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At least 127 records · Page 7

Ammonia Offgassing from SA9T

NH3 is a degradation product of SA9T, a solid-amine sorbent developed by Hamilton Sundstrand, that is continually emitted into the gas stream being conditioned by this sorbent. NH3 offgassing rates were measured using FTIR spectroscopy using a packed bed at similar contact times as offgassing tests conducted at Hamilton Sundstrand and at the Ames Research Center. The bed was challenged with moist air at several flow rates and humidities and NH3 concentration of the effluent was measured for several hours. The NH3 offgassing rates in open-loop testing were calculated from the steady state outlet NH3 concentration and flow rate. NH3 offgassing rates from SA9T were found to be influenced by the contact time with the adsorbent (flow rate) and by the humidity of the inlet gas stream, which are consistent with previous studies. Closed-loop vacuum-swing adsorption cycling rates verified that NH3 offgassing continues when a constant source of water vapor is present.

Monje, Oscar↗

Rapid Cycle Amine (RCA 2.0) System Development

The Rapid Cycle Amine (RCA) system is a low power assembly capable of simultaneously removing carbon dioxide (CO2) and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. Two solid amine sorbent beds are alternated between an uptake mode and a regeneration mode. During the uptake mode, the sorbent is exposed to an air steam (ventilation loop) to adsorb CO2 and water vapor, while during the regeneration mode, the sorbent rejects the adsorbed CO2 and water vapor to a vacuum source. The two beds operate such that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. A novel valve assembly provides a simple means of diverting the process air flow through the uptake bed while simultaneously directing the vacuum source to the regeneration bed. Additionally, the valve assembly is designed to allow for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The process can be controlled by a compact, low power controller design with several modes of operation available to the user. Together with NASA, United Technologies Corporation Aerospace Systems has been developing RCA 2.0 based on performance and design feedback on several sorbent bed test articles and valve design concepts. A final design was selected in November 2011 and fabricated and assembled between March and August 2012, with delivery to NASA-JSC in September 2012. This paper will provide an overview on the RCA system design and results of pre-delivery testing.

Papale, William↗

Rapid Cycle Amine (RCA 2.0) System Development

The Rapid Cycle Amine (RCA) system is a low-power assembly capable of simultaneously removing carbon dioxide (CO2) and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. Two solid amine sorbent beds are alternated between an uptake mode and a regeneration mode. During the uptake mode, the sorbent is exposed to an air steam (ventilation loop) to adsorb CO2 and water (H2O) vapor, whereas during the regeneration mode, the sorbent rejects the adsorbed CO2 and H2O vapor to a vacuum source. The two beds operate such that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. A novel valve assembly provides a simple means of diverting the process air flow through the uptake bed while simultaneously directing the vacuum source to the regeneration bed. Additionally, the valve assembly is designed to allow for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The process can be controlled by a compact, low-power controller design with several modes of operation available to the user. Together with NASA Johnson Space Center, Hamilton Sundstrand Space Systems International, Inc. has been developing RCA 2.0 based on performance and design feedback on several sorbent bed test articles and valve design concepts. A final design of RCA 2.0 was selected in November 2011 and fabricated and assembled between March and August 2012, with delivery to NASA Johnson Space Center in September 2012. This paper provides an overview of the RCA system design and results of pre-delivery testing.

Papale, William↗

Rapid Cycle Amine (RCA) 3.0 System Development

The Rapid Cycle Amine (RCA) 3.0 system is currently under development by NASA, the Lyndon B. Johnson Space Center (JSC) in conjunction with United Technologies Corporation Aerospace Systems (UTAS). The RCA technology is a new carbon dioxide (CO2) and humidity removal system that has been baselined for the Advanced Extravehicular Mobility Unit (AEMU) Portable Life Support System. The evolution of the RCA development has progressed through several iterations of technology readiness levels including RCA 1.0, RCA 2.0, and RCA 3.0 test articles. The RCA is an advancement over currently technologies due to its unique regeneration capability. The RCA is capable of simultaneously removing CO2 and humidity from an influent air steam and subsequent regeneration when exposed to a vacuum source. The RCA technology uses two solid amine sorbent beds in an alternating fashion to adsorb CO2 and water (uptake mode) and desorb CO2 and water (regeneration mode) at the same time. The two beds operate in an efficient manner so that while one bed is in the uptake mode, the other is in the regeneration mode, thus continuously providing an on-service sorbent bed by which CO2 and humidity may be removed. The RCA 2.0 and 3.0 test articles were designed with a novel valve assembly which allows for switching between uptake and regeneration modes with only one moving part while minimizing gas volume losses to the vacuum source by means of an internal pressure equalization step during actuation. The RCA technology also is low power, small, and has performed extremely well in all development testing thus far. A final design was selected for the RCA 3.0, fabricated, assembled, and performance tested in 2014 with delivery to NASAJSC in January 2015. This paper will provide an overview on the RCA 3.0 system design and results of pre-delivery testing with references to the development of RCA 1.0 and RCA 2.0.

