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At least 253 records · Page 14

NH 3 -Mediated Reactive Capture and Conversion: Integrating CO 2 Absorption from Flue Gas with CO Production via NH 4 HCO 3 Electrolysis

Efficient carbon capture and utilization require strategies that minimize energy penalties of CO 2 regeneration and compression. Reactive capture and conversion (RCC) address this challenge by integrating capture with direct electrochemical conversion. Here, we show an NH3-mediated tandem RCC system that couples capture of CO 2 from simulated flue gas (10% v/v CO 2 in N 2 ) with electroreduction of NH 4 HCO 3 to CO over a Ni single-atom catalyst (Ni-SAC). Speciation modeling and capture experiments revealed that a deep CO 2 capture with C/N ratio of 0.65 was achieved using 2.5 M NH 3 from simulated flue gas. Electrolysis of the resulting NH 4 HCO 3 on the Ni- SAC delivered an 85% CO Faradaic efficiency at 100 mA/cm 2 with excellent tolerance to NH 3 /NH 4 + as confirmed by DFT calculations and ab initio molecular dynamics (AIMD) simulations. Further, the technoeconomic analysis established a levelized total cost of CO manufacturing of $25.43/kmol, gauging the practical viability. Overall, this study holds great potential to decarbonize the chemical manufacturing industry while reducing synthetic production costs.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electrochemical Conversion of CO 2 to Methyl Formate in a Flow Electrolyzer with Mixed Propylene Carbonate/Methanol Catholyte

Despite the promise of electrochemical carbon dioxide reduction as a technology for the production of clean fuels and decarbonization of the chemical industry, research has mostly focused on aqueous systems with a relatively limited set of products that have been achieved via electrosynthesis. Increasingly, CO 2 electroreduction in nonaqueous solvents is being pursued to develop new avenues for expanding the suite of products that can be made with high selectivity. CO 2 reduction in alcohols coupled with in situ esterification to produce esters is one such route that utilizes nonaqueous electrolyte. To be practical, such electrochemical syntheses need to be translated to a high-performance reactor such as a flow electrolyzer. However, many organic solvents, such as alcohols, wet and flood porous electrodes, thus impeding reactor performance. In this work, methanol was mixed with propylene carbonate as a catholyte for a gas-fed CO 2 flow electrolyzer that avoided cathode flooding. Simultaneously, a dual aqueous anolyte was used for water oxidation as a scalable and sustainable anodic half-reaction. The performance effect of methanol concentration, catholyte acidity, CO 2 flow rate, and dilute water in the catholyte were investigated. With 10 vol % methanol in 90 vol % propylene carbonate, 63% faradaic efficiency for methyl formate ester product was sustained without cathode flooding. However, improvements are still needed to lower the cell resistance and further increase the operating current density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rare earth metals production using alternative feedstock that eliminates HF

This work reports the successful production of rare earth (RE) metal using Na-RE-F. Presently, RE metals are primarily produced using RE-fluoride due to its higher air and moisture stability compared to RE-chloride. However, its preparation requires the use of corrosive and hazardous chemicals, such as hydrofluoric acid (HF) or ammonium bifluoride (NH 4 HF 2 ). The present study demonstrates that Na-RE-F is an alternative salt to the typically used RE-fluoride. The Na-RE-F for this work is produced via a scalable hydrometallurgical approach using three different RE salts as feedstock, including acetate, nitrate, and chloride. HF is neither used nor generated during the salt preparation process. Furthermore, the Na-RE-F powder dries in air (without dry HF), and only water evolves during the drying process. Analyses of the Na-RE-F show that NaF liberates as a flux during the heating process, which lowers the salt reduction temperature to <900 °C, thus minimizing or eliminating the need for additional flux. Calciothermic reduction of the Na-RE-F salt is successfully employed to obtain RE metal. This work represents a safer, greener, and more widely deployable approach for producing the RE metals needed for permanent magnets which support the transition to a cleaner society through the decarbonization of the transportation industry.

