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NASA NTRS1981

Organic solids produced by electrical discharge in reducing atmospheres - Tholin molecular analysis

The complex dark brown solid of a class called tholins, produced on passage of an electrical discharge through a roughly equimolar mixture of methane and ammonia with 2.6% water vapor, is analyzed by vacuum pyrolysis followed by gas chromatography and mass spectrometry. Pyrolyzates include a wide range of aliphatic and aromatic nitriles, alkanes, alkenes, aromatic hydrocarbons, pyrrole, and pyridine. This tholin is remarkably stable to 950 C. It and its degradation products are candidate constituents of planetary aerosols in the outer solar system and of the grains in the interstellar medium.

Khare, B. N.↗

NASA NTRSDate not supplied

Comprehensive Evaluation of Electrochemical Hydrogen Separator as Hydrogen Recovery Solution for Plasma Pyrolysis Assembly

The previously tested State-of-the-Art (SOA) air revitalization architecture onboard the International Space Station recovers approximately 50% of the oxygen (O 2 ) from metabolic carbon dioxide (CO 2 ) via the Sabatier process. Maximum O 2 recovery is required to reduce resupply mass for long-duration manned missions. O 2 recovery is constrained by the limited availability of reactant hydrogen (H 2 ) from water (H 2 O) electrolysis, and Sabatier-produced methane (CH 4 ) is vented as a waste product resulting in a continuous loss of reactant H 2 . The Plasma Pyrolysis Assembly (PPA) has the potential to substantially increase O 2 recovery by post-processing the Sabatier-produced methane to recover H 2 . The PPA decomposes CH 4 into predominately H 2 and acetylene (C 2 H 2 ). A separation system is needed to purify the H 2 from the PPA stream before it is recycled back to the Sabatier reactor. Two sub-scale electrochemical H 2 separation systems, developed by Skyre, Incorporated, were delivered to NASA for evaluation. Complimentary of the previous submittal, ICES-2023-260, this paper reports a summation of Phase I and Phase II testing and evaluation of the C 2 H 2 removal systems as well as lessons learned.

Plasma Pyrolysis Assembly↗

NASA NTRS2011

Plasma Pyrolysis Assembly Regeneration Evaluation

In April 2010 the Carbon Dioxide Reduction Assembly (CRA) was delivered to the International Space Station (ISS). This technology requires hydrogen to recover oxygen from carbon dioxide. This results in the production of water and methane. Water is electrolyzed to provide oxygen to the crew. Methane is vented to space resulting in a loss of valuable hydrogen and unreduced carbon dioxide. This is not critical for ISS because of the water resupply from Earth. However, in order to have enough oxygen for long-term missions, it will be necessary to recover the hydrogen to maximize oxygen recovery. Thus, the Plasma Pyrolysis Assembly (PPA) was designed to recover hydrogen from methane. During operation, the PPA produces small amounts of carbon that can ultimately reduce performance by forming on the walls and windows of the reactor chamber. The carbon must be removed, although mechanical methods are highly inefficient, thus chemical methods are of greater interest. The purpose of this effort was to determine the feasibility of chemically removing the carbon from the walls and windows of a PPA reactor using a pure carbon dioxide stream.

Medlen, Amber↗

NASA NTRS2013

Trash to Gas: Converting Space Waste into Useful Supply Products

The cost of sending mass into space with current propulsion technology is very expensive, making every item a crucial element of the space mission. It is essential that all materials be used to their fullest potential. Items like food, packaging, clothing, paper towels, gloves, etc., normally become trash and take up space after use. These waste materials are currently either burned up upon reentry in earth's atmosphere or sent on cargo return vehicles back to earth: a very wasteful method. The purpose of this project was to utilize these materials and create useful products like water and methane gas, which is used for rocket fuel, to further supply a deep space mission. The system used was a thermal degradation reactor with the configuration of a down-draft gasifier. The reactor was loaded with approximately 100g of trash simulant and heated with two external ceramic heaters with separate temperature control in order to create pyrolysis and gasification in one zone and incineration iri a second zone simultaneously. Trash was loaded into the top half of the reactor to undergo pyrolysis while the downdraft gas experienced gasification or incineration to treat tars and maximize the production of carbon dioxide. Minor products included carbon monoxide, methane, and other hydrocarbons. The carbon dioxide produced can be sent to a Sabatier reactor to convert the gas into methane, which can be used as rocket propellant. In order to maximize the carbon dioxide and useful gases produced, and minimize the unwanted tars and leftover ashen material, multiple experiments were performed with altered parameters such as differing temperatures, flow rates, and location of inlet air flow. According to the data received from these experiments, the process will be further scaled up and optimized to ultimately create a system that reduces trash buildup while at the same time providing enough useful gases to potentially fill a methane tank that could fuel a lunar ascent vehicle or other deep space mission.

