Application of chemically modified waste tucumã (Astrocaryum aculeatum) seeds in the biosorption of methylene blue: kinetic and thermodynamic parameters.

Dye effluents cause diverse environmental problems. Methylene blue (MB) dye stands out since it is widely used in the textile industry. To reduce the pollution caused by the MB, we developed biosorbents from tucumã seeds, where the in natura seeds were treated with NaOH (BT) and H3PO4 (AT) solutions and characterized by Boehm titration, point of zero charges, FTIR, TGA, BET, and SEM. It was observed that the acid groups predominate on the surface of the three biosorbents. The process was optimized for all biosorbents at pH = 8, 7.5 g/L, 240 min, C0 = 250 mg/L, and 45 ℃. BT was more efficient in removing MB (96.20%; QMax = 35.71 mg/g), while IT and AT removed around 60% in similar conditions. The adsorption process best fits Langmuir and Redlich-Peterson isotherms, indicating a hybrid adsorption process (monolayer and multilayer) and pseudo-second-order kinetics. Thermodynamic data confirmed an endothermic and spontaneous adsorption process, mainly for BT. MB was also recovered through a desorption process with ethanol, allowing the BT recycling and reapplication of the dye. Thus, an efficient and sustainable biosorbent was developed, contributing to reducing environmental impacts.

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.

Application of a Novel Green Nano Polymer for Chemical EOR Purposes in Sandstone Reservoirs: Synergetic Effects of Different Fluid/Fluid and Rock/Fluid Interacting Mechanisms.

In this research, a novel natural-based polymer, the Aloe Vera biopolymer, is used to improve the mobility of the injected water. Unlike most synthetic chemical polymers used for chemical-enhanced oil recovery, the Aloe Vera biopolymer is environmentally friendly, thermally stable in reservoir conditions, and compatible with reservoir rock and fluids. In addition, the efficiency of the Aloe Vera biopolymer was investigated in the presence of a new synthetic nanocomposite composed of KCl-SiO2-xanthan. This chemically enhanced oil recovery method was applied on a sandstone reservoir in Southwest Iran with crude oil with an API gravity of 22°. The Aloe Vera biopolymer's physicochemical characteristics were initially examined using different analytical instruments. The results showed that the Aloe Vera biopolymer is thermally stable under reservoir conditions. In addition, no precipitation occurred with the formation brine at the salinity of 80,000 ppm. The experimental results showed that adding ethanol with a 10% volume percentage reduced interfacial tension to 15.3 mN/m and contact angle to 108°, which was 52.33 and 55.56% of these values, respectively. On the other hand, adding nanocomposite lowered interfacial tension and contact angle values to 4 mN/m and 48°, corresponding to reducing these values by 87.53 and 71.42%, respectively. The rheology results showed that the solutions prepared by Aloe Vera biopolymer, ethanol, and nanocomposite were Newtonian and fitted to the Herschel-Bulkley model. Finally, core flooding results showed that the application of a solution prepared by Aloe Vera biopolymer, ethanol, and nanocomposite was effective in increasing the oil recovery factor, where the maximum oil recovery factor of 73.35% was achieved, which could be attributed to the IFT reduction, wettability alteration, and mobility improvement mechanisms.

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.

Insight into Nano-chemical Enhanced Oil Recovery from Carbonate Reservoirs Using Environmentally Friendly Nanomaterials.

The use of nanoparticles (NPs) in enhanced oil recovery (EOR) processes is very effective in reducing the interfacial tension (IFT) and surface tension (ST) and altering the wettability of reservoir rocks. The main purpose of this study was to use the newly synthesized nanocomposites (KCl/SiO2/Xanthan NCs) in EOR applications. Several analytical techniques including X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM) were applied to confirm the validity of the synthesized NCs. From the synthesized NCs, nanofluids were prepared at different concentrations of 100-2000 ppm and characterized using electrical conductivity, IFT, and ST measurements. From the obtained results, it can be observed that 1000 ppm is the optimal concentration of the synthesized NCs that had the best performance in EOR applications. The nanofluid with 1000 ppm KCl/SiO2/Xanthan NCs enabled reducing the IFT and ST from 33 and 70 to 29 and 40 mN/m, respectively. However, the contact angle was highly decreased under the influence of the same nanofluid to 41° and the oil recovery improved by an extra 17.05% OOIP. To sum up, KCl/SiO2/Xanthan NCs proved highly effective in altering the wettability of rocks from oil-wet to water-wet and increasing the cumulative oil production.

