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At least 55 records · Page 3

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

Development of a Rapid Cycling CO2 and H2O 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 eight hours worth of carbon dioxide (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. 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 CO2 and humidity duration-limiting elements in the life support system. The material also has applications in other areas of space exploration including long duration exploration missions requiring regenerable technologies and possibly the Crew Exploration Vehicle (CEV) spacecraft. This paper summarizes the results of the sorbent development, testing, and evaluation efforts to date.

Alptekin, Gokhan

High temperature regenerative H.sub.2 S sorbents

Efficient, regenerable sorbents for removal of H.sub.2 S from high temperature gas streams comprise porous, high surface area particles. A first class of sorbents comprise a thin film of binary oxides that form a eutectic at the temperature of the gas stream coated onto a porous, high surface area refractory support. The binary oxides are a mixture of a Group VB or VIB metal oxide with a Group IB, IIB or VIII metal oxide such as a film of V-Zn-O, V-Cu-O, Cu-Mo-O, Zn-Mo-O or Fe-Mo-O coated on an alumina support. A second class of sorbents consist of particles of unsupported mixed oxides in the form of highly dispersed solid solutions of solid compounds characterized by small crystallite size, high porosity and relatively high surface area. The mixed oxide sorbents contain one Group IB, IIB or VIIB metal oxide such as copper, zinc or manganese and one or more oxides of Groups IIIA, VIB or VII such as aluminum, iron or molybdenum. The presence of iron or aluminum maintains the Group IB, IIB or VIIB metal in its oxidized state. Presence of molybdenum results in eutectic formation at sulfidation temperature and improves the efficiency of the sorbent.

Flytani-Stephanopoulos, Maria

Sorbent, Sublimation, and Icing Modeling Methods: Experimental Validation and Application to an Integrated MTSA Subassembly Thermal Model

This paper details the validation of modeling methods for the three core components of a Metabolic heat regenerated Temperature Swing Adsorption (MTSA) subassembly, developed for use in a Portable Life Support System (PLSS). The first core component in the subassembly is a sorbent bed, used to capture and reject metabolically produced carbon dioxide (CO2). The sorbent bed performance can be augmented with a temperature swing driven by a liquid CO2 (LCO2) sublimation heat exchanger (SHX) for cooling the sorbent bed, and a condensing, icing heat exchanger (CIHX) for warming the sorbent bed. As part of the overall MTSA effort, scaled design validation test articles for each of these three components have been independently tested in laboratory conditions. Previously described modeling methodologies developed for implementation in Thermal Desktop and SINDA/FLUINT are reviewed and updated, their application in test article models outlined, and the results of those model correlations relayed. Assessment of the applicability of each modeling methodology to the challenge of simulating the response of the test articles and their extensibility to a full scale integrated subassembly model is given. The independent verified and validated modeling methods are applied to the development of a MTSA subassembly prototype model and predictions of the subassembly performance are given. These models and modeling methodologies capture simulation of several challenging and novel physical phenomena in the Thermal Desktop and SINDA/FLUINT software suite. Novel methodologies include CO2 adsorption front tracking and associated thermal response in the sorbent bed, heat transfer associated with sublimation of entrained solid CO2 in the SHX, and water mass transfer in the form of ice as low as 210 K in the CIHX.

Bower, Chad

Performance Evaluation of Engineered Structured Sorbents for Atmosphere Revitalization Systems On Board Crewed Space Vehicles and Habitats

Engineered structured (ES) sorbents are being developed to meet the technical challenges of future crewed space exploration missions. ES sorbents offer the inherent performance and safety attributes of zeolite and other physical adsorbents but with greater structural integrity and process control to improve durability and efficiency over packed beds. ES sorbent techniques that are explored include thermally linked and pressure-swing adsorption beds for water-save dehumidification and sorbent-coated metal meshes for residual drying, trace contaminant control, and carbon dioxide control. Results from sub-scale performance evaluations of a thermally linked pressure-swing adsorbent bed and an integrated sub-scale ES sorbent system are discussed.

Howard, David F.

Carbon-Based Regenerable Sorbents for the Combined Carbon Dioxide and Ammonia Removal for the Primary Life Support System (PLSS)

Results are presented on the development of reversible sorbents for the combined carbon dioxide and trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs). Since ammonia is the most important TC to be captured, data on TC sorption presented in this paper are limited to ammonia, with results relevant to other TCs to be reported at a later time. The currently available life support systems use separate units for carbon dioxide, trace contaminants, and moisture control, and the long-term objective is to replace the above three modules with a single one. Furthermore, the current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is non-regenerable, and the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. The objective of this study was to demonstrate the feasibility of using carbon sorbents for the reversible, concurrent sorption of carbon dioxide and ammonia. Several carbon sorbents were fabricated and tested, and multiple adsorption/vacuum-regeneration cycles were demonstrated at room temperature, and also a carbon surface conditioning technique that enhances the combined carbon dioxide and ammonia sorption without impairing sorbent regeneration.

