Experimental Study of Pore-Scale Mechanisms of Carbonated Water Injection

Carbon dioxide (CO₂) injection is a well-established method for increasing recovery from oil reservoirs. However, poor sweep efficiency has been reported in many CO₂ injection projects due to the high mobility contrast between CO₂ and oil and water. Various injection strategies including gravity stable, WAG and SWAG have been suggested and, to some extent, applied in the field to alleviate this problem. An alternative injection strategy is carbonated water injection (CWI). In CWI, CO₂ is delivered to a much larger part of the reservoir compared to direct CO₂ injection due to a much improved sweep efficiency. In CWI, CO₂ is used efficiently and much less CO₂ is required compared to conventional CO₂ flooding, and hence the process is particularly attractive for reservoirs with limited access to large quantities of CO₂ (offshore reservoirs or reservoirs far away from inexpensive natural CO₂ resources). This article describes the results of a pore-scale study of the process of CWI by performing high-pressure visualisation flow experiments. The experimental results show that CWI, compared to unadulterated (conventional) water injection, improves oil recovery as both a secondary (before water flooding) and a tertiary (after water flooding) recovery method. The mechanisms of oil recovery by CWI include oil swelling, coalescence of the isolated oil ganglia and flow diversion due to flow restriction in some of the pores as a result of oil swelling and the resultant fluid redistribution. In this article the potential benefit of a subsequent depressurisation period on oil recovery after the CWI period is also investigated.     

Oil Recovery by Low Salinity Water Injection into a Reservoir: A New Study of Tertiary Oil Recovery Mechanism

Low salinity water injections for oil recovery have shown seemingly promising results in the case of clay-bearing sandstones saturated with asphaltic crude oil. Reported data showed that low salinity water injection could provide up to 20% pore volume (PV) of additional oil recovery for core samples and up to 25% PV for reservoirs in near wellbore regions, compared with brine injection at the same Darcy velocity. The question remains as to whether this additional recovery is also attainable in reservoirs. The answer requires a thorough understanding of oil recovery mechanism of low salinity water injections. Numerous hypotheses have been proposed to explain the increased oil recovery using low salinity water, including migration of detached mixed-wet clay particles with absorbed residual oil drops, wettability alteration toward increased water-wetness, and emulsion formation. However, many later reports showed that a higher oil recovery associated with low salinity water injection at the common laboratory flow velocity was neither necessarily accompanied by migration of clay particles, nor necessarily accompanied by emulsion. Moreover, increased water-wetness has been shown to cause the reduction of oil recovery. The present study is based on both experimental and theoretical analyses. Our study reveals that the increased oil recovery is only related to the reduction of water permeability due to physical plugging of the porous network by swelling clay aggregates or migrating clay particles and crystals. At a fixed apparent flow velocity, the value of negative pressure gradient along the flow path increases as the water permeability decreases. Some oil drops and blobs can be mobilized under the increased negative pressure gradient and contribute to the additional oil recovery. Based on the revealed mechanism, we conclude that low salinity water injection cannot be superior to brine injection in any clay-bearing sandstone reservoir at the maximum permitted injection pressure. Through our study of low salinity water injection, the theory of tertiary oil recovery has been notably improved.     

Influence of Permeability Heterogeneity on Miscible CO<Subscript>2</Subscript> Flooding Efficiency in Sandstone Reservoirs: An Experimental Investigation