Synergistic Efficiency of Zinc Oxide/Montmorillonite Nanocomposites and a New Derived Saponin in Liquid/Liquid/Solid Interface-Included Systems: Application in Nanotechnology-Assisted Enhanced Oil Recovery.

Oil production faces challenges such as limited oil production from carbonate reservoirs, high oil production costs, and environmental issues. Chemical flooding as an enhanced oil recovery (EOR) method (CEOR) can increase oil production by the use of chemical additives such as surfactants into the reservoirs. Surfactants can increase oil recovery by interfacial tension (IFT) reduction and alteration of the rock wettability from oil-wet to water-wet. The synthesis of chemicals such as synthetic surfactants is usually costly and harmful to the environment. To solve these problems, many researchers have oriented on the use of natural surfactants instead of synthetic ones within the CEOR process. A new approach to increase the efficiency of CEOR is the synergizing of the chemical additives with nanoparticles as a hybrid fluid, which is known as the nanotechnology-assisted EOR method. In this research, a natural surfactant derived from Cyclamen persicum (CP) plant was extracted, and its performance was optimized with the zinc oxide/montmorillonite (ZnO/MMT) nanocomposite in a synergistic usage. At the optimum concentration of the surfactant, the measurements of the IFT and the contact angle show 57.78 and 61.58% optimizations, respectively. Also, in the presence of NaCl, the performance of CP is improved. IFT and contact angle measurements were also conducted for ZnO/MMT nanofluids and CP-ZnO/MMT as hybrid nanofluids. Results indicate that ZnO/MMT nanocomposites can alter the wettability of the carbonate rock to the water-wet state. Also, the CP-ZnO/MMT hybrid nanofluid shows a good potential in both IFT reduction and altering wettability from oil-wet to water-wet. Finally, to investigate the effects of solutions on increasing oil recovery factor (RF), the optimum concentrations of the surfactant, nanocomposite, and hybrid solutions were selected for dynamic core flooding experiments, and improvements showed oil RF increases of 8.2, 6, and 13%, respectively.

Date-Leaf Carbon Particles for Green Enhanced Oil Recovery.

Green enhanced oil recovery (GEOR) is an environmentally friendly enhanced oil recovery (EOR) process involving the injection of green fluids to improve macroscopic and microscopic sweep efficiencies while boosting tertiary oil production. Carbon nanomaterials such as graphene, carbon nanotube (CNT), and carbon dots have gained interest for their superior ability to increase oil recovery. These particles have been successfully tested in EOR, although they are expensive and do not extend to GEOR. In addition, the application of carbon particles in the GEOR method is not well understood yet, requiring thorough documentation. The goals of this work are to develop carbon nanoparticles from biomass and explore their role in GEOR. The carbon nanoparticles were prepared from date leaves, which are inexpensive biomass, through pyrolysis and ball-milling methods. The synthesized carbon nanomaterials were characterized using the standard process. Three formulations of functionalized and non-functionalized date-leaf carbon nanoparticle (DLCNP) solutions were chosen for core floods based on phase behavior and interfacial tension (IFT) properties to examine their potential for smart water and green chemical flooding. The carboxylated DLCNP was mixed with distilled water in the first formulation to be tested for smart water flood in the sandstone core. After water flooding, this formulation recovered 9% incremental oil of the oil initially in place. In contrast, non-functionalized DLCNP formulated with (the biodegradable) surfactant alkyl polyglycoside and NaCl produced 18% more tertiary oil than the CNT. This work thus provides new green chemical agents and formulations for EOR applications so that oil can be produced more economically and sustainably.

Hydrogen storage potential of coals as a function of pressure, temperature, and rank.

