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 storage in Majiagou carbonate reservoir in China: Geochemical modelling on carbonate dissolution and hydrogen loss

Underground hydrogen storage (UHS) appears to be promising means for large-scale hydrogen storage. Carbonate reservoirs can play an important role in hydrogen storage in particular in Western China and Middle East region. However, little work has been done to address the potential risks and uncertainties associated with carbonate dissolution and hydrogen loss as a result of hydrogen-brine-carbonate geochemical reactions. We thus performed geochemical modelling to assess the potential of UHS in Majiagou carbonate formation, China. Kinetic models of the dissolution/precipitation of calcite, dolomite and quartz were developed to characterize hydrogen loss, mineral dissolution and water chemistry variations up to 500 years.The results show that the percentage of hydrogen loss due to fluid-rock interactions is only 6.6% for the first year, but could increase to 81.1% at the end of 500 years during UHS in Majiagou formation, indicating that carbonate reservoirs is suitable for hydrogen seasonal storage but may not be a good candidate for long-term storage. Meanwhile, totally 0.0646% of calcite would dissolve into formation brine over 500 years, bringing potential risks on caprock and wellbore stability and formation integrity. Besides, we observed a considerable amount of methane generated along with H₂-brine-carbonate interactions. Our works provide a framework to assess the hydrogen storage capacity of carbonate reservoirs using geochemical modelling, and can be also applied to other types of storage deposits.     

Impact of wettability on storage and recovery of hydrogen gas in the lesueur sandstone formation (Southwest hub project,Western Australia)

Geological storage has been proposed as a new technology to temporarily store significant amounts of hydrogen (H₂) gas in depleted gas reservoirs, underground salt caverns, or saline aquifers. Often, such subsurface reservoirs naturally contain trace amounts of organic acids, and these compounds can considerably alter the wettability of reservoir rocks, causing them to become less water-wet. We carried out Molecular Dynamics (MD) simulations of contact angles in a quartz-brine-H₂ system to evaluate wettability in realistic subsurface situations. MD simulations suggest that Humic acid makes quartz more hydrophobic, which can affect the overall behaviour of the storage reservoir. For the first time, this effect was experimentally investigated for a natural sandstone reservoir from the South West Hub Project, i.e., the Lesueur Sandstone (LS) formation. Multi-stage core flooding experiments were conducted on the same LS plug to investigate the impact of wettability alteration on initial and residual hydrogen saturation/trapping at depth. First, consecutive brine-H₂ drainage-imbibition cycles were carried out on the natural sample; the result indicated that the rock-brine-H₂ system was essentially water-wet. Then, the sample was aged in Humic acid with a molarity of 10⁻² M for 42 days at 5 °C and 0.1 MPa. The wettability of the storage system shifted toward a less water-wet state, i.e., more hydrophobic. As a result of Humic acid ageing, the initial hydrogen saturation reduced from 29% to 15%, and the residual hydrogen trapping reduced from 23% to 11%. This is attributed to a change induced in the capillary force (i.e., snap-off) controlled by wettability and pore size. In addition, the wettability change induced by Humic acid increased the hydrogen recovery rate from 20.7% to 26.7%.     

Thermodynamic characterization of H2-brine-shale wettability: Implications for hydrogen storage at subsurface

Large-scale underground hydrogen storage (UHS) appears to play an important role in the hydrogen economy supply chain, hereby supporting the energy transition to net-zero carbon emission. To understand the movement of hydrogen plume at subsurface, hydrogen wettability of storage rocks has been recently investigated from the contact angles rock-H₂-brine systems. However, hydrogen wettability of shale formations, which determines the sealing capacity of the caprock, has not been examined in detail. In this study, semi-empirical correlations were used to compute the equilibrium contact angles of H₂/brine on five shale samples with various total organic content (TOC) at various pressures (5–20 MPa) and at 343 K. The H₂ column height that can be securely trapped by the shale and capillary pressures were calculated. The shale's H₂ sealing capacity decreased with increasing pressure, increasing depth and TOC values. The CO₂/brine equilibrium contact angles were generally higher than H₂/brine equilibrium, suggesting that CO₂ could be used as favorable cushion gas to maintain formation pressure during UHS. The utmost height of H₂ that can be safely trapped by shale 3 (with TOC of 23.4 wt%) reduced from 8950 to 8750 M while that of shale 5 (with TOC of 0.081 wt%) reduced slightly from 9100 M to 9050 M as the pressure was increased from 5 to 20 MPa. The capillary entry pressure decreased with increasing depth and shale TOC, implying that the capillary trapping effect, as well as the over-pressure required to move brines from the pores by hydrogen displacement, reduces with increasing depth, and shale TOC. However, the shales remained at strongly water-wet conditions, having an equilibrium contact angles of not more than 17° at highest pressure and TOC. The study suggests that the increasing contact angles with increasing pressure and shale TOC, as well as decreasing column height and capillary pressure with increasing depth for H₂-brine-shale systems might not be sufficient to exert significant influence on structural trapping capacities of shale caprocks due to low densities of hydrogen.     