36 MATERIALS SCIENCE↗

From Fossil Fuels to Green Mines: Understanding Hydrogen-Shale Interactions for Secure Underground Storage

Hydrogen-powered mining trucks are rapidly gaining traction as a key driver of decarbonization in the mining industry. This surge necessitates a decisive shift towards renewable energy sources, primarily for hydrogen production. However, the inherent intermittency of renewables poses a challenge for continuous operations, demanding efficient storage solutions for hydrogen fuel. Hydrogen, derived from renewables, requires large-scale storage, with underground hydrogen storage (UHS) in depleted oil and gas reservoirs projected to provide this capacity. An impermeable seal (caprock) overlying depleted reservoirs is crucial for preventing leakage and ensuring secure storage. Shale, a potential caprock, has been recognized for its effectiveness in containing natural gas for geological time-periods. This study investigates the impact of hydrogen exposure on the matrix permeability of Marcellus shale, a key factor influencing its sealing capacity. A novel time-resolved approach was employed, measuring matrix permeability after each exposure to understand the dynamic interactions between hydrogen and the shale matrix. Samples were exposed to hydrogen in pressure reactions at realistic reservoir conditions at varying time durations. Preliminary results reveal an initial increase in permeability, while subsequent exposures show a decrease, indicating potential microstructural changes.

08 HYDROGEN↗

Evaluation of Thermal & Mechanical Properties of Additively Manufactured Monolithic SiC for Solar Receiver Applications

Increasing the operating temperatures of solar receivers is paramount to the efficiency of concentrated solar thermal (CST) and solar power (CSP) systems. Owing to its high temperature stability combined with excellent thermal and optical properties, SiC has been the material of choice for application in high-temperature solar receivers. State-of-the-art SiC volumetric concentrating solar air receivers such as the honeycomb design have successfully demonstrated in field exit air temperatures approaching 800oC. However, a successful application of CST systems for the decarbonization of heat reliant industrial sectors requires significant increases in the temperature capability of SiC receiver technology. Supported by an award from the Solar Technology Office (SETO), US Department of Energy (DOE), GE Research in collaboration with Heliogen Holdings Inc, is engaged in the development of an ultra-High Operating Temperature SiC-matrix Solar Thermal Air Receiver (HOTSSTAR) enabled by additive manufacturing. The program objective is to design and demonstrate a techno-economically viable SiC air receiver technology that can achieve exit air temperatures up to 1100oC for CST applications. We report and discuss the results of our testing and evaluation of thermal and mechanical properties of reaction-bonded SiC fabricated via binder jet printing to support the receiver component design, development, and analyses.

14 SOLAR ENERGY↗

Use of Lignin-Based Admixture as Water Reducer (WRA) for Tailoring the Rheological Properties of Mortars for 3D-Printing

Efforts towards decarbonizing construction materials and industrial processes related to cement and concrete can be aided via multifaceted approaches that target alternative admixtures as well as precision control of fabrication. Chemical admixtures for water reduction have played a crucial role in the development of advanced mortar and concrete mixtures. Newer biomass processing techniques developed for aviation fuel production from corn stover biomass produce a highly reactive lignin byproduct that is suitable for chemical modifications to mimic the properties of commonly used polycarboxylate ethers (PCEs) with a smaller carbon footprint. These lignin-based plasticizers developed at NREL can be used in place of petrochemical-derived superplasticizers to tailor the rheological properties of cement-based systems for applications such as additive manufacturing while reducing the carbon intensity of the concrete mix. Lignosulfonates derived from paper pulping were historically used as water reducers only to be displaced with the rise of PCEs. The present study examines the use of a NREL produced lignin-based water reducing admixture (WRA), in cement pastes and mortar mixtures for 3D-printing at small- (mm) scale. The experimental program consisted of different formulations of oxidized lignin-based WRAs added in variable dosages to cement pastes with a fixed water-to-cement ratio. The objective is to achieve an appropriate workability, extrudability and buildability of mortar mixtures to produce 3D-printed specimens. The rheological characterization was performed to compare the initial yield stress and viscosity of the different mixtures with lignin-based admixture with respect to conventional PCE superplasticizers. The rheological characterization shows that the proposed material act as an effective water-reducer in cement systems, affecting the yield stress, plastic viscosity, and structuration rate of the mixtures evaluated. On the other hand, the effect on early hydration process of the cement pastes containing lignin-based admixtures is comparable to conventional superplasticizers.

