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Results for “oxidative coupling of methane”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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27 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1993

Prediction of prompt NO(x) in hydrocarbon air flames

The gas turbine industry is directing particular attention to very low NOx combustors, whether for aircraft or land based CCGT systems. These low NOx combustors frequently use liquid fuels or natural gas burning under very lean premixed conditions with air or under rich-lean conditions, although only the first case is studied here. In land based systems, diluted steam or nitrogen are sometimes injected into the combustion chambers to reduce flame temperature. The NOx emissions from such systems are the product of three chemical mechanisms which are interrelated: the hydrocarbon prompt NO, the thermal NO (extended Zeldovich mechanism), and the nitrous oxide route to NO. Formation of NO2 from NO also occurs, as well as emission of carbon monoxide and unburnt hydrocarbons. When the fuel-oxidant proportion decreases towards leaner conditions, flame temperatures are lowered, resulting in the total NO being reduced and the thermal-NO contribution greatly diminished to the benefit of the remaining two mechanisms of NO formation. While knowledge of the elementary reactions and their chemical kinetics concerning methane and simple hydrocarbons combustion has existed for a number of years, its use for computer modeling is limited to simple flow dynamics configurations. Nevertheless, understanding of such combusting flows under a wide range of experimental conditions allows for analogies or speculations with more complex actual systems. Such understanding can be achieved by means of one dimensional laminar premixed flame modeling, with a full chemical mechanism which incorporates the three routes of NO formation. Complementary to this understanding is the modeling of the actual combustion system using a full description of the fluid dynamics coupled with a reduced chemical scheme, which is then compared against the first model. The objective of this investigation is to evaluate the relative importance of the three mechanisms of NO formation in lean premixed methane-air combustion with increasing pressure using the one dimensional plug flow package PREMIX, and to test the validity of a three dimensional model with a global chemical mechanism against the one dimensional model in the atmospheric pressure case. Methane is chosen because it is the only mechanism which is reasonably well known and is a good guide to the behavior of other hydrocarbons. The mixture ratio chosen is richer than that in lean gas turbines, but the combustion of this mixture with the low preheat gives realistic gas turbine final flame temperatures. Conditions of NO2 formation are also analyzed in the one dimensional model and results extrapolated to the case of gas turbines.

Valerie Dupont↗
NASA NTRS2015

Investigation of Benthic Foraminiferal Non-Traditional Stable Isotopes to Reconstruct Methane Fluxes in Sedimentary Environments

Methane (CH4) is an important greenhouse gas, with a global warming potential much higher than carbon dioxide (CO2) on a short time scale. Even if the residence time of CH4 in the atmosphere is relatively short (tens of years), one of the products of CH4 oxidation is CO2, a greenhouse gas with a much longer residence time in the atmosphere (tens to hundreds of years). CH4 has been proposed as one of the trigger mechanisms for rapid global climate change today and in the geological past. With regards to the geological past, numerous studies proposed the benthic foraminiferal carbon isotope ratio (Delta13C) as a tool to reconstruct the impact of marine CH4 on rapid climate changes; however, the investigation of modern benthic foraminiferal Delta13C have produced inconclusive results. CH4 has a distinctive hydrogen isotope (Delta(D)) and Delta13C signature compared to seawater, and sulfate reduction, often coupled to CH4 anaerobic oxidation in sediments, changes the sulfur isotope signature (Delta34S) of the remaining sulfate in porewater. Therefore, we hypothesize that the Delta(D) and Delta34S signature of infaunal benthic foraminiferal species can provide a complementary approach to Delta13C to study CH4 dynamics in sedimentary environments. Here, we present the preliminary results obtained analyzing Uvigerina peregrina Delta(D) and Delta34S from three different locations at Hydrate Ridge, offshore Oregon. Unfortunately, the lack of chemical data related to the moment of foraminiferal calcification makes difficult to build a robust relationship among the U. peregrina stable isotopes and the CH4 fluxes at the sampling sites. However, our results look very promising, as each site is characterized by a different Delta(D) and Delta34S signature. We emphasize that this study represents the first step in the development of new proxies (Delta(D)) and Delta34S), which may complement the more traditional benthic foraminiferal Delta13C values, to reconstruct marine CH4 fluxes in the geological past.

Borrelli, C.↗
NASA NTRS1991

Biospheric-atmospheric coupling on the early Earth

Theoretical calculations performed with a one-dimensional photochemical model have been performed to assess the biospheric-atmospheric transfer of gases. Ozone reached levels to shield the Earth from biologically lethal solar ultraviolet radiation (220-300 nm) when atmospheric oxygen reached about 1/10 of its present atmospheric level. In the present atmosphere, about 90 percent of atmospheric nitrous oxide is destroyed via solar photolysis in the stratosphere with about 10 percent destroyed via reaction with excited oxygen atoms. The reaction between nitrous oxide and excited oxygen atoms leads to the production of nitric oxide in the stratosphere, which is responsible for about 70 percent of the global destruction of oxygen in the stratosphere. In the oxygen/ozone deficient atmosphere, solar photolysis destroyed about 100 percent of the atmospheric nitrous oxide, relegating the production of nitric oxide via reaction with excited oxygen to zero. Our laboratory and field measurements indicate that atmospheric oxygen promotes the biogenic production of N2O and NO via denitrification and the biogenic production of methane by methanogenesis.