In this study, we systematically investigate the effect of core-scale heterogeneity on the performance of miscible CO₂ flooding under various injection modes (secondary and tertiary). Manufactured heterogeneous core plugs are used to simulate vertical and horizontal heterogeneity that may be present in a reservoir. A sample with vertical heterogeneity (i.e. a layered sample) is constructed using two axially cut half plugs each with a distinctly different permeability value. In these samples, the permeability ratio (PR) defines the ratio between the permeabilities of adjacent half plugs. Horizontal heterogeneity (i.e. a composite sample) is introduced by stacking two or three short cylindrical core segments each with a different permeability value. Our special sample construction techniques have also enabled us to investigate the effect of permeability ratio and crossflow in layered samples and axial arrangement of core segments in composite samples on the ultimate recovery of the floods. Core flooding experiments are conducted with an n-Decane–brine–CO₂ system at a pore pressure of 17.2 MPa and a temperature of 343 K. At this temperature, the minimum miscibility pressure of CO₂ with n-Decane is 12.6–12.7 MPa so it is expected that at 17.2 MPa CO₂ is fully miscible with n-Decane. The results obtained for both the composite and layered samples indicate that CO₂ injection would achieve the highest recovery factor (RF) when performed under the secondary mode (e.g. layered: 79.00%, composite: 89.83%) compared with the tertiary mode (e.g. layered: 73.2%, composite: 86.2%). This may be attributed to the effect of water shielding which impedes the access of the injected CO₂ to the residual oil under the tertiary injection mode. It is also found that the oil recovery from a layered sample decreases noticeably with an increase in the PR as higher PR makes the displacement more uneven due to CO₂ channelling. The RFs of 93.4, 87.89, 77.9 and 69.8% correspond to PRs of 1, 2.5, 5, and 12.5, respectively. In addition, for the layered samples, crossflow was found to have an important role during the recovery process; however, due to excessive channelling, this effect tends to diminish as PR increases. Compared with the layered heterogeneity, the effect of composite heterogeneity on the RF seems to be very subtle as the RF is found to be almost independent from the permeability sequence along the length of a composite sample. This outcome may have been caused by the small diameter of the plugs resulting in invariable 1-D floods.     

Coreflooding Studies to Evaluate the Impact of Salinity and Wettability on Oil Recovery Efficiency

In this work, coreflood studies were carried out to determine the recovery benefits of low salinity waterflood compared to high salinity waterflood and the role of wettability in any observed recovery benefit. Two sets of coreflood experiments were conducted; the first set examined the EOR potential of low salinity floods in tertiary oil recovery processes, while the second set of experiments examined the secondary oil recovery potential of low salinity floods. Changes in residual oil saturation with variation in wettability, brine salinity and temperature were monitored. All the coreflood tests gave consistent increase in produced oil, corresponding to reduction in residual oil saturation and increase in water-wetness (for the second set of experiments) with decrease in brine salinity and increase in brine temperature.     

An Experimental Study of CO<Subscript>2</Subscript> Exsolution and Relative Permeability Measurements During CO<Subscript>2</Subscript> Saturated Water Depressurization

Dissolution of CO₂ into brine is an important and favorable trapping mechanism for geologic storage of CO₂. There are scenarios, however, where dissolved CO₂ may migrate out of the storage reservoir. Under these conditions, CO₂ will exsolve from solution during depressurization of the brine, leading to the formation of separate phase CO₂. For example, a CO₂ sequestration system with a brine-permeable caprock may be favored to allow for pressure relief in the sequestration reservoir. In this case, CO₂-rich brine may be transported upwards along a pressure gradient caused by CO₂ injection. Here we conduct an experimental study of CO₂ exsolution to observe the behavior of exsolved gas under a wide range of depressurization. Exsolution experiments in highly permeable Berea sandstones and low permeability Mount Simon sandstones are presented. Using X-ray CT scanning, the evolution of gas phase CO₂ and its spatial distribution is observed. In addition, we measure relative permeability for exsolved CO₂ and water in sandstone rocks based on mass balances and continuous observation of the pressure drop across the core from 12.41 to 2.76 MPa. The results show that the minimum CO₂ saturation at which the exsolved CO₂ phase mobilization occurs is from 11.7 to 15.5%. Exsolved CO₂ is distributed uniformly in homogeneous rock samples with no statistical correlation between porosity and CO₂ saturation observed. No gravitational redistribution of exsolved CO₂ was observed after depressurization, even in the high permeability core. Significant differences exist between the exsolved CO₂ and water relative permeabilities, compared to relative permeabilities derived from steady-state drainage relative permeability measurements in the same cores. Specifically, very low CO₂ and water relative permeabilities are measured in the exsolution experiments, even when the CO₂ saturation is as high as 40%. The large relative permeability reduction in both the water and CO₂ phases is hypothesized to result from the presence of disconnected gas bubbles in this two-phase flow system. This feature is also thought to be favorable for storage security after CO₂ injection.     

