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Bulk Storage of Hydrogen

The technical aspects and economics of bulk hydrogen storage in underground pipes, lined rock caverns (LRC) and salt caverns are analyzed. Hydrogen storage in underground pipes is more economical than in geological caverns for useable amounts <20-t-H2. However, because the pipe material is a major cost factor, the capital and operating costs for this storage method do not decrease appreciably with an increase in the amount of stored H2. Unlike underground pipes, the installed capital cost of salt caverns decreases appreciably from ~$95/kg-H2 at 100 t-H2 stored to <$19/kg-H2 at 3000 t-H2 stored. Over the same scale, the annual storage cost decreases from ~$17/kg-H2 to ~$3/kg-H2. Like salt caverns, the installed capital cost of lined rock caverns decreases from ~$160/kg-H2 at 100 t-H2 stored to <$44/kg-H2 at 3000 t-H2 stored. Storing >750-t useable H2 requires multiple caverns. The cost of salt caverns scales more favorably with size because the salt caverns are larger than lined rock caverns and need to be added at a slower rate as the storage capacity is increased.

Bulk storage of hydrogen↗

Sensitivity Analysis of Salt Storage Cavern Mechanical Integrity Test Parameters

This report examines the sensitivity of salt cavern Mechanical Integrity Tests (MIT) to uncertainties in key test parameters. MIT's are used by cavern operators to detect and quantify leak rates in access wells in underground salt storage caverns and involve a suite of measured and assumed parameters that have a direct impact on the sensitivity of the testing to detect actual leaks from the cavern storage system. Determining the sensitivity of the testing to these different parameters provides a basis for understanding the results from, and informing the design criteria for, this type of testing. Without fully understanding the sensitivity of the test to the testing parameters, it is possible that the test results may not accurately reflect the integrity of the cavern system; an actual leak may be missed, or an intact system may be interpreted as leaking. This report reviews the main parameters included in MITs and examines how selected changes in their values can impact test results. The deviations used in the sensitivity analyses were designed to be within the ranges believed to be similar to those which may be encountered during testing. The results show that small, plausible fluctuations in some of the parameters measured values can have a significant impact on the testing results. Of the parameters studied here, the sensitivity analyses showed the order of importance to be (from highest to lowest): nitrogen-oil interface depth measurement, well bore temperature, well head pressure, and finally the internal geometry of the testing interval.

42 ENGINEERING↗

Technology Strategy Assessment: Findings from Storage Innovations 2030 Bidirectional Hydrogen Storage

