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Gasifiers, heat transfer, gas stability, quench, water-gas shift reaction, reforming-methanation, other catalytic reactions, compressors and expanders, acid-gas removal, the fuel cell, and catalytic combustors are described. System pressure drops, efficiency of rotating power equipment, heat exchangers, chemical reactions, steam systems, and the fuel cell subsystems are discussed.
This report presents the results of a study examining the potential of in-situ propellant production (ISPP) on Mars to aid in achieving a low cost Mars Sample Return (MSR) mission. Two versions of such a mission were examined: a baseline version employing a dual string spacecraft, and a light weight version employing single string architecture with selective redundancy. Both systems employed light weight avionics currently being developed by Lockheed Martin, Jet Propulsion Lab and elsewhere in the aerospace community, both used a new concept for a simple, light weight parachuteless sample return capsule, both used a slightly modified version of the Mars Surveyor lander currently under development at Lockheed Martin for flight in 1998, and both used a combination of the Sabatier-electrolysis and reverse water gas shift ISPP systems to produce methane/oxygen propellant on Mars by combining a small quantity of imported hydrogen with the Martian CO2 atmosphere. It was found that the baseline mission could be launched on a Delta 7925 and return a 0.5 kg sample with 82 percent mission launch margin;over and beyond subsystem allocated contingency masses . The lightweight version could be launched on a Mid-Lite vehicle and return a 0.25 kg sample with 11 percent launch margin, over and above subsystem contingency mass allocations.
Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is a waste of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduce the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (i) recover hydrogen from the excess methane produced by the S/E process, (ii) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (iii) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. The goals of a research program on recovery of hydrogen from methane are (in descending priority order): 1) Study the kinetics of pyrolysis to arrive at a pyrolysis reactor design that produces high yields in a confined volume at the lowest possible operating temperature; 2) Study the kinetics of carbon burnoff to determine whether high yields can be obtained in a confined volume at acceptable operating temperatures; and 3) Investigate catalytic techniques for depositing carbon as a fine soot which can be physically separated from the reactor. In the JPL program, we have made significant measurements in regard to goal 1, cursory measurements in regard to goal 2, and would plan to pursue goal 3 if additional resources are secured.
Sabatier/Electrolysis (S/E) is a leading process for producing methane and oxygen for application to Mars ISPP. One significant problem with this process is that it produces an excess of methane for combustion with the amount of oxygen that is produced. Therefore, one must discard roughly half of the methane to obtain the proper stoichiometric methane/oxygen mixture for ascent from Mars. This is wasteful of hydrogen, which must be brought from Earth and is difficult to transport to Mars and store on Mars. To reduced the problem of transporting hydrogen to Mars, the S/E process can be augmented by another process which reduces overall hydrogen requirement. Three conceptual approaches for doing this are (1) recover hydrogen from the excess methane produced by the S/E process, (2) convert the methane to a higher hydrocarbon or other organic with a lower H/C ratio than methane, and (3) use a separate process (such as zirconia or reverse water gas shift reaction) to produce additional oxygen, thus utilizing all the methane produced by the Sabatier process. We report our results here on recovering hydrogen from the excess methane using pyrolysis of methane. Pyrolysis has the advantage that it produces almost pure hydrogen, and any unreacted methane can pass through the S/E process reactor. It has the disadvantage that disposing of the carbon produced by pyrolysis presents difficulties. Hydrogen may be obtained from methane by pyrolysis in the temperature range 10000-12000C. The main reaction products are hydrogen and carbon, though very small amounts of higher hydrocarbons, including aromatic hydrocarbons are formed. The conversion efficiency is about 95% at 12000C. One needs to distinguish between thermodynamic equilibrium conversion and conversion limited by kinetics in a finite reactor.
