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NASA NTRS1978

Catalytic decomposition of methanol for onboard hydrogen generation

The steam reformation of an equimolar mixture of methanol and water on a copper chromite catalyst was studied at three furnace temperatures and at feed space velocities from 800 to 2600 per hour. The hydrogen space velocity could be related to the reactor temperature by the equation Sv = A exp (-omega T), where A and omega are constants determined for each value of alpha and T is temperature. At a methanol conversion of 0.87 and a reactor temperature of 589 K, the extrapolated value of the hydrogen space velocity was 9400 per hour. This velocity was used to estimate the size of an onboard hydrogen reactor for automotive applications. Such a reactor would need only about 0.8 liter of catalyst to produce 7630 STP liters (1.5 lb) of hydrogen per hour. This quantity of catalyst would fit into nine tubes 17.8 centimeters along and 2.54 centimeters in inside diameter, which is smaller than most mufflers. The reactor products would contain 12 to 13 percent more chemical energy than the incoming methanol and water.

Brabbs, T.↗

NASA NTRS1990

Oxidation kinetics of model compounds of metabolic waste in supercritical water

In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

Webley, Paul A.↗

NASA NTRS1997

Commercialization of a Direct Methanol Fuel Cell System

This paper describes a major breakthrough in energy technology developed at the Jet Propulsion Laboratory that can be used in a wide variety of portable, remote, and transportation applications without polluting the environment. The status, performance, and design considerations of the JPL non-polluting, direct methanol, fuel cell system for consumer equipment and transportation applications are reported herein. This new fuel cell technology utilizes the direct oxidation of a 3 percent aqueous liquid methanol solution as the fuel and air (O&sub2;) as the oxidant. The only products are CO&sub2; and water. Therefore, because recharging can be accomplished by refueling with methanol, vehicles can enjoy unlimited range and extended use compared to battery operated devices requiring recharging time and power accessibility.

fuel↗

NASA NTRS1982

Vehicle conversion to hybrid gasoline/alternative fuel operation

The alternative fuels considered are compressed natural gas (CNG), liquefied natural gas (LNG), liquid petroleum gas (LPG), and methanol; vehicles were required to operate in a hybrid or dual-fuel gasoline/alternative fuel mode. Economic feasibility was determined by comparing the costs of continued use of gasoline fuel with the use of alternative fuel and retrofitted equipment. Differences in the amounts of future expenditures are adjusted by means of a total life-cycle costing. All fuels studied are technically feasible to allow a retrofit conversion to hybrid gasoline/alternative fuel operation except for methanol. Conversion to LPG is not recommended for vehicles with more than 100,000 km (60,000 miles) of prior use. Methanol conversion is not recommended for vehicles with more than 50,00 km (30,000 miles).

Donakowski, T. D.↗

NASA NTRS1981

Hydrogen engines based on liquid fuels, a review

The concept of storing hydrogen as part of a liquid fuel, such as gasoline or methanol, and subsequent onboard generation of the hydrogen from such liquids, is reviewed. Hydrogen generation processes, such as steam reforming, partial oxidation, and thermal decomposition are evaluated in terms of theoretical potential and practical limitations, and a summary is presented on the major experimental work on conversion of gasoline and methanol. Results of experiments indicate that onboard hydrogen generation from methanol is technically feasible and will yield substantial improvements in fuel economy and emissions, especially if methanol decomposition is brought about by the use of engine exhaust heat; e.g., a methanol decomposition reactor of 3.8 provides hydrogen-rich gas for a 4 cylinder engine (1.952), and 80% of the methanol is converted, engine exhaust gas being the only heat supply. A preliminary outline of the development of a methanol-based hydrogen engine and a straight hydrogen engine is presented.

