Evaluating Diatomaceous Earth for Long-Term Use in Hydrogen Storage.

Efficient hydrogen storage is essential for its use as a sustainable energy carrier. Diatomaceous earth, a high-surface-area siliceous geomaterial, shows potential as a physisorption material for hydrogen storage. This study analyzes diatomaceous earth's long-term characteristics when subjected to high-pressure hydrogen injection. The diatomaceous earth was subjected to a hydrogen pressure of 1200 psi for a period of 80 days at room temperature. Neither notable morphological or mineralogical changes were observed. Nevertheless, there was a slight reduction in fine particles and a slight increase in larger particles. The Brunauer-Emmett-Teller (BET) surface area decreased slightly with a significant decrease in pore width. However, the hydrogen adsorption at 77 K temperature was increased significantly (45.5%) after the hydrogen storage test. Moreover, there was a delayed release of molecular water as the temperature increased. These changes suggest that a condensation reaction has occurred involving some of the opal-A silanol groups (Si-O-H), producing molecular water. Bonding through siloxane bridges (Si-O-Si) results in a significant decrease in pore width and increased hydrophobicity (i.e., the interaction between diatomaceous surface and H2 was increased), thereby enhancing hydrogen adsorption capacity. These findings indicate that diatomaceous earth holds promise as a material for hydrogen storage, with the potential for its hydrogen adsorption capacity to improve over time.

Physiochemical characterization of metal organic framework materials: A mini review.

Metal-organic frameworks (MOFs) are promising materials offering exceptional performance across a myriad of applications, attributable to their remarkable physicochemical properties such as regular porosity, crystalline structure, and tailored functional groups. Despite their potential, there is a lack of dedicated reviews that focus on key physicochemical characterizations of MOFs for the beginners and new researchers in the field. This review is written based on our expertise in the synthesis and characterization of MOFs, specifically to provide a right direction for the researcher who is a beginner in this area. In this way, experimental errors can be reduced, and wastage of time and chemicals can be avoided when new researchers conduct a study. In this article, this topic is critically analyzed, and findings and conclusions are presented. We reviewed three well-known XRD techniques, including PXRD, single crystal XRD, and SAXS, which were used for XRD analysis depending on the crystal size and the quality of crystal morphology. The TGA profile was an effective factor for evaluating the quality of the activation process and for ensuring the successful investigation for other characterizations. The BET and pore size were significantly affected by the activation process and selective benzene chain cross-linkers. FTIR is a prominent method that is used to investigate the functional groups on pore surfaces, and this method is successfully used to evaluate the activation process, characterize functionalized MOFs, and estimate their applications. The most significant methods of characterization include the X-ray diffraction, which is utilized for structural identification, and thermogravimetric analysis (TGA), which is used for exploring thermal decomposition. It is important to note that the thermal stability of MOFs is influenced by two main factors: the metal-ligand interaction and the type of functional groups attached to the organic ligand. The textural properties of the MOFs, on the other hand, can be scrutinized through nitrogen adsorption-desorption isotherms experiments at 77 K. However, for smaller pore size, the Argon adsorption-desorption isotherm at 87.3 K is preferred. Furthermore, the CO2 adsorption isotherm at 273 K can be used to measure ultra-micropore sizes and sizes lower than these, which cannot be measured by using the N2 adsorption-desorption isotherm at 77 K. The highest BET was observed in high-valence MOFs that are constructed based on the metal-oxo cluster, which has an excellent ability to control their textural properties. It was found that the synthesis procedure (including the choice of solvent, cross-linker, secondary metal, surface functional groups, and temperature), activation method, and pressure significantly impact the surface area of the MOF and, by extension, its structural integrity. Additionally, Fourier-transform infrared spectroscopy plays a crucial role in identifying active MOF functional groups. Understanding these physicochemical properties and utilizing relevant characterization techniques will enable more precise MOF selection for specific applications.

Strain measurement with multiplexed FBG sensor arrays: An experimental investigation.

