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At least 253 records · Page 14

Photo-Reactive Amine-Based Direct Air Capture and Conversion of CO2

This study presents a novel photochemical approach to direct air capture (DAC) and CO2 conversion, utilizing a ruthenium-modified mesoporous TiO2 composite infused with linear polyethyleneimine (L-PEI) and enhanced by light absorbing and earth abundant titanium nitride (TiN). This light-activated system operates at ambient pressure and addresses long-standing challenges in conventional amine-based thermal reactive carbon capture (RCC), including amine degradation and CO2 slip. Our findings demonstrate that L-PEI effectively stabilizes CO2 adsorption and facilitates high-yield methanation over 50 cycles with a non-flammable forming gas mixture (approximately 5% H2). Comparatively, composites incorporating small-molecule amines exhibited poor stability under illumination, while highly mobilie branched PEI (B-PEI) formulations suffered from significant catalyst deactivation. A technoeconomic analysis suggests that methane synthesis via this platform could be achieved at costs below $5/kg under current electrocatalytic hydrogen pricing. These findings highlight the potential of this approach to enhance energy security by enabling decentralized, scalable fuel production from atmospheric CO2.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multi-Scale Modeling and Prototype Development for Electrochemical CO2 Reduction (CRADA Final Report)

In this CRADA project, Lawrence Livermore National Laboratory, Stanford University, SLAC National Laboratory, and TotalEnergies collaboratively executed a multidisciplinary investigation of electrochemical reduction of CO2 to produce sustainable fuels and chemicals. Overall, the project led to an increased understanding of the fundamental processes involved in CO2 electrolysis, from the atomistic scale to the full electrolyzer device scale, ultimately leading to design guidelines for CO2 electrolyzers that will help in their future commercialization. As the model systems, Ag- and Cu-based catalysts were investigated in various forms depending on the electrochemical platform that was utilized to study the activity, selectivity, and durability towards electrochemical CO2 reduction. By employing experimental, theoretical, and computational techniques, the project team experimentally validated multi-physics models, evaluated the experimental levers that lead to increased electrolyzer reaction selectivity and energy efficiency, and used computational optimization to design higher performance electrodes. The learnings of this project were extensively documented in publicly available peer-reviewed journal publications and conference presentations, which serve as a foundation for further work to build from.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Realistic Estimation of CO2 Emission Reductions Due to Building Retrofit

Constant CO2 emission factors of electricity are often used to study the emissions of buildings. However, in the era of increased renewable energy for power generation, emission factors of electricity are dynamically changing. This study is to investigate the impact of dynamic CO2 emission factors, which are more realistic than constant ones, on the emission reductions due to building retrofits. The results reveal that if dynamic CO2 emission factors are used for U.S. medium office buildings, improving the efficiency of lighting or electric equipment will lead to more emission reductions in locations with high wind power penetration (e.g., 12% more reductions in Rochester) and fewer reductions in locations with high solar power penetration (e.g., 8% fewer reductions in San Diego). As for improving envelope insulation, dynamic CO2 emission factors have more impact on the emission reductions in hot climates than in cold climates.

Lou, Yingli↗

Creep behavior of austenitic steels in CO2 and the effect of specimen thickness

Steels have a proven track record of safe operation in steam power plants for decades. Interest in developing supercritical CO2 power cycles as a more efficient and sustainable alternative to steam cycles has driven a need to understand steel performance in these new environments. In particular, the potential of the high temperature CO2 environment to influence the creep behavior of the steel must be determined. Prior research on this topic between the 1960s and 1980s found conflicting conclusions, but nevertheless raised the possibility that carburization during CO2 exposure may strongly affect the creep behavior. This raises concerns particularly for thin-sectioned components such as compact heat exchangers, where even small rates of carburization can become problematic over long operating lifetimes. To shed light on this issue, this research investigates the creep behavior of austenitic stainless steel 347H and 309H (a higher Cr alternative) at 650°C. Specimens of 0.5, 1.0, and 2.0 mm thickness were tested to further assess the effect of steel thickness. Both steels show a reduction in creep life in CO2 relative to air, with 309H showing slightly better performance than 374H. Analysis is ongoing to determine the reason for degraded creep properties.

