Development of an efficient alternative to recovery O 2 from metabolic CO 2 via electrolysis operated at ambient temperature and driven by a highly selective catalysis
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Jesus Dominguez↗
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Trade Study Analysis of a Cryogenic Oxygen Architecture for Lunar Outpost Life Support
A trade study was performed to compare the use of cryogenic liquid oxygen (LOX) with high pressure gaseous oxygen (GOX) and electrolysis approaches for Lunar outpost life support, which consists of a surface habitat and pressurized rover. This study presents the mission details pertaining to a Lunar outpost architecture, discusses the viable concept of operations for each architecture, and compares the equivalent system mass (ESM) of the cryogenic LOX, high pressure GOX, and electrolysis approaches across different parameter trades, e.g. mission duration or extravehicular activity frequency, for the single and 10-year mission architectures. For a single nominal mission, high pressure GOX is favored for short missions (< 50 days); cryogenic LOX is favored for a wide-range of mission durations (50 – 270 days); and the electrolysis approach is favored for long missions (> 270 days). However, when considering a 10-year mission architecture, each additional resupply negatively impacts cryogenic LOX due to the additional replacement tankage. Thus, over a 10-year mission, an electrolysis approach, which can provide all life support O2 utilizing solely recovered H2O, appears to be favored over cryogenic LOX. However, a real electrolysis system may need resupplied H2O due to incomplete closure of the air revitalization loop. Thus, the cryogenic LOX approach was compared with the electrolysis approaches utilizing 100% resupplied or 100% recovered H2O to approximate the resupplied to recovered H2O ratio, i.e. the degree of loop closure, where one approach trades over the other. Additionally, gaps were identified, which are expected to affect the viability and trade of cryogenic LOX. These include the development of cryogenic pumps and vaporizers to generate high pressure GOX from LOX as well as understanding payload limitations which can affect O2 resupply.
ECLSS↗
Oxygen Production from Lunar Regolith using Ionic Liquids
The objective of this work and future follow-on work is to develop a safe, efficient, and recyclable method for oxygen and/or metals extraction from lunar regolith, in support of establishing a manned lunar outpost. The approach is to solubilize the oxides that comprise lunar regolith in media consisting of ionic liquids (ILs) and/or their mixtures at temperatures at or below 300 C. Once in solution, electrolysis can either be performed in-situ to generate oxygen at the anode and hydrogen and/or metals (silicon, iron, aluminum, titanium, etc.) at the cathode. Alternatively, the water that is generated during the solubilization process can be distilled out and condensed into a separate IL and then electrolysized to produce hydrogen and oxygen. In the case of lunar regolith, this method could theoretically produce 44g oxygen per 100g of regolith. The oxygen can be used for human life support and/or as an oxidizer for rocket fuels, and the metals can be used as raw materials for construction and/or device fabrication. Moreover, the hydrogen produced can be used to re-generate the acidic medium, which can then be used to process additional regolith, thereby making the materials recyclable and limiting upmass requirements. An important advantage of IL acid systems is that they are much "greener" and safer than conventional materials used for regolith processing such as sulfuric or hydrochloric acids. They have very low vapor pressures, which means that they contain virtually no toxic and/or flammable volatile content, they are relatively non-corrosive, and they can exhibit good stability in harsh environments (extreme temperatures, hard vacuum, etc.). Furthermore, regolith processing can be achieved at lower temperatures than other processes such as molten oxide electrolysis or hydrogen reduction, thereby reducing initial power requirements. Six ILs have been synthesized and tested for their capability to dissolve lunar simulant, and for electrochemical and thermal stability. The results showed that ILs can be very efficient electrolytes; in particular IL/phosphoric-acid mixtures appear extremely promising for solubilizing lunar simulant. Results from preliminary experiments for distillation of water produced from the oxygen within the metal oxides of the simulant and the hydrogen from the acid indicates that over 75% of the oxygen from the simulant can be harvested as water at a temperature of 150 C. A method for collection of oxygen from electrolysis of the water derived from solubilizing simulant was developed by using a liquid nitrogen trap to liquefy and collect the oxygen. Although precise quantification of the liquid oxygen trapped is difficult to obtain, the amount of hydrogen and oxygen collected from electrolysis of water in this system was greater than 98%. This set-up also included a portable mass spectrometer for the identification of gases released from electrolysis cells. Regeneration of ILs through re-protonation was also demonstrated. Four sequential re-generations of an IL following solubilization of simulant showed no significant differences in amounts of simulant dissolved. Follow-on work for this project should include more studies of IL/phosphoric acid systems. Also, much more work is necessary for defining methods for electrolysis and purification of metals from regolith solubilized in ILs, and for developing a system to use the produced hydrogen to regenerate the spent IL. Finally, design and development of flight breadboard and prototype hardware is required.
