Search NASA⌕ Search

SEARCH · Search NASA

Results for “carbon capture & utilization”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Wyoming Trails Carbon Hub (WyoTCH)

The Wyoming Trails Carbon Hub (WyoTCH) project completed a front-end engineering and design (FEED) study for a commercial-scale, open-access carbon dioxide (CO 2 ) transport pipeline in Wyoming under U.S. Department of Energy (DOE) Award DEFE0032347, funded through the Bipartisan Infrastructure Law Carbon Capture Technology Program and administered by the National Energy Technology Laboratory. The project’s approach of designing a multi-source, multi-destination pipeline, rather than a dedicated line serving a single project, would lower the barrier to entry for individual CO 2 projects. The projects would leverage Wyoming's concentrated industrial and power generation CO 2 sources, its existing CO 2 pipeline infrastructure, and its extensive CO 2 storage and utilization capacity. This is the project's final technical report.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

Process Design and Techno-Economic Analysis of the Modular Staged Pressurized Oxy-Combustion (SPOC) Power Plant for Biomass

This work describes the process design and techno-economic analysis (TEA) of the modular stage pressurized oxy-combustion (SPOC) power plant for biomass firing and coal-biomass co-firing. The SPOC process was modelled using Aspen Plus®, and largely based on a previous model designed by this group for SPOC coal firing. To enable comparison with current National Energy Technology Laboratory (NETL) Bio-Energy Carbon Capture and Storage (BECCS) studies, a 550 MWe SPOC power plant with a supercritical Rankine cycle (241 bar, 593°C, and 593°C), and 90% carbon capture was modeled, and hybrid poplar biomass was chosen. Two cases were evaluated, namely 100% biomass (carbon negative) and 25% biomass co-firing (carbon neutral), and the 100% Powder River Basin coal firing case was chosen for comparison purposes. In the SPOC process, oxygen is produced via a cryogenic air separation unit (ASU) and the heat generated from the compression of air is integrated into the steam cycle and utilized for boiler feed water regeneration. Unique to the SPOC process, the boilers are arranged in a series-parallel configuration, with minimized flue gas recirculation. The flue gas is cooled and scrubbed in the direct-contact cooler (DCC) column, and the water leaving the bottom of the DCC is at a sufficiently high temperature that it can be used for boiler feed water heating, improving plant thermal efficiency. The SPOC efficiencies were above the BECCS cases with capture, and no efficiency penalty on the SPOC plant was observed with an increase of biomass in the mix mostly due to the higher oxygen content in biomass that resulted in lower oxygen requirement from the ASU, and the higher moisture in biomass that due to the key benefit of the SPOC process can be partially recovered as latent heat.

Magalhaes, Duarte↗
DOE OSTI2022

Mining Air for Fuels and Fine Chemicals

The Intergovernmental Panel on Climate Change’s 2021 report underscores that Direct Air Capture (DAC) is an essential component to limiting global warming to 2 °C, yet separating CO 2 from air and its subsequent concentration for conversion into carbon neutral fuels/chemicals or permanent storage remains energy intensive and costly. Further, most DAC technologies rely on repetitive capture and release cycles that reduces the amount of time the DAC materials are able to collect CO 2 and increases wear and tear. Moisture swing (MS) sorption within anion exchange materials utilizes differences in relative humidity to capture and concentrate CO 2 up to 500-fold with negligible energy inputs and low-cost sorbents. Molecular modeling predicts that membranes with a dry and wet side would actively transport CO 2 from its dry side to its wet side against a counter flow of H 2 O evaporating on the dry side, however, existing MS materials are too brittle to be processed into membranes to test this hypothesis. This project brought together experts in DAC materials and design, techno-economic analysis and project management at Arizona State University (ASU), polymer processing at University of Texas at Austin (UTA) and modeling gas transport and exchange at Norther Arizona University (NAU) to develop hollow fiber membranes that use energy from water evaporation to continuously pump CO 2 from air against a concentration gradient to the membranes interior and requiring significantly less energy than current DAC technologies. While this project did not meet its ultimate objectives of demonstrating an active CO 2 pumping membrane, a number of key accomplishments were made in developing low-cost, flexible anion exchange membranes (AEM) at 3.5 m 2 scale, characterizing the ionic and molecular transport within MS materials, and developing several analytical and mathematical models of the MS and pumping process leading to new fundamental knowledge about key rate limiting steps of CO 2 flux in anion exchange membranes at low water activity. Technoeconomic models show that if CO 2 fluxes ≥ 25 µmol CO 2 m -2 s -1 (membrane surface area) are achieved that cost ≤ $\$$100/tonne CO 2 captured, purified and compressed to pipeline quality is possible. The knowledge gained in this research will guide future research in developing new materials toward overcoming these rate limiting steps that in turn could enable transformative and disruptive DAC technologies needed for capturing gigatons of CO 2 per year needed to limiting global warming to 2 °C.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