Rozman, Kyle A.↗

Effect of Pore Connectivity on the Behavior of Fluids Confined in Sub-Nanometer Pores: Ethane and CO2 Confined in ZSM-22

The behavior of fluids under nano-confinement varies from that in bulk due to an interplay of several factors including pore connectivity. In this work, we use molecular dynamics simulations to study the behavior of two fluids—ethane and CO2 confined in ZSM-22, a zeolite with channel-like pores of diameter 0.55 nm isolated from each other. By comparing the behavior of the two fluids in ZSM-22 with that reported earlier in ZSM-5, a zeolite with pores of similar shape and size connected to each other via sinusoidal pores running perpendicular to them, we reveal the important role of pore connectivity. Further, by artificially imposing pore connectivity in ZSM-22 via inserting a 2-dimensional slab-like inter-crystalline space of thickness 0.5 nm, we also studied the effect of the dimensionality and geometry of pore connectivity. While the translational motion of both ethane and CO2 in ZSM-22 is suppressed as a result of connecting the pores by perpendicular quasi-one-dimensional pores of similar dimensions, the effect of connecting the pores by inserting the inter-crystalline space is different on the translational motion of the two fluids. For ethane, pores connected via inter-crystalline space facilitate translational motion but suppress rotational motion, whereas in the case of CO2, both types of motion are suppressed by pore connection due to the strong interaction of CO2 with the surface of the substrate.

Kummali, Mohammed Musthafa (ORCID:000000028082555X↗

Field Measurement of Central CO2 Heat Pump Water Heater for Multifamily Retrofit

Domestic hot water heating of multifamily buildings accounts for a substantial portion of the energy load of existing buildings. This load is made up of both the energy required to produce hot water and the energy needed to maintain the temperature of the heated water within a building’s distribution piping so that heat can be promptly delivered to building occupants as needed. Properly designed heat pump water heater (HPWH) systems have the ability to improve efficiency in both water heating and temperature control operations. Further, CO2 heat pump technology reflects a shift away from traditional refrigerants and toward refrigerants with low global warming potential (GWP). In this paper’s case study, a design consisting of multiple CO2 heat pump water heaters (commonly used in single-family homes) with a novel “swing tank” was proposed to meet the demand for domestic hot water heating and recirculation loop temperature maintenance. The proposed design was applied to the retrofit of a 60-unit, low-rise, multi-family building located in the Pacific Northwest of the United States. The purpose of this paper is to verify the performance of the system including the proposed “swing tank” in a centralized SHW system using CO2 HPWH. It also provides practical information and lessons learned from the retrofit project. Long-term monitoring data showed that the system had a coefficient of performance (COP) of three or greater and provided an average of 20 gallons of hot water per day per apartment. The results of this work indicate that residential-scale CO2 HPWH equipment and a “swing tank” design can efficiently provide domestic hot water heating and temperature maintenance for mid-sized multifamily buildings.

Banks, Adria↗

flat10MIP: an emissions-driven experiment to diagnose the climate response to positive, zero and negative CO2 emissions

Abstract. The proportionality between global mean temperature and cumulative emissions of CO2 predicted in Earth system models (ESMs) is the foundation of carbon budgeting frameworks. Deviations from this behavior could impact estimates of required net-zero timings and negative emissions requirements to meet the Paris Agreement climate targets. However, existing ESM diagnostic experiments do not allow for direct estimation of these deviations as a function of defined emissions pathways. Here, we perform a set of climate model diagnostic experiments for the assessment of transient climate response to cumulative CO2 emissions (TCRE), the Zero Emissions Commitment (ZEC), and climate reversibility metrics in an emissions-driven framework. The emissions-driven experiments provide consistent independent variables simplifying simulation, analysis and interpretation, with emissions rates more comparable to recent levels than existing protocols using model-specific compatible emissions from the CMIP DECK 1pctCO2 experiment, where emissions rates tend to increase during the experiment, such that at the time of CO2 doubling in year 70, emissions are much greater than present-day values. A base experiment, “esm-flat10”, has constant emissions of CO2 of 10 GtC per year (near-present-day values), and initial results show that the TCRE estimated in this experiment is about 0.1 K less than that obtained using 1pctCO2. A subset of ESMs exhibit land carbon sinks that saturate during this experiment. A branch experiment, esm-flat10-zec, illustrates that both positive and negative ZEC effects are less pronounced under esm-flat10 than under 1pctCO2 – the magnitude of ZEC50 in ESMs is, on average, reduced by 30 % compared with 1pctCO2 branch experiments. A final experiment, esm-flat10-cdr, assesses climate reversibility under negative emissions, where we find that peak warming may occur before or after net zero and that the asymmetry in temperature at a given level of cumulative emissions between the positive and negative emissions phases is well described by ZEC in most models. Further, we find that existing probabilistic simple climate model (SCM) ensembles tend to overestimate temperature reversibility compared with ESMs, highlighting the need for additional constraints. We propose a set of climate diagnostic indicators to quantify various aspects of climate reversibility. These experiments were suggested as potential candidates in CMIP7 and have since been adopted as “fast track” simulations.