Tsoras, Alexandra↗

NASA NTRS2017

Particulate filtration from emissions of a plasma pyrolysis assembly reactor using regenerable porous metal filters

Microwave-based plasma pyrolysis technology is being studied as a means of supporting oxygen recovery in future spacecraft life support systems. The process involves the conversion of methane produced from a Sabatier reactor to acetylene and hydrogen, with a small amount of solid carbon particulates generated as a side product. The particles must be filtered before the acetylene is removed and the hydrogen-rich gas stream is recycled back to the CRA. We discuss developmental work on porous metal media filters for removing the carbon particulate emissions from the PPA exit gas stream and to provide in situ media regeneration capability. Because of the high temperatures involved in oxidizing the deposited carbon during regeneration, there was particular focus in this development on the materials that could be used, the housing design, and heating methods. This paper describes the design and operation of the filter and characterizes their performance from integrated testing at the Environmental Chamber (E-Chamber) at MSFC.

particulates↗

DOE OSTI2025

Microwave-assisted dehydrogenation of fossil fuels using iron-based alumina nanocomposites

Hydrogen is mainly produced via steam reforming of methane and gasification of coal, with enormous CO 2 emissions in both cases. Microwave-assisted thermocatalytic decomposition (pyrolysis) is of interest as a method for hydrogen production from fossil fuels with no CO 2 emissions. For successful implementation of this technology, it is necessary to develop decomposition catalysts that are also good microwave absorbers and can be produced from inexpensive materials via a robust synthetic route. Recently, iron-based alumina nanocomposites, fabricated by solution combustion synthesis (SCS), have shown promising microwave-absorbing and catalytic properties in the pyrolysis of plastics. The reported project explored the feasibilities of improving such catalysts and using them for the microwave-assisted pyrolysis of liquid fossil fuels, viz., diesel fuel, gasoline, and crude oil. The research focused on how SCS parameters affect the material properties and pyrolysis performance.

02 PETROLEUM↗

NASA NTRS2010

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Socki, Richard A.↗

DOE OSTI2025

Hydrogen Production from Polyethylene Pyrolysis

Hydrogen is anticipated to play a pivotal role in the future of clean energy and decarbonization efforts, serving as an energy storage medium, a power generation source, and a clean fuel for transportation. While most hydrogen is produced from carbonaceous fossil feedstocks like natural gas, petroleum, and coal, there is growing interest in using refuse-derived fuels such as waste plastics and municipal solid waste (MSW) as alternative feedstocks. Thermochemical processes such as pyrolysis and catalytic cracking can convert nonrecyclable plastics and organic MSW components to produce hydrogen with lower life cycle greenhouse gas emissions when coupled with CO 2 capture. Such approaches not only address waste-management challenges but also reduce methane emissions from landfills. Furthermore, waste feedstocks are low cost and can support meeting demands for hydrogen across various industries. In this work we examined production of hydrogen from high-density polyethylene (HDPE) as a model polymer using pyrolysis. Analytical studies of pyrolysis utilizing gas chromatography–mass spectrometry (GC/MS) provide insights into conversion pathways for plastic waste, potentially reducing the environmental footprint of traditional hydrogen production methods. This work generates a baseline methodology for hydrogen production from plastic pyrolysis with and without a catalyst and the necessary product distribution baseline from key single plastics. The effect of pyrolysis temperature on the conversion of HDPE was evaluated both with and without a catalyst(s), and the product distributions measured via GC/MS were identified and hydrogen formation was quantified. These results will help guide future research efforts to optimize catalysts and processes for more efficient hydrogen production and mixed plastic waste management.

Catalysts↗

NASA NTRS2014

An Approach for Hydrogen Recycling in a Closed-loop Life Support Architecture to Increase Oxygen Recovery Beyond State-of-the-Art

State‐of‐the‐art atmosphere revitalization life support technology on the International Space Station is theoretically capable of recovering 50% of the oxygen from metabolic carbon dioxide via the Carbon Dioxide Reduction Assembly (CRA). When coupled with a Plasma Pyrolysis Assembly (PPA), oxygen recovery increases dramatically, thus drastically reducing the logistical challenges associated with oxygen resupply. The PPA decomposes methane to predominantly form hydrogen and acetylene. Because of the unstable nature of acetylene, a down‐stream separation system is required to remove acetylene from the hydrogen stream before it is recycled to the CRA. A new closed‐loop architecture that includes a PPA and downstream Hydrogen Purification Assembly (HyPA) is proposed and discussed. Additionally, initial results of separation material testing are reported.