Paley, Mark Steven↗
Ground Test Stand Development for One-step Electrochemical Production of High-Pressure Oxygen
NASA designed a test rig, High-Pressure Oxygen Generation Assembly (HPOGA) to test a novel method of electrolysis as an alternative technology to the state-of-the-art Oxygen Generation Assembly (OGA) currently on the International Space Station (ISS). This approach involves utilizing a specialized electrolysis cell stack designed to both generate and compress high-pressure oxygen up to 3600 PSIG. The design eliminates the need for an external compressor and hydrogen separator, streamlining the oxygen generation process. HPOGA tests the viability of an electrolysis cell stack for extended life usage. Within the system, there are several key subsystems: nitrogen, high/low pressure oxygen, hydrogen, water recirculation, and water injection. The water injection subsystem supplies deionized (DI) water to a centralized reservoir for consumption. Subsequently, a water recirculation loop transfers the DI water across the cathode side of the electrolysis cell stack with constant flow rate. The result is a supply of hydrogen in the water loop and oxygen accumulation on the anode side of the cell stack. Hydrogen is evaporated out as part of the hydrogen sub-system which also measures hydrogen/oxygen concentration for safety. The oxygen subsystem is responsible for managing high pressure oxygen, O2 exhaust, and conducting hydrogen/oxygen concentration measurements. The nitrogen subsystem serves dual functions, purging the hydrogen/oxygen subsystems, and regulating pressure in both high/low-pressure O2 sections via pneumatic back pressure regulators. Various sensors monitor pressure, temperature, humidity, gas concentration and flow rate in each subsystem. This paper presents the design and testing of a comprehensive test stand, which serves to operate and functionally verify the performance of the electrolysis cell while offering valuable lessons learned.
electrolysis↗
Preliminary Testing of Electrolytic Silver Ion Generation for Spacecraft Potable Water Systems
Anodic dissolution of silver electrodes, or “silver electrolysis,” is being investigated as a means of imparting biocidal silver into potable water on exploration spacecraft. This method of water disinfection is used commercially in hospitals and marine vessels, but the spacecraft application poses unique challenges such as low water conductivity, increased importance of electrode longevity, and an interface with other systems that may be sensitive to any particles released in the electrolysis process. Testing has shown that due to the low conductivity of the water, the electroactive area of the cell can be scaled linearly to achieve a target electrolysis current despite the general non-linearity of electrochemical systems. More importantly, however, the low conductivity dictates that a large electroactive area and minimal electrode gap be employed in the design. Furthermore, thermodynamic considerations suggest that a low applied voltage is necessary to avoid undesired electrode reactions that could negatively impact long-term performance. Preliminary testing of long-term electrode health suggests that anodic oxide formation may not present as significant a challenge as anticipated; however, further testing in a system closed to the atmosphere is required to rule out the influence of atmospheric CO2 on the pH of the process water. Comparison of filtered and unfiltered silver concentration measurements indicates that release of particles larger than 0.2 μm was negligible in this preliminary test. A test article has been developed to facilitate further testing of silver electrolysis, which continues to be a candidate technology for spacecraft potable water disinfection.