Sanderson, Benjamin M↗

BETO 2021 Peer Review - Feasibility Study of Utilizing Electricity to Produce Intermediates from CO2 and Biomass

Capturing and converting CO2 generated from bioethanol facilities into valuable products, leveraging renewable electricity as the primary energy input, could increase overall biorefinery carbon utilization by as much as 40% and provide a means to decarbonize fuels and chemicals production. However, significant uncertainty exists around the costs, carbon intensity, risks, and technical challenges associated with electron-driven CO2 reduction. Thus, the overarching objective of this project is to guide existing and future research and development efforts by addressing these knowledge gaps for utilizing renewable electricity and CO2 to improve biorefinery economics and carbon utilization. By September 2023, this project will develop and publish a comprehensive design report for the integration of CO2 utilization into two existing conceptual biorefinery designs, which will include conceptual process models, pioneer and nth plant economics, identification and quantification of technological risks, and projections for future cost reductions.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Seamlessly Fuel Flexible Heat Pump with Optimal Model-based Control Strategies to Reduce Peak Demand, Utility Cost and CO2 Emission

This research develops a novel hybrid fuel heat pump system for space heating of residential and small commercial buildings with built-in optimization and control. Whereas conventional dual fuel systems either run on gas or electricity at any given moment, the proposed seamlessly fuel flexible heat pump (SFFHP) simultaneously consumes gas and electricity and continuously optimizes the proportion of each. The building air flows across the heat pump condenser first and then flows across the furnace coil, and this reduces the heat pump temperature lift. The SFFHP delivers energy savings by allowing each subsystem (gas furnace and electric heat pump) to operate where it performs best to improve energy efficiency, minimize energy cost, and minimize carbon footprint. The capacities of the electric heat pump and gas furnace are continuously adjusted based on ambient conditions, utility price signals, and marginal grid emission signals. An optimal model predictive control strategy was developed with the goal of minimizing utility cost and minimizing CO2 emission. Two case studies were conducted to simulate the performance of SFFHP during the heating season in Chicago and Los Angeles, respectively. Compared with a conventional electric heat pump, SFFHP yields 33% utility cost reduction and 49% CO2 emission reduction in Chicago. Similarly, it achieves 23% utility cost reduction and 17% CO2 emission reduction in Los Angeles. Case studies demonstrate that SFFHP can deliver significant reductions in peak demand, utility cost, and CO2 emission. Due to the hybrid fuel nature of this novel equipment, user comfort will always be maintained. The fuel flexibility makes it an attractive option for demand response programs.

