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At least 145 records · Page 8

Design for an Integrated Open-Loop System for Carbon Dioxide Removal using Liquid Amine

Manned Space missions require maintaining a safe environment for the crew that can both sustain a breathable atmosphere and remove pollutants. Carbon dioxide, while not toxic in low concentrations, accumulates as crew members work and breath and can eventually affect the crew’s health. Therefore, a constant, passive system to remove the carbon dioxide build up is necessary for long-term missions. Currently, the prevailing liquid sorbent used in submarines and industrial flue gas utilizes the primary amine, monoethanolamine (MEA), to capture, transfer, and remove carbon dioxide from air. Diglycolamine (DGA) is an alternate primary amine that has similar performance and less volatility. It is currently being studied at Ames Research Center (ARC) and is the primary candidate for the operation of the sub-scale liquid amine test stand. The test stand is used to investigate liquid flow and liquid gas interfaces to assist in a system design for microgravity applications. The test stand includes a wedge design utilizes capillary action to hold the liquid while allowing gas-liquid interaction for carbon dioxide transfer. These wedge trays are placed in a contactor unit to remove carbon dioxide from the air stream, a degasser unit to replenish the liquid amine, and a capillary condensing heat exchanger (CCHX) to recapture water lost in the degasser unit. Nominal operating conditions for the contactor are a gas flow rate of 26scfm enriched with pure CO2 to 2600ppm and a liquid mixture of 65/35 vol% DGA/H2O at 0.65mL/min while the degasser was operated at 100°C and 1 atm. This paper discusses the challenges and limitations of a fully integrated system which will influence the design of a new subscale test stand.

Adrian Cortez↗

CO 2 Capture with Capsules of Ionic Liquid/Amines

Carbon capture remains an urgent issue that has gained a great deal of attention over the past few decades. Aqueous amines have excellent selectivity, but present corrosion and volatility issues, whereas ionic liquids (ILs) have negligible volatility and tunable physical properties, but high viscosities. One approach to improve the practical performance of these liquids is encapsulating them in a CO 2 permeable polymer shell to enhance the accessibility of the liquid and the CO 2 absorption rate. In this work, we report the encapsulation of a mixture of amine and IL (i.e., monoethanolamine (MEA) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ])) and demonstrate enhanced carbon capture performance. A soft-template approach and interfacial polymerization are used to give capsules with liquid core (64 wt %) and polyurea shell. Compared to the bulk liquid, the encapsulated liquid shows improved thermal stability over cycles of absorption at 25 °C, and desorption at 75 °C. The capsules with core of [BMIM][BF 4 ]-MEA show 0.2 mol CO 2 /kg of capsules at 1 bar CO 2 , compared to the bulk liquid, which has 0.05 mol CO 2 /kg of sorbent. This is attributed to the limited evaporation of the amines. Alternatively, the same capsules but with 5 wt % of piperazine (Pz) in the core have doubled gravimetric CO 2 capacity of the capsules (0.4 mol CO 2 /kg of capsules); performance is evaluated over 10 capture–release cycles showing minimal mass loss. Characterization of the CO 2 uptake of the polymer shell itself reveals that the shell contributes only ~10% of the observed capacity, likely attributed to amine functionalities of the polymer. Here, this facile approach to encapsulating such “active” liquids can be applied to other CO 2 selective solvents that are volatile, viscous, and corrosive.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ammonium-Coordinated Exchanger (ACE) Sorbents for Aqueous Oxyanion Metal Recovery/Removal

Ammonium coordinated exchanger (ACE) sorbents recovery/remove anionic contaminant/critical metals from water. Heavy reliance of the U.S. on foreign critical mineral (CM) supplies presents national security and economics risks. This prompted government action. Domestically recovering CM from unconventional water sources, largely through adsorption processes, could alleviate this problem. Acid mine drainage and mineral leachates are viable sources

amines↗

The influence of exogenous amines on the electrochemical CO 2 reduction activity of a cobalt–pyridyldiimine catalyst

Studying the interactions between CO 2 sorbents and electrocatalysts for the electrochemical CO 2 reduction reaction (e-CO 2 RR) can offer viable strategies to advance the development of the Reactive Capture of CO 2 (RCC). In this report we studied the effect of amines on the performance of the [Co(PDI-Py)] catalyst for the e -CO 2 RR. The presence of amines shifts the onset potential for the e -CO 2 RR more positive and increases the catalytic activity while maintaining the high Faradaic efficiency (≥90%) for CO production.

