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Hydrogen and Power Co-Production Using Direct sCO 2 Power Cycles

This report presents the techno-economic analysis (TEA) results of integrating a modified autothermal reforming (ATR) hydrogen (H 2 ) production plant with a natural gas-fired, utility-scale power plant based on the direct supercritical carbon dioxide (sCO 2 ) power cycle. In this study, the H 2 production and the power plant are fully integrated in terms of heat, fuel, and carbon capture and storage (CCS). The ATR process has significant waste heat available for heat integration with a direct-fired sCO 2 power plant that benefits the power plant efficiency. The off-gas stream from the modified ATR process is primarily carbon dioxide (CO 2 ), carbon monoxide (CO), and residual H 2 . As supplemental fuel, it has beneficial heating value in the CO and H 2 that can be used in the direct sCO 2 power cycle. Finally, the direct sCO 2 power plant can isolate the CO 2 produced at the facility for CCS.

08 HYDROGEN↗

Strategies to Valorize the Hydrothermal Liquefaction-Derived Aqueous Phase into Fuels and Chemicals

Valorization options for the aqueous fraction produced by the hydrothermal liquefaction of terrestrial feedstocks were developed. The processes focused on carboxylic acids, which are abundant in the aqueous fraction. A clean up process for the aqueous phase based on activated carbon absorption followed by liquid-liquid extraction was demonstrated that significantly reduces color bodies and inorganic contaminants while simultaneously concentrating desirable organic constituents. Conversion of the cleaned aqueous phase was then demonstrated for both a ketonization reaction and steam reforming. Condensed phase ketonization over LaxZryOz catalyst was found to exhibit both excellent hydrothermal stability and ketonization activity. Necessity for feedstock cleanup was established and stable condensed phase ketonization operation was demonstrated for ~100 hours with HTL-process derived material. Steam reforming was also demonstrated by employing a dual-bed catalyst configuration whereby carboxylic acids first undergo ketonization over CeO2 in the vapor phase followed by steam reforming of the ketone intermediates over Co/CeO2. The dual-bed approach reduced coke deposition and thus catalyst stability improved. Techno-economic analysis was used to assess economic viability for producing fuel from the bio-oil fraction and either propene (formed via hydrogenation and dehydration of acetone, the primary ketonization product) or hydrogen from the aqueous stream. The ketonization and steam reforming cases were separately modeled and benchmarked to a process utilizing anaerobic digestion. Resulting minimum fuel selling prices of $3.7, $4.2, and $4.3/GGE were obtained for the production of olefins via ketonization, reduction and dehydration; steam reforming; and anaerobic digestion processes, respectively. Both the steam reforming and anaerobic digestion processes benefited by avoiding the need for natural gas by producing the hydrogen on-site required for biocrude hydrotreatment. However, the condensed ketonization process had the lowest minimum fuel selling price because of the co-product olefins generated for sale.

Biomass, hydrothermal liquefaction, techno economi↗

Demonstration of Electrolyzer Operation at a Nuclear Plant to Allow for Dynamic Participation in an Organized Electricity Market and In-House Hydrogen Supply

