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At least 19 records

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Ru/Al2O3 Catlayst

Mars Atmospheric Conversion to Methane and Water: An Engineering Model of the Sabatier Reactor with Characterization of Ru/Al2O3 for Long Duration Use on Mars

The Atmospheric Processing Module (APM) is a Mars In-Situ Resource Utilization (ISRU) technology designed to demonstrate conversion of the Martian atmosphere into methane and water. The Martian atmosphere consists of approximately 95 carbon dioxide (CO2) and residual argon and nitrogen. APM utilizes cryocoolers for CO2 acquisition from a simulated Martian atmosphere and pressure. The captured CO2 is sublimated and pressurized as a feedstock into the Sabatier reactor, which converts CO2 and hydrogen to methane and water. The Sabatier reaction occurs over a packed bed reactor filled with Ru/Al2O3 pellets. The long duration use of the APM system and catalyst was investigated for future scaling and failure limits. Failure of the catalyst was detected by gas chromatography and temperature sensors on the system. Following this, characterization and experimentation with the catalyst was carried out with analysis including x-ray photoelectron spectroscopy and scanning electron microscopy with elemental dispersive spectroscopy. This paper will discuss results of the catalyst performance, the overall APM Sabatier approach, as well as intrinsic catalyst considerations of the Sabatier reactor performance incorporated into a chemical model.

Catlayst

Integrated Simulations of the Sabatier and Carbon Vapor Deposition Reactor to Understand Its Impacts to Operations and Performance

The carbon vapor deposition (CVD) reactor is a technology developed by Honeywell Aerospace to convert methane, at high temperatures, into hydrogen and solid carbon. This element is coupled with a Sabatier reactor to support a closed-loop environmental control and life support system with the aim of achieving nearly complete oxygen recovery (> 95%). Initial open-loop, brassboard CVD reactor tests and simulations have shown the CVD’s ability to achieve moderately high methane conversion and high hydrogen selectivity. However, in an integrated system, additional deficiencies are expected due to recycling of unreacted or extraneous species from the Sabatier reactor (e.g., carbon dioxide, hydrogen, water) and CVD reactor (e.g., hydrocarbons, methane, etc.). Sabatier and CVD reactor models were integrated and simulated to predict potential impacts to individual reactors’ and the overall system’s performance. The simulations showed that increasing the recycle of the CVD effluent hydrogen combined with decreasing the system inlet hydrogen flow rate (i.e., drawing a stoichiometric flow rate from an electrolyzer) can lead to an oxygen recovery of > 95%. However, system integration comes at a detriment to the individual reactors. The simulations show the initial conversion from the integrated system (Sabatier = 87% and CVD = 59%) to be lower than the standalone systems (Sabatier = 91% and CVD = 69%). Furthermore, transient simulations show substrate densification, leading to worsening methane conversion coupled with increasing acetylene production, which is commensurate with soot formation. Simulations predict a shortening of the maintenance interval (i.e., time until CVD methane conversion drops below 50%) in the integrated system, which would increase the consumable substrate mass. These analyses highlight the importance of long-duration, integrated tests to corroborate these findings as well as suggest potential modifications (e.g., intermediate gas separations) to improve performance.

Air Revitalization

Carbon kinetic isotope effect in the reaction of CH4 with HO

The carbon kinetic isotope effect in the CH4 + HO reaction is measured experimentally and the use of carbon isotope ratios to diagnose atmospheric methane is examined. The chemical, photolysis, and analytical experimental conditions and procedures are described. It is determined that the CH4 + HO reaction has a carbon kinetic isotope effect of 1.010 + or 0.007 for k(12)k(13) (rate constants ratio) at 297 + or - 3 K. This value is compared with the data of Rust and Stevens (1980). Causes for the poor correlation between the data at high methane conversions are discussed. It is supposed that the difference between the k(12) and k(13) values is due to a difference in the activation energy of the two reactions.

Davidson, J. A.

