Carbonated water flooding (CWI) increases oil production due to favorable dissolution effects and viscosity reduction. Accurate modeling of CWI performance requires a simulator with the ability to capture the true physics of such process. In this study, compositional modeling coupled with surface complexation modeling (SCM) are done, allowing a unified study of the influence in oil recovery of reduction of salt concentration in water. The compositional model consists of the conservation equations of total carbon, hydrogen, oxygen, chloride and decane. The coefficients of such equations are obtained from the equilibrium partition of chemical species that are soluble both in oleic and the aqueous phases. SCM is done by using the PHREEQC program, which determines concentration of the master species. Estimation of the wettability as a function of the Total Bound Product (TBP) that takes into account the concentration of the complexes in the aqueous, oleic phases and in the rock walls is performed. We solve analytically and numerically these equations in 1 - D in order to elucidate the effects of the injection of low salinity carbonated water into a reservoir containing oil equilibrated with high salinity carbonated water.

This paper is concerned with the study of the main wave interactions in a system of conservation laws in geochemical modeling. We study the modeling of the chemical complexes on the rock surface. The presence of stable surface complexes affects the relative permeability. We add terms representing surface complexes to the accumulation function in the model presented in [14]. This addition allows to take into account the interaction of ions with the rock surface in the modeling of the oil recovery by the injection of carbonated water. Compatibility hypotheses with the modeling are made on the coefficients of the system to obtain meaningful solutions. We developed a Riemann solver taking into account the complexity of the interactions and bifurcations of nonlinear waves. Such bifurcations occur at the inflection and resonance surfaces. We present the solution of a generalized eigenvalue problem in a (n+1)-dimensional case, which allows the construction of rarefaction curves. A method to find the discontinuous solutions is also presented. We find the solution path for some examples.

We develop a method based on concept of exergy-return on exergy-investment (ERoEI) to determine the energy efficiency and CO₂ footprint of polymer and surfactant enhanced oil recovery (EOR). This integrated approach considers main surface and subsurface elements of the chemical EOR methods. The main energy investment in oil recovery by water injection is mainly related to circulation of water with respect to exergy of the oil produced. At large water cuts of >90%, more than 70% of the total invested energy is spent on pumping the fluids. Consequently, production of barrels of oil is associated with large amounts of CO₂ emission for mature oil fields with large water cuts. Our analysis shows that injection of polymer increases the energy efficiency of the oil recovery system. Because of additional oil (exergy gain) and less water circulation (exergy investment), the project-time averaged energy invested (and consequently CO₂ emitted) to produce one barrel of oil from polymer flooding is less than that of the water flooding at large water cuts. We conclude that polymer injection into reservoirs with high water cut can be a solution for two major challenges of the transition period: (1) meet the global energy demand via an increase in oil recovery and (2) reduce the CO₂ footprint of oil production (more and cleaner oil). For surfactant-polymer EOR, the extent of improvement in energy efficiency depends on the incremental gain and the simplicity of the formulations.

This paper presents an assessment of the life-cycle exergetic efficiency and CO2 footprint of the underground biomethanation process. The subsurface formation, hosting microorganisms required for the reaction, is utilized to convert CO2 and green (produced from renewable energy) hydrogen to the so-called "green"or synthetic methane. The net exergy gain and CO2 intensity of the biomethanation process are compared to the alternative options of (1) green H2 storage (no energy upgrading process to CH4) and (2) fossil-based CH4 with carbon capture and storage (CCS), i.e., blue CH4. It is found that with the current state of the technology and within the assumptions of this study, the exergy return on the exergy invested for underground biomethanation does not outperform the direct storage and utilization of green H2. The maximum exergetic efficiency of the biomethanation process is calculated to be 15-33% for electricity and 36-47% for heating, while the overall exergetic efficiency of the direct use of H2 for electricity is estimated to be between 20 and 61%. Moreover, the energy produced from the underground biomethanation process has the largest CO2 intensity among the studied options. Depending on the technology used in the CCS and hydrogen production stages, the CO2 intensity of the electricity generated from synthetic CH4 can be as large as 142 g CO2/MJe, which is at least 56-73% larger than those of the two other studied cases.

