Pore scale investigation of hydrogen injection in sandstone via X-ray micro-tomography

The challenge associated with large-scale hydrogen storage is a pertinent one to achieve a hydrogen economy. The increasing global demand for clean and green energy is the driving force to propel such an economy. Furthermore, hydrogen is also considered an alternative energy source compared to fossil fuel as a clean energy alternative. Hydrogen geo-storage in a deep saline aquifer, depleted oil and gas reservoirs can resolve this challenge. We assess the potential of a saline aquifer in a sandstone formation to store hydrogen through first-of-its-kind x-ray micro-computed tomography miniature coreflood experiments. The investigation shows that ~65% of the sandstone's pore volume can be occupied by hydrogen when injected at a slow rate. Residual saturation of hydrogen upon brine injection can be ~41%.     

The effect of clay on initial and residual saturation of hydrogen in clay-rich sandstone formation: Implications for underground hydrogen storage

Understanding wettability in rock-brine-hydrogen systems is essential for dependable predictions of capillary/residual trapping in clay-rich sandstone formations. Despite being the most used technique, wettability assessment based on contact angle measurements is confronted with inherent uncertainties that limit its reliability. In contrast, core flooding techniques provide a more direct and realistic picture of wettability and its time evolution. Nuclear Magnetic Resonance (NMR) allows us to evaluate the initial and residual hydrogen saturations and distribution along the core specimen. It is a fast, reliable, and effective way of inferring the impact of wettability on hydrogen migration, and residual trapping in prospective geo-storage rock formations. Recent publications have reported the evaluation of wettability in a brine-hydrogen-rock system where the rock is a clean sandstone (no clays). Here we evaluate the impact of the presence of clays in a sandstone, which has not been reported yet. NMR monitoring was employed to characterize the initial and residual hydrogen saturations in the Bandera Grey (BG) sandstone. To investigate the impact of clay minerals on hydrogen saturation, same rock sample was characterized in its natural state, and after heating it to 700 °C for 12 h in an air environment to burn off clay minerals, During the NMR core flooding experiments, ten pore volumes (PVs) were injected/withdrawn during the drainage/imbibition cycles at a fluid injection rate of 2 mL/min under room temperature and 1000 psi confining pressure. Due to the hydrophilicity of quartz and clay, the tested BG sandstone (clay-rich sandstone) shows a significant residual/trapped saturation (～3.5% can be reproduce); therefore, clay-rich sandstone may not be ideal for hydrogen storage unless cushion gas is used.The results show that initial and residual hydrogen saturations were slightly changed after firing (from 16% to 18% for initial and from 14% to 13% for residual). This also suggests that the wettability of the BG sandstone-brine-hydrogen system is slightly impacted by clay content and type. We also observed that clay firing at 700 °C has little effect on the porosity and gas permeability of the BG sandstone. Moreover, X-ray powder diffraction (XRD) results showed that quartz content increases from 68.1% to 76.2%, Kaolinite transformed into illite and clinochlore disappeared. The disappearance of chlorite after firing suggests that it is transformed into another clay type.     

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.     

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%.     

Sensitivity of ferromagnetic resonance in PdCo alloyed films to hydrogen gas

In this work we study the ferromagnetic resonance (FMR) response of Co_xPd_1-x alloy samples with varying compositions (x = 0.65, 0.39, 0.24 and 0.14). We find significant differences in the FMR response of the samples to the presence of hydrogen gas in the samples’ environment. Without any special processing, the films with x = 0.39 and 0.24 demonstrated behaviour which is promising for application in hydrogen gas sensing. Using FMR in the alloy thin films, we were able to measure hydrogen gas concentration in a very broad range - from 0.05% to 100%.     