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↗
DOE OSTI2025

Atomistic Insights into the Reactive Diffusion of CO 2 in Guanidine-Based Facilitated Transport Membranes

The pressing need to address climate change has led to significant advancements in carbon dioxide (CO 2 ) capture technologies. Notably, facilitated transport membranes (FTMs) are distinguished by their exceptional selectivity and permeance, attributed to their reversible chemical reactions with CO 2 . This study, for the first time, sheds light on the reactive diffusion mechanism of CO 2 in FTMs, utilizing 1,1,3,3-tetramethylguanidine (TMG) as a mobile carrier. Specifically, state-ofthe- art molecular dynamics (MD) simulations, augmented by a reparameterized reactive force field (ReaxFF) capable of describing atomistic interactions and reaction pathways, are conducted to investigate the transport of CO 2 in TMG. The analysis of mean squared displacement (MSD) and diffusion coefficients reveals a clear hierarchy in the mobility of reaction components. Our findings highlight a unique hopping diffusion mechanism between bicarbonate ions and TMG molecules, increasing the diffusivity of reacted CO 2 by 1.4 times. The hopping events observed not only enhance our understanding of molecular mobility but also offer a means to boost the performance of FTMs in CO 2 capture applications. Overall, this research lays the groundwork for the future design of FTMs with optimal carrier properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Detecting the undetected: Dealing with non-routine events using advanced M&V meter-based savings approaches

In a rapidly evolving energy industry, utilities are dealing with new challenges like integrating distributed energy resources and market saturation for advanced lighting retrofits. Demand-side management programs require new approaches to meet aggressive carbon reduction goals. Advanced measurement & verification (M&V) is an energy data analysis method using smart meter data in combination with analytics to quantify energy efficiency project savings. Advanced M&V shows great promise for supporting next generation commercial programs including retro commissioning, multi-measure retrofits, and behavior change programs. Advanced M&V captures real project impacts at the meter, but sometimes non-project events can also impact consumption (so-called “non-routine events” [NREs]). Accurately detecting and accounting for NREs is important for reducing uncertainty of savings estimates and helps manage investment risk for different stakeholders (e.g., utilities, building owners, ESCOs). Recent research has shown promise in establishing data-driven techniques to identify and adjust for NREs, but fundamental questions still remain, such as: how can you distinguish NREs from acceptable noise in energy consumption profiles? What is the frequency and magnitude of NREs? Can their detection and adjustment be automated and streamlined? This paper documents the state of the art in NRE quantification and analysis. The results of research to quantify the frequency, nature and direction of NREs, and methods and metrics for determining a trigger threshold for taking action on NREs are presented. The paper also documents the latest technical guidance on application of NRE detection and adjustment methods.

Fernandes, Samuel↗
DOE OSTI2026

Insights from Initial Engineering Designs of Point Source Capture at Industrial Facilities

Initial engineering design studies examining the application of state-of-the-art carbon capture technology at industrial plants contain generally overlooked real-world design considerations for near-term deployment of point source capture (PSC). The implementation of PSC across a wide range of industrial applications presents unique challenges associated with fluctuating CO<sub>2</sub> concentrations, flue gas composition, and utility and land availability. In this article, seven recent industrial retrofit PSC projects are reviewed to investigate the impact of site-specific factors on project design and cost. Across the seven projects, three capture technology classes and four industrial applications are considered, allowing insight into industry-specific opportunities for PSC technology synergy. Common challenges across projects and proposed design solutions are highlighted to propagate ideas and solutions to close the technology gaps and accelerate learning rates.