silver↗
The development of an electrochemical technique for in situ calibrating of combustible gas detectors
A program to determine the feasibility of performing in situ calibration of combustible gas detectors was successfully completed. Several possible techniques for performing the in situ calibration were proposed. The approach that showed the most promise involved the use of a miniature water vapor electrolysis cell for the generation of hydrogen within the flame arrestor of a combustible gas detector to be used for the purpose of calibrating the combustible gas detectors. A preliminary breadboard of the in situ calibration hardware was designed, fabricated and assembled. The breadboard equipment consisted of a commercially available combustible gas detector, modified to incorporate a water vapor electrolysis cell, and the instrumentation required for controlling the water vapor electrolysis and controlling and calibrating the combustible gas detector. The results showed that operation of the water vapor electrolysis at a given current density for a specific time period resulted in the attainment of a hydrogen concentration plateau within the flame arrestor of the combustible gas detector.
Shumar, J. W.↗
Regenerative fuel cell study for satellites in GEO orbit
Summarized are the results of a 12-month study to identify high performance regenerative hydrogen-oxygen fuel cell concepts for geosynchronous satellite application. Emphasis was placed on concepts with the potential for high energy density (W-hr/lb) and passive means for water and heat management to maximize system reliability. Both polymer membrane and alkaline electrolyte fuel cells were considered, with emphasis on the alkaline cell because of its high performance, advanced state of development, and proven ability to operate in a launch and space environment. Three alkaline system concepts were studied. The first, the integrated design, utilized a configuration in which the fuel cell and electrolysis cells are alternately stacked inside a pressure vessel. Product water is transferred by diffusion during electrolysis and waste heat is conducted through the pressure wall, thus using completely passive means for transfer and control. The second alkaline system, the dedicated design, uses a separate fuel cell and electrolysis stack so that each unit can be optimized in size and weight based on its orbital operating period. The third design was a dual function stack configuration, in which each cell can operate in both fuel cell and electrolysis mode, thus eliminating the need for two separate stacks and associated equipment. Results indicate that using near term technology energy densities between 46 and 52 W-hr/lb can be achieved at efficiencies of 55 percent. System densities of 115 W-hr/lb are contemplated.
Levy, Alexander↗
Electrochemical processing of solid waste
The investigation into electrolysis as a means of waste treatment and recycling on manned space missions is described. The electrochemical reactions of an artificial fecal waste mixture was examined. Waste electrolysis experiments were performed in a single compartment reactor, on platinum electrodes, to determine conditions likely to maximize the efficiency of oxidation of fecal waste material to CO2. The maximum current efficiencies for artificial fecal waste electrolysis to CO2 was found to be around 50 percent in the test apparatus. Experiments involving fecal waste oxidation on platinum indicates that electrodes with a higher overvoltage for oxygen evolution such as lead dioxide will give a larger effective potential range for organic oxidation reactions. An electrochemical packed column reactor was constructed with lead dioxide as electrode material. Preliminary experiments were performed using a packed-bed reactor and continuous flow techniques showing this system may be effective in complete oxidation of fecal material. The addition of redox mediator Ce(3+)/Ce(4+) enhances the oxidation process of biomass components. Scientific literature relevant to biomass and fecal waste electrolysis were reviewed.
Bockris, J. OM.↗
Space station propulsion test bed
A test bed was fabricated to demonstrate hydrogen/oxygen propulsion technology readiness for the intital operating configuration (IOC) space station application. The test bed propulsion module and computer control system were delivered in December 1985, but activation was delayed until mid-1986 while the propulsion system baseline for the station was reexamined. A new baseline was selected with hydrogen/oxygen thruster modules supplied with gas produced by electrolysis of waste water from the space shuttle and space station. As a result, an electrolysis module was designed, fabricated, and added to the test bed to provide an end-to-end simulation of the baseline system. Subsequent testing of the test bed propulsion and electrolysis modules provided an end-to-end demonstration of the complete space station propulsion system, including thruster hot firings using the oxygen and hydrogen generated from electrolysis of water. Complete autonomous control and operation of all test bed components by the microprocessor control system designed and delivered during the program was demonstrated. The technical readiness of the system is now firmly established.
