Stacked storage systems are a viable carbon management operation, especially in regions with potential growth in CO₂ enhanced oil recovery (EOR) projects. Under a carbon constrained environment, the industrial Texas Gulf Coast is an ideal area for development of stacked storage operations, with a characteristically high CO₂ intensity and abundance of aging oil fields. The development of EOR along the Texas Gulf Coast is limited by CO₂ supply constraints. A stacked storage system is implemented with an EOR project to manage the temporal differences between the operation of a coal-fired power plant and EOR production. Currently, most EOR operations produce natural CO₂ from geologic formations. A switch to anthropogenic CO₂ sources would require an EOR operator to handle volumes of CO₂ beyond EOR usage. The use of CO₂ in an EOR operation is controlled and managed to maximize oil production, but increasing injection rates to handle the volume of CO₂ captured from a coal plant can decrease oil production efficiency. With stacked storage operations, a CO₂ storage reservoir is implemented with an EOR project to maintain injection capacity equivalent to a coal plant's emissions under a carbon constrained environment. By adding a CO₂ storage operation, revenue can still be generated from EOR production, but it is considerably less than just operating an EOR project. The challenge for an efficient stacked storage project is to optimize oil production and maximize profits, while minimizing the revenue reduction of pure carbon sequestration. There is an abundance of saline aquifers along the Texas Gulf Coast, including the Wilcox, Vicksburg, and Miocene formations. To make a stacked storage system more viable and reduce storage costs, maximizing injectivity is critical, as storage formations are evaluated on a cost-per-ton injected basis. This cost-per-ton injected criteria, also established as injection efficiency, incorporates reservoir injectivity and depth dependant drilling costs to determine the most effective storage formation to incorporate with an EOR project. With regionally adequate depth to maximize injectivity while maintaining reasonable drilling costs, the Vicksburg formation is typically the preferred storage reservoir in a stacked storage system along the Texas Gulf Coast. Of the eleven oil fields analyzed on a net present value basis, the Hastings field has the greatest potential for both EOR and stacked storage operations. / text

With a number of advantages hitherto unrecognized, nanoparticle-stabilized emulsions and foams have recently been proposed for enhanced oil recovery (EOR) applications. Long-distance transport of nanoparticles is a prerequisite for any such EOR applications. The transport of the particles is limited by the degree to which the particles are retained by the porous medium. In this work, experiments that quantify the retention and provide insight into the mechanisms for nanoparticle retention in porous media are described. Sedimentary rock samples (Boise sandstone and Texas Cream limestone) were crushed into single grains and sieved into narrow grain size fractions. In some cases, clay (kaolinite or illite) was added to the Boise sandstone samples. These grain samples were packed into long (1 ft – 15 ft) slim tubes (ID = 0.93 cm) to create unconsolidated sandpack columns. The columns were injected with aqueous dispersions of silica-cored nanoparticle (with and without surface coating) and flushed with brine. The nanoparticle effluent concentration history was measured and the nanoparticle recovery was calculated as a percentage of the injected nanoparticle dispersion. Fifty experiments were performed in this fashion, varying different experimental parameters while maintaining others constant to allow direct comparisons between experiments. The parameters analyzed in this thesis are: specific surface area of the porous medium, lithology, brine salinity, interstitial velocity, residence time, column length, and temperature. Our results indicate that retention is not severe, with an 8% average of the injected amount, for all our experiments. From the parameters analyzed, specific surface area was the most influential variable, with a linear effect on nanoparticle retention independently of lithology. Salinity increased nanoparticle retention slightly and delayed nanoparticle arrival. Velocity, residence time and length are coupled parameters and were studied jointly; they had a minor effect on retention. Temperature had a marginal effect, as we observed an approximate 2% increase in retention at 80°C compared to 21°C. Both surface coated and bare silica nanoparticles were successfully transported, so surface coating does not appear to be a prerequisite for transport for the particle and rock systems studied. / text