FEED Studies↗
DOE OSTI2026

Green Methanol via an Integrated Direct Air Capture, CO 2 Electrolyzer, and Hydrogenation Reactor

This project pioneered a groundbreaking reactor design to produce green methanol by harnessing the electrochemical CO 2 reduction reaction (eCO 2 RR), a cornerstone of power-to-fuels technology. The effort integrated three innovative technologies to achieve carbon-neutral methanol production at a target cost of under $\$$800/ton: 1. Direct Air Capture (DAC): Using a cutting-edge sorbent material developed at Holocene, scalable models were developed to integrate captured atmospheric CO₂ into the reactor system. 2. Intermediate-Temperature CO 2 Electrolyzer: Developed by the University of Tennessee (UTK), this electrolyzer utilizes a cost-effective, proton-conducting solid acid electrolyte (CsH 2 PO 4 , CDP) and a mixed-metal oxide cathode. It achieves high faradaic efficiencies (>98%) by effectively suppressing hydrogen evolution at high current densities, converting CO 2 to CO with remarkable selectivity. 3. Catalysis and Reactor Engineering: Oak Ridge National Laboratory (ORNL) contributed world-class expertise in heterogeneous catalysis and reactor design. Their advanced ASPEN modeling drove systems integration and supported techno-economic and life cycle analyses. This effort was further bolstered by partnerships with industry leaders Air Company and Plug Power, who provided critical guidance on scaling, systems engineering, and the integration of water electrolyzers into large-scale operations. During Phase 1, the team focused on modeling and validating a lab-scale reactor demonstrating the feasibility of the integrated approach. Key accomplishments include a 52% increase in current density at 0.8 V while maintaining >98% CO faradaic efficiency, successful 10× scale-up of the electrolyzer with performance within 5% of coin-cell results, best-in-class durability (168-hour test at 0.6 V with 0.14 mA/cm 2 -h degradation), validated TEA confirming the $\$$800/ton methanol target, and completed preliminary LCA showing potential for net-negative GHG emissions under renewable energy scenarios.

10 SYNTHETIC FUELS↗
DOE OSTI2022

Compositions and methods for carbon dioxide capture

An aqueous solvent composition is provided, comprising a nucleophilic component having one or more sterically unhindered primary or secondary amine moieties, a Brønsted base component having one or more basic nitrogen moieties, a water-soluble organic solvent, and water. A biphasic composition is provided, comprising one or more carbamate compounds, one or more conjugate acids of Brønsted base, a water-soluble organic solvent, and water. A biphasic CO2 absorption process is also provided, utilizing the biphasic solvent composition.

Lu, Yongqi↗
DOE OSTI2024

Performance and Cost Potential of sCO2 Bottoming Cycle for Gas Turbines with Carbon Capture – Paper 32

This study investigates the performance and economic potential of sCO2 bottoming cycles for H-class gas turbine-based NGCC plants with a post-combustion capture system. A portion of the gas turbine exhaust heat is used for the generation of steam required for a solvent-based capture system while the rest of the waste heat is utilized in an sCO2 bottoming cycle for power generation. Overall, the performance and LCOE of investigated sCO2 bottoming cycles are similar to those of a state-of-the-art triple-pressure reheat steam Rankine cycle. As the gas turbine exhaust temperature increases (beyond 630oC), sCO2 bottoming cycles begin to show greater performance and economic benefits compared to a steam Rankine cycle with ~0.7 percentage point higher plant efficiency and 1.4% lower LCOE.

Pidaparti, Sandeep↗
DOE OSTI2024

CFD and systems engineering to minimize membrane-based carbon capture costs

In this study, we propose a superstructure for membrane-based carbon capture, addressing these challenges through the formulation of an optimization problem. The case study considers a flue gas with a flowrate of 1000 mol/s and a 30 % CO2 (molar basis), which is representative of steel plants. Reduced models, derived from rigorous CFD simulations of membrane modules, are utilized to enhance the efficiency of the optimization process. The reduced model includes specific input variables such as inlet flow rate, retentate and permeate pressures, and inlet CO2 concentration; while the CO2 recovery and purity in the permeate side are considered as output variables. In this way, we exploit the information from the CFD simulations in the superstructure, aiding in the selection of the optimal configuration for the multi-stage membrane process. The results underscore the efficiency of a multi-stage membrane design, showing capture costs around 45 $/t-CO2.

