The demand for energy and new oil reservoirs around the world has increased rapidly while oil recovery from depleted reservoirs has become more difficult. Oil production from fractured carbonate reservoirs by water flooding is often inefficient due to the commonly oil-wet nature of matrix rocks. Chemical enhanced oil recovery (EOR) processes such as surfactant-induced wettability alteration and interfacial tension reduction are required to decrease the residual oil saturation in matrix blocks, leading to incremental oil recovery. However, improvement in recovery will depend on the degree of wettability alteration and interfacial tension (IFT) reduction, which in turn are functions of matrix permeability, fracture intensity, temperature, pressure, and fluid properties. The oil recovery from fractured carbonate reservoirs is frequently considered to be dominated by the spontaneous imbibition mechanism which is a combination of viscous, capillary, and gravity forces. The primary purpose of this study is to model wettability alteration in the lab scale for both coreflood and imbibition cell tests using the chemical flooding reservoir simulator. The experimental recovery data for fractured carbonate rocks with different petrophysical properties were history-matched with UTCHEM, The University of Texas in-house compositional chemical flooding simulator, using a highly heterogeneous permeability distribution. Extensive simulation work demonstrates the validity and ranges of applicability of upscaled procedures, and also indicates the importance of viscous and capillary forces in larger fields. The results of this work will be useful for designing field-scale chemical EOR processes. / text

The scope of work can be divided into; the measurement of the rheological properties of a new emulsified acid system that can be suitable for high temperature applications, a study of the performance of the new emulsified acid in stimulating both calcite and dolomite formations, measuring the reaction rate and diffusion coefficient when the new emulsified acid systems react with both calcite and dolomite, and testing the new emulsified acid using core samples obtained from carbonate reservoirs. The droplet size has a practical impact on the performance of emulsified acid. A good understanding and characterization of the emulsified acid by its size distribution will lead to better understanding of its stability, rheology and how it reacts with carbonate rocks. The influence of the concentration of the new emulsifier on the droplet size, droplet size distribution and upon the rheology of emulsified acids is studied in detail. The emulsified acid reaction kinetics with calcite rocks was studied before in few studies, and very little work was done with dolomite. One of the main objectives of the present work is to study in detail the reaction of the emulsified acid with both calcite and dolomite rocks using the rotating disk apparatus. Most of the previous studies on the emulsified acid were done using core samples that were saturated with brine or deionized water. One of the main objectives of the present work is to study in detail the effect of the presence of crude oil in the reservoir rock on the performance of emulsified acids. Lastly, an innovative technique of emulsifying the chelating agents is evaluated for high temperature applications. The rheology of the emulsified chelating agent is measured using an HPHT rheometer. Also, the reaction of the new emulsified chelating agent with calcite is studied using the rotating disk apparatus, and coreflood experiments were performed using chelating agents and calcite core samples.

Carbon dioxide (CO2) sequestration is defined as the removal of gas that would be emitted into the atmosphere and its subsequent storage in a safe, sound place. CO2 sequestration in underground formations is currently being considered to reduce the amount of CO2 emitted into the atmosphere. However, a better understanding of the chemical and physical interactions between CO2, water, and formation rock is necessary before sequestration. These interactions can be evaluated by the change in mineral content in the water before and after injection, or from the change in well injectivity during CO2 injection. It may affect the permeability positively due to rock dissolution, or negatively due to precipitation. Several physical and chemical processes cover the CO2 injection operations; multiphase flow in porous media is represented by the flow of the brine and CO2, solute transportation is represented by CO2 dissolution in the brine forming weak carbonic acid, dissolution-deposition kinetics can be seen in the rock dissolution by the carbonic acid and the deposition of the reaction products, hydrodynamic instabilities due to displacement of less viscous brine with more viscous CO2 (viscous fingering), capillary effects and upward movement of CO2 due to gravity effect. The objective of the proposed work is to correlate the formation damage to the other variables, i.e. pressure, temperature, formation rock type, rock porosity, water composition, sulfates concentration in the water, CO2 volume injected, water volume injected, CO2 to water volumetric ratio, CO2 injection rate, and water injection rate. In order to achieve the proposed objective, lab experiments will be conducted on different rock types (carbonates, limestone and dolomite, and sandstone) under pressure and temperature that simulate the field conditions. CO2 will be used at the supercritical phase and different CO2-water-rock chemical interactions will be addressed. Quantitative analysis of the experimental results using a geochemical simulator (CMG-GEM) will also be performed. The results showed that for carbonate cores, maintaining the CO2/brine volumetric ratio above 1.0 reduced bicarbonate formation in the formation brine and helped in minimizing precipitation of calcium carbonate. Additionally, increasing cycle volume in WAG injection reduced the damage introduced to the core. Sulfate precipitation during CO2 sequestration was primarily controlled by temperature. For formation brine with high total dissolved solids (TDS), calcium sulfate precipitation occurs, even at a low sulfate concentration. For dolomite rock, temperature, injection flow rate, and injection scheme don't have a clear impact on the core permeability, the main factor that affects the change in core permeability is the initial core permeability. Sandstone cores showed significant damage; between 35% and 55% loss in core permeability was observed after CO2 injection. For shorter WAG injection the damage was higher; decreasing the brine volume injected per cycle, decreased the damage. At higher temperatures, 200 and 250 degrees F, more damage was noted than at 70 degrees F.