Software for space systems flight operations has its roots in the early days of the space program when computer systems were incapable of supporting highly complex and flexible control logic. Control systems relied on fast data acquisition and supervisory control from a roomful of systems engineers on the ground. Even though computer hardware and software has become many orders of magnitude more capable, space systems have largely adhered to this original paradigm In an effort to break this mold, Kennedy Space Center (KSC) has invested in the development of model-based diagnosis and control applications for ten years having broad experience in both ground and spacecraft systems and software. KSC has now partnered with Ames Research Center (ARC), NASA's Center of Excellence in Information Technology, to create a new paradigm for the control of dynamic space systems. ARC has developed model-based diagnosis and intelligent planning software that enables spacecraft to handle most routine problems automatically and allocate resources in a flexible way to realize mission objectives. ARC demonstrated the utility of onboard diagnosis and planning with an experiment aboard Deep Space I in 1999. This paper highlights the software control system collaboration between KSC and ARC. KSC has developed a Mars In-situ Resource Utilization testbed based on the Reverse Water Gas Shift (RWGS) reaction. This plant, built in KSC's Applied Chemistry Laboratory, is capable of producing the large amount of Oxygen that would be needed to support a Human Mars Mission. KSC and ARC are cooperating to develop an autonomous, fault-tolerant control system for RWGS to meet the need for autonomy on deep space missions. The paper will also describe how the new system software paradigm will be applied to Vehicle Health Monitoring, tested on the new X vehicles and integrated into future launch processing systems.
This viewgraph presentation provides information on potential In Situ Propellant Production (ISPP) technologies for Mars. The presentation discusses Sabatier reactors, water electrolysis, the advantages of methane fuel, oxygen production, PEM cell electrolyzers, zirconia solid electrolyte cells, reverse water gas shift (RWGS), molten carbonate electrolysis, liquid CO2, and ionic liquids.
The Reverse Water Gas Shift system (RWGS) is a complex physical system designed to produce oxygen from the carbon dioxide atmosphere on Mars. If sent to Mars, it would operate without human supervision, thus requiring a reliable automated system for monitoring and control. The RWGS presents many challenges typical of real-world systems, including: noisy and biased sensors, nonlinear behavior, effects that are manifested over different time granularities, and unobservability of many important quantities. In this paper we model the RWGS using a hybrid (discrete/continuous) Dynamic Bayesian Network (DBN), where the state at each time slice contains 33 discrete and 184 continuous variables. We show how the system state can be tracked using probabilistic inference over the model. We discuss how to deal with the various challenges presented by the RWGS, providing a suite of techniques that are likely to be useful in a wide range of applications. In particular, we describe a general framework for dealing with nonlinear behavior using numerical integration techniques, extending the successful Unscented Filter. We also show how to use a fixed-point computation to deal with effects that develop at different time scales, specifically rapid changes occuring during slowly changing processes. We test our model using real data collected from the RWGS, demonstrating the feasibility of hybrid DBNs for monitoring complex real-world physical systems.
Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems.
The Mars atmospheric capture and gas separation project is selecting, developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Trace gases will be required to be separated from Martian atmospheric gases to provide pure C02 to processing elements. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and should be captured as welL To achieve these goals, highly efficient gas separation processes will be required. These gas separation techniques are also required across various areas within the ISRU project to support various consumable production processes. The development of innovative gas separation techniques will evaluate the current state-of-the-art for the gas separation required, with the objective to demonstrate and develop light-weight, low-power methods for gas separation. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from un-reacted carbon oxides (C02- CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, (3) carbon oxides from oxygen from a trash/waste processing reaction, and (4) helium from hydrogen or oxygen from a propellant scavenging process. Potential technologies for the separations include freezers, selective membranes, selective solvents, polymeric sorbents, zeolites, and new technologies. This paper and presentation will summarize the results of an extensive literature review and laboratory evaluations of candidate technologies for the capture and separation of C02 and other relevant gases.
