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NASA NTRS2014

Catalytic Tar Reduction for Assistance in Thermal Conversion of Space Waste for Energy Production

The Trash to Gas (TtG) project investigates technologies for converting waste generated during spaceflight into various resources. One of these technologies was gasification, which employed a downdraft reactor designed and manufactured at NASA's Kennedy Space Center (KSC) for the conversion of simulated space trash to carbon dioxide. The carbon dioxide would then be converted to methane for propulsion and water for life support systems. A minor byproduct of gasification includes large hydrocarbons, also known as tars. Tars are unwanted byproducts that add contamination to the product stream, clog the reactor and cause complications in analysis instrumentation. The objective of this research was to perform reduction studies of a mock tar using select catalysts and choose the most effective for primary treatment within the KSC downdraft gasification reactor. Because the KSC reactor is operated at temperatures below typical gasification reactors, this study evaluates catalyst performance below recommended catalytic operating temperatures. The tar reduction experimentation was observed by passing a model tar vapor stream over the catalysts at similar conditions to that of the KSC reactor. Reduction in tar was determined using gas chromatography. Tar reduction efficiency and catalyst performances were evaluated at different temperatures.

energy conversion↗

NASA NTRS2018

Utilizing Ionic Liquids to Enable the Future of Closed-Loop Life Support Technology

Current oxygen recovery technology onboard the International Space Station only recovers approximately 50% of the oxygen from metabolic carbon dioxide, thus requiring resupply mass in order to sustain life onboard. Future long duration manned missions will require maximum oxygen recovery in order to reduce resupply mass. Complete recovery of oxygen can be achieved through Bosch technology. The challenge with this technology is that the solid carbon produced during the process results in undesired catalyst resupply mass. Although there have been several approaches to solve this challenge, in order to totally eliminate the need for resupply only one potential process has been identified. This process is a fully-regenerable Ionic Liquid (IL)-based Bosch system that employs in situ resources. In 2016, efforts were made that proved the feasibility of an IL-based Bosch system. ILs were used to electroplate iron onto a copper substrate and to regenerate the iron by extracting the iron from the copper substrate and product carbon. In 2017, efforts were initiated to scale the proposed technology. Here we report the results of those efforts as well as an IL-based Bosch system concept and basic reactor design.

Brown, Brittany R.↗

NASA NTRS1992

Catalytic methods using molecular oxygen for treatment of PMMS and ECLSS waste streams, volume 2

Catalytic oxidation has proven to be an effective addition to the baseline sorption, ion exchange water reclamation technology which will be used on Space Station Freedom (SSF). Low molecular weight, polar organics such as alcohols, aldehydes, ketones, amides, and thiocarbamides which are poorly removed by the baseline multifiltration (MF) technology can be oxidized to carbon dioxide at low temperature (121 C). The catalytic oxidation process by itself can reduce the Total Organic Carbon (TOC) to below 500 ppb for solutions designed to model these waste waters. Individual challenges by selected contaminants have shown only moderate selectivity towards particular organic species. The combined technology is applicable to the more complex waste water generated in the Process Materials Management System (PMMS) and Environmental Control and Life Support System (ECLSS) aboard SSF. During the phase 3 Core Module Integrated Facility (CMIF) water recovery tests at NASA MSFC, real hygiene waste water and humidity condensate were processed to meet potable specifications by the combined technology. A kinetic study of catalytic oxidation demonstrates that the Langmuir-Hinshelwood rate equation for heterogeneous catalysts accurately represent the kinetic behavior. From this relationship, activation energy and rate constants for acetone were determined.

Akse, James R.↗

NASA NTRS2018

Static Controls Performance Tool for Lunar Landers

This document presents a static analysis tool used to evaluate the controllability of Lunar landers. This was created as part of the NASA Lunar Cargo Transportation and Landing by Soft Touchdown (Lunar CATALYST) program. This tool is capable of accepting typical design information such as location and direction of thrusters, maximum thruster forces, gravity vectors, and center of mass locations. The tool evaluates how far the center of gravity can move from its starting position while still maintaining control. This type of analysis is intended to support results produced by time domain simulations. The code created for this project was implemented in Python, and it was designed to be integrated into systems level optimization tools to yield first-cut results on optimal thruster placement.

