmospheric transport can adversely affect surface flux estimates inferred from surface, aircraft or satellite observations of greenhouse gas concentrations using inverse models. We present a novel, compact shortwave infrared spectrometer (GHOST) for installation on the NASA Global Hawk unmanned aerial vehicle to provide tropospheric column observations of CO2, CO, CH4, H2O and HDO over the ocean to address the need for large-scale, simultaneous, finely resolved measurements of key GHGs. These species cover a range of lifetimes and source processes, and measurements of their tropospheric columns will reflect the vertically integrated signal of their vertical and horizontal transport within the troposphere. The primary science objectives of GHOST are to: 1) provide observations which can be used to test atmospheric transport models; 2) validate satellite observations of GHG column observations over oceans, thus filling a critical gap in current validation capabilities; and 3) complement in-situ tropopause transition layer tracer observations from other instrumentation on board the Global Hawk to provide a link between upper and lower troposphere concentration measurements. The GHOST spectrometer system comprises a target acquisition module (TAM), a fibre slicer and feed system, and a multiple order spectrograph. The TAM design utilises a gimbal behind an optical dome, which is programmed to direct solar radiation reflected by the ocean surface into a fibre optic bundle. The fibre slicer and feed system then splits the light into the four spectral bands using order sorting filters. The fibres corresponding to each band are arranged with a small sideways offset to correctly centre each spectrum on the detector array. The spectrograph design is unique in that a

  8. Water stable isotopes: application to the water cycle and climate variations study

    International Nuclear Information System (INIS)

    Risi, C.

    2009-12-01

    The stable isotopic composition of water (H 2 16 , HDO, H 2 18 , H 2 17 ) is a promising tracer of the present day water cycle and past climates. While the isotopic composition recorded in polar ice core have long been used to reconstruct past temperatures, however, what controls the isotopic composition of the tropical precipitation is more complex. The goal of this thesis is thus to better understand the processes that affect the isotopic composition of tropical precipitation and atmospheric water, more particularly in the tropics. Since most of the tropical precipitation arises from atmospheric convection, and most isotopic archives are on land, we focus more particularly on the impact of convective and land surface processes. In turn, what can be learned about convection and land surface processes using isotopic measurements? Can they help constrain their representation in models? At the inter-annual to climate change scale, what information about the tropical climate variability is recorded in isotopic signals observed in archives? First, we investigate the influence of convection on water stable isotopes. We use both (1) numerical modeling, with a hierarchy of models (single column model, two-dimensional model of squall lines, general circulation model) and (2) data analysis, using isotopic data from rain collected in the Sahel during the African Monsoon Multidisciplinary Analysis campaign, at the event and intra-event scales. These studies highlight the strong impact of convection on the precipitation composition, and stress the importance of rain evaporation and convective or meso-scale subsidence in controlling the rain isotopic composition. Convection also plays an important role on isotopic profiles in the upper troposphere-lower stratosphere. Second, we study what information about climatic variability is recorded by water stable isotopes in precipitation. We analyze simulations of present day and past climates with LMDZ, and evaluate to what extent

  9. Long open-path measurements of greenhouse gases in air using near-infrared Fourier transform spectroscopy

    Science.gov (United States)

    Griffith, David W. T.; Pöhler, Denis; Schmitt, Stefan; Hammer, Samuel; Vardag, Sanam N.; Platt, Ulrich

    2018-03-01

    In complex and urban environments, atmospheric trace gas composition is highly variable in time and space. Point measurement techniques for trace gases with in situ instruments are well established and accurate, but do not provide spatial averaging to compare against developing high-resolution atmospheric models of composition and meteorology with resolutions of the order of a kilometre. Open-path measurement techniques provide path average concentrations and spatial averaging which, if sufficiently accurate, may be better suited to assessment and interpretation with such models. Open-path Fourier transform spectroscopy (FTS) in the mid-infrared region, and differential optical absorption spectroscopy (DOAS) in the UV and visible, have been used for many years for open-path spectroscopic measurements of selected species in both clean air and in polluted environments. Near infrared instrumentation allows measurements over longer paths than mid-infrared FTS for species such as greenhouse gases which are not easily accessible to DOAS.In this pilot study we present the first open-path near-infrared (4000-10 000 cm-1, 1.0-2.5 µm) FTS measurements of CO2, CH4, O2, H2O and HDO over a 1.5 km path in urban Heidelberg, Germany. We describe the construction of the open-path FTS system, the analysis of the collected spectra, several measures of precision and accuracy of the measurements, and the results a four-month trial measurement period in July-November 2014. The open-path measurements are compared to calibrated in situ measurements made at one end of the open path. We observe significant differences of the order of a few ppm for CO2 and a few tens of ppb for CH4 between the open-path and point measurements which are 2 to 4 times the measurement repeatability, but we cannot unequivocally assign the differences to specific local sources or sinks. We conclude that open-path FTS may provide a valuable new tool for investigations of atmospheric trace gas composition in

  10. Intercomparison of open-path trace gas measurements with two dual-frequency-comb spectrometers

    Directory of Open Access Journals (Sweden)