Recent national policy statements have established that the ultimate destination of NASA's human exploration program is Mars. In Situ Resource Utilization (ISRU) is a key technology required to ,enable such missions and it is appropriate to review progress in this area and continue to advance the systems required to produce rocket propellant, oxygen, and other consumables on Mars using the carbon dioxide atmosphere and other potential resources. The Mars Atmospheric Capture and Gas separation project is selecting, developing, and demonstrating techniques to capture and purify Martian atmospheric gases for their utilization for the production of hydrocarbons, oxygen, and water in ISRU systems. Trace gases will be required to be separated from Martian atmospheric gases to provide pure CO2 to processing elements. In addition, other Martian gases, such as nitrogen and argon, occur in concentrations high enough to be useful as buffer gas and should be captured as well. To achieve these goals, highly efficient gas separation processes will be required. These gas separation techniques are also required across various areas within the ISRU project to support various consumable production processes. The development of innovative gas separation techniques will evaluate the current state-of-the-art for the gas separation required, with the objective to demonstrate and develop light-weight, low-power methods for gas separation. Gas separation requirements include, but are not limited to the selective separation of: (1) methane and water from unreacted carbon oxides (C02-CO) and hydrogen typical of a Sabatier-type process, (2) carbon oxides and water from unreacted hydrogen from a Reverse Water-Gas Shift process, (3)/carbon oxides from oxygen from a trash/waste processing reaction, and (4) helium from hydrogen or oxygen from a propellant scavenging process. Potential technologies for the separations include' freezers, selective membranes, selective solvents, polymeric sorbents, zeolites, and new technologies. This paper summarizes the results of an extensive literature review of candidate technologies for the capture and separation of CO2 and other relevant gases. This information will be used to prioritize the technologies to be developed further during this and other ISRU projects.
Utilizing carbon dioxide to produce water and hence oxygen is critical for sustained manned missions in space, and to support both NASA's cabin Atmosphere Revitalization System (ARS) and In-Situ Resource Utilization (ISRU) concepts. For long term missions beyond low Earth orbit, where resupply is significantly more difficult and costly, open loop ARS, like Sabatier, consume inputs such as hydrogen. The Bosch process, on the other hand, has the potential to achieve complete loop closure and is hence a preferred choice. However, current single stage Bosch reactor designs suffer from a large recycle penalty due to slow reaction rates and the inherent limitation in approaching thermodynamic equilibrium. Developmental efforts are seeking to improve upon the efficiency (hence reducing the recycle penalty) of current single stage Bosch reactors which employ traditional steel wool catalysts. Precision Combustion, Inc. (PCI), with support from NASA, has investigated the potential for utilizing catalysts supported over short-contact time Microlith substrates for the Bosch reaction to achieve faster reaction rates, higher conversions, and a reduced recycle flows. Proof-of-concept testing was accomplished for a staged Bosch process by splitting the chemistry in two separate reactors, first being the reverse water-gas-shift (RWGS) and the second being the carbon formation reactor (CFR) via hydrogenation and/or Boudouard. This paper presents the results from this feasibility study at various operating conditions. Additionally, results from two 70 hour durability tests for the RWGS reactor are discussed.
Oxygen and water resupply make open loop atmosphere revitalization (AR) systems unfavorable for long-term missions beyond low Earth orbit. Crucial to closing the AR loop are carbon dioxide reduction systems with low mass and volume, minimal power requirements, and minimal consumables. For this purpose, NASA is exploring using Bosch-based systems. The Bosch process is favorable over state-of-the-art Sabatier-based processes due to complete loop closure. However, traditional operation of the Bosch required high reaction temperatures, high recycle rates, and significant consumables in the form of catalyst resupply due to carbon fouling. A number of configurations have been proposed for next-generation Bosch systems. First, alternative catalysts (catalysts other than steel wool) can be used in a traditional single-stage Bosch reactor to improve reaction kinetics and increase carbon packing density. Second, the Bosch reactor may be split into separate stages wherein the first reactor stage is dedicated to carbon monoxide and water formation via the reverse water-gas shift reaction and the second reactor stage is dedicated to carbon formation. A series system will enable maximum efficiency of both steps of the Bosch reaction, resulting in optimized operation and maximum carbon formation rate. This paper details the results of testing of both single-stage and two-stage Bosch systems with alternative catalysts at reduced temperatures. These results are compared to a traditional Bosch system operated with a steel wool catalyst.
Future manned missions to deep space or planetary surfaces will undoubtedly require highly robust, efficient, and regenerable life support systems that require minimal consumables. To meet this requirement, NASA continues to explore a Bosch‐based carbon dioxide reduction system to recover oxygen from CO2. In order to improve the equivalent system mass of Bosch systems, we seek to design and test a "Series Bosch" system in which two reactors in series are optimized for the two steps of the reaction, as well as to explore the use of in situ materials as carbon deposition catalysts. Here we report recent developments in this effort including assembly and initial testing of a Reverse Water‐Gas Shift reactor (RWGSr) and initial testing of two gas separation membranes. The RWGSr was sized to reduce CO2 produced by a crew of four to carbon monoxide as the first stage in a Series Bosch system. The gas separation membranes, necessary to recycle unreacted hydrogen and CO2, were similarly sized. Additionally, we report results of preliminary experiments designed to determine the catalytic properties of Martian and Lunar regolith simulant for the carbon deposition step.