Pedrozo, Hector A.↗
DOE OSTI2025

Systems Analysis of Biomass and Coal Co-firing Power Plants with Deep Carbon Capture Toward Net-zero Emissions

Achieving a net-zero emission economy in the United States requires integrating diverse low-carbon and negative-emission technologies into the existing fossil fuel-dominant power fleet. Potential technologies from the low-carbon portfolio include renewable power, fossil power with carbon capture and storage (CCS), bioenergy with CCS (BECCS), and direct air capture (DAC). Renewable power is a clean energy source but has to pair with costly battery storage to provide dispatchable electricity. Fossil power with CCS offers dispatchable electricity yet still relies on DAC to offset residual emissions, even when deploying deep CCS with more than 90% CO2 capture. Coal-biomass co-firing with CCS, a subset of BECCS, is a reliable energy production technology that can be retrofitted from existing electricity generation units (EGUs). Power plant retrofit maximizes the use of the current U.S. coal power fleet without the need for large-scale deployment of new renewable power, battery storage, or DAC. Retrofitting coal-biomass co-firing with deep CCS in EGUs is a promising option, but not a universal solution. Biomass co-firing at a power plant introduces economic challenges and indirectly poses pressure on land and water resources. Meanwhile, retrofitting deep CCS affects plant efficiency and raises electricity generation costs. Overall, the technical feasibility and economic viability of plant retrofits vary across EGUs, as they are contingent upon the regional availability of biomass, unit-specific characteristics, site-specific fuel supply costs, and adjacent CO2 storage potential. Government incentives like 45Q can improve the retrofit viability, though the impact requires further quantification. A comprehensive analysis at the unit level is essential to address the question regarding the fate of the U.S. coal-fired electricity generation fleet toward the net-zero emission goal. This study conducts a systematic techno-economic-environmental assessment of EGUs to identify the viability of biomass co-firing and deep CCS retrofits in the U.S. coal-fired power fleet. Specifically, it characterizes the techno-economic performance of deep carbon capture, estimates life cycle greenhouse gas (GHG) emissions, and conducts a fleet-level assessment on retrofit viability. The key objectives are (1) to estimate the unit-specific performance and retrofitted cost under various biomass co-firing levels and CO2 capture rates; (2) to determine the possibility of reaching net-zero emission at the fleet level; (3) to quantify the cumulative capacities that are suitable for plant retrofits under current and future biomass supply scenarios; and (4) to improve the understanding of policy impacts on such retrofits to help the power sector’s transition to a net-zero economy. Techno-economic Model of Deep Carbon Capture. This study develops the performance and economic models for Monoethanolamine-based post-combustion CO2 capture at 95–99% capture rates. The process is simulated in Aspen Plus, analyzing the performance of carbon capture technology by varying the plant sizes, solvent lean loading, CO2 concentrations, and flue gas inlet temperature. Based on the key inputs and output parameters of CO2 capture, a reduced-order performance model of deep carbon capture is formulated. In addition, an engineering-economic model integrating the performance metrics is developed to estimate the capital as well as operation and maintenance (O&M) costs. Capital cost estimations follow the framework of the Integrated Environmental Control Model (IECM) and incorporate data regressions from three technical reports by IECM, the National Energy Technology Laboratory (NETL), and the National Renewable Energy Laboratory. The O&M cost estimation utilizes the actual inventory consumption rate and labor requirements. Both performance and cost models are embedded into IECM v13.0-beta, a fossil-fuel power plant modeling tool. Life Cycle Assessment of Power Plants. This study estimates the GHG emissions of power plants through life cycle assessment (LCA). The LCA scope includes fuel supply, combustion-based power generation, and CO2 transport and storage. The fuel-based life cycle module is designed following the framework of the NETL Unit Process Library and CO2U LCA Guidance Toolkit. The module is then incorporated into IECM v13.0-beta. The process-based LCA is applied to estimate the GHG emissions of coal and biomass supply, coal- and coal-biomass co-firing power plant operation, as well as CO2 pipeline transport and geographical sequestration. An uncertainty analysis is conducted to quantify the variability and uncertainty associated with the LCA using the Latin Hypercube Sampling (LHS) method. Fleet-level Assessment. This study evaluates the technical and economic feasibility of selected coal-fired EGUs, examines the role of tax credits in retrofit viability, and assesses the competitiveness of retrofitted units against other low-carbon options. Unit screening identifies EGUs for the study, focusing on new, efficient baseload units with air pollution controls. The power plant databases are then established to organize unit-specific information on performance and operating conditions from the relevant public databases. Biomass for co-firing retrofits is selected based on home and neighboring county availability, ensuring sustained operation with at least a 5% co-firing level. The CO2 storage site is determined by state-level storage potential, with ArcGIS Pro and NETL CO2 Saline Storage Cost Model used to identify the optimal balance between the nearest transport distances and affordable storage costs. The latest IECM v13.0-beta is then employed to configure and evaluate the eligible EGUs with or without the deployment of deep CCS and biomass co-firing. A supply curve is established to illustrate the cumulative installed capacity suitable for retrofits at different cost levels. A sensitivity analysis on tax credits for carbon sequestration is performed. Finally, a unit-level cost comparison is conducted among retrofitted plants, renewable power with battery storage, and abated fossil fuels with DAC. Expected Results. This study evaluates the technical, economic, and environmental metrics of each EGU across an array of CO2 capture rates and biomass co-firing level scenarios. Unit-level comparisons will identify critical factors influencing technical performance. The supply curves with and without tax incentives will provide insights into the impact of tax credits on biomass co-firing and CCS deployment. The cost comparisons with renewables and DAC-retrofit will assess the competitiveness of the retrofitted units. Life cycle emissions from each unit will be assessed to identify the scenarios under which net-zero emissions can be achieved. These analyses are expected to determine the total coal-fired capacity suitable for serving as a low-carbon energy source with or without tax incentives. The study results are novel in identifying optimal unit-specific strategies for producing carbon-neutral power, whether through retrofitting EGUs with deep CCS, biomass co-firing, DAC, or installing renewable power with battery. The findings will provide insight into nationwide efforts to ensure reliable, affordable, and low-carbon electricity. It also will inform investment decisions and policies in the deployment of deep carbon capture and negative emission technologies for a net-zero energy future.

