Hydrogen tightness evaluation in bedded salt rock cavern: A case study of Jintan,China

Hydrogen is regarded as one of the most important energy sources for the future. Safe, large-scale storage of hydrogen contributes to the commercial development of the hydrogen industry. Use of bedded salt caverns for natural gas storage in China provides a new option for underground hydrogen storage (UHS). In this study, the physical properties of multicomponent gases in UHS and salt rock are reviewed and discussed, along with the flow of hydrogen in the surrounding salt rock. Mathematical models of the two-phase multicomponent flow of the gas–brine system in the UHS were established. A numerical model of a simplified elliptical salt cavern was built to simulate the migration of the gas–brine system in the UHS. The hydrogen tightness of the UHS was evaluated through simulation with different storage strategies, salt rock and interlayer permeabilities, and gas components. The results indicate that: (1) Cyclic injection and withdrawal facilitate hydrogen leakage, which is accelerated by increasing the frequency. (2) The huff-n-puff of hydrogen gas in the injection and withdrawal cycles forces the gas into pore space and enhances the relative permeability of the gas phase. The migration of hydrogen and brine weakens the hydrogen tightness. Brine saturation is an important index for evaluating the hydrogen tightness of UHS. (3) The leakage rate of UHS increases with an increase in the permeability of the salt rock and interlayer and the total thickness of the interlayers. The average permeability K_wa weighted by the thickness of layers for the bedded salt formation is proposed to integrate three variables to facilitate field application of the simulation results. The critical K_wa is less than 3.02 × 10⁻¹⁷ m² if the recommended annual hydrogen leakage rate is less than 1%. (4) The difference between hydrogen and other gas species is another important factor in the leakage rate and should be considered. This study provides theoretical guidance for evaluating the feasibility of UHS in salt caverns and site selection in China.     

Hydrogen wettability of clays: Implications for underground hydrogen storage

This study investigates the ability of hydrogen (H₂) to wet clay surfaces in the presence of brine, with implications for underground hydrogen storage in clay-containing reservoirs. Rather than measuring contact angles directly with hydrogen gas, a suite of other gases (carbon dioxide (CO₂), argon (Ar), nitrogen (N₂), and helium (He)) were employed in the gas-brine-clay system under storage conditions (moderate temperature (333 K) and high pressures (5, 10, 15, and 20 MPa)), characteristic of a subsurface environment with a shallow geothermal gradient. By virtue of analogies to H₂ and empirical correlations, wettabilities of hydrogen on three clay surfaces were mathematically derived and interpreted. The three clays were kaolinite, illite, and montmorillonite and represent 1:1, 2:1 non-expansive, and 2:1 expansive clay groups, respectively. All clays showed water-wetting behaviour with contact angles below 40° under all experimental set-ups. It follows that the presence of clays in the reservoir (or caprock) is conducive to capillary and/or residual trapping of the gas. Another positive inference is that any tested gas, particularly nitrogen, is suitable as cushion gas to maintain formation pressure during hydrogen storage because they all turned out to be more gas-wetting than hydrogen on the clay surfaces; this allows easier displacement and/or retrieval of hydrogen during injection/production. One downside of the predominant water wettability of the clays is the upstaged role of biogeochemical reactions at the wetted brine-clay/silicate interface and their potential to affect porosity and permeability. Water-wetting decreased from kaolinite as most water-wetting clay over illite to montmorillonite as most hydrogen-wetting clay. Their wetting behaviour is consistent with molecular dynamic modelling that establishes that the accessible basal plane of kaolinite's octahedral sheet is highly hydrophilic and enables strong hydrogen bonds whereas the same octahedral sheet in illite and montmorillonite is not accessible to the brine, rendering these clays less water-wetting.     