Abney, Morgan B.↗

NASA NTRS2024

Reliable and Efficient Electrochemical Recovery of O 2 from Metabolic CO 2 at the International Space Station (ISS)

Maximum O 2 recovery from metabolic carbon dioxide (CO 2 ) is desired for future long-duration missions beyond Low Earth Orbit (LEO). The O 2 recovery for the Environmental Control and Life Support System (ECLSS) at the International Space Station (ISS), presently limited to 50% (Sabatier), must be highly reliable and efficient and recover a minimum of 75% oxygen (O 2 ) from metabolic CO 2 . An alternative technology development effort currently underway at NASA Marshall Space Flight Center (MSFC) via a Microfluidic Electrochemical Reactor (MFECR) approach has the potential to increase O 2 recovery significantly and reduce the complexity of the ECLSS O 2 recovery at the ISS as it would replace three pieces, the CO 2 Reduction Assembly (CRA) (Sabatier reactor), the Oxygen Generation Assembly (OGA), and the Plasma Pyrolysis Assembly (PPA). The MFECR's electrochemical process generates ethylene (C 2 H 4 ) and carbon moxide (CO) instead of methane (CH 4 ) (Sabatier) as a byproduct, eliminating the need for further dehydrogenation through the PPA. As in the OGA, the MFECR's electrochemical process generates O 2 and hydrogen (H 2 ) from the water electrolysis process. MSFC and the University of Texas in Arlington (UTA) have jointly designed and fabricated an MFECR's single cell that operates at ambient conditions and utilizes a proprietary catalysis highly selective on reducing CO 2 to C 2 H 4 and CO at the cathode. This MFECR's single cell consists of gas diffusion layers at the cathode and anode for respective intake of CO 2 and output of O 2 from the catalytic layer. This approach is expected to substantially improve the ISS ECLSS sustainability and reduce power and weight requirements as the MFECR would replace three units currently installed in the ISS. In this paper, the authors discuss the outcome of preliminary tests, the current development, and the evaluation efforts on different alternatives for the cathode and the anode configurations, the setup of the MFECR at an engineering development unit (EDU) scale, and the O 2 recovery performance, and evaluation efforts on different alternatives on not only the configuration and setup of the MFECR at an Engineering Design Unit (EDU) scale but also the selection of component materials.

Jesus A Dominguez↗

DOE OSTI2026

A Comprehensive Greenhouse Gas Assessment of Biomass-Based Carbon Dioxide Removal and Storage

Biomass with Carbon Removal and Sequestration (BiCRS) is a suite of technological pathways that provide a relatively affordable and high-potential way to remove carbon dioxide from the atmosphere and simultaneously re-purpose residual biomass. BiCRS technologies are individually optimized to different biomass feedstocks, temperatures and oxygen, with the goal of capturing a high percentage of biomass-derived carbon dioxide and storing it in permanent below-ground storage (i.e. geologic storage). The current standard for BiCRS life cycle assessments does not account for carbon dioxide, methane and nitrous oxide (CO 2 , CH 4 , and N 2 O) fluxes from surface soil amendment of BiCRS byproducts (e.g. char, ash) and their alternate fates. This is partly due to a paucity of empirical data due to the novelty of BiCRS conversion technologies, the range in feedstocks, and the heterogeneity of soils to which they might be amended. To fill this gap in in the life-cycle assessment (LCA) and provide a realistic range of parameters for a soil amendment component of the BiCRS LCA, we conducted an incubation experiment to measure soil carbon changes, microbial respiration, methane fluxes, and nitrous oxide fluxes from two different soils amended with char- and ash- byproducts from biomass after gasification to hydrogen, fast pyrolysis to bio-oil, and torrefaction.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2014

Novel Catalysts and Processing Technologies for Production of Aerospace Fuels from Non-Petroleum Raw Materials

Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these nontraditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and H2) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tröpsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activities are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.

space processing↗

NASA NTRS2017

Particulate Filtration from Emissions of a Plasma Pyrolysis Assembly Reactor Using Regenerable Porous Metal Filters

Agui, Juan H.↗

NASA NTRS2014

Novel Catalysts and Processing Technologies for Production of Aerospace Fuels from Non-Petroleum Raw Materials