Chullen, Cinda↗

Design and Development Comparison of Rapid Cycle Amine 1.0, 2.0, and 3.0

The development of the Rapid Cycle Amine (RCA) swing-bed technology for carbon dioxide (CO2) removal has been in progress since favorable results were published in 1996. Shortly thereafter, a prototype was designed, developed, and tested successfully and delivered to Johnson Space Center in 1999. An improved prototype was delivered to NASA in 2006 and was notated as RCA 1.0 and sized for the extravehicular activity (EVA). The new RCA swing-bed technology is a regenerative system which employs two alternating solid-amine sorbent beds to remove CO2 and water. The two- bed design employs a chemisorption process whereby the beds alternate between adsorbtion and desorbsion. This process provides for an efficient operation of the RCA so that while one bed is in adsorb (uptake) mode, the other is in the desorb (regeneration) mode. The RCA has now progressed through several iterations of technology readiness levels. Test articles have now been designed, developed, and tested for the advanced space suit portable life support system (PLSS) including RCA 1.0, RCA 2.0, and RCA 3.0. The RCA 3.0 was the most recent RCA fabrication and was delivered to NASA-JSC in June 2015. The RCA 1.0 test article was designed with a pneumatically actuated linear motion spool valve. The RCA 2.0 and 3.0 test articles were designed with a valve assembly which allows for switching between uptake and regeneration modes while minimizing gas volume losses to the vacuum source. RCA 2.0 and 3.0 also include an embedded controller design to control RCA operation and provide the capability of interfacing with various sensors and other ventilation loop components. The RCA technology is low power, small, and has fulfilled all test requirements levied upon the technology during development testing thus far. This paper will provide an overreview of the design and development of RCA 1.0, 2.0 and 3.0 including detail differences between the design specifications of each.

Chullen, Cinda↗

Design and Development Comparison of Rapid Cycle Amine 1.0, 2.0, and 3.0

The development of the Rapid Cycle Amine (RCA) swing-bed technology for carbon dioxide (CO2) removal has been in progress since favorable results were published in 1996. Shortly thereafter, a prototype was designed, developed, and tested successfully and delivered to Johnson Space Center in 1999. An improved prototype (RCA 1.0) was delivered to NASA in 2006 and sized for the extravehicular activity (EVA). The RCA swing-bed technology is a regenerative system which employs two alternating solid-amine sorbent beds to remove CO2 and water. The two-bed design employs a chemisorption process whereby the beds alternate between adsorption and desorption. This process provides for an efficient RCA operation that enables one bed to be in adsorb (uptake) mode, while the other is in the desorb (regeneration) mode. The RCA has progressed through several iterations of technology readiness levels. Test articles have now been designed, developed, and tested for the advanced space suit portable life support system (PLSS) including RCA 1.0, RCA 2.0, and RCA 3.0. The RCA 3.0 was the most recent RCA fabrication and was delivered to NASA-JSC in June 2015. The RCA 1.0 test article was designed with a pneumatically actuated linear motion spool valve. The RCA 2.0 and 3.0 test articles were designed with a valve assembly which allows for switching between uptake and regeneration modes while minimizing gas volume losses to the vacuum source. RCA 2.0 and 3.0 also include an embedded controller design to control RCA operation and provide the capability of interfacing with various sensors and other ventilation loop components. The RCA technology is low power, small, and has fulfilled all test requirements levied upon the technology during development testing thus far. This paper will provide an overview of the design and development of RCA 1.0, 2.0 and 3.0 including detail differences between the design specifications of each. Nomenclature.

