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At least 127 records · Page 7

Amine-functionalized porous organic polymers for carbon dioxide capture

Recent developments in CO 2 capture using porous organic polymers (POPs) have received accrescent attention due to their sorbent properties such as high CO 2 uptake capacity and selectivity, tunable chemical structure and permanent porosity. POPs are constructed using two and/or three-dimensional organic monomers (building blocks) linked to each other through covalent bonding, creating high porosity. The pore structure in POPs is exceptionally stable, which leads to their cyclable CO 2 adsorption performance. However, POPs generally suffer from low CO 2 uptake and selectivity due to their interaction with CO 2 in physisorption limits (20–40 kJ mol -1 ). Similar to that in other physisorbents, the CO 2 uptake capacity of POPs further decreases under humid conditions. Pursuant to these limitations, amine functionalization in POPs has resulted in enhanced CO 2 uptake performance with improved CO 2 selectivity over non-polar gases such as N 2 . More importantly, several types of amine-functionalized POPs showed that the CO 2 uptake could remain intact under humid conditions such as in post-combustion flue gas. This review article covers recent developments in amine-functionalized porous organic polymers. Three main categories of amine functionalization, such as direct amine synthesis, amine impregnation and amine grafting, were investigated in detail by considering the effect of amines on the sorbent properties and CO 2 capture performance of POPs. The recent findings in amine-functionalized POPs were investigated including porous polymeric networks (PPNs), covalent organic frameworks (COFs), amine linked POPs, hyper-crosslinked polymers (HCPs), conjugated microporous polymers (CMPs), benzimidazole linked polymers (BILPs), porous aromatic frameworks (PAFs) and polymers of intrinsic microporosity (PIMs).

36 MATERIALS SCIENCE↗

Development of a Rapid Cycling CO(sub 2) and H(sub 2)O Removal Sorbent

The National Aeronautics and Space Administration (NASA) planned future missions set stringent demands on the design of the Portable Life Support System (PLSS), requiring dramatic reductions in weight, decreased reliance on supplies and greater flexibility on the types of missions. Use of regenerable systems that reduce weight and volume of the Extravehicular Mobility Unit (EMU) is of critical importance to NASA, both for low orbit operations and for long duration manned missions. The carbon dioxide and humidity control unit in the existing PLSS design is relatively large, since it has to remove and store 8 hours worth of CO2. If the sorbent regeneration can be carried out during the extravehicular activity (EVA) with a relatively high regeneration frequency, the size of the sorbent canister and weight can be significantly reduced. The progress of regenerable CO2 and humidity control is leading us towards the use of a rapid cycling amine system. TDA Research, Inc. is developing compact, regenerable sorbent materials to control CO2 and humidity in the space suit ventilation loop. The sorbent can be regenerated using space vacuum during the EVA, eliminating all carbon dioxide and humidity duration-limiting elements in the life support system. The material also has applications in other areas of space exploration such as the Orion spacecraft and other longer duration exploration missions requiring regenerable technologies. This paper summarizes the results of the sorbent development, testing, and evaluation efforts to date. The results of a preliminary system analysis are also included, showing the size and volume reductions for PLSS provided by the new system.

Paul, Heather↗

Testing of an Amine-Based Pressure-Swing System for Carbon Dioxide and Humidity Control

Hamilton Sundstrand has developed a stable and efficient amine-based carbon dioxide (CO2) and water vapor (H2O) sorbent, SA9T, that is well-suited for use in a spacecraft environment. The sorbent is efficiently packaged in pressure-swing regenerable beds that are thermally linked to improve removal efficiency and minimize vehicle thermal loads, and the flows are all controlled with a single spool valve. The SA9T sorbent technology has already been baselined for the new Orion spacecraft. However, more data was needed on the operational characteristics of the package in a simulated spacecraft environment. This amine-based technology, referred to as the CO2 And Moisture Removal Amine Swing-bed (CAMRAS) by the Exploration Life Support Air Team at Johnson Space Center (JSC), was tested at JSC during the last third of 2006. Two series of tests on the CAMRAS were performed at simulated metabolic loads of four and/or six crewmen in a closed chamber. Tests were run at a variety of cabin temperatures and with a range of operating conditions varying cycle time, available vacuum pressure, blower speed, and crew activity levels. Results of this testing are presented and potential flight operational strategies discussed.

