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Continuum source molecular beam to provide highly directed gas flows for determining capture coefficient of gaseous carbon dioxide and water vapor
ABSTRACT Carbon dioxide removal technologies such as bioenergy with carbon capture and storage (BECCS) are required if the effects of climate change are to be reversed over the next century. However, BECCS demands extensive land use change that may create positive or negative radiative forcing impacts upstream of the BECCS facility through changes to in situ greenhouse gas fluxes and land surface albedo. When quantifying these upstream climate impacts, even at a single site, different methods can give different estimates. Here we show how three common methods for estimating the net ecosystem carbon balance of bioenergy crops established on former grassland or former cropland can differ in their central estimates and uncertainty. We place these net ecosystem carbon balance forcings in the context of associated radiative forcings from changes to soil N 2 O and CH 4 fluxes, land surface albedo, embedded fossil fuel use, and geologically stored carbon. Results from long term eddy covariance measurements, a soil and plant carbon inventory, and the MEMS 2 process‐based ecosystem model all agree that establishing perennials such as switchgrass or mixed prairie on former cropland resulted in net negative radiative forcing (i.e., global cooling) of −26.5 to −39.6 fW m −2 over 100 years. Establishing these perennials on former grassland sites had similar climate mitigation impacts of −19.3 to −42.5 fW m −2 . However, the largest climate mitigation came from establishing corn for BECCS on former cropland or grassland, with radiative forcings from −38.4 to −50.5 fW m −2 , due to its higher plant productivity and therefore more geologically stored carbon. Our results highlight the strengths and limitations of each method for quantifying the field scale climate impacts of BECCS and show that utilizing multiple methods can increase confidence in the final radiative forcing estimates.
Atmospheric carbon poses an existential threat to civilization via global climate change. Hundreds of gigatonnes of carbon dioxide must be removed from earth’s atmosphere in the next three decades, necessitating a low-cost, energy-efficient process to extract low concentrations of carbon dioxide for conversion to a stable material permanently stored for thousands of years. In this work, the challenge of removing gigatonnes of CO 2 is described via the scale of effort and the thermodynamics of collecting and reducing this diffuse chemical, the accumulation of which imparts a substantial entropy penalty on any atmospheric carbon capture process. The methods of CO 2 reduction combined with upstream direct air capture (DAC) including absorption, membrane separation, and adsorption are compared with biomass torrefaction and permanent burial (BTB). A Monte Carlo model assesses the mass, energy, and economics of the full process of biomass torrefaction from biomass collection and transport to stable carbon burial to determine that 95% of scenarios could remove carbon for less than $200 per CO 2 -tonne-equivalent. Torrefied carbon is further discussed for its long-term stability and availability at the scale required to substantially mitigate the threat of climate change.
Abstract Although pyrazine‐linked hybrid ultramicroporous materials (HUMs, pore size <7 Å) are benchmark physisorbents for trace carbon dioxide (CO 2 ) capture under dry conditions, their affinity for water (H 2 O) mitigates their carbon capture performance in humid conditions. Herein, we report on the co‐adsorption of H 2 O and CO 2 by TIFSIX‐3‐Ni—a high CO 2 affinity HUM—and find that slow H 2 O sorption kinetics can enable CO 2 uptake and release using shortened adsorption cycles with retention of ca. 90 % of dry CO 2 uptake. Insight into co‐adsorption is provided by in situ infrared spectroscopy and ab initio calculations. The binding sites and sorption mechanisms reveal that both CO 2 and H 2 O molecules occupy the same ultramicropore through favorable interactions between CO 2 and H 2 O at low water loading. An energetically favored water network displaces CO 2 molecules at higher loading. Our results offer bottom‐up design principles and insight into co‐adsorption of CO 2 and H 2 O that is likely to be relevant across the full spectrum of carbon capture sorbents to better understand and address the challenge posed by humidity to gas capture.