Aretskin-Hariton, Eliot D.↗

NASA NTRS1996

Microwave Regenerable Air Purification Device

The feasibility of using microwave power to thermally regenerate sorbents loaded with water vapor, CO2, and organic contaminants has been rigorously demonstrated. Sorbents challenged with air containing 0.5% CO2, 300 ppm acetone, 50 ppm trichloroethylene, and saturated with water vapor have been regenerated, singly and in combination. Microwave transmission, reflection, and phase shift has also been determined for a variety of sorbents over the frequency range between 1.3-2.7 GHz. This innovative technology offers the potential for significant energy savings in comparison to current resistive heating methods because energy is absorbed directly by the material to be heated. Conductive, convective and radiative losses are minimized. Extremely rapid heating is also possible, i.e., 1400 C in less than 60 seconds. Microwave powered thermal desorption is directly applicable to the needs of Advance Life Support in general, and of EVA in particular. Additionally, the applicability of two specific commercial applications arising from this technology have been demonstrated: the recovery for re-use of acetone (and similar solvents) from industrial waste streams using a carbon based molecular sieve; and the separation and destruction of trichloroethylene using ZSM-5 synthetic zeolite catalyst, a predominant halocarbon environmental contaminant. Based upon these results, Phase II development is strongly recommended.

Atwater, James E.↗

NASA NTRS2005

A Theoretical Investigation of Oxidation Efficiency of a Volatile Removal Assembly Reactor Under Microgravity Conditions

Volatile Removal Assembly (VRA) is a subsystem of the Closed Environment Life Support System (CELSS) installed in the International Space Station. It is used for removing contaminants (volatile organics) in the wastewater produced by the space station crews. The major contaminants are formic acid, ethanol, and propylene glycol. The VRA contains a slim packbed reactor (3.5 cm diameter and four 28 cm long tubes in series) to perform catalyst oxidation of wastewater at elevated pressure and temperature under microgravity conditions. In the reactor, the contaminants are burned with oxygen gas (O2) to form water and carbon dioxide (CO2) that dissolves in the water stream. Optimal design of the reactor requires a thorough understanding about how the reactor performs under microgravity conditions. The objective of this study was to develop a mathematical model to interpret experimental data obtained from normal and microgravity conditions, and to predict the performance of VRA reactor under microgravity conditions. Catalyst oxidation kinetics and the total oxygen-water contact area control the efficiency of catalyst oxidation for mass transfer, which depends on oxygen gas holdup and distribution in the reactor. The process involves bubbly flow in porous media with chemical reactions in microgravity environment. This presents a unique problem in fluid dynamics that has not been studied. Guo et al. (2004) developed a mathematical model that predicts oxygen holdup in the VRA reactor. No mathematical model has been found in the literature that can be used to predict the efficiency of catalyst oxidation under microgravity conditions.

Guo, Boyun↗

NASA NTRS2010

Producing Hydrogen by Plasma Pyrolysis of Methane

Plasma pyrolysis of methane has been investigated for utility as a process for producing hydrogen. This process was conceived as a means of recovering hydrogen from methane produced as a byproduct of operation of a life-support system aboard a spacecraft. On Earth, this process, when fully developed, could be a means of producing hydrogen (for use as a fuel) from methane in natural gas. The most closely related prior competing process - catalytic pyrolysis of methane - has several disadvantages: a) The reactor used in the process is highly susceptible to fouling and deactivation of the catalyst by carbon deposits, necessitating frequent regeneration or replacement of the catalyst. b) The reactor is highly susceptible to plugging by deposition of carbon within fixed beds, with consequent channeling of flow, high pressure drops, and severe limitations on mass transfer, all contributing to reductions in reactor efficiency. c) Reaction rates are intrinsically low. d) The energy demand of the process is high.