Pore-scale Simulation of Water Alternate Gas Injection

We use a three-dimensional mixed-wet random network model representing Berea sandstone to compute displacement paths and relative permeabilities for water alternating gas (WAG) flooding. First we reproduce cycles of water and gas injection observed in previously published experimental studies. We predict the measured oil, water and gas relative permeabilities accurately. We discuss the hysteresis trends in the water and gas relative permeabilities and compare the behavior of water-wet and oil-wet media. We interpret the results in terms of pore-scale displacements. In water-wet media the water relative permeability is lower during water injection in the presence of gas due to an increase in oil/water capillary pressure that causes a decrease in wetting layer conductance. The gas relative permeability is higher for displacement cycles after first gas injection at high gas saturation due to cooperative pore filling, but lower at low saturation due to trapping. In oil-wet media, the water relative permeability remains low until water-filled elements span the system at which point the relative permeability increases rapidly. The gas relative permeability is lower in the presence of water than oil because it is no longer the most non-wetting phase.     

Impact of CO<Subscript>2</Subscript> Injection on Flow Behavior of Coalbed Methane Reservoirs

On the basis of observations at four enhanced coalbed methane (ECBM)/CO₂ sequestration pilots, a laboratory-scale study was conducted to understand the flow behavior of coal in a methane/CO₂ environment. Sorption-induced volumetric strain was first measured by flooding fresh coal samples with adsorptive gases (methane and CO₂). In order to replicate the CO₂–ECBM process, CO₂ was then injected into a methane-saturated core to measure the incremental “swelling.” As a separate effort, the permeability of a coal core, held under triaxial stress, was measured using methane. This was followed by CO₂ flooding to replace the methane. In order to best replicate the conditions in situ, the core was held under uniaxial strain, that is, no horizontal strain was permitted during CO₂ flooding. Instead, the horizontal stress was adjusted to ensure zero strain. The results showed that the relative strain ratio for CO₂/methane was between 2 and 3.5. The measured volumetric strains were also fitted using a Langmuir-type model, thus enabling calculation of the strain at any gas pressure and using the analytical permeability models. For permeability work, effort was made to increase the horizontal stress to achieve the desired zero horizontal strain condition expected under in situ condition, but this became impossible because the “excess” stress required to maintain this condition was very large, resulting in sample failure. Finally, when CO₂ was introduced and horizontal strain was permitted, permeability reduction was an order of magnitude greater, suggesting that the “excess” stress would have reduced it significantly further. The positive finding of the work was that the “excess” stresses associated with injection of CO₂ are large. The excess stresses generated might be sufficient to cause microfracturing and increased permeability, and improved injectivity. Also, there might be a weakening effect resulting from repeated CO₂ injection, as has been found to be the case with thermal cycling of rocks.     

CO<Subscript>2</Subscript> injection into saline carbonate aquifer formations I: laboratory investigation

Although there are a number of mathematical modeling studies for carbon dioxide (CO₂) injection into aquifer formations, experimental studies are limited and most studies focus on injection into sandstone reservoirs as opposed to carbonate ones. This study presents the results of computerized tomography (CT) monitored laboratory experiments to analyze permeability and porosity changes as well as to characterize relevant chemical reactions associated with injection and storage of CO₂ in carbonate formations. CT monitored experiments are designed to model fast near well bore flow and slow reservoir flows. Highly heterogeneous cores drilled from a carbonate aquifer formation located in South East Turkey were used during the experiments. Porosity changes along the core plugs and the corresponding permeability changes are reported for different CO₂ injection rates and different salt concentrations of formation water. It was observed that either a permeability increase or a permeability reduction can be obtained. The trend of change in rock properties is very case dependent because it is related to distribution of pores, brine composition and thermodynamic conditions. As the salt concentration decreases, porosity and the permeability decreases are less pronounced. Calcite deposition is mainly influenced by orientation, with horizontal flow resulting in larger calcite deposition compared to vertical flow.     