Abstract Although pyrazine‐linked hybrid ultramicroporous materials (HUMs, pore size <7 Å) are benchmark physisorbents for trace carbon dioxide (CO 2 ) capture under dry conditions, their affinity for water (H 2 O) mitigates their carbon capture performance in humid conditions. Herein, we report on the co‐adsorption of H 2 O and CO 2 by TIFSIX‐3‐Ni—a high CO 2 affinity HUM—and find that slow H 2 O sorption kinetics can enable CO 2 uptake and release using shortened adsorption cycles with retention of ca. 90 % of dry CO 2 uptake. Insight into co‐adsorption is provided by in situ infrared spectroscopy and ab initio calculations. The binding sites and sorption mechanisms reveal that both CO 2 and H 2 O molecules occupy the same ultramicropore through favorable interactions between CO 2 and H 2 O at low water loading. An energetically favored water network displaces CO 2 molecules at higher loading. Our results offer bottom‐up design principles and insight into co‐adsorption of CO 2 and H 2 O that is likely to be relevant across the full spectrum of carbon capture sorbents to better understand and address the challenge posed by humidity to gas capture.
Gas absorption towers with structured packing and solvent have been used for Carbon Dioxide (CO 2 ) Capture for about many decades. To overcome process limitations and practical disadvantages for CO 2 capture from the stationary emitter (e.g. NG and coal power plant), many new designs have been proposed and explored at the various scales in the last decade with aim of either low energy penalty or low capital cost. To reduce the size of the absorption tower and hence the total cost of CO 2 capture, the University of Kentucky Center for Applied Energy Research Center (UK CAER) has designed and built a novel CO 2 capture absorption tower or Compact Absorber, integrated into an existing large-bench scale CO 2 capture unit. The Compact Absorber has three sections. The top of the column is a fogging section where the solvent is sprayed through a nozzle producing droplets flowing downward in a co-current fashion with the flue gas. The center of the column is a frothing section where the solvent and flue gas flow through regenerative frothing screens designed by Industrial Climate Solutions, Inc. The bottom of the column is a typical structured packing section were the flue gas and solvent flow in a counter-current fashion. The parametric campaign will be conducted in order to optimize the operating parameters for CO 2 capture including liquid/gas ratio, lean loading, and temperature, liquid residence time. A simulated flue gas with 14% CO 2 will be used along with a UK CAER developed proprietary solvent. The 100-hour parametric campaign is designed using a statistical approach of the Sequential Design of Experiments (sDOE). sDOE is one of the CCSI tools that provides an adaptive statistical approach for designing future experiments based on the results of previous experiments. Application of a typical DOE provides the user with the minimum number of experiments required to get the same data, but sDOE allows the user to make an informed choice of experiments based on the results of previous experiments. The complete absorption column has been constructed and has been partially commissioned. Initial data has been collected by operating using the fogging section and the frothing section. The fogging section produces solvent droplets of about 100 μm sauter mean diameter and as small as 25 μm using a hydraulic nozzle by BETE. The frothing section produces bubbles of about 5mm with high mixing of solvent promoting the higher mass transfer from gas to liquid. The absorber reaches the capture efficiency of about 50% with only two sections in operation. Based on the current results, it can be deduced that increasing the solvent feed temperature and including the packed section for absorption the capture efficiency will increase further. Initial data will be collected using all three sections of the absorber and will be used for sDOE. Non-Uniform Space Filling model of sDOE will be used to prioritize the input conditions resulting into maximum capture efficiency. sDOE is performed using the platform called Framework Optimization, Quantification of Uncertainty, and Surrogates (FOQUS). The method and results demonstrating the progress of the parametric campaign from the initial set of experiments to the final stage of obtaining optimized parameters using sDOE tool will be presented in detail.
This report provides a summary of feedback from the “Reactive CO 2 Capture: Process Integration for the New Carbon Economy” workshop held February 18-19, 2020. The focus of this workshop was to discuss approaches for merging carbon dioxide (CO 2 ) capture and CO 2 conversion/utilization systems into an integrated "reactive capture" strategy. By the workshop’s definition, reactive capture (RC) of CO 2 is the coupled process of capturing CO 2 from a mixed gas stream and converting it into a valuable product without going through a purified CO 2 intermediate. Participants were able to identify four key themes and associated calls to action for the reactive capture community: (1) essential role of partnerships; (2) critical challenges; (3) defining the value proposition; and (4) approach to support technological advancement.