This document details the execution of Cooperative Agreement DE-EE0008849, “demonstration of electrolyzer operation at a nuclear plant to allow for dynamic participation in an organized electricity market and in-house hydrogen supply” during the performance period of 10/1/2019 – 9/30/2024. The project was funded by the U.S. Department of Energy’s Office of Energy Efficiency and Renewable Energy (EERE). Constellation Energy Generation, LLC (formerly Exelon Generation Company, LLC) is the prime recipient of the award. Other members of the project team are INL, NREL, ANL and Nel Hydrogen. The main project objective was to demonstrate an end-to-end integrated grid-scale carbon-free H 2 production, storage and utilization pilot plant at a nuclear generating facility. The project also aimed to evaluate market opportunities and regulatory requirements related to the participation of integrated hydrogen production and nuclear plant facilities in organized power markets, by demonstrating dynamic control and operation of the electrolyzer and assessing the economics of dynamic participation combined with the revenue streams from hydrogen production. On March 7th , 2023 Constellation started hydrogen production at it’s Nine Mile Point Nuclear Plant in Oswego, New York. The PEM electrolyzer operating at Nine Mile Point uses 1.25 megawatt of nuclear electricity to produce 560 kilograms of clean hydrogen per day, more than enough to meet the plant’s operational hydrogen use. It will also help set the stage for possible large-scale deployments at other clean energy centers in Constellation’s fleet that would couple clean hydrogen production with storage and other on-site uses. Employing the lessons learned from the 1.25 MW demonstration-scale, nuclear-powered clean hydrogen production facility at Nine Mile Point, Constellation was a major participant in the MachH2 hydrogen hub recently selected for up to $\$$1 billion by the Department of Energy (DOE) as part of the bipartisan Infrastructure Investment and Jobs Act. Constellation will use a portion of the hub funding to build the world’s largest nuclear-powered clean hydrogen production facility at its LaSalle Clean Energy Center in Illinois. The project was featured in a number of news articles and press releases and received 2 awards. At the 2023 DOE HFTO’s Annual Merit Review meeting, the P.I. Dr. Uuganbayar Otgonbaatar and project manager Robert Beaumont were recognized for “outstanding achievements in the development and demonstration of a first-of-a-kind clean hydrogen production facility, powered by carbon-free nuclear energy, at the Nine Mile Point Nuclear Station in Oswego, New York.” The project was also awarded 2023 Nuclear Energy Institute’s Top Innovative Practice award.

08 HYDROGEN↗

Scalable neutral H 2 O 2 electrosynthesis by platinum diphosphide nanocrystals by regulating oxygen reduction reaction pathways

Despite progress in small scale electrocatalytic production of hydrogen peroxide (H 2 O 2 ) using a rotating ring-disk electrode, further work is needed to develop a non-toxic, selective, and stable O 2 -to-H 2 O 2 electrocatalyst for realizing continuous on-site production of neutral hydrogen peroxide. We report ultrasmall and monodisperse colloidal PtP 2 nanocrystals that achieve H 2 O 2 production at near zero-overpotential with near unity H 2 O 2 selectivity at 0.27 V vs. RHE. Density functional theory calculations indicate that P promotes hydrogenation of OOH* to H 2 O 2 by weakening the Pt-OOH* bond and suppressing the dissociative OOH* to O* pathway. Atomic layer deposition of Al 2 O 3 prevents NC aggregation and enables application in a polymer electrolyte membrane fuel cell (PEMFC) with a maximum r(H 2 O 2 ) of 2.26 mmol h -1 cm -2 and a current efficiency of 78.8% even at a high current density of 150 mA cm -2 . Catalyst stability enables an accumulated neutral H 2 O 2 concentration in 600 mL of 3.0 wt% (pH = 6.6).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Iron based catalysts for production of carbon and hydrogen from decomposition of methane

The invention provides a calcined Fe x —Al y —O z based catalyst for the decomposition of hydrocarbons such as methane to produce hydrogen and carbon. The catalyst comprises iron oxide mixed with aluminum oxide and calcined at temperatures above 1100° C., where Fe x —Al y —O z is a chemical composition with x>0.1, y>0.1, z≥0 and 0 2 and carbon. In an embodiment, carbon is separated from the catalyst and the catalyst is reused for continuous methane decomposition to produce H 2 .

