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At least 361 records · Page 20

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↗

Thin film fuel cell electrodes.

Earlier work shows that fuel cell electrodes prepared by sputtering thin films of platinum on porous vycor substrates avoid diffusion limitations even at high current densities. The presented study shows that the specific activity of sputtered platinum is not unusually high. Performance limitations are found to be controlled by physical processes, even at low loadings. Catalyst activity is strongly influenced by platinum sputtering parameters, which seemingly change the surface area of the catalyst layer. The use of porous nickel as a substrate shows that pore size of the substrate is an important parameter. It is noted that electrode performance increases with increasing loading for catalyst layers up to two microns thick, thus showing the physical properties of the sputtered layer to be different from platinum foil. Electrode performance is also sensitive to changing differential pressure across the electrode. The application of sputtered catalyst layers to fuel cell matrices for the purpose of obtaining thin total cells appears feasible.

Asher, W. J.↗

The effects of aniline impurities on monopropellant hydrazine thruster performance

Both a 0.45-N and a 0.9-N thruster representative of the designs being flown on 3-axis stabilized spacecraft were used in testing various grades of hydrazine for the phenomenon of monopropellant hydrazine thruster catalyst bed poisoning. Both designs employed Shell 405 ABSG spontaneous catalyst. It is found that pulse shape distortion can be minimized, if not eliminated, by using aniline-free hydrazine. The mechanisms for both steady-state and pulse-mode performance loss are associated with the formation of a catalyst coke similar to the polycyclic aromatic poisons encountered in the petroleum industry. These poisoning mechanisms are reversible, with high-temperature operation being required to drive off the aniline coke deposits. It is recommended that a purified-grade hydrazine be considered for any mission that imposes operational conditions on a thruster which can result in aniline-induced poisoning of the catalyst bed.

Holcomb, L.↗

Recommendations of the panels: Panel on ozone destruction techniques

Catalyst materials to reduce weight, size, and cost of the ozone removal device were developed. Catalyst bed lifetime, competitive reactivity contaminants in the inlet air on the catalyst bed efficiency for ozone removal, and the kinetics and mechanism by which ozone is destroyed on selected catalysts were studied.

Wydeven, T.↗

Optimization of the catalytic oxidation of CO for closed-cycle CO2 laser applications

This report develops a basis for the design of a catalyst bed for the recombination of CO and O2 in a closed-cycle CO2 laser system. The catalyst is 1% Pt on SnO2 having a BET surface area of 6.7 sq m/g and a specific void volume of 0.374 cu cm/g. The design conditions are: a catalyst bed temperature of 100 C and a circulating flow rate of 10 lambda/min. Under these conditions, the required quantity of catalyst for prolonged laser operation of 668g. The rat law for the reaction of a stoichiometric mixture of 1% CO + 1/2% O2 in helium was determined to be overall first order; however, additional experiments with non-stoichiometric gas mixtures of CO and O2 are needed to determine the order of the CO concentration and the order of the O2 concentration in the rate law.

Miller, I. M.↗

Biosynthetic Porphyrins and the Origin of Photosynthesis

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

David Mauzerall↗

Transmission electron microscopic examination of phosphoric acid fuel cell components

Transmission electron microscopy (TEM) was used to physically characterize tested and untested phosphoric acid fuel cell (PAFC) components. Those examined included carbon-supported platinum catalysts, carbon backing paper, and Teflon-bonded catalyst layers at various stages of fabrication and after testing in pressurized PAFC's. Applicability of electron diffraction and electron energy loss spectroscopy for identifying the various phases was explored. The discussion focuses on the morphology and size distribution of platinum, the morphology and structural aspects of Teflon in catalyst layers, and the structural evidence of carbon corrosion. Reference is made to other physical characterization techniques where appropriate. A qualitative model of the catalyst layer that emerged from the TEM studies is presented.

Pebler, A.↗

Catalytic ignition of hydrogen and oxygen propellants

An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalyst are presented.

Zurawski, Robert L.↗

Catalytic ignition of hydrogen and oxygen propellants

An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen propellants. Shell 405 granular catalyst and a monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant temperature, and back pressure were varied parametrically in testing to determine the operational limits of the catalytic igniter. The test results show that the gaseous hydrogen and oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. A cyclic life of nearly 2000, 2 sec pulses at nominal operating conditions was demonstrated with the catalytic igniter. The results of the experimental program and the established operational limits for a catalytic igniter using the Shell 405 catalysts are presented.

