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This poster presents results of Task 9.0, Advanced Modeling Support of CDR Pilot Projects, of the Carbon Dioxide Removal program (CDR FWP23). Specifically, the poster presents the multi-scale modelling framework to investigate alternate processes configuration for DAC applications including Vacuum-Assisted Temperature Swing Adsorption (TVSA) process and sweep gas for regeneration.
AIChE Fall Meeting 2023, Orlando, FL, November 5-10, 2023.
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Direct air capture (DAC) processes for extraction of CO 2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al 2 O 3 , is explored in detail. By combining CO 2 adsorption measurements, oxidative degradation rates, elemental analyses, solid-state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. Here we demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.
Direct air capture (DAC) of CO 2 coupled with geologic storage is a promising climate change mitigation strategy, with some applications employing amines supported on porous solids as CO 2 sorbents. While branched poly(ethylenimine) (PEI) is the standard benchmark amine material, it suffers from limited oxidative stability. Poly(propylenimine) (PPI), as an alternative, has previously demonstrated improved resistance to degradation under harsh oxidative conditions. Linear and branched PEI are commercially available, though at different molecular weights, while PPI is not commercially available. For this reason, a comparative study of all four polymers (linear PEI, branched PEI, linear PPI, branched PPI) has not been reported for DAC. In this study, we synthesize and compare low-molecular-weight (∼800 g/mol) linear (L) and branched (B) PEI and PPI supported on a model support, SBA-15 silica. These materials are evaluated for CO 2 adsorption under dry, DAC-relevant conditions (400 ppm of CO 2 , 30 °C). LPPI exhibited the highest amine efficiency at all loadings, reaching a maximum of 0.14 mmol CO 2 /mmol N, outperforming BPEI, while LPEI consistently showed the lowest uptake capacity. Temperature-programmed desorption reveals that the structure of the amine polymer impacts the CO 2 binding strength, with branched polymers displaying higher desorption energies of 102−111 kJ/mol. In situ infrared spectroscopy experiments show that all sorbents preferentially capture CO 2 as ammonium carbamate. Isobaric CO 2 uptake studies further underscore the influence of polymer mobility and support pore crowding on performance, while demonstrating the sorbents’ performance at elevated temperatures and CO 2 concentrations. All materials demonstrated good stability over 25 adsorption−desorption cycles using thermal regeneration in an inert gas purge, with only BPPI displaying a 10−11% decrease in capacity/amine efficiency during cycling, possibly due to the loss of low molecular weight, oligomeric amines. This is the first side-by-side comparison of the CO 2 sorption properties of linear and branched PEI and PPI with similar molecular weights. These findings highlight the significant role of polymer architecture in CO 2 capture efficiency and inform future designs of durable, high-performance DAC sorbents.
Direct air capture (DAC) of CO 2 represents one of the most promising technologies to achieve negative carbon emissions. In this work, the superbase ionic liquids (ILs)-modified carbon substrates were developed for DAC of CO 2 by harnessing the strong CO 2 binding capability of IL and the ordered porous channels of the carbon supports. Detailed porosity analysis revealed that the IL with an aromatic cation and an oxygenate anion preferred to fill the micropores, and a thin layer was created on the surface of the mesopores. Strong π-π interaction between the IL layer and the carbon surface was disclosed by wide-angle X-ray scattering (WAXS) analysis, leading to enhanced thermal stability of the IL phase. For the same lL coating amount, the DAC of CO 2 evaluation revealed that a larger mesopore size and pore volume in the carbon/IL composite materials led to higher CO 2 uptake capacity by exposing more active sites to integrate CO 2 from diluted sources. Further, the thermodynamic analysis confirmed the critical role of IL coating in providing strong chemisorption sites and significantly improved selectivity to enrich the diluted CO 2 from the air atmosphere. This work provides guidance on leveraging the scaffolds' surface properties and porosities of the scaffolds to optimize DAC of CO 2 behavior.
