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 carbonate reservoirs are a class of reservoirs characterized by high conductivity fractures surrounding low permeability matrix blocks. In these reservoirs, wettability alteration is a key method for recovering oil. Water imbibes into the matrix blocks upon water flooding if the reservoir rock is water-wet. However, many carbonate reservoirs are oil-wet. Surfactant solution was used to enhance spontaneous imbibition between the fractures and the matrix by both wettability alteration and ultra-low interfacial tensions. The first part of this study was devoted to determining the wettability of reservoir rocks using Amott-Harvey Index method, and also evaluating the performance of surfactants on wettability alteration, based on the contact angle measurement and spontaneous imbibition rate and ultimate oil recovery on oil-wet reservoir cores. The reservoir rocks have been found to be slightly oil-wet. One cationic surfactant BTC8358, one anionic surfactant and one ultra-low IFT surfactant formulation AKL-207 are all found to alter the wettability towards more water-wet and promote oil recovery through spontaneous imbibition. The second part of the study focused on the parameters that affect wettability alteration by surfactants. Some factors such as core dimension, permeability and heterogeneity of porous medium are evaluated in the spontaneous imbibition tests. Higher permeability leads to higher imbibition rate and higher ultimate oil recovery. Heterogeneity of core samples slows down the imbibition process if other properties are similar. Core dimension is critical in upscaling from laboratory conditions to field matrix blocks. The imbibition rate is slower in larger dimension of core. Further, we investigated the effects of EDTA in surfactant-mediated spontaneous imbibition. Since high concentration of cationic divalent ions in the aqueous solution markedly suppresses the surfactant-mediated wettability alteration, EDTA improved the performance of surfactant in the spontaneous imbibition tests. It is proposed in the thesis that surfactant/EDTA-enhanced imbibition may involve the dissolution mechanism. More experiments should be conducted to verify this mechanism. The benefits of using EDTA in the surfactant solution include but not limited to: altering the surface charge of carbonate to negative, producing the in-situ soap, reducing the brine hardness, decreasing the surfactant adsorption, and creating the water-wet area by dissolving the dolomite mineral. / 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 goal of this work is to change the wettability of a carbonate rock from oil wet-mixed-wet towards water-wet at high temperature and high salinity. Only simple surfactant systems (single surfactant, dual surfactants) in dilute concentration were tried for this purpose. It was thought that the change in wettability would help to recover more oil during secondary surfactant flood as compared to regular waterflood. Three types of surfactants, anionic, non-ionic and cationic surfactants in dilute concentrations (<0.2 wt%) were used. Initial surfactant screening was done on the basis of aqueous stability at these harsh conditions. Contact angle experiments on aged calcite plates were done to narrow down the list of surfactants and spontaneous imbibition experiments were conducted on field cores for promising surfactants. Secondary waterflooding was conducted in cores with and without the wettability altering surfactants. It was observed that barring a few surfactants, most were aqueous unstable by themselves at these harsh conditions. Dual surfactant systems, a mixture of a non-ionic and a cationic surfactant increased the aqueous stability of the non-ionic surfactants. One of the dual surfactant system, a mixture of Tergitol NP-10 and Dodecyl trimethyl ammonium bromide, proved very effective for wettability alteration and could recover 70-80% of OOIP during spontaneous imbibition. Secondary waterflooding with the wettability altering surfactant (without alkali or polymer) increased the oil recovery over the waterflooding without the surfactants (from 29% to 40% OOIP). Surfactant adsorption calculated during the coreflood showed an adsorption of 0.24 mg NP-10/gm of rock and 0.20 mg DTAB/gm of rock. A waterflood done after the surfactant flood revealed change in the relative permeability before and after the surfactant flood suggesting change in wettability towards water-wet. / 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.

No description available.

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.

Thesis (Ph. D.)--University of Texas at Austin, 2008. / Vita. Includes bibliographical references.

[pt] Evidências experimentais demonstram o potencial da injeção de emulsões no aumento do fator de recuperação de óleo. O mecanismo responsável por esta melhor varredura do reservatório é a redução da mobilidade da água em regiões do reservatório já varridas por água. Esta redução pode ser associada ao bloqueio parcial de gargantas do meio poroso por gotas da fase dispersa da emulsão. A eficiência deste bloqueio parcial depende fortemente da geometria do poro, das características morfológicas e propriedades físicas da emulsão injetada. A utilização eficiente deste método de recuperação é limitada pela falta de entendimento fundamental de como emulsões escoam através de um meio poroso. Este trabalho tem como objetivo estudar o escoamento de emulsões através de gargantas de poros, que são modeladas fisicamente por micro- capilares com garganta nos experimentos desenvolvidos nesta pesquisa. Os resultados mostram como a permeabilidade varia com as propriedades e características morfológicas da emulsão e parâmetros geométricos do micro-capilar. Estes dados definem as propriedades necessárias de emulsões em função das características do reservatório para a obtenção do efeito de bloqueio parcial desejado e servem de entrada de dados para modelo de rede de capilares de escoamento de emulsões em meios porosos. / [en] Experimental evidences show the potential of emulsion injection in the improvement of oil recovery factor. The responsible mechanism for this better reservoir sweep is the water mobility reduction in regions already swept by water. This reduction can be associated with partial blockage of porous media throats by droplets of emulsion dispersed phase. The efficiency of this partial blockade strongly depends on pore geometry, morphological characteristics and physical properties of the injected emulsion. The efficient use of this recovery method is limited by the lack of fundamental understanding of how emulsions flow through a porous medium. This work aims to study the flow of emulsions through pores throats, which are physically modeled by constricted micro- capillaries in the experiments presented here. The results show how permeability varies with geometrical parameters of micro-capillaries, emulsion properties and morphological characteristics. These data define the necessary properties of emulsions according to the reservoir characteristics to obtain the desired blocking effect and serve as input data to capillaries network model of flow of emulsions in porous media.