Zurawski, Robert L.↗

Electrocatalysts for oxygen electrodes in fuel cells and water electrolyzers for space applications

In most instances separate electrocatalysts are needed to promote the reduction of O2 in the fuel cell mode and to generate O2 in the energy storage-water electrolysis mode in aqueous electrochemical systems operating at low and moderate temperatures (T greater than or equal to 200 C). Interesting exceptions are the lead and bismuth ruthenate pyrochlores in alkaline electrolytes. These catalysts on high area carbon supports have high catalytic activity for both O2 reduction and generation (1,2). Rotating ring-disk electrode measurements provide evidence that the O2 reduction proceeds by a parallel four-electron pathway. The ruthenates can also be used as self-supported catalysts to avoid the problems associated with carbon oxidation, but the electrode performance so far achieved in the research at Case Western Reserve University (CWRU) is considerably less. At the potentials involved in the anodic mode the ruthenate pyrochlores have substantial equilibrium solubility in concentrated alkaline electrolyte. This results in the loss of catalyst into the bulk solution and a decline in catalytic activity. Furthermore, the hydrogen generation counter electrode may become contaminated with reduction products from the pyrochlores (lead, ruthenium). A possible approach to this problem is to immobilize the pyrochlore catalyst within an ionic-conducting solid polymer, which would replace the fluid electrolyte within the porous gas diffusion O2 electrode. For bulk alkaline electrolyte, an anion-exchange polymer is needed with a transference number close to unity for the Oh(-) ion. Preliminary short-term measurements with lead ruthenates using a commercially available partially-fluorinated anion-exchange membrane as an overlayer on the porous gas-fed electrode indicate lower anodic polarization and virtually unchanged cathodic polarization.

Prakash, Jai↗

Oxygen electrodes for rechargeable alkaline fuel cells

Electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells are being investigated and developed. Candidate support materials were drawn from transition metal carbides, borides, nitrides and oxides which have high conductivity (greater than 1 ohm/cm). Candidate catalyst materials were selected largely from metal oxides of the form ABO sub x (where A = Pb, Cd, Mn, Ti, Zr, La, Sr, Na, and B = Pt, Pd, Ir, Ru, Ni (Co) which were investigated and/or developed for one function only, O2 reduction or O2 evolution. The electrical conductivity requirement for catalysts may be lower, especially if integrated with a higher conductivity support. All candidate materials of acceptable conductivity are subjected to corrosion testing. Materials that survive chemical testing are examined for electrochemical corrosion activity. For more stringent corrosion testing, and for further evaluation of electrocatalysts (which generally show significant O2 evolution at at 1.4 V), samples are held at 1.6 V or 0.6 V for about 100 hours. The surviving materials are then physically and chemically analyzed for signs of degradation. To evaluate the bifunctional oxygen activity of candidate catalysts, Teflon-bonded electrodes are fabricated and tested in a floating electrode configuration. Many of the experimental materials being studied have required development of a customized electrode fabrication procedure. In advanced development, the goal is to reduce the polarization to about 300 to 350 mV. Approximately six support materials and five catalyst materials were identified to date for further development. The test results will be described.

Swette, L.↗

Thermal synthesis and hydrolysis of polyglyceric acid

Polyglyceric acid was synthesized by thermal condensation of glyceric acid at 80 C in the presence and absence of two mole percent of sulfuric acid catalyst. The acid catalyst accelerated the polymerization over 100-fold and made possible the synthesis of insoluble polymers of both L- and DL-glyceric acid by heating for less than 1 day. Racemization of L-glyceric acid yielded less than 1 percent D-glyceric acid in condensations carried out at 80 C with catalyst for 1 day and without catalyst for 12 days. The condensation of L-glyceric acid yielded an insoluble polymer much more readily than condensation of DL-glyceric acid. Studies of the hydrolysis of poly-DL-glyceric acid revealed that it was considerably more stable under mild acidic conditions compared to neutral pH. The relationship of this study to the origin of life is discussed.

Weber, Arthur L.↗

A computer program for the design of optimum catalytic monoliths for CO2 lasers

Pulsed CO2 lasers have many applications in aeronautics, space research, weather monitoring and other areas. Full exploitation of the potential of these lasers is hampered by the dissociation of CO2 that occurs during laser operation. The development of closed-cycle CO2 lasers requires active CO-O2 recombination (CO oxidation) catalysts and design methods for implementation of catalysts inside lasers. The performance criteria and constraints involved in the design of catalyst configurations for use in a closed-cycle laser are discussed, and several design studies performed with a computerized design program that was written are presented. Trade-offs between catalyst activity and dimensions, flow channel dimensions, pressure drop, O2 conversion and other variables are discussed.

Guinn, K.↗

The e-beam sustained CO2 laser amplifier

The design features of an e-beam sustained CO2 amplifier are described. The amplifier is designed specifically as a catalyst test-bed to study the performance of room temperature precious metal CO-oxidation catalysts under e-beam sustained operation. The amplifier has been designed to provide pulse durations of 30 microseconds in a discharge volume of 2 litres. With a gas flow velocity of 2 metres per second, operation at repetition rates of 10 Hz is accommodated. The system is designed for sealed-off operation and a catalyst bed is housed in the gas circulation system downstream from the discharge region. CO and oxygen monitors are used for diagnosis of gas composition in the amplifier so that catalyst performance can be monitored in situ during sealed lifetests.