Abstract Direct air capture (DAC) processes for extraction of CO 2 from ambient air are unique among chemical processes in that they operate outdoors with minimal feed pretreatments. Here, the impact of humidity on the oxidative degradation of a prototypical solid supported amine sorbent, poly(ethylenimine) (PEI) supported on Al 2 O 3 , is explored in detail. By combining CO 2 adsorption measurements, oxidative degradation rates, elemental analyses, solid‐state NMR and in situ IR spectroscopic analysis in conjunction with 18 O labeling of water, a comprehensive picture of sorbent oxidation is achieved under accelerated conditions. We demonstrated that the presence of water vapor can play an important role in accelerating the degradation reactions. From the study we inferred the identity and kinetics of formation of the major oxidative products, and the role(s) of humidity. Our data are consistent with a radical mediated autooxidative degradation mechanism.
Direct air capture (DAC) of CO 2 by solid porous materials represents an attractive “negative emission” technology. However, state-of-the-art sorbents based on supported amines still suffer from unsolved high energy consumption and stability issues. For this work, taking clues from the CO 2 interaction with superbase-derived ionic liquids (SILs), high-performance and tunable sorbents in DAC of CO 2 was developed by harnessing the power of CaO- and SIL-engineered sorbents. Deploying mesoporous silica as the substrate, a thin CaO layer was first introduced to consume the surface-OH groups, and then active sites with different basicities (e. g., triazolate and imidazolate) were introduced as a uniformly distributed thin layer. The as-obtained sorbents displayed high CO 2 uptake capacity via volumetric (at 0.4 mbar) and breakthrough test (400 ppm CO 2 source), rapid interaction kinetics, facile CO 2 releasing, and stable sorption/desorption cycles. Operando diffuse reflectance infrared Fourier transformation spectroscopy (DRIFTS) analysis under simulated air atmosphere and solid-state NMR under 13 CO 2 atmosphere demonstrated the critical roles of the SIL species in low-concentration CO 2 capture. The fundamental insights obtained in this work provide guidance on the development of high-performance sorbents in DAC of CO 2 by leveraging the combined advantages of porous solid scaffolds and the unique features of CO 2 -philic ionic liquids.
Direct air capture of CO 2 using amino acid absorbents, such as glycine or sarcosine, is constrained by the relatively slow mass transfer of CO 2 through the air–aqueous interface. Our recent study showed a marked improvement in CO 2 capture by introducing CO 2 -permeable oligo-dimethylsiloxane (ODMS-MIM + ) oligomers with cationic (imidazolium, MIM + ) headgroups. Here, in this work, we have employed all-atom molecular dynamics simulations in combination with subensemble analysis using network theory to provide a detailed molecular picture of the behavior of CO 2 and the glycinate anions (Gly – ) at the ODMS-MIM + decorated air–aqueous interfaces. We show that the cationic head groups of the surfactants enhance the concentration and lifetime of Gly – in the interfacial region, while ODMS tails promote the physisorption of CO 2 in the interfacial region. Together, these two factors increase the effective region of contact and the probability of interactions between CO 2 and Gly – compared to that of the pure air–aqueous interface. The fundamental insights gained in this work establish essential foundations for developing hybrid systems with oligomer-decorated interfaces to maximize the overall CO 2 capture rates.
Direct air capture (DAC) technologies are limited by the poor understanding of the dynamic role of interfaces in modulating the chemisorption of CO 2 from air into solutions. While the reactivity of aqueous amine-based solvents in the bulk environment is strongly inhibited by nonequilibrium solvent effects, promoting DAC at interfaces posits a possibility to reduce the coupling with the solvent and significantly accelerate DAC. Building on an experimentally proven concept to bring an anionic glycine absorbent to the interface through ion-pairing interactions with a positively charged surfactant, we establish the fundamental time scales for key elementary steps involved in DAC with rate theory and enhanced-sampling ab initio molecular dynamics simulations. Here, we elucidate the mechanism by which water influences the free energy barriers and dynamical crossing-recrossing of those barriers, affecting the reaction rates. We find that water reorganizes to partially dehydrate [-NH 2 ], facilitating S N 2-based CO 2 conversion to a zwitterion, which then releases a proton via overhydration of [-NH 2 ]. The low-density interfacial water favors dehydration over overhydration, leading to a comparatively higher barrier (slower kinetics) for proton release. The barrier-recrossing events neutralize this effect, letting both steps occur at the same time scale (sub-microseconds) and making the overall DAC process faster at the interface than in the bulk water. Such an understanding of environment-sensitive solvent effects on the reaction kinetics will help design tailored interfaces for enhanced CO 2 capture kinetics via control of solvation and ion paring.