Geochemical reactions-induced hydrogen loss during underground hydrogen storage in sandstone reservoirs

Underground hydrogen storage (UHS) appears to be an important means as a large-scale and long-term energy storage solution. A primary concern of UHS is the in-situ geochemical reactions-induced hydrogen loss. In this context, we performed geochemical modelling to examine the hydrogen loss associated with hydrogen dissolution and fluid-rock interactions using PHREEQC (Version 3) as a function of temperature and pressure. We also performed geochemical modelling with kinetics to investigate the potential hydrogen loss in two commercial gas storage reservoirs (Tubridgi and Mondarra) in Western Australia against the reservoir mineralogy, fluid properties, depth and temperature.Our results show that increasing pressure and temperature only slightly increases hydrogen solubility in brines without minerals. Increasing salinity slightly decreases the solubility of hydrogen in brines. The saturated hydrogen aqueous solution almost does not react with silicate and clay minerals, which is favorable for underground hydrogen storage in quartz-rich sandstone reservoirs. However, unlike silicate and clay minerals, carbonates like calcite triggers up to 9.5% hydrogen loss due to calcite dissolution induced hydrogen dissociation process. Kinetic simulations show that Tubridgi only leads to 0.72% of hydrogen loss, and Mondarra causes 2.76% of hydrogen loss as a result of reservoir calcite dissolution and hydrogen dissociation in brines in 30-year time. Nearly over 87% of calcite cement from Mondarra may be dissolved in 30-year, suggesting potential risks associated with wellbore stability. In conclusion, geochemical reactions-induced hydrogen loss would be minor for UHS in porous media, and we argue that deep calcite-free reservoirs together with calcite-free caprocks would be preferable for underground hydrogen storage.     

A unified phase equilibrium model for hydrogen solubility and solution density

For the transition to a clean and sustainable energy production from renewable sources like solar or wind power, large and secure storage of energy is required to compensate for the intermittent nature of these sources. Hydrogen could be a suitable energy carrier and hydrogen geological storage could provide the large capacities required. During storage hydrogen will be brought in contact with the formation fluids present, resulting in dissolution and possibly inducing geochemical reactions. Therefore in this work an accurate, consistent and reliable hydrogen solubility model is established, which allows to calculate the hydrogen solubility in the formation fluid and the corresponding variation of fluid density. The model accounts for system pressure, temperature and formation fluid salinity as well as the molar fraction, fugacity coefficient, Henry's constant, Poynting factor and activity coefficient of hydrogen. In the range of typical hydrogen geological storage conditions of 273–373 K, 1–50 MPa and 0–5 mol/kg NaCl this model can reproduce all available experimental data and predict hydrogen solubility in the formation fluid and the formation fluid density accurately. The model can predict hydrogen solubility within a maximum relative error of 5% for pure water and 15% for brines within the salinity range considered, which is in the range of uncertainty of measurement data. For realistic hydrogen gas geological storage, the model is extended to represent also H₂-N₂ or H₂-CH₄ mixed gas systems as well as mixed electrolyte solutions containing Na, K, Ca, Mg, Cl or SO₄ and combinations of those. Model derivation, model calculations and implementation as well as an application example are presented to demonstrate the applicability of the developed methods and the model.     

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.     

