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Combined modeling and experiments uncover the influence of epoxide-functionalization on hydrogen bonding and mobility within poly(ethylenimine) CO 2 sorbents, rationalizing the antidegradation benefits conferred by functionalization.
Carbon dioxide (CO2) and humidity control is a key function of the spacesuit Portable Life Support Subsystem (PLSS). The latest spacesuit design utilizes a pressure swing bed containing a solid amine sorbent to scrub CO2 and humidity produced by the crewmember from the ventilation loop. The solid amine sorbent removes CO2 and humidity from the ventilation loop through a chemisorption mechanism. Simultaneously, CO2 and humidity are desorbed to vacuum via the two-bed pressure swing system during operation. This continuous regeneration allows for longer Extravehicular Activity (EVA) times while minimizing maintenance, consumables, and power usage. This concept has been in development for over 20 years, during which many prototypes and design iterations have been fabricated and evaluated. This paper discusses the recent Rapid Cycle Amine (RCA) design, development, and testing that has been done to advance the technology. The most recent fabrication is the RCA 3.0. It was delivered to NASA Johnson Space Center in 2015 and has since been tested at the component level and at the integrated PLSS level. The purpose of the component level testing was to understand CO2 removal capacity, end-of-life performance, and establish a baseline performance prior to integrated testing. The RCA 3.0 was integrated into the Exploration Extravehicular Mobility Unit (xEMU) PLSS for a comprehensive Design Verification Test (DVT) series. The integrated testing provided the benefit of characterizing the impact performance degradation has on the system. Many of the RCA requirements were developed through analysis, based on the limitations of the PLSS and, in some cases, assumptions about the system and flow behavior. Integrated testing was an opportunity to validate those requirements and assumptions. While the RCA 3.0 was being tested, the next design iteration, RCA 4.0, was under development. The RCA 4.0 preliminary design phase began in late-2019 and shortly after the Preliminary Design Review, the critical design phase began in 2021. The design work has concluded with the completion of a Pre-Manufacturing Review in 2022. This paper provides an overview of the RCA 4.0 system design, summarizes the results of integrated RCA 3.0 testing, and discusses the pertinence of driving requirements such as mass, volume, and power consumption.
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.
A computer program is described which can be used to predict the transient performance of vacuum-desorbed sorbent beds for CO2 or water removal, and composite beds of two sorbents for simultaneous humidity control and CO2 removal. The program was written primarily for silica gel and molecular sieve inorganic sorbents, but can be used for a variety of adsorbent materials. Part 2 of this report describes a computer program which can be used to predict performance for multiple-bed CO2-removal sorbent systems. This program is an expanded version of the composite sorbent bed program described in Part 1.
The objective of this project was to design, seek necessary approvals, build and operate a large-scale pilot sorbent-based post combustion carbon capture system (CCS) at a coal fired power generation facility. TDA’s CCS uses a highly stable, low-cost, high-capacity physical adsorbent to effectively remove CO 2 via a combination vacuum and concentration swing adsorption (VCSA) process. The CCS is integrated with the power plant flue gas exhaust, which is rich in CO 2 (~13% vol. CO 2 ) and removes more than 90% of the plant’s overall carbon emissions.
Sorption-enhanced steam biogas reforming is an attractive approach for hydrogen production from renewable resources, with the performance of the CO 2 sorbents being a critical factor. In this study, Sr 2 MnO 4 was investigated as a redox-activated CO 2 sorbent for sustainable hydrogen production from biogas. The Sr 2 MnO 4 sorbents exhibited a CO 2 sorption capacity of over 26 g per 100 g of sorbents, along with excellent cyclic stability in thermogravimetric analysis. Complete regeneration of the sorbent was achieved with a relatively small temperature swing (100 °C). Fixed-bed reactor experiments further demonstrated the application of Sr 2 MnO 4 sorbents in sorption-enhanced steam biogas reforming. Biogas simulants with varying CO 2 contents were converted to ~94 vol% H 2 before CO 2 breakthrough. Stable CO 2 capacity and hydrogen production were maintained over 20 cycles. In addition, optimization of the regeneration duration enabled the generation of highly pure CO 2 and more efficient use of O 2 . These results support the feasibility of biogas-to‑hydrogen conversion with net-negative carbon emissions through integration with CO 2 capture and sequestration.
