Chemical flooding has been studied for 50 years. However, never have the conditions encouraging its growth been as good as right now. Those conditions being new, improved technology and oil prices high enough to make implementation economical. The objective of this work was to develop economical, robust chemical formulations and processes that recover oil in field pilots when properly implemented. This experimental study goes through the process of testing surfactants to achieve optimal phase behavior, coreflooding with the best chemical formulations, improving the formulation and testing it in more corefloods, and then finally recommending the formulation to be tested in a field pilot. The target reservoir contains a light (34° API, 10 cP), non-reactive oil at about 22° C. The formation is a moderate permeability (50 - 300 mD) sandstone with a high clay content (up to 13%). Different surfactants and surfactant mixtures were tested with the oil including alkyl benzene sulfonates (ABS), Guerbet alcohol sulfates (GAS), alkyl propoxy sulfates, and internal olefin sulfonates (IOS). The best formulation contained 0.75% TDA -13PO-SO₄, 0.25% C₂₀₋₂₄ IOS, 0.75% isobutanol (IBA), 1% Na₂CO₃, all which are mixed in a softened fresh water from a supply well. Corefloods recovered 93% of residual oil from reservoir cores. Core flood experiments were also done with the alkali sodium carbonate to measure the effluent pH in a Bentheimer sandstone core with a cation exchange capacity (CEC) of 2 meq/100g. Floods at frontal velocities of 100, 10, and 0.33 ft/D were performed with 0.3 pore volume slugs of 0.7% Na₂CO₃ at 86° C. The effluent was analyzed for ions and pH breakthrough. It was found that the pH breakthrough occurred before surfactant breakthrough would be expected as desired although the pH was lower at a frontal velocity of 0.33 ft/D than at the higher velocities. The Na₂CO₃ consumption was 0.244, 0.238, and 0.207 meq/100 g rock at velocities of 100, 10, and 0.33 ft/D, respectively. In addition, a no-alkaline formulation consisting of a new large hydrophobe ether carboxylate surfactant mixed with an internal olefin sulfonate was tested on an active oil and it successfully recovered 99% of the waterflood remaining oil from an Ottawa sand pack with no salinity gradient and no alkali. The final residual oil saturation after the chemical flood (S[subscript orc]) was only 0.005 / text

Studying chemical enhanced oil recovery (EOR) in a high-temperature/high-salinity (HT/HS) reservoir will help expand the application of chemical EOR to more challenging environments. Until recently, chemical EOR was not recommended at reservoirs that contain high concentrations of divalent cations without the need to recondition the reservoir by flooding it with less saline/ less hardness brines. This strategy was found ineffective in preparing the reservoir for chemical flooding. Surfactants used for chemical flooding operating in high temperatures tend to precipitate when exposed to high concentrations of divalent cations and will partition to the oil phase at high salinities. In this study amphoteric surfactant was used to replace the traditionally used anionic surfactants. Amphoteric surfactants show higher multivalent cations tolerance with better thermal stability. A modified amphoteric surfactant with lower adsorption properties was evaluated for oil recovery. Organic alkali was used to eliminate the water softening process when preparing the chemical solution and reduce potential scale problems caused by precipitation due to incompatibility between chemical slug containing alkali and formation brine. Using organic alkali helped in minimizing softening required when preparing an alkali-surfactant-polymer (ASP) solution using seawater. Solution prepared with organic alkali showed the least injectivity decline when compared to traditional alkalis (NaOH and Na2CO3) and sodium metaborate. Adding organic alkali helped further reduce IFT values when added to surfactant solution. Amphoteric surfactant was found to produce low IFT values at low concentrations and can operate at high salinity / high hardness conditions. When mixed with polymer it improved the viscosity of the surfactant-polymer (SP) solution when prepared in high salinity mixing water (6% NaCl). When prepared in seawater and tested in reservoir temperature (95°C) no reduction in viscosity was found. Unlike the anionic surfactant that causes reduction in viscosity of the SP solution at reservoir temperature. This will not require increasing the polymer concentration in the chemical slug. Unlike the case when anionic surfactant was used and more polymer need to be added to compensate the reduction in viscosity. Berea sandstone cores show lower recovery compared to dolomite cores. It was also found that Berea cores were more sensitive to polymer concentration and type and injectivity decline can be a serious issue during chemical and polymer injection. Dolomite did not show injectivity decline during chemical and polymer flooding and was not sensitive to the polymer concentration when a polymer with low molecular weight was used. CT scan was employed to study the displacement of oil during ASP, SP, polymer and surfactant flooding. The formation and propagation oil bank was observed during these core flood experiments. ASP and SP flooding showed the highest recovery, and formation and propagation of oil bank was clearer in these experiments compared to surfactant flooding. It was found that in Berea sandstone with a permeability range of 50 to 80 md that the recovery and fluid flow was through some dominating and some smaller channels. This explained the deviation from piston-like displacement, where a sharp change in saturation in part of the flood related to the dominated channels and tapered front with late arrival when oil is recovered from the smaller channels. It was concluded that the recovery in the case of sandstone was dominated by the fluid flow and chemical propagation in the porous media not by the effectiveness of the chemical slug to lower the IFT between the displacing fluid and oil.