Levine, J. S.↗
NASA NTRS2001

Chemistry-Climate Interactions in the GISS GCM: Tropospheric Chemistry Model Description and Evaluation - Part 1

A tropospheric chemistry module has been developed for use within the Goddard Institute for Space Studies (GISS) general circulation model (GCM) to study interactions between chemistry and climate change. The model uses a simplified chemistry scheme based on CO-NOx-CH4 chemistry, and also includes a parameterization for emissions of isoprene, the most important non-methane hydrocarbon. The model reproduces present day annual cycles and mean distributions of key trace gases fairly well, based on extensive comparisons with available observations. Examining the simulated change between present day and pre-industrial conditions, we find that the model has a similar response to that seen in other simulations. It shows a 45% increase in the global tropospheric ozone burden, within the 25% - 57% range seen in other studies. Annual average zonal mean ozone increases by more than 125% at Northern Hemisphere middle latitudes near the surface. Comparison of model runs that allow the calculated ozone to interact with the GCM's radiation and meteorology with those that do not shows only minor differences for ozone. The common usage of ozone fields that are not calculated interactively seems to be adequate to simulate both the present day and the pre-industrial ozone distributions. However, use of coupled chemistry does alter the change in tropospheric oxidation capacity, enlarging the overall decrease in OH concentrations from the pre-industrial to the present by about 10% (-5.3% global annual average in uncoupled mode, -5.9% in coupled mode). This indicates that there may be systematic biases in the simulation of the pre-industrial to present day decrease in the oxidation capacity of the troposphere (though a 10% difference is well within the total uncertainty). Global annual average radiative forcing from pre-industrial to present day ozone change is 0.32 W/sq m. The forcing seems to be increased by about 10% when the chemistry is coupled to the GCM. Forcing values greater than 0.8 W/sq m are seen over large areas of the United States, Southern Europe, North Africa, the Middle East, Central Asia, and the Arctic. Radiative forcing is greater than 1.5 W/sq m over parts of these areas during Northern summer Though there are local differences, the radiative forcing is overall in good agreement with the results of other modeling studies in both its magnitude and spatial distribution, demonstrating that the simplified chemistry is adequate for climate studies.

Shindell, Drew T.↗
NASA NTRS1996

Chemical Characteristics of Continental Outflow Over the Tropical South Atlantic Ocean from Brazil and Africa

The chemical characteristics of air parcels over the tropical South Atlantic during September - October 1992 are summarized by analysis of aged marine and continental outflow classifications. Positive correlations between CO and CH3CL and minimal enhancements of C2CL40, and various ChloroFluoroCarbon (CFC) species in air parcels recently advected over the South Atlantic basin strongly suggest an impact on tropospheric chemistry from biomass burning on adjacent continental areas of Brazil and Africa. Comparison of the composition of aged Pacific air with aged marine air over the South Atlantic basin from 0.3 to 12.5 km altitude indicates potential accumulation of long-lived species during the local dry season. This may amount to enhancements of up to two-fold for C2H6, 30% for CO, and 10% for CH3Cl. Nitric oxide and NO(x) were significantly enhanced (up to approx. 1 part per billion by volume (ppbv)) above 10 km altitude and poorly correlated with CO and CH3Cl. In addition, median mixing ratios of NO and NO(x) were essentially identical in aged marine and continental outflow air masses. It appears that in addition to biomass burning, lightning or recycled reactive nitrogen may be an important source of NO(x) to the upper troposphere. Methane exhibited a monotonic increase with altitude from approx. 1690 to 1720 ppbv in both aged marine and continental outflow air masses. The largest mixing ratios in the upper troposphere were often anticorrelated with CO, CH3Cl, and CO2, suggesting CH, contributions from natural sources. We also argue, based on CH4/CO ratios and relationships with various hydrocarbon and CFC species, that inputs from biomass burning and the northern hemisphere are unlikely to be the dominant sources of CO, CH4 and C2H6 in aged marine air. Emissions from urban areas would seem to be necessary to account for the distribution of at least CH4 and C2H6. Over the African and South American continents an efficient mechanism of convective vertical transport coupled with large-scale circulations conveys biomass burning, urban, and natural emissions to the upper troposphere over the South Atlantic basin. Slow subsidence over the eastern South Atlantic basin may play an important role in establishing and maintaining the rather uniform vertical distribution of long-lived species over this region. The common occurrence of values greater than 1 for the ratio CH3OOH/H2O2 in the upper troposphere suggests that precipitation scavenging effectively removed highly water soluble gases (H2O2, HNO3, HCOOH, and CH3COOH) and aerosols during vertical convective transport over the continents. However, horizontal injection of biomass burning products over the South Atlantic, particularly water soluble species and aerosol particles, was frequent below 6 km altitude.

