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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

CO 2 -selective membranes containing amino acid salts for CO 2 /N 2 separation

In this paper, facilitated transport membranes comprising polyvinylamine (PVAm) as fixed carrier and different amino acid salts (AAS) as mobile carriers were synthesized for post-combustion capture. The AAS carriers were prepared by deprotonating alanine (Ala), lysine (Lys), and proline (Pro) with 2-(1-piperazinyl)ethylamine (PZEA). CO 2 separation performances of the membranes with these AAS carriers were compared, and the AAS effectiveness to facilitate transport of CO 2 was in the order of PZEA-Pro > PZEA-Lys > PZEA-Ala. Here, the membrane comprising 35 wt.% PVAm and 65 wt.% PZEA-Pro at 57 °C rendered a promising CO 2 permeance of 936 GPU and a CO 2 /N 2 mixed gas selectivity of 193. When the PVAm was reduced to 15 wt.%, i.e., its 20 wt.% was replaced by the mobile carrier of PZEA-Sar (sarcosinate), the permeance further improved to 947 GPU with a remarkable CO 2 /N 2 selectivity of 210. Moreover, thermal gravimetric analysis showed a good thermal stability of the membrane, and membrane stability testing also gave stable transport performance. Furthermore, spectroscopic ellipsometry analysis exhibited a uniform membrane selective layer and an excellent agreement on the membrane thickness of ca. 170 nm measured independently by SEM. In addition, the membranes presented in this paper surpassed both the Robeson upper bound and the modified upper bound, indicating a great potential for CO 2 capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Amine-Appended Metal–Organic Frameworks as Switch-Like Adsorbents for Energy-Efficient Carbon Capture

The goal of this final project report is to comprehensively summarize the work conducted on project FP-00006194. In accordance with the Project Management Plan (PMP) revised May 2019, and Statement of Project Objectives (SOPO) within, Lawrence Berkeley National Laboratory (LBNL), with industrial partners such as Mosaic Materials, Svante, and Electricore, as well as CCSI 2 , has developed a cost-effective post-combustion CO 2 capture system using diamineappended metal–organic frameworks (MOFs). This project involved (i) synthesis and characterization of framework materials that exhibit a switch-like CO 2 adsorption behavior, (ii) scaling-up of MOF production, development of production cost models, and fabrication of materials, and (iii) deployment of materials in a patented VeloxoTherm process and characterization to optimize the material’s performance in the context of real process streams and conditions. During each of the four project budget periods, the project team met Success Criteria for Year 1 to 3; however, because of the decision to halt the project in Q1 2021, Success Criteria for Year 4 were not achieved.

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

Computational Evaluation of Carriers in Facilitated Transport Membranes for Postcombustion Carbon Capture

Incorporating molecular amines as mobile carriers in facilitated transport membranes (FTMs) has been demonstrated to significantly enhance the CO 2 permeance and CO 2 /N 2 selectivity of the membrane for CO 2 capture from flue gas. In this study, by employing computational techniques including density functional theory calculations and molecular simulations, the role of mobile carriers has been systematically studied at a molecular level from the perspectives of the amine–CO 2 reaction chemistry, diffusivities of carriers and gases, and N 2 solubility. The latter two properties were also investigated as a function of water uptake. The water uptake values of FTMs were experimentally quantified too. The introduction of mobile carriers was shown to substantially enhance the diffusivities of CO 2 reaction products compared to FTMs without mobile carriers. The choice of mobile carriers was also demonstrated to influence the separation performance. Computationally, 2-(1-piperazinyl)ethylamine sarcosinate (PZEA-Sar) exhibited a faster reaction kinetics and slightly higher CO 2 absorption capacity as compared to piperazine glycinate (PZ-Gly). Experimentally, the FTM incorporating PZEA-Sar mobile carriers also showed a higher CO 2 permeance. The good agreement validated the computational models employed and insights generated in this study. In conclusion, the outcomes of this work shed light on the future design and selection of carrier structures, and the adopted computational approaches can be employed to discover promising mobile carrier candidates.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2020