Siriwardane, Ranjani↗

Technoeconomic assessment of hydrogen cogeneration via high temperature steam electrolysis with a light-water reactor

Increased electricity production from renewable energy resources, coupled with low natural gas (NG) prices, has caused existing light-water reactors (LWRs) to experience diminishing returns from the electricity market. This reduction in revenue is forcing LWRs to consider alternative revenue streams, such as introduction hydrogen production or desalination, to remain profitable. This paper performs a technoeconomic assessment (TEA) regarding the viability of retrofitting existing pressurized-water reactors (PWRs) to produce green hydrogen (H 2 ) via high-temperature steam electrolysis (HTSE). Such an integration would allow nuclear facilities to expand into additional markets that may be more profitable in the long term and eliminate CO 2 emissions from the hydrogen production process. Here, to accommodate such an integration, a detailed single market levelized cost of hydrogen (LCOH) and multimarket analyses were conducted of HTSE process operation, requirements, costing, and flexibility. Alongside this costing analysis, market analyses were conducted on the electric and hydrogen markets in the PJM interconnect. Utilizing a novel stochastic, dispatch optimization approach results suggest that a positive gain is achievable, and by operating in multiple markets, the nuclear facility can avoid the sale of electricity during times of low electricity market pricing, while maintaining the ability to capitalize on the high electricity market pricing. It should be noted that the analysis conducted is a differential cash flow analysis and, as such, does not present profit levels. LCOH analysis results demonstrate the potential exists to produce hydrogen at a cost as low as $1.20/kg. This price is lower than traditional steam methane reforming (SMR) allowing nuclear based hydrogen production to disrupt the existing hydrogen production market.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Public Reference Data for Megawatt-Scale Hydrogen Electrolysis - Simulated Marine Hydrokinetic Tidal Turbine

The U.S. Department of Energy and National Laboratory of the Rockies (NLR) demonstrate hydrogen electrolysis, hydrogen compression and storage, and variable hydrogen fuel cell power production using megawatt-scale equipment at NLR’s Flatirons Campus as part of the Advanced Research on Integrated Energy Systems (ARIES) initiative. This dataset is part of that effort and is intended for academic, national laboratory, industrial, and other stakeholders to plan, design, and validate models of megawatt-scale hydrogen technologies and diverse energy infrastructure. These data provide a baseline for how existing hydrogen electrolysis technologies perform when coupled with other energy technologies. This dataset contains inputs and outputs from simulations of a floating marine hydrokinetic turbine over approximately half a tidal cycle (~6.6 hours). Inflow conditions were derived from field measurements in Alaska’s Cook Inlet and represent a tidal environment in which the current speed ramps from near 0 m/s to a peak of 3 m/s and back. The original acoustic doppler current profiler dataset is publicly available on the Marine and Hydrokinetic Data Repository. In a full tidal cycle, the flow reverses and the rotor would reorient; this reversal was not modeled. In the Cook Inlet campaign , turbulence intensity was similar in both directions. Two inflow cases are included. In the first case, labeled “raw” in the files, the measured current time series was used directly in the InflowWind module of OpenFAST. Speed and direction were applied as a function of time and elevation, uniformly in the horizontal direction. With full spatial coherence, this approach captures high turbulent variability and results in pronounced power fluctuations, so it is considered a conservative, near-worst-case representation of loading. In the second case, labeled “average” in the files, a 30-minute moving average was applied to extract the slowly varying mean speed. The residual fluctuations about this mean were used to generate spatially varying, full-field turbulence inputs with TurbSim, giving a more physically realistic representation of the inflow across the rotor disk. Two random realizations were used to produce distinct inflow conditions for two OpenFAST simulations representing a two-turbine array. The same turbulence intensity is applied across the full time series, producing larger fluctuations at the start and end, where the mean speed is low. The second case is the more appropriate framework for performance and power assessment but overpredicts turbulence at lower flow speeds and underpredicts it at higher speeds. As the floating platform moves and the rotor changes its x-position, Taylor’s frozen turbulence hypothesis used by InflowWind assumes a constant rather than a time-varying mean velocity, introducing some inaccuracy in the velocity plane sampling. The turbine modeled is the 500-kW Reference Model 1, a horizontal-axis two-bladed hydrokinetic turbine on a four-column floating semisubmersible substructure . Simulations were performed using OpenFAST v4.1 with the Reference Open Source Controller (ROSCO) v2.10. All input files required to reproduce the simulations are included. The electrolyzer is a 1.25-MW proton exchange membrane type MC250 system manufactured by Nel . This unit supports up to 2.5 MW, but NLR has only a single 1.25-MW stack. The datasets report hydrogen balance-of-plant and system data, all captured at 1 Hz, including hydrogen mass production measured with an Emerson Coriolis flow meter. The system controls hydrogen production by varying direct current applied to the stack, from a maximum of 3,000 A to a minimum safe operating current of 300 A, or 10%. Because the current–voltage characteristic changes as the stack ages and efficiency degrades, the actual minimum safe operating power changes over time. The simulated tidal turbine time series data was translated from power (kilowatts) to current (amperes) using a curve fit with calibration data and sent to the electrolyzer power supply at 1-Hz. Each zip file represents a single tidal electrolysis experiment and is named: {technology}_{inflow method}_{number of 500 kW tidal turbines connected} For instance, “tidal-500kW-RM1_average_2.zip” is a 6-hour experiment using the 500-kW tidal reference model, scaled by 2x (1-MW) to better match the electrolyzer maximum of 1.25MW, fed with the 30-minute moving average current case. Each zip folder contains the following files: A .csv file of raw data. An .xlsx file explaining all the fields in the raw data. A .png plot showing the time series of hydrogen production in kilograms per hour, electrolysis power consumption, and input wave power. A .csv file combines all tidal profiles as "combined_tidal_experiments.csv." A separate experiment, “characterization_200.zip,” shows the MC250 electrolyzer steady-state response with 30-minute load steps over 5 hours and is accessible with this entry.