Future manned missions to deep space or planetary surfaces will undoubtedly incorporate highly robust, efficient, and regenerable life support systems that require minimal consumables. To meet this requirement, NASA continues to explore a Bosch-based carbon dioxide reduction system to recover oxygen from CO2. In order to improve the equivalent system mass of Bosch systems, we seek to design and test a "Series Bosch" system in which two reactors in series are optimized for the two steps of the reaction, as well as to explore the use of in situ materials as carbon deposition catalysts. Here we report recent developments in this effort including assembly and initial testing of a Reverse Water-Gas Shift reactor (RWGSr) and initial testing of two gas separation membranes. The RWGSr was sized to reduce CO2 produced by a crew of four to carbon monoxide as the first stage in a Series Bosch system. The gas separation membranes, necessary to recycle unreacted hydrogen and CO2, were similarly sized. Additionally, we report results of preliminary experiments designed to determine the catalytic properties of Martian regolith simulant for the carbon formation step.
Long‐duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series‐Bosch (S‐Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S‐Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water‐Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand‐alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spend regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith‐based CFR are discussed.
Long-duration surface missions to the Moon or Mars will require life support systems that maximize resource recovery to minimize resupply from Earth. To address this need, NASA previously proposed a Series-Bosch (S-Bosch) oxygen recovery system, based on the Bosch process, which can theoretically recover 100% of the oxygen from metabolic carbon dioxide. Bosch processes have the added benefits of the potential to recover oxygen from atmospheric carbon dioxide and the use of regolith materials as catalysts, thereby eliminating the need for catalyst resupply from Earth. In 2012, NASA completed an initial design for an S-Bosch development test stand that incorporates two catalytic reactors in series including a Reverse Water-Gas Shift (RWGS) Reactor and a Carbon Formation Reactor (CFR). In 2013, fabrication of system components, with the exception of a CFR, and assembly of the test stand was initiated. Stand-alone testing of the RWGS reactor was completed to compare performance with design models. Continued testing of Lunar and Martian regolith simulants provided sufficient data to design a CFR intended to utilize these materials as catalysts. Finally, a study was conducted to explore the possibility of producing bricks from spent regolith catalysts. The results of initial demonstration testing of the RWGS reactor, results of continued catalyst performance testing of regolith simulants, and results of brick material properties testing are reported. Additionally, design considerations for a regolith-based CFR are discussed.
The atmosphere of Mars, which is 96 percent carbon dioxide (CO2), is a rich resource for the human exploration of the red planet, primarily by the production of rocket propellants and oxygen for life support. Three recent projects led by NASAs Kennedy Space Center have been investigating the processing of CO2. The first project successfully demonstrated the Mars Atmospheric Processing Module (APM), which freezes CO2 with cryocoolers and combines sublimated CO2 with hydrogen to make methane and water. The second project absorbs CO2 with Ionic Liquids and electrolyzes it with water to make methane and oxygen, but with limited success so far. A third project plans to recover up to 100 of the oxygen in spacecraft respiratory CO2. A combination of the Reverse Water Gas Shift reaction and the Boudouard reaction eventually fill the reactor up with carbon, stopping the process. A system to continuously remove and collect carbon has been tested with encouraging results.
The atmosphere of Mars, which is approximately 95% carbon dioxide (CO2), is a rich resource for the human exploration of the red planet, primarily by the production of rocket propellants and oxygen for life support. Three recent projects led by NASA's Kennedy Space Center have been investigating the processing of CO2. The first project successfully demonstrated the Mars Atmospheric Processing Module (APM), which freezes CO2 with cryocoolers and combines sublimated CO2 with hydrogen to make methane and water. The second project absorbs CO2 with Ionic Liquids and electrolyzes it with water to make methane and oxygen, but with limited success so far. A third project plans to recover up to 100% of the oxygen in spacecraft respiratory CO2. A combination of the Reverse Water Gas Shift reaction and the Boudouard reaction eventually fill the reactor up with carbon, stopping the process. A system to continuously remove and collect carbon is under construction.