Hydrogen (H2) and fuel cells applications are central to the realization of a global hydrogen economy. In this scenario, H2 may be produced from renewable biofuels via steam reforming and by solar powered water electrolysis. The purification required for fuel cell grade H2, whether in tandem or in situ within a catalytic reformer operating at 500 oC or above, would be greatly facilitated by the availability a cheaper and more robust option to palladium (Pd) dense metal membrane, currently the leading candidate. Here we describe our results on the feasibility of a completely novel membrane for hydrogen separation: Sandwiched Liquid Metal Membrane, or SLiMM, comprising of a low-melting, non-precious metal (e.g., Sn, In, Ga) film held between two porous substrates. Gallium was selected for this feasibility study to prove of the concept of SLiMM. It is molten at essentially room temperature, is non-toxic, and is much cheaper and more abundant than Pd. Our experimental and theoretical results indicate that the Ga SLiMM at 500 oC has a permeability 35 times higher than Pd, and substantially exceeds the 2015 DOE target for dense metal membranes. For developing a fundamental understanding of the thermodynamics and transport in liquid metals, a Pauling Bond Valence-Modified Morse Potential (PBV-MMP) model was developed. Based on little input, the PBV-MPP model accurately predicts liquid metal self-diffusion, viscosity, surface tension, as well as thermodynamic and energetic properties of hydrogen solution and diffusion in a liquid metal such as heat of dissociative adsorption, heat of solution, and activation energy of diffusion. The concept of SLiMM proved here opens up avenues for development practical H2 membranes, For this, improving the physical stability of the membrane is a key goal. Consequently, a thermodynamic theory was developed to better understand the change in liquid metal surface tension and contact angle as a function of temperature, pressure and gas-phase composition.

Micropores can constitute up to 100% of the total porosity within carbonate hosted hydrocarbon reservoirs, usually existing within micritic fabrics. There is, however, only a rudimentary understanding of the contribution that these pores make to reservoir performance and hydrocarbon recovery. To further our understanding, a flexible, object-based algorithm has been developed to produce 3D computational representations of end-point micritic fabrics. By methodically altering model parameters, the state-space of microporous carbonates is explored. Flow properties are quantified using lattice-Boltzmann and network modelling methods. In purely micritic fabrics, it has been observed that average pore radius has a positive correlation with single-phase permeability and results in decreasing residual oil saturations under both water-wet and 50% fractionally oil-wet states. Similarly, permeability increases by an order of magnitude (from 0.6md to 7.5md) within fabrics of varying total matrix porosity (from 18% to 35%) due to increasing pore size, but this has minimal effect on multi-phase flow. Increased pore size due to micrite rounding notably increases permeability in comparison to original rhombic fabrics with the same porosity, but again, multi-phase flow properties are unaffected. The wetting state of these fabrics, however, can strongly influence multi-phase flow; residual oil saturations vary from 30% for a water-wet state and up to 50% for an 80% oil wet fraction. flow when directly connected. Otherwise, micropores control single-phase permeability magnitude. Importantly in these fabrics, recovery is dependent on both wetting scenario and pore-network homogeneity; under water-wet imbibition, increasing proportions of microporosity yield lower residual oil saturations. Finally, in grain-based fabrics where mesopores form an independently connected pore network, micropores do not affect permeability, even when they constitute up to 50% of the total porosity. Through examination of these three styles of microporous carbonates, it is apparent that micropores can have a significant impact on flow and sweep characteristics in such fabrics.

The purpose of this study is to investigate the impact of solvent addition to bitumen froth on the wettability of froth solids. The wettability of solids determines the transportation/partitioning of the solids between phases, which in turn affects the solids and water rejection in a Clark hot water extraction process (CHWE). The impact of solvents treatment on the wettability of froth solids was studied using both a model system and a real bitumen froth system. The vulnerabilities of four kinds of model minerals to hydrocarbon contamination/wettability alteration in different solvents were compared and discussed by considering solvent composition and mineral types. The wettability of solids extracted from the industrial froth using different solvents was also compared. The XRD analysis on these solids confirmed the partitioning behavior of solids observed in model solids system. The results from this study indicate that the composition of paraffinic/aromatic solvent in an industrial froth treatment process could be tailor-optimized to achieve a better solids/water rejection. / Materials Engineering