Chemical enhanced oil recovery has regained its attention because of high oil price and the depletion of conventional oil reservoirs. This process is more complex than the primary and secondary recovery flooding and requires detailed engineering design for a successful field-scale application. An effective alkaline/co-solvent/polymer (ACP) formulation was developed and corefloods were performed for a cost efficient alternative to alkaline/surfactant/polymer floods by the research team at the department of Petroleum and Geosystems Engineering at The University of Texas at Austin. The alkali agent reacts with the acidic components of heavy oil (i.e. 170 cp in-situ viscosities) to form in-situ natural soap to significantly reduce the interfacial tension, which allows producing residual oil not contacted by waterflood or polymer flood alone. Polymer provides mobility control to drive chemical slug and oil bank. The cosolvent added to the chemical slug helps to improve the compatibility between in-situ soap and polymer and to reduce microemulsion viscosity. An impressive recovery of 70% of the waterflood residual oil saturation was achieved where the remaining oil saturation after the ACP flood was reduced to only 13.5%. The results were promising with very low chemical usage for injection. The UTCHEM chemical flooding reservoir simulator was used to model the coreflood experiments to obtain parameters for pilot scale simulations. Geological model was based on unconsolidated reservoir sand with multiple seven spot well patterns. However, facility capacity and field logistics, reservoir heterogeneity as well as mixing and dispersion effects might prevent coreflood design at laboratory from large scale implementation. Field-scale sensitivity studies were conducted to optimize the design under uncertainties. The influences of chemical mass, polymer pre-flush, well constraints, and well spacing on ultimate oil recovery were closely investigated. This research emphasized the importance of good mobility control on project economics. The in-situ soap generated from alkali-naphthenic acid reaction not only mobilizes residual oil to increase oil recovery, but also enhances water relative permeability and increases injectivity. It was also demonstrated that a closer well spacing significantly increases the oil recovery because of greater volumetric sweep efficiency. This thesis presents the simulation and modeling results of an ACP process for a viscous oil in high permeability sandstone reservoir at both coreflood and pilot scales. / text

