Large-scale storage of hydrogen in salt caverns for carbon footprint reduction

This article presents a geomechanical appraisal of green hydrogen (H₂) storage in salt caverns opened by solution mining as a technical contribution to carbon footprint reduction. The location of the salt cavern is speculative, within possible limits to be found in the salt deposits in the Gulf of Mexico of the USA, as the aim is to demonstrate the technical feasibility of the concept. It presents the conceptual design of the wells used for the solution mining of the caverns and the operation cycle of injection and withdrawal of hydrogen. The contribution of the study presented stems from the methodology adopted in the simulation of the geomechanical structural behavior of the salt cavern and in its design for storing hydrogen, which has thermomechanical properties more complex than natural gas. The numerical simulation considers the nonlinear physical viscoelastic and elastoplastic phenomena, with different constitutive laws for representing the geomechanical behavior of geomaterials. The constitutive laws based on deformation mechanisms are used (multi-mechanisms of deformation – M.D.) to simulate the creep of the salt rock. The article also presents a protocol for sizing the caverns, considering more than 40 years of experience in the design of conventional and solution mining of rock salt. It presents the concept of admissible halite creep strain and safety factors necessary to establish a stress belt that avoids hydrogen leaks at all stages of cavern construction and hydrogen storage. Using this methodology, the authors found that the cavern studied (220 m in height and 95 m in diameter) can hold 11,968,000 kg of working hydrogen.     

Large-scale hydrogen energy storage in salt caverns

Large-scale energy storage methods can be used to meet energy demand fluctuations and to integrate electricity generation from intermittent renewable wind and solar energy farms into power grids. Pumped hydropower energy storage method is significantly used for grid electricity storage requirements. Alternatives are underground storage of compressed air and hydrogen gas in suitable geological formations. Underground storage of natural gas is widely used to meet both base and peak load demands of gas grids. Salt caverns for natural gas storage can also be suitable for underground compressed hydrogen gas energy storage. In this paper, large quantities underground gas storage methods and design aspects of salt caverns are investigated. A pre-evaluation is made for a salt cavern gas storage field in Turkey. It is concluded that a system of solar-hydrogen and natural gas can be utilised to meet future large-scale energy storage requirements.     

Assessment of the potential for underground hydrogen storage in bedded salt formation

Salt formations of an appropriate thickness and structure, common over the globe, are potential sites for leaching underground caverns in them for storage of various substances, including hydrogen. Underground hydrogen storage, considered as underground energy storage, requires, in first order, an assessment of the potential for underground storage of this gas at various scales: region, country, specific place.The article presents the results of the assessment of the underground hydrogen storage potential for a sample bedded salt formation in SW Poland. Geological structural and thickness maps provided the basis for the development of hydrogen storage capacity maps and maps of energy value and heating value. A detailed assessment of the hydrogen storage capacity was presented for the selected area, for a single cavern and for the cavern field; a map of the energy value of stored hydrogen has also been presented. The hydrogen storage potential of the salt caverns was related to the demand for electricity and heat. The results show the huge potential for hydrogen storage in salt caverns.     

Modeling hydrogen storage capacities,injection and withdrawal cycles in salt caverns: Introducing the GeoH2 salt storage and cycling app

Salt caverns have been used as hydrogen (H₂) storage solutions in four locations worldwide with refineries and the petrochemical industry relying on these supplies as strategic back-up. The viability of storing H₂ within salt caverns is advantageous given their large volumetric capacities, their flexible operation with large injection and withdrawal rates, and for being a proven technology for the underground storage of a wide variety of gases and liquids. However, to our knowledge, there are no open-source web-based software tools to assess the technical potential of salt caverns for H₂ storage. This work aims to fill that gap by introducing the GeoH₂ Salt Storage and Cycling App, a computer program that models H₂ storage capacities, and injection/withdrawal cycles in salt caverns.The GeoH₂ Salt Storage and Cycling App is a web-based thermodynamic simulator, which consists of the following modules: (a) H₂ physical properties, (b) volumetric, (c) production, (d) injection, and (e) cycling. The physical properties module provides the user with the main thermodynamic, transport, and thermal properties of H₂. The volumetric module allows the user to estimate H₂ storage capacities in salt caverns. The production and the injection modules simulate the withdrawal and the injection of H₂, respectively. Finally, the cycling module models sequential withdrawal and injection processes.This study validates the results of the physical properties and the volumetric modules with real data. We validate the results of the production and the injection modules for synthetic cases using an open-source thermodynamic simulator.This work presents a novel tool suitable to assess the technical potential of H₂ storage, injection, withdrawal, and cycling operations in salt caverns. This application can also be used, along with subsurface geological information, as a first order screening tool to assess H₂ storage capacity at a regional or hub scale.     