Review on using the depleted gas reservoirs for the underground H2 storage: A case study in Niigata prefecture,Japan

Underground hydrogen storage (UHS) in depleted hydrocarbon reservoirs is a prospective choice to store enormous volumes of hydrogen (H₂). However, these subsurface formations must be able not only to store H₂ in an effective and secure manner, but also to produce the required volumes of H₂ upon demand. This paper first reviews the critical parameters to be considered for geological analysis and reservoir engineering evaluation of UHS. The formation depth, the interactions of rock-brine-H₂, the caprock (seal) and well integrity are the most prominent parameters as far as UHS is concerned. In respect of these critical parameters, tentative H₂ storage is screened from the existing gas storage fields in the Niigata prefecture of Japan, and it was revealed that the Sekihara gas field is a suitable candidate for UHS with a storage capacity of 2.06 × 10⁸ m³ and a depth of 1000 m. Then, a series of numerical simulations utilizing CMG software was conducted to find out the extent to which critical parameters alter H₂ storage capacity. The results demonstrated that this field, with a recovery factor of 82.7% in the sixth cycle of production is a prospective site for H₂ storage.     

Measurements and predictive models of high-pressure H2 solubility in brine (H2O+NaCl) for underground hydrogen storage application

In the context of Underground Hydrogen Storage (UHS), the stored gas is in direct contact with brine (residual brine from the cavern or formation water of deep aquifers). Therefore, knowledge of the phase equilibria (solubility of hydrogen in brine and water content in the hydrogen-rich phase) in the geological reservoir is necessary for the study of hydrogen mobility and reactivity, as well as the control, monitoring and optimization of the storage. The absence of measured data of high-pressure H₂ solubility in brine has recently led scientists to develop predictive models or to generate pseudo-data using molecular simulation. However, experimental measurements are needed for model evaluation and validation. In this work, an experimental apparatus based on the “static-analytic” method developed and used in our previous work for the measurement of gas solubility in brine was used. New solubility data of H₂ in H₂O+NaCl were measured more or less under the geological conditions of the storage, at temperatures between 323 and 373 K, NaCl molalities between 0 and 5m, and pressures up to 230 bar. These data were used to parameterize and evaluate three models (Geochemical, SW, and e-PR-CPA models) tested in this work. Solubility and water content tables were generated by the e-PR-CPA model, as well as a simple formulation (Setschenow-type relationship) for quick and accurate calculations (in the fitting range) of H₂ solubility in water and brine was proposed. Finally, the developed models estimate very well the water content in hydrogen-rich phase and capture and calculate precisely the salting-out effect on H₂ solubility.     

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.     

Salinity,temperature and pressure effect on hydrogen wettability of carbonate rocks

Hydrogen had been injected into the geologic formations, and the geologic formation wettability would influence the hydrogen storage. Hydrogen wettability of sandstone reservoirs (quartz), mica and other rocks have been explored in the previous study. However, the research on hydrogen wettability of carbonate rocks was lacked. In this study, we studied the carbonate rock wettability alteration when exposed to the hydrogen environments. Salinity, temperature and pressure effect on H₂/carbonate rock/brine wettability were explored. When the solutions ions concentration increased, the advancing/receding contact angle would increase, and divalent ions could make the contact angle higher than monovalent ion, which was because ions could compress the electric double layer. The carbonate rock powder in brine showed negative charge, and the zeta potential increased with higher ions concentration. When temperature increased and the pressure decreased, the contact angle would decrease, which was related to the H₂ gas density and molecular interactions.     

Hydrogen wettability in carbonate reservoirs: Implication for underground hydrogen storage from geochemical perspective

Hydrogen has been considered as a promising renewable source to replace fossil fuels to meet energy demand and achieve net-zero carbon emission target. Underground hydrogen storage attracts more interest as it shows potential to store hydrogen at large-scale safely and economically. Meanwhile, wettability is one of the most important formation parameters which can affect hydrogen injection rate, reproduction efficiency and storage capacity. However, current knowledge is still very limited on how fluid-rock interactions affect formation wettability at in-situ conditions. In this study, we thus performed geochemical modelling to interpret our previous brine contact angle measurements of H₂-brine-calcite system. The calcite surface potential at various temperatures, pressures and salinities was calculated to predict disjoining pressure. Moreover, the surface species concentrations of calcite and organic stearic acid were estimated to characterize calcite-organic acid electrostatic attractions and thus hydrogen wettability. The results of the study showed that increasing temperature increases the disjoining pressure on calcite surface, which intensifies the repulsion force of H₂ against calcite and increases the hydrophilicity. Increasing salinity decreases the disjoining pressure, leading to more H₂-wet and contact angle increment. Besides, increasing stearic acid concentration remarkably strengthens the adhesion force between calcite and organic acid, which leads to more hydrophobic and H₂-wet. In general, the results from geochemical modelling are consistent with experimental observations that decreasing temperature and increasing salinity and organic acid concentration increase water contact angle. This work also demonstrates the importance of involving geochemical modelling on H₂ wettability assessment during underground hydrogen storage.     