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Accurate simulation of chemical flooding requires a detailed understanding of numerous complex mechanisms and model parameters where grid size has a substantial impact upon results. In this research we show the effect of grid size on parameters such as phase behavior, interfacial tension, surfactant dilution and salinity gradient for chemical flooding of a very heterogeneous oil reservoir. The effective propagation of the surfactant slug in the reservoir is of paramount importance and the salinity gradient is a key factor in ensuring the process effectiveness. The larger the grid block size, the greater the surfactant dilution, which in turn erroneously reduces the effectiveness of the process indicated with low simulated oil recoveries. We show that the salinity gradient is not adequately captured by coarse grid simulations of heterogeneous reservoirs and this leads to performance predictions with lower recovery compared to fine grid simulations. Due to the highly coupled, nonlinear interactions of the many chemical and physical processes involved in chemical flooding, it is better to use fine-grid simulations rather than coarse grids with upscaled physical properties whenever feasible. However, the upscaling methodology for chemical flooding presented in this work accounts approximately for some of the more important effects, as demonstrated by comparison of fine grid and coarse grid results and is very different than the way other enhanced oil recovery methods are upscaled. This is a step towards making better performance predictions of chemical flooding for large field projects where it is not currently feasible to perform the large number of simulations required to properly consider different designs, optimization, risk and uncertainty using fine-grid simulations. / text

In the past thirty years, the development of compositional reservoir simulators using various equations of state (EOS) has been addressed in the literature. However, the development of compositional thermal simulators in conjunction with EOS formulation has been ignored, in particular. Therefore in this work, a fully implicit, parallel, compositional EOS-based simulator has been developed. In this model, an equation of state is used for equilibrium calculations among all phases (oil, gas, and aqueous). Also, the physical properties are calculated based on an equation of state, hence obviating the need for using steam tables for calculation of water/steam properties. The governing equations for the model comprise fugacity equations between the three phases, material balance, pore volume constraint and energy equations. The governing partial differential equations are solved using finite difference approximations. In the steam injection process, the solubility of oil in water-rich phase and the solubility of water in oil phase can be high. This model takes into account the solubility of water in oil phase and the solubility of hydrocarbon components in water-rich phase, using three-phase flash calculations. This simulator can be used in various thermal flooding processes (i.e. hot water or steam injections). Since the simulator was implemented for parallel computers, it is capable of solving large-scale thermal flooding problems. The simulator is successfully validated using analytical solutions. Also, simulations are carried out to compare this model with commercial simulators. The use of an EOS for calculation of various properties for each phase automatically satisfies the thermodynamic consistency requirements. On the other hand, using the K-value approach, which is not thermodynamically robust, may lead to results that are thermodynamically inconsistent. This simulator accurately tracks all components and mass transfer between phases using an EOS; hence, it will produce thermodynamically consistent results and project accurate prediction of thermal recovery processes. Electrical heating model, Joule heating and in-situ thermal desorption methods, and hot-chemical flooding model have also been implemented in the simulator. In the electrical heating model, electrical current equation is solved along with other governing equations by considering electrical heat generation. For implementation of the hot-chemical heating model, first the effect of temperature on the phase behavior model and other properties of the chemical flooding model is considered. Next, the material and energy balance and volume constraints equations are solved with a fully implicit method. The models are validated with other solutions and different cases are tested with the implemented models. / text

As easy target reservoirs are depleted around the world, the need for intelligent enhanced oil recovery (EOR) methods increases. The first part of this work is focused on modeling aspects of novel chemical EOR methods for naturally fractured reservoirs (NFR) involving wettability modification towards more water wet conditions. The wettability of preferentially oil wet carbonates can be modified to more water wet conditions using alkali and/or surfactant solutions. This helps the oil production by increasing the rate of spontaneous imbibition of water from fractures into the matrix. This novel method cannot be successfully implemented in the field unless all of the mechanisms involved in this process are fully understood. A wettability alteration model is developed and implemented in the chemical flooding simulator, UTCHEM. A combination of laboratory experimental results and modeling is then used to understand the mechanisms involved in this process and their relative importance. The second part of this work is focused on modeling surfactant/polymer floods using a fully implicit scheme. A fully implicit chemical flooding module with comprehensive oil/brine/surfactant phase behavior is developed and implemented in general purpose adaptive simulator, GPAS. GPAS is a fully implicit, parallel EOS compositional reservoir simulator developed at The University of Texas at Austin. The developed chemical flooding module is then validated against UTCHEM. / text