Chemistry↗

First Principles Modeling of the Thermal Amine Scrubber Flight Experiment’s Chemical Performance

The removal of atmospheric CO2 from a spacecraft is of particular importance to NASA’s mission, and is an area of continual study and technological advancement. One of the more recent advancements has been with reusable sorbents being regenerated with a combination of heat and vacuum. One such technology is the Thermal Amine Scrubber (TAS) flight experiment on the ISS, though several others are currently flying or preparing to fly. A model was created of the TAS to predict chemical performance, using fundamental chemistry and physics based on principles rather than empirical relations. Since the physical laws are true across all conditions, such a model enables greater model accuracy outside the bounds of test data, and allows for virtual testing of the hardware at conditions that are prohibitively difficult or expensive to actually test. This paper details the model’s development, operation, and correlation to data from the flight unit. The model is then compared to a data set taken from the flight unit under different flow, CO2 partial pressure, and bed configuration conditions, resulting in only a 2% error. The equations and principles laid forth in this paper are applicable to a wide range of thermally regenerated sorbents, and additional models of a similar nature would allow for potentially the most straightforward and direct method of comparison of technologies available to date.

CO2 removal↗

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↗

New chemistry for enhanced carbon capture: beyond ammonium carbamates

Carbon capture and sequestration is necessary to tackle one of the biggest problems facing society: global climate change resulting from anthropogenic carbon dioxide (CO 2 ) emissions. Despite this pressing need, we still rely on century-old technology—aqueous amine scrubbers—to selectively remove CO 2 from emission streams. Amine scrubbers are effective due to their exquisite chemoselectivity towards CO 2 to form ammonium carbamates and (bi)carbonates, but suffer from several unavoidable limitations. In this perspective, we highlight the need for CO 2 capture via new chemistry that goes beyond the traditional formation of ammonium carbamates. In particular, we demonstrate how ionic liquid and metal–organic framework sorbents can give rise to capture products that are not favourable for aqueous amines, including carbamic acids, carbamate–carbamic acid adducts, metal bicarbonates, alkyl carbonates, and carbonic acids. These new CO 2 binding modes may offer advantages including higher sorption capacities and lower regeneration energies, though additional research is needed to fully explore their utility for practical applications. Overall, we outline the unique challenges and opportunities involved in engineering new CO 2 capture chemistry into next-generation technologies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Regulation of Sub-Atmospheric Pressure for Constant and Cyclic Gas Loads During Testing of Spacesuit Components

New iterations of the various subsystems within the spacesuit will benefit from a new sorbent technology. For example, sorbents used in the Trace Contaminant Control (TCC) and the Rapid Cycle Amine (RCA) systems within the Exploration Portable Life Support System (xPLSS), part of the Extra-Vehicular Mobility Unit (xEMU). For proper validation, the sub-atmospheric pressure needs to be maintained within a simulated 2 ft 3 spacesuit volume. The traditional approach, which involves placing the entire vent loop within a hypobaric chamber, is not practical for the widespread testing of components and prototypes, as these specialized chambers are costly and not widely available. A two-stage regulator based sub-atmospheric pressure system is presented in this work. The method regulates the pressure based on pressure differentials between the pressure regulation pump, the test system, and the ambient environment. The performance of this system is demonstrated using data collected during a 150+ hour non-regenerative TCC sorbent evaluation, several 24-hour regenerative TCC sorbent evaluations with different regeneration cycles, and an 8-hour RCA sorbent evaluation, all under xEMU operating conditions. For regulation, the inlet regulator was set to propagate a small leak to increase the stability of the system as the gas load from the testing system changes. It was also found that controlling the input flow rate that replaces the material lost during regeneration is critical for ensuring the stability of the system. This system provided excellent pressure regulation, without adjustments, for constant loads during shorter time evaluations (hours), while longer time evaluations (days) are easily obtainable with periodic regulator adjustments. A second method is under development to address longer-term stability and to automate pressure regulation. It will incorporate flow and pressure measurements to dynamically control a set of electronically controlled proportional valves for adjusting the pumping speed and air bleed supply.

Nicholas F Materer↗

Design Concepts for an Optimized, Modular, and Scalable Liquid Amine Test Stand

The Air Revitalization Labs at NASA Ames Research Center (ARC) is investigating liquid amines to for their performance removing spacecraft carbon dioxide (CO2) for crewed space missions. Development of the current one-crew scale amine test stand stems from several modifications to a test stand initially built at NASA Johnson Space Center (JSC) This sub-scale system has been modified to incorporate a flow spreader for the inlet air stream, an updated contactor design for CO2 capture, a degasser to regenerate the liquid sorbent and recover the captured CO2, and a condenser to reduce water loss. Results from the existing integrated liquid amine test stand have provided valuable insight, but continued performance optimization requires design and build of a new integrated test system. New design concepts will institute a modular configuration to allow for interfacing with novel contactor and degasser architecture, parallel or series flow pathways for the air stream and liquid sorbent, and scaling up to a 4-crew CO2 removal system.