We conducted measurements of hydrogen adsorption on three coal samples of varying ranks at high pressure (0 to 102 bar) and elevated temperatures (303 K to 333 K) to assess their hydrogen storage potential. The excess adsorption capacity increased with increasing pressure but decreased with increasing temperature irrespective of coal rank. The highest hydrogen adsorption recorded was 0.721 mol/kg for the anthracite coal at 303 K and 102 bar. Furthermore, the hydrogen adsorption capacity correlated positively with coal vitrinite and fixed carbon contents (i.e. the high-rank coal exhibited greater adsorption), while all samples depicted predominantly type-I adsorption behavior for the entire pressure range. Micropore analysis and Fourier-transform infrared spectroscopy measurements were conducted to explore the microstructural and surface chemistry associated with these adsorption trends. The micropore content of the three samples followed the order: anthracite > sub-bituminous > bituminous, while H2 adsorption followed the trend: anthracite > bituminous > sub-bituminous - i.e., no direct correlation between coal micropore content and its H2 adsorption capacity - attributable to high clay content of bituminous coal which lowered its micropore content. Moreover, bituminous, and sub-bituminous samples exhibited an abundance of oxygen-containing functional groups, while anthracite coal depicted notable aromatic content - suggesting that the H2 adsorption capacity is a complex function of coal surface chemistry and micropore content. Overall, high-rank coal seams at high pressure and temperature showed the largest hydrogen adsorption i.e., analogous to CO2 adsorption potential albeitat lower absolute values. These results, therefore, provide preliminary data on the hydrogen storage potential of coal seams and the associated scientific understanding of the mechanisms causing hydrogen adsorption.

Hydrogen wettability of carbonate formations: Implications for hydrogen geo-storage.

HYPOTHESIS: The mitigation of anthropogenic greenhouse gas emissions and increasing global energy demand are two driving forces toward the hydrogen economy. The large-scale hydrogen storage at the surface is not feasible as hydrogen is very volatile and highly compressible. An effective way for solving this problem is to store it in underground geological formations (i.e. carbonate reservoirs). The wettability of the rock/H2/brine system is a critical parameter in the assessment of residual and structural storage capacities and containment safety. However, the presence of organic matters in geo-storage formations poses a direct threat to the successful hydrogen geo-storage operation and containment safety. EXPERIMENTS: As there is an intensive lack of literature on hydrogen wettability of calcite-rich formations, advancing (θa) and receding (θr) contact angles of water/H2/calcite systems were measured as a function of different parameters, including pressure (0.1-20 MPa), temperature (298-353 K), salinity (0-4.95 mol.kg-1), stearic acid (as a representative of organic acid) concentration (10-9 - 10-2 mol/L), tilting plate angle (0° - 45°) and surface roughness (RMS = 341 nm, 466 nm, and 588 nm). FINDINGS: The results of the study show that at ambient conditions, the system was strongly water-wet, but became intermediate wet at high pressure. The water contact angle strongly increased with stearic acid concentration making the calcite surface H2-wet. Moreover, the contact angle increased with salinity and tilting plate angle but decreased with temperature and surface roughness. We conclude that the optimum conditions for de-risking H2 storage projects in carbonates are low pressures, high temperatures, low salinity, and low organic surface concentration. Therefore, it is essential to measure these effects to avoid overestimation of hydrogen geo-storage capacities and containment security.

Coal fines migration: A holistic review of influencing factors.

Coal fines can substantially influence coal seam gas reservoir permeability, thus impeding the flow of gas in coal microstructure. The coal fines generation and migration are influenced by several factors, wherein coal fines are generally hydrophobic and aggregate in natural coal seam gas (CSG) under prevailing conditions of pH, salinity, temperature and pressure. This aggregation behaviour can damage the coal matrix and cleat system permeabilities, leading to a considerable reduction of proppant pack conductivity (i.e. fracture conductivity). Several datasets have been reported within the literature on this subject in the last decade. However, a more up-to-date discussion of this area is key to understanding coal fines migration and associated knowledge. Thus, in this review, we conduct a systematic investigation of coal fines and their influencing factors. Here, coal fines are introduced, followed by an initial holistic investigation of their generation, plugging, movement, redistribution and production. Then, in order to enhance current understandings of the subject matter, a parametric evaluation of the factors noted earlier is conducted, based on recently published literature. Subsequently, the published mathematical and analytical models for fines generation are reviewed. Finally, the implications and challenges associated with coal fines mitigation are discussed.

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.

Zeta potential of CO2-rich aqueous solutions in contact with intact sandstone sample at temperatures of 23 °C and 40 °C and pressures up to 10.0 MPa.