Biomass Co-firing↗
NASA NTRS2024

Fundamental Experimental Tests and Modeling of LOX/CH4 Engines at High Pressures

In recent years, the space travel industry has grown exponentially, resulting in the need for a low-cost, efficient rocket engine fuel. As such, there has been renewed interest in utilizing liquid natural gas (LNG) as it is less likely to soot than kerosene-based fuels and has widespread availability and low cost of use as compared to the traditional RP-X and even liquid methane (LCH4) fuels due to the reduced need for refinement. However, current literature does not fully cover varying blends of natural gas and the effects that impurities have on natural gas/methane fuels, with most studies being confined to low-pressure applications. Therefore, new experimental ignition delay time measurements at rocket engine relevant pressures are essential to ensure current chemical kinetic models capture the ignition behavior at these elevated conditions and to determine the optimal purity levels for a reliable, cost-efficient, aerospace-grade LCH4/LNG fuel. The current work explores various blends of natural gas/methane fuel with various impurities, including higher hydrocarbons as well as nitrogen-carriers. A shock tube study was carried out to study the ignition delay times and carbon monoxide time histories of these natural gas blends utilizing chemiluminescence and laser absorption spectroscopy at 20, 50 and 100 atm over temperatures ranging from 1400-1700K and at an equivalence ratio of 1. The experimental data was then compared to two different chemical kinetic mechanisms: the industry-standard GRI 3.0 and the in-house UCF 2022. The data is used to improve chemical kinetic mechanisms and modeling of LNG fuels for rocket engine applications.

