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At least 19 records

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↗

Propylamine Functionalized Porous Fiber Sorbents with High Oxidation Stability for Direct Air Capture

Amine-based sorbents are highly effective for direct air capture (DAC) due to their excellent CO2 capture efficiency under ultra-dilute conditions. However, these sorbents can suffer degradation when exposed to combinations of heat, oxygen, and other atmospheric components, indicating a need for improved sorbent stability. In this study, we developed amidoxime functionalized polymer of intrinsic microporosity (PIM-1-AO) fibers with tethered amines, specifically tris(2-aminoethyl)amine (TAEA) and tris(3-aminopropyl)amine (TAPA), denoted as PIM-1-AO-TAEA and PIM-1-AO-TAPA, respectively. In addition, large scale sorbent fiber spinning has been successfully performed by producing meters of fibers in the lab. We demonstrated that substituting TAEA with TAPA, which has propyl chains instead of ethyl chains, reduces oxidative degradation under regeneration conditions. The findings revealed that PIM-1-AO-TAPA not only significantly outperforms PIM-1-AO-TAEA after accelerated aging process, but also outperforms any other sorbent used in DAC aged under similar conditions. Moreover, PIM-1-AO-TAPA sorbent fibers showed one of the highest amine efficiencies (0.25) considering the low amine loading (21%) coupled with robust CO2 uptake performance (1.12 mmol/g) under DAC conditions.

amine-based sorbent↗

Influence of Transition Metal Ion Contaminants on the Performance of Amine-Based Solid Sorbents in Direct Air Capture

Amine-functionalized solid sorbents are a class of sorbent materials proposed for direct air capture (DAC) of CO 2 , yet their long-term performance is susceptible to degradation under realistic operating conditions. Many amines are not thermodynamically stable in air, and amine sorbents oxidize while in use during DAC temperature swing adsorption processes. In this study, we investigate the role of transition metal ion contaminants, specifically Cu 2+ , Fe 2+ , and Ni 2+ , on the oxidative degradation of poly(ethylenimine) (PEI)-impregnated SBA-15 sorbents. By introducing metal ions via different modes mimicking both synthesis-related impurities and impurities derived from environmental exposure, we systematically evaluate sorbent stability after exposure to dry air at an elevated temperature. Thermogravimetric CO 2 uptake measurements reveal that even trace levels of Cu and Fe (as low as ∼4 ppm) can lead to measurable sorbent deactivation after oxidative aging, despite negligible loss in the performance of the control samples. In situ infrared, UV–vis, and X-ray photoelectron spectroscopies indicate that these metals catalyze radical-driven oxidation pathways, altering the chemical structure of the sorbent and accelerating degradation. Our findings underscore the need to account for trace metal contamination during DAC sorbent synthesis and deployment and highlight the importance of environmental contamination pathways.

CO2 capture↗

Energy-Efficient Direct Air Capture System for High Purity CO 2 Separation

The primary objective of this project is to demonstrate the University of Cincinnati’s direct air capture (DAC) sorbent technology in a monolithic structure installed in a passive air contactor (PAC). The modified amine-based sorbent technology provides reduced heat of desorption and resistance to thermal and oxidative degradations for robust and long-term performances and cost effective sorbent management. During the project period, additional amine modifications were developed and a U.S./PCT patent application was filed.

42 ENGINEERING↗

Development of an Amine-based System for Combined Carbon Dioxide, Humidity, and Trace Contaminant Control

A number of amine-based carbon dioxide (CO2) removal systems have been developed for atmosphere revitalization in closed loop life support systems. Most recently, Hamilton Sundstrand developed an amine-based sorbent, designated SA9T, possessing approximately 2-fold greater capacity compared to previous formulations. This new formulation has demonstrated applicability for controlling CO2 levels within vehicles and habitats as well as during extravehicular activity (EVA). System volume is competitive with existing technologies. Further enhancements in system performance can be realized by incorporating humidity and trace contaminant control functions within an amine-based atmosphere revitalization system. A 3-year effort to develop prototype hardware capable of removing CO2, H2O, and trace contaminants from a cabin atmosphere has been initiated. Progress pertaining to defining system requirements and identifying alternative amine formulations and substrates is presented.