    E. M. Waxman

    2017-09-01

    Full Text Available We present the first quantitative intercomparison between two open-path dual-comb spectroscopy (DCS instruments which were operated across adjacent 2 km open-air paths over a 2-week period. We used DCS to measure the atmospheric absorption spectrum in the near infrared from 6023 to 6376 cm−1 (1568 to 1660 nm, corresponding to a 355 cm−1 bandwidth, at 0.0067 cm−1 sample spacing. The measured absorption spectra agree with each other to within 5 × 10−4 in absorbance without any external calibration of either instrument. The absorption spectra are fit to retrieve path-integrated concentrations for carbon dioxide (CO2, methane (CH4, water (H2O, and deuterated water (HDO. The retrieved dry mole fractions agree to 0.14 % (0.57 ppm for CO2, 0.35 % (7 ppb for CH4, and 0.40 % (36 ppm for H2O at  ∼  30 s integration time over the 2-week measurement campaign, which included 24 °C outdoor temperature variations and periods of strong atmospheric turbulence. This agreement is at least an order of magnitude better than conventional active-source open-path instrument intercomparisons and is particularly relevant to future regional flux measurements as it allows accurate comparisons of open-path DCS data across locations and time. We additionally compare the open-path DCS retrievals to a World Meteorological Organization (WMO-calibrated cavity ring-down point sensor located along the path with good agreement. Short-term and long-term differences between the open-path DCS and point sensor are attributed, respectively, to spatial sampling discrepancies and to inaccuracies in the current spectral database used to fit the DCS data. Finally, the 2-week measurement campaign yields diurnal cycles of CO2 and CH4 that are consistent with the presence of local sources of CO2 and absence of local sources of CH4.

  11. High Pressure Biomass Gasification

    Energy Technology Data Exchange (ETDEWEB)

    Agrawal, Pradeep K [Georgia Tech Research Corporation, Atlanta, GA (United States)

    2016-07-29

    According to the Billion Ton Report, the U.S. has a large supply of biomass available that can supplement fossil fuels for producing chemicals and transportation fuels. Agricultural waste, forest residue, and energy crops offer potential benefits: renewable feedstock, zero to low CO2 emissions depending on the specific source, and domestic supply availability. Biomass can be converted into chemicals and fuels using one of several approaches: (i) biological platform converts corn into ethanol by using depolymerization of cellulose to form sugars followed by fermentation, (ii) low-temperature pyrolysis to obtain bio-oils which must be treated to reduce oxygen content via HDO hydrodeoxygenation), and (iii) high temperature pyrolysis to produce syngas (CO + H2). This last approach consists of producing syngas using the thermal platform which can be used to produce a variety of chemicals and fuels. The goal of this project was to develop an improved understanding of the gasification of biomass at high pressure conditions and how various gasification parameters might affect the gasification behavior. Since most downstream applications of synags conversion (e.g., alcohol synthesis, Fischer-Tropsch synthesis etc) involve utilizing high pressure catalytic processes, there is an interest in carrying out the biomass gasification at high pressure which can potentially reduce the gasifier size and subsequent downstream cleaning processes. It is traditionally accepted that high pressure should increase the gasification rates (kinetic effect). There is also precedence from coal gasification literature from the 1970s that high pressure gasification would be a beneficial route to consider. Traditional approach of using thermogravimetric analyzer (TGA) or high-pressure themogravimetric analyzer (PTGA) worked well in understanding the gasification kinetics of coal gasification which was useful in designing high pressure coal gasification processes. However

  12. High-Power Single-Mode 2.65-micron InGaAsSb/AlInGaAsSb Diode Lasers

    Science.gov (United States)

    Frez, Clifford F.; Briggs, Ryan M.; Forouhar, Siamak; Borgentun, Carl E.; Gupta, James

    2013-01-01

    Central to the advancement of both satellite and in-situ science are improvements in continuous-wave and pulsed infrared laser systems coupled with integrated miniaturized optics and electronics, allowing for the use of powerful, single-mode light sources aboard both satellite and unmanned aerial vehicle platforms. There is a technological gap in supplying adequate laser sources to address the mid-infrared spectral window for spectroscopic characterization of important atmospheric gases. For high-power applications between 2 to 3 micron, commercial laser technologies are unsuitable because of limitations in output power. For instance, existing InP-based laser systems developed for fiber-based telecommunications cannot be extended to wavelengths longer than 2 micron. For emission wavelengths shorter than 3 micron, intersubband devices, such as infrared quantum cascade lasers, become inefficient due to band-offset limitations. To date, successfully demonstrated singlemode GaSb-based laser diodes emitting between 2 and 3 micron have employed lossy metal Bragg gratings for distributed- feedback coupling, which limits output power due to optical absorption. By optimizing both the quantum well design and the grating fabrication process, index-coupled distributed-feedback 2.65-micron lasers capable of emitting in excess of 25 mW at room temperature have been demonstrated. Specifically, lasers at 3,777/cm (2.65 micron) have been realized to interact with strong absorption lines of HDO and other isotopologues of H2O. With minor modifications of the optical cavity and quantum well designs, lasers can be fabricated at any wavelength within the 2-to-3-micron spectral window with similar performance. At the time of this reporting, lasers with this output power and wavelength accuracy are not commercially available. Monolithic ridge-waveguide GaSb lasers were fabricated that utilize secondorder lateral Bragg gratings to generate single-mode emission from InGaAsSb/ Al

  13. Millimeter wave spectroscopic measurements of stratospheric and mesospheric constituents over the Italian Alps: stratospheric ozone

    Directory of Open Access Journals (Sweden)