Houseman, J.↗

NASA NTRSDate not supplied

Plasma Chemical Conversion and Resource Generation Beyond Low-Earth Orbit

As humanity gears up for its return to the moon after more than half a century, collaborative efforts between NASA, Artemis Accords Partners, and private industry are underway to establish the necessary infrastructure and technologies for lunar habitation and eventual Mars exploration. However, the traditional ISS resupply and waste management model is impractical and economically infeasible for prolonged missions to the Moon and Mars. Advanced chemical conversion technologies are needed to generate vital consumable products from local planetary resources (ISRU) and recycled gasses and waste within semi-closed loop life-support systems. Low-temperature plasma reactors are emerging power-to-gas technologies with the potential to facilitate various chemical synthesis processes with hardware commonality and redundancy. In plasma-based systems, electrical power is used to ionize a feedstock gas, creating a highly reactive environment that leverages electron excitation chemistry to break stable molecular bonds and form value added products. Unlike thermal chemical processes, plasma reactors operate at non-equilibrium conditions, allowing for lower-temperature operation and instantaneous start-up, making them adaptable to intermittent power availability. Moreover, their scalability permits deployment in both portable astronaut systems and large-scale industrial setups for colonies. One promising application of plasmas is for CO 2 conversion. Carbon dioxide comprises 96% of the Martian atmosphere and is a byproduct of human respiration, which typically must be scrubbed and vented from space habitats. A plasma source integrated with membrane separation technology could generate a stream of oxygen for life support and rocket propellant. CO 2 splitting may also be beneficial as a precursor to manufacture carbon-based products and fuels in situ, like methane, methanol, and polyethylene. Plasma-assisted CO 2 conversion is a simpler case to study without the concern of selectivity and is the first step toward complex chemical synthesis. This work presents preliminary experimental case study from a plasma reactor for CO 2 conversion and casts a vision for the potential of plasma technologies in a sub-architecture for resource production to enable the next generation of human spaceflight activities.

Plasma↗

NASA NTRS1978

A systems examination of the opportunities of coal for California

Because of decreasing availability of petroleum fuels and natural gas, it is imperative that alternative means be developed for meeting demands. The options available for importing energy derived from coal are examined. These include: (1) electric power generated from coal; (2) coal gasification near the mine site for conversion to substitute natural gas or liquid products such as methanol or hydrocarbons; and (3) converting the coal directly to liquid hydrocarbons similar to a synthetic crude oil. Comment is made on the long lead times required between conception and completion of facilities of this type. Because of political and economic impediments, excessive delays have resulted in cancellation of projects. The need for statesmen and citizens with vision and courage to act is summarized.

Hathaway, W. M.↗

NASA NTRS1982

Hybrid fuel cell/diesel generation total energy system, part 2

Meeting the Goldstone Deep Space Communications Complex (DGSCC) electrical and thermal requirements with the existing system was compared with using fuel cells. Fuel cell technology selection was based on a 1985 time frame for installation. The most cost-effective fuel feedstock for fuel cell application was identified. Fuels considered included diesel oil, natural gas, methanol and coal. These fuel feedstocks were considered not only on the cost and efficiency of the fuel conversion process, but also on complexity and integration of the fuel processor on system operation and thermal energy availability. After a review of fuel processor technology, catalytic steam reformer technology was selected based on the ease of integration and the economics of hydrogen production. The phosphoric acid fuel cell was selected for application at the GDSCC due to its commercial readiness for near term application. Fuel cell systems were analyzed for both natural gas and methanol feedstock. The subsequent economic analysis indicated that a natural gas fueled system was the most cost effective of the cases analyzed.

Blazek, C. F.↗

NASA NTRS2005

Improved Anode for a Direct Methanol Fuel Cell

A modified chemical composition has been devised to improve the performance of the anode of a direct methanol fuel cell. The main feature of the modified composition is the incorporation of hydrous ruthenium oxide into the anode structure. This modification can reduce the internal electrical resistance of the cell and increase the degree of utilization of the anode catalyst. As a result, a higher anode current density can be sustained with a smaller amount of anode catalyst. These improvements can translate into a smaller fuel-cell system and higher efficiency of conversion. Some background information is helpful for understanding the benefit afforded by the addition of hydrous ruthenium oxide. The anode of a direct methanol fuel cell sustains the electro-oxidation of methanol to carbon dioxide in the reaction CH3OH + H2O--->CO2 + 6H(+) + 6e(-). An electrocatalyst is needed to enable this reaction to occur. The catalyst that offers the highest activity is an alloy of approximately equal numbers of atoms of the noble metals platinum and ruthenium. The anode is made of a composite material that includes high-surface-area Pt/Ru alloy particles and a proton-conducting ionomeric material. This composite is usually deposited onto a polymer-electrolyte (proton-conducting) membrane and onto an anode gas-diffusion/current-collector sheet that is subsequently bonded to the proton-conducting membrane by hot pressing. Heretofore, the areal density of noble-metal catalyst typically needed for high performance has been about 8 mg/cm2. However, not all of the catalyst has been utilized in the catalyzed electro-oxidation reaction. Increasing the degree of utilization of the catalyst would make it possible to improve the performance of the cell for a given catalyst loading and/or reduce the catalyst loading (thereby reducing the cost of the cell). The use of carbon and possibly other electronic conductors in the catalyst layer has been proposed for increasing the utilization of the catalyst by increasing electrical connectivity between catalyst particles. However, the relatively low density of carbon results in thick catalyst layers that impede the mass transport of methanol to the catalytic sites. Also, the electrical conductivity of carbon is less than 1/300th of typical metals. Furthermore, the polymer-electrolyte membrane material is acidic and most metals are not chemically stable in contact with it. Finally, a material that conducts electrons (but not protons) does not contribute to the needed transport of protons produced in the electro-oxidation reaction.