Briley, G. L.↗
Integrated regenerative fuel cell experimental evaluation
An experimental test program was conducted to investigate the performance characteristics of an integrated regenerative fuel cell (IRFC) concept. The IRFC consists of a separate fuel cell unit and electrolysis cell unit in the same structure, with internal storage of fuel cell product water and external storage of electrolysis cell produced hydrogen and oxygen. The fuel cell unit incorporates an enhanced Orbiter-type cell capable of improved performance at reduced weight. The electrolysis cell features a NiCo2O4 catalyst oxygen evolution eletrode with a porous Teflon cover to retard electrolyte loss. Six complete IRFC assemblies were assembled and performance tested at an operating temperature of 200 F (93.3 C) and reactant pressures up to 170 psia (117.2 n/cu cm) on IRFC No. 4. Anomalous pressure charge/discharge characteristics were encountered during performance evaluation. A reversible fuel cell incorporating a proprietary bi-functional oxygen electrode operated satisfactory at 200 F (93.3 C) at reactant pressures up to 50 psia (41.4 n/cu cm) as a regenerative fuel cell for one cycle, before developing an electrical short in the fuel cell mode. Electrolysis cell 300-hour endurance tests demonstrated the electrolyte retention capability of the electrode Teflon cover and the performance stability of the bi-functional oxygen electrode at high potential.
Martin, Ronald E.↗
Oxygen and iron production by electrolytic smelting of lunar soil
Work during the past year involved two aspects: (1) electrolysis experiments on a larger scale than done before, and (2) collaboration with Carbotek Inc. on design for a lunar magma electrolysis cell. It was demonstrated previously that oxygen can be produced by direct electrolysis of silicate melts. Previous experiments using 50-100 mg of melt have succeeded in measuring melt resistivities, oxygen production efficiencies, and have identified the character of metal products. A series of experiments using 1-8 grams of silicate melt, done in alumina and spinel containers sufficiently large that surface tension effects between the melt and the wall are expected to have minor effect on the behavior of the melt in the region of the electrodes were completed. The purpose of these experiments was to demonstrate the durability of the electrode and container materials, demonstrate the energy efficiency of the electrolysis process, further characterize the nature of the expected metal and spinel products, measure the efficiency of oxygen production and compare to that predicted on the basis of the smaller-scale experiments, and identify any unexpected benefits or problems of the process. Four experimental designs were employed. Detailed results of these experiments are given in the appendix ('Summary of scaling-up experiments'); a general report of the results is given in terms of implications of the experiments on container materials, cathode materials, anode materials, bubble formation and frothing of the melt, cell potential, anode-cathode distance, oxygen efficiency, and energy efficiency.
Colson, R. O.↗
Trade Study of Five In-Situ Propellant Production Systems 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 with water electrolysis and methanol synthesis, 3) Sabatier process for methane product ion with water electrolysis, 4) Sabatier process with water electrolysis and partial methane pyrolysis, and 5) Sabatier/RWGS combination with water electrolysis.
Green, S. T.↗
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.↗
Separation of Carbon Monoxide and Carbon Dioxide for Mars ISRU-Concepts
Solid oxide electrolyzers, such as electrolysis cells utilizing yttria-stabilized zirconia, can produce oxygen from Mars atmospheric carbon dioxide and reject carbon monoxide and unreacted carbon dioxide in a separate stream. The oxygen-production process has been shown to be far more efficient if the high-pressure, unreacted carbon dioxide can be separated and recycled back into the feed stream. Additionally, the mass of the adsorption compressor can be reduced. Also, the carbon monoxide by-product is a valuable fuel for space exploration and habitation, with applications from fuel cells to production of hydrocarbons and plastics. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU. Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, respectively. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU, Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, Research needs for the design shown are as follows: (1) The best adsorbent for the process must be determined. (2) Adsorption isotherms must be measured, both for pure components and mixtures. (3) Mathematical modeling must be performed to provide a solid framework for design. (4) The separation system must be constructed and tested. (5) System integration must be studied.