Wojtowicz, Marek A.

Performance Degradation of Amine-Infused Fiber Sorbents for Direct Air Capture: Mechanisms and Solutions

Sorbent stability poses significant impacts on longterm performance of direct air capture (DAC) of CO 2 and levelized cost of capture (LCOC). We report the DAC performance degradation of amine-infused fiber sorbents based on poly(ethylenimine) (PEI), mesoporous SiO 2 , and cellulose acetate (CA) over CO 2 cyclic sorption cycles in a nonoxidative environment. Infrared and nuclear magnetic resonance spectra indicate that the aminolysis reactions between CA ester moieties and PEI amine sites lead to the formation of acetamides and hence lower CO 2 affinities of the sorbents. This stability issue can be remedied by hydrolysis treatment of the CA fiber sorbents before PEI impregnation or replacing CA with poly(ether sulfone). This study underscores the importance of selecting proper support or additive materials of DAC contactors that are compatible with active species of CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Scalable Fabrication of a Fibrous Amine-functionalized Matrix (FAM) Sorbent for Critical Mineral Recovery

We report a novel flat sheet Fibrous Amine-functionalized Matrix (FAM) sorbent platform designed for efficient and selective capture of CM from dilute solutions. The FAM sorbent features crosslinked amine microfilms coated onto/within a glass fiber matrix, providing fast mass transfer and excellent mechanical stability. Systematic batch and flow-through tests with FAM revealed rapid metal uptake kinetics and high capacity for representative species, achieving ~90 mg/g of Gallium, ~100 mg/g of Cobalt, and ~90 mg/g for Neodymium. Moreover, multiple eluents, including mineral acids and complexing agents, enabled highly effective desorption of adsorbed metals, demonstrating the feasibility of regenerating FAM sorbents. Importantly, tests with authentic coal ash leachate demonstrated strong selectivity toward U.S. Department of Energy (DOE)-listed CM and rare earth elements over abundant base cations, confirming the robustness of FAM in realistic complex solutions. The flat sheet geometry was amenable to scaling into durable spiral wound modules, highlighting the potential for future regeneration and reuse. This work establishes FAM sorbents as a promising platform for the recovery of CM from wastewaters, advancing both resource sustainability and environmental stewardship.

critical mineral recovery

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

Thermally Enhanced Acidity for Regeneration of Carbon Dioxide Sorbent

The thermal regeneration of CO2 sorbent is the most energy-consuming step in the CO2-capturing process. Although the addition of an acid can induce CO2 release, it does not regenerate the sorbent because the acid forms a salt with the basic sorbent and diminishes its capability for capturing CO2. In this work, a novel approach based on thermally enhanced acidity was studied. This approach utilizes an additive that does not affect the sorbent at room temperature, but its acidity significantly increases at elevated temperatures, which assists the thermal release of CO2. M-cresol was added to an aqueous solution of morpholine. The CO2 capture and release of the mixture were compared to those of a control solution without m-cresol. The amounts of carbamate, bicarbonate, and unreacted morpholine were quantitatively determined using 1H NMR and weight analysis. The results showed that m-cresol did not affect the reactivity of morpholine in the formation of carbamate with CO2 at room temperature. At elevated temperatures, the acidity of m-cresol increased according to Van’t Hoff’s equation, which resulted in a significantly higher rate of CO2 release than that of the control. Given the low cost of m-cresol and its derivatives, this approach could lead to practical technology in the near future.

Energy & Fuels

Waste-Heat-Driven Cooling Using Complex Compound Sorbents

Improved complex-compound sorption pumps are undergoing development for use as prime movers in heat-pump systems for cooling and dehumidification of habitats for humans on the Moon and for residential and commercial cooling on Earth. Among the advantages of sorption heat-pump systems are that they contain no moving parts except for check valves and they can be driven by heat from diverse sources: examples include waste heat from generation of electric power, solar heat, or heat from combustion of natural gas. The use of complex compound sorbents in cooling cycles is not new in itself: Marketing of residential refrigerators using SrCl2 was attempted in the 1920s and 30s and was abandoned because heat- and mass-transfer rates of the sorbents were too low. Addressing the issue that gave rise to the prior abandonment of complex compound sorption heat pumps, the primary accomplishment of the present development program thus far has been the characterization of many candidate sorption media, leading to large increases in achievable heat- and mass-transfer rates. In particular, two complex compounds (called "CC260-1260" and "CC260-2000") were found to be capable of functioning over the temperature range of interest for the lunar-habitat application and to offer heat- and mass-transfer rates and a temperature-lift capability adequate for that application. Regarding the temperature range: A heat pump based on either of these compounds is capable of providing a 95-K lift from a habitable temperature to a heat-rejection (radiator) temperature when driven by waste heat at an input temperature .500 K. Regarding the heat- and mass-transfer rates or, more precisely, the power densities made possible by these rates: Power densities observed in tests were 0.3 kilowatt of cooling per kilogram of sorbent and 2 kilowatts of heating per kilogram of sorbent. A prototype 1-kilowatt heat pump based on CC260-2000 has been built and demonstrated to function successfully.