Production of mature oil fields emits significant amount of CO₂ related to circulation and handling of large volumes of gas and water. This can be reduced either by (1) using a low-carbon energy source and/or (2) reducing the volumes of the non-hydrocarbon produced/injected fluids. This paper describes how improved oil recovery techniques can be designed to reduce CO₂ intensity (kgCO₂/bbl oil) of oil production by efficient use of the injectants. It is shown that CO₂ emissions associated with injection of chemicals is strongly influenced by water cut at the start of the project, extent of the water cut reduction, and chemical utilization factor defined as the volume of produced oil per mass or volume of the injectant. As an example, for the oil field considered in this study, 3–8% reduction in water cut can result in 50–80% reduction in its CO₂ intensity. In addition to the incremental oil production with lower CO₂ intensity, the earlier implementation of enhanced oil recovery methods can extend the lifetime of the mature fields if carbon emission cut-offs are applied. In case of CO₂ enhanced oil recovery (EOR), the large storage potential for CO₂ can significantly reduce the overall CO₂ emissions of oil, albeit at a large energetic cost. For CO₂ EOR using CO₂ captured from gas power plants, improving the utilization factor from 2 bbl/tCO₂ to 4 bbl/tCO₂ can reduce the CO₂ intensity of the produced oil from 120 kgCO₂/bbl to 80 kgCO₂/bbl (33% reduction).

A method based on the concept of exergy-return on exergy-investment is developed to determine the energy efficiency and CO₂ intensity of polymer and surfactant enhanced oil recovery techniques. Exergy is the useful work obtained from a system at a given thermodynamics state. The main exergy investment in oil recovery by water injection is related to the circulation of water required to produce oil. At water cuts (water fraction in the total liquid produced) greater than 90%, more than 70% of the total invested energy is spent on injection and lift pumps, resulting in large CO₂ intensity for the produced oil. It is shown that injection of polymer with or without surfactant can considerably reduce CO₂ intensity of the mature waterflood projects by decreasing the volume of produced water and the exergy investment associated with its circulation. In the field examples considered in this paper, a barrel of oil produced by injection of polymer has 2–5 times less CO₂ intensity compared to the baseline waterflood oil. Due to large manufacturing exergy of the synthetic polymers and surfactants, in some cases, the unit exergy investment for production of oil could be larger than that of the waterflooding. It is asserted that polymer injection into reservoirs with large water cut can be a solution for two major challenges of the energy transition period: (1) meet the global energy demand via an increase in oil recovery and (2) reduce the CO₂ intensity of oil production (more and cleaner energy).

This work uses pilot examples of CO₂ enhanced oil recovery to analyze whether and under which circumstances it is exergetically favorable to sequester CO₂ through enhanced oil recovery. We find that the net storage efficiency (ratio between the stored and captured CO₂) of the carbon capture and storage (CCS)-only projects is maximally 6–56% depending on the fuel used in the power plants. With the current state of technology, the CCS process will re-emit a minimum of 0.43–0.94 kg of CO₂ per kg of CO₂ stored. From thermodynamics point of view, CO₂ enhanced oil recovery (EOR) with CCS option is not sustainable, i.e., during the life cycle of the process more energy is consumed than the energy produced from oil. For the CCS to be efficient in reducing CO₂ levels (1) the exergetic cost of CO₂ separation from flue gas should be reduced, and/or (2) the capture process should not lead to additional carbon emission. Furthermore, we find that the exergy recovery factor of CO₂-EOR depends on the CO₂ utilization factor, which is currently in the low range of 2–4 bbl/tCO₂ based on the field data. Exergetically, CO₂ EOR with storage option produces 30–40% less exergy compared to conventional CO₂ enhanced oil recovery projects with CO₂ supplied from natural sources; however, this leads to storage of >400 kg of extra CO₂ per barrel of oil produced.