CO 2 geological storage: Critical insights on plume dynamics and storage efficiency during long-term injection and post-injection periods

In the quest for net-zero greenhouse gas emission, CO 2 capture and storage technologies play a prominent role. Estimates suggest a potential of sequestering up to several thousand metric gigatons of CO 2 . However, some of the main challenges in its development are an assessment of reservoir-specific storage capacities due to variabilities and heterogeneities in the underlying properties (structure, formations, facies, petrophysics, reservoir architecture, and others) and understanding the migration of CO 2 in the subsurface. How much CO 2 can be stored in a reservoir, and how quickly can it be injected? What will be the dominant storing (trapping) mechanisms? These questions, among others, remain as challenges to the commercial deployment of this technology. This article critically investigates CO 2 plume characteristics and determines the evolving contributions of different trapping mechanisms during a 100-year injection period. Here, simulation results on the CO 2 plume dynamics indicate that lateral propagation is much larger than vertical propagation. The ratio of average lateral to vertical dispersion ranged between 6.3 and 18.8 for the cases investigated. On average, for all the scenarios investigated, the free phase (mobile supercritical CO 2 ) is the dominant trapping mechanism (in terms of the amount of CO 2 stored) during the injection period, accounting up to 45% of the CO 2 injected. Both residual (30%) and solubility (25%) trapping storage ratios decline with time during injection, and no significant mineral trapping appeared during the 100-year injection period. However, the behavior of CaCO 3 suggests a predominant dissolution of CaCO 3 , especially in the vicinity of the injection well.

03 NATURAL GAS↗
DOE OSTI2025

Multiphase computational fluid dynamics modeling of reacting flows in absorption columns for carbon capture

First-principles derived computational fluid dynamics (CFD) simulations have been proposed as a fundamental tool for investigating solvent-based CO 2 absorption in packed columns due to their ability to accurately represent the underlying nonlinear, multiscale dynamics. Numerous studies have previously utilized such CFD simulations to investigate hydrodynamics of columns with structured and random packings by assessing the key hydrodynamic metrics such as the interfacial and wetted areas. While mapping such metrics for different conditions is essential to the optimization of absorption columns, it is not sufficient, as the CO 2 capture rate depends also on the coupled, nonlinear dynamics from the underlying chemical reaction kinetics, thermodynamics, and heat-transfer rates. In this work, we present detailed CFD simulation results augmented by incorporating the effects of interfacial physical mass transfer of CO 2 , heat release from chemical reaction kinetics, and thermophysical property variations from resulting temperature gradients. We demonstrate the applicability of the proposed approach in numerically assessing the performance of packed columns by evaluating key hydrodynamic quantities, CO 2 absorption rates, and temperature rise in a reference column with packings that are structurally similar to the Sulzer Mellapak™ 250.Y packing, for different solvent inflow velocities and temperatures. Predictions from simulation results are found to be consistent with the trends in experimental observations from the literature, suggesting that the predictive capabilities of the simulation framework can be leveraged to guide the future development of absorber-column designs and optimized process flowsheets.

Absorption columns↗
DOE OSTI2023

Impacts of Permeability Heterogeneity and Background Flow on Supercritical CO 2 Dissolution in the Deep Subsurface

Motivated by CO 2 capture and sequestration (CCS) design considerations, we consider the coupled effects of permeability heterogeneity and background flow on the dissolution of a supercritical CO 2 lens into an underlying deep, confined aquifer. We present the results of a large-scale Monte Carlo simulation study examining the interaction of background flow rate and three parameters describing multi-Gaussian log-permeability fields: mean, variance, and correlation length. Hundreds of high-resolution simulations were performed using the PFLOTRAN finite volume software to model CO 2 dissolution in a kilometer-scale aquifer over 1,000 years. Predictive dimensionless scaling relationships relating CO 2 dissolution rate to heterogeneity statistics, Rayleigh (Ra) and Péclet (Pe) numbers were developed for both gravitationally dominated free convection to background flow-dominated forced convection regimes. An empirical criterion, Pe = Ra 3/4 , was discovered for regime transition. All simulations converged quickly to a quasi-steady, approximately linear dissolution rate. However, this rate displayed profound variability between permeability field realizations sharing the same heterogeneity statistics, even under mild permeability heterogeneity. In general, increased heterogeneity was associated with a lower mean and higher variance of dissolution rate, undesirable from a CCS design perspective. The relationship between dissolution rate and background flow was found to be complex and nonlinear. Dimensionless scaling relationships were uncovered for a number of special cases. Results call into question the validity of the Boussinesq approximation in the context of modest-to-high background flow rates and the general applicability of numerical simulations without background flow.