Lin, Amy B.↗

Hybrid Sorbents for 129 I Capture from Contaminated Groundwater

Radioiodine ( 129 I) poses a risk to the environment due to its long half-life, toxicity, and mobility. It is found at the U.S. Department of Energy Hanford Site due to legacy releases of nuclear wastes to the subsurface where 129 I is predominantly present as iodate (IO 3 – ). To date, a cost-effective and scalable cleanup technology for 129 I has not been identified, with hydraulic containment implemented as the remedial approach. Here, novel high-performing sorbents for 129 I remediation with the capacity to reduce 129 I concentrations to or below the US Environmental Protection Agency (EPA) drinking water standard and procedures to deploy them in an ex-situ pump and treat (P&T) system are introduced. Furthermore, this includes implementation of hybridized polyacrylonitrile (PAN) beads for ex-situ remediation of IO 3 – -contaminated groundwater for the first time. Iron (Fe) oxyhydroxide and bismuth (Bi) oxyhydroxide sorbents were deployed on silica substrates or encapsulated in porous PAN beads. In addition, Fe–, cerium (Ce)–, and Bi–oxyhydroxides were encapsulated with anion-exchange resins. The PAN–bismuth oxyhydroxide and PAN–ferrihydrite composites along with Fe- and Ce-based hybrid anion-exchange resins performed well in batch sorption experiments with distribution coefficients for IO 3 – of >1000 mL/g and rapid removal kinetics. Of the tested materials, the Ce-based hybrid anion-exchange resin was the most efficient for removal of IO 3 – from Hanford groundwater in a column system, with 50% breakthrough occurring at 324 pore volumes. The functional amine groups on the parent resin and amount of active sorbent in the resin can be customized to improve the iodine loading capacity. These results highlight the potential for IO 3 – remediation by hybrid sorbents and represent a benchmark for the implementation of commercially available materials to meet EPA standards for cleanup of 129 I in a large-scale P&T system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cation Effects on CO 2 Delivery to Cu Electrode in Reactive Capture of CO 2

The direct electrochemical conversion of captured CO 2 , known as reactive capture of CO 2 (RCC), remains a formidable challenge in heterogeneous catalysis. Given that amines are one of the most widely used capture agents for CO 2 , it would be desirable to electrochemically reduce the resultant adducts, such as carbamate, directly in RCC. However, current understanding suggests that the primary species undergoing reduction in RCC with amines is the CO 2 dissociated from the sorbent. Herein, we employ ab initio molecular dynamics (AIMD) with DFT to analyze how the nature of alkali metal cations in the electrolyte affects carbamate at the Cu surface, thereby assessing the possibility of promoting RCC by cation effects. The simulations show that the carbamate’s orientation with respect to the electrode is governed by the optimal distance between the carbamate and the cation, specifically how this distance aligns with the cation’s hydration spheres. Moreover, the slow-growth AIMD results indicate that the CO 2 dissociation barrier correlates with the orientation of carbamate at the interface. When the carbamate resides beyond the cation’s first hydration sphere, it adopts a flat orientation with respect to the surface that promotes the release of CO 2 from the capture agent. In contrast, when the carbamate disrupts the first hydration sphere and exhibits a strong cation−π interaction, it adopts an upright orientation that is less conducive to CO 2 release. These findings reveal a nontrivial cation effect in RCC, suggesting that it should be possible to optimize RCC via the choice of the electrolyte.

ab initio molecular dynamics↗

First Human Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Orion Atmosphere Revitalization System (ARS). In two previous years at this conference, reports were presented on extensive Johnson Space Center (JSC) testing of the technology in a representative environment with simulated human metabolic loads. The next step in developmental testing at JSC was to replace the simulated humans with real humans; this testing was conducted in the spring of 2008. This first instance of human testing of a new Orion ARS technology included several cases in a sealed Orione-quivalent free volume and three cases using emergency breathing masks connected directly to the ARS loop. Significant test results presented in this paper include comparisons between the standard metabolic rates for CO2 and water vapor production published in Orion requirements documents and real-world rate ranges observed with human test subjects. Also included are qualitative assessments of process flow rate and closed-loop pressure-cycling tolerability while using the emergency masks. Recommendations for modifications to the Orion ARS design and operation, based on the test results, conclude the paper.

Lin, Amy↗

Space Suit Environment Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Orion Atmosphere Revitalization System (ARS). In two previous years at this conference, reports were presented on extensive Johnson Space Center (JSC) testing of this technology in a sea-level pressure environment with simulated human metabolic loads. Another paper at this year s conference discusses similar testing with real human metabolic loads, including some closed-loop testing with emergency breathing masks. The Orion ARS is designed to also support extravehicular activity operations from a depressurized cabin. The next step in developmental testing at JSC was, therefore, to test this ARS technology in a typical closed space suit loop environment with low-pressure pure oxygen inside the process loop and vacuum outside the loop. This was the first instance of low-pressure oxygen loop testing of a new Orion ARS technology, and was conducted with simulated human metabolic loads in December 2008. The test investigated pressure drops through two different styles of prototype suit umbilical connectors and general swing-bed performance with both umbilical configurations as well as with a short jumper line installed in place of the umbilicals. Other interesting results include observations on the thermal effects of swing-bed operation in a vacuum environment and a recommendation of cycle time to maintain acceptable atmospheric CO2 and moisture levels.