Global warming and greenhouse gas (GHG) emissions have recently become the significant focus of engineering research. The geological sequestration of greenhouse gases such as carbon dioxide (CO₂) is one approach that has been proposed to reduce the greenhouse gas emissions and slow down global warming. Geological sequestration involves the injection of produced CO₂ into subsurface formations and trapping the gas through many geological mechanisms, such as structural trapping, capillary trapping, dissolution, and mineralization. While some progress in our understanding of fluid flow in porous media has been made, many petrophysical phenomena, such as multi-phase flow, capillarity, geochemical reactions, geomechanical effect, etc., that occur during geological CO₂ sequestration remain inadequately studied and pose a challenge for continued study. It is critical to continue to research on these important issues. Numerical simulators are essential tools to develop a better understanding of the geologic characteristics of brine reservoirs and to build support for future CO₂ storage projects. Modeling CO₂ injection requires the implementation of multiphase flow model and an Equation of State (EOS) module to compute the dissolution of CO₂ in brine and vice versa. In this study, we used the Integrated Parallel Accurate Reservoir Simulator (IPARS) developed at the Center for Subsurface Modeling at The University of Texas at Austin to model the injection process and storage of CO₂ in saline aquifers. We developed and implemented new petrophysical models in IPARS, and applied these models to study the process of CO₂ sequestration. The research presented in this dissertation is divided into three parts. The first part of the dissertation discusses petrophysical and computational models for the mechanical, geological, petrophysical phenomena occurring during CO₂ injection and sequestration. The effectiveness of CO₂ storage in saline aquifers is governed by the interplay of capillary, viscous, and buoyancy forces. Recent experimental data reveals the impact of pressure, temperature, and salinity on interfacial tension (IFT) between CO₂ and brine. The dependence of CO₂-brine relative permeability and capillary pressure on IFT is also clearly evident in published experimental results. Improved understanding of the mechanisms that control the migration and trapping of CO₂ in the subsurface is crucial to design future storage projects for long-term, safe containment. We have developed numerical models for CO₂ trapping and migration in aquifers, including a compositional flow model, a relative permeability model, a capillary model, an interfacial tension model, and others. The heterogeneities in porosity and permeability are also coupled to the petrophysical models. We have developed and implemented a general relative permeability model that combines the effects of pressure gradient, buoyancy, and capillary pressure in a compositional and parallel simulator. The significance of IFT variations on CO₂ migration and trapping is assessed. The variation of residual saturation is modeled based on interfacial tension and trapping number, and a hysteretic trapping model is also presented. The second part of this dissertation is a model validation and sensitivity study using coreflood simulation data derived from laboratory study. The motivation of this study is to gain confidence in the results of the numerical simulator by validating the models and the numerical accuracies using laboratory and field pilot scale results. Published steady state, core-scale CO₂/brine displacement results were selected as a reference basis for our numerical study. High-resolution compositional simulations of brine displacement with supercritical CO₂ are presented using IPARS. A three-dimensional (3D) numerical model of the Berea sandstone core was constructed using heterogeneous permeability and porosity distributions based on geostatistical data. The measured capillary pressure curve was scaled using the Leverett J-function to include local heterogeneity in the sub-core scale. Simulation results indicate that accurate representation of capillary pressure at sub-core scales is critical. Water drying and the shift in relative permeability had a significant impact on the final CO₂ distribution along the core. This study provided insights into the role of heterogeneity in the final CO₂ distribution, where a slight variation in porosity gives rise to a large variation in the CO₂ saturation distribution. The third part of this study is a simulation study using IPARS for Cranfield pilot CO₂ sequestration field test, conducted by the Bureau of Economic Geology (BEG) at The University of Texas at Austin. In this CO₂ sequestration project, a total of approximately 2.5 million tons supercritical CO₂ was injected into a deep saline aquifer about ~10000 ft deep over 2 years, beginning December 1st 2009. In this chapter, we use the simulation capabilities of IPARS to numerically model the CO₂ injection process in Cranfield. We conducted a corresponding history-matching study and got good agreement with field observation. Extensive sensitivity studies were also conducted for CO₂ trapping, fluid phase behavior, relative permeability, wettability, gravity and buoyancy, and capillary effects on sequestration. Simulation results are consistent with the observed CO₂ breakthrough time at the first observation well. Numerical results are also consistent with bottomhole injection flowing pressure for the first 350 days before the rate increase. The abnormal pressure response with rate increase on day 350 indicates possible geomechanical issues, which can be represented in simulation using an induced fracture near the injection well. The recorded injection well bottomhole pressure data were successfully matched after modeling the fracture in the simulation model. Results also illustrate the importance of using accurate trapping models to predict CO₂ immobilization behavior. The impact of CO₂/brine relative permeability curves and trapping model on bottom-hole injection pressure is also demonstrated. / text

Water injection has been practiced to displace the hydrocarbons towards adjacent wells and to support the reservoir pressure at or above the bubble point. Recently, waterflooding in sandstone reservoirs, as secondary and tertiary modes, proved to decrease the residual oil saturation. In calcareous rocks, water from various resources (deep formation, seawater, shallow beds, lakes and rivers) is generally injected in different oil fields. The ions interactions between water molecules, salts ions, oil components, and carbonate minerals are still ambiguous. Various substances are usually added before or during water injection to enhance oil recovery such as dilute surfactant. Various methods were used including surface charge (zeta potential), static and dynamic contact angle, core flooding, inductively coupled plasma spectrometry, CAT scan, and geochemical simulation. Limestone and dolomite particles were prepared at different wettability conditions to mimic the actual carbonate reservoirs. In addition to seawater and dilute seawater (50, 20, 10, and 1 vol%), formation brine, shallow aquifer water, deionized water and different crude oil samples were used throughout this study. The crude oil/water/carbonates interactions were also investigated using short and long (50 cm) limestone and dolomite rocks at different wettability and temperature conditions. The aqueous ion interactions were extensively monitored via measuring their concentrations using advanced analytical techniques. The activity of the free ions, complexes, and ion pairs in aqueous solutions were simulated at high temperatures and pressures using OLI electrolyte simulation software. Dilute seawater decreased the residual oil saturation in some of the coreflood tests. Hydration and dehydration processes through decreasing and increasing salinity showed no impact on calcite wettability. Effect of individual ions (Ca, Mg, and Na) and dilute seawater injection on oil recovery was insignificant in compare to the dilute surfactant solutions (0.1 wt%). The reaction mechanisms were confirmed to be adsorption of hydroxide ions, complexes and ion pairs at the interface which subsequently altered the surface potential from positive to negative. Results in this study indicate multistage waterflooding can enhance oil recovery in the field under certain conditions. Mixed streams simulation results suggest unexpected ions interactions (NaCO3-1, HSO4-1, NaSO4-1 and SO4-2) with various activities trends especially at high temperatures.