Methane↗
DOE OSTI2021

Recent Cryogenic Carbon Capture™ Field Test Results

Sustainable Energy Solutions (SES) has been developing Cryogenic Carbon Capture™ (CCC) since 2008. In that time, two processes have been developed, the External Cooling Loop and Compressed Flue Gas CCC processes (CCC-ECL and CCC-CFG, respectively). The CCC-ECL process cools the flue gas with an external refrigerant loop. This process currently captures up to 1 tonne of CO2 per day (TPD). SES has tested CCC-ECL on real flue gas slip streams from subbituminous coal, bituminous coal, biomass, natural gas, shredded tires, and municipal waste fuels at field sites that include utility power stations, heating plants, cement kilns, and pilot-scale research reactors. The CO2 concentrations from these tests ranged from 5 to 22% on a dry basis. CO2 capture ranged from 95-99+% during these tests. Several other condensable species were also captured including NO2, SO2 and PMxx at 95+%. NO was also captured at a modest rate. The CCC-CFG process has been scaled up to a 0.25 ton per day system. This system has been tested on real flue gas streams including subbituminous coal, bituminous coal, and natural gas at field sites that include utility power stations, heating plants, and pilot-scale research reactors. CO2 concentrations for these tests ranged from 5 to 15% on a dry basis. CO2 capture ranged from 95-99+% during these tests. Several other condensable species were also captured including NO2, SO2, and PMxx at 95+%. NO was also captured at 90+%. Hg capture was also verified and the resulting effluent from CCC-CFG was below a 1ppt concentration. This paper will focus on discussion of the capabilities of CCC generally, the results of CCC-ECL field testing, and future steps surrounding the development of this technology. Test results that will be presented have been collected during 9 months of testing at a commercial power plant under funding from the US Department of Energy (DOE) and the host utility. Testing of one of the systems at a commercial cement plant in the United States will also be discussed. During this testing, the system captured CO2 from the cement plant and stored the CO2 in pressurized tanks. These tanks were provided to a partner company that later used the CO2 in a CO2 utilization demonstration. The CO2 was utilized to cure concrete manufactured using cement from the same plant where the CO2 was captured. This integrated capture and utilization demonstration was the first time that the cement industry has shown in the field that it can sequester its CO2 emissions in its main product stream. This represents a potential game changing solution for industrial CO2 emissions. Operational data and host-site feedback indicate that the CCC process is ideally suited for deployment into a variety of commercial environments. A few areas of de-risking remain to make sure the technology can meet very strict industrial reliability standards. These areas of de-risking are identified and discussed. The product CO2 is shown to meet specification for many uses including industrial and merchant applications. The technology is nearing readiness for deployment at commercial scale and several initial target markets have been identified.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2024

Modeling bicarbonate formation in an alkaline solution with multi-level quantum mechanics/molecular dynamics simulations

Understanding carbonate speciation and how it may be modulated is essential for the advancement of carbon dioxide (CO 2 ) capture and storage technologies, which often rely on the transformation of CO 2 into carbonate, e.g. via the formation of carbonate minerals. To date, few atomic-level, quantum-mechanics-based simulations have been carried out to characterize how carbonic acid (H 2 CO 3 ) and bicarbonate ($HCO^{-}_{3}$) form in aqueous solution, and how pH affects this process. Recently, Martirez and Carter utilized rare-event sampling density functional theory molecular dynamics simulations in combination with multi-level embedded correlated wavefunction theory, thus accounting for both solvent dynamics and electron correlation accurately, to elucidate the mechanism of H 2 CO 3 formation in neutral solution (J. Am. Chem. Soc., 145, 12561, 2023). Here, we perform a complementary simulation using the same method to map out the energetics of $HCO^{-}_{3}$ formation from dissolved CO 2 in basic solution. We find that, as in H 2 CO 3 formation, including water dynamics is important to obtain an accurate prediction of the energetics for the aforementioned reaction. Furthermore, only with MD did we identify the correct pathway for the reaction, in which water – not hydroxide – acts as the initial nucleophile and only at the transition state does it lose a proton.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Interannual variability of spring and summer monsoon growing season carbon exchange at a semiarid savanna over nearly two decades