In conventional rock mechanics testing, radial strain measuring devices are usually attached to the sample's surface at its mid-height. Although this procedure provides a realistic picture of the lateral deformation undergone by homogeneous samples, however, this assumption may not be accurate if the tested rock has significant heterogeneity. Fibre Bragg Grating (FBG) sensors have recently been introduced to various rock testing applications due to their versatility over conventional strain gauges and radial cantilevers. FBG sensors have small size, multiplexing capability, and immunity to magnetic interference. The main objective of this study is to explore and understand the capabilities of FBG sensing for strain measurement during rock mechanics testing, including under confining. To do so, two limestone plugs (Savonnières limestone) and one acrylic Poly Methyl Methacrylate (PMMA) plug, all of 38 mm diameter, were prepared. The acrylic plug and one of the Savonnières samples plugs were subjected to Unconfined Compressive Strength (UCS) tests. The second Savonnières plug was subjected to a hydrostatic test up to 20 MPa confining at room temperature. FBG sensors of 125 µm cladding diameter with ceramics (Ormocer) coating were glued on the surface of each sample, spreading across the entire sample's height. Strain gauges and cantilever-type radial gauges were used on the samples submitted to UCS for comparison. Results show that radial strain measurements and calculated elastic properties derived from the FBG readings for samples are comparable to readings from the conventional strain gauges and cantilever-type devices. Apparent bulk moduli based on volumetric strain computed from FBG radial strain readings during the hydrostatic test on the Savonnières sample was consistent with benchtop measurements conducted on the Savonnières sample and another plug extracted from the same parental block, as well as published literature data. Moreover, variations in the calculated elastic properties are interpreted as evidence that the FBG sensors detected heterogeneities in the samples' inner structure, which can be seen in the density profiles computed from x-ray CT images. Such observation confirms the potential of the presented FBG sensors configuration for 3D strain mapping in rock mechanics tests.

Influence of Henna Extracts on Static and Dynamic Adsorption of Sodium Dodecyl Sulfate and Residual Oil Recovery from Quartz Sand.

The application of surfactant flooding for enhanced oil recovery (EOR) promotes hydrocarbon recovery through reduction of oil-water interfacial tension and alteration of oil-wet rock wettability into the water-wet state. Unfortunately, surfactant depletion in porous media, due to surfactant molecule adsorption and retention, adversely affects oil recovery, thus increasing the cost of the surfactant flooding process. Chemical-based materials are normally used as inhibitors or sacrificial agents to minimize surfactant adsorption, but they are quite expensive and not environmentally friendly. Plant-based materials (henna extracts) are far more sustainable because they are obtained from natural sources. However, there is limited research on the application of henna extracts as inhibitors to reduce dynamic adsorption of the surfactant in porous media and improve oil recovery from such media. Thus, henna extracts were introduced as an eco-friendly and low-cost sacrificial agent for minimizing the static and dynamic adsorption of sodium dodecyl sulfate (SDS) onto quartz sand in this study. Results showed that the extent of surfactant adsorption was inversely proportional to the henna extract concentration, and the adsorption of the henna extract onto the quartz surface was a multilayer adsorption that followed the Freundlich isotherm model. Precisely, the henna extract adsorption on quartz sand is in the range of 3.12-4.48 mg/g (for static adsorption) and 5.49-6.73 mg/g (for dynamic adsorption), whereas the SDS adsorption on quartz sand was obtained as 2.11 and 4.79 mg/g at static and dynamic conditions, respectively. In the presence of 8000 mg/L henna extract, SDS static and dynamic adsorption was significantly reduced by 64 and 82%, respectively. At the same conditions, the residual oil recovery increased by 9.2% over normal surfactant flooding. The study suggests that the use of henna extracts as a sacrificial agent during SDS flooding could result in the reduction of static and dynamic adsorption of surfactant molecules on quartz sand, thus promoting hydrocarbon recovery from sandstone formations.

Influence of mineralogy and surfactant concentration on zeta potential in intact sandstone at high pressure.

HYPOTHESIS: Zeta-potential in the presence of brine has been studied for its application within hydrocarbon reservoirs. These studies have shown that sandstone's zeta-potential remains negatively charged, non-zero, and levels-off at salinities > 0.4 mol.dm-3, thus becoming independent of salinity when ionic strength is increased further. However, research conducted to date has not yet considered clay-rich (i.e. clay ≥ 5 wt%) sandstones. EXPERIMENTS: Firstly, streaming potential measurements were conducted on Bandera Gray sandstones (clay-rich and clay-poor) with 0.6 and 2 mol.dm-3 NaCl brine-saturated in pressurised environments (6.895 MPa overburden and 3.447 MPa back-pressure). Secondly, the streaming potential was determined at identical conditions for the effect of two surfactants, SDBS and CTAB, at concentrations of 0.01 and 0.1 wt% on the clay-poor sample in 0.6 mol.dm-3 NaCl. Thirdly, a comparison of zeta potentials determined via electrophoretic and streaming potential was conducted. Accordingly, this work analyses the effects of mineralogy and surfactants within this process. FINDINGS: Clay-rich sandstone possessed lower zeta-potentials than clay-poor sandstone at the two tested salinities. SDBS reduced zeta-potential and yielded higher repulsive forces rendering the rock more hydrophilic. Additionally, electrophoretic zeta-potentials were higher when compared to streaming zeta-potentials. Mechanisms for the observed phenomena are also provided.