Lin, Amy↗

First Human Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Orion Atmosphere Revitalization System (ARS). In two previous years at this conference, reports were presented on extensive Johnson Space Center (JSC) testing of the technology in a representative environment with simulated human metabolic loads. The next step in developmental testing at JSC was to replace the simulated humans with real humans; this testing was conducted in the spring of 2008. This first instance of human testing of a new Orion ARS technology included several cases in a sealed Orion-equivalent free volume and three cases using emergency breathing masks connected directly to the ARS loop. Significant test results presented in this paper include comparisons between the standard metabolic rates for CO2 and water vapor production published in Orion requirements documents and real-world rate ranges observed with human test subjects. Also included are qualitative assessments of process flow rate and closed-loop pressure-cycling tolerability while using the emergency masks. Recommendations for modifications to the Orion ARS design and operation, based on the test results, conclude the paper.

Lin, Amy↗

2009 Continued Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Orion Atmosphere Revitalization System (ARS). In three previous years at this conference, reports were presented on extensive Johnson Space Center (JSC) testing of this technology in a sea-level pressure environment with simulated and real human metabolic loads in both open and closed-loop configurations. The test article design was iterated a third time before the latest series of such tests, which was performed in the first half of 2009. The new design incorporates a canister configuration modification for overall unit compactness and reduced pressure drop, as well as a new process flow control valve that incorporates both compressed gas purge and dual-end vacuum desorption capabilities. This newest test article is very similar to the flight article designs. Baseline tests of the new unit were performed to compare its performance to that of the previous test articles. Testing of compressed gas purge operations helped refine launchpad operating condition recommendations developed in earlier testing. Operating conditions used in flight program computer models were tested to validate the model projections. Specific operating conditions that were recommended by the JSC test team based on past test results were also tested for validation. The effects of vacuum regeneration line pressure on resulting cabin conditions was studied for high metabolic load periods, and a maximum pressure is recommended.

Button, Amy Lin↗

Space Suit Environment Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Orion Atmosphere Revitalization System (ARS). In three previous years at this conference, reports were presented on extensive Johnson Space Center (JSC) testing of this technology. That testing was performed in a sea-level pressure environment with both simulated and real human metabolic loads, and in both open and closed-loop configurations. The Orion ARS is designed to also support space-suited operations in a depressurized cabin, so the next step in developmental testing at JSC was to test the ARS technology in a typical closed space suit-loop environment with low-pressure oxygen inside the process loop and vacuum outside the loop. This was the first instance of low-pressure, high-oxygen, closed-loop testing of the Orion ARS technology, and it was conducted with simulated human metabolic loads in March 2009. The test investigated pressure drops and flow balancing through two different styles of prototype suit umbilical connectors. General swing-bed performance was tested with both umbilical configurations, as well as with a short jumper line installed in place of the umbilicals. Other interesting results include observations on the thermal effects of swing-bed operation in a vacuum environment and a recommendation of cycle time to maintain acceptable suit atmospheric CO2 and moisture levels.

Button, Amy B.↗

2009 Continued Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Orion Atmosphere Revitalization System (ARS). In three previous years at this conference, reports were presented on extensive Johnson Space Center (JSC) testing of this technology in a sea-level pressure environment, with simulated and real human metabolic loads, in both open and closed-loop configurations. The test article design was iterated a third time before the latest series of such tests, which was performed in the first half of 2009. The new design incorporates a canister configuration modification for overall unit compactness and reduced pressure drop, as well as a new process flow control valve that incorporates both compressed gas purge and dual-end vacuum desorption capabilities. This newest test article is very similar to the flight article designs. Baseline tests of the new unit were performed to compare its performance to that of the previous test articles. Testing of compressed gas purge operations helped refine launchpad operating condition recommendations developed in earlier testing. Operating conditions used in flight program computer models were tested to validate the model projections. Specific operating conditions that were recommended by the JSC test team based on past test results were also tested for validation. The effects of vacuum regeneration line pressure on resulting cabin conditions was studied for high metabolic load periods, and a maximum pressure is recommended

Button, Amy B.↗

Reduced Pressure Cabin Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Atmosphere Revitalization System for moderate duration missions of the Orion Multipurpose Crew Vehicle. In previous years at this conference, reports were presented on extensive Johnson Space Center testing of this technology in a sea-level pressure environment with simulated and actual human metabolic loads in both open and closed-loop configurations. In 2011, the technology was tested in an open cabin-loop configuration at ambient and two sub-ambient pressures to compare the performance of the system to the results of previous tests at ambient pressure. The testing used a human metabolic simulator with a different type of water vapor generation than previously used, which added some unique challenges in the data analysis. This paper summarizes the results of: baseline and some matrix testing at all three cabin pressures, increased vacuum regeneration line pressure with a high metabolic load, a set of tests studying CO2 and water vapor co-adsorption effects relative to model-predicted performance, and validation tests of flight program computer model predictions with specific operating conditions.