Chullen, Cinda↗

(abstract) Development of Sorbent Bed Assembly for a Periodic 10K Solid Hydrogen Cryocooler

A closed-cycle 10K sorption cryocooler is being fabricated for microgravity testing during a future space shuttle mission. A critical component of this cryogenic refrigerator is the metal hydride sorbent bed assembly (SBA). The SBA uses hydrides which absorb hydrogen gas at low pressure, (i.e., about 0.25 MPa from liquid hydrogen at 25K and below 0.2 kPa from solid hydrogen near 10K) and subsequently delivers hydrogen at nearly 10 MPa to a storage reservoir to repeat the Joule-Thomson (J-T) expansion process. The SBA includes three independent hydride beds where two contain LaNi(sub 4.8)Sn(sub 0.2) alloy and the third ZrNi. Detailed descriptions will be given for the three beds, which have specialized design features to enhance performance at each step of operation. In particular, two beds must rapidly absorb hydrogen in order for the J-T cold stage to reach 10K within two minutes from a 65K holding temperature. Performance characterization results will be compared to model analyses of the SBA.

applications microgravity↗

Batch Scale Production of 3D Printed Extraction Sorbents Using a Low-Cost Modification to a Desktop Printer

This study reports a simple modification to a commercial resin 3D printer that significantly reduces the amount of prepolymer material needed for the production of extraction sorbents. Here, the modified printing platform is demonstrated in the printing of two imidazolium-based ionic liquid (IL) monomers. Two geometries resembling a blade-type polymeric ionic liquid (PIL) sorbent used in thin-film microextraction and a fiber-type sorbent used in solid-phase microextraction (SPME) were printed. The SPME PIL sorbents were used to extract 10 organic contaminants, including plasticizers, antimicrobial agents, UV filters, and pesticides, from water followed by high-performance liquid chromatographic (HPLC) analysis. To compare the extraction performance of the SPME sorbents, seven fibers printed with the same prepolymer composition from the same printing batch as well as different batches were evaluated. The results revealed highly reproducible extraction efficiencies for all tested sorbents with no statistical difference in their extraction performance. Method validation showed acceptable linearity ($R$ 2 > 0.92) for all analytes with limits of detection and limits of quantification ranging from 0.13 to 45 μg L –1 and 0.43 to 150 μg L –1 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding and mitigating degradation in amine-based sorbents for CO 2 direct air capture

The success of direct air capture (DAC) of CO 2 depends on sorbents that combine high capacity, low energy requirements, and long-term durability. Amine-based sorbents-including solid-supported aminopolymers, grafted amines, and amine-functionalized resins-remain the leading candidates, but their limited lifetimes drive up costs and constrain deployment. In this review, we outline the current understanding of amine-based sorbent degradation with an emphasis on clearly identifying what is known about structure-property-performance relationships, as well as important knowledge gaps. More specifically, we discuss how polymer chemistry, sorbent design variables, and environmental and process conditions contribute to performance loss. In parallel, we outline how advances in spectroscopy, modeling, and accelerated testing are beginning to illuminate chemical and physical degradation mechanisms. Looking forward, we identify future research directions that will be critical for gaining a deeper understanding of degradation, as well as opportunities for developing innovative mitigation strategies for improving the lifetime of amine-based sorbents.

organic↗

Integrating crystallographic and computational approaches to carbon-capture materials for the mitigation of climate change

Here, this article presents an overview of the current state of the art in the structure determination of microporous carbon-capture materials, as discussed at the recent NIST workshop “Integrating Crystallographic and Computational Approaches to Carbon-Capture Materials for the Mitigation of Climate Change”. The continual rise in anthropogenic CO 2 concentration and its effect on climate change call for the implementation of carbon capture technologies to reduce the CO 2 concentration in the atmosphere. Porous solids, including metal–organic frameworks (MOFs), are feasible candidates for gas capture and storage applications. However, determining the structure of these materials represents a significant obstacle in their development into advanced sorbents. The existing difficulties can be overcome by integrating crystallographic methods and theoretical modeling. The workshop gathered experimentalists and theorists from academia, government, and industry to review this field and identify approaches, including collaborative opportunities, required to develop tools for rapid determination of the structures of porous solid sorbents and the effect of structure on the carbon capture performance. We highlight the findings of that workshop, especially in the need for reference materials, standardized procedures and reporting of sorbent activation and adsorption measurements, standardized reporting of theoretical calculations, and round-robin structure determination.