42 ENGINEERING↗
DOE OSTI2024

Molten‐Salt‐Mediated Chemical Looping Oxidative Dehydrogenation of Ethane with In‐Situ Carbon Capture and Utilization

Abstract The molten‐salt‐mediated oxidative dehydrogenation (MM‐ODH) of ethane (C 2 H 6 ) via a chemical looping scheme represents an effective carbon capture and utilization (CCU) method for the valorization of ethane‐rich shale gas and concurrent mitigation of carbon dioxide (CO 2 ) emissions. Here, stepwise experimentation with Li 2 CO 3 ‐Na 2 CO 3 ‐K 2 CO 3 (LNK) ternary salts (i) assessed how each component of the LNK mixture impacted ethane MM‐ODH performance and (ii) explored physicochemical and thermodynamic mechanisms behind melt‐induced changes to ethylene (C 2 H 4 ) and carbon monoxide (CO) yields. Of fifteen screened LNK compositions, nine exhibited ethylene yields greater than 50 % at 800 °C while maintaining C 2 H 4 selectivities of 85 % or higher. LNK salts rich in Li 2 CO 3 content yielded more ethylene and CO on average than their counterparts, and net CO 2 capture per cycle reached a maximum of ~75 %. Extended MM‐ODH cycling also demonstrated long‐term stability of a high‐performing LNK medium. Density functional theory (DFT) calculations andab initiomolecular dynamics (AIMD) simulations suggested that the molten salt does not directly activate C 2 H 6 . Meanwhile, an empirical model informed by experimental data and reaction thermodynamics adequately predicted overall MM‐ODH performance from LNK composition and provided insights into the system′s primary drivers.

Chemistry↗
DOE OSTI2021

CO 2 utilization in built environment via the P CO 2 swing carbonation of alkaline solid wastes with different mineralogy

Carbon mineralization to solid carbonates is one of the reaction pathways that can not only utilize captured CO 2 but also potentially store it in the long term. In this study, the dissolution and carbonation behaviors of alkaline solid wastes (i.e., waste concrete) was investigated. Concrete is one of the main contributors to a large carbon emission in the built environment. Thus, the upcycling of waste concrete via CO 2 utilization has multifaceted environmental benefits including CO 2 emission reduction, waste management and reduced mining. Unlike natural silicate minerals such as olivine and serpentine, alkaline solid wastes including waste concrete are highly reactive, and thus, their dissolution and carbonation behaviors vary significantly. Here, both conventional acid (e.g., hydrochloric acid) and less studied carbonic acid (i.e., CO 2 saturated water) solvent systems were explored to extract Ca from concrete. Non-stoichiometric dissolution behaviors between Ca and Si were confirmed under far-from-equilibrium conditions (0.1 wt% slurry density), and the re-precipitation of the extracted Si was observed at near-equilibrium conditions (5 wt% slurry density), when the Ca extraction was performed at a controlled pH of 3. These experiments, with a wide range of slurry densities, provided valuable insight into Si re-precipitation phenomena and its effect on the mass transfer limitation during concrete dissolution. Next, the use of the partial pressure of CO 2 for the pH swing carbon mineralization process was investigated for concrete, and the results were compared to those of Mg-bearing silicate minerals. In the P CO 2 swing process, the extraction of Ca was significantly limited by the precipitation of the carbonate phase (i.e., calcite), since CO 2 bubbling could not provide a low enough pH condition for concrete–water–CO 2 systems. Furthermore, this study showed that the two-step carbon mineralization via P CO 2 swing, that has been developed for Mg-bearing silicate minerals, may not be viable for highly reactive Ca-bearing silicate materials (e.g., concrete). The precipitated calcium carbonate (PCC) derived from waste concrete via a pH swing process showed very promising results with a high CO 2 utilization potential as an upcycled construction material.

