Foam has been used as a mobility control technique in CO₂ flooding to improve volumetric sweep efficiency. Stabilizing CO₂ foam with nanoparticle instead of surfactant has some notable advantages. Nanoparticle-stabilized foam is very stable because a large adsorption energy is required to bring nanoparticles to the bubble interfaces. As a solid, nanoparticle can potentially withstand the high temperature in the reservoir, providing a robust foam stability for an extended period of time. The ability of nanoparticles to generate foam only above a threshold shear rate is promising as foam can be engineered to form only in the high permeability zone. These nanoparticles are hundreds of times smaller than pore throats and thus can travel in the reservoir without plugging the pore throats. Surface-modified silica nanoparticle was found to stabilize CO₂ -in-water foam at temperature up to 80 ˚C and salinity as high as 7.2 wt%. The foam was generated through the co-injection of aqueous nanoparticle dispersion and CO₂ into consolidated rock cores, primarily sandstones, with and without an induced fracture in the core. A critical shear rate for foam generation was found to exist in both matrix and fracture, however, this critical rate varied with the experiment conditions. The effects of experimental parameters on the critical shear rate and foam apparent viscosity were also investigated. Additionally, the flow distribution calculation in fractured sandstone cores revealed a diversion of flow from fracture toward matrix once foam was generated, suggesting conformance control potential in fractured reservoirs. In order to study foam rheology, high-permeability beadpack was installed upstream of the core to serve as a foam generator. This allows the foam mobility to be measured solely while being transported through the core, without the complicating effect of transient foam generation in the core. The injection of the pre-generated foam into the core at residual oil condition was found to reduce the residual oil saturation to the same level as CO₂ flood, however, with the advantage of mobility control. The 'coalescence-regeneration' mechanism of foam transport in porous media possibly allowed the foam's CO₂ to contact and mobilize the residual oil. The injection of the foam slug followed by a slug of only CO₂ was also tested, showing similar viscosification as the continuous foam injection, however, required less nanoparticles. / text

The study of multiphase flow in porous media is highly relevant to many problems of great scientific importance, such as CO2 storage and enhanced oil recovery. Even though significant progress has been made in these areas, many challenges still remain. For instance, the leakage of stored CO2 may occur due to the capillary trapping failure of cap rock. Approximately 70% of oil cannot be easily recovered from underground, because the oil is held in tight porous rocks. Although CO2 storage and enhanced oil recovery are engineering processes at a geological scale, they are predominantly controlled by the transport and displacement of CO2 and reservoir fluids in aquifers and reservoirs, which are further controlled by wetting and fluid properties at pore scale. This work focuses on experimental investigations of pore-scale wetting and displacement of fluids and CO2 in porous core samples. Pore wetting, which has been measured based on contact angle, is a principal control on multiphase flow through porous media. However, contact angle measurement on other than flat surfaces still remains a challenge. In order to indicate the wetting in a small pore, a new pore contact angle measurement technique is developed in this study to directly measure the contact angles of fluids and CO2 in micron-sized pores. The equilibrium and dynamic contact angles of various liquids are directly measured in single glass capillaries, by studying the effects of surface tension, viscosity and chemical structure. The pore contact angles are compared with the contact angles on a planar substrate. The pore contact angle of a confined liquid in a glass capillary differs from the contact angle measured on a flat glass surface in an open space. Surface tension is not the only dominant factor affecting contact angle. The static contact angle in a glass pore also varies with liquid chemical structure. Viscosity and surface tension can significantly affect the dynamic pore contact angle. A new empirical correlation is developed based on our experimental data to describe dynamic pore wetting. The CO2-fluid contact angle in porous media is an important factor affecting the feasibility of long-term permanent CO2 storage. It determines CO2 flow and distribution in reservoirs or aquifers, and thus ultimately finally the storage capacity. CO2-fluid contact angles were measured in small water-wet pores and oil-wet pores, investigating the effect of CO2 phase (gas/liquid/supercritical). The CO2 phase significantly affects the CO2-fluid contact angle in an oil-wet pore. Supercritical CO2-fluid contact angles are larger than gas CO2-fluid contact angles, but are smaller than liquid CO2-fluid contact angles. However, this significant CO2 phase effect on contact angle was not observed in a water-wet pore. Another key issue considered in this study is two-phase flow displacement in porous media. This strongly relates to the important macroscopic parameters for multiphase flow transport in porous media, such as capillary pressure and relative permeability. Here CO2-water displacements are studied by conducting CO2 flooding experiments in a sandstone core sample, considering the effects of CO2 phase, pressure and CO2 injection rate. The capillary pressure-saturation curve, water production behaviour and relative permeability are investigated for gas CO2-water, liquid CO2-water and supercritical CO2-water displacements in porous media. The pressure-dependant drainage capillary pressures are obtained as a result of CO2-water interfacial tension. Various water production behaviours are obtained for gas CO2-water and liquid CO2-water displacements, mainly due to the effect of CO2 dissolution. The significant irregular capillary pressure-saturation curves and water production behaviors can be observed for the supercritical CO2-water displacements. The water and CO2 relative permeabilities for CO2-water displacements in a porous media are then predicted.