Development of a carbon formation reactor for carbon dioxide reduction

Applied research, engineering development, and performance evaluation were conducted on a process for formation of dense carbon by pyrolysis of methane. Experimental research showed that dense (0.7 to 1.6 g/cc bulk density and 1.6 to 2.2 g/cc solid density) carbon can be produced by methane pyrolysis in quartzwool-packed quartz tubes at temperatrues of 1100 to 1300 C. This result supports the condensation theory of pyrolytic carbon formation from gaseous hydrocarbons. A full-scale Breadboard Carbon Formation Reactor (CFR) was designed, fabricated, and tested at 1100 to 1200 C with 380 to 2280 sccm input flows of methane. Single-pass conversion of methane to carbon ranged from 60 to 100 percent, with 89 percent average conversion. Performance was projected for an Advanced Carbon Reactor Subsystem (ACRS) which indicated that the ACRS is a viable option for management of metabolic carbon on long-duration space missions.

Noyes, G.

Porous Silica Sol-Gel Glasses Containing Reactive V2O5 Groups

Porous silica sol-gel glasses into which reactive vanadium oxide functional groups incorporated exhibit number of unique characteristics. Because they bind molecules of some species both reversibly and selectively, useful as chemical sensors or indicators or as scrubbers to remove toxic or hazardous contaminants. Materials also oxidize methane gas photochemically: suggests they're useful as catalysts for conversion of methane to alcohol and for oxidation of hydrocarbons in general. By incorporating various amounts of other metals into silica sol-gel glasses, possible to synthesize new materials with broad range of new characteristics.

Stiegman, Albert E.

Photodissociation of cyanoacetylene: Application to the atmospheric chemistry of Titan

The quantum yield and reaction threshold for the photochemical dissociation of cyanoacetylene into a hydrogen atom and the cyanoethynyl radical have been determined. The quantum yield at 185 nm is approximately 0.09. The threshold is approximately 240 nm. Combination of this data with literature values shows that production of excited-state cyanoacetylene is the major primary process resulting from irradiation between 185 and 254 nm. Also determined are the relative rate constants for the abstraction of a hydrogen atom from hydrogen, methane, and ethane by the cyanoethynyl radical (k(H2):k(CH4):k(C2H6) = 1:9.3:63). Implications of these results for the proposal that hydrogen abstraction plays an important role in the conversion of methane to ethane and in the protection of unsaturated compounds from photoconsumption in the atmosphere of Titan are discussed.

Clarke, David W.

Integrated Oxygen-Recovery System

System for revitalizing breathing air in enclosed environment converts carbon dioxide and water to oxygen and methane. Chemical conversions take place in reactor module containing solid-metal-cathode water electrolyzer integrated with Sabatier reactor. According to design estimates, fully developed version of system sized to maintain breathable air for four persons, occupies 67 percent less volume, weighs 60 percent less, and consumes 3.4 percent less power than system of same capacity in which electrolyzer and Sabatier reactor are distinct components. Although oxygen primary desired end product in system originally contemplated, product methane also of value in industrial version of system.

Schubert, F. H.

Photochemistry of the atmosphere of Uranus

A detailed one-dimensional photochemical model incorporating vertical transport by eddy and molecular diffusion is used to study the importance of chemical and physical processes that control the hydrocarbon abundances in the stratosphere of Uranus. The study includes updated photochemical reaction rates and photolysis branching ratios; explicit calculation of the condensation rate of condensing species; and appropriate boundary conditions at the tropopause. It is found that the basic photochemical process generally produces low net conversion efficiencies of methane to higher hydrocarbons. However, even with these low efficiencies, the total condensation rate, which represents the net rate of conversion of methane to hydrocarbons, is roughly 2 x 10 to the -16th g/cm sec, in agreement with the upper range of the low condensation rate for the production of the stratospheric aerosol layer as determined by Pollack et al. (1987). Furthermore, a range of vertical transport rates is required to separately match the observational constraints on hydrocarbon abundances. The solar reflection data refer to the sunlit polar region of Uranus and require an eddy diffusion coefficient of K approx. = 50 sq cm/sec for globally averaged insolation or K approx = 1500 (Nh/N) exp 1/2 for overhead sun. The Voyager 2 Utraviolet Spectrometer solar occultation data refer to the equatorial regions, thus implying a large latitudinal gradient in stratospheric hydrocarbon abundance.

Summers, Michael E.