Ion-selective membranes are necessary components of many electrochemical systems including fuel cells, electrolyzers, redox flow batteries, and electrodialyzers. Perfluorinated sulfonated membranes (PFSMs) dominate these applications due to their excellent combination of fast ion transport, stability, and processability. However, perfluorinated cation exchange membranes (CEMs) are expensive, and their production process involves chemistry that generates toxic perfluorinated chemicals. The development of affordable, nonfluorinated membranes with a competitive combination of high ion selectivity, transport, and stability could help enable the widespread use of the technologies listed above while hastening the development of emerging electrochemical systems, including aqueous alkaline CO 2 sorbent regeneration. To this end, we pursue the use of thin-film composite polyamide (PA-TFCs) membranes–those that typically find application in reverse osmosis and nanofiltration desalination–as cation-selective exchange membranes. Given their negative surface charge under neutral-to-alkaline conditions, PA-TFCs can serve as effective CEMs in these pH regimes. We prepared a series of PA-TFCs from traditional monomers (trimesoyl chloride and piperazine) and compared their thicknesses, charge densities, water transport properties, ion transport properties, and long-term stability in a high pH environment to traditional CEMs (Nafion and FKE) and commercial nanofiltration and reverse osmosis membranes. We find that some of the best-performing PA-TFC membranes have similar resistances and Na + transference numbers compared to Nafion 117 in Na 2 SO 4 and NaHCO 3 -containing solutions. This proof-of-principle study suggests that further optimization of PA-TFCs could enable cost-effective ion exchange membrane alternatives to PFSMs.
Available data on amine-based sorbents used for the direct air capture (DAC) process were gathered and analyzed to identify the correlations between various aspects of these sorbents and the operating conditions they are used in. It is demonstrated that a moderately high temperature (∼ 50 °C) can help with higher CO 2 capture capacity. Furthermore, the effect of sorbent preparation method on its activity and stability was studied. Also, the influence of amine groups and support choice on amine efficiency and CO 2 capture capacity was discussed. The DAC process conditions proved to play a major role in determining the optimal sorbent. An outlook for characteristics to be sought for in future DAC sorbents for CO 2 removal is proposed.
A supramolecular complexation approach is developed to improve the CO 2 chemisorption performance of solvent-lean amine sorbents. Operando spectroscopy techniques reveal the formation of carbamic acid in the presence of a crown ether. Here, the reaction pathway is confirmed by theoretical simulation, in which the crown ether acts as a proton acceptor and shuttle to drive the formation and stabilization of carbamic acid. Improved CO 2 capacity and diminished energy consumption in sorbent regeneration are achieved.
Direct air capture (DAC) of CO 2 via solvent-based absorption is considered a promising negative-emission technology. However, the low concentration of CO 2 in the air and slow transport into the solvent make DAC notoriously challenging to implement without costly investments. In this study, we explore the fundamental role that the bulk and surface properties of CO 2 -permeable polymer membranes play in enhancing the efficiency of the solution sorption process in passive DAC of CO 2 . This work leverages various spectroscopic and computational studies to demonstrate that a hybrid system, comprising a reusable CO 2 -permeable polymer layer placed atop an aqueous amino acid (AA) solution, can outperform a pure aqueous AA system by 2-fold. Here we show how the enhanced solubility of CO 2 in the polymer layer can improve the transport of CO 2 into the aqueous phase, while the chemistry of the polymer can control the interfacial barrier for CO 2 permeation and the interfacial concentration of reactive AAs. The derived knowledge of the material properties achieved here can aid in the design of DAC systems with improved performance.
The effects of individual component salts on MgO hydration and subsequent carbonation have not been systematically investigated despite the increase in utilization of seawater and other brines in the production of MgO-containing next-generation cements, fire retardants, and sorbents for CO2. Here, we present a study of MgO hydration in the presence of individual saltwater cations at a range of concentrations, as well as binary mixtures at seawater concentrations, and subsequent carbonation. We observed that the presence of the cations increased MgO dissolution rates and that the subsequent carbonation extent of the hydrated material remained constant or even increased. Since the presence of these salts during hydration does not show negative effects on subsequent carbonation in our experimental study, the application of seawater and other brines containing high concentrations of these salts to hydrate MgO in industrial processes is likely feasible.
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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.