Li, Zhenning↗

High CO2 Capture Rate Cost and Performance for F- and H-Class Natural Gas Combined Cycles (NGCC)

The National Energy Technology Laboratory (NETL) is updating its study titled “Cost and Performance Baselines for Fossil Energy Plants, Volume 1: Bituminous Coal and Natural Gas to Electricity.” Revision 4 was published in 2019. Pulverized coal (PC) and natural gas combined cycle (NGCC) cases with carbon capture in that study capture carbon dioxide (CO2) at 90% efficiency. Field-testing of post-combustion CO2 capture technology as well as vendor and industry feedback on projects currently in the planning stages (including FEED projects sponsored by DOE) indicate that capture rates as high as 95% are feasible for both coal- and natural gas-fueled electricity generating units. Technology suppliers (as reflected in vendor-supplied information provided to DOE for this study that included cost and performance estimates for both NGCC (97%) and PC (99%) study cases) as well as subject matter experts acknowledge and support that solvent-based post-combustion CO2 capture technologies are capable of achieving CO2 removal rates beyond 95% on low-purity streams representative of fossil-fueled combustion; however, the relatively limited experience with design and operation of capture systems that can routinely, reliably, and economically achieve very high removal rates (e.g., 97% for NGCC flue gas) requires further study. This presentation will address performance and cost estimates for 90%, 95%, and 97% capture for F- and H-class NGCC plants. This presentation was given at the 2022 Pittsburgh Coal Conference.

Fout, Timothy↗

Multi-Parameter Optical Fiber Sensing of Humidity, CH4, CO2, and Corrosion

In this work, the previously demonstrated capability of the optical fiber sensor (OFS) for successful monitoring of humidity has been extended to monitor the humidity, CH4, and CO2 with different gas composition based on the strain produced along the single mode fiber (SMF) sensor. This is enabled by absorption of H2O/gases on to the commercially available polyacrylate coated jacketed portion of the fiber resulting a change in strain. Under equilibrium, a differential microstrain was observed along the jacketed portion of the SMF with N2, CH4, and CO2 at different humidity conditions, while the unjacketed portion of the fiber was used only for sensing pressure/temperature induced strain. In case of N2 at 800 psig pressure, the observed microstrain was approximately 80, 65, 50 and 35 µε at 100, 75.0, 46.8, and 23.4 RH% respectively. Comparatively, a microstrain of approximately 95 µε was observed with 100% RH CH4 which demonstrates that SMF produces a measurable CH4 response alongside water. Similarly, the observed microstrain with CO2 was approximately 105, 90, 85, 80, and 70 µε at 100, 75.0, 46.8, 23.4, and 0 RH% respectively. Linear regression and principal component analysis of these dataset provided deconvolution of the impact of strain from H2O, CH4, and CO2 enabling good cross sensitivity. Additionally, modified OFS comprising of Fe coated fiber section was employed to monitor corrosion, using Fe as corrosion proxy, under harsh corrosive environment.

Mainali, Badri↗

Multi-Parameter Optical Fiber Sensing of Humidity, CH4, CO2, and Corrosion

In this work, the previously demonstrated capability of the optical fiber sensor (OFS) for successful monitoring of humidity has been extended to monitor the humidity, CH4, and CO2 with different gas composition based on the strain produced along the single mode fiber (SMF) sensor. This is enabled by absorption of H2O/gases on to the commercially available polyacrylate coated jacketed portion of the fiber resulting a change in strain. Under equilibrium, a differential microstrain was observed along the jacketed portion of the SMF with N2, CH4, and CO2 at different humidity conditions, while the unjacketed portion of the fiber was used only for sensing pressure/temperature induced strain. In case of N2 at 800 psig pressure, the observed microstrain was ~80, ~65, ~50 and ~35 µε at 100, 75.0, 46.8, and 23.4 RH% respectively. Comparatively, a microstrain of ~95 µε was observed with 100% RH CH4 which demonstrates that SMF produces a measurable CH4 response alongside water. Similarly, the observed microstrain with CO2 was ~105, ~90, ~85, ~ 80, and ~70 µε at 100, 75.0, 46.8, 23.4, and 0 RH% respectively. Linear regression and principal component analysis of these dataset provided deconvolution of the impact of strain from H2O, CH4, and CO2 enabling good cross sensitivity. Additionally, modified OFS comprising of Fe coated fiber section was employed to monitor corrosion based on the increase in backscattered intensity amplitude of the light being passed once corrosion occurs.