Pore-network models have been used to derive relative-permeability and capillary-pressure relations, which are important for oil-recovery predictions and processes. Here, we show that relative-permeability and capillary-pressure relations on large scales can be obtained much faster with the effective-medium approximation. Our approach differs from previous work in that we use various shapes of non-circular pores and combinations of different shapes. We use a finite-element approach to compute the hydraulic conductivity of arbitrarily shaped prisms, which are partly filled with oil and water. Our present interest is confined to water-wet media. Striking features of the obtained constitutive relations are that the water relative permeabilities show a marked reduction below a critical water saturation—at which there is no infinite cluster of completely filled water pores—but the water relative permeabilities continue to be finite even at very low water saturations because of corner flow. The capillary pressure remains finite even at low water saturations. Primary-drainage oil relative permeabilities are non-zero at low oil saturations, which is in line with early gas breakthrough for the solution-gas drive oil-recovery mechanism. We compare the results obtained with the effective-medium approximation to the results obtained with a pore-network model consisting of a simple-cubic lattice of prisms. The comparison shows that the pore-network generated relative-permeability curves are completely dissimilar to the effective-medium approximation derived relative-permeability curves. Furthermore, below and near the percolation threshold, the pore-network results differ significantly from one realization to another and/or from one network size to another network size. The network-model results show discontinuous behavior at the percolation threshold. This implies that pore-network results are scale dependent and the pore-network sizes up to 301 × 301 × 301 (the limitation determined by the available computer power) studied here are still far from a representative elementary volume (REV).

In hydraulic fracturing, fracturing fluids are used to create fractures in a hydrocarbon reservoir throughout transported proppant into the fractures. The application of many fields proves that conventional fracturing fluid has the disadvantages of residue(s), which causes serious clogging of the reservoir's formations and, thus, leads to reduce the permeability in these hydrocarbon reservoirs. The development of clean (and cost-effective) fracturing fluid is a main driver of the hydraulic fracturing process. Presently, viscoelastic surfactant (VES)-fluid is one of the most widely used fracturing fluids in the hydraulic fracturing development of unconventional reservoirs, due to its non-residue(s) characteristics. However, conventional single-chain VES-fluid has a low temperature and shear resistance. In this study, two modified VES-fluid are developed as new thickening fracturing fluids, which consist of more single-chain coupled by hydrotropes (i.e., ionic organic salts) through non-covalent interaction. This new development is achieved by the formulation of mixing long chain cationic surfactant cetyltrimethylammonium bromide (CTAB) with organic acids, which are citric acid (CA) and maleic acid (MA) at a molar ratio of (3:1) and (2:1), respectively. As an innovative approach CTAB and CA are combined to obtain a solution (i.e., CTAB-based VES-fluid) with optimal properties for fracturing and this behaviour of the CTAB-based VES-fluid is experimentally corroborated. A rheometer was used to evaluate the visco-elasticity and shear rate & temperature resistance, while sand-carrying suspension capability was investigated by measuring the settling velocity of the transported proppant in the fluid. Moreover, the gel breaking capability was investigated by determining the viscosity of broken VES-fluid after mixing with ethanol, and the degree of core damage (i.e., permeability performance) caused by VES-fluid was evaluated while using core-flooding test. The experimental results show that, at pH-value (6.17), 30 (mM) VES-fluid (i.e., CTAB-CA) possesses the highest visco-elasticity as the apparent viscosity at zero shear-rate reached nearly to 106 (mPa·s). Moreover, the apparent viscosity of the 30 (mM) CTAB-CA VES-fluid remains 60 (mPa·s) at (90 °C) and 170 (s^-1) after shearing for 2-h, indicating that CTAB-CA fluid has excellent temperature and shear resistance. Furthermore, excellent sand suspension and gel breaking ability of 30 (mM) CTAB-CA VES-fluid at 90 (°C) was shown; as the sand suspension velocity is 1.67 (mm/s) and complete gel breaking was achieved within 2 h after mixing with the ethanol at the ratio of 10:1. The core flooding experiments indicate that the core damage rate caused by the CTAB-CA VES-fluid is (7.99%), which indicate that it does not cause much damage. Based on the experimental results, it is expected that CTAB-CA VES-fluid under high-temperature will make the proposed new VES-fluid an attractive thickening fracturing fluid.