Bio-conversion of water hyacinths into methane gas, part 1

Bio-gas and methane production from the microbial anaerobic decomposition of water hyacinths (Eichhornia crassipes) (Mart) Solms was investigated. These experiments demonstrated the ability of water hyacinths to produce an average of 13.9 ml of methane gas per gram of wet plant weight. This study revealed that sample preparation had no significant effect on bio-gas and/or methane production. Pollution of water hyacinths by two toxic heavy materials, nickel and cadmium, increased the rate of methane production from 51.8 ml/day for non-contaminated plants incubated at 36 C to 81.0 ml/day for Ni-Cd contaminated plants incubated at the same temperature. The methane content of bio-gas evolved from the anaerobic decomposition of Ni-Cd contaminated plants was 91.1 percent as compared to 69.2 percent methane content of bio-gas collected from the fermentation of non-contaminated plants.

Wolverton, B. C.

Photosynthesis of organic compounds in the atmosphere of Jupiter

An efficient conversion of CH4 to hydrocarbons and HCN takes place when NH3 is photolysed in the presence of CH4, H2, and He using a 184.9 nm light source. The extent of NH3 decomposition after a 1 hr exposure was determined spectrophotometrically; CH4, N2, and C2 and C3 hydrocarbons were detected and analyzed by mass spectrometry. Photolysis of one molar equivalent of NH3 results in the loss of 0.84 molar equivalent of CH4, which apparently reacts with hot hydrogen atoms produced by photolysis. The 8% of the NH3 which is not converted to N2 probably is converted to organic amines and nitrile derivatives. The results indicate that NH3 photolysis is a highly probable mechanism for the conversion of methane to more complex hydrocarbons in the upper atmosphere of Jupiter, and predict the occurrence of HCN, NH2NH2, and higher hydrocarbons in the Jovian atmosphere above the NH3 clouds.

Ferris, J. P.

Volatiles on satellites of the outer solar system

Molecules of cosmochemically abundant elements can act as volatiles and hence play a dominant role in the climatic and surficial evolution of solid bodies. Examples on terrestrial planets are H2O on Earth and H2O and CO2 on Mars. Analogous processes in the outer solar system focussing on CH4, its associated hydrocarbons, and N2 on Titan and Triton, the large moons of Saturn and Neptune were explored. A kilometer-deep C2H6-CH4 ocean was proposed for the surface of Titan to reconcile data on the lower atmosphere with understanding of the photochemical conversion of methane to heavier hydrocarbons. If such ocean exists, then it has dissolved in it an amount of N2 equal to the present atmospheric abundance. Since N2 contributes with CH4 a substantial greenhouse effect, the atmospheric physical and chemical characteristics are strongly coupled to those of the ocean, which change with time as methane is photolyzed in the stratosphere. Some relationship exists to the runaway greenhouse model for primordial Venus and the possible climatic implications of the buffering of Earth's atmospheric CO2 by the oceans. Two important diagnostics, measurable in Titan's atmosphere, of the conditions under which icy satellites formed are the abundances of noble gases and the CHd/CH4 radio. Both of these indicators have been altered during the evolution of Titan's surface-atmosphere system, the former by interaction with the ocean and the latter by progressive photolysis of methane into heavier hydrocarbons. The physical state and composition of volatiles on the surface of Triton is controversial, but plausibly could include CH4 N2 and perhaps CO. If condensed CH4 and N2 are widespread, their transformation to and from the vapor phase dominates the surface energy balance with sunlight. The extreme seasonal modulation of subsolar latitude on Triton is thus primarily expressed by volatile transport rather than large teperature changes, with possibly drastic observational consequences. The presence of two volatile species differing greatly in their vapor pressures make Triton a crude analog of Mars. Triton might be more appropriately regarded as a deep-freeze version of Titan.

Lunine, J. I.

Particulate filtration from emissions of a plasma pyrolysis assembly reactor using regenerable porous metal filters

Microwave-based plasma pyrolysis technology is being studied as a means of supporting oxygen recovery in future spacecraft life support systems. The process involves the conversion of methane produced from a Sabatier reactor to acetylene and hydrogen, with a small amount of solid carbon particulates generated as a side product. The particles must be filtered before the acetylene is removed and the hydrogen-rich gas stream is recycled back to the CRA. We discuss developmental work on porous metal media filters for removing the carbon particulate emissions from the PPA exit gas stream and to provide in situ media regeneration capability. Because of the high temperatures involved in oxidizing the deposited carbon during regeneration, there was particular focus in this development on the materials that could be used, the housing design, and heating methods. This paper describes the design and operation of the filter and characterizes their performance from integrated testing at the Environmental Chamber (E-Chamber) at MSFC.