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.     

Structural analysis of microbiomes from salt caverns used for underground gas storage

Salt caverns are a safe and well-proven reservoir for large-scale natural gas storage and hence, a potential hydrogen storage. Contrary to natural gas, hydrogen is a favorable energy source for many microorganisms. Microorganisms are ubiquitously abundant in the upper lithosphere and therefore expected to be present also in subsurface geological formations potentially selected for H₂ storage, such as salt caverns. Thus, future salt cavern hydrogen storage requires monitoring of the cavern microbiome, to evaluate and prevent unwanted microbial activities. In this study, we analyzed the microbiomes of brines sampled from the bottom of five German natural gas storage caverns. All brines were colonized by microorganisms in considerable cell numbers ranging from 2 × 10⁶ cells ml^?1 to 7 × 10⁶ cells ml^?1. The structures of the microbiomes were characterized by 16S rRNA gene amplicon sequencing. A core community detected in all five studied caverns consists of members affiliated to the Halobacteria, Halanaerobiales and Balneolales. Further, a phylotype belonging to the extremely halophilic, lithoautotrophic and sulfate-reducing genus Desulfovermiculus was found. Examination of microbial activity also included measuring hydrochemical parameters in order to assess the salt concentrations and the availability of nutrients and potential microbial carbon sources or metabolites. NaCl (4.7 M) was the main salt and sulfate (at average 40.8 mM) the main electron acceptor; methanol (up to 37.5 mM) and ethanol (up to 6.9 mM) were of anthropogenic origin and found in higher concentrations. Some putative microbial metabolites were found in lower concentrations (butyrate, ≤0.7 mM; formate, ≤0.08 mM; acetate, ≤0.5 mM; lactate, ≤0.06 mM); their potential relation to microbial activity is discussed. We propose a guideline for sampling and subsequent chemical and molecular biological analysis for future characterization of microbial communities of salt cavern brines.     

Hydrogen underground storage in Romania,potential directions of development,stakeholders and general aspects

Romania is a country with relatively good opportunities to manage the transition from the dependence on fossil energy to an energy industry based on renewable energy sources (RES), supported by hydrogen as an energy carrier. In order to ensure Romania's energy security in the next decades, it will be necessary to consider a fresh approach incorporating a global long-term perspective based on the latest trends in energy systems. The present article focuses on an analysis of the potential use of salt caverns for hydrogen underground storage in Romania. Romanian industry has a long technical and geological tradition in salt exploitation and therefore is believed to have the potential to use the salt structures also in the future for gas and specifically hydrogen underground storage. This paper indicates that more analysis works needs to be undertaken in order to value this potential, based on which macroeconomic decisions then can be taken. The present work examines the structures of today's energy system in Romania and features an analysis of Romania's current potential of hydrogen underground storage as well as, reports on the potential use of this hydrogen in chemical industry, the transport sector and salt industry in Romania and highlighting issues implied by a possible introduction and use of hydrogen and fuel cell technologies.     