Atwater, James↗

NASA NTRS2015

Resource Prospector: A Lunar Volatiles Prospecting and ISRU Demonstration Mission

A variety of recent observations have indicated several possible reservoirs of water and other volatiles. These volatiles, and in particular water, have the potential to be a valuable or enabling resource for future exploration. NASA's Human Exploration and Operations Mission Directorate (HEOMD) Advanced Exploration Systems (AES) is supporting the development of Resource Prospector (RP) to explore the distribution and concentration of lunar volatiles prospecting and to demonstrate In-Situ Resource Utilization (ISRU). The mission includes a NASA developed rover and payload, and a lander will most likely be a contributed element by an international partner or the Lunar Cargo Transportation and Landing by Soft Touchdown (CATALYST) initiative. The RP payload is designed to: (1) locate near-subsurface volatiles, (2) excavate and analyze samples of the volatile-bearing regolith, and (3) demonstrate the form. extractability and usefulness of the materials. RP is being designed with thought given to its extensibility to resource prospecting and ISRU on other airless bodies and Mars. This presentation will describe the Resource Prospector mission, the payload and measurements, and concept of operations

In-Situ Resource Utilization (ISRU)↗

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 NTRS2017

Ionic Liquids Enabling Revolutionary Closed-Loop Life Support

Minimizing resupply from Earth is essential for future long duration manned missions. The current oxygen recovery system aboard the International Space Station is capable of recovering approximately 50% of the oxygen from metabolic carbon dioxide. For long duration manned missions, a minimum of 75% oxygen recovery is targeted with a goal of greater than 90%. Theoretically, the Bosch process can recover 100% of oxygen, making it a promising technology for oxygen recovery for long duration missions. However, the Bosch process produces elemental carbon which ultimately fouls the catalyst. Once the catalyst performance is compromised, it must be replaced resulting in undesired resupply mass. Based on the performance of a Bosch system designed by NASA in the 1990's, a three year Martian mission would require approximately 1315 kg (2850 lbs) of catalyst resupply. It may be possible to eliminate catalyst resupply with a fully regenerable system using an Ionic Liquid (IL)-based Bosch system. In 2016, we reported the feasibility of using ILs to produce an iron catalyst on a copper substrate and to regenerate the iron catalyst by extracting the iron from the copper substrate and product carbon. Additionally, we described a basic system concept for an IL-based Bosch. Here we report the results of efforts to scale catalyst preparation, catalyst regeneration, and to scale the carbon formation processing rate of a single reactor.

Brown, Brittany R.↗

NASA NTRS2017

Ionic Liquids Enabling Revolutionary Closed-Loop Life Support

Minimizing resupply from Earth is essential for future long duration manned missions. The current oxygen recovery system aboard the International Space Station is capable of recovering approximately 50% of the oxygen from metabolic carbon dioxide. For long duration manned missions, a minimum of 75% oxygen recovery is targeted with a goal of greater than 90%. Theoretically, the Bosch process can recover 100% of oxygen, making it a promising technology for oxygen recovery for long duration missions. However, the Bosch process produces elemental carbon which ultimately fouls the catalyst. Once the catalyst performance is compromised, it must be replaced resulting in undesired resupply mass. Based on the performance of a Bosch system designed by NASA in the 1990's, a three year Martian mission would require approximately 1315 kg (2850 lbs) of catalyst resupply. It may be possible to eliminate catalyst resupply with a fully regenerable system using an Ionic Liquid (IL)-based Bosch system. In 2016, we reported the feasibility of using ILs to produce an iron catalyst on a copper substrate and to regenerate the iron catalyst by extracting the iron from the copper substrate and product carbon. Additionally, we described a basic system concept for an IL-based Bosch. Here we report the results of efforts to scale catalyst preparation, to scale catalyst regeneration, and to scale the carbon formation processing rate of a single reactor.