Polymer flooding is economically successful in reservoirs where the water flood mobility ratio is high, and/or the reservoir heterogeneity is adverse, because of the improved sweep resulting from the mobility-controlled oil displacement. The performance of a polymer flood can be further improved if the process is dynamically controlled using updated reservoir models and a closed-loop production optimization scheme is implemented. However, the formulation of an optimal production strategy is based on uncertain production forecasts resulting from uncertainty in spatial representation of reservoir heterogeneity, geologic scenarios, inaccurate modeling, scaling, just to cite a few factors. Assessing the uncertainty in reservoir modeling and transferring it to uncertainty in production forecasts is crucial for efficiently controlling the process. This dissertation presents a feedback control framework that (1) assesses uncertainty in reservoir modeling and production forecasts, (2) updates the prior uncertainty in reservoir models by integrating continuously monitored production data, and (3) formulates optimal injection/production rates for the updated reservoir models. This approach focuses on assessing uncertainty in reservoir modeling and production forecasts originated mainly by uncertain geologic scenarios and spatial variations of reservoir properties (heterogeneity). This uncertainty is mapped in a metric space created by comparing multiple reservoir models and measuring differences in effective heterogeneity related to well connectivity and well responses characteristic of polymer flooding. Continuously monitored production data is used to refine the uncertainty map using a Bayesian inversion algorithm. In contrast to classical approach of history matching by model perturbation, a model selection problem is implemented where highly probable reservoir models are selected to represent the posterior uncertainty in production forecasts. The model selection procedure yields the posterior uncertainty associated with the reservoir model. The production optimization problem is solved using the posterior models and a proxy model of polymer flooding to rapidly evaluate the objective function and response surfaces to represent the relationship between well controls and an economic objective function. The value of the feedback control framework is demonstrated with two examples of polymer flooding where the economic performance was maximized. / text

Polymers play a key role in several EOR processes such as polymer flooding, surfactant-polymer flooding and alkaline-surfactant-polymer flooding due to their critical importance of mobility control in achieving high oil recovery from these processes. Numerical simulators are used to predict the performance of all of these processes and in particular the injection rate of the chemical solutions containing polymer; since the economics is very sensitive to the injection rates. Injection rates are governed by the injection viscosity, thus, it is very important to model the polymer viscosity accurately. For the predictions to be accurate, not only the viscosity model must be accurate, but also the calculation of equivalent shear rate in each gridblock must be accurate because the non-Newtonian viscosity models depend on this shear rate. As the size of the gridblock increases, the calculation of this velocity becomes less numerically accurate, especially close to wells. This research presents improvements in polymer viscosity model. Using the improvements in shear thinning model, the laboratory polymer rheology data was better matched. For the first time, polymer viscosity was modeled for complete range of velocity using the Unified Viscosity Model for published laboratory data. New models were developed for relaxation time, time constant and high shear viscosity during that match. These models were then used to match currently available HPAM polymer's laboratory data and predict its viscosity for various concentrations for full flow velocity range. This research presents the need for injectivity correction when large grid sizes are used. Use of large grid sizes to simulate large reservoir due to computation constraints induces errors in shear rate calculations near the wellbore and underestimate polymer solution viscosity. Underestimated polymer solution viscosities lead to incorrect injectivity calculation. In some cases, depending on the well grid block size, this difference between a fine scale and a coarse simulation could be as much as 100%. This study focuses on minimizing those errors. This methodology although needs some more work, but can be used in accurate predictions of reservoir simulation studies of chemical enhanced oil recovery processes involving polymers. / text