A review on worldwide underground hydrogen storage operating and potential fields

Overreliance on fossil fuels for human energy needs, combined with the associated negative environmental consequences in terms of greenhouse gas emissions, has shifted our focus to renewable energy sources. Hydrogen has been identified by researchers as an energy source. Hydrogen is a non-carbon-based energy resource that has the potential to replace fossil fuels. This resource is seen as an alternative fuel since it may be produced using environmentally friendly methods.Hydrogen storage is a critical component of the hydrogen economy, particularly when hydrogen utilization on a large scale is required. This paper presents a review of worldwide underground operating and potential sites to provide a clear understanding of the current status of hydrogen storage in the world.The literature survey indicated that underground geological structures have been used to successfully store hydrogen. Some of the criteria used to select these sites for underground hydrogen storage include but are not limited to geological conditions, storage location, availability of brine, presence of insoluble impurities such as dolostone, limestone, or shale, and socio-economic characteristics.The key issues with the hydrogen storage in the subsurface geological structures include but are not limited to microbial, hydrogeological, hydrodynamics, geomechanics, and geochemical facilitated by injected hydrogen which significantly impact the success and operational efficiency of the projects.     

Hydrogen generation by electrolysis and storage in salt caverns: Potentials,economics and systems aspects with regard to the German energy transition

The Plan-DelyKaD project focused on an in-depth comparison of relevant electrolysis technologies, identified criteria for and selected most relevant salt cavern sites in Germany, studied business case potentials for applying hydrogen taken from storage to different end-users and engaged in identifying the future role of hydrogen from large scale storage in the German energy system. The focus of this paper is on the latter three topics above. The bottom-up investigation of most suitable salt cavern sites was used as input for a model-based analysis of microeconomic and macroeconomic aspects. The results identify dimensions and locations of possible hydrogen storages mostly in Northern Germany with ample potential to support the integration of fluctuating renewable electricity into the German power system. The microeconomic analysis demonstrates that the most promising early business case for hydrogen energy from large scale storage is its application as a fuel for the mobility sector. From a system perspective the analysis reveals that an optimized implementation of hydrogen generation via electrolysis and storage in salt caverns will have a positive impact on the power system in terms of reduced curtailments of wind power plants and lower residual peak loads.     

Modeling phase equilibrium of hydrogen and natural gas in brines: Application to storage in salt caverns

In this work, the e-PPC-SAFT equation of state has been parameterized to predict phase equilibrium of the system H₂ + CH₄ + H₂O + Na⁺Cl^? in conditions of temperature, pressure and salinities of interest for gas storage in salt caverns. The ions parameters have been adjusted to match salted water properties such as mean ionic coefficient activities, vapor pressures and molar densities. Furthermore, binary interaction parameters between hydrogen, methane, water, Na⁺ and Cl^? have been adjusted to match gas solubility data through Henry constant data. The validity ranges of this model are 0–200 °C for temperatures, 0–300 bar for pressures, and 0 to 8 mol_NaCl/kg_H2O for salinities. The e-PPC-SAFT equation of state has then been used to model gas storage in salt caverns. The performance of a storage of pure methane, pure hydrogen and a mixture methane + hydrogen have been compared. The simulations of the storage cycles show that integrating up to 20% of hydrogen in caverns does not have a major influence on temperature, pressure and water content compared to pure methane storage. They also allowed to estimate the thermodynamic properties of the system during the storage operations, like the water content in the gaseous phase. The developed model constitutes thus an interesting tool to help size surface installations and to operate caverns.     

Technical assessment of cryo-compressed hydrogen storage tank systems for automotive applications

On-board and off-board performance and cost of cryo-compressed hydrogen storage are assessed and compared to the targets for automotive applications. The on-board performance of the system and high-volume manufacturing cost were determined for liquid hydrogen refueling with a single-flow nozzle and a pump that delivers liquid H₂ to the insulated cryogenic tank capable of being pressurized to 272 atm. The off-board performance and cost of delivering liquid hydrogen were determined for two scenarios in which hydrogen is produced by central steam methane reforming (SMR) or by central electrolysis. The main conclusions are that the cryo-compressed storage system has the potential of meeting the ultimate target for system gravimetric capacity, mid-term target for system volumetric capacity, and the target for hydrogen loss during dormancy under certain conditions of minimum daily driving. However, the high-volume manufacturing cost and the fuel cost for the SMR hydrogen production scenario are, respectively, 2–4 and 1.6–2.4 times the current targets, and the well-to-tank efficiency is well short of the 60% target specified for off-board regenerable materials.     