08 HYDROGEN↗

Microstructural characterization of cold-worked 316 stainless steel flux thimble tubes irradiated up to 100 dpa in a commercial Pressurized Water Reactor

Two flux thimble tubes (FTT) made of 15% cold-worked 316 stainless steel (SS) were harvested from Ringhals Pressurized Water Reactor (PWR) Unit 2, with peak damages of 76 and 100 displacements per atom (dpa) after 29 and 34 years’ service, respectively. Specimens sectioned from parent tubes were comprehensively characterized with nominal damage levels of ~0, ~41, ~74, 76, and 100 dpa at a nominal temperature range of 285-323 °C. Both FTTs contained helium and hydrogen gases as transmutation products. The helium follows a production rate of ~9.8 appm/dpa, while environmental factors complicate hydrogen production obscuring an exact H/dpa ratio. Irradiation-induced dislocation loops, nano-cavities, solute clusters, and microsegregation were all observed. The dislocation loops and nano-cavities indicated saturation at 41 dpa. The solute clusters continued to evolve with Ni-Si clusters formed at 41 dpa, and Ni-Si-Mn-P clusters formed at 74 and 100 dpa, but neither clusters exhibited distinct diffraction patterns at any damage levels. Solute clusters were observed to frequently be co-located with dislocation loops, but fully decorated loops were rarely detected. Significant radiation-induced segregation (RIS) was observed around grain boundaries at all damage levels. The modified inverse Kirkendall (MIK) model captured the RIS behavior of major elements. Large cavities within or around an Mn-S rich region were observed for the first time. Through all the damage levels, void swelling is always below 0.05%, making significant dimensional change unlikely in core internals when used at similar conditions. Meanwhile, the role of overwhelming nanocavities, presumably helium bubbles, should be considered in other potential degradation mechanisms, including irradiation-assisted stress corrosion cracking, embrittlement, and loss of fracture toughness, which remain the concerns for extended operation of nuclear power plants.