Supported amine adsorbents are promising materials for direct air capture (DAC) of CO 2 due to their high CO 2 capacity and relatively low energy requirement for regeneration. For a DAC process, it is essential to properly define operating parameters to achieve high sorbent productivity (amount of CO 2 captured per unit quantity of sorbent material over unit time). It is furthermore essential to understand the kinetic behavior of the process under the influence of various operating conditions such as the inlet air velocity, sorbent composition, and humidity to select an effective range of operating conditions to maximize sorbent productivity. Here, the dynamic behavior of a DAC process is probed using a fixed fiber sorbent contactor containing poly(ethylenimine) (PEI)-impregnated composite silica/cellulose acetate (CA) fibers. Throughout this study, experiments are conducted using both simulated air (398 ppm CO 2 balanced by N 2 ) and real indoor air (~400–500 ppm CO 2 ). The experimental behavior of the fibers using simulated air and indoor air is compared, and the influence of the inlet air velocity on the breakthrough behavior is assessed. By changing operating conditions, the impact on the fiber sorbent productivity (mmol CO 2 g fiber –1 h –1 ) is quantified to identify conditions that could favor high rates of CO 2 removal. The kinetics of steam-assisted CO 2 desorption are studied, identifying achievable desorption times. Productivities of 1.2 mmol CO 2 g fiber –1 h –1 are obtained using an inlet air velocity of 1.1 m s –1 . Performance trends show that further increasing the inlet air velocity will likely lead to even higher productivities.
The overall objective of this project was to complete an initial design of a commercial-scale, Carbon Capture and Storage system for Direct Air Capture (CCS-DAC) that separates and stores a minimum of 100,000 tonnes/year (t/yr.) net CO 2 from air. Three geographically diverse host sites will be used to determine the impact of different climates on the design and cost of the CCS-DAC systems; California (dry-hot), Louisiana (humid-hot), and Wyoming (mid-continental). In addition, the impact of using different low-carbon energy sources was also examined. The focus of this project was to geologically store the CO 2 , rather than the utilization of CO 2 . This Final Scientific/Technical Report is a collection of the deliverables for the project. The project team was able to successfully complete all the necessary tasks needed to determine the feasibility of the designs and operational needs of the DAC systems for each location. The data created by this allowed the project team to conduct the required evaluations to meet the requirements of the deliverables. The following deliverables were drafted and submitted to DOE prior to the conclusion of the project: (1) Initial Engineering Design; (2) Costing Estimate; (3) Techno-Economic Analysis (TEA); (4) Life Cycle Analysis (LCA); (5) Business Case Assessment; and (6) Technology EH&S Risk Assessment.
Microalgae biofuel production potential in the United States is constrained by a lack of suitable cultivation locations within a close proximity to CO2 point-sources. Initial estimates suggest that removing the requirement of a concentrated CO2 source expands resource potential ten-fold, allowing the projection of production levels that approach levels of current U.S. diesel consumption. Decoupling cultivation locations from concentrated CO2 point-sources requires direct capture of air-CO2 into the pond bulk at a rate sufficient to meet maximum expected carbon assimilation rates (10 g C/m2-day and higher). Enhancement of the ingassing rate via chemical reaction, the direct reaction of dissolved CO2 with hydroxide ions, has been proposed as a mechanism to increase the ingassing rate of air-CO2. The central objectives of this project are to validate whether chemically enhanced air-CO2 ingassing rates in large raceway ponds can meet or exceed the level required to support high levels of algae productivity, then subsequently identify alkaliphilic strains able to withstand such conditions while maintaining a biomass productivity that enables process economics. Full scale ponds (~1 acre, unlined) will be used to validate ingassing rates as a function of pH expected at scale in a series of abiotic experiments. To date, mass-transfer dynamics have been characterized in ponds ranging from 1 to 1,000 m2. Initial results will be presented describing the mass transfer coefficient in 1-acre (~4,000 m2), unlined ponds. The maximum expected carbon ingassing rate will be measured during ingassing trials, in which pond pH is displaced from equilibrium via the addition of a strong base, with the subsequent decrease in pH (and increase in dissolved inorganic carbon) corresponding to the air-CO2 absorption rate. A mass-transfer model, validated with experimental results, will be used to project ingassing rates expected at pond scales (10 acres) required for production of commodity chemicals.