Foam-assisted low interfacial tension and foam-improved sweep efficiency are attractive enhanced oil recovery (EOR) methods with numerous studies and researches have been conducted in the past few decades. For example, CO₂-Enhanced Oil Recovery (CO₂-EOR) is very efficient in terms of oil displacement. However, due to the low viscosity of super critical CO₂, the process usually suffers from poor sweep efficiency. One method of increasing sweep efficiency in CO₂-EOR has been identified through the use of surfactants to create "foams" or more correctly CO₂-in-water (C/W) macroemulsions. Polymer flooding techniques such as Alkali -- Polymer (AP), Surfactant -- Polymer (SP), and Alkali -- Surfactant -- Polymer (ASP) have been the only proven chemical EOR method in sandstone reservoirs with many successful pilot tests and field projects. However, the use of polymer is limited in carbonates due to unfavorable conditions related to natural characteristics of this type of lithology. In this case, foam-assisted EOR, specifically Alkali -- Surfactant -- Gas (ASG) process, can be an alternative for polymer flooding. It is a fact that large amount of the world's oil reserves resides in carbonate reservoirs. Therefore, an increase in oil recovery from carbonates would help meet the world's increasing energy demand. This study consists of two parts: (1) the development of new surfactant for creating CO₂ -- in -- water macroemulsions for improving sweep efficiency in CO₂ -- EOR processes; (2) systematic study of ASG method as a novel EOR technique and an alternative for polymer flooding in carbonate reservoirs. Both studies are related to the use of foam as a mobility control agent. In the first part, the design and synthesis of twin tailed surfactants for use at the CO₂/water interface is discussed. The hydrohobes for these surfactants are synthesized from epichlorohydrin and an excess alcohol. Subsequent ethoxylation of the resulting symmetrical dialkyl glycerin yields the water soluble dual tailed surfactants. The general characteristics of these surfactants in water are described. A comparison is carried out between twin-tailed dioctylglycerine surfactants and linear secondary alcohol surfactant based on results from a core flood. The results show that even above the cloud point of the surfactants, the twin tailed surfactants create a significant mobility reduction, likely due to favorable partitioning into the CO₂ phase. The data covers surfactant structures designed specifically for the CO₂-water interface and can be used by producers and service companies in designing new CO₂-floods, especially in areas that might not have been considered due to problems with reservoir heterogeneity. Second part contains a systematic study of ASG process on carbonate rocks through a series of experiments. The purpose is to demonstrate the performance as well as the potential of ASG as a new EOR technique. In this study, basic concepts in chemical EOR are presented, while the design of chemical formulation, phase behavior, and the role of foam are discussed in details. Experimental results showed relatively good recovery, low surfactant retention. However, pressure drop during chemical injections were high, which indicates the formation of both strong foam and viscous microemulsion at the displacement front when surfactant starts solubilizing oil. Overall, ASG showed good performance on carbonate rocks. Optimization can be made on surfactant formula to form less viscous microemulsion and therefore improve efficiency of the process. / text

Highly fractured and vuggy oil reservoirs represent a challenge for enhanced oil recovery (EOR) methods. The fractured networks provide flow paths several orders of magnitude greater than the rock matrix. Common enhanced oil recovery methods, including gases or low viscosity liquids, are used to channel through the high permeability fracture networks causing poor sweep efficiency and early breakthrough. The purpose of this research is to determine the feasibility of using foam in highly fractured reservoirs to produce oil-rich zones. Multiple surfactant formulations specifically tailored for a distinct oil type were analyzed by aqueous stability and foam stability tests. Several core floods were performed and targeted effects such as foam quality, injection rate, injection type, permeability, gas saturation, wettability, capillary pressure, diffusion, foam squeezing, oil flow, microemulsion flow and gravity segregation. Ultimately, foam was successfully propagated under various core geometries, initial conditions and injections methods. Consequently, fluids were able to divert to unswept matrix and improve the ultimate oil recovery. / text