Post Irradiation Examination, Isotope Dilution Mas↗

HydroGEN and H2NEW Data Hub

HydroGEN is a multi-lab consortium focused on early-stage R&D in H2 production, supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (HFTO). The consortium advances research and development (R&D) of innovative materials for advanced water splitting (AWS) technologies to enable clean, sustainable and low-cost ($1/kg H2) hydrogen production and fosters cross-cutting innovation using theory-guided applied materials R&D to advance all emerging water-splitting pathways for hydrogen production. Hydrogen from Next-generation Electrolyzers of Water (H2NEW) is a consortium of nine U.S. Department of Energy (DOE) national laboratories focused on making large-scale electrolyzers, which produce hydrogen from electricity and water, more durable, efficient, and affordable. The presentation introduces the HydroGEN data hub to the H2NEW consortium and encourages H2NEW members to use it to store and share data with team members and eventually the public. The two consortia share this data hub.

advanced water splitting technologies↗

Foundational Low-Carbon Hydrogen Research

HydroGEN is a multi-lab consortium focused on early-stage R&D in H2 production, supported by the U.S. Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Office (HFTO). The consortium advances research and development (R&D) of innovative materials for advanced water splitting (AWS) technologies to enable clean, sustainable and low-cost ($1/kg H2) hydrogen production and fosters cross-cutting innovation using theory-guided applied materials R&D to advance all emerging water-splitting pathways for hydrogen production. HydroGEN is focused on low technology readiness level AWS technologies, including low- (alkaline exchanged membrane electrolysis) and high-temperature electrolysis (proton-conducting solid oxide electrolysis), photoelectrochecmical (PEC) and solar thermochemical (STCH) water splitting. This presentation will provide an overview of the HydroGEN EMN, its relationship to the H2NEW consortium, technical highlights of a few lab-led R&D projects, and the community appproach to benchmarking and protocol development for advanced water splitting technologies. Low-carbon hydrogen plays a vital role in the carbon dioxide utilization and decarbonization of several chemical and fuel industries.

advanced water splitting materials AEM↗

Market Analysis: Upcycling Natural Gas Into Solid Carbon Products

The purpose of this report is to execute a market analysis to determine the potential market opportunities for natural gas-derived high-value carbon products and their associated applications. Currently, associated gas is released through the process of either venting or flaring. Vented or flared natural gas is presently lost to the atmosphere, despite the fact that it represents a significant resource of both carbon and hydrogen—two products that could have significant value. Transforming some of this underutilized supply into high-cost products could contribute to realizing the full value of United States (U.S.) natural gas resources. The products analyzed in this report are carbon fiber, carbon nanotubes, synthetic graphite, and carbon black. The report also touches on the market opportunities for hydrogen, a by-product of the pyrolysis process.

03 NATURAL GAS↗

Palm oil deoxygenation with glycerol as a hydrogen donor for renewable fuel production using nickel-molybdenum catalysts: The effect of support

Palm oil, one of the most widely used vegetable oils, offers significant potential as a sustainable feedstock for biofuel production. This study explores the deoxygenation of palm oil using glycerol as a hydrogen donor, with nickel-molybdenum (NiMo) catalysts supported on commercial alumina (Al 2 O 3 ), and zeolite (HZSM-5) comparing with self-prepared zirconia (ZrO 2 ). The catalysts were synthesized via incipient wetness impregnation and evaluated for their performance in biofuel production. NiMo/Al 2 O 3 exhibited the lowest oxygen removal efficiency (68.5 %), while NiMo/HZSM-5 achieved a higher oxygen removal (74.3 %) but also demonstrated the highest coke formation. The type of support material influenced the resulting biofuel range, with NiMo/HZSM-5 and NiMo/ZrO 2 favoring jet fuel production, whereas NiMo/Al 2 O 3 was more suitable for diesel production. Notably, NiMo/ZrO 2 exhibited the highest performance in palm oil deoxygenation while minimizing coke formation. These findings highlight NiMo/ZrO 2 as a promising catalyst for efficient and stable biofuel production, with the support material significantly influencing product yield and fuel quality.