Despite the broad range of interest and applications, controls on the electric surface charge and the zeta potential of silica in contact with aqueous solutions saturated with dissolved CO2 at conditions relevant to natural systems, remains unreported. There have been no published zeta potential measurements conducted in such systems at equilibrium, hence the effect of composition, pH, temperature and pressure remains unknown. We describe a novel methodology developed for the streaming potential measurements under these conditions, and report zeta potential values for the first time obtained with Fontainebleau sandstone core sample saturated with carbonated NaCl, Na2SO4, CaCl2 and MgCl2 solutions under equilibrium conditions at pressures up to 10 MPa and temperatures up to 40 °C. The results demonstrate that pH of solutions is the only control on the zeta potential, while temperature, CO2 pressure and salt type affect pH values. We report three empirical relationships that describe the pH dependence of the zeta potential for: i) dead (partial CO2 pressure of 10-3.44 atm) NaCl/Na2SO4, ii) dead CaCl2/MgCl2 solutions, and iii) for all live (fully saturated with dissolved CO2) solutions. The proposed new relationships provide essential insights into interfacial electrochemical properties of silica-water systems at conditions relevant to CO2 geological storage.

Hydrogen diffusion in coal: Implications for hydrogen geo-storage.

HYPOTHESIS: Hydrogen geo-storage is considered as an option for large scale hydrogen storage in a full-scale hydrogen economy. Among different types of subsurface formations, coal seams look to be one of the best suitable options as coal's micro/nano pore structure can adsorb a huge amount of gas (e.g. hydrogen) which can be withdrawn again once needed. However, literature lacks fundamental data regarding H2 diffusion in coal. EXPERIMENTS: In this study, we measured H2 adsorption rate in an Australian anthracite coal sample at isothermal conditions for four different temperatures (20 °C, 30 °C, 45 °C and 60 °C), at equilibrium pressure âˆ¼ 13 bar, and calculated H2 diffusion coefficient ( [Formula: see text] ) at each temperature. CO2 adsorption rates were measured for the same sample at similar temperatures and equilibrium pressure for comparison. FINDINGS: Results show that H2 adsorption rate, and consequently [Formula: see text] , increases by temperature. [Formula: see text] values are one order of magnitude larger than the equivalent [Formula: see text] values for the whole studied temperature range 20-60 °C. [Formula: see text] / [Formula: see text] also shows an increasing trend versus temperature. CO2 adsorption capacity at equilibrium pressure is about 5 times higher than that of H2 in all studied temperatures. Both H2 and CO2 adsorption capacities, at equilibrium pressure, slightly decrease as temperature rises.

Influence of organic molecules on wetting characteristics of mica/H2/brine systems: Implications for hydrogen structural trapping capacities.

HYPOTHESIS: Actualization of the hydrogen (H2) economy and decarbonization goals can be achieved with feasible large-scale H2 geo-storage. Geological formations are heterogeneous, and their wetting characteristics play a crucial role in the presence of H2, which controls the pore-scale distribution of the fluids and sealing capacities of caprocks. Organic acids are readily available in geo-storage formations in minute quantities, but they highly tend to increase the hydrophobicity of storage formations. However, there is a paucity of data on the effects of organic acid concentrations and types on the H2-wettability of caprock-representative minerals and their attendant structural trapping capacities. EXPERIMENT: Geological formations contain organic acids in minute concentrations, with the alkyl chain length ranging from C4 to C26. To fully understand the wetting characteristics of H2 in a natural geological picture, we aged mica mineral surfaces as a representative of the caprock in varying concentrations of organic molecules (with varying numbers of carbon atoms, lignoceric acid C24, lauric acid C12, and hexanoic acid C6) for 7 days. To comprehend the wettability of the mica/H2/brine system, we employed a contact-angle procedure similar to that in natural geo-storage environments (25, 15, and 0.1 MPa and 323 K). FINDINGS: At the highest investigated pressure (25 MPa) and the highest concentration of lignoceric acid (10-2 mol/L), the mica surface became completely H2 wet with advancing (θa= 106.2°) and receding (θr=97.3°) contact angles. The order of increasing θa and θr with increasing organic acid contaminations is as follows: lignoceric acid > lauric acid > hexanoic acid. The results suggest that H2 gas leakage through the caprock is possible in the presence of organic acids at higher physio-thermal conditions. The influence of organic contamination inherent at realistic geo-storage conditions should be considered to avoid the overprediction of structural trapping capacities and H2 containment security.