Brown, Brittany R.↗

NASA NTRS2011

Compact and Lightweight Sabatier Reactor for Carbon Dioxide Reduction

The utilization of CO2 to produce life support consumables, such as O2 and H2O, via the Sabatier reaction is an important aspect of NASA s cabin Atmosphere Revitalization System and In-Situ Resource Utilization architectures for both low-earth orbit and long-term manned space missions. In the current International Space Station (ISS) and other low orbit missions, metabolically-generated CO2 is removed from the cabin air and vented into space, resulting in a net loss of O2. This requires a continuous resupply of O2 via water electrolysis, and thus highlights the need for large water storage capacity. For long-duration space missions, the amount of life support consumables is limited and resupply options are practically nonexistent, thus atmosphere resource management and recycle becomes crucial to significantly reduce necessary O2 and H2O storage. Additionally, the potential use of the Martian CO2-rich atmosphere and Lunar regolith to generate life support consumables and propellant fuels is of interest to NASA. Precision Combustion, Inc. (PCI) has developed a compact, lightweight Microlith(Registered TradeMark)-based Sabatier (CO2 methanation) reactor which demonstrates the capability of achieving high CO2 conversion and near 100% CH4 selectivity at space velocities of 30,000-60,000 hr-1. The combination of the Microlith(Registered TradeMark) substrates and durable, novel catalyst coating permitted efficient Sabatier reactor operation that favors high reactant conversion, high selectivity, and long-term durability. This paper presents the reactor development and performance results at various operating conditions. Additionally, results from 100-hr durability tests and mechanical vibration tests are discussed.

Junaedi, Christian↗

NASA NTRS2001

The sugar model: catalytic flow reactor dynamics of pyruvaldehyde synthesis from triose catalyzed by poly-l-lysine contained in a dialyzer

The formation of pyruvaldehyde from triose sugars was catalyzed by poly-l-lysine contained in a small dialyzer with a 100 molecular weight cut off (100 MWCO) suspended in a much larger triose substrate reservoir at pH 5.5 and 40 degrees C. The polylysine confined in the dialyzer functioned as a catalytic flow reactor that constantly brought in triose from the substrate reservoir by diffusion to offset the drop in triose concentration within the reactor caused by its conversion to pyruvaldehyde. The catalytic polylysine solution (400 mM, 0.35 mL) within the dialyzer generated pyruvaldehyde with a synthetic intensity (rate/volume) that was 3400 times greater than that of the triose substrate solution (12 mM, 120 mL) outside the dialyzer. Under the given conditions the final yield of pyruvaldehyde was greater than twice the weight of the polylysine catalyst. During the reaction the polylysine catalyst was poisoned presumably by reaction of its amino groups with aldehyde reactants and products. Similar results were obtained using a dialyzer with a 500 MWCO. The dialyzer method of catalyst containment was selected because it provides a simple and easily manipulated experimental system for studying the dynamics and evolutionary development of confined autocatalytic processes related to the origin of life under anaerobic conditions.

Biogenesis↗

NASA NTRS1984

Photochemistry of porphyrins: a model for the origin of photosynthesis

A series of porphyrins and catalysts has been prepared as a model for the origin of photosynthesis on the primordial earth. These compounds have been used to test the hypotheses that (1) the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis, and (2) the proto-photosythetic function of biogenetic porphyrins (biosynthetic chlorophyll precursors) was the oxidation of organic molecules by photoexcited porphyrins with the attendant emission of molecular hydrogen. This paper describes experiments in which photoexcited biogenetic porphyrins oxidize ethylenediamine tetraacetic acid (EDTA). The concomitant reduction of protons to hydrogen gas occurs in the presence of a colloidal platinum catalyst. The addition of methyl viologen, a one-electron shuttle, increases the amount of molecular hydrogen generated during long irradiations and the quantum yield of hydrogen production. When the porphyrin and catalyst are held in association by molecular complexes, the increased efficiency of electron transfer produces higher yields of hydrogen gas.