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

Enhanced Thermal Conductivity in a Diamine-Appended Metal-Organic Framework as a Result of Cooperative CO 2 Adsorption

Using diamine-appended variants of the metal-organic framework M 2 (dobpdc) (M = Mg, Mn, Fe, Co, Zn; dobpdc 4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) exhibit exceptional CO 2 capture properties owing to a unique cooperative adsorption mechanism, and thus hold promise for use in the development of energy- and cost-efficient CO 2 separations. Understanding the nature of thermal transport in these materials is essential for such practical applications, however, as temperature rises resulting from exothermic CO 2 uptake could potentially offset the energy savings offered by such cooperative adsorbents. Here, molecular dynamics (MD) simulations are employed in investigating thermal transport in bare and e-2-appended Zn 2 (dobpdc) (e-2 = N -ethylethylenediamine), both with and without CO 2 as a guest. In the absence of CO 2 , the appended diamines function to enhance thermal conductivity in the ab -plane of e-2-Zn 2 (dobpdc) relative to the bare framework, as a result of noncovalent interactions between adjacent diamines that provide additional heat transfer pathways across the pore channel. Upon introduction of CO 2 , the thermal conductivity along the pore channel (the c -axis) increases due to the cooperative formation of metal-bound ammonium carbamates, which serve to create additional heat transfer pathways. In contrast, the thermal conductivity of the bare framework remains unchanged in the presence of zinc-bound CO 2 but decreases in the presence of additional adsorbed CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Direct flue gas capture for algae cultivation and subsequent valorization: evaluating life cycle emissions and costs

Algae cultivation and processing is an important pathway under discussion within the broader CO 2 capture and utilization umbrella. Here, we discuss the results of a life-cycle analysis and techno-economic analysis of a pilot-scale photobioreactor that uses flue gas directly from natural gas or biogas combustion at 3–5% CO 2 concentration. The system requires minimal freshwater use as it has been successfully run with industrial wastewater and has a much smaller areal footprint compared with open pond cultivation. Introducing the flue gas directly to the photobioreactor avoids the need for CO 2 separation and pressurization, which is undertaken in many other algae cultivation systems. For the end-use of the biomass, the default case assumes conversion of algae to liquid fuels via hydrothermal liquefaction. The results indicate that the pilot-scale system has a higher cost, and comparable greenhouse gas emissions compared to pond-based systems, especially as the grid is anticipated to evolve to a lower carbon intensity. The costs of algae biofuel production range from $\$12–16$ per GGE at the current pilot scale. Depending on whether the source of the carbon is fossil or biogenic, the net emissions are 68 g CO 2 e per MJ and −4 g CO 2 e per MJ respectively. If the marine algae species is used instead of the freshwater species, it offers an additional 16 g CO 2 e per MJ carbon fixation in the form of calcium carbonate. The findings point to broadly desirable trends in GHG emissions and costs, while the discussion aims to shed light on areas that could further improve the scalability of the system.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2021

A Review of Well Integrity Based on Field Experience at Carbon Utilization and Storage Sites

Maintaining well integrity is critical to the success of geologic carbon storage (GCS) and carbon dioxide enhanced oil recovery (CO 2 -EOR) operations. Wells that experience leakage because of integrity issues can potentially become a risk to the environment or human health if they release previously captured CO 2 back into the atmosphere or into freshwater aquifers. There are many GCS and CO 2 -EOR sites in operation around the world. However, well integrity experiences at these sites are not widely documented in the public domain. This study details findings from a survey of well integrity experiences elicited from operators of GCS and CO 2 -EOR sites. The goal of the survey was to obtain information about site characteristics and operator experiences with well integrity, monitoring methods, and risk assessment of legacy wells. Literature relevant to the survey questions was also reviewed and summarized to provide context for survey responses and identify areas where field experiences with well integrity do and do not align with the current state of research. We highlight the current state-of-practice, identify research needs, and provide context for future interactions between researchers, operators, and regulators on issues related to well integrity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Filer City Biomass Carbon Removal and Storage (BiCRS) Net-Negative Study