Flow process and energy release of hydrogen in fluorine

Hydrogen is a clean energy source and fluorine is a strong oxidant. The chemical reaction between the two will make the utilization of hydrogen energy significantly improved, which is a new way to develop and utilize hydrogen energy. In this study, the ANSYS Fluent software is used to solve the reaction kinetics process, which has great advantages in the simulation of combustion and chemical reaction flow, and Computational fluid dynamics (CFD) adopts numerical methods to solve the Navier-Stokes (N–S) partial differential equation. Here, the CFD code ANSYS Fluent is performed to calculate the two-dimensional compressible reaction flow, therefore, we use the methods to explore the flow process and reaction energy release of hydrogen in fluorine and a new ways of hydrogen energy development is explored. The initial stage of the explosion for F₂ filling into H₂/air in the pipeline is volatile. Chemical reactions for F₂ filling into H₂/air in the pipeline interact with flows for F₂ filling into H₂/air in the pipeline. Energy release of hydrogen in fluorine depends on the flow and mixing process. When F₂ is filled into a premixed H₂/air in the pipeline with a length of 0.9 m and a diameter of 0.1 m, the explosion pressure reaches 0.307MPa–0.408 MPa and the explosion temperature reaches 2698 K–3107 K. The explosion reaction is very rapid and only takes about 40 ms to reach equilibrium. The higher the incident pressure at the pressure inlet, the smaller the peak pressure and temperature are, when the reaction reaches equilibrium.     

Interfacial tension and contact angle measurements for hydrogen-methane mixtures/brine/oil-wet rocks at reservoir conditions

In this study, we measured the interfacial tensions (IFTs) of brine/hydrogen-methane (H₂–CH₄) mixtures. We also measured the static contact angles of H₂–CH₄ mixtures in contact with brine and oil-wet sandstone and limestone rocks at reservoir conditions. The measurements were conducted using pendant drop and rising/captive bubble techniques. The techniques were first validated for pure gas/brine IFT and contact angle systems. Then, the impacts of temperature and H₂–CH₄ mixture fraction in contact with oil-wet rocks were investigated systematically. IFT values of H₂–CH₄ mixture/brine diminished with increasing temperature and decreasing hydrogen fraction. It is revealed that, under the studied conditions, H₂–CH₄ mixtures exhibit comparable weakly water-wet behavior on oil-wet sandstone and limestone rocks with contact angles ranged within [52.42°-71.1°] independent of temperature. The results also indicated that IFT of H₂–CH₄ mixture/brine decreases with increased temperature and methane fraction. Finally, the mechanisms accountable for the observed rock-fluid interaction behaviors at different conditions were discussed.     

Separation dynamics of hydrogen isotope gas in mesoporous and microporous adsorbent beds at 77 K: SBA-15 and zeolites 5A,Y, 10X

The separation of a hydrogen isotope mixture on porous materials was studied using equilibrium and breakthrough experiments. The adsorption equilibria of H₂ and D₂ on SBA-15 with mesopores and molecular sieves 5A, Y, and 10X with micropores were measured at 77 K using the volumetric method. The breakthrough experiments of a H₂ and D₂ mixture in each adsorbent bed were carried out at various conditions of flow rate and pressure. The equilibrium ratio of D₂ to H₂ on mesoporous molecular sieves was larger than the ratio on microporous molecular sieves (SBA-15 > 10X > Y > 5A), but the difference among the adsorbents decreased with increases in pressure. On the other hand, the order of breakthrough separation factor showed the opposite result (SBA-15 < 10X < Y < 5A). The breakthrough separation factors for zeolite 10X was approximately equal to the equilibrium ratio of D₂ to H₂ at the corresponding partial pressures, whereas zeolites 5A and Y showed higher breakthrough separation factors than their equilibrium ratios. In SBA-15, the separation factors from breakthrough results were even smaller than the corresponding equilibrium ratio. In the microporous adsorbent with a limited pore size (zeolite 5A in the study), the diffusion mechanism contributed to the separation of hydrogen isotope gases as one of key factors.     