    V. Romaniello

    2007-06-01

    Full Text Available Measurements of rotational lines emitted by middle atmospheric trace gases have been carried out from the Alpine station of Testa Grigia (45.9°N, 7.7°E, elev. 3500 m by means of a Ground-Based Millimeter-wave Spectrometer (GBMS. Observations of species such as O3, HNO3, CO, N2O, HCN, and HDO took place during 4 winter periods, from February 2004 to March 2007, for a total of 116 days of measurements grouped in about 18 field campaigns. By studying the pressure-broadened shape of emission lines the vertical distribution of the observed constituents is retrieved within an altitude range of ?17-75 km, constrained by the 600 MHz pass band and the 65 kHz spectral resolution of the back-end spectrometer. This work discusses the behavior of stratospheric O3 during the entire period of operation at Testa Grigia. Mid-latitude O3 columnar content as estimated using GBMS measurements can vary by large amounts over a period of very few days, with the largest variations observed in December 2005, February 2006, and March 2006, confirming that the northern winter of 2005-2006 was characterized by a particularly intense planetary wave activity. The largest rapid variation from maximum to minimum O3 column values over Testa Grigia took place in December 2006 and reached a relative value of 72% with respect to the average column content for that period. During most GBMS observation times much of the variability is concentrated in the column below 20 km, with tropospheric weather systems and advection of tropical tropospheric air into the lower stratosphere over Testa Grigia having a large impact on the observed variations in column contents. Nonetheless, a wide variability is also found in middle stratospheric GBMS O3 measurements, as expected for mid-latitude ozone. We find that O3 mixing ratios at ?32 km are very well correlated with the solar illumination experienced by air masses over the previous ?15 days, showing that already at 32 km

  14. Human inflammatory and resolving lipid mediator responses to resistance exercise and ibuprofen treatment

    Science.gov (United States)

    Markworth, James F.; Vella, Luke; Lingard, Benjamin S.; Tull, Dedreia L.; Rupasinghe, Thusitha W.; Sinclair, Andrew J.; Maddipati, Krishna Rao

    2013-01-01

    Classical proinflammatory eicosanoids, and more recently discovered lipid mediators with anti-inflammatory and proresolving bioactivity, exert a complex role in the initiation, control, and resolution of inflammation. Using a targeted lipidomics approach, we investigated circulating lipid mediator responses to resistance exercise and treatment with the NSAID ibuprofen. Human subjects undertook a single bout of unaccustomed resistance exercise (80% of one repetition maximum) following oral ingestion of ibuprofen (400 mg) or placebo control. Venous blood was collected during early recovery (0–3 h and 24 h postexercise), and serum lipid mediator composition was analyzed by LC-MS-based targeted lipidomics. Postexercise recovery was characterized by elevated levels of cyclooxygenase (COX)-1 and 2-derived prostanoids (TXB2, PGE2, PGD2, PGF2α, and PGI2), lipooxygenase (5-LOX, 12-LOX, and 15-LOX)-derived hydroxyeicosatetraenoic acids (HETEs), and leukotrienes (e.g., LTB4), and epoxygenase (CYP)-derived epoxy/dihydroxy eicosatrienoic acids (EpETrEs/DiHETrEs). Additionally, we detected elevated levels of bioactive lipid mediators with anti-inflammatory and proresolving properties, including arachidonic acid-derived lipoxins (LXA4 and LXB4), and the EPA (E-series) and DHA (D-series)-derived resolvins (RvD1 and RvE1), and protectins (PD1 isomer 10S, 17S-diHDoHE). Ibuprofen treatment blocked exercise-induced increases in COX-1 and COX-2-derived prostanoids but also resulted in off-target reductions in leukotriene biosynthesis, and a diminished proresolving lipid mediator response. CYP pathway product metabolism was also altered by ibuprofen treatment, as indicated by elevated postexercise serum 5,6-DiHETrE and 8,9-DiHETrE only in those receiving ibuprofen. These findings characterize the blood inflammatory lipid mediator response to unaccustomed resistance exercise in humans and show that acute proinflammatory signals are mechanistically linked to the induction of a

  15. A decadal time series of water vapor and D / H isotope ratios above Zugspitze: transport patterns to central Europe

    Science.gov (United States)

    Hausmann, Petra; Sussmann, Ralf; Trickl, Thomas; Schneider, Matthias

    2017-06-01

    , -246] ‰), and STIs (1.2 [1.1, 1.3] × 103 ppmv, -384 [-397, -372] ‰). For TUS events, {H2O, δD} observations depend on surface temperature in the source region and the degree of dehydration having occurred during updraft in warm conveyor belts. During TNA events (dry convection of boundary layer air) relatively moist and weakly HDO-depleted air masses are imported. In contrast, STI events are associated with import of predominantly dry and HDO-depleted air masses. These long-range-transport patterns potentially involve the import of various trace constituents to the central European free troposphere, i.e., import of pollution from North America (e.g., aerosol, ozone, carbon monoxide), Saharan mineral dust, stratospheric ozone, and other airborne species such as pollen. Our results provide evidence that {H2O, δD} observations are a valuable proxy for the transport of such tracers. To validate this finding, we consult a database of transport events (TNA and STI) covering 2013-2015 deduced by data filtering from in situ measurements at Zugspitze and lidar profiles at nearby Garmisch. Indeed, the FTIR data related to these verified TNA events (27 days) exhibit characteristic fingerprints in IWV (5.5 [4.9, 6.1] mm) and δDcol (-266 [-284, -247] ‰), which are significantly distinguishable from the rest of the time series (4.3 [4.1, 4.5] mm, -316 [-324, -308] ‰). This holds true for 136 STI days considering uncertainties of ±1 SE (4.2 [4.0, 4.3] mm, -322 [-327, -316] ‰) with respect to the remainder (4.6 [4.5, 4.8] mm, -302 [-307, -297] ‰). Furthermore, deep stratospheric intrusions to the Zugspitze summit (in situ humidity and beryllium-7 data filtering) show a significantly lower mean value (-334 [-337, -330] ‰) of lower-tropospheric δD (3-5 km a.s.l.) than the rest of the 2005-2015 time series (-284 [-286, -282] ‰) considering uncertainty of ±2 SE. Our results show that consistent {H2O, δD} observations at Zugspitze can serve as an operational

  16. Loss of Water to Space from Mars: Processes and Implications

    Science.gov (United States)

    Kass, D. M.