Recently, there is an increased interest in reactive flow in porous media, in groundwater, agricultural and fuel recovery applications. Reactive flow modeling involves vastly different reaction rates, i.e., differing by many orders of magnitude. Solving the ensuing model equations can be computationally intensive. Categorizing reactions according to their speeds makes it possible to greatly simplify the relevant model equations. Indeed some reactions proceed so slow that they can be disregarded. Other reactions occur so fast that they are well described by thermodynamic equilibrium in the time and spatial region of interest. At intermediate rates kinetics needs to be taken into account. In this paper, we categorize selected reactions as slow, fast or intermediate. We model 2D radially symmetric reactive flow with a reaction-convection-diffusion equation. We show that we can subdivide the PeDa_II phasespace in three regions. Region I (slow reaction); reaction can be ignored, region II (intermediate reaction); initially kinetics need to be taken into account, region III (fast reaction); all reaction takes places in a very narrow region around the injection point. We investigate these aspects for a few specific examples. We compute the location in phase space of a few selected minerals depending on salinity and temperature. We note that the conditions, e.g., salinity and temperature may be essential for assigning the reaction to the correct region in phase space. The methodology described can be applied to any mineral precipitation/decomposition problem and consequently greatly simplifies reactive flow modeling in porous media.

This paper describes miscible displacement upon air injection in a porous medium saturated with oil corresponding to conditions of high-pressure air injection (HPAI). We assume that injection fluids and produced fluids are fully miscible with the oil at the prevailing high pressure. We use three pseudo-components, viz., oxygen, oil, and an inert component, which includes nitrogen, carbon dioxide, etc. To model the fingering instabilities, we follow a similar procedure as proposed by Koval (SPE J. 3(02):145–154, 1963) and include the reaction between oxygen and oil in the Koval model. The equations are solved numerically, using a finite element software package (COMSOL). The results show that a combustion wave is formed. We study the performance at low and high viscosities and show that the reaction improves the speed and degree of recovery at later times.