Vanadium peroxide molecules undergo stoichiometric direct air capture of carbon dioxide, wherein reactivity towards carbon capture via both peroxide and adventitious superoxide ligands trends with the size of the alkali countercation.
The feasibility and performance of nuclear energy coupled with Negative Emission Technology (NET) processes were investigated in this report. Three overarching questions from nuclear NET systems guided this research: which NET would be able to use heat and/or electricity from nuclear power plants (NPPs); what is the performance and cost of a nuclear NET system; and what would be the market outlook for this system? Among the various NETs that are actively being developed, several were found to potentially benefit from coupling with an NPP via (1) large amounts of decarbonized and constant-output electricity; (2) free waste heat or cheap low-temperature heat; or (3) high-temperature heat. NPPs were found to be compatible with Direct Air Capture (DAC) systems, and a detailed techno-economic analysis of coupled NPP&DAC systems was performed. Preliminary analysis also indicated that biomass and water-based NETs are potentially compatible with NPPs, but further work is needed to quantify the performance of these nuclear NET systems. Design and performance analyses were completed for both liquid solvent DAC (L-DAC) and solid sorbent DAC (S-DAC) technologies. A 1.0-GWth NPP coupled with L-DAC and S-DAC was found to be able to capture 12–15 Mt CO 2 /yr and 1.0–1.5 Mt CO 2 /yr, respectively. While the L-DAC process enables much greater CO 2 capture than the S-DAC process when both are sized with a 1 GWth NPP, the NPP&L-DAC system considered also requires >2 GWth natural gas oxy-combustion to reach adequate temperature in the calciner. CO 2 generated from natural gas combustion is also captured as part of the calcination process, in addition to the CO 2 captured from air, resulting in overall CO 2 sequestration of close to 30% more than what is captured from air. The cost of carbon capture calculated with the levelized cost of DAC (LCOD) had a range of $\$170–260$/tCO 2 for NPP&L-DAC systems and a range of $\$650–680$/tCO 2 for NPP&S-DAC systems. For both DAC systems, the NPP provides economic benefit when compared to previous National Energy Technology Laboratory (NETL) studies of non-nuclear DAC systems, leading to reduction of LCOD by 5–7% for L-DAC, and 8–13% for S-DAC. For the NPP&DAC systems, a preliminary market analysis reviewed potential CO 2 market prices and eligibility for incentives. The estimated potential revenues for CO 2 capture (coming from federal incentive, CO 2 commodity markets, or offset market) is in the range of $\$170–979$ tCO 2 , and the results show that because of lower LCOD, the NPP&L-DAC process would be more attractive to a market than the NPP&S-DAC process. The large investment needed for NPP&DAC processes would require long-term certainty of sufficient market size, CO 2 prices, and incentives. Enabling NPPs to ramp DAC operation up or down based on electricity market price is not expected to significantly increase revenues of the NPP&DAC system. This is because the revenues from CO 2 sequestration are required to be very high to justify the deployment and continuous operation of the very expensive DAC technologies. In this analysis, several new research questions were uncovered, and follow-up analyses are recommended for further investigation, including a detailed feasibility study of NPP coupled with other NET systems such as biomass pyrolysis and gasification with carbon capture and storage, and seawater carbon capture.