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Bosch Reactor Development for High Percentage Oxygen Recovery from Carbon Dioxide

This next Generation Life Support Project entails the development and demonstration of Bosch reaction technologies to improve oxygen recovery from metabolically generated oxygen and/or space environments. A primary focus was placed on alternate carbon formation reactor concepts to improve useful catalyst life for space vehicle applications, and make use of in situ catalyst resources for non-terrestrial surface missions. Current state-of-the-art oxygen recovery systems onboard the International Space Station are able to effectively recover approximately 45 percent of the oxygen consumed by humans and exhausted in the form of carbon dioxide (CO2). Excess CO2 is vented overboard and the oxygen contained in the molecules is lost. For long-duration missions beyond the reaches of Earth for resupply, it will be necessary to recover greater amounts of constituents such as oxygen that are necessary for sustaining life. Bosch technologies theoretically recover 100 percent of the oxygen from CO2, producing pure carbon as the sole waste product. Challenges with this technology revolve around the carbon product fouling catalyst materials, drastically limiting catalyst life. This project successfully demonstrated techniques to extend catalyst surface area exposure times to improve catalyst life for vehicle applications, and demonstrated the use of Martian and lunar regolith as viable catalyst Bosch Reactor Development for High Percentage Oxygen Recovery From Carbon Dioxide materials for surface missions. The Bosch process generates carbon nanotube formation within the regolith, which has been shown to improve mechanical properties of building materials. Production of bricks from post reaction regolith for building and radiation shielding applications were also explored.

Howard, David

Demonstration of Robustness and Integrated Operation of a Series-Bosch System

Manned missions beyond low Earth orbit will require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. Bosch technology is one option to maximize oxygen recovery, in the form of water, from metabolically-produced carbon dioxide (CO2). A two stage approach to Bosch, called Series-Bosch, reduces metabolic CO2 with hydrogen (H2) to produce water and solid carbon using two reactors: a Reverse Water-Gas Shift (RWGS) reactor and a carbon formation (CF) reactor. Previous development efforts demonstrated the stand-alone performance of a NASA-designed RWGS reactor designed for robustness against carbon formation, two membrane separators intended to maximize single pass conversion of reactants, and a batch CF reactor with both transit and surface catalysts. In the past year, Precision Combustion, Inc. (PCI) developed and delivered a RWGS reactor for testing at NASA. The reactor design was based on their patented Microlith® technology and was first evaluated under a Phase I Small Business Innovative Research (SBIR) effort in 2010. The RWGS reactor was recently evaluated at NASA to compare its performance and operating conditions with NASA's RWGS reactor. The test results will be provided in this paper. Separately, in 2015, a semi-continuous CF reactor was designed and fabricated at NASA based on the results from batch CF reactor testing. The batch CF reactor and the semi-continuous CF reactor were individually integrated with an upstream RWGS reactor to demonstrate the system operation and to evaluate performance. Here, we compare the performance and robustness to carbon formation of both RWGS reactors. We report the results of the integrated operation of a Series-Bosch system and we discuss the technology readiness level.

Abney, Morgan B.

Evolving Maturation of the Series-Bosch System

Human exploration missions to Mars and other destinations beyond low Earth orbit require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. In order to meet this requirement, NASA has continued the development of a Series-Bosch System, a two stage reactor process that reduces carbon dioxide (CO2) with hydrogen (H2) to produce water and solid carbon. Theoretically, the Bosch process can recover 100% of the oxygen (O2) from CO2 in the form of water, making it an attractive option for long duration missions. The Series Bosch system includes a reverse water gas shift (RWGS) reactor, a carbon formation reactor (CFR), an H2 extraction membrane, and a CO2 extraction membrane. In 2016, the results of integrated testing of the Series Bosch system showed great promise and resulted in design modifications to the CFR to further improve performance. This year, integrated testing was conducted with the modified reactor to evaluate its performance and compare it with the performance of the previous configuration. Additionally, a CFR with the capability to load new catalyst and remove spent catalyst in-situ was built. Flow demonstrations were performed to evaluate both the catalyst loading and removal process and the hardware performance. The results of the integrated testing with the modified CFR as well as the flow demonstrations are discussed in this paper.