Development of a novel simulator for modelling underground hydrogen and gas mixture storage

Underground hydrogen storage can store grid-scale energy for balancing both short-term and long-term inter-seasonal supply and demand. However, there is no numerical simulator which is dedicated to the design and optimisation of such energy storage technology at grid scale. This study develops novel simulation capabilities for GPSFLOW (General Purpose Subsurface Flow Simulator) for modelling grid-scale hydrogen and gas mixture (e.g., H₂–CO₂–CH₄–N₂) storage in cavern, deep saline aquifers and depleted gas fields.The accuracy of GPSFLOW is verified by comparisons against the National Institute of Standard and Technology (NIST) online thermophysical database and reported lab experiments, over a range of temperatures from 20 to 200 °C and pressure up to 1000 bar. The simulator is benchmarked against an existing model for modelling pure H₂ storage in a synthetic aquifer. Several underground hydrogen storage scenarios including H₂ storage in a synthetic salt cavern, H₂ injection into a CH₄-saturated aquifer experiment, and hydrogen storage in a depleted gas field using CO₂ as a cushion gas are used to test the GPSFLOW's modelling capability. The results show that GPSFLOW offers a robust numerical tool to model underground hydrogen storage and gas mixture at grid scale on multiple parallel computing platforms.     

Initial and residual trapping of hydrogen and nitrogen in Fontainebleau sandstone using nuclear magnetic resonance core flooding

Hydrogen is among a few promising energy carriers of the future mainly due to its zero-emission combustion nature. It also plays an important role in the transition from fossil fuel to renewable. Hydrogen technology is relatively immature and serious knowledge gaps do exist in its production, transport, storage, and utilization. Although the economical generation of hydrogen to the scale required for such transition is still the biggest technical and environmental challenge, unlocking the large-scale but safe storage is similarly important. It is difficult to store hydrogen in solid and liquid states and storing it in the gaseous phase requires a huge volume which is just available in subsurface porous media. Sandstone is the most abundant and favourable medium for such storage as carbonate rock might not be suitable due to potential geochemical reactions.It is well established in the literature that interaction of the host rock-fluid and injected gas plays a crucial role in fluid flow, residual trapping, withdrawal, and more generally storing capacity. Such data for the hydrogen system is extremely rare and are generally limited to contact angle measurements, while being not representative of the reality of rock-brine-hydrogen interaction(s). Therefore, we have conducted, for the first time, a series of core flooding experiments using Nuclear Magnetic Resonance (NMR) to monitor hydrogen (H₂) and Nitrogen (N₂) gas saturations during the drainage and imbibition stages under pressure and temperature that represent shallow reservoirs. To avoid any geochemical reaction during the test, we selected a clean sandstone core plug of 99.8% quartz (Fontainebleau with a gas porosity of 9.7% and a permeability of 190 mD).Results show significantly low initial and residual H₂ saturations in comparison with N₂, regardless of whether the injection flow rate or capillary number were the same or not. For instance, when the same injection flow rate was used, H₂ saturation during primary drainage was 4% and it was <2% after imbibition. On other hand, N₂ saturation during the primary drainage was 26% and it was 17% after imbibition. However, when the same capillary number of H₂ was utilised for the N₂ experiment, the N₂ saturation values were ～15% for initial gas saturation and 8% for residual gas saturation. Our results promisingly support the idea of hydrogen underground storage; however, we should emphasise that more sandstone rocks of different clay mineralogy should be investigated before reaching a conclusive outcome.     

Role of methane as a cushion gas for hydrogen storage in depleted gas reservoirs

Depleted natural gas reservoirs play an important role as a viable option for large-scale hydrogen storage and production. However, its deployment depends on the accurate knowledge of the cushion gas (such as CH₄, CO₂, and N₂) compositions, which are key components affecting the rock-fluid interfacial phenomenon. In addition, there are currently few reported studies on rock/brine/gas-mixture wettability and gas-mixture/brine surface tension representing this type of reservoir. Hence, we report the feasibility of using CH₄ as a cushion gas (in the presence of CO₂ and N₂) for H₂ storage at various pressures (500 up to 3000 psi), temperatures (30 up to 70) ^oC, and salinities (2 up to 20) wt.% using drop shape analyzer equipment. Contact angle (CA) and surface tension (ST) experiments were extensively conducted for the different gas mixtures (H₂–CH₄–CO₂–N₂) to establish relevant data for H₂ storage in depleted gas reservoirs.Our result indicates that unless when the rock's initial wetting state is altered, the studied gas-mixture compositions (Test case 1: 80% H₂ – 10% CH₄ – 5% CO₂ – 5% N₂; case 2: 70% H₂ – 20% CH₄ – 5% CO₂ – 5% N₂; case 3: 60% H₂ – 30% CH₄ – 5% CO₂ – 5% N₂; case 4: 50% H₂ – 40% CH₄ – 5% CO₂ – 5% N₂; case 5: 40% H₂ – 50% CH₄ – 5% CO₂ – 5% N₂; case 6: 30% H₂ – 60% CH₄ – 5% CO₂ – 5% N₂; and case 7: 20% H₂ – 70% CH₄ – 5% CO₂ – 5% N₂) will exhibit comparable wettability behavior as the CAs ranged between [20 to 41°] irrespective of the reservoir pressure, temperature, and salinity. ST decreases with increasing temperature and linearly with increasing pressure. ST for each gas mixture increased with salinity. ST decreases systematically with increasing CH₄ fraction (at any given salinity, temperature, and pressure) with the highest observed in Test case 1 and the lowest in Test case 7 compositions. Test cases 3 and 4 with H₂ (50–60%) and CH₄ (30–40%) fractions was selected as the optimal gas mixture based on CA and ST for H₂ storage and withdrawal. The study's findings offer precise and useful input data for the reservoir-scale simulation used in geo-storage optimization in depleted natural gas reservoirs.     