Western Australia basalt-CO2-brine wettability at geo-storage conditions.

HYPOTHESIS: CO2 geo-storage is a technique, where millions of tonnes of CO2 are stored in underground formations every year for permanent immobilization to reduce greenhouse gas emissions. Among promising geo-storage formations, basalt is attracting keen interest from researchers and industry. However, the literature severely lacks information on the wetting behaviour of basaltic rocks at geo-storage conditions. EXPERIMENTS: To enable a more general statement of basalt-scCO2-brine contact angles, the wettability of a basalt from Western Australia was compared with a similar rock type from Iceland. This study reports the advancing and receding contact angles for a basalt-scCO2-brine system at pressures ranging from 0.1 to 20 MPa and temperatures of 298 and 323 K, respectively. Based on the experimental data, the amount of CO2, expressed by the column height, which could be safely trapped beneath the basalt was then calculated. FINDINGS: The basalt was initially water-wet but with increasing pressure, it was converted sequentially from a water-wet to an intermediate-wet and then finally into a completely CO2-wet template at pressures exceeding 15 MPa and 323 K. Under those experimental conditions, found in the field at depths below 1500 m, injected supercritical CO2 into a porous basalt reservoir is assumed to flow freely in lateral and vertical directions and is less impeded by capillary/residual trapping, potentially leading to CO2 leakage. It is suggested that the injection depth should not be chosen too deep to avoid increased free CO2 plume mobility. It is found from CO2 column height calculations that at 800 m depth (a minimum requirement to keep CO2 supercritical), the height of the CO2 column that can be safely trapped below the cap rock, was still 100 m but shrank to nil at ≥1500 m.

Effect of humic acid on CO2-wettability in sandstone formation.

HYPOTHESIS: Millions of tons of CO2 are stored in CO2 geological storage (CGS) formations (depleted oil reservoirs and deep saline aquifers) every year. These CGS formations naturally contain small concentrations of water-soluble organic components in particular humic acid (HA), which may drastically affect the rock wettability - a significant factor determining storage capacities and containment security. Hence, it is essential to characterise the effect of humic acid concentration on CO2-wettability and its associated impact on storage capacity. EXPERIMENTAL: To achieve this, we measured advancing and receding contact angles at reservoir conditions using the pendant drop tilted plate method for various humic acid concentrations (1, 10, and 100 mg/L) as a function of pressure (0.1-25 MPa), temperature (303-333 K), and brine salinity (0-0.3 M NaCl). Further, the influence of humic acid adsorption on the mineral's surface was examined by several independent techniques. RESULTS: Our results demonstrate that humic acid significantly changes rock wettability from water-wet (0-50°) towards CO2-wet (90-110°). An increase in pressure, temperature, and salinity had a similar effect. Humic acid adsorption also increased the surface roughness of the substrates. We conclude that even trace amounts of humic acid (i.e. 1 mg/L), which exist in storage aquifers, significantly increase CO2-wettability and thus reduce structural and residual trapping capacities. Therefore, it is pertinent to account for these humic acid concentrations to de-risk CGS projects.

Influence of Organic Acid Concentration on Wettability Alteration of Cap-Rock: Implications for CO2 Trapping/Storage.

Every year, millions of tons of CO2 are stored in CO2-storage formations (deep saline aquifers) containing traces of organic acids including hexanoic acid C6 (HA), lauric acid C12 (LuA), stearic acid C18 (SA), and lignoceric acid C24 (LiA). The presence of these molecules in deep saline aquifers is well documented in the literature; however, their impact on the structural trapping capacity and thus on containment security is not yet understood. In this study, we therefore investigate as to how an increase in organic acid concentration can alter mica water wettability through an extensive set of experiments. X-ray diffraction (Figure S2), field emission scanning electron microscopy, total organic carbon analysis, Fourier-transform infrared spectroscopy, atomic force microscopy, and energy-dispersive X-ray spectroscopy were utilized to perceive the variations in organic acid surface coverage with stepwise organic acid concentration increase and changes in surface roughness. Furthermore, thresholds of wettability that may indicate limits for structural trapping potential (θr < 90°) have been discussed. The experimental results show that even a minute concentration (∼10-5 mol/L for structural trapping) of lignoceric acid is enough to affect the CO2 trapping capacity at 323 K and 25 MPa. As higher concentrations exist in deep saline aquifers, it is necessary to account for these thresholds to derisk CO2-geological storage projects.

Synergetic Effect of Surfactant Concentration, Salinity, and Pressure on Adsorbed Methane in Shale at Low Pressure: An Experimental and Modeling Study.