Transportation fuels production (including aerospace propellants) from non-traditional sources (gases, waste materials, and biomass) has been an active area of research and development for decades. Reducing terrestrial waste streams simultaneous with energy conversion, plentiful biomass, new low-cost methane sources, and/or extra-terrestrial resource harvesting and utilization present significant technological and business opportunities being realized by a new generation of visionary entrepreneurs. We examine several new approaches to catalyst fabrication and new processing technologies to enable utilization of these non-traditional raw materials. Two basic processing architectures are considered: a single-stage pyrolysis approach that seeks to basically re-cycle hydrocarbons with minimal net chemistry or a two-step paradigm that involves production of supply or synthesis gas (mainly carbon oxides and hydrogen) followed by production of fuel(s) via Sabatier or methanation reactions and/or Fischer-Tropsch synthesis. Optimizing the fraction of product stream relevant to targeted aerospace (and other transportation) fuels via modeling, catalyst fabrication and novel reactor design are described. Energy utilization is a concern for production of fuels for either terrestrial or space operations; renewable sources based on solar energy and/or energy efficient processes may be mission enabling. Another important issue is minimizing impurities in the product stream(s), especially those potentially posing risks to personnel or operations through (catalyst) poisoning or (equipment) damage. Technologies being developed to remove (and/or recycle) heteroatom impurities are briefly discussed as well as the development of chemically robust catalysts whose activity are not diminished during operation. The potential impacts on future missions by such new approaches as well as balance of system issues are addressed.

propellants↗

NASA NTRS1976

Clean fuels from biomass

The paper discusses the U.S. resources to provide fuels from agricultural products, the present status of conversion technology of clean fuels from biomass, and a system study directed to determine the energy budget, and environmental and socioeconomic impacts. Conversion processes are discussed relative to pyrolysis and anaerobic fermentation. Pyrolysis breaks the cellulose molecules to smaller molecules under high temperature in the absence of oxygen, wheras anaerobic fermentation is used to convert biomass to methane by means of bacteria. Cost optimization and energy utilization are also discussed.

Hsu, Y.-Y.↗

NASA NTRS2012

Advanced PPA Reactor and Process Development

Design and development of a second generation Plasma Pyrolysis Assembly (PPA) reactor is currently underway as part of NASA s Atmosphere Revitalization Resource Recovery effort. By recovering up to 75% of the hydrogen currently lost as methane in the Sabatier reactor effluent, the PPA helps to minimize life support resupply costs for extended duration missions. To date, second generation PPA development has demonstrated significant technology advancements over the first generation device by doubling the methane processing rate while, at the same time, more than halving the required power. One development area of particular interest to NASA system engineers is fouling of the PPA reactor with carbonaceous products. As a mitigation plan, NASA MSFC has explored the feasibility of using an oxidative plasma based upon metabolic CO2 to regenerate the reactor window and gas inlet ports. The results and implications of this testing are addressed along with the advanced PPA reactor development work.

Wheeler, Raymond↗

NASA NTRS2012

Advanced Plasma Pyrolysis Assembly (PPA) Reactor and Process Development

Design and development of a second generation Plasma Pyrolysis Assembly (PPA) reactor is currently underway as part of NASA's Atmosphere Revitalization Resource Recovery effort. By recovering up to 75% of the hydrogen currently lost as methane in the Sabatier reactor effluent, the PPA helps to minimize life support resupply costs for extended duration missions. To date, second generation PPA development has demonstrated significant technology advancements over the first generation device by doubling the methane processing rate while, at the same time, more than halving the required power. One development area of particular interest to NASA system engineers is fouling of the PPA reactor with carbonaceous products. As a mitigation plan, NASA MSFC has explored the feasibility of using an oxidative plasma based upon metabolic CO2 to regenerate the reactor window and gas inlet ports. The results and implications of this testing are addressed along with the advanced PPA reactor development.

Wheeler, Richard R., Jr.↗

NASA NTRS2013

Trash-to-Gas: Converting Space Trash into Useful Products

NASA's Logistical Reduction and Repurposing (LRR) project is a collaborative effort in which NASA is determined to reduce total logistical mass through reduction, reuse and recycling of various wastes and components of long duration space missions and habitats. LRR is focusing on four distinct advanced areas of study: Advanced Clothing System, Logistics-to-Living, Heat Melt Compactor and Trash to Supply Gas (TtSG). The objective of TtSG is to develop technologies that convert material waste, human waste and food waste into high-value products. High-value products include life support oxygen and water, rocket fuels, raw material production feedstocks, and other energy sources. There are multiple pathways for converting waste to products involving single or multi-step processes. This paper discusses thermal oxidation methods of converting waste to methane. Different wastes, including food, food packaging, Maximum Absorbent Garments (MAGs), human waste simulants, and cotton washcloths have been evaluated in a thermal degradation reactor under conditions promoting pyrolysis, gasification or incineration. The goal was to evaluate the degradation processes at varying temperatures and ramp cycles and to maximize production of desirable products and minimize high molecular weight hydrocarbon (tar) production. Catalytic cracking was also evaluated to minimize tar production. The quantities of CO2, CO, CH4, and H2O were measured under the different thermal degradation conditions. The conversion efficiencies of these products were used to determine the best methods for producing desired products.

Caraccio, Anne J.↗