Investigation of porous silicon thin films for electrochemical hydrogen storage

In this study, nanoporous silicon (PS) layers have been elaborated and used for hydrogen storage. The effect of the thickness, porosity and specific surface area of porous silicon on the amount of hydrogen chemically bound to the nanoporous silicon structures is studied by Infrared spectroscopy (FTIR), cyclic voltammetry (CV), contact angle and capacitance –voltage measurements. The electrochemical characterization and hydrogen storage were carried out in a three-electrode cell, using sulfuric acid 3 M H₂SO₄ as electrolyte by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatic charge/discharge. The results indicate the presence of two oxidation peaks at 0.2 V and 0.4 V on the anodic side corresponding to hydrogen desorption and a reduction peak at −0.2 V on the cathodic side corresponding to the sorption of hydrogen. Moreover, the EIS studies performed on PS electrode in 3 M H₂SO₄ show that the hodograph contains a semicircle at high frequency region and a line in the lower frequency zone. An equivalent circuit has been proposed; the values of the equivalent circuit elements corresponding to the experimental impedance spectra have been determined and discussed. Finally, the highest hydrogen storage in PS was 86 mAh/g. This storage capacity decreases by only 7% of the initial capacity value, after 40 cycles.     

A framework for assessing economics of blue hydrogen production from steam methane reforming using carbon capture storage & utilisation

Hydrogen (H₂) generation using Steam Methane Reforming (SMR) is at present the most economical and preferred pathway for commercial H₂ generation. This process, however, emits a considerable amount of CO₂, ultimately negating the benefit of using H₂ as a clean industrial feedstock and energy carrier. That has prompted growing interest in enabling CO₂ capture from SMR for either storage or utilisation and producing zero-emission “blue H₂”. In this paper, we propose a spatial techno-economic framework for assessing blue hydrogen production SMR hubs with carbon capture, utilisation and storage (CCUS), using Australia as a case study. Australia offers a unique opportunity for developing such ‘blue H₂’ hubs given its extensive natural gas resources, availability of known carbon storage reservoirs and an ambitious government target to produce clean/zero-emission H₂ at the cost of <A$2 kg^?1 by 2030. Our results highlight that the H₂ production costs are unsurprisingly dominated by natural gas, with the additional capital requirement of carbon capture and storage (CCS) also playing a critical role. These outcomes are especially pertinent for eastern Australian states, as they are experiencing high natural gas costs and would generally require extensive CO₂ transport and storage infrastructure to tap potential storage reservoirs, ultimately resulting in a higher cost of producing H₂ (>A$2.7 kg_H2^?1). On the other hand, Western Australia offers lower gas pricing and relatively lesser storage costs, which would lead to more economically favourable hydrogen production (<A$2.2 kg_H2^?1). We further explore the possibility of utilising the emissions captured at blue SMR hubs by converting them into formic acid through CO₂ electroreduction, yielding revenue that will decrease the cost of blue H₂ and reduce the reliance on CO₂ storage. Our analysis reveals that formic acid production utilising a 10 MW CO₂ electrolyser can potentially reduce H₂ production costs by between 4 and 9%. Further cost reduction is possible by scaling the CO₂ electrolyser capacity to convert a larger portion of the emissions captured, albeit at the cost of higher capital investment, electricity consumption and saturating the market for formic acid. Thus, carbon utilisation for a range of products with high market demand represents a more promising approach to replacing the need for costly carbon storage. Overall, our modelling framework can be adapted for global application, particularly for regions interested in generating blue H₂ and extended to include other CO₂ utilisation opportunities and evaluate other hydrogen production technologies.     