Button, Amy↗

The Orion Atmosphere Revitalization Technology in Manned Ambient Pressure Space Suit Testing

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Atmosphere Revitalization System (ARS) for moderate duration missions of the Orion Multipurpose Crew Vehicle. The Orion ARS is designed to support not only open-cabin operations, tests of which have been reported in previous years at this conference, but also closed space suit-loop operations. A previous low-pressure suit loop test was performed with a human metabolic simulator, and humans wearing emergency masks were tested in a closed-loop configuration before that. In late 2011, simple tests were performed in a suit-loop configuration with human test subjects in prototype space suits with prototype umbilicals at ambient and two slightly above-ambient pressures. Trace contaminant filters and a prototype blower were also incorporated into the test rig. This paper discusses the performance of the ARS technology in that 2011 test configuration.

Button, Amy↗

Reduced Pressure Cabin Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by Hamilton Sundstrand and baselined for the Atmosphere Revitalization System for moderate duration missions of the Orion Multipurpose Crew Vehicle. In previous years at this conference, reports were presented on extensive Johnson Space Center testing of this technology in a sea-level pressure environment with simulated and actual human metabolic loads in both open and closed-loop configurations. In 2011, the technology was tested in an open cabin-loop configuration at ambient and two sub-ambient pressures to compare the performance of the system to the results of previous tests at ambient pressure. The testing used a human metabolic simulator with a different type of water vapor generation than previously used, which added some unique challenges in the data analysis. This paper summarizes the results of: baseline and some matrix testing at all three cabin pressures, increased vacuum regeneration line pressure with a high metabolic load, a set of tests studying CO2 and water vapor co-adsorption effects relative to model-predicted performance, and validation tests of flight program computer model predictions with specific operating conditions.

Button, Amy↗

Reduced Pressure Cabin Testing of the Orion Atmosphere Revitalization Technology

An amine-based carbon dioxide (CO2) and water vapor sorbent in pressure-swing regenerable beds has been developed by United Technologies Corp. Aerospace Systems (UTAS, formerly Hamilton Sundstrand) and baselined for the Atmosphere Revitalization System for moderate duration missions of the Orion Multipurpose Crew Vehicle (MPCV). In previous years at this conference, reports were presented on extensive Johnson Space Center testing of this technology in a sea-level pressure environment with simulated and actual human metabolic loads in both open and closed-loop configurations. In 2011, the technology was tested in an open cabin-loop configuration at ambient and two sub-ambient pressures to compare the performance of the system to the results of previous tests at ambient pressure. The testing used a human metabolic simulator with a different type of water vapor generation than previously used, which added some unique challenges in the data analysis. This paper summarizes the results of: baseline and some matrix testing at all three cabin pressures, increased vacuum regeneration line pressure testing with a high metabolic load, a set of tests studying CO2 and water vapor co-adsorption effects relative to model-predicted performance, and validation tests of flight project computer model predictions with specific operating conditions.

Button, Amy B.↗

Solid Amine CO2 Adsorbent Degradation: Insights from Experiments and Atomistic Simulations

Direct air capture (DAC) has received significant attention this decade as a viable solution to limit global warming, although large-scale deployment is currently not economically feasible. To reach the ambitious cost target set by the U.S. of $100/ton CO2 captured and stored, significant improvements must be made to sorbent lifetime and capacity. Aminosilanes grafted onto silica supports are promising candidates for deployment in DAC systems due to their relatively high oxidative stability and low regeneration temperature. Despite myriad advancements in the field, there still exists a fundamental knowledge gap relating sorbent structure to performance. In this work, we grafted various aminosilanes onto the highly porous silica SBA-15 and characterized both oxidative stability and CO2 capacity. Material properties systematically investigated included amine moiety (primary vs. secondary), silane group structure, number of linkages to the silica support, and co-addition of impregnated amines (e.g., PEI), among others. A fixed bed system was used to execute accelerated degradation studies in the presence of humidity and varying temperatures to simulate realistic operating conditions. Atomistic simulations were combined with the experimental results to gain mechanistic insight, ultimately informing the design of next-generation materials

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