Valdez, Thomas↗

NASA NTRS1977

On-orbit performance of the 12 GHz, 200 watt transmitter experiment package for CTS

Performance characteristics from on-orbit tests of the Transmitter Experiment Package (TEP) for the Communications Technology Satellite (CTS) are presented. The TEP consists of a Power Processing System (PPS), an Output Stage Tube (OST), and a Variable Conductance Heat Pipe System (VCHPS), all of which are described. The OST is a coupled-cavity traveling-wave tube with a multistage depressed collector and a stepped velocity-tapered slow-wave structure for efficiency enhancement. It has an RF output power of 240 W and an overall efficiency of 51.5% at a center band frequency of 12.080 GHz. The PPS provides the required operating voltages, regulation, control, and protection for the OST. It has a measured dc-dc conversion efficiency of 86.5% to 88.5%. The VCHPS consists of a fin radiator and three dual-artery stainless steel heat pipes using methanol and a mixture of inert gases. Test results presented include efficiencies, RF output power, frequency response, and performance with single and multiple (two) carriers frequency-modulated by video signals.

Alexovich, R. E.↗

NASA NTRS1995

Supporting technology for the development of Controlled Ecological Life Support Systems (CELSS)

To support the development of Controlled Ecological Life Support Systems (CELSS) in the space program, a metabolic simulator has been selected for use in a closed chamber to test functions of the CELSS. This metabolic simulator is a catalytic reactor which oxidizes the methyl acetate to produce carbon dioxide and water vapor. In this project, kinetic studies of catalytic oxidation of methyl acetate were conducted using monolithic and pellet catalysts with 0.5% (by weight) platinum (Pt) on aluminum oxide (Al2O3). The reaction was studied at a pressure of one atmosphere and at temperatures varying from 160 C to 420 C. By-products were identified at the exit of the preheater and reactor. For the kinetic study with the monolithic catalyst, a linear regression method was used to correlate the kinetic data with zero-order, first-order and Langmuir-Hinshelwood models. Results indicate that the first-order model represents the data adequately at low concentrations of methyl acetate. For higher concentrations of methyl acetate, the Langmuir-Hinshelwood model best represents the kinetic data. Both rate constant and adsorption equilibrium constants were estimated from the regression. A Taguchi orthogonal array (L(sub 9)) was used to investigate the effects of temperature, flow rate, and concentration on the catalytic oxidation of methyl acetate. For the monolithic catalyst, temperature exerts the most significant effect, followed by concentration of methyl acetate. For the pellet catalyst, reaction temperature is the most significant factor, followed by gas flow rate and methyl acetate concentration. Concentrations of either carbon dioxide or oxygen were seen to have insignificant effect on the methyl acetate conversion process. Experimental results indicate that the preheater with glass beads can accomplish thermal cracking and catalytic reaction of methyl acetate to produce acetic acid, methanol, methyl formate, and 1-propanol. The concentration of all by-products was measured in ppmv (parts per million by volume). At higher temperatures, greater amounts of these products are produced, as expected. In all cases, methanol was the predominant concentration detected, followed by methyl formate. At temperatures lower than 320 C for the P-type monolithic catalyst, methanol, acetic acid, and acetone were detected, whereas, for the E-type monolithic catalyst, only methanol was detected at 160 C. Both P and E types of the monolithic catalyst were specified with the same substrates (ceramic), washcoat (Al2O3), and promoter (Pt). However, the manufacturing and treatment procedures were quite different. It was therefore concluded that the performance of the E-type monolithic catalyst is superior to that of the P-type for oxidation of methyl acetate. At higher reaction temperatures, e.g., above 420 C, all reactants and byproducts were completely oxidized using these two types of monolithic catalyst to produce carbon dioxide and water vapor. A complex heterogenous catalytic reaction mechanism was proposed to explain the formation of the byproducts (methanol, acetic acid, and methyl formate) as the methyl acetate traveled through the preheater packed with glass beads. The by-product, 1-propanol, may be formed only through a homogeneous reaction, since it is difficult to develop a reasonable sequence of heterogeneous reaction steps to explain its formation. The homogeneous thermal decomposition of methyl acetate to form free radicals was proposed to explain the formation of 1-propanol, and also methanol, in the preheater. A dual-site catalytic reaction mechanism was proposed for the oxidation of methyl acetate over Pt/Al2O3 monolithic catalyst. The dual-site mechanism describes the chemisorption of oxygen molecules as well as a physical adsorption of methyl acetate on the active sites. On the active sites, methyl acetate is oxidized rapidly to form carbon dioxide and water vapor. A rate equation derived from this mechanism gives the Langmuir-Hinshelwood rate formula which has been observed from the experimental data obtained in this project for high methyl acetate concentration (greater than 1000 ppmv) over a monolithic catalyst. If the oxygen concentration is very high and methyl acetate concentration is very low, the reaction rate equation is then reduced to a first-order with respect to methyl acetate concentration. The first-order model has also been observed from the experimental data obtained in this project for low methyl acetate concentration (less than 1000 ppmv).