Pore-Scale Monitoring of Wettability Alteration by Silica Nanoparticles During Polymer Flooding to Heavy Oil in a Five-Spot Glass Micromodel

It is well known that the oil recovery is affected by wettability of porous medium; however, the role of nanoparticles on wettability alteration of medium surfaces has remained a topic of debate in the literature. Furthermore, there is a little information of the way dispersed silica nanoparticles affect the oil recovery efficiency during polymer flooding, especially, when heavy oil is used. In this study, a series of injection experiments were performed in a five-spot glass micromodel after saturation with the heavy oil. Polyacrylamide solution and dispersed silica nanoparticles in polyacrylamide (DSNP) solution were used as injected fluids. The oil recovery as well as fluid distribution in the pores and throats was measured with analysis of continuously provided pictures during the experiments. Sessile drop method was used for measuring the contact angles of the glass surface at different states of wettability after coating by heavy oil, distilled water, dispersed silica nanoparticles in water (DSNW), polyacrylamide solution, and DSNP solution. The results showed that the silica nanoparticles caused enhanced oil recovery during polymer flooding by a factor of 10%. The distribution of DSNP solution during flooding tests in pores and throats showed strong water-wetting of the medium after flooding with this solution. The results of sessile drop experiments showed that coating with heavy oil, could make an oil-wet surface. Coating with distilled water and polymer solution could partially alter the wettability of surface to water-wet and coating with DSNW and DSNP could make a strongly water-wet surface.     

Matched Boundary Extrapolation Solutions for CO<Subscript>2</Subscript> Well-Injection into a Saline Aquifer

The injection of supercritical CO₂ through wells into deep brine reservoirs is a topic of interest for geologic carbon sequestration. The injected CO₂ is predominantly immiscible with the brine and its low density relative to brine leads to strong buoyancy effects. The displacement of brine by CO₂ in general is a multidimensional, complex nonlinear problem that requires numerical methods to solve. The approximations of vertical equilibrium and complete gravity segregation (sharp interface) have been introduced to reduce the complexity and dimensionality of the problem. Furthermore, for the radial displacement process considered here, the problem can be formulated in terms of a similarity variable that reduces spatial and temporal dependencies to a single variable. However, the resulting ordinary differential equation is still nonlinear and exact solutions are not available. The existing analytical solutions are approximations limited to certain parameter ranges that become inaccurate over a large portion of the parameter space. Here, I use a matched boundary extrapolation method to provide much greater accuracy for analytical/semi-analytical approximations over the full parameter range.     

Effects of CO<Subscript>2</Subscript> Compressibility on CO<Subscript>2</Subscript> Storage in Deep Saline Aquifers

The injection of supercritical CO₂ in deep saline aquifers leads to the formation of a CO₂ plume that tends to float above the formation brine. As pressure builds up, CO₂ properties, i.e. density and viscosity, can vary significantly. Current analytical solutions do not account for CO₂ compressibility. In this article, we investigate numerically and analytically the effect of this variability on the position of the interface between the CO₂-rich phase and the formation brine. We introduce a correction to account for CO₂ compressibility (density variations) and viscosity variations in current analytical solutions. We find that the error in the interface position caused by neglecting CO₂ compressibility is relatively small when viscous forces dominate. However, it can become significant when gravity forces dominate, which is likely to occur at late times of injection.     

STREAMLINE-BASED MATHEMATICAL MODEL FOR CO2 MISCIBLE FLOODING

According to the research theory of improved black oil simulator, a practical mathematical model for C02 miscible flooding was presented. In the model, the miscible process simulation was realized by adjusting oil/gas relative permeability and effective viscosity under the condition of miscible flow. In order to predict the production performance fast, streamline method is employed to solve this model as an alternative to traditional finite difference methods. Based on streamline distribution of steady-state flow through porous media with complex boundary confirmed with the boundary element method (BEM), an explicit total variation diminishing (TVD) method is used to solve the one-dimensional flow problem. At the same time, influences of development scheme, solvent slug size, and injection periods on CO2 drive recovery are discussed. The model has the advantages of less information need, fast calculation, and adaptation to calculate CO2 drive performance of all kinds of patterns in a random shaped porous media with assembly boundary. It can be an effective tool for early stage screening andmiscible oil field.reservoir dynamic management of the CO2 miscible oil field.     