Evaluation of catalytic subcritical water gasification of food waste for hydrogen production: Effect of process conditions and different types of catalyst loading

Food waste is a kind of wet bio-waste which has been a challenge for the ecological environment and disposal. In this paper, hydrogen production from subcritical water gasification (SbWG) of food waste with and without catalyst loading was systematically investigated. The effects of reaction temperature (300–360 °C), residence time (30–90 min), food waste concentration (10–30 wt%) and catalysts (Ni/γ-Al₂O₃, Ni/ZrO₂, NaOH, KOH, and FeCl₃) were studied within a pressure range of 10.5–20 MPa. The optimal process condition for SbWG of food waste without catalysts loading was determined to be 360 °C and 90 min with 10 wt% food waste. The liquid products and hydrochar were characterized by TOC, TGA/DTG, and SEM. The TOC concentration of liquid products decreased vastly with increasing reaction temperature. The highest H₂ yield (1.88 mol/kg), H₂ mole fraction (35.01%), and H₂ selectivity (53.86%) were achieved at 360 °C for 90 min with 5 wt% loading of KOH. It can be concluded that the performance of the catalysts for improving hydrogen production in SbWG of food waste was in the following order: KOH > NaOH > Ni/γ-Al₂O₃ > Ni/ZrO₂ > FeCl₃. The catalytic SbWG can be a potential alternative for energy conversion of food waste and hydrogen production.     

Evaluating the hydrogen storage potential of shut down oil and gas fields along the Norwegian continental shelf

The underground hydrogen storage (UHS) capacities of shut down oil and gas (O&G) fields along the Norwegian continental shelf (NCS) are evaluated based on the publicly available geological and hydrocarbon production data. Thermodynamic equilibrium and geochemical models are used to describe contamination of hydrogen, loss of hydrogen and changes in the mineralogy. The contamination spectrum of black oil fields and retrograde gas fields are remarkably similar. Geochemical models suggest limited reactive mineral phases and meter-scale hydrogen diffusion into the caprock. However, geochemical reactions between residual oil, reservoir brine, host rock and hydrogen are not yet studied in detail. For 23 shut down O&G fields, a theoretical maximum UHS capacity of ca. 642 TWh is estimated. We conclude with Frigg, Nordost Frigg, and Odin as the best-suited shut down fields for UHS, having a maximum UHS capacity of ca. 414 TWh. The estimates require verification by site-specific dynamic reservoir models.     

Electrochemical hydrogen discharge of high-strength low alloy steel for high-pressure gaseous hydrogen storage tank: Effect of discharging temperature

Hydrogen discharge technique of high-strength low alloy steel for high-pressure gaseous hydrogen storage tank was developed by using an electrochemical technique. The electrochemical hydrogen discharge of high-strength low alloy steel were investigated in a deaerated borate buffer solution (0.3 M H₃BO₃ + 0.074 M N₂B₄O₇, pH = 8.4). By applying a potential of +630 mV_SCE which is higher than the hydrogen equilibrium potentials and lower than the pitting potential, the oxidation reaction of metal (Fe → Fe²⁺ + 2e⁻) is limited and oxidation reaction of the hydrogen (H₂ + 2OH⁻ → 2H₂O + 2e⁻) was induced simultaneously. Thus, the pre-charged hydrogen inside the specimen was eliminated effectively without any damage to the specimen. The electrochemical hydrogen discharge method was performed at 25 °C, 50 °C and 75 °C. The efficiency of hydrogen discharge was accelerated with increasing temperature because the exchange current density of hydrogen is increased with temperature.     

