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Measuring thermal diffusivity and gap conductance in uranium nitride and Zircaloy relevant for microreactor applications

Heat transfer across nuclear fuels and structural interfaces is an important factor for evaluating the performance of nuclear power systems. Specifically, heat generated as nuclear fuel fissions must be transported through the cladding material and through the reactor to reach the steam turbine for power generation. As new microreactor designs emerge, maximizing the efficiency of this heat transfer process becomes crucial to make them commercially viable. This article examines thermal diffusivity and gap conductance in uranium nitride (UN) fuel and Zircaloy-4 (Zry4) cladding using light flash analysis (LFA). Thermal diffusivity measurements were made on monolithic UN pellets and Zry4 exposed to carbon at peak operating temperatures of microreactors and show that carbon ingress has a minimal effect on thermal diffusivity when compared with identical materials not exposed to carbon. Evaluation of gap conductance at the UN-Zry4 interface was done using one-dimensional two-layer thermal transport models as a function of applied pressure. Here the results show that increasing pressure on the UN-Zry4 interface leads to gains in gap conductance per unit area in fuel-cladding assemblies at microreactor operating temperatures. While many other variables are expected to influence UN-Zry4 interfacial gap conductance (e.g. contact surface roughness, porosity, localized heating, environmental gas pressure), the work offers a demonstration of using a conventional LFA apparatus to determine this parameter at elevated temperatures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

NPP Simulators for Coupled Thermal and Electric Power Dispatch

The Light Water Reactor Sustainability (LWRS) program within the United States Department of Energy supports extending the operation of the U.S. commercial nuclear power plant (NPP) fleet. Within the LWRS program, the Flexible Plant Operation and Generation (FPOG) Pathway works to diversify the revenue streams of light water reactors (LWRs) by opening opportunities for the co-generation of non-electric products in addition to supplying electrical power to the grid. Recent events have added greater motivation to these efforts. For example, the recent Inflation Reduction Act (IRA) passed by the U.S. federal government offers substantial tax incentives for producing clean hydrogen, the technology readiness level of dispatchable and high-efficiency hydrogen production has dramatically increased in a short time, and societal response to world climate change is driving a transition away from fossil fuels. Producing hydrogen with maximum efficiency using nuclear power requires dispatching both electrical and thermal power from the nuclear plant to the hydrogen plant, so testing concepts of operations for combined electrical and thermal power dispatch (TPD) from an NNP to a hydrogen plant is of interest. This report documents achievement of the Light Water Reactor Sustainability (LWRS) program milestone “Install and demonstrate a vendor-developed simulator on the Human Systems Simulation Laboratory (HSS) for dispatch of LWR electrical power to a close-coupled electrolysis plant” with a due date of Dec. 22, 2022. Several factors provide motivation for this effort. Coupling the power generation deck of a nuclear power plant to a hydrogen production facility introduces new possibilities for operational transients that must be addressed. In particular, the performance of the integrated system during startup and shutdown of the hydrogen production facility, as well as offnormal conditions, need to be evaluated to ensure there are no adverse effects on the operation of the existing NPP. The concept of operations involving the NPP, the hydrogen plant, and the electric power grid must be tested using NPP simulators and operating procedures that have been modified for TPD operations. These tests must also include dynamic simulations of the coupled tertiary thermal and electric loads as well as coordinated activities with NPP operators, tertiary load operators and grid power coordinators. The report summarizes progress in developing and testing full-scope NPP simulators at the HSSL, including a generic BWR simulator from GSE Systems, Inc. and generic PWR simulator from Westinghouse. In the case of the TPD-GBWR Simulator from GSE Systems, Inc., a BWR is thermally coupled to a high temperature electrolysis (HTE) plant that produces hydrogen and oxygen from de-ionized water. The hydrogen plant is not explicitly simulated but only included as a transient heat sink. A thermal power dispatch (TPD) system transfers heat between the steam systems at the BWR and the hydrogen plant. Operational results from two versions of the modified simulator are presented. The first version uses synthetic oil as a heat transfer fluid in a closed delivery heat loop (DHL) that generates steam at the hydrogen plant. The second version uses steam as the heat transfer fluid in a delivery steam line (DSL) to provide steam to the hydrogen plant. For both versions, the estimated thermal power delivery distance is approximately one kilometer. The amount of thermal power dispatched in the simulators is 15% of the total reactor thermal power such that the simulators provide a tool to study the feasibility of coupling a BWR to industrial processes that benefit from a combination electrical and thermal power dispatch. Ongoing work within a CRADA is also developing a full-scope PWR simulator provided by Westinghouse for both thermal and electric power coupling. This simulator is based on a PWR plant with two three-loop Westinghouse reactors. Westinghouse PWRs are sufficiently similar that a simulator of a three-loop reactor is an appropriate representation for two-loop and four-loop PWR reactors. The three-loop simulator will initially be modified for close-coupling to a 100 MW HTE hydrogen production plant that will require approximately 25 MW of thermal power while operating at its maximum rated capacity. The simulator testing will include full coupling to dynamic simulations of a hydrogen production plant and a representative bulk electric grid. The simulator provided by Westinghouse is similar to the GPWR simulator that INL has already obtained from GSE Systems but has a few important added benefits. First, the Westinghouse simulator is based on digital controls and has additional screens that can be called up to show parameter trends to assist operators in decision-making. The Westinghouse simulator also has upgrades to the controls and hardware representations, such as valve actuators, that make it more realistic and flexible in terms of accurately sim