36 MATERIALS SCIENCE↗

Discerning molecular-level CO 2 adsorption behavior in amine-modified sorbents within a controlled CO 2 /H 2 O environment towards direct air capture

Sorbents designed for direct air capture (DAC) play a crucial role in the pursuit of achieving net-zero carbon dioxide emissions. This study elucidates CO 2 adsorption from dilute, humidified CO 2 streams onto an amine-modified benchmark DAC adsorbent via solid-state NMR spectroscopy. Various NMR techniques, including 1D 1 H MAS, 13 C MAS, 2D 1 H– 13 C HETCOR NMR, and 1 H R 2 and R 1ρ relaxometry reveal the impact of CO 2 partial pressure and H 2 O on CO 2 adsorption behavior. Here we find that CO 2 concentration governs the stepwise formation of ammonium carbamate, carbamic acid, and physisorbed CO 2 , where relative humidity (RH) at a desired low (<400 ppm) CO 2 loading affects total CO 2 uptake. The relaxation studies reveal the cooperative or competitive nature of H 2 O–CO 2 sorption in CO 2 -dilute humid gas, and in particular polymer swelling upon humidification. From those results, we demonstrate that the observed absorption capacity enhancement by humidity is caused by pore opening due to sorbent swelling, and not by bicarbonate formation. This NMR-discerned speciation provides insights into sorption behavior at different RHs in dilute CO 2 gas streams, simulating real-world atmospheric conditions, and governs the design of efficient and adaptable material-process combinations for solid sorbent DAC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Copper and bismuth-based sorbent characterization in simulated iodine off-gas streams

The effective capture of volatile radioiodine, a fission product present in used nuclear fuel (UNF), is of paramount importance for development of used fuel reprocessing schemes to prevent release of radioiodine during unit operations and to meet regulatory standards for air emissions. A well-studied method for iodine capture in off-gas streams is the use of silver-functionalized zeolite phases (AgZ), which exploit chemisorption of I to Ag. Advances into other Ag-functionalized materials, including aerogels and metal organic frameworks (MOFs), are underway [1]. Additional metals with the capability to chemisorb iodine, including Cu, Bi, and Sn, [1] are being evaluated as alternatives to Ag for potential applicability to iodine management in off-gas systems. The design of novel functionalized sorbents with Cu and Bi, including composites with metal particles embedded in PAN substrates [2] and composites with metal sulfides embedded in PAN [3], is an ongoing area of study for improved iodine capture. Previously reported work on novel PAN-based metal sorbents has provided the synthesis, characterization, and iodine capture efficiency of this new class of sorbent. Specifically, the metal sulfide PAN composites are found to be easy to produce and reproduce, as well as having a high iodine loading potential under static conditions [3]. Due to the favorable testing previously performed with metal sulfide PAN composites, further testing into the performance of these composites under gas streams containing I2(g) in combination with NO2(g) and H2O(g) is needed. Humid streams of NO2(g) may arise from dissolver off-gas streams, when used fuel is dissolved in HNO3(aq) [4]. NO2(g) has been found to reduce AgZ sorption capacity for I because of oxidation of Ag, the chemisorbing agent, to Ag2O [5]. It follows that performance evaluation of novel sorbents under highly oxidizing conditions such as NO2(g) streams is critical. Therefore, the objective of this study is to determine the effect of flowing NO2(g) and H2O(g) streams on iodine sorption capacity and sorbent performance. This work utilizes custom-built gas handling capabilities for sorbent exposure along with solid-state characterization techniques to assess the physical and chemical properties of sorbents before and after exposure.