Topics covered include: Fully Integrated, Miniature, High-Frequency Flow Probe Utilizing MEMS Leadless SOI Technology; Nanoscale Surface Plasmonics Sensor With Nanofluidic Control; Advanced Dispersed Fringe Sensing Algorithm for Coarse Phasing Segmented Mirror Telescopes; Neural Network Back-Propagation Algorithm for Sensing Hypergols; Bulk Moisture and Salinity Sensor; Change-Based Satellite Monitoring Using Broad Coverage and Targetable Sensing; Circularly Polarized Microwave Antenna Element with Very Low Off-Axis Cross-Polarization; Ultra-Low Heat-Leak, High-Temperature Superconducting Current Leads for Space Applications; Flash Cracking Reactor for Waste Plastic Processing; An Automated Safe-to-Mate (ASTM) Tester; Wireless Chalcogenide Nanoionic-Based Radio-Frequency Switch; Compute Element and Interface Box for the Hazard Detection System; DOT Transmit Module; Composite Aerogel Multifoil Protective Shielding; Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems; Polymer-Reinforced, Non-Brittle, Lightweight Cryogenic Insulation; Controlled, Site-Specific Functionalization of Carbon Nanotubes with Diazonium Salts; Regenerable Sorbent for CO2 Removal; Sprayable Aerogel Bead Compositions With High Shear Flow Resistance and High Thermal Insulation Value; Lexan Linear Shaped Charge Holder with Magnets and Backing Plate; Robotic Ankle for Omnidirectional Rock Anchors; Wind, Wave, and Tidal Energy Without Power Conditioning; An Active Heater Control Concept to Meet IXO Type Mirror Module Thermal-Structural Distortion Requirement; Waterless Clothes-Cleaning Machine; Integrated Electrical Wire Insulation Repair System; LVGEMS Time-of-Flight Mass Spectrometry on Satellites; Surface Inspection Tool for Optical Detection of Surface Defects; Per-Pixel, Dual-Counter Scheme for Optical Communications; Certification-Based Process Analysis; Surface Navigation Using Optimized Waypoints and Particle Swarm Optimization; Smart-Divert Powered Descent Guidance to Avoid the Backshell Landing Dispersion Ellipse; Estimating Foreign-Object-Debris Density from Photogrammetry Data; Adaptive Sampling of Spatiotemporal Phenomena with Optimization Criteria; Building a 2.5D Digital Elevation Model From 2D Imagery; Eyes on the Earth 3D; Target Trailing With Safe Navigation for Maritime Autonomous Surface Vehicles; Adams-Based Rover Terramechanics and Mobility Simulator - ARTEMIS; ISTP CDF Skeleton Editor; Uplink Summary Generator (ULSGEN) Version 1.0; Robotics On-Board Trainer (ROBoT); Software Engineering Tools for Scientific Models; Automatic Data Filter Customization Using a Genetic Algorithm; Tracker Toolkit; Towards Efficient Scientific Data Management Using Cloud Storage; On a Formal Tool for Reasoning About Flight Software Cost Analysis; A Nanostructured Composites Thermal Switch Controls Internal and External Short Circuit in Lithium Ion Batteries; Spacecraft Crew Cabin Condensation Control; and Functional Near-Infrared Spectroscopy Signals Measure Neuronal Activity in the Cortex.
No abstract available
One of NASA/Johnson Space Center's test articles of the amine-based carbon dioxide (CO2) and water vapor sorbent system known as the CO2 And Moisture Removal Amine Swing-bed, or CAMRAS, was incorporated into a payload on the International Space Station (ISS). The intent of the payload is to demonstrate the spacecraft-environment viability of the core atmosphere revitalization technology baselined for the new Orion vehicle. In addition to the air blower, vacuum connection, and controls needed to run the CAMRAS itself, the payload incorporates a suite of sensors for scientific data gathering, a water save function, and an air save function. The water save function minimizes the atmospheric water vapor reaching the CAMRAS unit, thereby reducing ISS water losses that are otherwise acceptable, and even desirable, in the Orion environment. The air save function captures about half of the ullage air that would normally be vented overboard every time the cabin air-adsorbing and space vacuum-desorbing CAMRAS beds swap functions. The JSC team conducted 1000 hours of on-orbit Amine Swingbed Payload testing in 2013. This paper presents the basics of the payload's design and history, as well as a summary of the test results, including comparisons with prelaunch testing.
One of NASA Johnson Space Center's test articles of the amine-based carbon dioxide (CO2) and water vapor sorbent system known as the CO2 And Moisture Removal Amine Swing-bed, or CAMRAS, was incorporated into a payload on the International Space Station (ISS). The intent of the payload is to demonstrate the spacecraft-environment viability of the core atmosphere revitalization technology baselined for the new Orion vehicle. In addition to the air blower, vacuum connection, and controls needed to run the CAMRAS, the payload incorporates a suite of sensors for scientific data gathering, a water save function, and an air save function. The water save function minimizes the atmospheric water vapor reaching the CAMRAS unit, thereby reducing ISS water losses that are otherwise acceptable, and even desirable, in the Orion environment. The air save function captures about half of the ullage air that would normally be vented overboard every time the cabin air-adsorbing and space vacuum-desorbing CAMRAS beds swap functions. The JSC team conducted 1000 hours of on-orbit Amine Swingbed Payload testing in 2013 and early 2014. This paper presents the basics of the payload's design and history, as well as a summary of the test results, including comparisons with prelaunch testing.
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.