Preliminary investigation on hydrogen-rich gas production by co-steam-reforming of biomass and crude glycerin

Hydrogen production from renewable biomass is of great interests. Co-steam-reforming of biomass and crude glycerin with the ratio of 1:1(w/w) was investigated in a fixed-bed gasifier aiming at improving biomass to hydrogen conversion, focusing on the effects of temperature, pressure, H₂O/C ratio and Ca/C ratio on producing gas composition. The results show that high temperature and low pressure favors hydrogen production. With temperature increasing from 650 to 825 °C, H₂ yield shows a linear increase from 0.053 mol/kg to 0.059 mol/kg. Both H₂ yield and its mole fraction increase obviously with the increasing H₂O/C ratio. No influence on gas production is found for Ca/C ratio > 1. The study reveals the optimum condition for producing hydrogen is: temperature of 700-750 °C, pressure of 0.1 MPa, H₂O/C ratio of 1.7-2.25 and Ca/C ratio of 1. Our experimental analysis shows co-steam-reforming of biomass and crude glycerin for hydrogen production is feasible and promising.     

Influence of capillary threshold pressure and injection well location on the dynamic CO2 and H2 storage capacity for the deep geological structure

The subject of this study is the analysis of influence of capillary threshold pressure and injection well location on the dynamic CO₂ and H₂ storage capacity for the Lower Jurassic reservoir of the Sierpc structure from central Poland. The results of injection modeling allowed us to compare the amount of CO₂ and H₂ that the considered structure can store safely over a given time interval. The modeling was performed using a single well for 30 different locations, considering that the minimum capillary pressure of the cap rock and the fracturing pressure should not be exceeded for each gas separately.Other values of capillary threshold pressure for CO₂ and H₂ significantly affect the amount of a given gas that can be injected into the reservoir. The structure under consideration can store approximately 1 Mt CO₂ in 31 years, while in the case of H₂ it is slightly above 4000 tons. The determined CO₂ storage capacity is limited; the structure seems to be more prospective for underground H₂ storage. The CO₂ and H₂ dynamic storage capacity maps are an important element of the analysis of the use of gas storage structures. A much higher fingering effect was observed for H₂ than for CO₂, which may affect the withdrawal of hydrogen. It is recommended to determine the optimum storage depth, particularly for hydrogen. The presented results, important for the assessment of the capacity of geological structures, also relate to the safety of use of CO₂ and H₂ underground storage space.     

Hydrogen production by glycerol steam reforming with in situ hydrogen separation: A thermodynamic investigation

Thermodynamic features of hydrogen production by glycerol steam reforming with in situ hydrogen extraction have been studied with the method of Gibbs free energy minimization. The effects of pressure (1–5 atm), temperature (600–1000 K), water to glycerol ratio (WGR, 3–12) and fraction of H₂ removal (f, 0–1) on the reforming reactions and carbon formation were investigated. The results suggest separation of hydrogen in situ can substantially enhance hydrogen production from glycerol steam reforming, as 7 mol (stoichiometric value) of hydrogen can be obtained even at 600 K due to the hydrogen extraction. It is demonstrated that atmospheric pressure and a WGR of 9 are suitable for hydrogen production and the optimum temperature for glycerol steam reforming with in situ hydrogen removal is between 825 and 875 K, 100 K lower than that achieved typically without hydrogen separation. Furthermore, the detrimental influence of increasing pressure in terms of hydrogen production becomes marginal above 800 K with a high fraction of H₂ removal (i.e., f = 0.99). High temperature and WGR are favorable to inhibit carbon production.     