Tiago Faria Costa↗

Detecting Reactive Products in Carbon Capture Polymers with Chemical Shift Anisotropy and Machine Learning

Aminopolymers are attractive sorbents for CO 2 direct air capture applications due to their high density of amine groups, which can readily react with atmospheric levels of CO 2 to form chemisorbed species. The identity of these chemisorbed species and the functional groups that form upon oxidative degradation depends on both material properties and processing conditions, forming a variety of carbonyl-type sites such as ammonium carbamates, bicarbonates, carbonates, carbamic acids, ureas, and amides. 13 C solid-state nuclear magnetic resonance (NMR) is often used to help elucidate the identity of these reacted species, but it is challenging due to the narrow chemical shift range of carbonyl sites. Herein, we demonstrate the application of a two-dimensional (2D) chemical shift anisotropy (CSA) recoupling pulse sequence (ROCSA) to obtain CSA tensor values at each isotropic chemical shift, overcoming limitations of isotropic peak resolution. CSA tensor values describe the local chemical environment and can readily differentiate between the chemisorbed and degradation products. To aid identification, we also developed a k-nearest neighbor (kNN) classification model to distinguish the functional groups via their CSA tensor parameters. This methodology was demonstrated on poly(ethylenimine) in γ-Al 2 O 3 exposed to CO 2 and showed that the chemisorbed products are ammonium carbamate and a mixed carbamate–carbamic acid species. The sample was analyzed again after desorption at 100 °C inducing mild degradation, and the remaining products were strongly bound carbamate and urea species. In conclusion, the combination of 2D CSA measurements coupled with a kNN classification model enhances the ability to accurately identify chemisorbed or degradation products in complex carbon capture materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synergistic direct air capture of CO 2 with aqueous guanidine/amino acid solvents

We report that Methylglyoxal-bis(iminoguanidine) (MGBIG) has been recently identified as a promising sorbent for direct air capture (DAC) of carbon dioxide via crystallization of guanidinium carbonate salts. In this study, the effects of aqueous amino acids and oligopeptides, such as glycine, sarcosine, serine, arginine, taurine, lysine, and glycylglycine, on the efficacy of DAC by crystallization of MGBIG carbonate have been investigated. While most of the amino acids studied were found to precipitate with MGBIG, thereby rendering the sorbent unavailable for DAC, sarcosine, the only amino acid in the series with a secondary amine group, remained soluble in the presence of MGBIG, leading to enhanced DAC compared to MGBIG alone. Specifically, for the same amount of MGBIG (5 mmol), the addition of a small amount of sarcosine to the aqueous solvent–as little as 0.5 mmol–led to extraction of six times as much CO 2 from the air (4.15 mmol vs. 0.7 mmol). Thus, aqueous MGBIG and sarcosine work in synergy, offering the prospect for an effective DAC process.

36 MATERIALS SCIENCE↗

Correlation of Amine Swingbed On-Orbit CO2 Performance with a Hardware Independent Predictive Model

The Amine Swingbed Payload is an experimental system deployed on the International Space Station (ISS) that includes a two-bed, vacuum regenerated, amine-based carbon dioxide (CO2) removal subsystem as the principal item under investigation. The aminebased subsystem, also described previously in various publications as CAMRAS 3, was originally designed, fabricated and tested by Hamilton Sundstrand Space Systems International, Inc. (HSSSI) and delivered to NASA in November 2008. The CAMRAS 3 unit was subsequently designed into a flight payload experiment in 2010 and 2011, with flight test integration activities accomplished on-orbit between January 2012 and March 2013. Payload activation was accomplished in May 2013 followed by a 1000 hour experimental period. The experimental nature of the Payload and the interaction with the dynamic ISS environment present unique scientific and engineering challenges, in particular to the verification and validation of the expected Payload CO2 removal performance. A modeling and simulation approach that incorporates principles of chemical reaction engineering has been developed for the amine-based system to predict the dynamic cabin CO2 partial pressure with given inputs of sorbent bed size, process air flow, operating temperature, half-cycle time, CO2 generation rate, cabin volume and the magnitude of vacuum available. Simulation runs using the model to predict ambient CO2 concentrations show good correlation to on-orbit performance measurements and ISS dynamic concentrations for the assumed operating conditions. The dynamic predictive modelling could benefit operational planning to help ensure ISS CO2 concentrations are maintained below prescribed limits and for the Orion vehicle to simulate various operating conditions, scenarios and transients.