Cavern integrity for underground hydrogen storage in the Brazilian pre-salt fields

Over the years, energy has depended on petroleum-based fuels. However, global warming and the energy crisis have drastically impacted the markets. It urges investing in renewable energy resources, such as hydrogen. Therefore, this work focuses on the hydrogen storage process in salt caverns, as these rocks have relevant properties, such as low permeability, relevant creep, and self-healing. A workflow for cavity integrity analysis is proposed. Hydrogen storage provokes variations in temperature and pressure inside the cavern. The gas thermodynamics is represented through a diabatic solution, which updates the gas pressure and temperature at each time step. The thermomechanical formulation is implemented into an in-house framework GeMA, which couples different physics. Four case studies are analyzed, and the discussions compared mechanical and thermomechanical models. Results demonstrate the importance of thermal effects, as temperature amplitudes may compromise rock integrity, for instance, inducing tensile stresses and affecting permeability.     

Lithium hydrazide as a potential compound for hydrogen storage

The Metal–N–H system for hydrogen storage has been developed in recent years and is considered to be a promising solution. Here we report a potential compound for hydrogen storage, LiNHNH₂, which is a white solid with 8.0 mass% theoretical hydrogen content and can be synthesized from anhydrous hydrazine and n-butyllithium in diethyl ether. The thermodynamic behaviours and hydrogen storage properties of this compound were firstly investigated and are discussed in this paper. We demonstrate the decomposition pathway of LiNHNH₂ and reveal that an alkali metal hydride such as LiH can significantly increase the hydrogen desorption from LiNHNH₂. Moreover, LiNHNH₂ can also be used for destabilizing other hydrogen storage systems owing to its instability.     

Technical assessment of compressed hydrogen storage tank systems for automotive applications

The performance and cost of compressed hydrogen storage tank systems has been assessed and compared to the U.S. Department of Energy (DOE) 2010, 2015, and ultimate targets for automotive applications. The on-board performance and high-volume manufacturing cost were determined for compressed hydrogen tanks with design pressures of 350 bar (∼5000 psi) and 700 bar (∼10,000 psi) capable of storing 5.6 kg of usable hydrogen. The off-board performance and cost of delivering compressed hydrogen was determined for hydrogen produced by central steam methane reforming (SMR). The main conclusions of the assessment are that the 350-bar compressed storage system has the potential to meet the 2010 and 2015 targets for system gravimetric capacity but will not likely meet any of the system targets for volumetric capacity or cost, given our base case assumptions. The 700-bar compressed storage system has the potential to meet only the 2010 target for system gravimetric capacity and is not likely to meet any of the system targets for volumetric capacity or cost, despite the fact that its volumetric capacity is much higher than that of the 350-bar system. Both the 350-bar and 700-bar systems come close to meeting the Well-to-Tank (WTT) efficiency target, but fall short by about 5%.     

The accuracy of hydrogen sorption measurements on potential storage materials

The most common gas phase hydrogen sorption measurement techniques used for the characterisation of potential hydrogen storage materials are the volumetric, or manometric, and gravimetric methods and temperature-programmed desorption (TPD), also known as thermal desorption spectroscopy (TDS). In this article previous work relating to the accuracy of these measurements, including some comparative studies, is reviewed, together with some relevant standards and related guidelines. The potential sources of error in hydrogen sorption measurements performed volumetrically and gravimetrically are also discussed, together with some of those related to TPD. The issues covered include sample degassing procedures, hydrogen compressibility, gas purity and differences in helium and hydrogen leak rates.     

In-situ hydrogen wettability characterisation for underground hydrogen storage

Hydrogen storage in subsurface aquifers or depleted gas reservoirs represents a viable long-term energy storage solution. There is currently a scarcity of subsurface petrophysical data for the hydrogen system. In this work, we determine the wettability and Interfacial Tension (IFT) of the hydrogen-brine-quartz system using captive bubble, pendant drop and in-situ 3D micro-Computed Tomography (CT) methods. Effective contact angles ranged between 29° and 39° for pressures 6.89–20.68 MPa and salinities from distilled water to 5000 ppm NaCl brine. In-situ methods, novel to hydrogen investigations, confirmed the water-wet system with the mean of the macroscopic and apparent contact angle distributions being 39.77° and 59.75° respectively. IFT decreased with increasing pressure in distilled water from 72.45 mN/m at 6.89 MPa to 69.43 mN/m at 20.68 MPa. No correlation was found between IFT and salinity for the 1000 ppm and 5000 ppm brines. Novel insights into hydrogen wetting in multiphase environments allow accurate predictions of relative permeability and capillary pressure curves for large scale simulations.     