Rocketfeller, Uwe

Long Duration Sorbent Testbed

The Long Duration Sorbent Testbed (LDST) is a flight experiment demonstration designed to expose current and future candidate carbon dioxide removal system sorbents to an actual crewed space cabin environment to assess and compare sorption working capacity degradation resulting from long term operation. An analysis of sorbent materials returned to Earth after approximately one year of operation in the International Space Station's (ISS) Carbon Dioxide Removal Assembly (CDRA) indicated as much as a 70% loss of working capacity of the silica gel desiccant material at the extreme system inlet location, with a gradient of capacity loss down the bed. The primary science objective is to assess the degradation of potential sorbents for exploration class missions and ISS upgrades when operated in a true crewed space cabin environment. A secondary objective is to compare degradation of flight test to a ground test unit with contaminant dosing to determine applicability of ground testing.

Howard, David F.

Novel Liquid Sorbent C02 Removal System for Microgravity Applications

Removing Carbon Dioxide (CO2) from a spacecraft environment for deep space exploration requires a robust system that is low in weight, power, and volume. Current state-of-the-art microgravity compatible CO2 removal systems, such as the carbon dioxide removal assembly (CDRA), utilize solid sorbents that demand high power usage due to high desorption temperatures and a large volume to accommodate for their comparatively low capacity for CO2. Additionally, solid sorbent systems contain several mechanical components that significantly reduce reliability and contribute to a large overall mass. A liquid sorbent based system has been evaluated as an alternative is proposed to consume 65% less power, weight, and volume than solid based CO2 scrubbers. This paper presents the design of a liquid sorbent CO2 removal system for microgravity applications.

Rogers, Tanya

Monolithic Trace-Contaminant Sorbents Fabricated from 3D-Printed Polymer Precursors

The current trace-contaminant (TC) removal technology for use in Extravehicular Activities (EVAs) involves the use of a packed bed of acid-impregnated granular charcoal, which is difficult to regenerate. In this paper, results are presented on the development of vacuum-regenerable TC sorbents for use in the Portable Life Support System (PLSS). The sorbents are derived from 3D-printed polymer monoliths (e.g., honeycomb structures), which are then carbonized and activated in order to develop porosity, and also to enhance the TC-sorption capacity. Results are presented on the following aspects of carbon-sorbent development: (1) precursor selection; (2) monolith fabrication; (3) shape retention and strength; (4) carbon surface and porosity characterization; (5) TC-sorption capacity and vacuum-regeneration; (6) pressure drop; and (7) sub-scale sorbent prototype. The use of predominantly microporous monolithic carbon is associated with the following benefits: (a) high TC-sorption capacity; (b) low pressure drop; (c) rapid vacuum (pressure-swing) desorption due to thin monolith walls and low pressure drop; (d) good thermal management (high thermal conductivity and low adsorption/desorption thermal effects associated with physisorption); and (e) good resistance to dusty environments.

Portable Life Support System (PLSS)

Literature Review of Microwave Regeneration of CO2 Capture Sorbent Materials

Utilizing liquid amines for air revitalization applications has been of continued interest for many decades. They have the advantage of being regenerable sorbents with long lifetimes and a high acuteness for carbon dioxide. While their usage on Earth for flue gas and submarines has been explored for some time now, they are still being researched for use in microgravity environments. To succeed in a microgravity environment, such as usage on the International Space Station, an air revitalization system that is reliant on liquid amines as its sorbent must have a low Equivalent System Mass (ESM), among many other performance parameters. One way of optimizing this ESM number is through bringing down the systems power consumption with the use of microwave heating of the liquid sorbent. Microwave heating allows the liquid sorbent to be heated in a much more efficient way when compared to conventional types of heating techniques, such as convection or conduction. This paper will explore the physical mechanisms behind microwave heating, and how it could potentially be applied to a liquid amine carbon capture system, laying out any concerns and future constraints that a system designer may encounter.