    2001-12-01

    One of the major sinks for water on Mars is the loss to space. This occurs via a complex series of processes that transport the individual atoms to the upper atmosphere, where several escape mechanisms remove them. Hydrogen and deuterium are lost primarily by Jeans escape. Non-thermal processes also remove H and D, but are only important in determining D loss at solar minimum under modern conditions. The present H loss rate is equivalent to the loss of 10-3~pr-\\micron~yr-1 of water. The loss of oxygen is more complicated. The three main processes are indirect (or ionospheric) sputtering, solar wind pickup of O+, and O2+ dissociative recombination. Their relative importance has varied over the history of Mars. The combined effect of the O loss processes is to remove a ~ 50~m global layer of water over the last 3.5 Gyr. Based on photochemical modeling, the loss of oxygen and hydrogen are balanced (over geological timescales) by a feedback process. During the early history of Mars, impact erosion and hydrodynamic blow-off may have removed significant water. But, it is difficult to estimate their quantitative effects. The transport of individual H, D and O atoms to the exosphere where they can escape is not completely understood. It occurs primarily via intermediate species, H2, HD, O2 and CO2. The H2 and HD are formed by photolysis of water and the odd hydrogen photochemistry. One open issue is the mechanism regulating the partitioning of D between HDO and HD (which controls the supply of D available for escape from the exosphere). The various loss processes isotopically enrich Martian water since the exospheric escape source region is depleted. Jeans escape and the transport from the lower atmosphere further fractionate hydrogen, the most useful isotopic system. Based on recent observations, the D/H fractionation factor, F ~ 0.02. Measurements of atmospheric water vapor indicate it is enriched in deuterium, with a D/H ratio ~ 5 times the terrestrial value. Since

  17. Catalytic production of biodiesel

    Energy Technology Data Exchange (ETDEWEB)

    Theilgaard Madsen, A.

    2011-07-01

    The focus of this thesis is the catalytic production of diesel from biomass, especially emphasising catalytic conversion of waste vegetable oils and fats. In chapter 1 an introduction to biofuels and a review on different catalytic methods for diesel production from biomass is given. Two of these methods have been used industrially for a number of years already, namely the transesterification (and esterification) of oils and fats with methanol to form fatty acid methyl esters (FAME), and the hydrodeoxygenation (HDO) of fats and oils to form straight-chain alkanes. Other possible routes to diesel include upgrading and deoxygenation of pyrolysis oils or aqueous sludge wastes, condensations and reductions of sugars in aqueous phase (aqueous-phase reforming, APR) for monofunctional hydrocarbons, and gasification of any type of biomass followed by Fischer-Tropsch-synthesis for alkane biofuels. These methods have not yet been industrialised, but may be more promising due to the larger abundance of their potential feedstocks, especially waste feedstocks. Chapter 2 deals with formation of FAME from waste fats and oils. A range of acidic catalysts were tested in a model fat mixture of methanol, lauric acid and trioctanoin. Sulphonic acid-functionalised ionic liquids showed extremely fast convertion of lauric acid to methyl laurate, and trioctanoate was converted to methyl octanoate within 24 h. A catalyst based on a sulphonated carbon-matrix made by pyrolysing (or carbonising) carbohydrates, so-called sulphonated pyrolysed sucrose (SPS), was optimised further. No systematic dependency on pyrolysis and sulphonation conditions could be obtained, however, with respect to esterification activity, but high activity was obtained in the model fat mixture. SPS impregnated on opel-cell Al{sub 2}O{sub 3} and microporous SiO{sub 2} (ISPS) was much less active in the esterification than the original SPS powder due to low loading and thereby low number of strongly acidic sites on the

  18. Effects of P/Ni ratio and Ni content on performance of γ-Al{sub 2}O{sub 3}-supported nickel phosphides for deoxygenation of methyl laurate to hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Zhena; Tang, Mingxiao; Chen, Jixiang, E-mail: jxchen@tju.edu.cn

    2016-01-01

    Graphical abstract: - Highlights: • The formation of AlPO{sub 4} was unfavorable for that of nickel phosphides. • The phase compositions of nickel phosphide depended on the amount of reduced P. • Catalytic activity was determined by surface Ni site density and catalyst acidity. • HDO pathway was promoted by increasing P/Ni ratio and Ni content. • Nickel phosphide gave much higher carbon yield and lower H{sub 2} consumption than Ni. - Abstract: γ-Al{sub 2}O{sub 3}-supported nickel phosphides (mNi-Pn) were prepared by the TPR method and tested for the deoxygenation of methyl laurate to hydrocarbons. The effects of the P/Ni ratio (n = 1.0–2.5) and Ni content (m = 5–15 wt.%) in the precursors on their structure and performance were investigated. Ni/γ-Al{sub 2}O{sub 3} was also studied for comparison. It was found that the formation of AlPO{sub 4} in the precursor inhibited the reduction of phosphate and so the formation of nickel phosphides. With increasing the P/Ni ratio and Ni content, the Ni, Ni{sub 3}P, Ni{sub 12}P{sub 5} and Ni{sub 2}P phases orderly formed, accompanying with the increases of their particle size and the amount of weak acid sites (mainly due to P-OH group), while the CO uptake and the amount of medium strong acid sites (mainly related to Ni sites) reached maximum on 10%Ni-P1.5. In the deoxygenation reaction, compared with Ni/γ-Al{sub 2}O{sub 3}, the mNi-Pn catalysts showed much lower activities for decarbonylation, C−C hydrogenolysis and methanation due to the ligand and ensemble effects of P. The conversion and the selectivity to n-C11 and n-C12 hydrocarbons achieved maximum on 10%Ni-P 2.0 for the 10%Ni-Pn catalysts and on 8%Ni-P2.0 for the mNi-P2.0 catalysts, while the turnover frequency (TOF) of methyl laurate mainly increased with the P/Ni ratio and Ni content. We propose that TOF was influenced by the nickel phosphide phases, the catalyst acidity and the particle size as well as the synergetic effect between the Ni site and