No description available.

Sandstone acidizing using mud acid is a quick and complex process where dissolution and precipitation occur simultaneously. Retarded mud acids are less reactive with the rock reducing the reaction rate hence increased penetration into the formation to remove deep damage. To understand thoroughly the retarded mud acid system, an in-depth investigation of the reaction of HF (hydrofluoric) and H2SiF6 (fluorosilic acid) with alumino silicates and the retarded system is undertaken using coreflood analysis and mineralogy analysis using the inductively coupled plasma. Coreflood analysis is used to understand and investigate the permeability changes in the sandstone rock as the retarded mud acid is injected at different conditions and the inductively coupled plasma (ICP) is used to investigate the effluent samples from the coreflood analysis to properly understand this system. Several issues that have not been addressed previously in literature are identified and discussed, including an optimum flowrate when sandstone is acidized, by acidizing the sandstone rock with a retarded acid system at various flowrates and determining the initial and final permeabilities. Also investigated is the retarded acids compatibility with ferric iron and a comparison of the retarded acid system to regular acid to consequently enable a thorough understanding of the retarded mud acid system using aluminum chloride (AlRMHF). Based on the work done, it is found that the absence of a hydrochloric (HCl) preflush is very detrimental to the sandstone core as calcium fluoride is precipitated and the retarded acid system is found to be compatible with iron(III) as an impurity. The regular acid (RMHF) dissolves considerably more silicon and produces more fines than the AlRMHF. 1cc/min is found to be the optimum flowrate when a sandstone core is acidized with AlRMHF. At this low flowrate, less silicon is dissolved, more aluminum is seen in the effluent and more calcium is dissolved. The retarded aluminum acid system considerably reduces the rate of reaction as evidenced in the dissolution reaction when compared to a regular mud acid system. This reduced rate of reaction implies deeper acid penetration and ultimately deeper damage removal.

<p>This dissertation focused on the development of mass spectrometric methodologies, separation techniques, and engineered devices for the optimal analysis of complex mixtures relevant to the energy sector, such as alternative fuels, petroleum-based fuels, crude oils, and processed base oils. Mass spectrometry (MS) has been widely recognized as a powerful tool for the analysis of complex mixtures. In complex energy samples, such as petroleum-based fuels, alternative fuels, and oils, high-resolution MS alone may not be sufficient to elucidate chemical composition information. Separation before MS analysis is often necessary for such highly complex energy samples. For volatile samples, in-line two-dimensional gas chromatography (GC×GC) can be used to separate complex mixtures prior to ionization. This technique allows for a more accurate determination of the compounds in a mixture, by simplifying the mixture into its components prior to ionization, separation based on mass-to-charge ratio (<i>m/z</i>), and detection. A GC×GC coupled to a high-resolution time-of-flight MS was utilized in this research to determine the chemical composition of alternative aviation fuels, a petroleum-based aviation fuel, and alternative aviation fuel candidates and blending components as well as processed base oils.</p> Additionally, as the cutting edge of science and technology evolve, methods and equipment must be updated and adapted for new samples or new sector demands. One such case, explored in this dissertation, was the validation of an updated standardized method, ASTM D2425 2019. This updated standardized method was investigated for a new instrument and new sample type for a quadrupole MS to analyze a renewable aviation fuel. Lastly, the development and evaluation of a miniaturized coreflood device for analyzing candidate chemically enhanced oil recovery (cEOR) formulations of brine, surfactant(s), and polymer(s) was conducted. The miniaturized device was used in the evaluation of two different cEOR formulations to determine if the components of the recovered oil changed.