Mainali, Badri↗

Corrosion of Stainless and Carbon Steel in Aqueous Piperazine for CO2 Capture

Current obstacles that prevent commercial implementation of amine-scrubbing CO2 capture are the high costs. Reducing capital costs by appropriate selection of construction materials, which requires knowledge of material corrosion performance for the process, will improve the economic feasibility of this technology. Corrosion was evaluated in three pilot plant campaigns using aqueous piperazine with the Advanced Stripper (PZAS). 316L stainless steel (SS) experienced higher corrosion than 304 SS and 2205 duplex SS, and the corrosion rate showed strong dependence on the temperature. 304 and 2205 performed well at all locations and should be good construction materials for PZAS. Degraded PZ exacerbated 316L corrosion, and removal of PZ degradation products using a carbon adsorption bed significantly reduced corrosion. Carbon steel (CS) corrosion showed a weak temperature effect because the corrosion was more dependent on the protective siderite film. The protectiveness of the films was related to fluid velocity. Ni-based alloys corroded in PZ, and the rate increased with temperature. Corrosion of C1010 CS and SS (304, 316L, 430) was measured at absorber and water wash conditions on the bench-scale. Corrosion rate decreases with increasing PZ. 8 With more than 0.003 m PZ in solution, CS has acceptable corrosion performance. Corrosion of CS increases with increasing partial pressure of CO2, suggesting loading is another dominant parameter for carbon steel corrosion. Temperature has a less significant effect than PZ concentration and loading. CS corrosion increases with increasing flow velocity at both absorber and water wash conditions. SS had little corrosion at this lower temperature. Performance of siderite (FeCO3) protective films on CS was studied at representative stripper conditions on the bench-scale. Siderite films can deposit on the surface of CS in CO2-loaded PZ solution at temperatures >100 °C and protect CS from corrosion. The protection may fail in degraded PZ. Ethylenediamine (EDA) is one of the major contributors for the loss of film protectiveness or can be the surrogate for the effect of PZ degradation on siderite film protection. A link between protectiveness and the apparent density of siderite films was discovered. The apparent density of siderite films decreases with increasing flow velocity and decreasing CO2 loading, resulting in higher corrosion of CS.

Liu, Ching-Ting↗

CO2 Valorization via Rewiring Carbon Metabolic Network

Energizing the world sustainably requires revolutionizing the way we harness natural resources. New renewable technologies include the microbiological upgrading of CO2, the primary greenhouse gas that causes climate change. This project aims to develop a new bioeconomy by taking up CO2 and converting it into high-value products using an autotrophic microbe. Specifically, the team constructed an acetogenic bacterium, Clostridium ljungdahlii, and developed gas fermentation processes that convert syngas (CO2/H2/CO) to the platform compound 3-hydroxybutyrate (3HB). The project has achieved several key successes, including the design and construction of 3HB genes in the gas-fermenting bacterium, the identification of a native 3HB pathway, the conversion of syngas to 3HB through strain engineering, and the improvement of the conversion through rational and iterative strain development. The optimized strain has achieved industry-relevant production rates (0.1 g/L/h) and titers (9.2 g/L), and sustained continuous gas fermentation for 3HB production for > 50 days in a bench-top gas bioreactor. The project has both industrial and scientific implications, including the exploitation of host microbes and processes to improve industrial-scale production of value-added compounds from CO2, and the promotion of gas fermentation technology. The team is also strengthening R&D synergies with other teams and industrial partners in the CO2 consortium, developing cutting-edge approaches for rapid and rational engineering of gas-fermenting hosts, and dissecting the thermodynamics and kinetics of processes for biological syngas valorization. So far, one patent application and one research article have resulted from this work, and the team anticipates additional significant outcomes from this project.

3-hydroxybutyrate↗

Geochemical narrowing of cement fracture aperture during multiphase flow of supercritical CO2 and brine

For carbon capture and storage operations, wells are used as a necessary conduit for injecting CO2 at depth, but they can also act as leakage conduits if the cement seals are compromised. The specific objective of this research was to investigate the nature of self-healing of a fracture within cement under multiphase flow of CO2 and brine, and to compare this to a newly developed model. This was accomplished through a laboratory investigation, flowing reacting supercritical CO2 and brine through a cement fracture with multiphase flow. The influent end of the fracture was degraded as evidenced by the formation of cracks across the surface. At the effluent end of the fracture, the initial aperture of 137 µm was reduced to 50 µm. This reduction by 87 µm was similar to results from a recently developed model tested in this study, which predicted an aperture reduction of 80 µm. Our results demonstrated that the model accurately predicted the reactions which occurred in this multiphase flow system.