  19. Water stable isotope measurements of Antarctic samples by means of IRMS and WS-CRDS techniques

    Science.gov (United States)

    Michelini, Marzia; Bonazza, Mattia; Braida, Martina; Flora, Onelio; Dreossi, Giuliano; Stenni, Barbara

    2010-05-01

    of the sample in the box. In the WS-CRDS the path of laser is longer, producing higher-sensitivity measurements. The instrument is paired with an autosampler and can be used without it and the vaporizer to analyze directly the isotopic composition of the water vapour in the atmosphere. In addition, the instrument can be moved from the laboratory and also used for outdoor measurements. The more important improvements over traditional IRMS techniques are that WS-CRDS needs less sample in order to perform the analysis (water equilibration techniques) and the analyses are faster. Coversely, memory effects may affect the measurements so there is the need to increase the number of injection to have a high precision measurement. The laboratory of Isotope Geochemistry of the Department of Geosciences has recently acquired a WS-CRDS system from PICARRO. The isotopic data obtained with this new method have been compared with the ones obtained by means of IRMS methods. An HDO device coupled with a Thermo Finnigan Delta Plus Advantage mass spectrometer has been used, using the well know CO2 and H2/water equilibration technique. At the moment of the writing of the abstract the mean difference between the values obtained using PICARRO and using the traditional IRMS method is of the order of 0.1 per mil for the ratio 18O/16O and 1.00 per mil for the ratio D/H, but further measurements are currently underway. O'Keef A., Deacon D.A.G., 1988. Cavity ring-down optical spectrometer for absorption measurements using pulsed laser sources, Rev. Sci. Instrum., 59, 2544.

  20. Isotopes in the Arctic atmospheric water cycle

    Science.gov (United States)

    Bonne, Jean-Louis; Werner, Martin; Meyer, Hanno; Kipfstuhl, Sepp; Rabe, Benjamin; Behrens, Melanie; Schönicke, Lutz; Steen Larsen, Hans Christian; Masson-Delmotte, Valérie

    2016-04-01

    The ISO-ARC project aims at documenting the Arctic atmospheric hydrological cycle, by assessing the imprint of the marine boundary conditions (e.g. temperature variations, circulation changes, or meltwater input) to the isotopic composition of the atmospheric water cycle (H218O and HDO) with a focus on North Atlantic and Arctic oceans. For this purpose, two continuous monitoring water vapour stable isotopes cavity ring-down spectrometers have been installed in July 2015: on-board the Polarstern research vessel and in the Siberian Lena delta Samoylov research station (N 72° 22', E 126° 29'). The Polarstern measurements cover the summer 2015 Arctic campaign from July to mid-October, including six weeks in the Fram Strait region in July- August, followed by a campaign reaching the North Pole and a transect from the Norwegian Sea to the North Sea. These vapour observations are completed by water isotopic measurements in samples from the surface ocean water for Polarstern and from precipitation in Samoylov and Tiksi (120 km south-east of the station). A custom-made designed automatic calibration system has been implemented in a comparable manner for both vapour instruments, based on the injection of different liquid water standards, which are completely vaporised in dry air at high temperature. Subsequent humidity level can be adjusted from 2000 to at least 30000 ppm. For a better resilience, an independent calibration system has been added on the Samoylov instrument, allowing measurements of one standard at humidity levels ranging from 2000 to 15000 ppm: dry air is introduced in a tank containing a large amount of liquid water standard, undergoing evaporation under a controlled environment. The measurement protocol includes an automatic calibration every 25 hours. First instrument characterisation experiments depict a significant isotope-humidity effect at low humidity, dependant on the isotopic composition of the standard. For ambient air, our first isotope

  1. D/H fractionation in the H2-H2O system at supercritical water conditions: Compositional and hydrogen bonding effects

    Science.gov (United States)

    Foustoukos, Dionysis I.; Mysen, Bjorn O.

    2012-06-01

    A series of experiments has been conducted in the H2-D2-D2O-H2O-Ti-TiO2 system at temperatures ranging from 300 to 800 °C and pressures between ∼0.3 and 1.3 GPa in a hydrothermal diamond anvil cell, utilizing Raman spectroscopy as a quantitative tool to explore the relative distribution of hydrogen and deuterium isotopologues of the H2 and H2O in supercritical fluids. In detail, H2O-D2O solutions (1:1) were reacted with Ti metal (3-9 h) in the diamond cell, leading to formation of H2, D2, HD, and HDO species through Ti oxidation and H-D isotope exchange reactions. Experimental results obtained in situ and at ambient conditions on quenched samples indicate significant differences from the theoretical estimates of the equilibrium thermodynamic properties of the H-D exchange reactions. In fact, the estimated enthalpy for the H2(aq)-D2(aq) disproportionation reaction (ΔHrxn) is about -3.4 kcal/mol, which differs greatly from the +0.16 kcal/mol predicted for the exchange reaction in the gas phase by statistical mechanics models. The exothermic behavior of the exchange reaction implies enhanced stability of H2 and D2 relative to HD. Accordingly, the significant energy difference of the internal H2(aq)-D2(aq)-HD(aq) equilibrium translates to strong differences of the fractionation effects between the H2O-H2 and D2O-D2 isotope exchange relationships. The D/H fractionation factors between H2O-H2(aq) and D2O-D2(aq) differ by 365‰ in the 600-800 °C temperature range, and are indicative of the greater effect of D2O contribution to the δD isotopic composition of supercritical fluids. The negative ΔHrxn values for the H2(aq)-D2(aq)-HD(aq) equilibrium and the apparent decrease of the equilibrium constant with increasing temperature might be because of differences of the Henry’s law constant between the H- and D-bearing species dissolved in supercritical aqueous solutions. Such effects may be attributed to the stronger hydrogen bonding in the O-H⋯O relative to the