particulates

Particulate Filtration from Emissions of a Plasma Pyrolysis Assembly Reactor Using Regenerable Porous Metal Filters

Microwave-based plasma pyrolysis technology is being studied as a means of supporting oxygen recovery in future spacecraft life support systems. The process involves the conversion of methane produced from a Sabatier reactor to acetylene and hydrogen, with a small amount of solid carbon particulates generated as a side product. The particles must be filtered before the acetylene is removed and the hydrogen-rich gas stream is recycled back to the CRA. We discuss developmental work on porous metal media filters for removing the carbon particulate emissions from the PPA exit gas stream and to provide in situ media regeneration capability. Because of the high temperatures involved in oxidizing the deposited carbon during regeneration, there was particular focus in this development on the materials that could be used, the housing design, and heating methods. This paper describes the design and operation of the filter and characterizes their performance from integrated testing at the Environmental Chamber (E-Chamber) at MSFC.

Agui, Juan H.

Recover Gas from Liquids in Low Gravity

This document is the final report resulting from the work conducted by undergraduate students at the University of South Alabama during the 2019/2020 academic year. Currently, on the International Space Station a solid adsorbent material is used to remove CO 2 from cabin air; however, liquid absorbent/reactive based systems are appealing because they may offer greater CO 2 capture efficiency. When liquids are used to capture CO 2 a regeneration step is required to release the CO 2 from the fluid for subsequent processing. During regeneration aerosolized droplets of water and liquid amines are produced creating a 2-phase fluid stream. Because the CO 2 stream is to be sent to a Sabatier reactor for conversion into methane, the droplets of the water and amines must be removed, necessitating the need for a vapor/liquid separation process in a microgravity environment. This class was tasked with designing a system to separate the aerosolized droplets from the gas stream. An ionic liquid was assumed to be the amine based absorber fluid that was used to capture the CO 2 , which is a key assumption because the ionic liquid has vanishingly low vapor pressure. The lack of volatility of the ionic liquid eliminates the need to manage an aerosolized amine resulting in only an aerosolized water air separation. To solve this challenge an undergraduate class used systems engineering to design and construct a hydrophobic screen separation apparatus for a 2-phase, vapor/liquid flow. The apparatus was constructed, but initial testing was not possible due to the closure of the University labs due to the corona-virus pandemic.

T Grant Glover

Determination of the isotopic composition of atmospheric methane and its application in the Antarctic

A procedure for establishing the C-13/C-12 ratio and the C-14 abundance in the atmospheric methane is discussed. The method involves air sample collection, measurement of the methane mixing ratio by gas chromotography followed by quantitative conversion of the methane in the air samples to CO2 and H2O, and analysis of the resulting CO2 for the C-13/C-12 ratio by stable isotope ratio mass spectrometry and measurement of C-14 content by accelerator mass spectrometry. The carbon isotropic composition of methane in air collected at Baring Head, New Zealand, and in air collected on aircraft flights between New Zealand and Antarctica is determined by the method, and no gradient in the composition between Baring Head and the South Pole station is found. As the technique is refined, and more data is gathered, small seasonal and long-term variations in C-13 are expected to be resolved.

Lowe, David C.

Methane-Powered Vehicles

Liquid methane is beginning to become an energy alternative to expensive oil as a power source for automotive vehicles. Methane is the principal component of natural gas, costs less than half as much as gasoline, and its emissions are a lot cleaner than from gasoline or diesel engines. Beech Aircraft Corporation's Boulder Division has designed and is producing a system for converting cars and trucks to liquid methane operation. Liquid methane (LM) is a cryogenic fuel which must be stored at a temperature of 260 degrees below zero Fahrenheit. The LM system includes an 18 gallon fuel tank in the trunk and simple "under the hood" carburetor conversion equipment. Optional twin-fuel system allows operator to use either LM or gasoline fuel. Boulder Division has started deliveries for 25 vehicle conversions and is furnishing a liquid methane refueling station. Beech is providing instruction for Northwest Natural Gas, for conversion of methane to liquid state.

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