Phase Behaviour,Fluid Properties and Recovery Efficiency of Immiscible and Miscible Condensate Displacements by SCCO<Subscript>2</Subscript> Injection: Experimental Investigation

This paper presents a quantitative investigation of the interfacial tension dependent relative permeability (IFT-DRP) and displacement efficiency of supercritical CO₂ injection into gas-condensate reservoirs. A high-pressure high-temperature experimental laboratory was established to simulate reservoir conditions and to perform relative permeability measurements on sandstone cores at a constant reservoir temperature of 95°C and displacement velocity of 10 cm/h. This investigation covers immiscible displacements (1100 and 2100 psi), near-miscible displacement (3000 psi) and miscible displacements (4500 and 5900 psi). The coreflooding results demonstrated that displacement pressure is a key factor governing the attainment of optimum sweep efficiency. The ultimate condensate recovery increased by almost threefold when CO₂ was injected at near-miscible conditions (i.e., 23.40% ultimate recovery at 1100 psi compared to 69.70% at 3000 psi). Miscible flooding was found to give the optimum condensate recovery (9% extra ultimate recovery compared to near-miscible injection). Besides improving the ultimate recovery, miscible floods provided better mobility ratios and delayed gas breakthrough (0.62 PV BT at 5900 psi compared to 0.21 PV BT at 1100 psi). In addition to the elimination of IFT forces in miscible displacements, favourable ratios of fluid properties and phase behaviour relationships between the SCCO₂ and condensate were believed to be the driving force for the improved recovery as they provided a stabilising effect on the displacement front and stimulated swelling of the condensate volume. This paper incorporates the theoretical aspects of phase behaviour and fluid properties that largely affect the microscopic displacement efficiency and serves as a practical guideline for operators to aid their project designs and enhance their recovery capabilities.     

Injection and Storage of CO<Subscript>2</Subscript> in Deep Saline Aquifers: Analytical Solution for CO<Subscript>2</Subscript> Plume Evolution During Injection

Injection of fluids into deep saline aquifers is practiced in several industrial activities, and is being considered as part of a possible mitigation strategy to reduce anthropogenic emissions of carbon dioxide into the atmosphere. Injection of CO₂ into deep saline aquifers involves CO₂ as a supercritical fluid that is less dense and less viscous than the resident formation water. These fluid properties lead to gravity override and possible viscous fingering. With relatively mild assumptions regarding fluid properties and displacement patterns, an analytical solution may be derived to describe the space–time evolution of the CO₂ plume. The solution uses arguments of energy minimization, and reduces to a simple radial form of the Buckley–Leverett solution for conditions of viscous domination. In order to test the applicability of the analytical solution to the CO₂ injection problem, we consider a wide range of subsurface conditions, characteristic of sedimentary basins around the world, that are expected to apply to possible CO₂ injection scenarios. For comparison, we run numerical simulations with an industry standard simulator, and show that the new analytical solution matches a full numerical solution for the entire range of CO₂ injection scenarios considered. The analytical solution provides a tool to estimate practical quantities associated with CO₂ injection, including maximum spatial extent of a plume and the shape of the overriding less-dense CO₂ front.     

Pressure Buildup During CO<Subscript>2</Subscript> Injection into a Closed Brine Aquifer

CO₂ injected into porous formations is accommodated by reduction in the volume of the formation fluid and enlargement of the pore space, through compression of the formation fluids and rock material, respectively. A critical issue is how the resulting pressure buildup will affect the mechanical integrity of the host formation and caprock. Building on an existing approximate solution for formations of infinite radial extent, this article presents an explicit approximate solution for estimating pressure buildup due to injection of CO₂ into closed brine aquifers of finite radial extent. The analysis is also applicable for injection into a formation containing multiple wells, in which each well acts as if it were in a quasi-circular closed region. The approximate solution is validated by comparison with vertically averaged results obtained using TOUGH2 with ECO2N (where many of the simplifying assumptions are relaxed), and is shown to be very accurate over wide ranges of the relevant parameter space. The resulting equations for the pressure distribution are explicit, and can be easily implemented within spreadsheet software for estimating CO₂ injection capacity.     