Li, Ku-Yen↗

NASA NTRS1995

Plasma processing of interstellar PAHs into solar system kerogen

Processes resulting in the formation of hydrocarbons of carbonaceous chondrites and the identity of the interstellar molecular precursors involved are an objective of investigations into the origin of the solar system and perhaps even life on earth. We have combined the resources and experience of an astronomer and physicists doing laboratory simulations with those of a chemical expert in the analysis of meteoritic hydrocarbons, in a project that investigated the conversion of polycyclic aromatic hydrocarbons (PAHs) formed in stellar atmospheres into alkanes found in meteorites. Plasma hydrogenation has been found in the University of Alabama at Birmingham Astrophysics Laboratory to produce from the precursor PAH naphthalene, a new material having an IR absorption spectrum (Lee, W. and Wdowiak, T.J., Astrophys. J. 417, L49-L51, 1993) remarkably similar to that obtained at Arizona State University of the benzene-methanol extract of the Murchison meteorite (Cronin, J.R. and Pizzarello, S., Geochim. Cosmochim. Acta 54, 2859-2868, 1990). There are astrophysical and meteoritic arguments for PAH species from extra-solar sources being incorporated into the solar nebula, where plasma hydrogenation is highly plausible. Conversion of PAHs into alkanes could also have occurred in the interstellar medium. The synthesis of laboratory analogs of meteoritic hydrocarbons through plasma hydrogenation of PAH species is underway, as is chemical analysis of those analogs. The objective is to clarify this heretofore uninvestigated process and to understand its role during the origin of the solar system as a mechanism of production of hydrocarbon species now found in meteorites. Results have been obtained in the form of time-of-flight spectroscopy and chemical analysis of the lab analog prepared from naphthalene.

NASA Discipline Exobiology↗

NASA NTRS1983

Short Shot Tower for Silicon

Drop length necessary to convert molten silicon to shot reduced by proposed new process. Conversion of silicon from powder or chunks to shot often simplifies processing. Shot is more easily handled in most processing equipment. Drops of liquid silicon fall through protective cloud of argon, then through rapidly cooling bath of methanol, where they quickly turn into solid shot.

Bates, H. E.↗

NASA NTRS1975

Semiconductor electrolyte photovoltaic energy converter

Feasibility and practicality of a solar cell consisting of a semiconductor surface in contact with an electrolyte are evaluated. Basic components and processes are detailed for photovoltaic energy conversion at the surface of an n-type semiconductor in contact with an electrolyte which is oxidizing to conduction band electrons. Characteristics of single crystal CdS, GaAs, CdSe, CdTe and thin film CdS in contact with aqueous and methanol based electrolytes are studied and open circuit voltages are measured from Mott-Schottky plots and open circuit photo voltages. Quantum efficiencies for short circuit photo currents of a CdS crystal and a 20 micrometer film are shown together with electrical and photovoltaic properties. Highest photon irradiances are observed with the GaAs cell.

Anderson, W. W.↗

NASA NTRS1999

Trade Study of Five In-Situ Propellant Production System for a Mars Sample Return Mission