Stanley, Christine

Evolving Maturation of the Series-Bosch System

Human exploration missions to Mars and other destinations beyond low Earth orbit require highly robust, reliable, and maintainable life support systems that maximize recycling of water and oxygen. In order to meet this requirement, NASA has continued the development of a Series-Bosch System, a two stage reactor process that reduces carbon dioxide (CO2) with hydrogen (H2) to produce water and solid carbon. Theoretically, the Bosch process can recover 100% of the oxygen (O2) from CO2 in the form of water, making it an attractive option for long duration missions. The Series Bosch system includes a reverse water gas shift (RWGS) reactor, a carbon formation reactor (CFR), an H2 extraction membrane, and a CO2 extraction membrane. In 2016, the results of integrated testing of the Series Bosch system showed great promise and resulted in design modifications to the CFR to further improve performance. This year, integrated testing was conducted with the modified reactor to evaluate its performance and compare it with the performance of the previous configuration. Additionally, a CFR with the capability to load new catalyst and remove spent catalyst in-situ was built. Flow demonstrations were performed to evaluate both the catalyst loading and removal process and the hardware performance. The results of the integrated testing with the modified CFR as well as the flow demonstrations are discussed in this paper.

Abney, Morgan B.

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Bosch Carbon Catalyst Regeneration in Water III: Experiments for and Related to Thermal Shock

Bosch technology has the potential to close the atmospheric revitalization loop by providing theoretically 100% regeneration of metabolic carbon dioxide into oxygen. The main obstacle to using Bosch technology is over-pressurization issues in the carbon formation reactor. Prior work on Bosch catalyst regeneration established that agitating carbon coated beads in water broke up pressure causing clogs and regenerated the catalyst surface. This process proved to be time consuming with experiments taking at least one hour to regenerate ten grams of carbon coated beads. In an attempt to shorten the processing time, thermally shocking the carbon coated beads prior to mechanical agitation was tested. Agitating the carbon coated beads after exposure to a saturated steam environment was also tested to ensure that the steam generated by thermally shocking the carbon coated beads would not cause adverse effects. The rationale behind thermally shocking the carbon coated beads is that the bead would pull away from the carbon shell due to a difference in the thermal expansion coefficients. The results of this project show that the processing time can be cut in half when compared to previous work, and that saturated steam has little to no effect on regeneration.

Bosch Process

The Bosch process.

Many previous studies have been carried out to elucidate certain aspects of the Bosch process wherein CO2 is reacted over an iron catalyst to form carbon and water at temperatures around 1100 F. These results are assembled, and with the aid of new experimental data, are used to analyze the various reactions involved. It is shown that CO2 and H2 will not usually react to deposit carbon unless water is removed in a recycle loop. The critical importance of large catalyst areas is stressed relative to catalyst pretreatment processes. It is shown that in most operating Bosch reactions, mass transfer controls the rate of reaction, and it is suggested that the carbon filaments found are the expected result of such a rate limiting process. Typical recycle gas mixtures are considered, and maximum water yields are determined from various cases. A few suggestions are made to improve Bosch reaction performance, and a number of unresolved problems are noted.

Meissner, H. P.

Performance characterization of a Bosch CO sub 2 reduction subsystem

The performance of Bosch hardware at the subsystem level (up to five-person capacity) in terms of five operating parameters was investigated. The five parameters were: (1) reactor temperature, (2) recycle loop mass flow rate, (3) recycle loop gas composition (percent hydrogen), (4) recycle loop dew point and (5) catalyst density. Experiments were designed and conducted in which the five operating parameters were varied and Bosch performance recorded. A total of 12 carbon collection cartridges provided over approximately 250 hours of operating time. Generally, one cartridge was used for each parameter that was varied. The Bosch hardware was found to perform reliably and reproducibly. No startup, reaction initiation or carbon containment problems were observed. Optimum performance points/ranges were identified for the five parameters investigated. The performance curves agreed with theoretical projections.

Heppner, D. B.

Bosch - An alternate CO2 reduction technology

The Bosch process is the most promising CO2 reduction concept for future prolonged space missions. The paper presents the design of a three-person-capacity preprototype B-CRS (Bosch-based CO2 Reduction Subsystem). It is sized to reduce 3.0 kg/d CO2 generated by the crew and to supply the product water to an O2 generation subsystem to obtain O2. The design supports future development of the B-CRS as an alternative CO2 reduction subsystem to the Sabatier-based process presently under test at NASA. The discussion covers the Bosch CO2 reduction concept, process and hardware description, performance parameters, design specifications, subsystem schematic and operation, mechanical subsystem summary, control/monitor instrumentation, and subsystem packaging. A B-CRS with a proven technological base is an attractive CO2 reduction subsystem that eliminates overboard venting.

Heppner, D. B.

Bosch CO2 reduction unit research and development.