3D-printing↗

Detection and Quantitation of Hydrogen Emissions Role and Status of Detection Technology

Hydrogen is a critical strategy to decarbonize energy and manufacturing industries. Hydrogen is nontoxic and can be handled safely, but potential for secondary greenhouse impacts. Hydrogen releases arise from a variety of mechanisms (process, design features, "leaks") that contribute to total hydrogen releases. Detection methodologies will be critical to detect and quantify hydrogen emissions. Detection is to be integrated with advanced analytics (AI) and behavior modelling to effectively identify, quantify, and source locate hydrogen releases. Modelling of emissions will contribute to facility safety and reliability. DOE is committed to develop the tools to model and mitigate the impact of hydrogen releases which include: Support modeling to elucidate released hydrogen degradation; Support the development of tools for emissions quantitation; and Support engineering advancements to minimize hydrogen losses along the value chain (including process, design features, and leaks).

detection↗

Approach for High Methanol Substitution by Energy with Conventional and Bio Pilot Fuels

Green methanol is emerging as a promising route to decarbonize the commercial marine industry. However, methanol is not a drop-in fuel in the compression ignition engines that dominate the marine industry because it is difficult to ignite due to its low cetane number and high latent heat of vaporization. The most straight-forward way to use methanol in the compression ignition engines is to premix the methanol, such as with port fuel injection during the intake stroke, and igniting the methanol with a diesel pilot injection. Because diesel fuel is still used in this strategy, it does not fully displace the petroleum diesel fuel. To completely displace the petroleum-derived diesel fuel, this investigation presents experimental results comparing diesel and biodiesel pilot ignition in a dual-fuel strategy with methanol in a marine-variant of a Cat® C18 18 L engine with a 145 mm bore. Engine performance and emissions characteristics are presented that include effects of diesel vs. biodiesel across a series of fuel injection timing and other operating parameters, including intake manifold pressure and engine load. Results presented include in-cylinder pressure and combustion-related findings about heat release, methanol fuel energy substitution rates greater than 75% from 1 to 18 bar BMEP on a single cylinder engine at 1800 RPM. Criteria pollutants including particulate matter, NOx (NO and NO2), unburned fuel, and formaldehyde, as well as the overall BSFC and FSN of the combustion process relative to the baseline diesel operation.

Splitter, Derek [ORNL] (ORCID:0000000174044047)↗

Power Sector Decarbonization in South Asia: Pathways for Research, Modeling, and Implementation

Decarbonization of the power sector has far-reaching impact into the further decarbonization of the economy. In many comprehensive decarbonization pathways proposed for the world and for India electrification of transportation, buildings, and industry is the principal solution to decarbonizing those sectors. Therefore, electricity grids are likely to grow as more and new loads are added to them, and this growth will necessarily be from non-carbon emitting resources. This report outlines several key challenges for the power sector in planning, research, and development towards a decarbonized electric power grid. While these challenges will continue to evolve, this report focuses on formulating the important questions for the next two decades to align planning timeframes of India's and South Asia's power sector stakeholders, and to offer near-term research solutions for preparing the datasets, building the models, and designing the studies to answer questions and prepare for these changes.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Industrial Requirements Status Report and Down-Select of Candidate Technologies