Nalette, Tim↗

Solution and Active Site Speciation Drive Selectivity for Electrocatalytic Reactive Carbon Capture in Diethanolamine over Ni–N–C Catalysts

Direct conversion of captured forms of carbon, or reactive carbon capture (RCC), presents an opportunity to reduce the energy intensity and cost of direct CO 2 utilization from dilute sources. While amine-based sorbents effectively capture CO 2 , their use for RCC presents numerous challenges with typical pure metal catalysts used for electrochemical CO 2 reduction (CO 2 R). Here, using both theory and experiments, we find that Ni–N–C single atom catalysts are effective for RCC conversion to CO using a diethanolamine sorbent, in contrast to pure metal catalysts. Computational analysis reveals that RCC can proceed directly through direct reduction of the sorbent-CO 2 adduct or indirectly by C–N bond breaking facilitating CO 2 adsorption and subsequent reduction. We find that the latter mechanism is most prevalent at low overpotentials where we experimentally observe RCC selectivity. We also find experimentally that the rate of CO production for RCC with Ni–N–C catalysts can exceed pure bicarbonate solutions at intermediate sorbent concentration (0.1–0.5 M DEA) under dilute (10–25%) streams of CO 2 at low overpotentials. The coordination environment of Ni sites and the solution speciation influence their RCC activity, with changes in protonation to coordinating N/C atoms resulting in changing the RCC mechanism and consequent activity. In situ X-ray absorption spectroscopy and computational analysis reveal restructuring under RCC conditions due to hydrogen coadsorption with DEA that limits the stability of Ni–N–C catalysts. This work highlights the importance of carefully controlling the catalyst and solution environment to achieve active and stable RCC electrocatalysis.

Chemistry↗

Development of Next-Generation Additive Chemistry for Direct Air Capture Sorbents (CRADA Final Report)

Introducing antioxidant additives into amine-based DAC sorbents can extend their lifetime. These sorbents are readily prepared by physically mixing additives with amines, a straightforward approach using commercially available materials. Advancing this strategy requires understanding how additives function under varying conditions, especially humidity. This project aims to reveal how humidity and additive chemistry influence oxidative degradation of PEI-based sorbents, levereging LLNL’s expertise in physics-based computational modeling, and Global Thermostat (GT)’s expertise in materials synthesis, characterization, and degradation kinetics testing, to gain fundamental insights into the chemistries and mechanisms of PEI oxidative degradation, and develop design principles that enhance sorbent durability.

36 MATERIALS SCIENCE↗

Trace Contaminant Testing with the Orion Atmosphere Revitalization Technology

Every spacecraft atmosphere contains trace contaminants resulting from offgassing by cabin materials and human passengers. 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). Part of the risk mitigation effort for this new technology is the study of how atmospheric trace contaminants will affect and be affected by the technology. One particular area of concern is ammonia, which, in addition to the normal spacecraft sources, can also be off-gassed by the amine-based sorbent. In the first half of 2009, tests were performed with typical cabin atmosphere levels of five of the most common trace gases, most of which had not yet been tested with this technology. A subscale sample of the sorbent was exposed to each of the chemicals mixed into a stream of moist, CO2-laden air, and the CO2 adsorption capacity of the sorbent was compared before and after the exposure. After these typical-concentration chemicals were proven to have negligible effect on the subscale sample, tests proceeded on a full-scale test article in a sealed chamber with a suite of eleven contaminants. To isolate the effects of various test rig components, several extended-duration tests were run: without injection or scrubbing, with injection and without scrubbing, with injection and scrubbing by both the test article and dedicated trace contaminant filters, and with injection and scrubbing by only the test article. The high-level results of both the subscale and full-scale tests are examined in this paper.

Button, Amy Lin↗

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

In a crewed spacecraft environment, atmospheric carbon dioxide (CO2) and moisture control is crucial. Hamilton Sundstrand has developed a stable and efficient amine-based CO2 and water vapor 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. Flows are all controlled with a single spool valve. This technology has been baselined for the new Orion spacecraft. However, more data was needed on the operational characteristics of the package in a simulated spacecraft environment. A unit was therefore tested with simulated metabolic loads in a closed chamber at Johnson Space Center during the last third of 2006. Tests were run at a variety of cabin temperatures and with a range of operating conditions varying cycle time, vacuum pressure, air flow rate, and crew activity levels. Results of this testing are presented and potential flight operational strategies discussed.

Lin, Amy↗

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

In a crewed spacecraft environment, atmospheric carbon dioxide (CO2) and moisture control are crucial. Hamilton Sundstrand has developed a stable and efficient amine-based CO2 and water vapor 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. Flows are all controlled with a single spool valve. This technology has been baselined for the new Orion spacecraft. However, more data was needed on the operational characteristics of the package in a simulated spacecraft environment. A unit was therefore tested with simulated metabolic loads in a closed chamber at Johnson Space Center during the last third of 2006. Those test results were reported in a 2007 ICES paper. A second test article was incorporated for a third phase of testing, and that test article was modified to allow pressurized gas purge regeneration on the launch pad in addition to the standard vacuum regeneration in space. Metabolic rates and chamber volumes were also adjusted to reflect current programmatic standards. The third phase of tests was performed during the spring and summer of 2007. Tests were run with a range of operating conditions, varying: cycle time, vacuum pressure (or purge gas flow rate), air flow rate, and crew activity levels. Results of this testing are presented and potential flight operational strategies discussed.