99 GENERAL AND MISCELLANEOUS↗

Operational Parameter Database for Molten Salt Thermal Energy Storage Tank Modeling

The second generation of concentrated solar power (CSP) plants is characterized by the use of a central receiver (either cavity or external), two molten nitrate salt tanks (60 wt.% NaNO 3 and 40 wt.% KNO 3 ), and a steam Rankine power-generation cycle connected through a primary heat exchanger. Molten salt thermal energy storage (TES) tanks have been widely deployed in commercial CSP plants worldwide and have been essential for increasing plant dispatchability and capacity factor, while also reducing the levelized cost of electricity (LCOE). These systems enable energy storage at the gigawatt-hour scale, typically providing 6 to 17 hours of storage duration. Despite being a commercial technology, the multiple failures observed after only a few months or years of operation in plants around the world demonstrate the technology's relative infancy and highlight the need for further research to improve its reliability. The National Laboratory of the Rockies (NLR), in collaboration with industry partners and academic and research institutions, has been leading multiple projects funded by the U.S. Department of Energy (DOE). These projects focus on addressing molten salt tank failures by improving tank design and welding fabrication practices, evaluating new alloys and weld fillers, and providing guidelines for tank commissioning and safe operation. In particular, this report presents modeling results on the effect of key tank operation parameters during 60 minutes of operation, including the mass flow rate and temperature of the salt inflow, tank salt inventory temperature, and inventory level for a representative molten salt tank design. These results form a database of tank operation behaviors that captures the effects of each specific parameter during charging, charging/discharging, and discharging processes.

14 SOLAR ENERGY↗

Model-Based Diagnostics and Mitigation of Cyber Threats

The report summarizes key tasks performed to develop a toolkit for detecting cyber-attack events in instrumentation and control (I&C) systems of nuclear power plants. The toolkit connects the state-of-the-art GPWR Simulator with the RELAP5 code providing best-estimate nuclear steam supply system (NSSS) analyses, via the application programming interface (API), and allows users to introduce potential cyber-attack scenarios into power plant operational simulation. This summary for the project reflects topical reports submitted during the project as well as a journal paper published in 2022. The focus areas of the summary include: (1) modeling I&C systems for the AP1000 Generation III+ nuclear plant and GPWR simulator, (2) simulation and monitoring of plant response to cyber-attack events, (3) API structure for the toolkit interfacing the GPWR simulator and RELAP5 code, and (4) restructuring of the three-loop NSSS software of GPWR to model the two-loop AP1000 structure. Discussed in some details are (a) the attack tree analysis assessing the susceptibility of the AP1000 I&C system, resulting in reactor trips, in terms of the attack possibility and component sensitivity and (b) realistic estimation of the time to steam generator trip due to cyber-intrusions in the GPWR Simulator. Finally, sample demonstrations of the cyber-security tool kit, in the form of the GPWR-RELAP5 API, are summarized.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Hydrogen engines based on liquid fuels, a review