The report discusses the potential for implementing Integrated Energy Systems (IES) using advanced nuclear reactors to provide thermal and electrical energy to carbon-emitting industries while reducing their carbon footprint. Nine different industries were reviewed to determine their decarbonization potential, how nuclear power can fit in, and the carbon footprint of each. The report also identifies specific integration points and streams for most processes, including temperature and pressure requirements of integrating nuclear power with industrial processes. The report also provides insights on advanced nuclear reactors and their potential for us in IES for decarbonization. The target audience for the report is broad, but mainly addressed to the industry leads and nuclear reactor developers. The report recommends that in the short term, a few processes should be identified to continue research and investigation so that front end engineering design work can provide technical analysis for integrating nuclear heat and replacing existing carbon-emitting thermal sources. The work emphasized the significant decarbonization opportunity across each of the technologies looked at as well as how novel and useful nuclear integration is to reduce the environmental impact of these significant industries.

02 PETROLEUM↗

The Demand for a Domestic Offshore Wind Energy Supply Chain

In March of 2021, the Biden-Harris Administration established a National Offshore Wind Target to install 30 GW by 2030. This ambitious goal was not only intended to help reduce dependencies on fossil fuels, but also represents an opportunity to establish a new and sustainable industry in the United States. The announcement referenced the potential benefits of establishing a domestic supply chain, including the opportunity for existing suppliers to produce thousands of components while creating tens of thousands of jobs over the course of the decade. This vision by the Biden-Harris Administration aligns with the perspective of the offshore wind industry. At a Leadership 100 event hosted by the Business Network for Offshore wind in 2019, offshore wind developers and manufacturers identified the need for a roadmap outlining a pathway to a domestic supply chain as the top priority facing the industry. Building up domestic manufacturing capabilities will not only energize local industries but can potentially de-risk individual project by reducing reliance on importing resources from European or Asian markets. Although establishing a domestic supply chain will require significant investment, it has the potential to create substantial benefits throughout the industry and, by extension, on the decarbonization goals of the United States. This study characterizes the challenges and opportunities facing the growth of a domestic supply chain industry and evaluates the potential benefits that could be achieved through the creation of the supply chain. This report is the first of a two-part series which will describe the full supply chain roadmap and the associated benefits; the current report focuses on the high-level deployment, workforce, and component requirements that need to be met to achieve the National Offshore Wind Target. We will present: 1. A deployment pipeline that demonstrates the pathway to 30 GW, the associated demand for major fixed-bottom and floating offshore wind components (turbines, foundations, cables, substations), and the vessel and port requirements to support these installation activities. 2. A series of sensitivity analyses showing how the demand for components, ports, and vessels changes for different technology pathways and availability of the global supply chain. 3. An estimate of the total number of jobs that would be required to support these deployment scenarios under varying levels of assumed domestic content. 4. A comprehensive list of the Tier 1, 2, and 3 components (finished components, subassemblies, and subcomponents) required to construct fixed-bottom and floating offshore wind projects. 5. A discussion of critical path components that represent a significant challenge, bottleneck, or risk for a future domestic supply chain.

17 WIND ENERGY↗

Lawrence Livermore National Laboratory (LLNL) Hybrid-Energy Technology for Power and Industrial Heat with Near-Zero or Negative CO 2 Emissions

Major contributors to global CO 2 emissions include electricity (27%) and industry (23%), such as cement manufacturing (8%). Using post-combustion technology to reduce CO 2 emissions by 85-90% could increase the cost of generating electricity with fossil fuel by 40-70%, while increasing cement-manufacturing cost by 75-140%. Both sectors are under pressure to reduce CO 2 emissions and are seeking cost-effective, energy-efficient solutions to decarbonizing energy.