LeVan, M. Douglas↗
ISRU Technologies for Mars Life Support
Life support systems can take advantage of elements in the atmosphere of Mars to provide for necessary consumables such as oxygen and buffer gas for makeup of leakage. In situ consumables production (ISCP) can be performed effectively in conjunction with in situ propellant production, in which oxygen and methane are manufactured for rocket fuel. This project considers ways of achieving the optimal system objectives from the two sometimes competing objectives of ISPP and ISCP. In previous years we worked on production of a nitrogen-argon buffer gas as a by- product of the CO2 acquisition and compression system. Recently we have been focusing on combined electrolysis of water vapor and carbon dioxide. Combined electrolysis of water vapor and carbon dioxide is essential for reducin,o the complexity of a combined ISPP/ISCP plant. Using a solid oxide electrolysis cell (SOEC) for this combined process would be most advantageous for it allows mainly gas phase reactions, O2 gas delivered from the electrolyzer is free of any H2O vapor, and SOE is already a proven technology for pure CO2 electrolysis. Combined SOEC testing is conducted at The University of Arizona in the Space Technologies Laboratory (STL) of the Aerospace and Mechanical Engineering Department.
Finn, John E.↗
The Effects of Controlled Environment on the Growth of Hydrogenomonas Bacteria in Continuous Cultures
The continuous culture of Hydrogenomonas is the intermediate step of a three-step closed life support cycle directed to the conversion of the human metabolic wastes, urea and carbon dioxide, into breathable oxygen and a food supplement. The potential advantages of this scheme have been discussed in an earlier paper. The other two steps of the complete cycle are: (1) The collection and recovery of the C02 removed from the cabin atmosphere by a regenerable C02 absorber, so that relatively pure C02 gas can be fed into the gas phase of the continuous culture; and (2) the electrolysis of water to produce breathable oxygen for the cabin supply, and by-product hydrogen, which is also fed to the gas phase of the closed culture vessel. There are three specific advantages in the use of this culture: (1) the bacteria use waste urea as a sole nitrogen source during growth, together with the C02 waste as a carbon source; the harvested excess of cells from a steady-state culture is a potential food for man; (2) the organism is not photosynthetic, so the equipment designer need not confine the culture in thin layers to have light available to all parts as is necessary in photosynthesis; and (3) the culture uses the by-product hydrogen from electrolysis as an energy source. Some oxygen must also be supplied to the culture environment, because the energy of the growth process is derived from the metabolic hydrogen-oxygen reaction, with the production of water that can be recycled to the electrolysis cell.
ENVIRONMENTAL CONTROL↗
Design and test status for life support applications of SPE oxygen generation systems
An advanced six-man rated oxygen generation system has been fabricated and tested as part of a NASA/JSC technology development program for a long lived, manned spacecraft life support system. Details of the design and tests results are presented. The system is based on the Solid Polymer Electrolyte (SPE) water electrolysis technology and its nominal operating conditions are 2760 kN/sq m (400 psia) and 355 K (180 F) with an electrolysis module current density capability up to 350 mA/sq cm (326 ASF). The system is centered on a 13-cell SPE water electrolysis module having a single cell active area of 214 sq cm (33 sq in) and it incorporates instrumentation and controls for single pushbutton automatic startup/shutdown, component fault detection and isolation, and self-contained sensors and controls for automatic safe emergency shutdown. The system has been tested in both the orbital cyclic and continuous mode of operation. Various parametric tests have been completed to define the system capability for potential application in spacecraft environmental systems.
Titterington, W. A.↗
Electrolytic hydrogen production: An analysis and review
The thermodynamics of water electrolysis cells is presented, followed by a review of current and future technology of commercial cells. The irreversibilities involved are analyzed and the resulting equations assembled into a computer simulation model of electrolysis cell efficiency. The model is tested by comparing predictions based on the model to actual commercial cell performance, and a parametric investigation of operating conditions is performed. Finally, the simulation model is applied to a study of electrolysis cell dynamics through consideration of an ideal pulsed electrolyzer.
Evangelista, J.↗