The concept of storing hydrogen as part of a liquid fuel, such as gasoline or methanol, and subsequent onboard generation of the hydrogen from such liquids, is reviewed. Hydrogen generation processes, such as steam reforming, partial oxidation, and thermal decomposition are evaluated in terms of theoretical potential and practical limitations, and a summary is presented on the major experimental work on conversion of gasoline and methanol. Results of experiments indicate that onboard hydrogen generation from methanol is technically feasible and will yield substantial improvements in fuel economy and emissions, especially if methanol decomposition is brought about by the use of engine exhaust heat; e.g., a methanol decomposition reactor of 3.8 provides hydrogen-rich gas for a 4 cylinder engine (1.952), and 80% of the methanol is converted, engine exhaust gas being the only heat supply. A preliminary outline of the development of a methanol-based hydrogen engine and a straight hydrogen engine is presented.

Houseman, J.↗

Performance and Economic Evaluation of sCO2 Bottoming Cycles for Natural Gas Combined Cycle Plants with Capture

Natural gas combined cycles (NGCCs) with carbon capture are expected to play a significant role in decarbonization of the power generation sector. NGCC plants generally use triple pressure reheat steam Rankine power cycles for the bottoming cycle. Some studies in the literature have investigated the application of recompression and cascade style supercritical CO2 (sCO2) cycles for NGCC bottoming cycle applications but these studies have focused on power plants without carbon capture. However, NGCC plants fitted with post-combustion solvent-based CO2 capture systems will require a significant amount of steam for solvent regeneration and this can have a major impact on the optimal sCO2 bottoming cycle design. This study investigates the performance and economic potential of sCO2 bottoming cycles for H-class gas turbine based NGCC plants with a post-combustion capture system. A portion of the gas turbine exhaust heat is used for generation of steam required for solvent-based capture system while the rest of the waste heat is utilized in an sCO2 bottoming cycle for power generation. Overall, the performance and LCOE of investigated sCO2 bottoming cycles is similar to that of a state-of-the-art triple pressure reheat steam Rankine cycle. As the gas turbine exhaust temperature increases (beyond 630oC), sCO2 bottoming cycles begin to show greater performance and economic benefits compared to a steam Rankine cycle.

Pidaparti, Sandeep↗

Heat Integration Optimization and Dynamic Modeling Investigation for Advancing the Coal-Direct Chemical Looping Process