Hydrate-based separation of the CO2 + H2 mixtures. Phase equilibria with isopropanol aqueous solutions and hydrogen solubility in CO2 hydrate

The gas hydrates' ability to preferentially bind one of the components of a gas mixture into a hydrate state makes it possible to consider hydrate-based technology as promising for the separation of gas mixtures. When a hydrate is obtained from a gas mixture, mixed hydrates with a complex composition inevitably occur. Issue of their composition determination stays apart. This a rather difficult task, which is complicated by the dissolution of small molecules such as hydrogen in the hydrate phase. This, in turn, impedes the analysis of the data obtained. In this work, the solubility of hydrogen in carbon dioxide hydrate in the range of 269.7–275.7 K and at partial H₂ pressure up to 4.5 MPa was experimentally determined. Hydrate composition was found to be CO₂·(0.01X)H₂·6.5H₂O at H₂ pressure of X MPa. The equilibrium conditions of hydrates formation in the systems of H₂O – CO₂ – H₂ and H₂O – 2-propanol – CO₂ – H₂ were also determined in a wide range of hydrogen concentrations. Hydrogen seems to be an indifferent diluent gas regarding CO₂ hydrate equilibrium pressure. The compositions of the equilibrium phases have been determined as well. It was shown that isopropanol does not form a double hydrate with СО₂, only sI СО₂ hydrate occurred in the studied systems. The obtained dependencies will be useful in analyzing the process of СО₂ + Н₂ gas mixtures separation by the hydrate-based method.     

Pore-scale imaging of hydrogen displacement and trapping in porous media

Hydrogen can act as an energy store to balance supply and demand in the renewable energy sector. Hydrogen storage in subsurface porous media could deliver high storage capacities but the volume of recoverable hydrogen is unknown. We imaged the displacement and capillary trapping of hydrogen by brine in a Clashach sandstone core at 2–7 MPa pore fluid pressure using X-ray computed microtomography. Hydrogen saturation obtained during drainage at capillary numbers of <10^?7 was ～50% of the pore volume and independent of the pore fluid pressure. Hydrogen recovery during secondary imbibition at a capillary number of 2.4 × 10^?6 systematically decreased with pressure, with 80%, 78% and 57% of the initial hydrogen recovered at 2, 5 and 7 MPa, respectively. Injection of brine at increasing capillary numbers up to 9.4 × 10^?6 increased hydrogen recovery. Based on these results, we recommend more shallow, lower pressure sites for future hydrogen storage operations in porous media.     

Characterization of an ammonia decomposition process by means of a multifunctional catalytic membrane reactor

Ammonia decomposition was studied in a multifunctional catalytic membrane reactor filled with Ruthenium catalyst and equipped with palladium-coated membranes. To characterize the system we measured NH₃ conversion, H₂ yield and its partial pressure, the internal and external temperatures of the reactor shell and the electric consumption under several NH₃ flow and pressure conditions. Experimental results showed that the combined effect of Ruthenium catalyst and palladium membranes allowed the reaction to reach the equilibrium in all the conditions we tested. At 450 °C the ammonia conversion resulted the most stationary, while at 7 bar the hydrogen yield was almost independent of both the ammonia flow and temperature. In addition, the experimental system used in this work showed high values of NH₃ conversion and H₂ permeation also without heating the ammonia tank and therefore renouncing to control the feeding gas pressure. When ultra-pure hydrogen is needed at a distal site, a reactor like this can be considered for in situ hydrogen production.     

Tuning hydrogen storage thermodynamic properties of ZrFe2 by partial substitution with rare earth element Y

ZrFe₂ delivers the advantages of high hydrogen storage capacity and easy activation, but its de-/hydriding pressure is too high for practical application. In this work, we alloyed ZrFe₂ with Y to obtain a single C15 Laves phase structure by the proper annealing process. The microstructure and hydrogen storage properties of Zr_1-xY_xFe₂ (x = 0.1–0.4) compounds were investigated. The results show that the cell volume increases and the dissociation pressure decreases with increasing Y content for the Zr–Y–Fe–H system. The Y alloying is beneficial for increasing hydrogen storage capacity despite the worsening plateau slope and hysteresis. The Zr_0·6Y_0·4Fe₂ exhibits the highest hydrogen absorption capacity of 1.77 wt%, while the Zr_0·8Y_0·2Fe₂ shows a dehydriding enthalpy of 25.06 kJ/mol H₂ and dehydriding entropy of 116.53 J/mol·K H₂, corresponding to the dissociation pressure of 59 atm at 298 K that is suitable for high-pressure hydrogen storage applications.