54 ENVIRONMENTAL SCIENCES↗

High-Fidelity Arc-Discharge Model for Hydrogen-Plasma-Smelting-Reduction of Iron Ore

Electrification and use of renewable hydrogen is currently a necessity for decarbonizing the iron-and-steel industry. In this regard, hydrogen plasma smelting reduction (HPSR) is a novel pathway that is being explored for reduction of iron ore. HPSR provides several decarbonization merits compared to conventional blast furnaces. Firstly, the use of renewable hydrogen drastically reduces the CO2 emissions compared to the use of coke. Secondly, renewable electricity in the form of a thermal plasma for making reactive hydrogen species (radicals, ions) are more efficient at reducing iron ore compared to neutral H2. Thirdly, a molten product compatible with downstream processes is obtained from the intense heat transfer from the plasma. However, the scale-up of this technology requires fundamental exploration of hydrogen plasma dynamics and its interaction with complex solid material that include phase changing iron-ore and slag. In this work, we present a first principles continuum scale model for thermal plasmas in Ar/H2 gas mixtures typically used for HPSR. The thermal plasma governing equations for mass, momentum and energy with Lorentz force and Joule heating source terms are solved along with electromagnetic equations for electrostatic and magnetic vector potential. Our solver will be based on Pele, a suite of reacting flow solvers designed for advanced scientific computing architectures (Henry De Frahan et al., Proceedings of SIAM Parallel Processing, 13-25, 2024), and will utilize adaptive mesh generation for enhanced resolutions at locations of intense physicochemical interactions. This study will present the impact of Ar to H2 ratios on excited/dissociated hydrogen species concentrations, plasma temperature and conductivity along with the impact of outgassed species (water, metal vapor, O, OH radicals) from ore surface on gas phase chemistry. Furthermore, the heat and species flux to the surface will be quantified as a function of applied voltages in a transferred arc configuration.

hydrogen plasma↗

Scaling Decarbonization Development Innovation with Emerging Community-Based Developers: Preprint

The building real estate development industry is being asked to lead in delivering building decarbonization solutions across the United States. However, creating decarbonized best practices and development innovation while increasing developer diversity and community ownership is often not a primary focus of this sector. To address these issues, we have created an incubator and support ecosystem specifically for the innovation scaling we have found in a leading group of emerging, small-scale developers. These leaders are not just working at the forefront of decarbonized development but addressing diversity and bolstering community generational wealth. We have found that small development firms are the ones who often take risks to innovate and demonstrate despite lacking a specific set of resources or support ecosystems focused on emerging decarbonization developers. Those with the fewest resources are being asked to lead our decarbonization innovation efforts. This paper documents the necessity of a cohort and incubator program to provide a decarbonization-specific ecosystem to support small developers and scale innovation. The incubator creates connections, fosters innovative strategies to access incentives and alternative funding, and assembles resources for small and emerging minority developers with the goal of sustainability and affordability. For instance, collaborative efforts with leading developers and utilities can enable the seamless integration of distributed energy resources through optimal metering and interconnection and significantly reduce the utility cost of electrification, benefiting the utility, the developer, and the tenant economically. The process described in this paper will result in case studies and how-to resources to provide tangible examples of innovation within the emerging development field.

carbon↗

Updated Manufactured Cost Analysis for Proton Exchange Membrane Water Electrolyzers

Enabling rapid and extensive decarbonization within the electric power and industrial sectors is likely to require high levels of renewable energy deployment, supported by technologies that store and transform renewable electricity into other useful forms. Within hard to decarbonize sectors such as organic chemicals and heavy-duty transportation, the use of low-carbon intensity hydrogen as a fuel and chemical building block is emerging as a near-term alternative to reduce their fossil-fuel dependency. Water splitting electrolysis to produce hydrogen requires only water and electricity as inputs, eliminating the use of natural gas in steam methane reforming, which is the conventional hydrogen production pathway. When powered by low-carbon electricity, electrolysis represents an important pathway towards cross-sectoral decarbonization.