  2. Performance of the Line-By-Line Radiative Transfer Model (LBLRTM for temperature, water vapor, and trace gas retrievals: recent updates evaluated with IASI case studies

    Directory of Open Access Journals (Sweden)

    M. J. Alvarado

    2013-07-01

    updated H2O spectroscopy. We also find that the use of a fixed ratio of HDO to H2O in LBLRTM may be responsible for a significant fraction of the remaining bias in the P-branch relative to the R-branch of the H2O ν2 band. There were no changes to O3 spectroscopy between the two model versions, and so both versions give positive a posteriori residuals of ~ 0.3 K in the R-branch of the O3 ν3 band. While the updates to the H2O self-continuum employed by LBLRTM v12.1 have clearly improved the match with observations near the CO2 ν3 band head, we find that these updates have significantly degraded the match with observations in the fundamental band of CO. Finally, significant systematic a posteriori residuals remain in the ν4 band of CH4, but the magnitude of the positive bias in the retrieved mixing ratios is reduced in LBLRTM v12.1, suggesting that the updated spectroscopy could improve retrievals of CH4 from satellite observations.

  3. The Atmospheric Chemistry Experiment (ACE): Mission Overview

    Science.gov (United States)

    Bernath, P. F.; Boone, C.; Walker, K.; McLeod, S.; Nassar, R.

    2003-12-01

    The ACE mission goals are: (1) to measure and to understand the chemical and dynamical processes that control the distribution of ozone in the upper troposphere and stratosphere, with a particular emphasis on the Arctic region; (2) to explore the relationship between atmospheric chemistry and climate change; (3) to study the effects of biomass burning in the free troposphere; (4) to measure aerosol number density, size distribution and composition in order to reduce the uncertainties in their effects on the global energy balance. ACE will make a comprehensive set of simultaneous measurements of trace gases, thin clouds, aerosols, and temperature by solar occultation from a satellite in low earth orbit. A high inclination (74 degrees) low earth orbit (650 km) gives ACE coverage of tropical, mid-latitudes and polar regions. The solar occultation advantages are high sensitivity and self-calibration. A high-resolution (0.02 cm-1) infrared Fourier Transform Spectrometer (FTS) operating from 2 to 13 microns (750-4100 cm-1) will measure the vertical distribution of trace gases, and the meteorological variables of temperature and pressure. The ACE concept is derived from the now-retired ATMOS FTS instrument, which flew on the Space Shuttle in 1985, 1992, 1993, 1994. Climate-chemistry coupling may lead to the formation of an Arctic ozone hole. ACE will provide high quality data to confront these model predictions and will monitor polar chemistry as chlorine levels decline. The ACE-FTS can measure water vapor and HDO in the tropical tropopause region to study dehydration and strat-trop exchange. The molecular signatures of massive forest fires will evident in the ACE infrared spectra. The CO2 in our spectra can be used to either retrieve atmospheric pressure or (if the instrument pointing knowledge proves to be satisfactory) for an independent retrieval of a CO2 profile for carbon cycle science. Aerosols and clouds will be monitored using the extinction of solar radiation at

  4. Lattice Boltzmann Simulation of Water Isotope Fractionation During Growth of Ice Crystals in Clouds

    Science.gov (United States)

    Lu, G.; Depaolo, D.; Kang, Q.; Zhang, D.

    2006-12-01

    The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically- symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over-saturation, determines crystal morphology, there are no existing quantitative models that directly relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be a direct relationship between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D Lattice-Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. The input parameters needed are the isotope-dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the sticking coefficient (or accommodation coefficient) for ice is uncertain. The ratio D/k is a length that determines the minimum scale of dendritic growth features and allows us to scale the numerical calculations to atmospheric conditions using a dimensionless Damkohler number

  5. Lattice Boltzmann Simulation of Kinetic Isotope Effect During Snow Crystal Formation

    Science.gov (United States)

    Lu, G.; Depaolo, D. J.; Kang, Q.; Zhang, D.

    2007-12-01

    The isotopic composition of precipitation, especially that of snow, plays a special role in the global hydrological cycle and in reconstruction of past climates using polar ice cores. The fractionation of the major water isotope species (HHO, HDO, HHO-18) during ice crystal formation is critical to understanding the global distribution of isotopes in precipitation. Ice crystal growth in clouds is traditionally treated with a spherically-symmetric steady state diffusion model, with semi-empirical modifications added to account for ventilation and for complex crystal morphology. Although it is known that crystal growth rate, which depends largely on the degree of vapor over- saturation, determines crystal morphology, there are no quantitative models that relate morphology to the vapor saturation factor. Since kinetic (vapor phase diffusion-controlled) isotopic fractionation also depends on growth rate, there should be direct relationships between vapor saturation, crystal morphology, and crystal isotopic composition. We use a 2D lattice Boltzmann model to simulate diffusion-controlled ice crystal growth from vapor- oversaturated air. In the model, crystals grow solely according to the diffusive fluxes just above the crystal surfaces, and hence crystal morphology arises from the initial and boundary conditions in the model and does not need to be specified a priori. Crystal growth patterns can be varied between random growth and deterministic growth (along the maximum concentration gradient for example). The input parameters needed are the isotope- dependent vapor deposition rate constant (k) and the water vapor diffusivity in air (D). The values of both k and D can be computed from kinetic theory, and there are also experimentally determined values of D. The deduced values of k are uncertain to the extent that the condensation coefficient for ice is uncertain. The ratio D/k is a length (order 1 micron) that determines the minimum scale of dendritic growth features

  6. The absorption spectrum of water vapor in the 2.2 μm transparency window: High sensitivity measurements and spectroscopic database

    International Nuclear Information System (INIS)

    Campargue, A.; Mikhailenko, S.N.; Vasilchenko, S.; Reynaud, C.; Béguier, S.; Čermák, P.; Mondelain, D.; Kassi, S.; Romanini, D.