This work supports the mission of the U.S. Department of Energy to promote American energy leadership, technological innovation, and economic growth through the development of technologies for cost effective carbon capture. While capture technologies can provide carbon dioxide for enhanced oil recovery, many capture materials suffer from oxidative, hydrolytic and/or thermal degradation which leads to capacity loss and unwanted emissions such as ammonia. Short lifetimes increase operational costs and cost studies suffer from uncertainty because the true lifetimes of many capture materials are unknown. In this study, a suite of capture materials were studied to quantify their degradation, provide insight into the mechanisms that lead to their uptake loss and provide validated accelerated aging protocols for industry.
Electrochemical conversion of CO 2 to useful products at temperatures below 100 °C are nearing the commercial scale. Pilot units for CO 2 conversion to CO are already in testing. Units to convert CO 2 to formic acid are projected to reach pilot scale in the next year. Further, several investigators are starting to observe industrially relevant rates of the electrochemical conversion of CO 2 conversion to ethanol and ethylene with the needed hydrogen coming from water. In each case, Faradaic efficiencies of 80% or more and currents above 200 mA/cm –2 can be reproducibly achieved. In this study we describe the key advances in nano catalysts that lead to the impressive performance, indicate where additional work is needed and provide benchmarks that others can use to compare their results.
The overall objective of this research project was to develop a non-invasive acoustic-emission (AE)-based technology that can accurately predict the location and movement of CO 2 through a confining layer in a carbon capture, utilization, and storage (CCUS) system. Specifically, the aim was to explore the feasibility of using the Haines jumps AEs as a passive method to track movement of CO 2 in reservoirs used for CCUS applications.
Separations involving gaseous small molecules, including acid gases, nitrous oxide, and hydrofluorocarbons, are vital to U.S. energy and technological dominance. However, many current separations technologies are too energy-intensive for broad deployment. Sorptive separations, in which a mixture of gases is contacted with a porous solid material, leading to separation based on the differing affinity of the gases for the solid, promise lower energy requirements compared to many existing technologies.
The contact angle is a critical factor for determining the effective mass transfer area for carbon dioxide (CO 2 ) capture via the chemical absorption process in a packed column, and thus the overall capture efficiency of the packed column. Many widely used commercial packings involve microscale features (perforation, corrugation, etc.) that may also affect the wetting behavior. This study proposes a systematic method of using a modified Wilhelmy plate to measure the effective contact angle to characterize the solvent and featured packing interaction. In lieu of computational efforts relying on assumptions guided by semi-informed correlation, the proposed method directly measures the effective contact angle as a function of the solvent and packing thermophysical and hydrodynamic properties. The characterization of the effective contact angle is then integrated in the computational fluid dynamics modeling to reduce uncertainty in the prediction of effective mas transfer area. Experiments were conducted for stainless steel coupons using water and aqueous sodium hydroxide (NaOH) solvent for verification of the proposed experimental protocol. The surface tension of the aqueous NaOH solvent was altered using surfactant and antifoam. The effective contact angle increases with the increased value of the surface tension for flat stainless steel sheets. On the other hand, effective contact angles do not vary in Mellapak coupons for aqueous monoethanolamine (MEA) and NaOH solvent. In this case, surface textures and sheet design play a dominant role in the surface tension of solvents. Furthermore, CO 2 loading has a significant effect on the contact angle for Mellapak coupons. As expected, the contact angle decreases with the increasing temperature of CO 2 capture solvents (MEA, EEMPA). The effective contact angle measurement using the Wilhelmy plate method can provide more accurate and efficient solvents for characterizing the solvent-packing surface interactions. Subsequently, the present method enhances the accuracy of the prediction of the effective mass transfer area in carbon capture by solvent absorption.