Papale, William↗

Pilot testing of CO2 capture from a coal-fired power plant—Part 2: Results from 1-MWe pilot tests

Abstract Using a 1-MWe slipstream pilot plant, solid-sorbent-based post-combustion CO2 capture was tested at a coal-fired power plant. Results from pilot testing were used to develop a preliminary full-scale commercial design. The sorbent selected for pilot-scale evaluation during this project consisted of an ion-exchange resin that incorporated amines covalently bonded to the substrate. A unique temperature-swing-absorption (TSA) process was developed that incorporated a three-stage fluidized-bed adsorber integrated with a single-stage fluidized-bed regenerator. Overall, following start-up and commissioning challenges that are often associated with first-of-a-kind pilots, the pilot plant operated as designed and expected, with a few key exceptions. The two primary exceptions were associated with: (i) handling characteristics of the sorbent, which were sufficiently different at operating temperature than at ambient temperature when design specifications were established with lab-scale testing; and (ii) CO2 adsorption in the transport line between the regenerator and adsorber that preloaded the sorbent with CO2 prior to entering the adsorber. Results from the pilot programme demonstrate that solid-sorbent-based post-combustion capture can be utilized to achieve 90% CO2 capture from coal-fired power plants.

Sjostrom, Sharon↗

Analytical Methods and Testbeds for Characterizing Adsorbents and Catalysts for Atmosphere Revitalization of Crewed Spacecraft

Spacecraft environmental control and life support systems (ECLSS) include a number of air revitalization (AR) technologies to provide breathable air and a comfortable living environment to the crew. Crew health and comfort is ensured by controlling human produced CO2 (1 kg person-1 day-1) and water vapor (~2 kg person-1 day-1), and by removing trace contaminants (TCs) from cabin air. These life support functions on-board the International Space Station (ISS) are carried out by the Carbon Dioxide Removal Assembly (CDRA), the Water Processor Assembly (WPA), and the trace contaminant control system (TCCS). During the development of the TCCS, new analytical and theoretical methods were developed in the 1970s for characterizing adsorption and desorption characteristics of activated carbons for the purpose of designing suitable AR technologies required for controlling airborne trace contaminants within spacecraft cabins during long exploration missions. The TCCS removes harmful volatile organic compounds and other trace contaminants from the circulating air. It consists of a granular activated carbon (GAC) bed for the removal of high molecular weight contaminants and ammonia followed by a heated catalytic bed for low molecular weight hydrocarbons. The high temperature catalytic oxidizer (HTCO) of the TCCS, which operates at 400°C and requires 120W average power, removes low molecular weight compounds such as carbon monoxide (CO), formaldehyde (CH2O), and methane (CH4), that pass through the GAC bed. The Air Revitalization Laboratory at the Kennedy Space Center (KSC) was established to develop new analytical methods for evaluating emerging ECLSS technologies for use in future AR architectures. General properties of adsorbents and catalysts are required for trace contaminant control system design calculations and vendor-supplied data are seldom available at relevant process conditions of interest to spacecraft cabin applications. To address this shortcoming, appropriate testbeds were developed to measure the desired properties of AR technologies being considered for use in ECLS architectures. Generally, the testbeds developed at KSC challenge the test media (activated carbon, impregnated activated carbon, catalysts, zeolites, solid amines, or pleated filters) with simulated spacecraft gas streams containing representative mixtures of trace contaminants (volatile organic compounds, ammonia, CO, CO2, or siloxanes) at the flow rates, temperatures, and relative humidity that will be encountered within manned spacecraft. Work performed at KSC funded by NASA’s Advanced Exploration (AES) Program has included: Identifying candidate sorbents to replace commercially obsolete impregnated carbons for NH3 control within the TCCS, characterizing their adsorptive capacities using simulated spacecraft gas streams, and ranking their appropriateness in various AR applications; evaluating novel low temperature catalysts for controlling CO and formaldehyde by traditional and photocatalytic methods for trace contaminant control; development of analytical methods to assess regenerable solid amine performance for CO2 control via pressure swing adsorption. The Air Revitalization lab was also funded to study trace contaminant control by other NASA programs. These include: screening of candidate sorbents for the design of new Charcoal HEPA Integrated Particle Scrubber (CHIPS) filters for removing siloxanes from cabin air; characterizing the performance of an impregnated activated carbon at low humidity for use in ORION ECLS; screening of sorbents for protecting the Sabatier 2.0 catalyst from DMSO2, siloxanes, NH3, and solid amine byproducts.

Monje, Oscar↗