Brown, M. J.↗

Catalytic ignition of hydrogen/oxygen

An experimental program was conducted to evaluate the catalytic ignition of gaseous hydrogen and oxygen. Shell 405 granular catalyst and a unique monolithic sponge catalyst were tested. Mixture ratio, mass flow rate, propellant inlet temperature, and back pressure were varied parametrically in testing to determine the operational limits of a catalytic igniter. The test results showed that the gaseous hydrogen/oxygen propellant combination can be ignited catalytically using Shell 405 catalyst over a wide range of mixture ratios, mass flow rates, and propellant injection temperatures. These operating conditions must be optimized to ensure reliable ignition for an extended period of time. The results of the experimental program and the established operational limits for a catalytic igniter using both the granular and monolithic catalysts are presented. The capabilities of a facility constructed to conduct the igniter testing and the advantages of a catalytic igniter over other ignition systems for gaseous hydrogen and oxygen are also discussed.

Green, James M.↗

Investigation of catalytic reduction and filter techniques for simultaneous measurements of NO, NO2, and HNO3 in the stratosphere

A concept for measuring stratospheric NOy-species is presented which utilizes the catalytic reduction of NO2 and HNO3 over heated metal catalysts and the chemisorption of HNO3 on Nylon. Using the Max Planck Institute for Aeronomy (MPAE) chemiluminescent balloon-borne sonde, stratospheric NO and NO2 profiles have been measured since 1983. NO is detected by chemiluminescence produced in reaction with O3 while NO2 needs first to be converted to NO over a heated stainless steel catalyst. To improve this technique for simultaneously measuring HNO3, the catalytic reduction of NO2 and HNO3 over several metal catalysts and the chemisorption of NO2 and HNO3 on Nylon have been investigated in laboratory tests. The results of these tests under simulated stratospheric conditions are presented in detail in this paper. They demonstrate that the simultaneous measurement of NO, NO2 and HNO3 is indeed possible with the combination of stainless steel or Au as a catalyst and a nylon filter.

Wendt, J.↗

The growth of zeolites A, X and mordenite in space

Zeolites are a class of crystalline aluminosilicate materials that form the backbone of the chemical process industry worldwide. They are used primarily as adsorbents and catalysts and support to a significant extent the positive balance of trade realized by the chemical industry in the United States (around $19 billion in 1991). The magnitude of their efforts can be appreciated when one realizes that since their introduction as 'cracking catalysts' in the early 1960's, they have saved the equivalent of 60 percent of the total oil production from Alaska's North Slope. Thus the performance of zeolite catalysts can have a profound effect on the U.S. economy. It is estimated that a 1 percent increase in yield of the gasoline fraction per barrel of oil would represent a savings of 22 million barrels of crude oil per year, representing a reduction of $400 million in the United States' balance of payments. Thus any activity that results in improvement in zeolite catalyst performance is of significant scientific and industrial interest. In addition, due to their 'stability,' uniformity, and, within limits, their 'engineerable' structures, zeolites are being tested as potential adsorbents to purify gases and liquids at the parts-per-billion levels needed in today's electronic, biomedical, and biotechnology industries and for the environment. Other exotic applications, such as host materials for quantum-confined semiconductor atomic arrays, are also being investigated. Because of the importance of this class of material, extensive efforts have been made to characterize their structures and to understand their nucleation and growth mechanisms, so as to be able to custom-make zeolites for a desired application. To date, both the nucleation mechanics and chemistry (such as what are the 'key' nutrients) are, as yet, still unknown for many, if not all, systems. The problem is compounded because there is usually a 'gel' phase present that is assumed to control the degree of supersaturation, and this gel undergoes a continuous 'polymerization' type reaction during nucleation and growth. Generally, for structure characterization and diffusion studies, which are useful in evaluating zeolites for improving yield in petroleum refining as well as for many of the proposed new applications (e.g., catalytic membranes, molecular electronics, chemical sensors) large zeolites (greater than 100 to 1000 times normal size) with minimum lattice defects are desired. Presently, the lack of understanding of zeolite nucleation and growth precludes the custom design of zeolites for these or other uses. It was hypothesized that the microgravity levels achieved in an orbiting spacecraft could help to isolate the possible effects of natural convection (which affects defect formation) and minimize sedimentation, which occurs since zeolites are twice as dense as the solution from which they are formed. This was expected to promote larger crystals by allowing growing crystals a longer residence time in a high-concentration nutrient field. Thus it was hypothesized that the microgravity environment of Earth orbit would allow the growth of large, more defect-free zeolite crystals in high yield.

Sacco, Albert, Jr.↗