Numerical Simulations of the Thermal Impact of Supercritical CO<Subscript>2</Subscript> Injection on Chemical Reactivity in a Carbonate Saline Reservoir

Geological sequestration of CO₂ offers a promising solution for reducing net emissions of greenhouse gases into the atmosphere. This emerging technology must make it possible to inject CO₂ into deep saline aquifers or oil- and gas-depleted reservoirs in the supercritical state (P > 7.4MPa and T > 31.1°C) to achieve a higher density and therefore occupy less volume underground. Previous experimental and numerical simulations have demonstrated that massive CO₂ injection in saline reservoirs causes a major disequilibrium of the physical and geochemical characteristics of the host aquifer. The near-well injection zone seems to constitute an underground hydrogeological system particularly impacted by supercritical CO₂ injection and the most sensitive area, where chemical phenomena (e.g. mineral dissolution/precipitation) can have a major impact on the porosity and permeability. Furthermore, these phenomena are highly sensitive to temperature. This study, based on numerical multi-phase simulations, investigates thermal effects during CO₂ injection into a deep carbonate formation. Different thermal processes and their influence on the chemical and mineral reactivity of the saline reservoir are discussed. This study underlines both the minor effects of intrinsic thermal and thermodynamic processes on mineral reactivity in carbonate aquifers, and the influence of anthropic thermal processes (e.g. injection temperature) on the carbonates’ behaviour.     

Injection of Acid Gas Mixtures in Sour Oil Reservoirs: Analysis of Near-Wellbore Processes with Coupled Modelling of Well and Reservoir Flow

The reinjection of sour or acid gas mixtures is often required for the exploitation of hydrocarbon reservoirs containing remarkable amounts of acid gases (H₂S and CO₂) to reduce the environmental impact of field exploitation and provide pressure support for enhanced oil recovery (EOR) purposes. Sour and acid gas injection in geological structures can be modelled with TMGAS, a new Equation of State (EOS) module for the TOUGH2 reservoir simulator. TMGAS can simulate the two-phase behaviour of NaCl-dominated brines in equilibrium with a non-aqueous (NA) phase, made up of inorganic gases such as CO₂ and H₂S and hydrocarbons (pure as well as pseudo-components), up to the high pressures (~100 MPa) and temperatures (~200°C) found in deep sedimentary basins. This study is focused on the near-wellbore processes driven by the injection of an acid gas mixture in a hypothetical high-pressure, under-saturated sour oil reservoir at a well-sector scale and at conditions for which the injected gas is fully miscible with the oil. Relevant-coupled processes are simulated, including the displacement of oil originally in place, the evaporation of connate brine, the salt concentration and consequent halite precipitation, as well as non-isothermal effects generated by the injection of the acid gas mixture at temperatures lower than initial reservoir temperature. Non-isothermal effects are studied by modelling in a coupled way wellbore and reservoir flow with a modified version of the TOUGH2 reservoir simulator. The described approach is limited to single-phase wellbore flow conditions occurring when injecting sour, acid or greenhouse gas mixtures in high-pressure geological structures.     

Effect of Well Orientation (Vertical vs. Horizontal) and Well Length on the Injection of CO<Subscript>2</Subscript> in Deep Saline Aquifers

Simulations of CO₂ injection into confined saline aquifers were conducted for both vertical and horizontal injection wells. The metrics used in quantifying the performances of different injection scenarios included changes in pressure near the injection well, mass of CO₂ dissolved into brine (solubility trapping), and storage efficiency, all evaluated with an assumed injection period of 50 years. Metrics were quantified as functions of well length, well orientation, CO₂ injection rate, and formation anisotropy (ratio of vertical to horizontal conductivity). When equal well lengths are compared, there is not a significant difference between the predicted performances of horizontal and vertical wells. However, the length of a horizontal well may exceed the length of a vertical well because the length of the horizontal well is not constrained to the vertical thickness of the geologic formation. Simulations show that, as the length of the horizontal well is allowed to increase, the geologic formation can receive a significantly higher CO₂ injection rate without exceeding a maximum allowable pressure. This result is observed in both isotropic and anisotropic formations, and suggests that horizontal wells may be advantageous under pressure-limited conditions. However, the use of horizontal wells does not significantly improve the storage efficiency, and under strongly anisotropic conditions, a vertical well provides higher storage efficiency than a horizontal well. We conclude that horizontal wells may be preferable if the goal is to sequester a large amount of CO₂ in a short period of time, but do not offer a significant advantage in terms of long-term capacity of a potential repository.     