Talbot, R. W.↗
NASA NTRS2015

Microlith-Based Catalytic Reactor for Air Quality and Trace Contaminant Control Applications

Traditionally, gaseous compounds such as methane, carbon monoxide, and trace contaminants have posed challenges for maintaining clean air in enclosed spaces such as crewed spacecraft cabins as they are hazardous to humans and are often difficult to remove by conventional adsorption technology. Catalytic oxidizers have provided a reliable and robust means of disposing of even trace levels of these compounds by converting them into carbon dioxide and water. Precision Combustion, Inc. (PCI) and NASA - Marshall (MSFC) have been developing, characterizing, and optimizing high temperature catalytic oxidizers (HTCO) based on PCI's patented Microlith® technology to meet the requirements of future extended human spaceflight explorations. Current efforts have focused on integrating the HTCO unit with a compact, simple recuperative heat exchanger to reduce the overall system size and weight while also reducing its energy requirements. Previous efforts relied on external heat exchangers to recover the waste heat and recycle it to the oxidizer to minimize the system's power requirements; however, these units contribute weight and volume burdens to the overall system. They also result in excess heat loss due to the separation of the HTCO and the heat recuperator, resulting in lower overall efficiency. Improvements in the recuperative efficiency and close coupling of HTCO and heat recuperator lead to reductions in system energy requirements and startup time. Results from testing HTCO units integrated with heat recuperators at a variety of scales for cabin air quality control and heat melt compactor applications are reported and their benefits over previous iterations of the HTCO and heat recuperator assembly are quantified in this paper.

Vilekar, Saurabh↗
NASA NTRS2010

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Socki, Richard A.↗
NASA NTRS1999

Portable fiber-coupled diode-laser-based sensor for multiple trace gas detection

Tunable narrowband mid-infrared radiation from 3.25 to 4.4 micrometers is generated by a compact fiber-coupled, difference-frequency-based spectroscopic source. A 20-mW external cavity diode laser (with a tuning range from 814 to 870 nm) and a 50-mW distributed-Bragg-reflector diode-laser-seeded ytterbium-doped fiber amplifier operating at 1083 nm are difference-frequency mixed in a multi-grating, temperature-controlled periodically poled LiNbO3 crystal. A conversion efficiency of 0.44 mW/(W2cm) (corresponding to a power of approximately equal to 3 microW at 3.3 micrometers) represents the highest conversion efficiency reported for a portable device. Performance characteristics of such a sensor and its application to spectroscopic detection of CO2, N2O, H2CO, HCl, NO2, and CH4 will be reported in this work.

Non-NASA Center↗
NASA NTRS2005

Modeling of Isotope Fractionation in Stratospheric CO2, N2O, CH4, and O3: Investigations of Stratospheric Chemistry and Transport, Stratosphere-Troposphere Exchange, and Their Influence on Global Isotope Budgets

Until recently, the stable isotopic composition of chemically and datively important stratospheric species, such as ozone (O3), carbon dioxide (CO2), nitrous oxide (N2O), and methane (CH4), was largely unexplored, despite indications from the few measurements available and theoretical studies that global-scale isotopic variations will provide a unique tool for quantifying rates of global-scale mass transport into, within, and out of the stratosphere and for understanding the mechanisms of chemical reactions involved in ozone production. The number and geographical extent of observations are beginning to increase rapidly, however, as access to the stratosphere, both directly and by remote-sensing, has increased over the last 10 years and as new analytical techniques have been developed that make global-scale isotope measurements by whole-air sampling more feasible. The objective of this study, begun in April 1999, is to incorporate into the Livermore 2D model the likely photochemical fractionation processes that determine the isotopic compositions of stratospheric CO2, N2O, CH4, and O3, and to use the model results and new observations from NASA field campaigns in 1996 and 1997 to investigate stratospheric chemistry and mass transport. Additionally, since isotopic signatures from the stratosphere are transferred to the troposphere by downward transport at middle and high latitudes, the isotopic compositions may also serve as sensitive tracers of stratosphere-totroposphere transport. Comparisons of model results with stratospheric and upper tropospheric observations from these campaigns, as well as with ground-based observations from new NOAA and NSF-sponsored studies, will help determine whether the magnitudes of the stratospheric fractionation processes are large enough to use as global-scale tracers of transport into the troposphere and, if so, will be used to help constrain the degree of coupling between the troposphere and the stratosphere.

Boering, Kristie A.↗