NorthStar Clean Energy Company (NorthStar) conducted the Filer City Biomass Carbon Removal and Storage (BiCRS) Net-Negative Study to develop a conceptual design and cost estimate for retrofitting the TES Filer City Station with post-combustion carbon capture technology in Mainstee Michigan. The Filer City BiCRS Net-Negative Study allowed NorthStar and team to confirm the commercial feasibility of a post-combustion carbon capture system applied to biomass-fired boilers. At the time of the study, there were no operating facilities in the world with carbon capture applied to flue gas from woody biomass as proposed for Filer City. Due to the solvent-agnostic nature of B&W’s SolveBright™ technology, the team determined that multiple amines, both traditional and proprietary, would be capable of 95% CO 2 capture efficiency with the steam available from Filer City’s existing boilers after modifications to burn 100% biomass. Based on the cost estimates produced, NorthStar can now confirm the Filer City BiCRS Project is economically viable with a combination of tax credits available from the Inflation Reduction Act of 2022 and high-quality Carbon Dioxide Removal Credits sold on the Voluntary Carbon Market. The Filer City BiCRS project is uniquely positioned to become one of the first projects to capture and sequester large volumes of CO 2 from a biogenic source, removing existing CO 2 from the atmosphere. The unlimited version of the Filer City Biomass Carbon Removal and Storage (BiCRS) Net-Negative Study Final Technical Report is attached.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2025

Acidities of MgO surface sites: implications for the formation mechanism of Mg(OH) 2

The hydroxylation of periclase (MgO) to brucite (Mg(OH) 2 ) is thought to be an important intermediate step when using MgO to capture CO 2 from the atmosphere. However, the mechanism of hydroxylation of MgO to form Mg(OH) 2 is poorly understood. In this work, we used atomic-scale density functional tight binding simulations coupled with the metadynamics rare event method to analyze the surface chemistry of MgO and the acid dissociation equilibrium constants (pK a ) of its surface sites. The method and parameters were validated by calculating the pK a for hydroxylation of the first shell water bound to aqueous Mg 2+ ion. The pK a value derived using a probabilistic method was 12.3, which is in fair agreement with the accepted value of 11.4, with the difference between them equal to a ∼5 kJ mol −1 error in the calculations. We then extended these pK a calculations to probe the hydroxylation reactions of the surface sites of the MgO(100)–water interface, arriving at pK a s of 5.4 to deprotonate terminal water molecules bound to the surface magnesium sites (η-OH 2 or 〉MgOH 2 ), and 13.9 to deprotonate hydroxylated bridging oxygen sites (μ 5 -oxo or 〉O). Hydroxide (OH − ) adsorption on the surface was also probed and found to be less thermodynamically favorable than deprotonation of the terminal water molecule. The plausibility of the computed pK a s was verified using an activity-based speciation model and compared to pH measurements of water equilibrated with MgO nanoparticles and single crystals. The model predicted a solution pH of 7.1 when surface sites buffered and the pH of 12.0 when MgO dissolution dominated. These are close to the experimental initial solution pHs of 7–7.5 and the long term pHs of ∼10.5. The similarity suggests that the calculated pK a values from the DFTB+/metadynamics simulations are plausible and that these methods can be a useful tool to probe reaction mechanisms involving covalent bonds.