An overview of the IAEA HEEP software and international programmes on hydrogen production using nuclear energy

Recent years have witnessed an increasing interest in hydrogen production using nuclear energy. A number of countries are actively exploring the option of nuclear hydrogen production and have established concrete roadmaps for near and far term achievements. This paper presents a summary of information presented at some IAEA technical meetings on status of nuclear hydrogen production including ongoing related R&D activities in Member States. The paper highlights, in addition, the IAEA hydrogen economic evaluation programme (HEEP) which has recently been developed under agreement and in collaboration with the BHABHA Atomic Research Centre (BARC). HEEP software can be used to perform the economics of the most promising processes for hydrogen production. Current processes considered in HEEP are: high and low temperature electrolysis, thermo-chemical processes including S-I process, conventional electrolysis and steam reforming. HEEP software is also suitable for comparative between nuclear and fossil energy sources, and for solely hydrogen production or cogeneration with electricity. The HEEP modelling includes various aspects of hydrogen economy including storage, transport, and distribution with options to eliminate or include specific details as required by the users.     

Detailed investigation of ion exchange in ball-milled LiH + MgB2 system using ultra-high field nuclear magnetic resonance spectroscopy

The present study with the detailed ¹H-⁶Li cross polarization NMR analysis confirms the formation of a ternary compound, (Mg_1−xLi_2x)B₂, during ball milling of LiH + (1/2)MgB₂ at room temperature. The ⁶Li sites in (Mg_1−xLi_2x)B₂ exhibit spinning sidebands (SSBs), whereas the ⁶Li sites in LiH do not. The SSBs and the very short spin-lattice relaxation time manifested by the ⁶Li sites in (Mg_1−xLi_2x)B₂ indicate that the Li ions in (Mg_1−xLi_2x)B₂ are located between the layered boron structures and close to Mg ions. The formation of (Mg_1−xLi_2x)B₂ explains the previous observation that the LiH + (1/2)MgB₂ mixture ball-milled effectively has a greatly enhanced hydriding kinetics at temperatures below the melting point of LiBH₄.     

Measurement of hydrogen dispersion in rock cores using benchtop NMR

Electrolysis followed by underground hydrogen storage (UHS) in both salt caverns and depleted oil and gas reservoirs is widely considered as a potential option to overcome fluctuations in energy provision from intermittent renewable sources. Particularly in the case of depleted oil and gas reservoirs, a denser layer of cushion gas (N₂, CH₄ or CO₂) can be accommodated in these storage volumes to allow for sufficient system pressure control as hydrogen is periodically injected and extracted. These gases/fluids are however fully soluble with hydrogen and thus with sufficient mixing can undesirably contaminate the extracted hydrogen product. Fluid mixing in a porous medium is typically characterized by a dispersion coefficient (K_L), which is hence a critical input parameter into reservoir simulations of underground hydrogen storage. Such dispersion data is however not readily available in the literature for hydrogen at relevant storage conditions. Here we have developed and demonstrated novel methodology for the measurement of K_L between hydrogen and nitrogen in a Berea sandstone at 50 bar as a function of displacement velocity (0.007–0.722 mm/s). This leverages off previous work quantifying K_L between carbon dioxide and methane in rock cores relevant to enhanced gas recovery (EGR). This used infrared (IR) spectroscopy to differentiate the two fluids, hydrogen is however IR invisible. Hence the required time-resolved quantification of hydrogen concentration emerging from the rock core is uniquely performed here using bench-top nuclear magnetic resonance (NMR). The resultant hydrogen-nitrogen dispersion data as a function of displacement velocity allows for the determination of dispersivity (α = 0.31 mm). This intrinsic rock property compares favorably with previous CO₂ dispersion measurements on similar sandstones, hence validating our methodology to some extent. In addition, at very low velocities, determination of the rock core tortuosity (τ, another intrinsic rock property) produces a value (τ = 10.9) that is similar to that measurement independently using pulsed field gradient NMR methods (τ = 11.3).     

Determination of bidirectional permeability of proton exchange membranes using a H nuclear magnetic resonance technique

Bidirectional permeability of proton exchange membranes was measured using a ¹H nuclear magnetic resonance (NMR) technique based on the assignment of characteristic peaks and derivation of a relationship between the peak areas and the concentrations of methanol, water and D₂O. The concentration variations of the liquids determined with NMR spectra showed that both methanol and the water transports were affected by the thickness and the chemical structure of membranes. Molar ratios of methanol to water diffused through membranes elucidated that chemical structures of membranes had a strong influence on the methanol transport, compared to thickness. Reverse-direction diffusion behaviors of membranes, back-diffusions, were also appraised with the D₂O amounts. The amounts of back-diffusions were much less than those of the water transported from the opposite direction, which is the first report on the direct measurements of back-diffusions. The results suggest that ¹H NMR technique can evaluate bidirectional transports of proton exchange membranes.     