08 HYDROGEN↗

Dehydroxylation kinetics of kaolinite and montmorillonite examined using isoconversional methods

The use of calcined clays as supplementary cementitious materials (SCMs) in concrete is a promising strategy towards decarbonizing the cement and concrete industry. This is especially relevant considering the ever-increasing demand for concrete. Comprehensive understanding of the kinetics of calcination is essential towards maximizing the potential reactivity of clay minerals while ensuring energy efficiency. In this study, the kinetics of the dehydroxylation of kaolinite and montmorillonite are investigated under non-isothermal conditions at constant heating rate. Activation energies ( E a ) are determined via Friedman differential and advanced Vyazovkin incremental methods over the isoconversional range; these are devoid of computational approximations, thus allowing kinetic analysis without assuming a specific reaction model. Kinetic equations—in the differential form as well as a combination of differential and integral forms are compared against the experimentally determined reaction models to identify the most probable dehydroxylation mechanism for kaolinite and montmorillonite. A reaction order mechanism is established for dehydroxylation of kaolinite, while montmorillonite is noted to undergo dehydroxylation via a single-step reversible diffusion-controlled process. Kinetic triplet—comprising activation energy, reaction model and pre-exponential factor—is used to predict isothermal calcination conditions, which is further verified using analytical techniques. Heat release rates of clay-portlandite blends from isothermal calorimetry are used within a thermodynamic framework to quantify reactivity of the calcined clays. Here, the study demonstrates a general approach based on isoconversional methods to predict calcination conditions for different clays that can be used in efficient and optimized production of blended cements or SCMs.

36 MATERIALS SCIENCE↗

Low Temperature CO 2 Hydrogenation on Unsupported Mo 2 C Catalysts

CO 2 hydrogenation to methanol, a key reaction for decarbonizing the fuel and chemical industries, requires catalyst formulations that hydrogenate CO 2 selectively to methanol at temperatures where methanol conversion is not significantly equilibrium limited (<423 K). Herein we report continuous CO 2 hydrogenation at low temperatures (348-408 K, H 2 /CO 2 = 0.1-50, 5-35 bar) with high selectivity to methanol (up to ca. 80%) over unsupported β-Mo 2 C catalysts. Active site density quantification via titration with trifluoroacetic acid at reaction temperatures enables an assessment of site-specific rates. Methanation and reverse water gas shift (RWGS) occur concurrently with methanol synthesis during CO 2 hydrogenation over Mo 2 C. Reaction pathway analysis, product cofeeds, and reversibility formalisms show that all products form through primary reaction pathways from CO 2 , but secondary reactions of CO contribute significantly to rates of methanation. Dependences of forward rates on reactant and product concentration determined by independently varying the CO 2 , H 2 , CO, H 2 O, CH 3 OH, and CH 4 pressure in conjunction with reversibility formalisms reveal that all products form through H-assisted CO 2 activation and involve partially hydrogenated CO 2 -derived intermediates. Here, these inferences were verified by quantitative agreement between measured site-time yields and site-time yields predicted by closed form kinetic rate expressions in an integral reactor model over widely varying conditions (85-2000 kPa H 2 , 80-1500 kPa CO 2 , 0-45 kPa H 2 O, 0-21 kPa CO, 0-25 kPa CH 3 OH, 0-75 kPa CH 4 , 5-87 mol Mo s s mol CO 2 -1 ). Coverages calculated based on the kinetic model reveal that the Mo 2 C surface is covered with bidentate CO- and CO 2 -derived intermediates of the stoichiometry H 2 CO 2 and H 2 CO, indicating that H 2 and CO x do not compete for surface occupancy but instead adsorb cooperatively to form partially hydrogenated intermediates. Hydrogenation of the CO-derived H 2 CO** intermediate favors methanation, while hydrogenation of CO 2 -derived H 2 CO 2 ** favors methanol synthesis. Together, these findings demonstrate the ability of unsupported Mo 2 C to catalyze the hydrogenation of CO 2 to methanol at low temperatures and provide insight into the reaction network and mechanisms involved in its formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