Adapa, Sai Krishna Reddy [Oak Ridge National Labor↗
DOE OSTI2023

Mechanistic insights to drive catalytic hydrogenation of formamide intermediates to methanol via deaminative hydrogenation

Amine-promoted hydrogenation of CO 2 to methanol typically proceeds via a formamide intermediate when amines are used as additives or if the hydrogenation is performed in carbon capture solvents. The catalysts used for the hydrogenation of the formamide intermediate dictate the selectivity of the products formed: 1) Deoxygenative hydrogenation (C–O bond cleavage) resulting in N-methylation of amine and deactivation of the solvent, 2) Deaminative hydrogenation (C–N bond cleavage) resulting in formation of methanol and regeneration of the solvent. To date, catalytic reductions of CO 2 with amine promoters suffer from poor selectively for methanol which we attribute to the limiting formamide intermediate, though to date, the conditions that favor C–N cleavage have yet to be fully understood. To better understand the reactivity of the formamide intermediates, a range of heterogenous catalysts were used to study the hydrogenation of formamide. Well-known gas phase CO 2 hydrogenation catalysts catalyze the hydrogenation of formamide to N-methyl product via C–O bond cleavage. However, the selectivity can be readily shifted to selective C–N bond cleavage by addition of an additive with sufficient basicity for both homogenous and heterogeneous catalytic systems. The base additive shifts the selectivity by deprotonating a hemiaminal intermediate formed in situ during the formamide hydrogenation. This prevents dehydration process leading to N-methylated product, which is a key capture solvent deactivation pathway that hinders amine use in carbon capture, utilization, and storage (CCUS). The findings from this study provide a roadmap on how to improve the selectivity of known heterogenous catalysts, enabling catalytic reduction of captured CO 2 to methanol.

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

Microfluidic Fabrication Techniques for High-Pressure Testing of Microscale Supercritical CO 2 Foam Transport in Fractured Unconventional Reservoirs

Pressure limitations of many microfluidic platforms have been a significant challenge in microfluidic experimental studies of fractured media. As a result, these platforms have not been fully exploited for direct observation of high-pressure transport in fractures. This work introduces microfluidic platforms that enable direct observation of multiphase flow in devices featuring surrogate permeable media and fractured systems. Such platforms provide a pathway to address important and timely questions such as those related to CO 2 capture, utilization and storage. This work provides a detailed description of the fabrication techniques and an experimental setup that may serve to analyze the behavior of supercritical CO 2 (scCO 2 ) foam, its structure and stability. Such studies provide important insights regarding enhanced oil recovery processes and the role of hydraulic fractures in resource recovery from unconventional reservoirs. This work presents a comparative study of microfluidic devices developed using two different techniques: photolithography/wet-etching/ thermal-bonding versus Selective Laser-induced Etching. Both techniques result in devices that are chemically and physically resistant and tolerant of high pressure and temperature conditions that correspond to subsurface systems of interest. Both techniques provide pathways to high-precision etched microchannels and capable lab-on-chip devices. Photolithography/wet-etching, however, enables fabrication of complex channel networks with complex geometries, which would be a challenging task for laser etching techniques. This work summarizes a step-by-step photolithography, wet-etching and glass thermal-bonding protocol and, presents representative observations of foam transport with relevance to oil recovery from unconventional tight and shale formations. In conclusion, this work describes the use of a high resolution monochromatic sensor to observe scCO 2 foam behavior where the entirety of the permeable medium is observed simultaneously while preserving the resolution needed to resolve features as small as 10 μm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Exploitation of Pore Structure for Increased CO 2 Selectivity in Type 3 Porous Liquids

CO 2 capture requires materials with high adsorption selectivity and an industrial ease of implementation. To address these needs, a new class of porous materials was recently developed that combines the fluidity of solvents with the porosity of solids. Type 3 porous liquids (PLs) composed of solvents and metal–organic frameworks (MOFs) offer a promising alternative to current liquid carbon capture methods due to the inherent tunability of the nanoporous MOFs. However, the effects of MOF structural features and solvent properties on CO 2 –MOF interactions within PLs are not well understood. Herein experimental and computational data of CO 2 gas adsorption isotherms were used to elucidate both solvent and pore structure influences on ZIF-based PLs. The roles of the pore structure including solvent size exclusion, structural environment, and MOF porosity on PL CO 2 uptake were examined. A comparison of the pore structure and pore aperture was performed using ZIF-8, ZIF-L, and amorphous-ZIF-8. Adsorption experiments here have verified our previously proposed solvent size design principle for ZIF-based PLs (1.8× ZIF pore aperture). Furthermore, the CO 2 adsorption isotherms of the ZIF-based PLs indicated that judicious selection of the pore environment allows for an increase in CO 2 selectivity greater than expected from the individual PL components or their combination. This nonlinear increase in the CO 2 selectivity is an emergent behavior resulting from the complex mixture of components specific to the ZIF-L + 2'-hydroxyacetophenone-based PL.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Development of Self-Assembly Supports Enabling Transformational Membrane Performance for Cost-Effective Carbon Capture