Hydrogen is the most common element in the universe, comprising nearly 75% of all normal matter, and it has been used by scientists for centuries, but it was not fully recognized as an element until 1766, when it was isolated by Henry Cavendish. Early work focused on the generation of hydrogen through the oxidation of metals in water, which released hydrogen gas. Hydrogen’s lighter-than-air and flammable properties were immediately used in engines, zeppelins, and as feedstock for a wide variety of chemical reactions. Several approaches were developed for the production of hydrogen with the most common being associated with the production and conversion of hydrocarbon-based fuels. Coal gasification, steam methane reforming, and other reformation processes provide the majority of current hydrogen production due to the relatively low cost of hydrogen produced through these processes. More than 95% of hydrogen production is used for industrial processes rather than energy storage. To facilitate affordable decarbonization of these industrial processes and to advance the use of hydrogen as a fuel in transportation, DOE launched the Hydrogen Shot as part of the Energy Earthshots Initiative. The goal of the Hydrogen Shot is to reduce the cost of clean hydrogen by 80% to $1/kg of clean hydrogen production within one decade (known as the “1 1 1” goal). This is distinct from the Long-Duration Storage Shot, which is the primary focus of this report; however, it is intrinsically linked to bidirectional hydrogen storage. Several important chemical synthesis processes are dependent upon hydrogen, and the production and use of hydrogen is generally driven by its connection to one of these markets. For example, ammonia is one of the most highly produced chemicals in the world and it depends chiefly on hydrogen. Ammonia is primarily used for agricultural fertilizer and is considered to be largely responsible for a doubling of agricultural production per unit of land over the last century. Another one of hydrogen’s primary uses is as a catalyst in petroleum refining during the desulfurization process. Beyond chemical production, hydrogen is used as a reductant in the production of steel and has been demonstrated as a substitute for metallurgical coal in the production of raw iron. It is even used in the hydrogenation reaction for food products to create more shelf-stable semi-solid fats. However, while hydrogen is produced on the order of 100 million metric tons/year globally to feed these industries, more than 95% of hydrogen is produced from hydrocarbons that emit CO2 during the process. Conversely, electrolysis is a process by which electricity is used to separate hydrogen and oxygen in water molecules, usually across a membrane. Hydrogen production via electrolysis lowers the carbon intensity of produced hydrogen when coupled with low-carbon electricity. Currently, global electrolysis capacity is on the order of 1 GW, which equates to about 500 metric tons/day of hydrogen production. To support large-scale industrial decarbonization, capacity will likely need to increase by two to three orders of magnitude. Electrolysis technology is broadly separated into groups that are defined by the electrolyte used, with further subdivision based on the operating characteristics. The majority of commercial electrolyzer systems are based around three main technology groups: liquid alkaline, proton exchange membrane, and solid oxide. Liquid Alkaline (LA) electrolysis is the oldest, most mature, least expensive, and most common commercial technology, with 400 plants in operation by 1902. Its hydrogen output is low relative to the size of the system due to a low current density. LA electrolysis utilizes a liquid potassium hydroxide solution as the electrolyte. Proton exchange membrane (PEM) electrolysis (also known as polymer electrolyte membrane electrolysis), described in 1960, relies on an acid-impregnated polymer membrane as the electrolyte and typically offers three to six times higher hydrogen production per unit cell area than LA electrolysis. Solid oxide electrolysis, or high-temperature electrolysis, utilizes a ceramic cell as the electrolyte and operates on steam rather than liquid water, enabling electrical efficiencies of more than 90%, which is up from 60% with PEM. Two pre-commercial electrolyzer technologies to note are alkaline exchange membrane (AEM) and proton-conducting solid oxide electrolysis cell (SOEC). AEM potentially has the advantages of both LA and PEM technologies in that it is able to use low-cost materials like LA but with the ability to operate at higher output pressures with a smaller footprint like PEM. Proton-conducting SOEC is similar to commercial SOEC, which uses an oxide-conducting ceramic; however, it uses a proton-conducting ceramic that has the potential to operate at lower temperatures and has lower capital costs. Each of these technologies is experiencing a rapid improvement in performance and a reduction in installed cost, and each appears to be well suited to specific applications. Besides differences in the type of electrolyzer used, the main difference in the architecture of bidirectional hydrogen systems is how the hydrogen is stored. Currently, the most cost-effective way to store large amounts of hydrogen gas is underground, such as in large salt caverns that have been hollowed out. These salt caverns are geographically concentrated in small portions of the United States and are not generally near large metropolitan areas; however, other subsurface architectures are being investigated to expand this reach. A more widely deployable option is aboveground pressurized tanks. These systems are about 10 times as expensive because of the materials and safety margins required to hold hydrogen at high pressures. A third option is using materials-based storage, such as liquid organic hydrogen carriers. By reversibly attaching the produced hydrogen to other molecules, it can be stored at near atmospheric pressure and room temperature. This has the potential to reduce the material cost of storage but may result in a reduction in the efficiency of the process because there are both hydrogen uptake and release processes. While materials-based storage has not been used extensively for large-scale hydrogen storage in the past, there is currently significant activity regarding developing materials and processes for use in large-scale hydrogen storage applications. Electrolysis-produced hydrogen offers an unusual opportunity for energy storage applications. Unlike more conventional energy storage approaches, such as batteries, which operate entirely within electrical markets, hydrogen is a valuable product beyond the electric market and can be directed to the most lucrative use. Hydrogen also can be directly converted back to electricity using either a fuel cell or turbine, or it can be sold to other markets, such as chemical synthesis, steel production, or even export. In this way, excess electricity can be upgraded to the most valuable product. Finally, its use can be actively managed between multiple off-takers; for example, local hydrogen storage can provide a specific amount of stored electricity and any excess can be exported to ammonia production. This flexibility is amplified by the fact that hydrogen storage has fully decoupled power and energy components, which allows for affordable scaling options. Together, this allows a substantial amount of creativity to enable the economic utilization of variable power resources while supporting decarbonization of the industry.