The proposed study of combined low salinity foam Injection using DLVO-theory (i.e., Derjaguin, Landau, Verwey, and Overbeek) and surface complexation modeling or SCM, is a follow up of a previous study of a Novel Hybrid Enhanced Oil Recovery Method by Smart Water-Injection and Foam-Flooding in Carbonate Reservoirs (SPE-196407-MS). The method combines the advantages of our new designed "smart-water" (i.e., ionically modified brine or low salinity) injection with foam drive recovery. Our new desined "smart-water" injection has a double enhancement effect. It leads to change the limestone rock (i.e., calcite) wettability from oil or mixed-wet to more water wet (i.e., stable water-film), and helps to improve the stability of the foam-film. In the previous study (SPE-196407-MS) we investigated the impact of our "smart water" or low salinity injection on the surface complexes by simulating one single base case scenario, which equivalent to [NaCl 0.4 mMol/liter]. We use computr program (PHREEQC) to obtain the equilibrium concentrations and zeta-potential (surface potential or electro-kinetic potential), and to invetigate the effect of water-salinity and CO₂ pressure for a given choice of the surfactant (i.e. carboxylic acid R-COOH). In addition, for the surface complexation model, we studied the model of Dzombak and Morel, which uses Debye Huckel activity coefficients (i.e., valid up to ionic strength I = 0.3 mol/kilogram of water) (SPE-196407-MS). In this contribution (OTC-30301-MS), we use the DLVO-theory and SCM (surface complexation modeling) to create multiple scenarios of smart water (i.e., ionically modified brine) to study its impact on surface complexes during fluid-rock interaction process (i.e., calcite-water interface and oil-water interface). To be specific, we use PHREEQC to simulate and compare two case scenarios; the case of low salinity (NaCl 0.4 mmol/kg-water) and the case of high salinity [NaCl 8500 mMol/liter]. Also, for better optimization of the factors affecting the surface complex modeling, in this work, we modified the model of Dzombak and Morel, by using more accurately activity coefficient given by Pitzer coefficients above (0.3 mol/kgwater) (i.e., valid up to ionic strength I = 6 mol/kg-water). Additionally, the surface charge and the surface complexes are calculated, implemented and built-in using geochemical code PHREEQC. Further input: fraction of sites that bind the carboxylic acids (R-COOH) and bind the carbonates (CaCO₃) surface complex are (1.67×10⁻⁶) and (4.1 × 10^-6) respectivly, and surface area per gram of solid is (1 m²/g) for both the oleic and calcite interface (Hassan, et al., 2020). Moreover, we applied Gibbs rule to determine the number of chemical degrees of freedom. In our case, we have two numbers of degrees of freedom, and its chosen to be pH and ionic strength. Also, we examined the effect of pH and carbon dioxide (CO₂)-pressure on the surface complexes (i.e., surface charge and surface potential) for both scenarios (i.e., low salinity [NaCl 0.4 mmol/kg-water] and high salinity [NaCl 8500 mmol/kg-water]) (Hassan, et al., 2020). Qualitatively we can state that, the stability of a water film between the rock-aqueous phase / oil aqueous phase interfaces is resolute by the active sites on carbonate rock (i.e., calcite) and oil. If they with a charge of the same sign, a water film is usually stable. The foam stability is determined by the double layer (charged surface + counter ions in solution) repulsion, which is electrostatic and attractive the Van der Waals forces, which are determined by the dielectric coefficients of the constituting layers. If the electrostatic forces dominate the foam film is considered stable. It is conjectured that, high carbon dioxide pressures have a destabilizing effect on the film for both cases (i.e., low salinity [NaCl 0.4 mmol/kg-water] and high salinity [NaCl 8500 mmol/kg-water]), as they reduce the surface potential. A decreased surface potential leads to a reducing electrostatic double layer repulsion (EDL) and thus destabilizes the stability of the foam film, whereas low salinity leads to less screening of the surface potential and thus improves the stability of the foam film lamellae. The activity coefficients are more accurately given by the Pitzer coefficients above (0.3 mol/kg-water) (i.e., valid up to 6 [mol/kg-water]). It is shown that, manipulating surface complexes by imposing different salinity and pH can help to obtain mixed-wet or oil-wet behavior, with more favorable residual oil saturations, accepting the occurrence of less favorable mobility ratios. Clearly, the choice of optimal conditions is case dependent; if the mobility ratio is already favorable as to be expected with foam flow, mixed-wet conditions are favored with low residual oil saturations. Thus, an optimal choice of the pH that at the same time leads to a stable brine film on the calcite surface, and a stable foam film requires fine tuning.