Chemical Enhanced Oil Recovery methods have been growing in popularity as a result of the depletion of conventional oil reservoirs and high oil prices. These processes are significantly more complex when compared to waterflooding and require detailed engineering design before field-scale implementation. Coreflood experiments that have been performed on reservoir rock are invaluable for obtaining parameters that can be used for field-scale flooding simulations. However, the design used in these floods may not always scale to the field due to heterogeneities, chemical retention, mixing and dispersion effects. Reservoir simulators can be used to identify an optimum design that accounts for these effects but uncertainties in reservoir properties can still cause poor project results if it not properly accounted for. Different reservoirs will be investigated in this study, including more unconventional applications of chemical flooding such as a 3md high-temperature, carbonate reservoir and a heterogeneous sandstone reservoir with very high initial oil saturation. The goal of the research presented here is to investigate the impact that select reservoir uncertainties can have on the success of the pilot and to propose methods to reduce the sensitivity to these parameters. This research highlights the importance of good mobility control in all the case studies, which is shown to have a significant impact on the economics of the project. It was also demonstrated that a slug design with good mobility control is less sensitive to uncertainties in the relative permeability parameters. The research also demonstrates that for a low-permeability reservoir, surfactant propagation can have a significant impact on the economics of a Surfactant-Polymer Flood. In addition to mobilizing residual oil and increasing oil recovery, the surfactant enhances the relative permeability and this has a significant impact on increasing the injectivity and reducing the project life. Injecting a high concentration of surfactant also makes the design less sensitive to uncertainties in adsorption. Finally, it was demonstrated that for a heterogeneous reservoir with high initial oil saturation, optimizing the salinity gradient will significantly increase the oil recovery and will also make the process less sensitive to uncertainties in the cation exchange capacity. / text

The effect of brine ionic composition on oil recovery was studied for a limestone reservoir rock at a high temperature. Contact angle, imbibition, core flood and ion analysis were used to find the brines that improve oil recovery and the associated mechanisms. Contact angle experiments showed that modified seawater containing Mg[superscript 2+] and SO4[superscript 2-] and diluted seawater change aged oil-wet calcite plates to more water-wet conditions. Seawater with Ca[superscript 2+], but without Mg[superscript 2+] or SO₄[superscript 2-] was unsuccessful in changing calcite wettability. Modified seawater containing Mg[superscript 2+] and SO₄[superscript 2-], and diluted seawater spontaneously imbibe into the originally oil-wet limestone cores. Modified seawater containing extra SO₄[superscript 2-] and diluted seawater improve oil recovery from 40% OOIP (for formation brine waterflood) to about 80% OOIP in both secondary and tertiary modes. The residual oil saturation to modified brine injection is approximately 20%. Multi ion exchange and mineral dissolution are responsible for desorption of organic acid groups which lead to more water-wet conditions. Further research is needed for scale-up of these mechanisms from cores to reservoirs. / text