Chemical Compositions in Salinity Waterflooding of Carbonate Reservoirs: Theory

Higher oil recovery after waterflood in carbonate reservoirs is attributed to increasing water wettability of the rock that in turn relies on complicated surface chemistry. In addition, calcite mineral reacts with aqueous solutions and can alter substantially the composition of injected water by mineral dissolution. Carefully designed chemical and/or brine flood compositions in the laboratory may not remain intact while the injected solutions pass through the reactive reservoir rock. This is especially true for a low-salinity waterflood process, where some finely tuned brine compositions can improve flood performances, whereas others cannot. We present a 1D reactive transport numerical model that captures the changes in injected compositions during water flow through porous carbonate rock. We include highly coupled bulk aqueous and surface carbonate-reaction chemistry, detailed reaction and mass transfer kinetics, 2:1 calcium ion exchange, and axial dispersion. At typical calcite reaction rates, local equilibrium is established immediately upon injection. In SI, we validate the reactive transport model against analytic solutions for rock dissolution, ion exchange, and longitudinal dispersion, each considered separately. Accordingly, using an open-source algorithm (Charlton and Parkhurst in Comput Geosci 37(10):1653–1663, 2011. https://doi.org/10.1016/j.cageo.2011.02.005), we outline a design tool to specify chemical/brine flooding formulations that correct for composition alteration by the carbonate rock. Subsequent works compare proposed theory against experiments on core plugs of Indiana limestone and give examples of how injected salinity compositions deviate from those designed in the laboratory for water-wettability improvement.

     

Characteristics of Salt-Precipitation and the Associated Pressure Build-Up during CO<Subscript>2</Subscript> Storage in Saline Aquifers

Mitigation and control of borehole pressure at the bottom of an injection well is directly related to the effective management of well injectivity during geologic carbon sequestration activity. Researchers have generally accepted the idea that high rates of CO₂ injection into low permeability strata results in increased bottom-hole pressure in a well. However, the results of this study suggested that this is not always the case, due to the occurrence of localized salt precipitation adjacent to the injection well. A series of numerical simulations indicated that in some cases, a low rate of CO₂ injection into high permeability formation induced greater pressure build-up. This occurred because of the different types of salt precipitation pattern controlled by buoyancy-driven CO₂ plume migration. The first type is non-localized salt precipitation, which is characterized by uniform salt precipitation within the dry-out zone. The second type, localized salt precipitation, is characterized by an abnormally high level of salt precipitation at the dry-out front. This localized salt precipitation acts as a barrier that hampers the propagation of both CO₂ and pressure to the far field as well as counter-flowing brine migration toward the injection well. These dynamic processes caused a drastic pressure build-up in the well, which decreased injectivity. By modeling a series of test cases, it was found that low-rate CO₂ injection into high permeability formation was likely to cause localized salt precipitation. Sensitivity studies revealed that brine salinity linearly affected the level of salt precipitation, and that vertical permeability enhanced the buoyancy effect which increased the growth of the salt barrier. The porosity also affected both the level of localized salt precipitation and dry-out zone extension depending on injection rates. High temperature injected CO₂ promoted the vertical movement of the CO₂ plume, which accelerated localized salt precipitation, but at the same time caused a decrease in the density of the injected CO₂. The combination of these two effects eventually decreased bottomhole pressure. Considering the injectivity degradation, a method is proposed for decreasing the pressure build-up and increasing injectivity by assigning a ‘skin zone’ that represents a local region with a transmissivity different from that of the surrounding aquifer.