The purpose of the project is to address the optimization and startup operation of a modular coal direct chemical looping (CDCL) combustion system integrated with a steam cycle for power generation to reduce the risks involved in further scale-up of the technology. The modular reactor design of the CDCL process provides flexibility in the fabrication of the reactor and in its operating capacity (i.e. turndown ratio) at the cost of a more complex heat exchange network (HEN) design and integration. To address the technology gaps and advance the efficiency and economic feasibility of the CDCL technology, the project will perform a detailed and comprehensive analysis of the integration of a modular CDCL reactor system and a steam cycle system under both static and transient conditions via HEN process performance simulations and system dynamic modeling, respectively. The scope of work consists of 1) Experimental and computational studies of the CDCL combustor reactor 2) Comprehensive static (i.e. steady-state) system HEN design analysis in CDCL 550 MWe commercial unit for power generation and 3) Dynamic modeling of site specific design of 10MWe CDCL large pilot plant. The project team has successfully developed and validated a kinetic model for the oxidation of oxygen carriers in the combustor using the unreacted shrinking core model (UCSM). The model is capable of capturing the oxidation kinetics of fully or partially reduced oxygen carrier particles. A computational fluid dynamics (CFD) model is developed to simulate the hydrodynamics, heat transfer, and chemical reaction occurring in the CDCL combustor. The model is developed in MFIX and ANSYS Fluent. Key aspects of CDCL combustor operation, including heat transfer, oxygen carrier oxidation, and the transport of oxygen carrier particles, are simulated using this CFD model. The HEN for a commercial scale 550 MWe CDCL power plant is simulated and optimized using ASPEN Plus. Practical design considerations are incorporated based on industrial experiences. The performance and cost for the commercial CDCL plant is updated based on these analyses. A dynamic model for the 10 MWe CDCL pilot plant is developed in ProTRAX simulation software. The model is based on the pilot plant design developed in project DE-FE0027654 “10 MWe CDCL Large Pilot Plang – Pre-FEED Study” and the steam cycle data obtained from Dover Light & Power plant. The transient behaviors during pilot plant load variation are simulated using the dynamic model.

01 COAL, LIGNITE, AND PEAT↗

Alstom’s Limestone Chemical Looping Gasification Process for High Hydrogen Syngas Generation

Alstom Power Inc., a wholly owned subsidiary of the General Electric Company (GE), is developing Limestone-based Chemical Looping (LCL™) Processes, utilizing limestone derived calcium sulfate as an oxygen carrier to transport oxygen from air to the fuel. The LCL™ process is a breakthrough technology with the potential to capture CO 2 and SO 2 from new and existing coal-fired power plants at reduced costs while maintaining high plant power generation efficiency. Chemical looping is a next generation advancement to oxy-combustion which would not require the significant investment in a cryogenic distillation type oxygen production plant. Instead of the energy-consuming oxygen plant, chemical looping uses a benign material to directly remove oxygen from the air and bring that oxygen into contact with the fuel. This "game changing" technology is the lowest cost-of-electricity technical approach that GE Power has identified to date for coal power with carbon capture. The technology has significantly lower capital costs compared to a conventional steam power plant with first generation carbon capture technologies. This new power plant concept is based on a hybrid combustion-gasification process utilizing high temperature chemical and thermal looping technology. In the air reactor, a solid oxygen carrier picks up oxygen from air through an oxidation reaction and leaves nitrogen behind. The hot oxygen-carrying solid carrier is then transported to a fuel reactor, where it releases oxygen. The released oxygen then converts the coal in the fuel reactor into combustion gases. The solid carrier is recycled back to the air reactor for regeneration completing the “chemical loop.” The regeneration step produces heat from which steam is produced for power generation while the process results in a concentrated carbon dioxide stream in which the carbon is captured for use or sequestration (CCUS). Limestone as a precursor for the oxygen carrier is abundant, benign, low cost, and is used in CFB and PC boilers for sulfur control. Challenges associated with this carrier include a complex reaction mechanism with possible side reactions leading to the release of SO 2 . The development of the Limestone Chemical Looping Gasification (LCL-G™) technology was co-funded by the Department of Energy under the DOE/NETL Cooperative Agreement No. DE- FE0023497, in parallel with the collaborative combustion (LCL-C™) program. In this report, the LCL-G™ experimental testing from the electrically-heated, once-through, 100 kW Pilot-Scale Test Facility (PSTF) is analysed and reviewed. The PSTF Oxidizer is a 50-foot tall, 100-mm diameter transport reactor, while the PSTF Reducer reactor is based upon a bubbling-bed design. The experimental data from four (4) test campaigns (denoted “Weeks”) are reviewed and discussed. The LCL-G™ (DE-FE0023497) project objectives for gasification are >90% carbon gasified in the Reducer and a H 2 :CO molar generation ratio of 2:1. These project performance metrics were not met by a single coal test, but they were individually approached in two separate tests.