Eddy covariance measurements of land-atmosphere energy, carbon, and water exchange now span multiple decades at some sites, supporting an improved understanding of flux interannual variability (IAV) and its ecophysiological and physical controls. Most eddy covariance IAV studies have focused on temperate forest ecosystems, where carbon fluxes are large and flux records are longest – but also where IAV is much lower than in dryland regions, which have been identified as an essential driver of the trend and variability in the global terrestrial carbon sink. In this study, we leveraged 19 years of continuous micrometeorological measurements at the AmeriFlux US-SRM mesquite savanna site in southern Arizona, USA to quantify the IAV, trends, and drivers of carbon fluxes during the distinct spring and summer growing seasons. We also assessed the ability of modern satellite and land surface models to capture the IAV of seasonal water and carbon fluxes. Annual net ecosystem production (NEP) was small and highly variable (23 +/- 64 gC m –2 yr –1 ). Precipitation and associated measures of water availability determined most of the variability in NEP, largely through their influence on annual and seasonal gross ecosystem productivity (GEP) as opposed to ecosystem respiration (ER). Root-zone soil moisture captured between 73% (spring) and 85% (summer) of GEP variability and between 73% (spring) and 58% (summer) of ER variability. Throughout the study period, soil moisture and greenness increased with associated increases in GEP, ER and NEP. These trends were strongly influenced by very productive and wet summer growing seasons during the last two years, which were characterized by abundant understory grass cover. Typically, less than half of the variability in growing season GEP and evapotranspiration was captured by satellite-based estimates and land surface model simulations with local site forcing and calibration, highlighting the ongoing utility of long-term datasets to support careful model testing and improvement.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Development of Carbon Molecular Sieves Hollow Fiber Membranes based on Polybenzimidazole Doped with Polyprotic Acids with Superior H 2 /CO 2 Separation Properties (Final Report)