Polymer flooding is a commercial enhanced oil recovery (EOR) method used to increase the sweep efficiency of water floods. Hydrolyzed polyacrylamide (HPAM), a synthetic commercial polymer, is widely used in commercial polymer floods and it is also used for mobility control of chemical floods using surfactants such as surfactant-polymer flooding and alkaline-surfactant-polymer flooding. The increase in the degree of hydrolysis of HPAM at elevated temperature or pH with time affects the polymer solution viscosity and its adsorption on rock surfaces. A polymer hydrolysis model based on published laboratory data was implemented in UTCHEM, a chemical EOR simulator, in order to assess the effect of hydrolysis on reservoir performance. Both 1D and 3D simulations were performed to validate the implementation of the model. The simulation results are consistent with the laboratory observations that show an increase in polymer solution viscosity as hydrolysis progresses. The numerical results indicate that hydrolysis occurs very rapidly and impacts the near wellbore region polymer injectivity. / text

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

In this study, the co-optimization of carbon dioxide sequestration and enhanced oil recovery and the co-optimization of carbon dioxide sequestration and methane recovery studies were discussed. Carbon dioxide emissions in the atmosphere are one of the reasons of global warming and can be decreased by capturing and storing carbon dioxide. Our aim in this study is to maximize the amount of carbon dioxide sequestered to decrease carbon dioxide emissions in the atmosphere and maximize the oil or methane recovery to increase profit or to make a project profitable. Experimental design and response surface methodology are used to co-optimize the carbon dioxide sequestration and enhanced oil recovery and carbon dioxide sequestration and methane recovery. At the end of this study, under which circumstances these projects are profitable and under which circumstances carbon dioxide sequestration can be maximized, are given. / text

Despite bold steps taken worldwide for the replacement or the reduction of the world’s dependence on fossil fuels, economic and societal realities suggest that a transition to alternative energy forms will be, at best, gradual. It also appears that exploration for new reserves is becoming increasingly more difficult both from a technical and an economic point of view, despite the advent of new technologies. These trends place renewed emphasis on maximizing oil recovery from known fields. In this sense, low-cost and reliable enhanced oil recovery (EOR) methods have a strong role to play. The goal of this dissertation is to explore, using computational simulations, the feasibility of the, so-called, seismic or elastic-wave EOR method, and to provide the mathematical/computational framework under which the method can be systematically assessed, and its feasibility evaluated, on a reservoir-specific basis. A central question is whether elastic waves can generate sufficient motion to increase oil mobility in previously bypassed reservoir zones, and thus lead to increased production rates, and to the recovery of otherwise unexploited oil. To address the many questions surrounding the feasibility of the elastic-wave EOR method, we formulate an inverse source problem, whereby we seek to determine the excitations (wave sources) one needs to prescribe in order to induce an a priori selected maximization mobility outcome to a previously well-characterized reservoir. In the industry’s parlance, we attempt to address questions of the form: how does one shake a reservoir?, or what is the “resonance” frequency of a reservoir?. We discuss first the case of wellbore wave sources, but conclude that surface sources have a better chance of focusing energy to a given reservoir. We, then, discuss a partial-differential-equation-constrained optimization approach for resolving the inverse source problem associated with surface sources, and present a numerical algorithm that robustly provides the necessary excitations that maximize a mobility metric in the reservoir. To this end, we form a Lagrangian encompassing the maximization goal and the underlying physics of the problem, expressed through the side imposition of the governing partial differential equations. We seek to satisfy the first-order optimality conditions, whose vanishing gives rise to a systematic process that, in turn, leads to the prescription of the wave source signals. We explore different (indirect) mobility metrics (kinetic energy or acceleration field maximization), and report numerical experiments under three different settings: (a) targeted formations within one-dimensional multi-layered elastic solids system of semi-infinite extent; (b) targeted formations embedded in a two-dimensional semi-infinite heterogeneous elastic solid medium; and (c) targeted poroelastic formations embedded within elastic heterogeneous surroundings in one dimension. The numerical experiments, employing hypothetical subsurface formation models subjected to, initially unknown, ground surface wave sources, demonstrate that the numerical optimizer leads robustly to optimal loading signals and the illumination of the target formations. Thus, we demonstrate that the theoretical framework for the elastic wave EOR method developed in this dissertation can systematically address the application of the method on a reservoir-specific basis. From an application point of view and based on the numerical experiments reported herein, for shallow reservoirs there is strong promise for increased production. The case of deeper reservoirs can only be addressed with further research that builds on the findings of this work, as we report in the last chapter. / text

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