    2017-01-01

    based on the HITRAN2012 list illustrate the advantages of the new list. The absence of many HDO lines is identified as most important deficiency of the HITRAN2012 list in the region. - Highlights: • High sensitivity CRDS and OF-CEAS of water vapor in the 2.2 µm transparency window. • About 400 lines measured and rovibrationallly assigned in five spectral intervals. • Comparison with previous FTS studies, HITRAN2012 and variational calculations. • A spectroscopic database is constructed for natural water between 4190 and 4550 cm"−"1. • It includes empirical positions, variational intensities and line profile parameters.

  7. The study of the martian atmosphere from top to bottom with SPICAM light on mars express

    Science.gov (United States)

    Bertaux, Jean-Loup; Fonteyn, D.; Korablev, O.; Chassefière, E.; Dimarellis, E.; Dubois, J. P.; Hauchecorne, A.; Cabane, M.; Rannou, P.; Levasseur-Regourd, A. C.; Cernogora, G.; Quemerais, E.; Hermans, C.; Kockarts, G.; Lippens, C.; de Maziere, M.; Moreau, D.; Muller, C.; Neefs, B.; Simon, P. C.; Forget, F.; Hourdin, F.; Talagrand, O.; Moroz, V. I.; Rodin, A.; Sandel, B.; Stern, A.

    2000-10-01

    into the long-term evolution of the atmosphere. The SPICAM Light IR sensor is inherited from the IR solar part of the SPICAM solar occultation instrument of Mars 96. Its main scientific objective is the global mapping of the vertical structure of H 2O, CO 2, CO, HDO, aerosols, atmospheric density, and temperature by the solar occultation. The wide spectral range of the IR spectrometer and its high spectral resolution allow an exploratory investigation addressing fundamental question of the possible presence of carbon compounds in the Martian atmosphere. Because of severe mass constraints this channel is still optional. An additional nadir near IR channel that employs a pioneering technology acousto-optical tuneable filter (AOTF) is dedicated to the measurement of water vapour column abundance in the IR simultaneously with ozone measured in the UV. It will be done at much lower telemetry budget compared to the other instrument of the mission, planetary fourier spectrometer (PFS).

  8. Hydrodesulfurization on Transition Metal Catalysts: Elementary Steps of C-S Bond Activation and Consequences of Bifunctional Synergies

    Science.gov (United States)

    Yik, Edwin Shyn-Lo

    surfaces. Our interpretations place HDS in a specific class of more general C-X hydrogenolysis reactions, including hydrodeoxygenation (HDO) that has gained popular appeal in recent biomass conversion processes. These hydrodearomatization routes, hydrogenolysis and hydrogenation, act as probes for studying hydrogen spillover, a frequently observed phenomenon in bifunctional systems. Indeed, we observe enhancements solely in the rates of thiophene hydrogenation when monofunctional catalysts, which generate equilibrated concentrations of surface H-species, are mixed with materials (e.g. Al 2O3) that cannot dissociate H2. Conventional mechanisms that suggest gas phase or surface diffusion of atomic H-species (or H +-e- pairs) are implausible across distances along insulating surfaces (i.e. SiO2, Al2O3). We propose, with kinetic-transport models that are consistent with all observed behaviors, that mobility of active H-species occurs through gas phase diffusion of thiophene-derived molecular H-carriers, whose formation rate on HDS sites can control maximum spillover enhancements. This synergy is disrupted when the ability of thiophene to form these H-carriers is suppressed, leading to an absence of spillover-mediated rates and further challenging any diffusive roles of atomic H-species. Such implications help guide optimal designs of bifunctional cascades to permit the uninhibited access and egress of larger molecules within both catalytic functions. (Abstract shortened by UMI.).

  9. Membrane Fractionation of Biomass Fast Pyrolysis Oil and Impact of its Presence on a Petroleum Gas Oil Hydrotreatment Fractionnement membranaire d’une huile de pyrolyse flash et impact de sa présence sur l’hydrotraitement d’un gazole atmosphérique

    Directory of Open Access Journals (Sweden)

    Pinheiro A.

    2013-09-01

    Full Text Available In order to limit the greenhouse effect causing climate change and reduce the needs of the transport sector for petroleum oils, transformation of lignocellulosic biomass is a promising alternative route to produce automotive fuels, chemical intermediates and energy. Gasification and liquefaction of biomass resources are the two main routes that are under investigation to convert biomass into biofuels. In the case of the liquefaction, due to the unstability of the liquefied products, one solution can be to perform a specific hydrotreatment of fast pyrolysis bio-oils with petroleum cuts in existing petroleum refinery system. With this objective, previous studies [Pinheiro et al. (2009 Energy Fuels 23, 1007-1014; Pinheiro et al. (2011 Energy Fuels 25, 804-812] have been carried out to investigate the impact of oxygenated model compounds on a Straight Run Gas Oil (SRGO hydrotreatment using a CoMo catalyst. The authors have demonstrated that the main inhibiting effects are induced from CO and CO2 produced during hydrodeoxygenation of esters and carboxylic acids. To go further, cotreatment of a fast pyrolysis oil with the same SRGO as used in the previous. studies was investigated in this present work. Firstly the bio-oil was separated into four fractions by membrane fractionation using 400 and 220 Da molecular weight cut-off membranes. The bio-oil and its fractions were analyzed by spectroscopic and chromatographic techniques. Then, one fraction (i.e. fraction enriched in compounds with molecular weight from 220 to 400 Da was mixed with the SRGO and co-treated. Despite some experimental difficulties mainly due to the emulsion instability, the hydrotreatment was successful. An inhibition has been observed on the hydro treating reactions of the SRGO in presence of the bio-oil fraction. The measurement of the CO/CO2/CH4 molar flowrate at the reactor outlet showed that the inhibition was due to the presence of CO and CO2 coming from HDO rather than to