Metal hydride hydrogen storage and compression systems for energy storage technologies

Along with a brief overview of literature data on energy storage technologies utilising hydrogen and metal hydrides, this article presents results of the related R&D activities carried out by the authors. The focus is put on proper selection of metal hydride materials on the basis of AB₅- and AB₂-type intermetallic compounds for hydrogen storage and compression applications, based on the analysis of PCT properties of the materials in systems with H₂ gas. The article also presents features of integrated energy storage systems utilising metal hydride hydrogen storage and compression, as well as their metal hydride based components developed at IPCP and HySA Systems.     

Preliminary assessment of underground hydrogen storage sites in Ontario,Canada

The replacement of coal-fired power plants with increasing proportions of renewable and nuclear energies in the province of Ontario highlights the need to balance seasonal energy demands. This can be achieved through power-to-gas technology, where excess energy is used to generate hydrogen gas through electrolysis, and the generation is coupled with underground hydrogen storage. This article presents a preliminary assessment regarding the potential for underground hydrogen storage in geological formations including salt and hard rock caverns, depleted oil and gas fields, and saline aquifers in Ontario, highlighting potential locations where future storage could be feasible. Southern Ontario presents many potential storage options, including Silurian bedded salts, depleted Ordovician natural gas reservoirs, saline aquifers in Cambrian sandstone and hard rock caverns in argillaceous limestones. Hard rock caverns in Precambrian crystalline rocks of the Canadian Shield are also discussed, in addition to the potential for the use of lined rock caverns. This work aims to provide a basis for further research regarding the appropriate location of underground hydrogen gas storage facilities in Ontario.     

Screening and ranking framework for underground hydrogen storage site selection in Poland

This paper proposes the use of the Analytic Hierarchy Process (AHP) in order to select the potential underground hydrogen storage sites. The preliminary selection and evaluation of hydrogen storage sites may be considered as a multi-criteria decision-making process. The use of a decision model based on 5 (for aquifers) or 6 geological criteria (in the case of salt and hydrocarbon deposits) has been proposed. A ranking of salt structures, aquifers, and crude oil and natural gas reservoirs, previously identified as the potential hydrogen storage sites in Poland, has been presented. The obtained results have confirmed that the AHP-based approach can be useful for preliminary selection of potential underground hydrogen storage sites. The proposed method enables one to objectively choose the most satisfactory decision, from the point of view of the adopted decision-making criteria, regarding the choice of the best structure.     

Li-decorated B2O as potential candidates for hydrogen storage: A DFT simulations study

Two-dimensional (2D) B₂O monolayer is considered as a potential hydrogen storage material owing to its lower mass density and high surface-to-volume ratio. The binding between H₂ molecules and B₂O monolayer proceeds through physisorption and the interaction is very weak, it is important to improve it through appropriate materials design. In this work, based on density functional theory (DFT) calculations, we have investigated the hydrogen storage properties of Lithium (Li) functionalized B₂O monolayer. The B₂O monolayer decorated by Li atoms can effectively improve the hydrogen storage capacity. It is found that each Li atom on B₂O monolayer can adsorb up to four H₂ molecules with a desirable average adsorption energy (E_ave) of 0.18 eV/H₂. In the case of fully loaded, forming B₃₂O₁₆Li₉H₇₂ compound, the hydrogen storage density is up to 9.8 wt%. Additionally, ab initio molecular dynamics (AIMD) calculations results show that Li-decorated B₂O monolayer has good reversible adsorption performance for H₂ molecules. Furthermore, the Bader charge and density of states (DOS) analysis demonstrate H₂ molecules are physically absorbed on the Li atoms via the electrostatic interactions. This study suggests that Li-decorated B₂O monolayer can be a promising hydrogen storage material.