01 COAL, LIGNITE, AND PEAT↗

Improvement of Alstom's Limestone-Based Chemical Looping Combustion Process for Higher Purity Flue Gas Production

Alstom Power Inc., a wholly owned subsidiary of the General Electric Company (GE), is developing Limestone-based Chemical Looping (LCL™) Processes, utilizing limestone derived calcium sulfate as an oxygen carrier to transport oxygen from air to the fuel. The LCL™ process is a breakthrough technology with the potential to capture CO 2 and SO 2 from new and existing coal-fired power plants at reduced costs while maintaining high plant power generation efficiency. Chemical looping is a next generation advancement to oxy-combustion which would not require the significant investment in a cryogenic distillation type oxygen production plant. Instead of the energy-consuming oxygen plant, chemical looping uses a benign material to directly remove oxygen from the air and bring that oxygen into contact with the fuel. This "game changing" technology is the lowest cost-of-electricity technical approach that GE Power has identified to date for coal power with carbon capture. The technology has significantly lower capital costs compared to a conventional steam power plant with first generation carbon capture technologies. This new power plant concept is based on a hybrid combustion-gasification process utilizing high temperature chemical and thermal looping technology. In the air reactor, a solid oxygen carrier picks up oxygen from air through an oxidation reaction and leaves nitrogen behind. The hot oxygen-carrying solid carrier is then transported to a fuel reactor, where it releases oxygen. The released oxygen then converts the coal in the fuel reactor into combustion gases. The solid carrier is recycled back to the air reactor for regeneration completing the “chemical loop.” The regeneration step produces heat from which steam is produced for power generation while the process results in a concentrated carbon dioxide stream in which the carbon is captured for use or sequestration (CCUS). Limestone as a precursor for the oxygen carrier is abundant, benign, low cost, and is used in CFB and PC boilers for sulfur control. Challenges associated with this carrier include a complex reaction mechanism with possible side reactions leading to the release of SO 2 . The present project (DOE/NETL Cooperative Agreement No. DE-FE0025073) report focuses on coal-fired Limestone Chemical Looping Combustion (LCL-C™) processes that can produce a higher purity flue gas stream and achieve an improved overall performance that will meet the stated DOE goal of generating power from coal while achieving greater than 90% CO2 removal at less than 35% increase in the Levelized Cost of Electricity (LCOE). It builds on the concurrent and synergistic limestone-based chemical looping combustion (LCL-C™) and gasification (LCL-G™) projects with the Department of Energy, that were executed in parallel with the present project. In this report, the LCL-C™ experimental testing from the electrically-heated, once-through, 100 kW Pilot-Scale Test Facility (PSTF) is analysed and reviewed. The PSTF Oxidizer is a 50-foot tall, 100-mm diameter transport reactor, while the PSTF Reducer reactor is based upon a bubbling-bed design. The experimental data from designated test periods (denoted “Weeks”) are reviewed and discussed. The application of high sulfur release in the Reducer (with proper sulfur management) exceeded the LCL-CTM performance targets. Furthermore, the ilmenite blend came within 1 percentage point of meeting all of the performance targets.

01 COAL, LIGNITE, AND PEAT↗

Techno-Economic Analysis of Greenfield Geothermal Hybrid Power Plants using a Solar or Natural Gas Steam Topping Cycle

