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At least 73 records · Page 4

A Comprehensive Greenhouse Gas Assessment of Biomass-Based Carbon Dioxide Removal and Storage

Biomass with Carbon Removal and Sequestration (BiCRS) is a suite of technological pathways that provide a relatively affordable and high-potential way to remove carbon dioxide from the atmosphere and simultaneously re-purpose residual biomass. BiCRS technologies are individually optimized to different biomass feedstocks, temperatures and oxygen, with the goal of capturing a high percentage of biomass-derived carbon dioxide and storing it in permanent below-ground storage (i.e. geologic storage). The current standard for BiCRS life cycle assessments does not account for carbon dioxide, methane and nitrous oxide (CO 2 , CH 4 , and N 2 O) fluxes from surface soil amendment of BiCRS byproducts (e.g. char, ash) and their alternate fates. This is partly due to a paucity of empirical data due to the novelty of BiCRS conversion technologies, the range in feedstocks, and the heterogeneity of soils to which they might be amended. To fill this gap in in the life-cycle assessment (LCA) and provide a realistic range of parameters for a soil amendment component of the BiCRS LCA, we conducted an incubation experiment to measure soil carbon changes, microbial respiration, methane fluxes, and nitrous oxide fluxes from two different soils amended with char- and ash- byproducts from biomass after gasification to hydrogen, fast pyrolysis to bio-oil, and torrefaction.

54 ENVIRONMENTAL SCIENCES↗

Assessing the Effect of Explicit Polarizability on Models of Carbon Dioxide Solvation in Ionic Liquids

Ionic liquids are an important possible carbon capture material because of their anomalously high sorption selectivity for carbon dioxide over other gases common in air. Many research groups have investigated the molecular origins of this property and provided important insights, including using 1D and 2D-IR spectroscopy. Molecular dynamics simulations have been indispensable to the interpretation of these experiments. In prior molecular dynamics simulation work, charge-scaled force fields have typically been used to provide a mean-field treatment of effects vital to ionic liquid systems such as charge transfer and polarization. Here, we compare models of carbon dioxide solvated in ionic liquids with explicit polarization to models of the same with implicit polarizability through charge-scaling. We calculate structural, dynamical, and spectroscopic properties, and make comparisons to the same items measured in experiment. In this study, we focus on two ionic liquids: 1-butyl-3- methylimidazolium (BMIM + ) paired with bis(trifluoromethane sulfonyl imide) (Tf 2 N − ) and 1-butyl-3-methylimidazolium (BMIM+) paired with hexafluorophosphate (PF 6 − ). We find that many structural, dynamical, and spectroscopic properties are changed when polarization is modeled explicitly. We also find that explicit polarizability softens local ion cages around the carbon dioxide and that the long-time diffusion of the carbon dioxide is gated by the reorganization of the ionic liquid molecules. Comparisons to experiment show modest improvement of many observables compared with experiment for the explicitly polarizable model over the charge-scaled model. Overall, our results show that charge-scaled force fields are likely sufficient to compute spectroscopic properties of carbon dioxide in ionic liquids and suggest some interpretive rules for understanding their structural and dynamical properties. Those using charge-scaled force fields should generally assume that the ion cages around solutes such as carbon dioxide are too stiff and cation-rich in their models and adjust their interpretations and predictions accordingly.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a prototype regeneration carbon dioxide absorber

A prototype regenerable carbon dioxide absorber was developed to maintain the environmental quality of the portable life support system. The absorber works on the alkali metal carbonate-bicarbonate solid-gas reaction to remove carbon dioxide from the atmosphere. The prototype sorber module was designed, fabricated, and tested at simulated extravehicular activity conditions to arrive at optimum design. The unit maintains sorber outlet concentration below 5 mm Hg. An optimization study was made with respect to heat transfer, temperature control, sorbent utilization, sorber life and regenerability, and final size of the module. Important parameters influencing the capacity of the final absorber unit were identified and recommendations for improvement were made.

Patel, P. S.↗

Evaluation of 2-μm Pulsed Integrated Path Differential Absorption Lidar for Carbon Dioxide Measurement—Technology Developments, Measurements, and Path to Space

The societal benefits of understanding climate change through the identification of global carbon dioxide sources and sinks led to the recommendation for NASA's Active Sensing of Carbon Dioxide Emissions over Nights, Days, and Seasons space-based mission for global carbon dioxide measurements. For more than 15 years, the NASA Langley Research Center has developed several carbon dioxide active remote sensors using the differential absorption lidar technique operating at 2-μm wavelength. Recently, an airborne double-pulsed integrated path differential absorption lidar was developed, tested, and validated for atmospheric carbon dioxide measurement. Results indicated 1.02% column carbon dioxide measurement uncertainty and 0.28% bias over the ocean. Currently, this technology is progressing toward triple-pulse operation targeting both atmospheric carbon dioxide and water vapor-the dominant interfering molecule on carbon dioxide remote sensing. Measurements from the double-pulse lidar and the advancement of the triple-pulse lidar development are presented. In addition, measurement simulations with a space-based IPDA lidar, incorporating new technologies, are also presented to assess feasibility of carbon dioxide measurements from space.