Development of Bosch CO2 reduction units for manned spacecraft application has been in progress for a decade. The Bosch process catalytically reacts CO2 with H2 to produce water and carbon. The water may then be electrolyzed to close the biological oxygen and process hydrogen loops. A critical problem has been to confine the reaction so that carbon does not block flow and stop the process. Reaction isolation within a replaceable catalyst cartridge has been successfully demonstrated. Objectives of the current development program are a 25% reduction in operating power, an 80% reduction in expendable weight, and minimized resupply volume.

Holmes, R. F.

Bosch CO2 Reduction System Development

Development of a Bosch process CO2 reduction unit was continued, and, by means of hardware modifications, the performance was substantially improved. Benefits of the hardware upgrading were demonstrated by extensive unit operation and data acquisition in the laboratory. This work was accomplished on a cold seal configuration of the Bosch unit.

Holmes, R. F.

Prototype Bosch CO2 reduction subsystem for the RLSE experiment

Requirements for the Bosch carbon dioxide reduction subsystem were established in a study of regenerative life support evaluation experiments. A detailed design is presented including a schematic, components list and characteristics, requirements summaries, and complete definition of life systems' advanced control/monitor instrumentation applied to the Bosch subsystem. Design information needed to proceed with the final design and fabrication of a preprototype system is presented.

Heppner, D. B.

Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts

The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

Manning, M. P.

Developments of Bosch Process Architectures for ISRU Terrestrial Applications

To effectively realize NASA’s goals of a sustainable presence on the Moon and be-yond, In-Situ Resource Utilization (ISRU) must be leveraged. To reduce launch mass for space missions, commodities such as oxygen and carbon can be produced in-situ. Oxygen can be used for life support and as a propellant, and carbon can be used for battery production, filtration, additive manufacturing, and steel casting. Carbon is a required reactant in the carbothermal reduction process, a leading candidate for oxygen production on the lunar surface. To pro-duce these consumables, the Carbon Utilization Technology for Lunar and Atmospheric Systems (CUTLAS) project is developing architectures that leverage the Bosch process. The Bosch process re-acts CO 2 and H 2 to produce carbon powder and water, which can then be electrolyzed, leaving O 2 and recycled H 2 . This process is also applicable to carbon dioxide emissions on Earth.

Carbon capture

Bosch CO2 Reduction System Development

Refinements in the design of a Bosch CO2 reduction unit for spacecraft O2 production are described. Sealing of the vacuum insulation jacket was simplified so that high vacuum and high insulation performance are easily maintained. The device includes a relatively simple concentric shell recuperative heat exchanger which operates at approximately 95% temperature effectiveness and helps lower power consumption. The influence of reactor temperature, pressure, and recycle gas composition on power consumption was investigated. In general, precise control is not required since power consumption is not very sensitive to moderate variations of these parameters near their optimum values. There are two process rate control modes which match flow rate to process demand. Catalyst conditioning, support, and packing pattern developments assure consistent starts, reduced energy consumption, and extended cartridge life. Operation levels for four or five men were maintained with overall power input values of 50 to 60 watts per man.

Holmes, R. F.

A mature Bosch CO2 reduction technology

The reduction of CO2 is one of the steps in closing the oxygen loop for long-duration manned space missions. Several units utilizing the Bosch process, which catalytically reduces CO2 with hydrogen, have been built and operated during the past decade. Each contributed substantial information affecting subsequent designs. Early challenges were primarily concerned with carbon control, materials durability, and reliability of reaction initiation. These were followed by concern about power consumption, expendable weight, volume, and process rate control. Suitable materials and techniques for carbon containment and process reliability have been demonstrated. Power requirements have been reduced by almost an order of magnitude. Methods for significant reductions in expendable weight and volume have been developed. The technology is at a state of maturity directly applicable to designs for space missions.

King, C. D.

Integrated testing of an electrochemical depolarized CO2 concentrator /EDC/ and a Bosch CO2 reduction subsystem /BRS/

An oxygen reclamation system (ORS) in a spacecraft has the task to revitalize the spacecraft atmosphere by recovering the elementary oxygen from metabolically produced carbon dioxide and water vapor. Life support subsystems which can form such an ORS are an electrochemical depolarized carbon dioxide concentrator (EDC), a Bosch carbon dioxide reduction subsystem (BRS), and an oxygen generation subsystem (OGS). A total recovery of the oxygen from metabolically generated carbon dioxide can be obtained with the aid of system composed of the considered three subsystems. Attention is given to the control concept which assures an integrated operation of the EDC, BRS, and OGS. A description is presented of the test results obtained during 86 days of testing.

Schubert, F. H.