The potential of hydrogen production from high and low-temperature electrolysis methods using solar and nuclear energy sources: the transition to a hydrogen economy in Brazil

Brazil has great potential for diversification and decarbonization of its energy matrix, with the insertion of a clean and renewable energy source such as hydrogen. This paper seeks to evaluate the surplus energy potential of solar and nuclear plants installed in the country for the production of green and purple hydrogen using high and low temperature electrolysis methods. Based on official reports and databases of energy production and demand, the results indicated that the total potential of surplus solar energy is equal to 4.29E+07 (kWh.d^?1). Further, the total potential of electricity production from the hydrogen obtained through surplus solar energy was equivalent to1.87E+07 (kWh.d^?1); and the total cost of producing solar hydrogen is equal to 1.07E+03 (USD.kWh^?1). In conclusion, the study contributed to demonstrate the pathways to the establishment of strategies that assist the transition to a hydrogen economy in Brazil.     

Investigation of water and CO2 (carbon dioxide) flooding using micro-CT (micro-computed tomography) images of Berea sandstone core using finite element simulations

The present study reports a numerical investigation of water and CO₂ (carbon dioxide) flooding at the pore scale of a porous medium. We use high resolution micro-computed tomography (micro-CT) images of Berea sandstone core to obtain the pore geometry. The numerical solution used for the simulation was carried out by a finite element based software package. Level Set method is used to determine the position of the interface between two immiscible fluids when oil is displaced by water and CO₂, respectively. The present formulation is validated against single-phase flow through the porous structure. It is found that, fluid flow inside the pore space takes place through preferential inlet and outlet pores. For two-phase flow, it is observed that continuous displacement of oil occurs during water flooding but CO₂ is able to displace oil at certain locations in the pores. Also, the separation of flow front is observed in the case of CO₂ flooding. A quantitative comparison of the results obtained in two types of flooding simulations suggests that water displaces a higher volume of oil than CO₂ in the time period for which the simulations are performed.     

Comprehensive assessment of system efficiency and competitiveness of nuclear power plants in combination with hydrogen complex

The strategy provides construction and commissioning of a number of new nuclear power units for the development of nuclear energy in Russia. The share of nuclear power plants increase in the energy systems of Russia is predicted from 19 to 22% in the future, up to 2050. Nuclear power plants planned to involve in the primary frequency control at the same time. All these circumstances exacerbate the problem of providing nuclear power plants with a basic electrical load in the night period, including during the daily period. The energy strategy of Russia provides for the production of hydrogen by low-carbon methods, one of which is water electrolysis using nuclear power. Hydrogen production is included in the development strategy of the at operating Russian NPPs. Hydrogen production planned at the Kola NPP by water electrolysis. Thus, the article provides a rationale for the effectiveness of combining nuclear power plants with a hydrogen complex based on the production of hydrogen by electrolysis of water. The effectiveness substantiated of the new principle of combination with overheating of the working fluid steam turbine cycle of the NPP taking into account the safety of handling hydrogen. A new system proposed for the combustion of hydrogen in oxygen, which makes it possible to overheat the working fluid of the NPP steam turbine cycle with undissociated steam, which significantly reduces the content of unreacted hydrogen in the working fluid flow. In addition, a system was developed and proposed for removing unreacted hydrogen and oxygen from the steam phase of the working fluid of the NPP steam turbine cycle. Thermodynamic and technical-economic new estimates are presented and analyzed of the efficiency of combining NPP with a hydrogen complex.     