The process of vapor extraction (VAPEX) is a recovery process which targets the heavy oil and bitumen resources. Owing to high viscosity values for these unconventional types of oil, the recovery processes in such reserves are still challenging. The unconventional oil recovery processes usually include a mechanism for reducing the oil viscosity by means of heat, solvent, or both. The process of VAPEX utilizes the injection of a light hydrocarbon solvent into a reservoir for recovering the viscous oil in place by diffusing into the oil and by providing sufficient mobility to the oil upon dilution. Although this process offers a variety of advantages over the alternative thermal recovery processes such as SAGD or CSS, it suffers from two major drawbacks. First, the oil production rates obtained in the VAPEX process are considerably lower than those obtained in the thermal processes. Second, the solvent cost is considerably high. We tried to tackle these two problems during this research and we searched for potentials for an improved VAPEX process. Three potentially improved occurrences of a VAPEX project were found when: 1) the injected solvent was superheated, 2) the wettability of media was altered to oil-wet, and 3) the vugs were distributed in the porous media. Warm VAPEX process is introduced in which the VAPEX process is thermally augmented through superheating the solvent vapor. An attractive feature of this process is the capability of the solvent in being able to condense at the bitumen-solvent interface, which provides the opportunity for the bitumen to be upgraded in-situ through asphaltene precipitation. The asphaltene precipitation was not observed during the conventional vapor extraction process and was only observed during the warm VAPEX process. Upon a moderate level of superheating, the production rate of bitumen was sufficiently improved while the solvent content of the produced oil was significantly decreased as a result of decreased solubility of solvent in the oil at elevated temperatures. Therefore, more oil was produced at lower costs. The warm VAPEX experiments were conducted at 4 temperature levels in high and low permeability media using Cold Lake bitumen and Lloydminster heavy oil blend, n-pentane was used as solvent. The warm VAPEX process was found to be more effective for Cold Lake bitumen and for less permeable media. The potential of in-situ upgrading decreased when the level of superheating increased. The second potential for an improved VAPEX process obtained when the wettability of porous medium was altered to oil-wet conditions. Although this wettability condition is harmful to steam-based recovery processes, such as SAGD, it becomes beneficial to VAPEX. For the application of VAPEX process in fractionally wet media the wettability of glass beads was altered to oil-wet conditions through silylation process, and the VAPEX experiments were conducted in a random packing of water-wet and oil-wet beads of similar size at 7 different compositions. A substantial increase in the oil production rate was observed in a completely oil-wet medium, compared to the water-wet medium. By increasing the fraction of oil-wet beads in the packing up to a critical composition, the production rate of live oil increased linearly with the increase in the fraction of oil-wet beads in the packing during the vapor extraction process. Beyond this critical composition, however, the production rate of live oil did not change significantly with further increase in the fraction of the oil-wet beads in the randomly packed medium. Vugs were also found to be beneficial to the production performance of the VAPEX process. The presence of vugs was investigated in synthesized vugular media at 4 different levels of vuggy-to-total pore volume ratios. The performance of vugular media was compared to that of the homogeneous sintered media. The vugs facilitated the production of oil during the VAPEX process by providing flow communication between the vugs and the surrounding matrix, and therefore, by providing a local high permeability pathways towards the production well. A peak in the oil production rate was observed whenever a series of vugs were simultaneously invaded by the solvent vapor. The overall production rate of oil was higher in vuggy media compared to a homogeneous media at the same overall porosity and permeability. Furthermore, the magnitude of residual oil saturation left behind was also slightly lower in vuggy medium because the vugs were perfectly drained. Finally, a constant rate air injection (CRAI) porosimetry method was developed for characterization of vugs in a vugular media. This method was successfully tested in different synthetic vugular media, and the results illustrated higher accuracy in CRAI porosimetry method compared to constant rate mercury porosimetry. CRAI porosimetry method was also employed for identification of higher permeability regions embedded in a matrix of lower permeability. The analysis of a typical porosimetry signal was also modified.

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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.

This thesis focuses on applying microfluidic techniques to analyze two carbon management methods; underground carbon sequestration and enhanced oil recovery. The small scale nature of microfluidic methods enables direct visualization of relevant pore-scale phenomena, enabling elucidation of parameters such as diffusion coefficients and critical compositions. In this work, a microfluidic platform was developed to control a two-phase carbon dioxide (CO2)-water interface for diffusive quantification with fluorescent techniques. It was found that the diffusion coefficient of CO2 in pure water was constant (1.86 [± 0.26] x10-9 m2/s) over a range of pressures. The effects of salinity on diffusivity were also measured in solutions, it was found that the diffusion coefficient varied up to 3 times. A microfluidic technique able to determine the critical composition of a model ternary mixture was also successfully implemented. Results indicate potential application of this approach to minimum miscibility pressure measurements used in enhanced oil recovery.