copper, bismuth, iodine capture, iodine sorbent, p↗

Continuously Regenerable Freeze-Out CO2 Control Technology

Carbon dioxide (CO2) removal technology development for portable life support systems (PLSS) has traditionally concentrated in the areas of solid and liquid chemical sorbents and semi-permeable membranes. Most of these systems are too heavy in gravity environments, require prohibitive amounts of consumables for operation on long term planetary missions, or are inoperable on the surface of Mars due to the presence of a CO2 atmosphere. This paper describes the effort performed to mature an innovative CO2 removal technology that meets NASA s planetary mission needs while adhering to the important guiding principles of simplicity, reliability, and operability. A breadboard cryogenic carbon dioxide scrubber (Cryo Scrubber) for a closed loop cryogenic PLSS was developed, designed, and tested, and a conceptual design suitable for a PLSS was developed based on the results of the breadboard testing. The Cryo Scrubber freezes CO2 and other trace contaminants out of expired vent loop gas using cooling available from a liquid oxygen (LOX) based PLSS. The device is continuously regenerable, with solid CO2 being removed from the cold freeze-out surfaces, sublimated, and vented overboard. Duration is limited only by the supply of LOX stored in the PLSS. Simplicity, reliability, and operability are universally important criteria for critical hardware on long duration Lunar or Mars missions. The Cryo Scrubber has no moving parts, requires no additional consumables, and uses no electrical power, contributing to its simplicity and reliability. It is easy to use; no operator action is required to prepare, use, or shut down the Cryo Scrubber, and it does not require charging or regeneration. The versatility of the concept allows for operation on earth, the moon, and Mars, and in microgravity.

Fricker, John↗

A Molecular Compound for Highly Selective Purification of Ethylene

Purification of C 2 H 4 from an C 2 H 4 /C 2 H 6 mixture is one of the most challenging separation processes, which is achieved mainly through energy-intensive, cryogenic distillation in industry. Sustainable, non-distillation methods are highly desired as alternatives. We discovered that the fluorinated bis(pyrazolyl)borate ligand supported copper(I) complex {[(CF 3 ) 2 Bp]Cu} 3 has features very desirable in an olefin–paraffin separation material. It binds ethylene exclusively over ethane generating [(CF 3 ) 2 Bp]Cu(C 2 H 4 ). This molecular compound exhibits extremely high and record ideal adsorbed solution theory (IAST) C 2 H 4 /C 2 H 6 gas separation selectivity, affording high purity (>99.5 %) ethylene that can be readily desorbed from separation columns. In-situ PXRD provides a “live” picture of the reversible conversion between [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) and the ethylene-free sorbent in the solid-state, driven by the presence or removal of C 2 H 4 . As a result, molecular structures of trinuclear {[(CF 3 ) 2 Bp]Cu} 3 and mononuclear [(CF 3 ) 2 Bp]Cu(C 2 H 4 ) are also presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Role of Polymer Architecture in CO 2 Capture from Air Using Supported Poly(alkylenimine)s: Linear vs Branched Polymers

Direct air capture (DAC) of CO 2 coupled with geologic storage is a promising climate change mitigation strategy, with some applications employing amines supported on porous solids as CO 2 sorbents. While branched poly(ethylenimine) (PEI) is the standard benchmark amine material, it suffers from limited oxidative stability. Poly(propylenimine) (PPI), as an alternative, has previously demonstrated improved resistance to degradation under harsh oxidative conditions. Linear and branched PEI are commercially available, though at different molecular weights, while PPI is not commercially available. For this reason, a comparative study of all four polymers (linear PEI, branched PEI, linear PPI, branched PPI) has not been reported for DAC. In this study, we synthesize and compare low-molecular-weight (∼800 g/mol) linear (L) and branched (B) PEI and PPI supported on a model support, SBA-15 silica. These materials are evaluated for CO 2 adsorption under dry, DAC-relevant conditions (400 ppm of CO 2 , 30 °C). LPPI exhibited the highest amine efficiency at all loadings, reaching a maximum of 0.14 mmol CO 2 /mmol N, outperforming BPEI, while LPEI consistently showed the lowest uptake capacity. Temperature-programmed desorption reveals that the structure of the amine polymer impacts the CO 2 binding strength, with branched polymers displaying higher desorption energies of 102−111 kJ/mol. In situ infrared spectroscopy experiments show that all sorbents preferentially capture CO 2 as ammonium carbamate. Isobaric CO 2 uptake studies further underscore the influence of polymer mobility and support pore crowding on performance, while demonstrating the sorbents’ performance at elevated temperatures and CO 2 concentrations. All materials demonstrated good stability over 25 adsorption−desorption cycles using thermal regeneration in an inert gas purge, with only BPPI displaying a 10−11% decrease in capacity/amine efficiency during cycling, possibly due to the loss of low molecular weight, oligomeric amines. This is the first side-by-side comparison of the CO 2 sorption properties of linear and branched PEI and PPI with similar molecular weights. These findings highlight the significant role of polymer architecture in CO 2 capture efficiency and inform future designs of durable, high-performance DAC sorbents.

adsorbents↗