08 HYDROGEN↗

Final Report UCLA-Thermochemical Storage with Anhydrous Ammonia

In ammonia-based thermochemical energy storage (TCES), ammonia is dissociated endothermically as it absorbs solar energy during the daytime. When energy is required, the reverse reaction releases energy to heat a working fluid such as steam, to produce electricity. Ammonia-based TCES has great advantages of simplicity, low cost reactants, and a strong industrial base in the conventional ammonia industry. The concept has been demonstrated over three decades of research at Australian National University, achieving a 24-hour demonstration of a complete system. At the start of this project, three challenges were identified that would have to be addressed to show that the system is technically and economically viable for incorporation into a CSP plant with an advanced, high temperature power block. All three of these challenges have now been addressed: 1. The ammonia synthesis reaction had not, to our knowledge, been carried out at temperatures consistent with modern power blocks (i.e., ~650°C). The technical feasibility of operating a reactor under high-temperature, near-equilibrium conditions was an unknown, and was therefore a technical risk. The project has successfully demonstrated steam heating to 650°C and energy recovery to steam at the 5 kWt level. 2. The ammonia system has a relatively low enthalpy of reaction combined with gas phase reactants. This is not a direct disadvantage since the reactants themselves are low cost. The challenge lies in storing the required volume of reactants cost effectively. Therefore, a second key goal was to show, through techno-economic analysis, that underground storage technologies can be used to store the energy-rich gas at a cost that is consistent with the SunShot cost goal. We have identified two promising technologies for gas storage: storage in salt caverns has an estimated cost of 1(USD)/kWht and storage in drilled shafts could be on the order of 7(USD)/kWht. Together these two options answer the technical challenge associated with storage of gas phase components. 3. While this project is primarily concerned with high-temperature heat recovery and methods to store the gaseous components, it is also important to consider the feasibility of the entire system. Consequently, an additional goal was to perform analysis to show the feasibility of integrating endothermic reactors within a tower receiver. A conceptual design of an ammonia dissociation receiver/reactor has been developed that fits into the same size cylindrical envelope as the molten salt receiver in SAM, and has the same design thermal capacity. The calculated thermal efficiency of this receiver is 94.6%. Thus, this investigation has established the technical feasibility of a surround field tower system using ammonia dissociation. With these challenges addressed, we proceeded to design a full-scale synthesis and heat recovery system. A model was developed and validated by comparison with our experimental data. A parametric study showed, among other things, the importance of using small tube diameters and spacing to enhance heat transfer. Multi-parameter optimization was used to find a design that minimizes the wall material volume. Finally, cost estimation shows that the ammonia system has good prospects of meeting the Sunshot 15(USD)/kWht target: estimated costs of the entire synthesis system for the 220 MWt plant with 6 hours of storage are 13(USD)/kWht using salt cavern storage and 18(USD)/kWht using shaft drilling. Costs per kWht are even lower with more hours of storage. With the established technology of ammonia synthesis as a starting point, the successes of the project have mitigated technical risks associated with high-temperature synthesis reaction, underground storage, and tower receiver design. Estimated costs are less than 15(USD)/kWht with salt cavern storage. It is now possible to map a time line to commercial deployment that is likely to be shorter and less risky than other thermochemical cycles under active investigation. UCLA has filed a patent that protects the new ideas developed during this project. Discussions are ongoing with potential investors with the aim of partnering for further work. As well as immediate improvements and extra work with the existing experimental system, a key goal is to extend it to a small solar-driven project at an early opportunity.

14 SOLAR ENERGY↗

Evaluation of Computational Method of High Reynolds Number Slurry Flow for Caverns Backfilling

The abandonment of salt caverns used for brining or product storage poses a significant environmental and economic risk. Risk mitigation can in part be addressed by the process of backfilling which can improve the cavern geomechanical stability and reduce the risk of fluid loss to the environment. This study evaluates a currently available computational tool, Barracuda, to simulate such processes as slurry flow at high Reynolds number with high particle loading. Using Barracuda software, a parametric sequence of simulations evaluated slurry flow at Reynolds number up to 15000 and loading up to 25%. Limitations come into the long time required to run these simulations due in particular to the mesh size requirement at the jet nozzle. This study has found that slurry-jet width and centerline velocities are functions of Reynolds number and volume fraction. The solid phase was found to spread less than the water-phase with a spreading rate smaller than 1, dependent on the volume fraction. Particle size distribution does seem to have a large influence on the jet flow development. This study constitutes a first step to understand the behavior of highly loaded slurries and their ultimate application to cavern backfilling.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Leveraging automotive fuel cells can supply zero-emission peak power in the near-term

An increasingly decarbonized yet resilient power grid requires the corresponding build-out of dispatchable zero-emission resources to supply peak power. However, there is a recognized dearth of solutions which can serve multi-day peak demand events both cost-effectively and with near-term deployability. Here, we find that pairing low-cost automotive fuel cells with hydrogen storage in salt caverns can serve as a peaker plant at less than 500 US$/kW at present, a fraction of the cost of conventional fossil fuel-fired peakers. We demonstrate the peaker’s value for long duration storage by comparing it with pumped hydro and assessing its profitability within Texas’ energy-only market region. Although deployment of these peakers is constrained by the presence of salt caverns, we show that a number of sites in the United States and Europe are endowed with suitable salt formations, while utilizing hydrogen storage in pressurized containers could form a location-agnostic peak power solution.

25 ENERGY STORAGE↗

Capacity Assessment and Cost Analysis of Geologic Storage of Hydrogen: A Case Study in Intermountain-West Region USA

Hydrogen is an integral component of the current energy transition roadmap to decarbonize the economy and create an environmentally-sustainable future. However, surface storage options (e.g., tanks) do not provide the required capacity or durability to deploy a regional or nationwide hydrogen economy. In this study, we have analyzed the techno-economic feasibility of the geologic storage of hydrogen in depleted gas reservoirs, salt caverns, and saline aquifers in the Intermountain-West (I-WEST) region. We have identified the most favorable candidate sites for hydrogen storage and estimated the volumetric storage capacity. Our results show that the geologic storage of hydrogen can provide at least 72% of total energy consumption of the I-WEST region in 2020. We also calculated the capital and levelized costs of each storage option. We found that a depleted gas reservoir is the most cost-effective candidate among the three geologic storage options. Interestingly, the cushion gas type plays a significant role in the storage cost when we consider hydrogen storage in saline aquifers. The levelized costs of hydrogen storage in depleted gas reservoirs, salt caverns, and saline aquifers with large-scale storage capacity are approximately $\$$1.15, $\$$2.50, and $\$$3.27 per kg of H 2 , respectively. Here, this work provides essential guidance for the geologic hydrogen storage in the I-WEST region.

08 HYDROGEN↗