This final technical report describes work conducted by Membrane Technology and Research, Inc. (MTR) for the U.S. Department of Energy (DOE), National Energy Technology Lab (NETL) on the development of membranes with transformational performance for carbon capture under award number DE-FE0031596. The work was performed from June 1, 2018 through May 31, 2024. For more than a decade, MTR has worked in partnership with DOE to develop an innovative membrane-based CO 2 capture process. This effort has included the first test of membrane modules with coal-fired flue gas at the Arizona Public Services (APS) Cholla plant in 2010; the accumulation of >11,000 hours of flue gas operation for Polaris modules on a bench-scale 1 tonne/day (TPD) system at the National Carbon Capture Center (NCCC); scale-up of first-generation (Gen-1) Polaris to a 20 TPD small pilot system, and successful operation of this system on a flue gas slipstream at NCCC and in integrated boiler testing at Babcock & Wilcox (B&W). Through continued development efforts, a second-generation (Gen-2) version of the Polaris membrane has been scaled-up to pilot production. This membrane offers 70% higher CO 2 permeance with similar selectivity to the base case Polaris. MTR also developed planar modules designed specifically for the low-pressure, high-volumetric flow rate process conditions of flue gas operation. These new modules have significantly lower pressure-drop values compared to the type originally used (spiral-wound modules), which results in significant energy savings. The goal of the work described in this report was to improve on the Polaris Gen-2 membrane with the ultimate aim to reduce the cost of carbon capture. The majority of the effort was to develop improved support membranes for the multi-layer composite structure of MTR’s Polaris membrane. Earlier work at MTR had identified the support structure as limiting membrane permeances, not because the support itself represents a permeation resistance, but because the distribution of pores at the surface of the support imposes a geometric restriction to diffusion in the layers above it. Support membranes were prepared from a range of polymers, including commercially available block copolymers and a custom synthesized block copolymer alternative. The best support membranes developed in this project reduced the geometric restriction by a factor of two to three. These supports then were used to produce Polaris composite membranes with improved permeances. The second topic was to create a high-selectivity version of the Polaris membrane. The high-selectivity version uses a novel selective polymeric material and high selectivities were confirmed in experiments at MTR. The material is not easily made into very thin films. Consequently, the permeances are significantly lower than the Polaris Gen-2 membrane. The utility of this membrane is therefore limited to the carbon dioxide purification step that produces liquid CO 2 . A Technical and Economic Analysis (TEA) was performed for a carbon capture system that uses both advanced membrane types. The TEA shows the novel advanced membranes reduce the cost of capture by 10%, from $63.32/tonne CO 2 to $56.90/tonne CO 2 (2022 USD). Most of the development work was carried out with laboratory-scale casting and coating equipment. A number, but not all, of the improvements identified have been implemented on commercial-scale manufacturing equipment. The focus of future work at MTR is to incorporate the advancements made into the Polaris membrane manufacturing process.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2023

An innovative carbonated cementitious material and its printability and carbon mineralization capacity

The main goal of this research is to develop a carbonated cementitious material (CCMs) mix design and demonstrate its rapid stiffening for manufacturing 3D printed or precast elements for building construction (i.e., concrete with enhanced durability and CO 2 capture efficiency). The material development employs hydrated Ca(OH) 2 , and its distinct reaction with CO 2 to form CaCO 3 . Different formulations and additives including polymer materials enable the thermomechanical properties that give these CCMs 3D printability comparable with cement materials used for similar applications. Here, printable and castable CCM formulations were successfully developed and demonstrated to mineralize CO 2 to form up to 57% CaCO 3 .

36 MATERIALS SCIENCE↗