Tiago Faria Costa

Xplo-SA9T: Optimization of Sorbent Technology With Existing and New Amine Variants for Carbon Dioxide Removal and Humidity Control

Scrubbing of the spacesuit air stream to control humidity and regulate carbon dioxide (CO 2 ) relies on amine-loaded resins, colloquially known as sorbents. The efficacy of Rapid Cycle Amine technology relies on the propensity of nitrogens toward adsorption of CO 2 while simultaneously offering regenerative properties under vacuum or positive pressure. The commonly utilized sorbent, SA9T, was recreated and evaluated further to increase stability and serve as a benchmark comparison for newly synthesized amine sorbent technologies. Ongoing storage studies with eight different environments will allow the development of applicable storage protocols and provide insight into possible ammonia generation pathways. Attempts to alleviate the known issues with SA9T included the alteration of the primary amine (tetraethylenepentamine), the choice of resin, and the particle size distribution. In-house CO 2 breakthrough experiments were conducted using a specialized apparatus that can simulate spacesuit conditions, offering high-quality triplicate capacity analysis affording direct comparison to known adsorbents in the literature. Thermo-Desorption Gas Chromatography Mass Spectrometry studies on the synthesized materials revealed any reagent or solvent offgassing while Nuclear Magnetic Resonance spectroscopy tracked the stability of the bound amine. Scanning Electron Microscope images of sieved materials provided a more accurate size interpretation facilitating synthetic design and pressure drop elimination. All efficient sorbents were synthesized to a commercial batch scale subsequent to evaluation including Xplo-SA9T.

John R Tidwell

Techno-Economic Analysis of Sorbent-Based Direct Air Capture Informed by EPC Input and Recent Technological Advancements

Direct air capture (DAC) technology has been developing at an accelerated rate. Independent, comprehensive, and transparent techno-economic analyses (TEAs) of DAC technologies are required to inform future development. NETL is publishing an update to the 2022 sorbent-based DAC case study report. This manuscript highlights select TEA results that will be presented in the upcoming NETL report. The analysis considers three sorbent-based DAC system configurations (direct steam temperature swing, indirect steam temperature swing, and direct steam temperature/vacuum swing) and two scenarios for providing the required electricity and steam (stand-alone system with a combined heat and power plant generating the required steam and electricity, and a purchased power case utilizing an electric boiler). Detailed sensitivity analyses are included and highlight the impact of external market factors, sorbent performance, and economies of scale. The potential for cost reductions by opting for temperature vacuum swing adsorption is highlighted. More detailed background and TEA results will be presented in the upcoming NETL report titled “Direct Air Capture Case Studies: Sorbent System (Revision 1)”.

carbon dioxide removal

Reactive Capture and Conversion of Carbon Dioxide to Methanol with ZnZrO 2 and Alkali-Promoted Mg 3 AlO x Mixed Oxide Catalytic Sorbents

Reactive capture and conversion (RCC) explores the use of a single-unit process to capture CO 2 and produce a product, in this case, methanol (MeOH). In this study, different configurations of a catalytic sorbent (CS) composed of ZnZrO 2 catalyst and Mg 3 AlO x sorbent with and without alkali modification are evaluated for CO 2 adsorption, steady-state catalysis with cofed CO 2 and H 2 , and transient RCC performance. A catalyst composed of a physical mixture of Mg 3 AlO x with ZnZrO 2 resulted in a slight increase in CO 2 uptake, with a low impact on the catalytic activity and RCC of the materials compared to ZnZrO 2 alone. In contrast, Na impregnation significantly increased the level of CO 2 uptake from 0.28 mmol/g (ZnZrO 2 alone) to 0.6 and 1.1 mmol/g for the CS with Na on the catalyst or Mg 3 AlO x , respectively. However, Na impregnation reduced the CO 2 conversion rate and MeOH selectivity during steady-state cofeed experiments at 300 °C and 6 bar. In contrast to steady-state catalysis conditions, RCC, which is a cyclic capture and conversion process, creates dynamic CO 2 and H 2 surface coverages, favoring CH 4 in the early stages of the conversion step and then CO and MeOH as the catalyst CO 2 coverage reduces. The highest MeOH productivity during RCC was achieved with CS that balanced the CO 2 uptake with only moderate catalyst rate reductions caused by Na addition. The optimal material, ZnZrO 2 +10%Na/Mg 3 AlO x , achieved a CO 2 uptake of 0.8 mmol/g and a MeOH productivity of 0.5 mmol/g with 100% selectivity at 260 °C and 6 bar during RCC. This marks the highest RCC MeOH productivity reported to date, although the process needs further optimization and even with optimization, may remain impractical. The results further demonstrate that optimization of catalytic sorbents under steady-state flow conditions does not easily correlate to transient capture and conversion cycles for methanol synthesis from CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH