Oil production from matured crude oil reservoirs is still associated with low recovery factors. Chemical enhanced oil recovery (EOR) is one of the techniques which can significantly improve the ...recovery factor of the trapped oil. This is mainly achieved by lowering the interfacial tension (IFT) of the crude oil–brine/aqueous chemical and increasing the viscosity of the injected fluid. Nanofluids have demonstrated potential in this respect, and we thus examined how such nanofluids behave when formulated with standard oilfield polymers, with a particular focus on their EOR efficiency. In this work, silica (SiO2) nanofluids with (NSP) or without (NP) surfactant (sodium dodecyl sulfate) added and with varying nanoparticle concentration were formulated with polyacrylamide (PAM) and characterized by DLS and ζ-potential measurements. These nanofluids were then tested in EOR core-flood experiments. Various studies involving the stability and viscosity of nanofluids, interfacial tension of the nanofluid-crude oil system, their effect on wettability alteration, and efficiency for EOR studies as a function of temperature have been reported. The efficiency of the nanofluid systems for IFT reduction and EOR has also been compared with the conventional polymer (P) and surfactant–polymer (SP) flood schemes. The SiO2 nanofluids significantly increased oil recoveries, particularly at higher temperatures, mainly due to IFT reduction, fluid viscosity increase, and wettability alteration (from intermediate-wet to strongly water-wet). We conclude that SiO2 nanofluids can potentially be attractive EOR chemicals, particularly for wettability alteration operations and high temperature applications.
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•Preparation of nanofluids (different nanoparticles concentration in different brine concentration).•SEM and AFM images (images taken before and after nano-modification).•EDS analysis ...(data were taken after nano-modification of the surfaces).•Effect of exposure time, brine concentration and nanoparticle concentration on contact angle.•Efficiency of used nanofluid (sustainability of silica nanoparticles).
Changing oil-wet surfaces toward higher water wettability is of key importance in subsurface engineering applications. This includes petroleum recovery from fractured limestone reservoirs, which are typically mixed or oil-wet, resulting in poor productivity as conventional waterflooding techniques are inefficient. A wettability change toward more water-wet would significantly improve oil displacement efficiency, and thus productivity. Another area where such a wettability shift would be highly beneficial is carbon geo-sequestration, where compressed CO2 is pumped underground for storage. It has recently been identified that more water-wet formations can store more CO2.
We thus examined how silica based nanofluids can induce such a wettability shift on oil-wet and mixed-wet calcite substrates. We found that silica nanoparticles have an ability to alter the wettability of such calcite surfaces. Nanoparticle concentration and brine salinity had a significant effect on the wettability alteration efficiency, and an optimum salinity was identified, analogous to that one found for surfactant formulations. Mechanistically, most nanoparticles irreversibly adhered to the oil-wet calcite surface (as substantiated by SEM–EDS and AFM measurements). We conclude that such nanofluid formulations can be very effective as enhanced hydrocarbon recovery agents and can potentially be used for improving the efficiency of CO2 geo-storage.
Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO2 is captured from ...large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO2 cannot percolate), (2) residual trapping (where the CO2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO2 through the rock are strongly influenced by the CO2–brine–rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO2-wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO2-wet. Note that CO2-wet surfaces dramatically reduce CO2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO2-wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO2-wettability and the ability to quantitatively predict it are currently limited although recent advances have been made. Moreover, data for real storage rock and real injection gas (which contains impurities) is scarce and it is an open question how realistic subsurface conditions can be reproduced in laboratory experiments. In conclusion, however, it is clear that in principal CO2-wettability can vary drastically from completely water-wet to almost completely CO2-wet, and this possible variation introduces a large uncertainty into trapping capacity and containment security predictions.
To extend applicability and to overcome limitations of combining rules for nonbond potential parameters, in this study, CLAYFF and DREIDING force fields are coupled at the level of atomic site ...charges to model quartz surfaces with chemisorpt hydrocarbons. Density functional theory and Bader charge analysis are applied to calculate charges of atoms of the OC bond connecting a quartz crystal and an alkyl group. The study demonstrates that the hydrogen atom of the quartz surface hydroxyl group can be removed and its charge can be redistributed among the oxygen and carbon atoms of the OC bond in a manner consistent with the results calculated at the density functional level of theory. Augmented with modified charges of the OC bond, force fields can then be applied to a practical problem of evaluation of the contact angle of a water droplet on alkylated quartz surfaces in a carbon dioxide environment, which is relevant for carbon geo-sequestration and in a broader context of oil and gas recovery. Alkylated quartz surfaces have been shown to be extremely hydrophobic even when the surface density of hydroxyl groups is close to the highest naturally observed density of 6.2 OH groups per square nanometer.
Today, bi - reforming of methane is considered as an emerging replacement for the generation of high-grade synthesis gas (H2:CO = 2.0), and also as an encouraging renewable energy substitute for ...fossil fuel resources. For achieving high conversion levels of CH4, H2O, and CO2 in this process, appropriate operation variables such as pressure, temperature and molar feed constitution are prerequisites for the high yield of synthesis gas. One of the biggest stumbling blocks for the methane reforming reaction is the sudden deactivation of catalysts, which is attributed to the sintering and coke formation on active sites. Consequently, it is worthwhile to choose promising catalysts that demonstrate excellent stability, high activity and selectivity during the production of syngas. This review describes the characterisation and synthesis of various catalysts used in the bi-reforming process, such as Ni-based catalysts with MgO, MgO–Al2O3, ZrO2, CeO2, SiO2 as catalytic supports. In summary, the addition of a Ni/SBA-15 catalyst showed greater catalytic reactivity than nickel celites; however, both samples deactivated strongly on stream. Ce-promoted catalysts were more found to more favourable than Ni/MgAl2O4 catalyst alone in the bi-reforming reaction due to their inherent capability of removing amorphous coke from the catalyst surface. Also, Lanthanum promoted catalysts exhibited greater nickel dispersion than Ni/MgAl2O4 catalyst due to enhanced interaction between the metal and support. Furthermore, La2O3 addition was found to improve the selectivity, activity, sintering and coking resistance of Ni implanted within SiO2. Non-noble metal-based carbide catalysts were considered to be active and stable catalysts for bi-reforming reactions. Interestingly, a five-fold increase in the coking resistance of the nickel catalyst with Al2O3 support was observed with incorporation of Cr, La2O3 and Ba for a continuous reaction time of 140 h. Bi-reforming for 200 h with Ni-γAl2O3 catalyst promoted 98.3% conversion of CH4 and CO2 conversion of around 82.4%. Addition of MgO to the Ni catalyst formed stable MgAl2O4 spinel phase at high temperatures and was quite effective in preventing coke formation due to enhancement in the basicity on the surface of catalyst. Additionally, the distribution of perovskite oxides over 20 wt % silicon carbide-modified with aluminium oxide supports promoted catalytic activity. NdCOO3 catalysts were found to be promising candidates for longer bi-reforming operations.
•Addition of dopants to the catalysts increased the stability, coke resistance & catalytic activity.•Ni–MgO–Al2O3 catalyst depicts higher CH4 conversion than other Ni based catalysts at 700–800 °C.•Co-precipitation technique depicts higher catalytic activity than wetness impregnation method.•Conversion of H2O and CH4 were greatly affected by the feed ratio of CO2/H2O.
Structural trapping, the most important CO2 geostorage mechanism during the first decades of a sequestration project, hinges on the traditional assumption that the caprock is strongly water wet. ...However, this assumption has not yet been verified; and it is indeed not generally true as we demonstrate here. Instead, caprock can be weakly water wet or intermediate wet at typical storage conditions; and water wettability decreases with increasing pressure or temperature. Consequently, a lower storage capacity can be inferred for structural trapping in such cases.
Key Points
Caprocks are intermediate wet or weakly water wet at typical storage conditions
CO2 wettability increases with pressure and thus depth
Structural storage capacities are significantly lower than previously predicted
CO2-wettability of sandstones is a key variable which determines structural and residual trapping capacities and strongly influences multi-phase fluid dynamics in the rock. An increasing number of ...researchers has now estimated this wettability by conducting contact angle measurements on quartz, however, there is a large uncertainty associated with the reported data. We demonstrate clearly that the main factor which leads to this broad data spread is due to surface contamination. It is clear that typically inappropriate cleaning methods were used which resulted in artificially high contact angle measurements. We used surface cleaning methods typically prescribed in the surface chemistry community and found that the water contact angle θ on a clean quartz substrate is low, 0–30°, and that θ increases with pressure. We conclude that quartz is strongly water-wet at high pressure conditions.
Hydrogen (H2) as a cleaner fuel has been suggested as a viable method of achieving the de-carbonization objectives and meeting increasing global energy demand. However, successful implementation of a ...full-scale hydrogen economy requires large-scale hydrogen storage (as hydrogen is highly compressible). A potential solution to this challenge is injecting hydrogen into geologic formations from where it can be withdrawn again at later stages for utilization purposes. The geo-storage capacity of a porous formation is a function of its wetting characteristics, which strongly influence residual saturations, fluid flow, rate of injection, rate of withdrawal, and containment security. However, literature severely lacks information on hydrogen wettability in realistic geological and caprock formations, which contain organic matter (due to the prevailing reducing atmosphere). We, therefore, measured advancing (θa) and receding (θr) contact angles of mica substrates at various representative thermo-physical conditions (pressures 0.1-25 MPa, temperatures 308–343 K, and stearic acid concentrations of 10−9 - 10−2 mol/L). The mica exhibited an increasing tendency to become weakly water-wet at higher temperatures, lower pressures, and very low stearic acid concentration. However, it turned intermediate-wet at higher pressures, lower temperatures, and increasing stearic acid concentrations. The study suggests that the structural H2 trapping capacities in geological formations and sealing potentials of caprock highly depend on the specific thermo-physical condition. Thus, this novel data provides a significant advancement in literature and will aid in the implementation of hydrogen geo-storage at an industrial scale.
•Caprock geological formations depict intermediate-wet conditions.•The increased pressure and reduced temperature inversely affects the hydrogen wettability.•Hydrophilic caprock geological formations turn to intermediate-wet in the existence of organic acids.
Maximum resolution zoom-into the irreversibly adsorbed silica agglomerates at 50°C.
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Nanofluid treatment of oil reservoirs is being developed to enhance oil recovery and increase ...residual trapping capacities of CO2 at the reservoir scale. Recent studies have demonstrated good potential for silica nanoparticles for enhanced oil recovery (EOR) at ambient conditions. Nanofluid composition and exposure time have shown significant effects on the efficiency of EOR. However, there is a serious lack of information regarding the influence of temperature on nanofluid performance; thus the effects of temperature, exposure time and particle size on wettability alteration of oil-wet calcite surface were comprehensively investigated; moreover, the stability of the nanofluids was examined. We found that nanofluid treatment is more efficient at elevated temperatures, while nanoparticle size had no influence. Mechanistically most nanoparticles were irreversibly adsorbed by the calcite surface. We conclude that such nano-formulations are potentially useful EOR agents and may improve the efficiency of CO2-storage even at higher reservoir temperatures.
•(Water+CO2) contact angle on quartz increases substantially with pressure and salinity.•(Water+CO2) contact angle on quartz increases slightly with temperature.•Surface roughness has only a minor ...influence on (water+CO2+quartz) contact angles.
The wetting characteristics of CO2 in rock are of vital importance in carbon geo-storage as they determine fluid dynamics and storage capacities. However, the current literature data has a high uncertainty, which translates into uncertain predictions in terms of containment security and economic project feasibility. We thus measured contact angles for the CO2/water/quartz system at relevant reservoir conditions, and analysed the effects of pressure (0.1 to 20)MPa, temperature (296 to 343)K, surface roughness (56 to 1300)nm, salt type (NaCl, CaCl2, and MgCl2) and brine salinities (0 to 35)wt%.
Water contact angles decreased with surface roughness, but increased with pressure, temperature, and brine salinity. Overall the contact angles were significantly increased at storage conditions (∼50°) when compared to ambient conditions (always 0°). Consequently quartz is weakly water-wet (not completely water-wet) at storage conditions, and structural and residual trapping capacities are reduced accordingly.
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