wellbore, cement, fracture, multiphase-flow, super↗

Alteration of Fractured Foamed Cement Exposed to CO2-Saturated Water: Implications for Well Integrity

Geologic CO2 storage (GCS) is a method to mitigate the adverse impact of global climate change. Potential leakage of CO2 from fractured cement at the wellbore poses a risk to the feasibility of GCS. Foamed cement is widely applied in deepwater wells where fragile geologic formations cannot support the weight of conventional cement. Thus, it is critical to know whether fractures in foamed cement self-seal in a similar manner as conventional cement systems. This study is the first to investigate the changes in physical and chemical attributes of foamed cement under dynamic flow conditions using CO2-saturated water. Self-sealing of fractures in the cement was observed at a solution flow rate of 0.1 mL/min and a pressure of 6.9 MPa. The formation of CaCO3 precipitates in pore spaces and fractures led to a decrease in permeability by 1 order of magnitude. The extents of self-sealing in foamed cement samples, specifically the 20 and 30% air volume formulations, were similar to that of conventional cements. We attribute this to the greater alteration depth in the foamed cement, which compensated for the reduced availability of Portlandite and higher initial porosity. The results can be used to evaluate the risk of leakage associated with foamed cement.

Geologcial Carbon Storage, Well Integrity in CO2 S↗

Ru-promoted perovskites as effective redox catalysts for CO2 splitting and methane partial oxidation in a cyclic redox scheme

The current study reports AxA’1-xByB’1-yO3- perovskite redox catalysts (RCs) for CO2-splitting and methane partial oxidation (POx) in a cyclic redox scheme. Strontium (Sr) and iron (Fe) were chosen as A and B site elements with A’ being lanthanum (La), samarium (Sm) or yttrium (Y), and B’ being manganese (Mn), or titanium (Ti) to tailor their equilibrium oxygen partial pressures (P_(O_2 ) s) for CO2-splitting and methane partial oxidation. DFT calculations were performed for predictive optimization of the oxide materials whereas experimental investigation confirmed the DFT predicted redox performance. The redox kinetics of the RCs improved significantly by 1 wt.% ruthenium (Ru) impregnation without affecting their redox thermodynamics. Ru impregnated LaFe0.375Mn0.625O3 (A=0, A’=La, B=Mn, and B’=0) was the most promising RC in terms of its superior redox performance (CH4/CO2 conversion >90% and CO selectivity~ 95%) at 800oC. Long-term redox testing over Ru impregnated LaFe0.375Mn0.625O3 indicated stable performance during the first 30 cycles following with a ~25% decrease in the activity during the last 70 cycles. Air treatment was effective to reactivate the redox catalyst. Detailed characterizations revealed the underlying mechanism for redox catalyst deactivation and reactivation. Furthermore, this study not only validated a DFT guided mixed oxide design strategy for CO2 utilization but also provides potentially effective approaches to enhance redox kinetics as well as long-term redox catalyst performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

CO2 upgrading into bioproducts using a two-step abiotic–biotic system

The valorization of CO2 to chemicals beyond C1-2 products is receiving significant interest; however, the direct electrosynthesis of Cn molecules (n > 4) remains a challenge. Here, we present a two-step abiotic-biotic system for upgrading CO2 into the biopolymer, poly(3-hydroxybutyrate). In the electrolysis system, CO2 is converted into C2 oxygenates using a Cu-Ag tandem electrocatalyst. The electrolysis process generates a liquid stream containing ~ 200 mM acetate in a bio-compatible electrolyte. This electrosynthesized acetate is then fed to a bioreactor, where the substrate is upgraded by Cupriavidus necator to biopolymer with a maximum rate of 32 ± 3.5 mg L-1 h-1. We further demonstrate the purification of the resulting biopolymer into a powder. The high productivity of the abiotic-biotic system demonstrates its feasibility for sustainable chemical manufacturing.

CO2 upgrading↗