It has been proposed that increased oil recovery in carbonates by modification of ionic composition or altering salinity occurs mainly at a temperature exceeding 70–80 °C. The argument was that elevated temperatures enhance adsorption of the potential determining ions which then modifies wettability to a less-oil-wetting state. According to this rationale, it becomes questionable if diluted brines or brines without these ions can be still applicable. Therefore, the aim of this paper is to investigate if the wettability alteration truly depends on temperature and if so how the trend with temperature can be explained. We followed a combined experimental and theoretical modeling approach. The effect of brine composition and temperature on carbonate wettability was probed by monitoring contact angle change of sessile oil droplets upon switching from high salinity to lower salinity brines. IFT measurements as a function of salinity and temperature along with extensive ζ-potential measurements as a function of salinity, pH, temperature, and rock type were conducted. Interaction potentials between oil and carbonate surfaces were estimated based on DLVO theory, and its consistency with oil-droplet data was checked to draw conclusions on plausible mechanisms. Three carbonate rocks (two limestones and one dolomite) were used along with two reservoir crude oils, high salinity formation water (FW), seawater (SW), and 25 times diluted seawater (25dSW) as low salinity (LS) brine. It was observed that (i) wettability alteration to a less-oil-wetting state can occur at ambient temperature for specific rock types and brines, and (ii) there is no univocal increase in response to SW and LS brine at elevated temperature. The largest improvement in wettability was observed for dolomite, while, among the limestones, only one rock type showed noticeable wettability improvement at elevated temperature with SW. The difference in behavior between limestones and dolomite indicates that the response to brine composition change depends on rock type and mineralogy of the sample. These observations are consistent with the ζ-potential trends with salinity at a given temperature. Dolomite generally shows more positive ζ-potential than limestones. However, even the two limestones react differently to lowering salinity and exhibit different magnitude of ζ-potential. Moreover, it is observed that, at a specific salinity, an increase in temperature leads to reduction of ζ-potential magnitude on both rock/brine and oil/brine interfaces toward zero potential. This can affect positively or negatively the degree of wettability alteration (to a less-oil-wetting state) at elevated temperature depending on the sign of oil/brine and rock/brine ζ-potential in SW/LS. The observed trends are reflected in the DLVO calculations which show consistency with contact angle trends with temperature and salinity. According to the DLVO calculation, the lack of response to SW/LS in some of the systems above can be explained by stronger electrostatic attractive forces und...

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Recently, several advanced nonlinear formulations were developed for compositional simulations [5,6]. All of these approaches propose a better way of dealing with phase changes. However, these formulations were never tested for complex realistic problems. The idea described in [5] was adapted for a general purpose simulation and tested against state of the art approaches [7]. For the problems of practical interest, this formulation demonstrated only insignificant improvements with respect to conventional methods.

Summary Thermodynamic equilibrium calculations in compositional flow simulators are used to find the partitioning of components among fluid phases, and they can be a time consuming kernel in a compositional flow simulation. We describe a tie-line-based compositional space parameterization (CSP) approach for dealing with immiscible gas-injection processes with large numbers of components. The multicomponent multiphase equilibrium problem is recast in terms of this parameterized compositional space, in which the solution path can be represented in a concise manner. This tie-line-based parameterization approach is used to speed up the phase behavior calculations of standard compositional simulation. Two schemes are employed. In the first method, the parameterization of the phase behavior is computed in a preprocessing step, and the results are stored in a table. During the course of a simulation, the flash calculation procedure is replaced by the solution of a multidimensional optimization problem in terms of the parameterized space. For processes where significant changes in pressure and temperature take place, this optimization procedure is combined with linear interpolation in tie-line space. In the second method, compositional space adaptive tabulation (CSAT) is used to accelerate the equation of state (EOS) computations associated with standard compositional reservoir simulation. The CSAT strategy takes advantage of the fact that, in gas injection processes, the solution path involves a limited number of tie-lines. The adaptively collected tie-lines are used to avoid redundant phase-stability checks in the course of a flow simulation. Specifically, we check if a given composition belongs to one of the tie-lines (or its extension) already in the table. If not, a new tie-line is computed and added to the table. The CSAT technique was implemented in a general-purpose research simulator (GPRS), which is designed for compositional flow simulation on unstructured grids. Using a variety of challenging models, we show that, for immiscible compositional processes, CSAT leads to significant speed up (at least a several-fold improvement) of the EoS calculations compared with standard techniques.

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Summary Compositional simulation is necessary for modeling complex enhanced oil recovery (EOR) processes. For accurate simulation of compositional processes, we need to resolve the coupling of the nonlinear conservation laws, which describe multiphase flow and transport, with the equilibrium phase behavior constraints. The complexity of the problem requires extensive computations and consumes significant time. This paper presents a new framework for the general compositional problem associated with multicomponent multiphase flow in porous media. Here, adaptive construction and interpolation using the supporting tie lines are used to obtain the phase state and the phase compositions. For the parameterization of the full solution of a complex compositional problem, we need only a limited number of supporting tie lines in the compositional space. The parameterized tie lines are triangulated using Delaunay tessellation, and natural-neighbor interpolation is used inside the simplexes. Then, the computation of the phase behavior in the course of a simulation becomes an iteration-free, table look-up procedure. The treatment of nonlinearities associated with complex thermodynamic behavior of the fluid is based on the new set of unknowns—tie-line parameters that allow for efficient representation of the subcritical region. For the supercritical region, we use the standard compositional variable set based on the overall composition. The efficiency and accuracy of the method are demonstrated for several multidimensional compositional problems of practical interest. In terms of the computational cost of the thermodynamic calculations, the proposed method shows results comparable to those of state-of-the-art techniques. Moreover, the method shows better nonlinear convergence in the case of near-miscible gas-injection simulation.