Different effects of temperature on supramolecular protein and non-protein materials in hydrogen storage

The storage of large quantities of hydrogen at ambient temperature is a key factor in establishing a hydrogen-based economy. One strategy for hydrogen storage is to exploit the interaction between H₂ and a solid material by physisorption of hydrogen on porous materials. However, physisorption materials containing MOF, porous carbons, zeolites, clathrates, and synthesized organic polymers physisorb only about 1 wt% of H₂ at ambient temperature. One approach to solving this problem is to prepare new classes of physisorption materials which exhibits a mechanism different from the reported materials in hydrogen storage. Here we report the synthesis of apo cross-linked ferritin supramolecules by disulfide bonds, and their holo form. Unlike non-protein adsorbents, the hydrogen storage capacity of these protein materials increases as a function of temperature over the range of 20–40 °C. The holo supramolecules enable the adsorption of hydrogen up to 3.51 wt% at 40 °C and 40 bar H₂. In contrast, non-protein physisorption materials such as activated carbon and nano Fe₂O₃ marginally adsorb hydrogen, and, as reported, their ability to adsorb hydrogen decreases with increasing temperature under the same experimental condition. These results demonstrate that protein materials have a unique hydrogen storage mechanism which offers new opportunities in exploration of physisorption materials at ambient temperature.     

Design of cluster structure units with large surface areas for high-capacity hydrogen storage: In the case of Si12C12H24

Using density functional theory, we designed novel cluster structure units with large surface areas for hydrogen storage through the surface functionalization of a stable Si₁₂C₁₂H₂₄ nanocage with CONH₂ organic molecules and Li atoms. Two structures, namely, Si₁₂C₁₂H₁₂(CONHLi)₁₂ and Si₁₂C₁₂H₁₂(CONLi₂)₁₂, are proposed. The structures are stable at room temperature and show suitable hydrogen adsorption energies. Modification can enlarge the surface area of the two structures compared with the original cluster. In addition, the O and N anions participate in the adsorption of H₂ molecules in addition to the Li cations. The average hydrogen binding energy for Si₁₂C₁₂H₁₂(CONHLi)₁₂·82H₂ is 0.135 eV/H₂ and the average hydrogen binding energy for Si₁₂C₁₂H₁₂(CONLi₂)₁₂·84H₂ is 0.134 eV/H₂ when these cluster structure units reach their maximum H₂ uptake capacity. The gravimetric hydrogen percentages are 13.18 and 12.60 wt%, respectively. With such a structural unit, a suitable linker allows the assembly of metal organic framework-like porous materials that display satisfactory hydrogen storage properties at room temperature.     

Glycerol conversion in the experimental study of catalytic hydrolysis of triglycerides for fatty acids production using Ni or Pd on Al2O3 or SiO2

In many reactions to produce biodiesel the glycerol represents 10 wt% of the total products therefore it is important to find an adequate destination of such byproduct. The catalytic hydrolysis of triglycerides is another way to produce biodiesel from fatty raw materials. This work shows the catalytic hydrolysis of triglycerides (soybean oil and tallow) with nickel (NiO) or palladium (PdO) catalysts supported on Al₂O₃ or SiO₂. The results showed the direct conversion of in situ generated glycerol into hydrogen (H₂) and carbon dioxide (CO₂). The glycerol conversion was evaluated through the capacity to hydrogenate the unsaturated fatty acids leading to the formation of stearic acid (saturated compound). The catalyst, temperature and time were varied and evaluated in the experiments utilizing the two different kinds of raw materials (beef tallow and soybean oil). Selectivity and statistical planning studies were performed to optimize the formation of stearic acid as it is linked to the hydrogenation of unsaturated compounds by hydrogen generated from the glycerol liquid reforming.     

Clean hydrogen generation and storage strategies via CO2 utilization into chemicals and fuels: A review

Hydrogen becomes one of the most clean energy sources. The major issues on hydrogen are lack of practical clean and high‐temperature processes and possible practical storage of clean hydrogen. An energy intensive of clean hydrogen storage via chemical and liquid fuel production route is the current demand. This article reviewed the most recent research for hydrogen (H₂) production by using several methods, such as thermochemical process, thermal decomposition, biological approaches, electrolysis, and photocatalytic method. H₂ storage types, including physical and chemical approaches, were also reviewed. The produced H₂ was stored as valuable chemicals and fuels via CO₂ hydrogenation reaction. Reactor designs are the illustrated number of design ranging from the fixed bed to the continuous stirred tank reactor. Catalyst type, catalytic system, and the related mechanism of CO₂ hydrogenation reaction to form alcohol, alkanes, and carboxylic acid were also discussed in detail.     