  10. Vibrational spectra of Cs2Cu(SO4)2·6H2O and Cs2Cu(SeO4)2·nH2O (n = 4, 6) with a crystal structure determination of the Tutton salt Cs2Cu(SeO4)2·6H2O

    Science.gov (United States)

    Wildner, M.; Marinova, D.; Stoilova, D.

    2016-02-01

    frequencies of νOD of matrix-isolated HDO molecules (spectral range of 2500-2200 cm-1) is discussed. An interesting feature of the spectra is the appearance of two groups of infrared bands corresponding to νOD, which are separated with 71 cm-1 (sulfate compound) and about 120 cm-1 (selenate compounds) due to the existence of two types of water molecules - those coordinated to the copper ions via shorter Cu-OH2 bonds and those coordinated to the copper ions via longer Cu-OH2 bonds. The spectroscopic experiments reveal that the equatorial water molecules in the hexahydrates exhibit a local molecular symmetry close to C2v (at least at ambient temperature), while those forming long Cu-OH2 bonds are strongly asymmetrically hydrogen bonded. The differences in the wavenumbers of the bands corresponding to the wagging modes have values larger than 100 cm-1, thus indicating strong distortions of the coordination sphere of the copper ions due to the Jahn-Teller effect.

  11. Obituary: William Merz Sinton, 1925-2004

    Science.gov (United States)

    Spencer, John Robert

    2004-12-01

    Bill Sinton, one of the pioneers of infrared planetary astronomy, died at his home in Flagstaff, Arizona, on March 16th 2004, at the age of 78. Bill was born in Baltimore on April 11, 1925. He developed lifelong interests in railroads and radios while still a child, and by age 15 he had already built a shortwave radio receiver and won his ham radio license. His abiding interest in electronic and mechanical devices would serve him well in his professional career. He fought with the 26th Infantry Division in the Second World War and was wounded in France in October 1944. After the war he obtained his bachelor's degree in physics at Johns Hopkins (1949). His doctoral work at the same institution, with John Strong, gave him his first taste of infrared astronomy, including the first measurements of the moon at 1-millimeter wavelength. He obtained his PhD, on the infrared spectrum and temperature of Venus, in 1953. During a 1-year postdoc at Johns Hopkins he probed the lunar subsurface by observing the cooling of the moon during eclipse at millimeter wavelengths, and observed the diurnal variation in Martian surface temperatures in the 10-micron window. He joined Harvard College Observatory as a research associate and lecturer in 1954, and became interested in the question of life on Mars and the then-plausible possibility that Mars's dark markings were due to vegetation. In 1956, using a monochromator that he built himself, he detected absorptions near 3.4 microns in the Martian spectrum which he attributed to a C-H stretch transition in Martian vegetation. These "Sinton bands," as they came to be known, sparked great interest at the time, and though at least some of the spectral structure was later found to be due to terrestrial HDO, and the presence of abundant organic molecules on the Martian surface was finally ruled out by the Viking landers, some of the spectral features that he detected appear to be intrinsic to Mars and are still not well understood. In 1957

  12. Techno-Economic Analysis of Camelina-Derived Hydroprocessed Renewable Jet Fuel and its Implications on the Aviation Industry

    Science.gov (United States)

    Shila, Jacob Joshua Howard

    Although the aviation industry contributes toward global economic growth via transportation of passengers and cargo, the increasing demand for air transportation causes concern due to the corresponding increase in aircraft engine exhaust emissions. Use of alternative fuels is one pathway that has been explored for reducing emissions in the aviation industry. Hydroprocessed renewable jet (HRJ) (also known as Hydroprocessed Esters and Fatty Acids - HEFA) fuels have been approved for blending with traditional jet fuel up to 50% by volume to be used as drop-in fuels. However, limited information exists on the economic viability of these fuels. While techno-economic studies have been conducted on the HRJ production process using soybean oil, different vegetable oils possess different hydrocarbon structures that affect the yield of HRJ fuels. This study involves the techno-economic analysis of producing Camelina-derived HRJ fuel using the option of hydro-deoxygenation (HDO). The hydrodeoxygenation option requires extra hydrogen and hence affects the overall cost of HRJ fuel production. Similar studies have been conducted on the production of Camelina-derived HRJ fuels using the same path of hydrodeoxygenation with minor contributions from both decarbonylation and decarboxylation reactions. This study, however, employs the UOP Honeywell procedure using the hydrodeoxygenation chemical reaction to estimate the breakeven price of Camelina-derived HRJ fuel. In addition, the study treats the cultivation of Camelina oilseeds, extraction of oilseeds, and the conversion of HRJ fuel as separate entities. The production of Camelina oilseed, Camelina oil, and finally Camelina-derived HRJ fuel is modeled in order to estimate the breakeven price of the fuel. In addition, the information obtained from the techno-economic analysis is used to assess the breakeven carbon price. All costs are analyzed based on 2016 US dollars. The breakeven price of Camelina oilseeds is found to be 228