A large percentage of oil and gas reservoirs in the most productive regions such as the Middle East, South America, and Southeast Asia are naturally fractured reservoirs (NFR). The major difference between conventional reservoirs and naturally fractured reservoirs is the discontinuity in media in fractured reservoir due to tectonic activities. These discontinuities cause remarkable difficulties in describing the petrophysical structures and the flow of fluids in the fractured reservoirs. Predicting fluid flow behavior in naturally fractured reservoirs is a challenging area in petroleum engineering. Two classes of models used to describe flow and transport phenomena in fracture reservoirs are discrete and continuum (i.e. dual porosity) models. The discrete model is appealing from a modeling point of view, but the huge computational demand and burden of porting the fractures into the computational grid are its shortcomings. The affect of natural fractures on the permeability anisotropy can be determined by considering distribution and orientation of fractures. Representative fracture permeability, which is a crucial step in the reservoir simulation study, must be calculated based on fracture characteristics. The diagonal representation of permeability, which is customarily used in a dual porosity model, is valid only for the cases where fractures are parallel to one of the principal axes. This assumption cannot adequately describe flow characteristics where there is variation in fracture spacing, length, and orientation. To overcome this shortcoming, the principle of the full permeability tensor in the discrete fracture network can be incorporated into the dual porosity model. Hence, the dual porosity model can retain the real fracture system characteristics. This study was designed to develop a novel approach to integrate dual porosity model and full permeability tensor representation in fractures. A fully implicit, parallel, compositional chemical dual porosity simulator for modeling naturally fractured reservoirs has been developed. The model is capable of simulating large-scale chemical flooding processes. Accurate representation of the fluid exchange between the matrix and fracture and precise representation of the fracture system as an equivalent porous media are the key parameters in utilizing of dual porosity models. The matrix blocks are discretized into both rectangular rings and vertical layers to offer a better resolution of transient flow. The developed model was successfully verified against a chemical flooding simulator called UTCHEM. Results show excellent agreements for a variety of flooding processes. The developed dual porosity model has further been improved by implementing a full permeability tensor representation of fractures. The full permeability feature in the fracture system of a dual porosity model adequately captures the system directionality and heterogeneity. At the same time, the powerful dual porosity concept is inherited. The implementation has been verified by studying water and chemical flooding in cylindrical and spherical reservoirs. It has also been verified against ECLIPSE and FracMan commercial simulators. This study leads to a conclusion that the full permeability tensor representation is essential to accurately simulate fluid flow in heterogeneous and anisotropic fracture systems. / text

The overall objective of this research was to gain an insight into the challenges encountered during chemical flooding under high hardness conditions. Different aspects of this problem were studied using a combination of laboratory experiments and simulation studies. Chemical Flooding is an important Enhanced Oil Recovery process. One of the major components of the operational expenses of any chemical flooding project, especially Alkali Surfactant Polymer (ASP) flooding is the cost of softening the injection brine to prevent the precipitation of the carbonates of the calcium and magnesium ions which are invariably present in the formation brine. Novel hardness tolerant alkalis like sodium metaborate have been shown to perform well with brines of high salinity and hardness, thereby eliminating the need to soften the injection brine. The first part of this research was aimed at designing an optimal chemical flooding formulation for a reservoir having hard formation brine. Sodium metaborate was used as the alkali in the formulation with the hard brine. Under the experimental conditions, sodium metaborate was found to be inadequate in preventing precipitation in the ASP slug. Factors affecting the ability of sodium metaborate to sequester divalent ions, including its potential limitations under the experimental conditions were studied. The second part of this research studied the factors affecting the ability of novel alkali and chelating agents like sodium metaborate and tetrasodium EDTA to sequester divalent ions. Recent studies have shown that both these chemicals showed good performance in sequestering divalent ions under high hardness conditions. A study of the geochemical species in solution under different conditions was done using the computer program PHREEQC. Sensitivity studies about the effect of the presence of different solution species on the performance of these alkalis were done. The third part of this research focused on field scale mechanistic simulation studies of geochemical scaling during ASP flooding. This is one of the major challenges faced by the oil and gas industry and has been found to occur when sodium carbonate is used as the alkali and the formation brine present in situ has a sufficiently high hardness content. The multicomponent and multiphase compositional chemical flooding simulator, UTCHEM was used to determine the quantity and composition of the scales formed in the reservoir as well as the injection and production wells. Reactions occurring between the injected fluids, in situ fluids and the reservoir rocks were taken into consideration for this study. Sensitivity studies of the effect of key reservoir and process parameters like the physical dispersion and the alkali concentration on the extent of scaling were also done as a part of this study. / text