Lin, Amy↗

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.↗

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↗

Aqueous Carbon Capture Using Guanidinium-Functionalized Hollow Fiber Sorbent Contactors

As part of the growing suite of technologies aimed at combatting rising temperatures, negative emissions technologies have become a powerful tool in the global effort to minimize the consequences of human-induced climate change. Among these, carbon removal from aqueous sources, which contain much higher carbon concentrations than the atmosphere, remains largely unexplored. Indeed, developing robust and efficient carbon capture materials for usage in complex aqueous environments remains a significant challenge. Here, we explore the potential of functionalizing polyvinylidene fluoride (PVDF) hollow fiber contactors grafted with a guanidinium-derived polymer sorbent for carbon removal from aqueous sources, including saline waters. Computational screening against amine-based analogs is utilized to identify guanidinium as a promising motif for bicarbonate (HCO 3 – ) ions binding. To leverage this finding, synthesis of a guanidinium polymer and subsequent covalent grafting onto PVDF hollow fibers is employed to structured polymer–sorbent–grafted hollow fiber contactors. Our prototype achieves an initial HCO 3 – removal of 34% with an increase to 98% after four cycles. The functionalized fibers demonstrate aqueous stability over 13 adsorption/desorption cycles in model NaHCO 3 solutions where regeneration is facilitated by a mild pH swing. Importantly, the system maintains selective performance in the presence of competitive chloride ions over multiple cycles; carbon removal remained above 10% even at high (10:1) NaCl/NaHCO 3 ratios. These findings demonstrate the feasibility of sorbent-based aqueous carbon removal and highlight its potential as a promising approach for negative emissions.

carbon capture↗

Transformational Sorbent System for Post-Combustion Carbon Capture (Final Report)

As part of this DOE Contract (Transformational Sorbent System for Post-Combustion Carbon Capture, DE-FE0031734),TDA Research Inc. developed a transformational sorbent system for post combustion CO 2 capture process that captures more than 95% of CO 2 emissions from a coal fired power plant, recovering CO 2 at 95% purity with a cost of CO 2 capture significantly lower than with amine-based system (~$30 per tonne (MT) of CO 2 captured). TDA’s transformational sorbent system uses a novel, highly stable, high-capacity metal organic framework (MOF) based CO 2 sorbent in a new vacuum/concentration swing adsorption (VCSA) process that allows us to use high efficiency vacuum pumps with a low auxiliary load. A pulverized coal fired power plant equipped with TDA’s transformational sorbent system for post combustion CO 2 capture is expected to efficiently produce electricity with a low Cost of Electricity (COE) and capture greater than 95% of the CO 2 from the power plant exhaust.

01 COAL, LIGNITE, AND PEAT↗

Application of Vacuum Swing Adsorption for Carbon Dioxide and Water Vapor Removal from Manned Spacecraft Atmospheres

In NASA's Vision for Space Exploration (Bush, 2004), (Griffin, 2007), humans will once again travel beyond the confines of earth's gravity, this time to remain there for extended periods. These forays will place unprecedented demands on launch systems. They must not only blast out of earth's gravity well as during the Apollo moon missions, but also liftoff the supplies needed to sustain a larger crew over much longer periods. Thus all spacecraft systems, including those for the separation of metabolic carbon dioxide and water from a crewed vehicle, must be minimized with respect to mass, power, and volume. Emphasis is also placed on system robustness both to minimize replacement parts and ensure crew safety when a quick return to earth is not possible. For short-term phases of manned space exploration, such as transit from the earth to the moon, venting of metabolic carbon dioxide and water to space is more efficient than the inclusion of large recycling systems on the spacecraft. The baseline system for the Orion spacecraft is an amine-based vacuum swing system (Smith, Perry et aI., 2006). As part of the development of an alternative approach, a sorbent-based CO2 and H2O removal system (Knox, Adams et aI., 2006), subscale testing was conducted to evaluate potential performance improvements obtainable by recuperating the heat of adsorption to aid in vacuum desorption. This bed design is shown in Figure 1, is depicted here with a lattice structure instead of reticulated foam for heat transfer. The slot widths are approximately 1.2 mm wide and 8.5 mm long. Bed depth is approximately 4.7 mm. Headers (not shown) were produced by the stereo lithography apparatus at MSFC.

Knox, J.↗