Electrochemical pH-swing strategies offer a promising avenue for cost-effective and energy-efficient carbon dioxide (CO 2 ) capture, surpassing the traditional thermally activated processes and humidity-sensitive techniques. The concept of elevating seawater’s alkalinity for scalable CO 2 capture without introducing additional chemical as reactant is particularly intriguing due to its minimal environmental impact. However, current commercial plants like chlor-alkali process or water electrolysis demand high thermodynamic voltages of 2.2 V and 1.23 V, respectively, for the production of sodium hydroxide (NaOH) from seawater. These high voltages are attributed to the asymmetric electrochemical reactions, where two completely different reactions take place at the anode and cathode. Here, we developed a symmetric electrochemical system for seawater alkalization based on a highly reversible and identical reaction taking place at the anode and cathode. We utilize hydrogen evolution reaction at the cathode, where the generated hydrogen is looped to the anode for hydrogen oxidation reaction. Theoretical calculations indicate an impressively low energy requirement ranging from 0.07 to 0.53 kWh/kg NaOH for established pH differences of 1.7 to 13.4. Experimentally, we achieved the alkalization with an energy consumption of 0.63 kWh/kg NaOH, which is only 38% of the theoretical energy requirements of the chlor-alkali process (1.64 kWh/kg NaOH). Further tests demonstrated the system’s potential of enduring high current densities (~20 mA/cm 2 ) and operating stability over an extended period (>110 h), showing its potential for future applications. Notably, the CO 2 adsorption tests performed with alkalized seawater exhibited remarkably improved CO 2 capture dictated by the production of hydroxide compared to the pristine seawater.
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.
The motivation for this report is the recent focus of the U.S. Department of Energy’s (DOE) gasification program to develop modular scale gasification processes for electricity generation and other applications. Mass-produced, modular gasification systems have been proposed to decrease the upfront capital costs and to encourage flexible deployment of advanced gasification technology using a diverse set of feedstocks. To fully realize the benefits of advanced gasification technology for power generation as well as other chemical applications, precombustion carbon dioxide (CO 2 ) capture must be considered. Therefore, the aim of this report is to assess the potential of integrating modular scale carbon capture processes with modular scale coal gasification technologies, and to help guide future research and development efforts in this area.
This document details the execution of Cooperative Agreement DE-FE0031847, “Front End Engineering Design of Linde-BASF Advanced Post-Combustion Carbon Dioxide (CO 2 ) Capture Technology at a Southern Company Natural Gas-Fired Power Plant” during the period of 10/1/2019 to 6/30/2022. The project was funded by the U.S. Department of Energy’s Office of Fossil Energy and Carbon Management (FECM) and managed by the National Energy Technology Laboratory (NETL). Southern Company Services, Inc. (SCS) was the prime recipient and led the project team. Other members of the project team included Linde, Inc. (Linde), Linde Engineering – Dresden (LED), and BASF. The overall goal of the project was to complete a front-end engineering design (FEED) study for installing the Linde-BASF post-combustion capture (PCC) technology at an existing domestic natural gas-fired combined cycle (NGCC) power plant within Southern Company’s portfolio of assets. The CO 2 capture plant was to be of commercial scale (at least 375 MWe) and include process units for pre-conditioning of the flue gas system, the CO 2 capture plant island, storage vessels, the CO 2 compression train, and any necessary components for integration into the NGCC plant. Mississippi Power’s Plant Daniel Unit #4 was chosen as the host site for the FEED with the target of capturing 90% of CO 2 emissions from the existing combustion turbines. The information produced by the FEED was used to develop a cost estimate of +/- 15% accuracy. Capital costs, excluding financing, are estimated at approximately $\$752$ million dollars (2021). The execution of a project based on this FEED study has an estimated duration of almost five years.
Carbon dioxide is a potentially valuable feedstock for carbon-based fuels or commodities but is only available in dilute streams. Many studies have focused on either the capture and concentration of CO 2 or the reduction of pure CO 2 streams. The direct reduction of sorbent-captured CO 2 in an integrated process would skip the energy-intensive CO 2 concentration and sorbent regeneration step. Herein, we report the electrocatalytic reduction of 1,3-bis(2,6-diisopropylphenyl)imidazolium-2-carboxylate (IPr·CO 2 ), which forms quantitatively from the reaction of sorbent 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) with 10% and 0.04% CO 2 streams, by catalyst [Pt(dmpe) 2 ](PF 6 ) 2 (dmpe = 1,2-bis(dimethylphosphino)ethane) to formate with >70% Faradaic efficiencies. Unexpectedly, experimental studies indicate that the proton source phenol facilitates rapid decarboxylation of IPr·CO 2 to release CO 2 , which is the substrate for reduction. Kinetic studies determined the rate of hydride transfer from a catalytic intermediate [HPt(dmpe) 2 ](PF 6 ) to form the C–H bond in formate to be 0.22 M –1 s –1 . Further details on the mechanism, transition state energy, and structure for hydride transfer to CO 2 , a common step in CO 2 reduction, were explored using computational methods.