Experimental investigations of fracturing fluid flowback and retention under forced imbibition in fossil hydrogen energy development of tight oil based on nuclear magnetic resonance

Experimental works have proved that imbibition under forced pressure (FP, the difference between hydraulic fluid pressure and original pore pressure) has a positive effect on fossil hydrogen energy development in tight oil reservoir. However, the knowledge of the influence of imbibition under forced pressure (forced imbibition, FI) on fracturing fluid flowback and water retention is still limited. In this paper, experiments were designed and conducted to reveal the mechanism of fracturing fluid flowback and water retention under imbibition effect in tight sandstones. As a comparison, unconsolidated sandstones were also investigated in this study. Core samples were divided into two categories: the imbibition ones (treated by imbibition) and the filtration ones (treated by displacement), in accordance with the real oil-water distribution after well shut-in. An imbibition core and a filtration core were stitched together to conduct a flowback experiment. During the experiment, fluid distribution in different pore sizes was monitored continuously by using a low-field nuclear magnetic resonance device. Results show that the flowback recovery in tight sandstones is much lower than that in unconsolidated sandstones due to the difference of pore structure. Meanwhile, forced imbibition leads to higher oil recovery than spontaneous imbibition (SI) in tight sandstones since forced pressure enhances water imbibition. The water imbibed into small-macro and macro pores contributes the major flowback recovery, but the imbibed water in micro pores is rather difficult to displace and finally retains in these pores during the flowback process. Overall, forced imbibition not only enhances oil recovery but also increases water retention, explaining the mechanism of well productivity increase by using the shut-in method in the field. This study can help to clarify the influence of forced imbibition on fracturing fluid flowback and enhancement of fossil hydrogen development, and further provide guidance for flowback designs.     

Analysis of nitrogen oxide emissions from modern vehicles using hydrogen or other natural and synthetic fuels in combustion chamber

The paper presents a calculated analysis of the equilibrium emission of nitrogen oxides on the exhaust of carburetor and diesel internal combustion engines. The temperature of fuel oxidation is assumed to be 1,400 °C while the pressure for carburetor and diesel engines is assumed to be 60 atm and 80 atm respectively. The studies have been carried out for natural and synthetic fuels such as hydrogen, ethanol, methanol, petroleum, diesel fuel and methane at the excess air coefficient corresponding to the fuel oxidation temperature of 1,400 °C. In the paper, the method for calculating the equilibrium composition based on the equilibrium constant and mass conservation equations has been applied. It is shown that with an increase in pressure from 1 atm to 60 atm for carburetor engines and up to 80 atm for diesel engines, the reaction of nitrogen dioxide formation may shift towards an increase in NO₂. The formation of NO may be not affected by the increase in pressure by virtue of the fact that the reaction proceeds without changes in the amount. It has been determined that NO is the major atmospheric pollutant. However, it would be advisable to use more extensively the fuels characterized by the lowest output of nitrogen dioxide (methane and methanol), since nitrogen dioxide (NO₂) related to the 2nd hazard class is appeared to be the most dangerous to humans. It has been revealed that the reduction in oxidation temperature using hydrogen as a fuel for electrochemical current generators may allow reducing nitrogen oxide emissions by more than an order of magnitude as compared to the best results for ICE.     

In-situ nitrogen doping in carbon nanotubes using a fluidized bed reactor and hydrogen storage behavior of the doped nanotubes

Nitrogen atoms were successfully doped into the lattice of carbon nanotubes (hereafter called N-CNT) by chemical vapor deposition in a fluidized bed reactor using a solid precursor Imidazole. X-ray Photoelectron Spectroscopy estimated that ～5.4 atom% of nitrogen was doped in the synthesized CNTs. The successful formation of N-CNTs was also confirmed by Fourier Transforms Infrared Spectroscopy. Transmission electron microscopy revealed the morphological features of N-CNTs and their changes with temperature. The use of fluidized bed resulted in the formation of uniform nature of N-CNTs. In-depth studies of influence of nitrogen doping in CNTs for hydrogen storage was studied by comparing with bare CNTs, also synthesized by a the same fluidized bed reactor. The hydrogen storage capacity for N-CNTs (0.8 wt.%) was enhanced significantly at very low temperature (163 K), compared to bare CNTs (0.28 wt.%).