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At least 19 records

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↗

Scalable Polymeric Few-Nanometer Organosilica Membranes with Hydrothermal Stability for Selective Hydrogen Separation

Nanoporous silica membranes exhibit excellent H 2 /CO 2 separation properties for sustainable H 2 production and CO 2 capture but are prepared via complicated thermal processes above 400 °C, which prevent their scalable production at a low cost. Here, we demonstrate the rapid fabrication (within 2 min) of ultrathin silica-like membranes (~3 nm) via an oxygen plasma treatment of polydimethylsiloxane-based thin-film composite membranes at 20 °C. The resulting organosilica membranes unexpectedly exhibit H2 permeance of 280-930 GPU (1 GPU = 3.347 x 10 -10 mol m -2 s -1 Pa -1 ) and H2/CO2 selectivity of 93-32 at 200 °C, far surpassing state-of-the-art membranes and Robeson’s upper bound for H 2 /CO 2 separation. When challenged with a 3 d simulated syngas test containing water vapor at 200 °C and a 340 d stability test, the membrane shows durable separation performance and excellent hydrothermal stability. The robust H 2 /CO 2 separation properties coupled with excellent scalability demonstrate the great potential of these organosilica membranes for economic H 2 production with minimal carbon emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of Low-Energy Hydrogen Separation Method Using Metal-Organic Frameworks (MOFs) for Closed-Loop ECLSS Air Revitalization (CLEAR)

The State-of-the-Art (SOA) air revitalization architecture onboard the International Space Station (ISS) recovered approximately 50% of the oxygen (O 2 ) from metabolic carbon dioxide (CO 2 ) via the Sabatier process from 2011 to 2017. O 2 recovery is currently constrained by the limited availability of reactant hydrogen (H 2 ) preventing complete conversion of CO 2 to H 2 O. Increasing O 2 recovery within Closed-Loop ECLSS is essential to reducing resupply mass for long-duration manned missions; specifically focusing on water (H 2 O) which supplies H 2 for Sabatier via water electrolysis. Past ground test endeavors at Marshall Space Flight Center (MSFC) have attempted to recover H 2 from Sabatier-produced CH 4 using technologies such as carbon vapor deposition (CVD) and plasma pyrolysis. The byproducts of these technologies can act as a catalyst poison or reactor deadload to the Sabatier reactor. Hydrogen separation techniques must be utilized to maintain the Sabatier catalyst during gas recycling and must be scalable, non-energy intensive, and safe to operate in a habitation setting. Research indicated that metal-organic frameworks (MOFs) could meet these criteria and were tested for their capability to capture the various carbon-based gaseous products of CVD and plasma pyrolysis such as acetylene (C 2 H 2 ), ethylene (C 2 H 4 ), ethane (C 2 H 6 ), and carbon monoxide (CO) which would purify the hydrogen gas stream passing through the MOF. A sub-scale adsorption column was developed by Marshall Space Flight Center to test three MOF candidates against a synthetic gas mixture comprised of process-relevant carbonous gases and hydrogen to evaluate the separation capability of the MOFs. The results of the hydrogen separation capability, isothermal desorption capability, and demonstrated cyclic reuse of the MOF are presented in this paper.

Kagen Crawford↗

Hydrogen separation with a graphenylene monolayer: Diffusion Monte Carlo study

Here, we performed fixed-node diffusion Monte Carlo (DMC) calculations to investigate structural and energetic properties of graphenylene (GPNL), a two-dimensional network of sp 2 -bonded carbon atoms with large near-circular pores, and its H 2 separation performance for gas mixtures. We have found that the energetic stability of a GPNL monolayer is comparable to that of γ-graphyne, as evidenced by its large cohesive energy of 6.755(3) eV/atom. Diffusion barriers of several gas molecules, including hydrogen, through a GPNL membrane were determined from the analysis of their adsorption energies depending on the adsorption distance, which led to our estimation for hydrogen selectivity with respect to other target molecules. DMC hydrogen selectivity of a GPNL monolayer was found to be exceptionally high at 300 K, as high as 10 10 –10 11 against CO and N 2 gases. This, along with high hydrogen permeance due to its generic pore structure, leads us to conclude that GPNL is a promising membrane to be used as a high-performance hydrogen separator from gas mixtures. We find that when compared to our DMC results, DFT calculations tend to overestimate H 2 selectivity, which is mostly due to their inaccurate description of short-range repulsive interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Device separates hydrogen from solution in water at ambient temperatures

Separator decreases the partial pressure of hydrogen gas dissolved in the water produced by fuel cells containing an alkaline electrolyte. The unit eliminates the hazards associated with the release of hydrogen from water solution when the hydrostatic pressure is rapidly decreased.

Albright, C. F.↗

Nickel-hydrogen separator development

The separator technology is a critical element in the nickel-hydrogen (Ni-H2) systems. Previous research and development work carried out at NASA Lewis Research Center has determined that separators made from zirconium oxide (ZrO2) and potassium titanate (PKT) fibers will function satisfactorily in Ni-H2 cells without exhibiting the problems associated with the asbestos separators. These separators and their characteristics were previously discussed. A program was established to transfer the separator technology into a commercial production line. A detailed plan of this program will be presented and the preliminary results will be discussed.

Gonzalez-Sanabria, O. D.↗

Nickel-hydrogen separator development

The separator technology is a critical element in the nickel-hydrogen (Ni-H2) systems. Previous research and development work carried out at NASA Lewis Research Center has determined that separators made from zirconium oxide (ZrO2) and potassium titanate (PKT) fibers will function satisfactorily in Ni-H2 cells without exhibiting the problems associated with the asbestos separators. A program has been established to transfer the separator technology into a commercial production line. A detailed plan of this program will be presented and the preliminary results will be discussed.