One of the goals of NASA''s HEDS enterprise is to establish a long-term human presence on Mars at a fraction of the cost of employing today''s technology. The most direct method of reducing mission cost is to reduce the launch mass of the spacecraft. If the propellants for the return phase of the mission are produced on Mars, the total spacecraft mass could be reduced significantly. An interim goal is a Mars Sample Return (MSR) mission, which is proposed to demonstrate the feasibility of in-situ propellant production (ISPP). Five candidate ISPP systems for producing two fuels and oxygen from the Martian atmosphere are considered in this design trade-off study:(1) Zirconia cell with methanol synthesis, (2) Reverse water gas shift (RWGS) with water electrolysis and methanol synthesis, (3) Sabatier process for methane production with water electrolysis, (4) Sabatier process with water electrolysis and partial methane pyrolysis, and (5) Sabatier/RWGS combination with water electrolysis. These systems have been the subject of numerous previous analytical studies and laboratory demonstrations. In this investigation, the systems are objectively compared on the basis of thermochemical performance models using a commonly used chemical plant analysis software package. The realistic effects of incomplete chemical conversion and gas phase separator performance are included in these models. This study focuses on the chemical processing and product separation subsystems. The CO2 compression upstream of the chemical plane and the liquefaction/storage components are not included here.

Green, S. T.↗

NASA NTRS2016

Conversion and Extraction of Insoluble Organic Materials in Meteorites

We endeavor to develop and implement methods in our laboratory to convert and extract insoluble organic materials (IOM) from low car-bon bearing meteorites (such as ordinary chondrites) and Precambrian terrestrial rocks for the purpose of determining IOM structure and prebiotic chemistries preserved in these types of samples. The general scheme of converting and extracting IOM in samples is summarized in Figure 1. First, powdered samples are solvent extracted in a micro-Soxhlet apparatus multiple times using solvents ranging from non-polar to polar (hexane - non-polar, dichloromethane - non-polar to polar, methanol - polar protic, and acetonitrile - polar aprotic). Second, solid residue from solvent extractions is processed using strong acids, hydrochloric and hydrofluoric, to dissolve minerals and isolate IOM. Third, the isolated IOM is subjected to both thermal (pyrolysis) and chemical (oxidation) degradation to release compounds from the macromolecular material. Finally, products from oxidation and pyrolysis are analyzed by gas chromatography - mass spectrometry (GCMS). We are working toward an integrated method and analysis scheme that will allow us to determine prebiotic chemistries in ordinary chondrites and Precambrian terrestrial rocks. Powerful techniques that we are including are stepwise, flash, and gradual pyrolysis and ruthenium tetroxide oxidation. More details of the integrated scheme will be presented.

Locke, Darren R.↗

NASA NTRS2002

Microgravity Compatible Reagentless Instrumentation for Detection of Dissolved Organic Acids and Alcohols in Potable Water

The Organic Acid and Alcohol Monitor (OAAM) program has resulted in the successful development of a computer controlled prototype analyzer capable of accurately determining aqueous organic acids and primary alcohol concentrations over a large dynamic range with high sensitivity. Formic, acetic, and propionic acid were accurately determined at concentrations as low as 5 to 10 micrograms/L in under 20 minutes, or as high as 10 to 20 mg/L in under 30 minutes. Methanol, ethanol, and propanol were determined at concentrations as low as 20 to 100 micrograms/L, or as high as 10 mg/L in under 30 minutes. Importantly for space based application, the OAAM requires no reagents or hazardous chemicals to perform these analyses needing only power, water, and CO2 free purge gas. The OAAM utilized two membrane processes to segregate organic acids from interfering ions. The organic acid concentration was then determined based upon the conductiometric signal. Separation of individual organic acids was accomplished using a chromatographic column. Alcohols are determined in a similar manner after conversion to organic acids by sequential biocatalytic and catalytic oxidation steps. The OAAM was designed to allow the early diagnosis of under performing or failing sub-systems within the Water Recovery System (WRS) baselined for the International Space Station (ISS). To achieve this goal, several new technologies were developed over the course of the OAAM program.

Akse, James R.↗

NASA NTRS1980

A 163 micron laser heterodyne radiometer for OH

A 163 micron (1.836 THz) radiometer developed for airplane and/or balloon platforms is described. The laser local oscillator is a CO2 pumped methanol laser operating at a frequency which is approx. 1 GHz from the J = 3/2 - 1/2 transition of OH. The laser is used directly as a local oscillator or is translated in frequency to closer coincidence with the OH emission, depending on achieved detector IF bandwidth. Frequency translation techniques which are described are diode mixing and a method of single sideband generation using an external Stark modulated gas cell. The photoconductive mixer used is a strained Ge crystal, doped with Ga, originally used as an incoherent detector. The uniaxial strain on the Ga doped Ge crystal shifts the threshold for photoconduction from 100/cm to frequencies as low as 50/cm. These detectors are currently being characterized as mixers in the laboratory. Of particular interest are the effect of local oscillator power and strain on IF, bandwidth detector impedance, and conversion loss. Preliminary results of these tests are described and compared with theorectical expectations.

Pickett, H. M.↗