Singh, Upendra N.↗

Carbon Dioxide Absorption Heat Pump

A carbon dioxide absorption heat pump cycle is disclosed using a high pressure stage and a super-critical cooling stage to provide a non-toxic system. Using carbon dioxide gas as the working fluid in the system, the present invention desorbs the CO2 from an absorbent and cools the gas in the super-critical state to deliver heat thereby. The cooled CO2 gas is then expanded thereby providing cooling and is returned to an absorber for further cycling. Strategic use of heat exchangers can increase the efficiency and performance of the system.

Jones, Jack A.↗

Performance Characterization and Simulation of Amine-Based Vacuum Swing Sorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and water (H2O) vapor concentrations in a space suit is critical to ensuring an astronauts safety, comfort, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxide (MetOx) canisters. Lithium hydroxide is a consumable material that requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications. The vacuum swing units control atmospheric concentrations of both CO2 and H2O through fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed experimentally and documented in previous reports. To support developmental e orts, a first principles model has also been established for the vacuum swing sorption technology. For the first time in several decades, a major re-design of Portable Life Support System (PLSS) for the extra-vehicular mobility unit (EMU) is underway. NASA at Johnson Space Center built and tested an integrated PLSS test bed of all subsystems under a variety of simulated EVA conditions of which the RCA prototype played a significant role. The efforts documented herein summarize RCA test performance and simulation results for single and variable metabolic rate experiments in an integrated context. In addition, a variety of off-nominal tests were performed to assess the capability of the RCA to function under challenging circumstances. Tests included high water production experiments, degraded vacuum regeneration, and deliberate valve/power failure and recovery.

Swickrath, Michael J.↗

Performance Characterization and Simulation of Amine-Based Vacuum Swing Adsorption Units for Spacesuit Carbon Dioxide and Humidity Control

Controlling carbon dioxide (CO2) and water (H2O) concentrations in the vapor phase of a space suit is critical to ensuring an astronauts safety, comfortability, and capability to perform extra-vehicular activity (EVA) tasks. Historically, this has been accomplished using lithium hydroxide (LiOH) and metal oxides (MetOx). Lithium hydroxide is a consumable material and requires priming with water before it becomes effective at removing carbon dioxide. MetOx is regenerable through a power-intensive thermal cycle but is significantly heavier on a volume basis than LiOH. As an alternative, amine-based vacuum swing beds are under aggressive development for EVA applications which control atmospheric concentrations of both CO2 and H2O through a fully-regenerative process. The current concept, referred to as the rapid cycle amine (RCA), has resulted in numerous laboratory prototypes. Performance of these prototypes have been assessed and documented from experimental and theoretical perspectives. To support developmental efforts, a first principles model has also been established for the vacuum swing adsorption technology. The efforts documented herein summarize performance characterization and simulation results for several variable metabolic profiles subjected to the RCA. Furthermore, a variety of control methods are explored including timed swing cycles, instantaneous CO2 feedback control, and time-averaged CO2 feedback control. A variety of off-nominal tests are also explored including high/low suit temperatures, increasingly high humidity cases, and dynamic pressure cases simulating the suit pre-breathe protocol. Consequently, this work builds on efforts previous efforts to fully bound the performance of the rapid cycle amine under a variety of nominal and off-nominal conditions.

Swickrath, Michael J.↗

The control of carbon dioxide cryodeposits

An experimental study has been conducted to investigate the parameters affecting the cryodeposition of carbon dioxide frost. In the investigation carbon dioxide frost was cryodeposited from a helium-carbon dioxide mixture into a layer of fibrous insulation surrounding a cylindrical cryogenic tank. Results of the study indicated that not only did deposition occur on the frost surface but also within the frost layer. Over the range of variables investigated both the frost density and the mass of frost deposited were most sensitive to the time of deposition, the percent of carbon dioxide in the purge-gas mixture, and the thickness of the insulation. Frost density and mass of frost deposition were found to increase with time and percent carbon dioxide, and to decrease with increasing insulation thickness.