Estimation of system-level hydrogen storage for metal-organic frameworks with high volumetric storage density

Metal organic framework (MOF) materials have emerged as the adsorbent materials with the highest H₂ storage densities on both a volumetric and gravimetric basis. While measurements of hydrogen storage at the material level (primarily at 77 K) have been published for hundreds of MOFs, estimates of the system-level hydrogen storage capacity are not readily available. In this study, hydrogen storage capacities are estimated at the system-level for MOFs with the highest demonstrated volumetric and gravimetric H₂ storage densities. System estimates are based on a single tank cryo-adsorbent system that utilizes a type-1 tank, multi-layer vacuum insulation, liquid N₂ cooling channels, in-tank heat exchanger, and a packed MOF powder inside the tank. It is found that with this powder-based system configuration, MOFs with ultra-high gravimetric surface areas and hydrogen adsorption amounts do not necessarily provide correspondingly high volumetric or gravimetric storage capacities at the system-level. Meanwhile, attributes such as powder packing efficiency and system cool-down temperature are shown to have a large impact on the system capacity. These results should shed light on the material properties that must to be optimized, as well as highlight the important design challenges for cryo-adsorbent hydrogen storage systems.     

Impacts of the subsurface storage of natural gas and hydrogen mixtures

The subsurface storage of hydrogen (H₂) provides a potential solution for load-balancing of the intermittent electricity production from renewable energy sources. In such technical concept, surplus electricity is used to power electrolyzers that produce H₂, which is then stored in subsurface formations to be used at times when renewable electricity is not available. Blending H₂ with natural gas (NG) for injection into depleted gas/oil reservoirs, which are already used for NG storage, is considered a good option due to the lower initial capital cost and investment needed, and potential lower operating costs. In this study, the potential impact of storing a mixture of H₂ and NG in an existing NG storage field was investigated. Relevant reservoir, caprock and cement samples from a NG storage formation in California were characterized with respect to their permeability, porosity, surface area, mineralogy and other structural characteristics, before and after undergoing 3-month incubation experiments with H₂/NG gas mixtures at relevant temperature and pressure conditions. The results indicated relatively small changes in porosity and mineralogy due to incubation. However, the observed changes in permeability were more dramatic. In addition, polymeric materials, similar to those used in NG storage operations were also incubated, and their dimensions were measured before and after incubation. These measurements indicated swelling due to the exposure to H₂. However, direct evidence of geochemical reactions involving H₂ was not observed.     

A porous 3d-4f heterometallic metal–organic framework for hydrogen storage

A heterometallic metal–organic framework, {[Ce(oda)₃Zn_1.5(H₂O)₃]·0.75H₂O}_n (1, H₂oda = oxydiacetic acid), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction analysis reveals that compound 1 belongs to hexagonal crystal system with space group P6/mcc and exhibits 3D porous framework. The hydrogen adsorption experiments suggest that 1 possesses reversible hydrogen storage capacity, up to 1.34 wt.% at 77 K and 0.86 wt.% at 298 K, respectively.     

The effect of various acids treatment on the purification and electrochemical hydrogen storage of multi-walled carbon nanotubes

The effects of HCl, HNO₃, H₂SO₄ and HF acids on the purification and the electrochemical hydrogen storage of multi-walled carbon nanotubes (MWCNTs) were studied. The MWCNTs were synthesized on Fe–Ni catalyst by thermal chemical vapor deposition method. The X-ray diffraction and thermal gravimetric analysis results indicated that the MWCNTs purified by HF acid had the highest impurities as compared with the other acids. The N₂ adsorption results at 77 K indicated that all the samples were mainly mesoporous and the purified MWCNTs by HF acid had the highest surface area as compared with the other acids. The hydrogen storage capacities of the purified MWCNTs by the following acids were in ascending order as: H₂SO₄, HCl, HNO₃ and HF. It was found that the 1–2 nm micropores in the MWCNTs are very important for hydrogen storage. Further, the presences of catalyst and defective sites in MWCNTs influence the hydrogen storage capacity.