Hydrogen/chemistry↗

NASA NTRS2016

Development Status for a Combined Solid Oxide Co-Electrolyzer and Carbon Formation Reactor System for Oxygen Regeneration

A critical component in spacecraft life support loop closure is the removal of carbon dioxide (CO2, produced by the crew) from the cabin atmosphere and chemical reduction of this CO2 to recover the oxygen. In 2015, we initiated development of an oxygen recovery system for life support applications consisting of a solid oxide co-electrolyzer (SOCE) and a carbon formation reactor (CFR). The SOCE electrolyzes a combined stream of carbon dioxide (CO2) and water (H2O) gas mixtures to produce synthesis gas (e.g., CO and H2 gas) and pure dry oxygen as separate products. This SOCE is being developed from a NASA GRC solid oxide fuel cell and stack design originally developed for aeronautics long-duration power applications. The CFR, being developed by pHMatter LLC, takes the CO and H2 output from the SOCE, and converts it primarily to solid carbon (C(s)) and H2O and CO2. Although the solid carbon accumulates in the CFR, the innovative design allows easy removal of the carbon product, requiring minimal crew member (CM) time and low resupply mass (1.0 kg/year/CM) for replacement of the solid carbon catalyst, a significant improvement over previous Bosch reactor approaches. In this work, we will provide a status of our Phase I efforts in the development and testing of both the SOCE and CFR prototype units, along with an initial assessment of the combined SOCE-CFR system, including a mass and power projections, along with an estimate of the oxygen recovery rate.

air revitalization↗

NASA NTRS2014

Series-Bosch Technology for Oxygen Recovery During Lunar or Martian Surface Missions

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.

Abney, Morgan B.↗

NASA NTRS2007

The ISS Water Processor Catalytic Reactor as a Post Processor for Advanced Water Reclamation Systems

Advanced water processors being developed for NASA s Exploration Initiative rely on phase change technologies and/or biological processes as the primary means of water reclamation. As a result of the phase change, volatile compounds will also be transported into the distillate product stream. The catalytic reactor assembly used in the International Space Station (ISS) water processor assembly, referred to as Volatile Removal Assembly (VRA), has demonstrated high efficiency oxidation of many of these volatile contaminants, such as low molecular weight alcohols and acetic acid, and is considered a viable post treatment system for all advanced water processors. To support this investigation, two ersatz solutions were defined to be used for further evaluation of the VRA. The first solution was developed as part of an internal research and development project at Hamilton Sundstrand (HS) and is based primarily on ISS experience related to the development of the VRA. The second ersatz solution was defined by NASA in support of a study contract to Hamilton Sundstrand to evaluate the VRA as a potential post processor for the Cascade Distillation system being developed by Honeywell. This second ersatz solution contains several low molecular weight alcohols, organic acids, and several inorganic species. A range of residence times, oxygen concentrations and operating temperatures have been studied with both ersatz solutions to provide addition performance capability of the VRA catalyst.

Nalette, Tim↗

NASA NTRS2011

Possible Responsibility of Silicone Materials for Degradation of the CO2 Removal System in the International Space Station

From data concerning the degradation of the CO2 removal system in the International Space Station (ISS) two important features were apparent: (1) The atmosphere within the International Space Station (ISS) contained many organic compounds including alcohols, halocarbons, aldehydes, esters, and ketones, inter alia. Various cyclosiloxanes Dn, hexamethylcyclotrisiloxane (D3) and its higher homologs (D4) and (D5) are also present presumably due to offgassing. (2) Screens within the zeolite-containing canisters, used for the removal of CO2, exhibited partial clogging due to zeolitic fragments (dust) along with "sticky" residues, that in toto significantly reduced the efficiency of the CO2 removal process. Samples of the ISS fresh zeolite, used zeolite, filter clogging zeolite particles and residual polymeric materials were examined using, inter alia, NMR, EM and HRSEM. These data were compared to equivalent samples obtained prior and subsequent to Dn polymerization experiments performed in our laboratories using the clean ISS zeolite samples as catalyst. Polysiloxane materials produced were essentially equivalent in the two cases and the EM images demonstrate a remarkable similarity between the ISS filter zeolite samples and the post-polymerization zeolite material from our experiments. In this regard even the changes in the Al/Si ratio from the virgin zeolite material to the filter samples and the post-polymerization laboratory samples samples is noteworthy. This research was supported by a contract from the Boeing Company

Baeza, Mario↗