This contribution focuses on surface complexes in the calcite-brine-surfactant system. This is relevant for the recovery of oil when using a new hybrid enhanced oil recovery (EOR) method, which combines smart-water (i.e., ionically modified brine) and foam-flooding (SWAF) of light oil with dissolved carbon dioxide (CO₂) at high pressure in carbonate (i.e., calcite) reservoirs. Using this new hybrid EOR-method (i.e., the SWAF-process) is not only economically attractive (i.e., it reduces opex costs) but also enhances the effectiveness of the production process, and thus reduces the environmental impact. Ionically modified brine (i.e., low-salinity) has a dual improvement effect. It not only leads to more stable foam lamellae, but also helps to change the carbonate rock wettability, leading for some conditions to more favorable relative permeability behavior. The mechanism for the modified permeability behavior in the presence of ionically modified brine is only partly understood. Therefore, we study this process initially in a zero dimensional (thermodynamics) setting, which can be used for the one dimensional (1D) displacement process with an oleic phase that contains carbon dioxide (CO₂) and an aqueous phase that contains both carbon dioxide (CO₂) and all the ionic substances. Using DLVO theory and surface complexation modeling to better understand the mechanism(s) of ionically modified brine as wettability modifier and foam stabilizer. We perform simulations using both (NaCl) and (MgCl₂) to show the effect of a divalent ion at the high-salinity (8500 mmol/kg-w) and low-salinity (0.4 mmol/kg-w) for both ambient-conditions at (25°C) and at the reservoir-conditions (80°C). We confine our analysis to a description that uses the Dzombak-Morel model of surface complexes, which is based on the Debye-Hückel theory (i.e., valid up to ionic strength of 0.3 (mol/kilogram of water)). We also investigate the effect of carbon dioxide (CO₂) on the stability of low-salinity foam-laminae. We model the foam-laminae, which contain as surface complex a (cationic) surfactant in an aqueous phase. We use the PHREEQC-software to calculate the surface charge and the surface potential. The presence of a carbon dioxide (CO₂) phase leads to dissolution of four valent C(IV) compounds in the aqueous film. PHREEQC also calculates the equilibrium concentrations and surface potential and allows the study of the effect of salinity and the carbon dioxide (CO₂) gas pressure. For the soap-film (foam-film) in a carbon dioxide (CO₂) atmosphere we do use Pitzer activity coefficients (i.e., valid up to 6 (mol/kilogram of water)). As our aim is to show the methodology and the versatility of this approach, we leave more realistic choices of these parameters for future work.sFor the conditions considered we can qualitatively state that, in the presence of (NaCl i.e., at pH > 10) and (MgCl₂ i.e., pH > 10.3), the low-salinity case shows a more stable water-film behavior at (25°C) and at (80°C) than the high-salinity case for both (25°C) and (80°C). Moreover, high carbon dioxide (CO₂) pressures have a destabilizing effect on the film, as they reduce the surface potential. A reduced surface potential leads to a decreasing electrostatic double layer repulsion and thus destabilizes the foam-film, whereas low-salinity leads to less screening of the surface potential and thus improves the stability of the foam-film. The low-salinity flow is characterized by a high residual oil saturation and low end-point permeability for the two phase oil-water flow. This leads to a more favorable mobility ratio and thus a more favorable displacement process. For the calcite surface an enhanced stability helps to stabilize the water film on the calcite surface if the oil-water surface charge has the same sign as the surface charge on the calcite surface. Our calculations show the pH range where the sign of these charges is the same or opposite at low-salinity and high-salinity conditions. Admittedly these calculations only show trends, but can be used to delineate optimal conditions for the application of “Smart Water Assisted Foam (SWAF) Flooding”. It is expected that the SWAF-process under the optimum conditions will make the proposed new hybrid Enhanced Oil Recovery (EOR) process environmentally and economically attractive.

We study systems of partial differential-algebraic equations (PDAEs) of first order. Classical solutions of the theory of hyperbolic partial differential equation such as discontinuities (shock and contact discontinuities), rarefactions and diffusive traveling waves are extended for variables living on a surface S, which is defined as solution of a set of algebraic equations. We propose here an alternative formulation to study numerically and theoretically the PDAEs by changing the algebraic conditions into partial differential equations with relaxation source terms (PDREs). The solution of such relaxed systems is proved to tend to the surface S, i.e., to satisfy the algebraic equations for long times. We formulate a unified numerical scheme for systems of PDAEs and PDREs. This scheme is naturally parallelizable and has faster convergence. We do not perform a rigorous analysis about the convergence or accuracy for the method, the evidence of its effectiveness is presented by means of simulations for physical and synthetical problems.

1D water oil displacement in porous media is usually described by the Buckley-Leverett equation or the Rapoport-Leas equation when capillary diffusion is included. The rectilinear geometry is not representative for near well oil displacement problems. It is therefore of interest to describe the radially symmetric Buckley-Leverett or Rapoport-Leas equation in cylindrical geometry (radial Buckley-Leverett problem). We can show that under appropriate conditions, one can apply a similarity transformation (r, t) → η= r²/ (2 t) that reduces the PDE in radial geometry to an ODE, even when capillary diffusion is included (as opposed to the situation in the rectilinear geometry (Yortsos, Y.C. (Phys. Fluids 30(10),2928–2935 1987)). We consider two cases (1) where the capillary diffusion is independent of the saturation and (2) where the capillary diffusion is dependent on the saturation. It turns out that the solution with a constant capillary diffusion coefficient is fundamentally different from the solution with saturation-dependent capillary diffusion. Our analytical approach allows us to observe the following conspicuous difference in the behavior of the dispersed front, where we obtain a smoothly dispersed front in the constant diffusion case and a power-law behavior around the front for a saturation-dependent capillary diffusion. We compare the numerical solution of the initial value problem for the case of saturation-dependent capillary diffusion obtained with a finite element software package to a partially analytical solution of the problem in terms of the similarity variable η.