The relatively low generation costs associated with wind, solar photovoltaic (PV), and natural-gas power plants make it challenging for geothermal power plants to produce and sell the power that has the reliability and sustainability characteristics that are greatly needed in U.S. power markets. This is especially true for geothermal resources with low-to-medium temperatures, which results in relatively low-thermal efficiency and generation costs that are higher than those for wind, solar PV, and natural gas. This analysis evaluates solar thermal- and natural-gas combustion waste heat recovery-based topping cycle hybridization of geothermal binary power plants. This approach provides several benefits that may allow geothermal power plants to generate power at more competitive costs. First, the addition of solar thermal energy or natural-gas combustion waste heat input to a geothermal power plant provides additional heat input that can be converted to electrical power. Second, the temperature level of the heat obtained from concentrating solar collectors or natural-gas combustion exhaust is higher than that of geothermal heat, which provides opportunities for improving the efficiency of the conversion of thermal energy to electrical power. Third, the ease with which solar thermal systems integrate with energy storage and the flexibility of natural gas means power generation can occur during peak demand periods. The hybrid cycles are compared to equivalently sized, co-located, independent geothermal, concentrating solar, and/or natural-gas power plants. The hybrid cycle tends to produce slightly more power than the standalone plants combined. However, the hybrid plant Levelized Cost of Energy (LCOE) is slightly higher than the LCOE of the combined standalone power plants for each of the case study locations investigated. Using the steam-topping cycle, organic Rankine cycle (ORC)-bottoming cycle hybrid plant design to combine a solar thermal resource and low- temperature geothermal resource (<120 degrees C) leads to a hybrid plant with a lower LCOE than a standalone geothermal-only system. Thus, hybrid plants may enable the economic development of geothermal resources in locations with low geothermal resource temperatures. However, in areas with higher geothermal resource temperatures (>120 degrees C), the geothermal-only plant has a lower LCOE than the hybrid cycle and thus could be developed without the need for solar heat addition. iv A geothermal-natural-gas reciprocating engine hybrid plant was evaluated for an Elk Hills, California case study location. The Elk Hills case study analysis indicates that when the natural-gas engine operates for more than 12 hours per day the hybrid plant can produce power at an LCOE lower than a standalone geothermal plant, and comparable to that of the standalone natural-gas reciprocating engine, while also reducing the carbon intensity of the power generated relative to the standalone natural-gas engine. This may represent a scenario in which the hybrid plant provides an opportunity for the deployment of a low-temperature geothermal resource that otherwise may have an LCOE too high to develop and operate as a standalone resource, while also reducing the carbon intensity of natural-gas generation sources. A "triple-hybrid" plant that combines natural gas, solar thermal, thermal energy storage, and geothermal was also investigated. A natural-gas combustion turbine (NGCT) is added to the geothermal-solar hybrid such that the hot exhaust gas from the gas turbine provides an alternative source of heat to the steam turbine of the hybrid cycle. Analysis results suggest that the triple-hybrid plant has a significantly higher energy generation and revenue than a standalone NGCT or the original geothermal-solar hybrid. The triple-hybrid design benefits most from using a smaller solar field so that the solar energy can be dispatched at the most valuable times available. The triple-hybrid plant also has a lower LCOE than the standalone NGCT. The triple-hybrid plant was evaluated making simple assumptions about the dispatch profile of the gas cycle, and more nuanced and realistic dispatching schedules should be analyzed in future work.

15 GEOTHERMAL ENERGY↗

Comprehensive process and environmental impact analysis of integrated DBD plasma steam methane reforming

Utilization of electricity generated from renewable sources to obtain hydrogen, H 2 , is of critical importance to decrease the overall carbon footprint. Here in this work, integration of a dielectric discharge barrier (DBD) plasma reactor to convert low calorific value gas, such as landfill gas or coal mine gas into hydrogen, into the existing steam methane reforming (SMR) technology was evaluated using process design considerations. In particular, a DBD-enhanced catalytic SMR reactor was modeled to operate at near atmospheric pressure and 500 °C sequentially with the conventional reformer to obtain ~ 65 kmol/hr H2 for distributed production. This allowed decreasing the size of the conventional reformer albeit at the increased overall electricity consumption. Calculated process economics showed that only at an electricity cost of less than $0.004/kWh does the hybrid DBD plasma process derived H 2 price become competitive with that of the conventional SMR. A Life Cycle Assessment framework was used to compare environmental impacts from the conventional SMR, hybrid DBD SMR and hybrid DBD SMR utilizing only onshore wind-derived electricity. Larger environmental impacts in the plasma reformer were obtained due to the use of electricity for the plasma reforming operation, which was modeled as coming from the typical U.S. grid mix. Utilizing only 100% wind-derived electricity provided certain environmental benefits, except for the ecotoxicity impact where the wind power scenario modeled here only reduced ecotoxicity impacts associated with electricity by 30%.