The goal of this project was to develop a highly efficient membrane-based process to capture CO 2 from coal-derived syngas with 95% CO 2 purity, achieving the cost of electricity (COE) 30% below the baseline capture approaches (i.e., Selexol process) when coupled with the advancement in other areas of the power generation facility. Our core approach is based on high-permeance hollow fiber membranes (HFMs) with superior H 2 /CO 2 separation properties at the syngas process conditions, which can then be further utilized to design membrane reactors for process intensification of H 2 production and purification and CO 2 capture. Three organizations with complementary skills collaborated to achieve the goal, including the University at Buffalo (UB), Los Alamos National Laboratory (LANL), and Trimeric Corporation (Trimeric). We formulated logical steps to bring the membrane technology from Technology Readiness Level (TRL) 3 (Experimental proof of concept) to TRL 4 (Laboratory scale validation in relevant environment). During the budget period (BP) 1, we screened various polymeric materials and identified polybenzimidazole doped with inorganic polyprotic acids as the desirable platform. The acid doping increases the H 2 /CO 2 selectivity, and the sequential carbonization increases H 2 permeability while retaining the high selectivity. By manipulating the acid type and doping level and the carbonization temperature, we demonstrated advanced carbon molecular sieving (CMS) materials with H 2 permeability of above 200 Barrer (1 Barrer = 10 -10 cm 3 (STP) cm cm -2 s -2 cmHg -1 ) and H 2 /CO 2 selectivity of above 40 at 200-300°C with simulated syngas containing CO and water vapor. For example, the PBI-(H 3 PO 4 ) 0.11 carbonized at 700 °C exhibits H 2 permeability of 200 Barrer and H 2 /CO 2 selectivity of 60 at 200 °C, and H 2 permeability of 240 Barrer and H 2 /CO 2 selectivity of 54 at 225 °C, which meets the targeted properties and surpasses Robeson’s upper bound. During the BP2, we focused on the conversion of the advanced CMS materials to stable HFMs. Membranes with H 2 permeance of 1,090 GPU (1 GPU = 10 -6 cm 3 (STP) cm -2 s -2 cmHg -1 ) and H 2 /CO 2 selectivity of 57 at 300 °C were successfully fabricated. The effects of temperature, gas compositions, pressure, and time on the separation properties were systematically investigated. Pencil modules were continuously evaluated for 219 h (dry pure gas) and 669 h (dry simulated syngas) and showed initial decline in permeance and increased H 2 /CO 2 selectivity over time, ultimately achieving a steady state stable value, indicating that the ageing phenomena in the nanoporous structures of the membranes during the test. Membrane reactors were fabricated based on the CMS membranes and evaluated for water-gas shift (WGS) reaction. The use of membranes slightly improves the conversion of the CO. However, parametric tests of the membrane reactors at various temperatures and flow rates need to be conducted, as well as the membranes with improved separation performance. We performed a sensitivity analysis on the impact of H 2 /CO 2 selectivity on the COE based on a hybrid process of a membrane unit and cryogenic unit developed by Membrane Technology and Research, Inc. (MTR). Three H 2 /CO 2 selectivity (40, 60, and 15) cases were developed and compared with the baseline capture process (Case B5B) provided by the DOE report. Increasing the membrane H 2 /CO 2 selectivity reduces COE, but the rate of the decrease of COE also diminishes. The COE values for H 2 /CO 2 selectivities of 40 and 60 were nearly the same. As the H 2 /CO 2 selectivity increases, the inert recycling decreases, leading to smaller equipment, less auxiliary power requirements, and less heating, cooling, and refrigeration duty. The refrigeration system used to liquefy the CO 2 is the most expensive piece of equipment and consumes the most electricity within the CO 2 capture process. Increasing the CO 2 concentration in the recycle stream would improve the economics of the process by reducing the refrigeration duty requirement of the unit and also allow for higher liquefaction temperatures. The high H 2 -selective membrane developed by our team may be applicable in other separation processes where lower pressure H 2 retains value. Typically, hydrogen retains its pressure when it is separated from syngas components. Residual components may be used as low-quality fuel and then vented to the atmosphere. Applications might include control of H 2 /CO ratios or mitigation of the water gas shift reaction by CO 2 recycling to the feed of a gasifier or steam methane reformer. To summarize, we have developed industrial HFMs with the best H 2 /CO 2 separation performance reported in the literature. The membranes demonstrate stability with simulated syngas and show great potential for membrane reactors for WGS reactions, lowering the cost of blue H 2 production.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Computed Tomography Scanning and Geophysical Measurements of the CarbonSAFE Seal Integrity Wells in the Illinois Basin

The U.S. Department of Energy’s (DOE) National Energy Technology Laboratory (NETL) researchers in Morgantown, West Virginia, utilized computed tomography (CT) facilities and the Multi-Sensor Core Logger (MSCL) to evaluate the integrity of three cores (Geophysical Monitor #2 (GM2), Verification Well #1 (VW #1), and Wabash #1 for the Illinois Basin Carbon Storage Assurance Facility Enterprise (CarbonSAFE) efforts. This work was carried out in collaboration with the Illinois State Geological Survey (ISGS) as part of their efforts to analyze cores from two field locations, including the Illinois Basin-Decatur Project (IBDP) and second stage Illinois Industrial Carbon Capture and Storage (IL-ICCS) sites at Decatur, Illinois, and the Wabash CarbonSAFE project at the Wabash Valley Resources Integrated Gasification Combined Cycle plant in Terre Haut, Indiana. The results of this study are presented in several formats and are available online on the Energy Data eXchange (EDX). The rock characterization was conducted using non-destructive techniques, allowing for future analysis of the cores. While the equipment used did not provide direct visualization of shale pore space, it allowed for detection of fractures and discontinuities. Low resolution CT imagery with the NETL medical CT scanner was performed on the entire core. Qualitative analysis of the medical CT images, coupled with x-ray fluorescence (XRF), P-wave, and magnetic susceptibility measurements from the MSCL were utilized to identify areas of interest for further study as well as fractured zones. The ability to quickly identify key areas for more detailed study with higher resolution will save time and resources in future studies. The combination of methods used provided a multi-scale analysis of this core and provided both a macro and micro description of the core that is relevant for many subsurface energy-related examinations traditionally performed at NETL.

58 GEOSCIENCES↗