The influence of an anionic surfactant, a cationic surfactant, and salinity on adsorbed methane (CH4) in shale was assessed and modeled in a series of systematically designed experiments. Two cases were investigated. In case 1, the crushed Marcellus shale samples were allowed to react with anionic sodium dodecyl sulfate (SDS) and brine. In case 2, another set of crushed Marcellus shale samples were treated with cetyltrimethylammonium bromide (CTAB) and brine. The surfactant concentration and salinity of brine were varied following the Box-Behnken experimental design. CH4 adsorption was then assessed volumetrically in the treated shale at varying pressures (1-50 bar) and a constant temperature of 30 °C using a pressure equilibrium cell. Mathematical analysis of the experimental data yielded two separate models, which expressed the amount of adsorbed CH4 as a function of SDS/CTAB concentration, salinity, and pressure. In case 1, the highest amount of adsorbed CH4 was about 1 mmol/g. Such an amount was achieved at 50 bar, provided that the SDS concentration is kept close to its critical micelle concentration (CMC), which is 0.2 wt %, and salinity is in the range of 0.1-20 ppt. However, in case 2, the maximum amount of adsorbed CH4 was just 0.3 mmol/g. This value was obtained at 50 bar and high salinity (∼75 ppt) when the CTAB concentration was above the CMC (>0.029 wt %). The findings provide researchers with insights that can help in optimizing the ratio of salinity and surfactant concentration used in shale gas fracturing fluid.

Carbon dioxide/brine wettability of porous sandstone versus solid quartz: An experimental and theoretical investigation.

HYPOTHESIS: Wettability plays an important role in underground geological storage of carbon dioxide because the fluid flow and distribution mechanism within porous media is controlled by this phenomenon. CO2 pressure, temperature, brine composition, and mineral type have significant effects on wettability. Despite past research on this subject, the factors that control the wettability variation for CO2/water/minerals, particularly the effects of pores in the porous substrate on the contact angle at different pressures, temperatures, and salinities, as well as the physical processes involved are not fully understood. EXPERIMENTS: We measured the contact angle of deionised water and brine/CO2/porous sandstone samples at different pressures, temperatures, and salinities. Then, we compared the results with those of pure quartz. Finally, we developed a physical model to explain the observed phenomena. FINDINGS: The measured contact angle of sandstone was systematically greater than that of pure quartz because of the pores present in sandstone. Moreover, the effect of pressure and temperature on the contact angle of sandstone was similar to that of pure quartz. The results showed that the contact angle increases with increase in temperature and pressure and decreases with increase in salinity.

Impact of pressure and temperature on CO2-brine-mica contact angles and CO2-brine interfacial tension: Implications for carbon geo-sequestration.

Precise characterization of wettability of CO2-brine-rock system and CO2-brine interfacial tension at reservoir conditions is essential as they influence capillary sealing efficiency of caprocks, which in turn, impacts the structural and residual trapping during CO2 geo-sequestration. In this context, we have experimentally measured advancing and receding contact angles for brine-CO2-mica system (surface roughness ∼12nm) at different pressures (0.1MPa, 5MPa, 7MPa, 10MPa, 15MPa, 20MPa), temperatures (308K, 323K, and 343K), and salinities (0wt%, 5wt%, 10wt%, 20wt% and 30wt% NaCl). For the same experimental matrix, CO2-brine interfacial tensions have also been measured using the pendant drop technique. The results indicate that both advancing and receding contact angles increase with pressure and salinity, but decrease with temperature. On the contrary, CO2-brine interfacial tension decrease with pressure and increase with temperature. At 20MPa and 308K, the advancing angle is measured to be ∼110°, indicating CO2-wetting. The results have been compared with various published literature data and probable factors responsible for deviations have been highlighted. Finally we demonstrate the implications of measured data by evaluating CO2 storage heights under various operating conditions. We conclude that for a given storage depth, reservoirs with lower pressures and high temperatures can store larger volumes and thus exhibit better sealing efficiency.

Influence of temperature and pressure on quartz-water-CO2 contact angle and CO2-water interfacial tension.

We measured water-CO2 contact angles on a smooth quartz surface (RMS surface roughness ∼40 nm) as a function of pressure and temperature. The advancing water contact angle θ was 0° at 0.1 MPa CO2 pressure and all temperatures tested (296-343 K); θ increased significantly with increasing pressure and temperature (θ=35° at 296 K and θ=56° at 343 K at 20 MPa). A larger θ implies less structural and residual trapping and thus lower CO2 storage capacities at higher pressures and temperatures. Furthermore we did not identify any significant influence of CO2-water equilibration on θ. Moreover, we measured the CO2-water interfacial tension γ and found that γ strongly decreased with increasing pressure up to ∼10 MPa, and then decreased with a smaller slope with further increasing pressure. γ also increased with increasing temperature.