Gonzalez-Sanabria, O. D.↗

Simulation of 12-bed vacuum pressure-swing adsorption for hydrogen separation from methanol-steam reforming off-gas

This study focuses on analysis of a 12-bed vacuum pressure-swing adsorption (VPSA) process capable of purifying hydrogen from a ternary mixture (H 2 /CO 2 /CO 75/24/1 mol%) derived from methanol-steam reforming. The process produces 9 kmol H 2 /h with less than 2 ppm and 0.2 ppm of CO2 and CO, respectively, to supply a polymer electrolyte membrane fuel cell. The process model is developed in Aspen Adsorption® using the “uni-bed” approach. A parametric study of H 2 purity and recovery with respect to adsorption pressure, adsorbent height, activated carbon:zeolite ratio, feed composition, and number of beds is performed. Results show 12-bed VPSA can meet the H 2 purity goals, with H 2 recovery as high as 75.75%. Adsorption occurs at 7 bar, the column height is 1.2 m, and the adsorbent ratio is 70%:30%. Furthermore, a 4-bed VPSA can achieve the same purity goals as the 12-bed process, but H 2 recovery decreases to 61.34%.

03 NATURAL GAS↗

Methane Post-Processing and Hydrogen Separation for Spacecraft Oxygen Loop Closure

State-of-the-art life support oxygen recovery technology on the International Space Station is based on the Sabatier reaction where only about half of the oxygen required for the crew is recovered from metabolic carbon dioxide (CO2). The Sabatier reaction produces water as the primary product and methane as a byproduct. Oxygen recovery is constrained by both the limited availability of reactant hydrogen from water electrolysis and Sabatier methane (CH4) being vented as a waste product resulting in a continuous loss of reactant hydrogen. Post-processing methane with the Plasma Pyrolysis Assembly (PPA) to recover this hydrogen has the potential to substantially increase oxygen recovery and thus dramatically reduce the logistical challenges associated with oxygen resupply. The PPA decomposes methane into predominantly hydrogen and acetylene. A purification system is necessary to purify hydrogen before it is recycled back to the Sabatier reactor. Testing and evaluation of acetylene removal systems and PPA system architectures are presented and discussed.

Greenwood, Zachary W.↗

Heat recovery from an electrochemical hydrogen separation system

An EHS system includes a EHS cell having an anode, a cathode, and a cooling plate disposed proximate at least one of the anode or the cathode, the cooling plate configured to receive water and configured to output steam or a mixture of water and steam. The system further includes a liquid-vapor separator (LVS) configured to receive the steam or the mixture of water and steam from the cooling plate and to separate water and steam. The LVS is configured to output water to the cooling plate.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

High-Temperature Proton-Conducting Ceramics Developed

High-temperature protonic conductors (HTPC) are needed for hydrogen separation, hydrogen sensors, fuel cells, and hydrogen production from fossil fuels. The HTPC materials for hydrogen separation at high temperatures are foreseen to be metal oxides with the perovskite structure A(sup 2+)B(sup 4+)C(sup 2-, sub 3) and with the trivalent cation (M(sup 3+)) substitution at the B(sup 4+)-site to introduce oxygen vacancies. The high affinity for hydrogen ions (H(sup +)) is advantageous for protonic transport, but it increases the reactivity toward water (H2O) and carbon dioxide (CO2), which can lead to premature membrane failure. In addition, there are considerable technological challenges related to the processing of HTPC materials. The high melting point and multi-cation chemistry of HTPC materials creates difficulties in in achieving high-density, single-phase membranes by solid-state sintering. The presence of secondary phases and grain-boundary interfaces are detrimental to the protonic conduction and environmental stability of polycrystalline HTPC materials.

Sayir, Ali↗

Toward Hydrogen Isotope Separations through Strong Hydrogen Adsorption at Open Copper(I) Sites in an Ultramicroporous Metal-Organic Framework

Metal-organic frameworks with coordinatively unsaturated metal sites (open metal sites) capable of engaging in orbital interactions with pi-acidic gases are of interest for enabling ambient-temperature gas separations, such as hydrogen isotope separations. In view of the weakly pi-acidic nature of H2, we sought to strengthen pi-backbonding-mediated H2 adsorption through pore confinement effects. Toward that end, we synthesized and characterized the ultramicroporous metal-organic framework CuxZn5-xCl4-yHz(bbta)3 (CuIZn-MFU-4; H2bbta = 1H,5H-benzo(1,2-d:4,5-d')bistriazole), featuring pi-basic trigonal pyramidal CuI sites that reside within 7 A of one another at their closest. Gas adsorption measurements reveal an H2 adsorption enthalpy of -38 kJ/mol, exceeding that of the larger-pore analog (CuIZn-MFU-4l; -33 kJ/mol) and representing the strongest H2 adsorption yet achieved in a metal-organic framework. The stronger H2 adsorption in CuIZn-MFU-4 is attributed to a combination of pore confinement effects and the increased ..sigma..-accepting nature of the CuI sites caused by a more electron-withdrawing bbta2- linker, as supported by structural, spectroscopic, and computational evidence. With the strongest H2 adsorption, equilibrium isotope effects in CuIZn-MFU-4 lead to a D2/H2 selectivity (as estimated by ideal adsorbed solution theory) of 1.35 even at 298 K, approaching the values reported below 200 K for conventional porous materials.

08 HYDROGEN↗