Predictive surface complexation model of the calcite-aqueous solution interface: The impact of high concentration and complex composition of brines.

Electrochemical interactions at calcite-water interface are characterized by the zeta potential and play an important role in many subsurface applications. In this work we report a new physically meaningful surface complexation model that is proven to be efficient in predicting calcite-water zeta potentials for a wide range of experimental conditions. Our model uses a two-stage optimization for matching experimental observations. First, equilibrium constants are optimized, and the Stern layer capacitance is optimized in the second stage. The model is applied to a variety of experimental sets that correspond to intact natural limestones saturated with equilibrated solutions of low-to-high salinity, and crushed Iceland Spar sample saturated with NaCl at non-equilibrium conditions. The proposed linear correlation of the Stern layer capacitance with the ionic strength is the main novel contribution to our surface complexation model without which high salinity experiments cannot be modelled. Our model is fully predictive given accurately known conditions. Therefore, the reported parameters and modelling protocol are of significant importance for improving our understanding of the complex calcite-water interfacial interactions. The findings provide a robust tool to predict electrochemical properties of calcite-water interfaces, which are essential for many subsurface applications including hydrology, geothermal resources, CO2 sequestration and hydrocarbon recovery.

Underground hydrogen storage: Influencing parameters and future outlook.

Underground hydrogen storage (UHS) is a promising technology with which large quantities of H2 can potentially be stored in the subsurface safely, economically and efficiently. As UHS is a relatively new technology, we critically reviewed all available data related to solid properties, fluid properties and solid-fluid interactions relevant to UHS. We also provide clear conclusions, and highlight research gaps. This review therefore advances fundamental understanding of UHS at multiple physical scales and provides key guidance for UHS project operations at reservoir scale.

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.

Interaction of low salinity surfactant nanofluids with carbonate surfaces and molecular level dynamics at fluid-fluid interface at ScCO2 loading.

HYPOTHESIS: The advanced low salinity aqueous formulations are yet to be validated as an injection fluid for enhanced oil recovery (EOR) from the carbonate reservoirs and CO2 geosequestration. Interaction of various ionic species present in the novel low salinity surfactant nanofluids with scCO2/CO2 saturated aqueous phase interface and at the interface of CO2 saturated aqueous phase/mixed wet (with CO2 and Decane) limestone surface at the conditions of low salinity at reservoir conditions are to yet to be understood. EXPERIMENTS: This study, carried out for the first time in low salinity at scCO2 loading conditions at 20 MPa pressure and 343 K temperature, comprises of wettability study of the limestone surface by aqueous phase contact angle measurements using ZrO2 nanoparticles (in the concentration range of 100-2000 mg/L) and 0.82 mM Hexadecyltrimethylammonium bromide (CTAB) surfactant. Molecular dynamics simulations results were used to understand the underlying mechanism of wettability alteration and interfacial tension (IFT) change. FINDINGS: This study reveals that a low dosage (100 mg/L) of ZrO2 nanoparticles forming ZrO2-CTAB nano-complexes helps in wettability alteration of the rock surface to more water-wetting state; certain ionic species augment this effect when used in appropriate concentration. Also, these nano-complexes helps in scCO2/CO2 saturated aqueous phase IFT reduction. This study can be used to design advanced low salinity injection fluids for water alternating gas injection for EOR and CO2 geosequestration projects.

A review on clay wettability: From experimental investigations to molecular dynamics simulations.

Clay is one of the most important mineral components in geological formations, and it is widely used in many industrial applications. One clay property, which is of key importance in many areas, e.g. mineral processing, agriculture, fundamental geologic understanding, hydrology, oil/water separation and multi-phase fluid flow, is clay wettability. However, clay wettability is a complex parameter which is determined by clay surface chemistry, in-situ aqueous and non-aqueous fluid chemistries, and geo-thermal conditions. Thus, a systematic review of published results on the wettability of six different clay minerals (kaolinite, montmorillonite, illite, mica, talc and pyrophyllite) is provided here, spanning from experimental studies to molecular dynamics simulations. This is integrated with a critical discussion to elucidate the origin of significant inconsistencies in the reported data. Finally, a range of conclusions is clearly established and a future outlook is given. This review will thus advance the understanding of clay wettability and provide guidance for the various applications discussed.

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.