36 MATERIALS SCIENCE↗

Technology for Electrically Enhanced Thermochemical Hydrogen (TEETH)

This is the Final Technical Report for the TEETH project. The TEETH concept couples high-temperature solar-thermochemical water splitting (TCWS) with electrochemical H 2 pumping through a proton conducting membrane (PCM) and capitalizes on the benefits of the individual technologies to synergistically providing new benefits. That is, TEETH is a coupled thermochemical/electrochemical process to produce H 2 from steam using solar energy. This approach is thermodynamically equivalent to other hybrid electrolytic processes but is unique in that the equilibrium of the reaction is driven forward by close coupling an electrically driven proton-conducting-membrane to the H 2 -producing reoxidation step. The process uniquely provides and benefits from the necessary H 2 /steam separation and, also unlike other hybrid processes, benefits thermodynamically from the use of readily generated high pressure steam. The concept also satisfies the objectives of previous concepts: 1) decreasing the reduction enthalpy (the reduction temperature), of the working metal-oxide (MO); 2) eliminating the need for a windowed receiver; and 3) widening the scope of material candidates, while also obviating the need for electrical connections to the working MO and avoiding the use of aqueous electrolytes and hydrated redox species (there is no liquid phase), without increasing mechanical complexity.

08 HYDROGEN↗

Toward Rational Design of Nickel Catalysts for Thermocatalytic Decomposition of Methane for Carbon Dioxide-Free Hydrogen and Value-Added Carbon Co-Product: A Review

Thermocatalytic decomposition of methane provides opportunities for hydrogen (H2) production with no emission of carbon dioxide. However, high-value carbon products need to be produced for economic deployment of thermocatalytic decomposition and to achieve a minimum H 2 selling price below the U.S, Department of Energy target of $ 1/kg H 2 . In this review, we re-evaluate data on catalyst development reported in the literature and propose correlations between catalyst characteristics, catalytic stability, and properties of carbon co-products. In the first part of the review, growth mechanisms for carbon nanotubes using state-of-the-art chemical vapor deposition are reviewed to catalog the effects of catalyst characteristics, the influence of carbon sources, interactions between metal particles and supports, and metal particle sizes on carbon growth. In the second part, representative developments in mono-, bi-, and tri-metallic nickel catalysts are highlighted. We present kinetic analysis of reactions catalyzed by mono-metallic nickel catalysts, which generates a correlation between metal particle size and catalyst stability. Rational design of Ni-based catalysts for TCD of methane requires attention to the size of the metal particle and effective normalization of the reaction rates. Further attention to the distribution of the metal particle sizes may help identify catalyst properties that contribute longevity and selectivity to processes that use them. While it is tempting to focus on the highest valued carbon products (e.g., CNTs and CFs), analysis of the markets for other carbon products suggests that a more flexible approach may generate comparable returns without the risk associated with specialization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ru-CoO heterostructured nanoparticles supported on nitrogen and sulfur codoped graphene nanosheets as effective electrocatalysts for hydrogen evolution reaction in alkaline media

Production of clean hydrogen energy from water splitting is vital for the future fuel industry, and nanocomposites have emerged as effective catalysts for the hydrogen evolution reaction (HER). In this study, Ru-CoO@SNG nanocomposites are prepared by controlled pyrolysis where Ru-CoO heterostructured nanoparticles are supported on nitrogen and sulfur codoped graphene oxide nanosheets. With a large surface area, the obtained composites exhibit a remarkable electrocatalytic activity toward HER in 1.0M KOH with an overpotential of only -90mV to reach the current density of 10 mA cm -2 , in comparison to -60mV for commercial Pt/C benchmark, along with high stability. Mechanistically, codoping of sulfur and nitrogen facilitates the dispersion of the nanoparticles, and the formation of Ru-CoO heterostructures increases the active site density, reduces the electron-transfer kinetics and boosts the catalytic performance. Further, results from this study highlight the unique potential of structural engineering in enhancing the electrocatalytic performance of heterostructured nanocomposites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