Sharpe, E. L.↗

Carbon Dioxide - Our Common "Enemy"

Health effects of brief and prolonged exposure to carbon dioxide continue to be a concern for those of us who manage this pollutant in closed volumes, such as in spacecraft and submarines. In both examples, considerable resources are required to scrub the atmosphere to levels that are considered totally safe for maintenance of crew health and performance. Defining safe levels is not a simple task because of many confounding factors, including: lack of a robust database on human exposures, suspected significant variations in individual susceptibility, variations in the endpoints used to assess potentially adverse effects, the added effects of stress, and the fluid shifts associated with micro-gravity (astronauts only). In 2007 the National Research Council proposed revised Continuous Exposure Guidelines (CEGLs) and Emergency Exposure Guidelines (EEGLs) to the U.S. Navy. Similarly, in 2008 the NASA Toxicology Group, in cooperation with another subcommittee of the National Research Council, revised Spacecraft Maximum Allowable Concentrations (SMACs). In addition, a 1000-day exposure limit was set for long-duration spaceflights to celestial bodies. Herein we examine the rationale for the levels proposed to the U.S. Navy and compare this rationale with the one used by NASA to set its limits. We include a critical review of previous studies on the effects of exposure to carbon dioxide and attempt to dissect out the challenges associated with setting fully-defensible limits. We also describe recent experiences with management of carbon dioxide aboard the International Space Station with 13 persons aboard. This includes the tandem operations of the Russian Vozduk and the U.S. Carbon Dioxide Removal System. A third removal system is present while the station is docked to the Shuttle spacecraft, so our experience includes the lithium hydroxide system aboard Shuttle for the removal of carbon dioxide. We discuss strategies for highly-efficient, regenerable removal of carbon dioxide that could meet the 1000-day SMAC of 0.5%, which would apply to long-duration voyages to Mars.

James, John T.↗

A Comprehensive Greenhouse Gas Assessment of Biomass-Based Carbon Dioxide Removal and Storage

Biomass-based Carbon Removal and Storage (BiCRS) is a suite of technological pathways that provide a relatively affordable and high-potential way to remove carbon dioxide from the atmosphere and simultaneously re-purpose residual biomass. BiCRS technologies are individually optimized to different biomass feedstocks, temperatures and oxygen, with the primary goal of capturing a high percentage of biomass-derived carbon dioxide and storing it in permanent below-ground storage (i.e. geologic storage), and a secondary goal of producing renewable energy. The current standard for BiCRS life cycle assessments does not account for greenhouse gas (carbon dioxide, methane and nitrous oxide) fluxes from surface soil amendment of BiCRS byproducts (e.g. char, ash) and their alternate fates. This is partly due to a paucity of empirical data due to the novelty of BiCRS conversion technologies, the range in feedstocks, and the heterogeneity of soils to which they might be amended. To fill this gap in in the life-cycle assessment and provide a realistic range of parameters for a soil amendment component of the BiCRS life cycle assessment, we conducted an incubation experiment to measure soil carbon changes, microbial respiration, methane fluxes, and nitrous oxide fluxes from two different soils amended with char- and ash- byproducts from biomass after gasification to hydrogen, fast pyrolysis to bio-oil, and torrefaction. Our results suggest that nitrous oxide and methane emission or consumption from BiCRS char amendments to soil are context dependent. Nitrous oxide emissions from amendments are higher in soils with higher pH, whereas some char amendments to low pH soil can reduce N 2 O emissions relative to control. In contrast, methane is emitted from BiCRS char amended to low pH soil, but consumed or neutral relative to control when amended to high pH soil. We present carbon and nitrogen mass balance throughout the experiment to help understand short-term durability of BiCRS chars and their counterfactuals, and preliminary suggestions for revisions to the broader BiCRS Measurement, Reporting, and Verification framework.

54 ENVIRONMENTAL SCIENCES↗

Bicarbonate-Carbonate Selectivity through Nanofiltration for Direct Air Capture of Carbon Dioxide