08 HYDROGEN↗

Impact of Technology Improvements on the Cost of Hydrogen Produced using SOEC Technology at Large Scale

National Energy Technology Laboratory (NETL) provides system-level process, cost, and market analyses on solid oxide cell (SOC) based technologies. Specifically, techno-economic analyses (TEA), market assessments, and other technology evaluations serve to guide the U.S. Department of Energy (DOE) Office of Fossil Energy and Carbon Management (FECM) Reversible Solid Oxide Fuel Cell (R-SOFC) Program technology goals and objectives. These studies are key to describing how the technologies contribute to improving domestic energy infrastructure in a clean, efficient manner. This effort focuses on hydrogen generation technologies, which have received recent attention due to their potential role in economy-wide decarbonization. In particular, the study is part of a series of investigations at NETL that seek to understand the techno-economic impacts of including SOC technology in energy production, hydrogen production, and/or storage configurations. The objective of this study is to establish a detailed TEA to assess the effectiveness of incremental technology improvements needed for solid oxide electrolysis cell (SOEC) technology to achieve the U.S. DOE’s Hydrogen Shot goal of hydrogen production at less than $1 per kilogram. To take advantage of the benefits of economies of scale, the SOEC hydrogen facilities are sized to produce ≈250,000 metric tons of hydrogen annually with an electrolysis load of one gigawatt (direct current). Some additional critical assumptions include stacks that operate near the thermo-neutral voltage of 1.28 V to avoid adverse thermal gradients, all necessary steam and heat is generated by electric boilers and heaters to enable green hydrogen production, and an air sweep is used to control the oxygen concentration in the air electrode exhaust stream. System efficiency and levelized costs of hydrogen (LCOH) for each case are presented.

Hackett, Gregory↗

CO 2 conversion to syngas via electrification of endothermal reactors: Process design and environmental impact analysis

CO 2 utilization via reverse water gas shift (rWGS) reaction has been proposed as a path to the sustainable utilization. Here this work presents a detailed process modelling study where steam methane reforming (SMR) generated hydrogen was combined with rWGS to produce syngas (CO + H 2 ) with various hydrogen-to-carbon oxide ratios. To further decrease CO 2 emissions that may offset the benefits of CO 2 converted in rWGS, electrification of endothermal reactors, both SMR and rWGS was considered where CO 2 emitting fuel burning in the furnace was replaced by the emerging ohmic (resistive) heating. Material and energy inventory obtained from process design calculations was used to perform Life Cycle Analysis (LCA) to calculate environmental impacts of CO 2 consumption and reactor electrification. The results showed that greenhouse gas emissions, in CO 2 kg equivalent, were the lowest when both SMR and rWGS were heated using wind-generated electricity, decreasing from 25 to 10 kg CO 2 equivalent for H 2 :CO = 2:1 while the conventional electricity mix used for furnace electrical heating across the board of scenarios generated highest environmental impacts, much higher than those that used natural gas as fuel. Process economics calculations suggested that, when both SMR and rWGS were electrically heated, the process only showed product syngas cost parity with the conventional fuel heated design when electricity cost was ~$0.008/kWh. This suggests that CO 2 utilization scenarios involving process electrification need to be carefully considered from the total design perspective so they do not produce more greenhouse gases than in conventional non-electrified scenarios.

42 ENGINEERING↗

Microwave-enhanced methane cracking for clean hydrogen production in shale rocks

Here, steam methane reforming (SMR) generates about 95% of hydrogen (H 2 ) in the U.S. using natural gas as a main feedstock. However, this technology also generates a large amount of carbon dioxide (CO 2 ), a major greenhouse gas causing global warming. Carbon capture and storage (CCS) technique is required, but the cost and safety of storing CO 2 underground are a concern. Here we propose a new approach using microwave/electromagnetic irradiation to produce clean hydrogen from unrecovered hydrocarbons within petroleum reservoirs. Solid carbon or CO 2 produced during this process will be simultaneously sequestrated underground without involving CCS. In this paper, we perform a series of experiments to investigate the in-situ hydrogen production from shale gas (methane) conversion by passing a methane stream through a packed shale rock sample heated by microwave. We found that methane conversion was significantly enhanced in the presence of Fe and Fe 3 O 4 particles as catalysts, with a conversion of 40.5% and 100% at reaction temperature of 500 °C and 600 °C, respectively. Methane conversion is promoted at a lower reaction temperature by the catalytic effect of minerals in shale. Additionally, the influences of catalysts, shale rock, and methane flow rate are characterized.

08 HYDROGEN↗

RODeO (Revenue Operation and Device Optimization Model) [SWR 20-67]

The Revenue, Operation, and Device Optimization (RODeO) model explores optimal system design and operation considering different levels of grid integration, equipment cost, operating limitations, financing, and credits and incentives. RODeO is a price-taker model formulated as a mixed-integer linear programming (MILP) model in the GAMS modeling platform. The objective is to maximizes the net revenue for a collection of equipment at a given site. The equipment includes generators (e.g., gas turbine, steam turbine, solar, wind, hydro, fuel cells, etc.), storage systems (batteries, pumped hydro, gas-fired compressed air energy storage, long-duration systems, hydrogen), and flexible loads (e.g., electric vehicles, electrolyzers, flexible building loads). The input data required by RODeO can be classified into three bins: 1) utility service data, which refers to retail utility rate information (meter cost, energy and demand charges), 2) electricity market data, which include energy and reserve prices, 3) other inputs, which refer to additional electrical demand, product output demand, technological assumptions, financial properties, and operational parameters.

Guerra Fernandez, Omar Jose↗

Intermetallic Strengthened Alumina-Forming Austenitic Steels for Energy Applications

In order to achieve energy conversion efficiencies of >50 % for steam turbines/boilers in power generation systems, the materials required must be strong, corrosion-resistant at high temperatures (>700°C), and economically viable. Austenitic steels strengthened with Laves phase and L1 2 precipitates, and alloyed with aluminum to improve oxidation resistance, are potential candidate materials for these applications. The creep resistance of these alloys is significantly improved through intermetallic strengthening (Laves-Fe 2 Nb + L1 2 -Ni 3 Al precipitates) without harmful effects on oxidation resistance. Microstructural and microchemical analyses of the recently developed alumina-forming austenitic (AFA) steels (Fe-14Cr-32Ni-3Nb-3Al-2Ti-based) indicated they are strengthened by Ni 3 Al(Ti) L1 2 , NiAl B 2 , Fe 2 Nb Laves phase and MC carbide precipitates. Different thermomechanical treatments (TMTs) were performed on these stainless steels in an attempt to further improve their mechanical properties. The thermo-mechanical processing produced nanocrystalline grains in AFA alloys and dramatically increased their yield strength at room temperature. Unfortunately, the TMTs didn’t increase the yield strengths of AFA alloys at ≥700ºC. At these temperatures, dislocation climb is the dominant mechanism for deformation of TMT alloys according to strain rate jump tests. After the characterization of aged AFA alloys, we found that the largest strengthening effect from L1 2 precipitates can be obtained by aging for less than 24 h. The coarsening behavior of the L1 2 precipitates was not influenced by carbon and boron additions. Failure analysis and post-mortem TEM analysis were performed to study the creep failure mechanisms of these AFA steels after creep tests. Though the Laves and B2-NiAl phase precipitated along the boundaries can improve the creep properties, cracks were still initiated and propagated along the boundaries, which suggests that the boundaries are still the weaker regions for causing fracture during creep, possibly due to the presence of a precipitatefree zone. The precipitate size distribution and kinetics of precipitate growth were quantified.

36 MATERIALS SCIENCE↗