Direct air capture (DAC) of carbon dioxide is one approach among many proposed that is capable of offsetting hard-to-avoid emissions. In previous work, we developed the alkalinity concentration swing (ACS) method, which is driven through concentrating an alkaline solution that has been loaded with atmospheric CO 2 by desalination technologies, such as reverse osmosis or capacitive deionization. Though the ACS is promising in terms of energy usage and implementation, its absorption rate and water requirements are infeasible for a large-scale DAC process. Here, we propose an improvement on the ACS, the bicarbonate-enriched alkalinity concentration swing (BE-ACS), which selects bicarbonate ions from a stream of aqueous alkaline solution that has absorbed atmospheric CO 2 . The bicarbonate-rich stream is then concentrated, which greatly increases its CO 2 partial pressure, and then CO 2 is extracted from solution. We experimentally investigate the use of pressure-driven nanofiltration (NF) membrane-based separation to select bicarbonate ions over carbonate ions. We screen commercial membranes and select one high-performance membrane for detailed studies, quantifying its bicarbonate-carbonate selectivity factor and bicarbonate-passage factor. Feed pH, the combined concentration of aqueous CO 2 , bicarbonate, and carbonate species (or dissolved inorganic carbon), alkalinity, and permeation flux are systematically varied to study NF separation properties. We find that the selectivity factor, which exceeds 30 times in certain regimes, increases with higher feed pH and higher alkalinity. Lastly, the performance metrics of the selected NF membrane are input into a theoretical BE-ACS cycle analysis, and the required energy input and cycle capacity output are evaluated. Ideal cycle energy is found to be as low as around 250 kJ/mol, with opportunities identified for further decreases through process engineering and forward osmosis energy recovery.

animal feed↗

Microcarbonation of Naphthalene: An Experimental and Computational Study of Photoionization in Naphthalene-Carbon Dioxide Clusters

The photoionization of naphthalene (N)-carbon dioxide (CO 2 ) clusters was studied using tunable vacuum ultraviolet (VUV) radiation from a synchrotron in the photon range of 8.0 to 13.7 eV, in combination with time-of-flight mass spectrometry. Clusters of monomer, dimer, and trimer naphthalene with CO 2 (N­(CO 2 ) 0–6 , N 2 ­(CO 2 ) 0–3 , N3) were observed. The lowest-energy conformers were obtained via a conformer search, followed by geometry optimizations at the ωB97X-V2/aug-cc-pVTZ (monomer) and ωB97X-V2/aug-cc-pVDZ (dimer) levels of theory. Carbon dioxide was found to preferentially cluster on top of the naphthalene molecule (in an out-of-plane configuration). From the mass spectra, photoionization intensity curves (PICs) were constructed, and appearance energies (AEs) were determined. No substantial trend in AE was observed with increasing size of the naphthalene-carbon dioxide clusters; rather, AE oscillations around the value for pure naphthalene were observed. These AE oscillations are also observed in a recently studied naphthalene-water cluster system, though in this system a slight downward trend in AE for pure naphthalene clusters (N1/2/3/4) was observed. The differences between the two systems are attributed to differing interaction strengths. In conclusion, understanding these differences may aid in determining how photoprocessing can proceed differently depending on the dominant matrix component in interstellar ices.

Wannenmacher, Anna [Lawrence Berkeley National Lab↗

Environmental carbon dioxide control

A study of environmental carbon dioxide control for NASA EVA missions found solid potassium carbonate to be an effective regenerable absorbent in maintaining low carbon dioxide levels. The supported sorbent was capable of repeated regeneration below 150 C without appreciable degradation. Optimum structures in the form of thin pliable sheets of carbonate, inert support and binder were developed. Interpretation of a new solid-gas pore closing model helped predict the optimum sorbent and analysis of individual sorbent sheet performance in a thin rectangular channel sorber can predict packed bed performance.

Onischak, M.↗

Development of a prototype regenerable carbon dioxide absorber

Design information was obtained for a new, regenerable carbon dioxide control system for extravehicular activity life support systems. Solid potassium carbonate was supported in a thin porous sheet form and fabricated into carbon dioxide absorber units. Carbon dioxide and water in the life support system atmosphere react with the potassium carbonate and form potassium bicarbonate. The bicarbonate easily reverts to the carbonate by heating to 150 deg C. The methods of effectively packing the sorbent material into EVA-sized units and the effects of inlet concentrations, flowrate, and temperature upon performance were investigated. The cycle life of the sorbent upon the repeated thermal regenerations was demonstrated through 90 cycles.

Onischak, M.↗

Preparing California’s Cap-and-Trade Program for 2045: Integrating Carbon Dioxide Removal

To meet California’s legislatively mandated 2045 carbon neutrality target (AB 1279, Muratsuchi), analyses from the California Air Resources Board (CARB) and Lawrence Livermore National Laboratory (LLNL) have shown that carbon dioxide removal—activities that permanently remove carbon dioxide (CO 2 ) from the atmosphere—will be necessary to remove greenhouse gas emissions that are otherwise too costly or difficult to reduce. This policy brief explores the policy, legal, and technical considerations for integrating carbon dioxide removal into the Cap-and-Trade Program.

54 ENVIRONMENTAL SCIENCES↗