In gas-condensate reservoirs, production rate starts to decrease when retrograde condensation occurs. As the bottomhole pressure drops below the dewpoint, gascondensate and water buildup impede flow of gas to the surface. To stop the impairment of the well, many publications suggest wettability alteration to gas-wetting as a permanent solution to the problem. Previous simulation work suggests an "optimum wetting state" to exist where maximum gas condensate well productivity is reached. This work has direct application in gas-condensate reservoirs, especially in identifying the most effective stimulation treatment which can be designed to provide the optimum wetting conditions in the near-wellbore region. This thesis presents an extensive experimental study on Berea sandstone rocks treated with a fluorinated polymer. Various concentrations of the polymer are investigated to obtain the optimum alteration in wettability to intermediate gas-wet. This wetting condition is achieved with an 8% polymer solution treatment, which yields maximum gas mobility, ultimately increasing the relative permeability curves and allowing enhanced recovery from gas-condensate wells. The treatments are performed mainly at room conditions, and also under high pressure and high temperature, simulating the natural environment of a reservoir. Several experimental techniques are implemented to examine the effect of treatments on wettability. These include flow displacement tests and oil imbibitions. The experimental work took place in the Wettability Research Lab in Texas A&M University at Qatar in Doha, Qatar. The studies in this area are important to improve the productivity of gas-condensate reservoirs where liquid accumulates, decreasing production of the well. Efficiency in the extraction of natural gas is important for the economic and environmental considerations of the oil and gas industry. Wettability alteration is one of the newest stimulation methods proposed by researchers, and shows great potential for future research and field applications.

Spent acid retention in the near-wellbore region causes reduction of relative permeability to gas and eventually curtailed gas production. In low-permeability gas carbonate reservoirs, capillary forces are the key parameters that affect the trapping of spent acid in the formation. Capillarity is a function of surface tension at the gas-liquid interface and contact angle of the fluids in the rock. To weaken capillary forces, surface tension should be low and contact angle should be large. This work provides a comprehensive study on the effect of various common acid additives on carbonate rock wettability, and surface tension and contact angle, as the main parameters that control capillarity. Surface tension and contact angle experiments were conducted using Drop Shape Analysis (DSA) instrument at high temperature and pressure. Core flood experiments were also conducted to study the overall impact of the acid additives on wettability by analyzing irreducible fluid saturation in the rocks before and after spent acid exposure. Spontaneous water imbibition was conducted in each case to check for permanent or long-term wettability change as a result of using these additives. Acid additives such as methanol and corrosion inhibitors reduced both surface tension and contact angle. Iron control agents had no impact on surface tension, however, they decreased contact angle at the lower concentration used. Formic and acetic acids did not affect the surface tension, but they had a reducing impact on the contact angle. According to the core flood experiment results, formic acid decreased irreducible fluid saturation whereas methanol increased irreducible fluid saturation. On the other hand, the fluorochemical surfactant tested changed the rock wettability into more gas wetting. Use of this chemical would help in recovering spent acid. The results of the spontaneous water imbibition tests showed that organic acids and iron control chemicals did not have a permanent impact on wettability of the rocks. However, the wettability change as a result of using fluorochemical surfactant would persist for a long time as this chemical forms a film on the rock surface.

Pore-scale simulation has become increasingly important in recent years as a tool to understand multiphase flow behavior. Wettability affects aspects of flow such as capillary-pressure saturation curves, residual saturation of each phase, and relative permeability. Simulation of wettability at the pore-scale is still a non-trivial problem, and many different approaches exist to model it. In this work, we implement a variational level set formulation to impose different contact angles at the solid-fluid-fluid contact line for two-phase flow in simple rhomboidal pore geometries, and calculate the maximum mean curvature (equivalently capillary pressure) for each case. We compare our results with a detailed set of analytical and experimental results in a range of pore geometries of varying wettability from Mason and Morrow (1994), and demonstrate the accuracy of this method. While the simulations shown are for relatively simple geometries, the method has the ability to handle arbitrarily complex geometry (such as input from X-ray microtomography imaging). / text

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Surfactant flooding in carbonate matrix acidizing treatment has been widely used for changing the wettability of the rock and to achieve low IFT values. Optimizing the type of surfactant and concentration for the specific oil field is very important in order to avoid formation damage and to reduce the treatment cost. We built an experimental procedure for screening the right surfactant to alter the wettability and aid in acidizing of Pekisko formation, Canada, which is strongly oil-wet and has high viscosity oil. Five surfactants were tested out of which three are cationic, one amphoteric and the other one was a fluoro-surfactant. Measurements were made of interfacial tension with different surfactant types/concentrations in brine with the oil and xylene, critical micelle concentration of each surfactant, solubility characteristics of the surfactants, compatibility of the chemical additives, wettability of the core after treating with surfactants, and core flooding in the laboratory to simulate matrix acidizing. From the results obtained we noted that the fluoro-surfactant can cause formation damage due to precipitation in the brine. So the compatibility of every chemical additive should be tested first. The use of xylene as a pre-flush solution lowered the CMC and hence reduced the cost of the surfactant treatment. Aromox, an amine based surfactant was best suited for matrix acidizing treatment of the Pekisko formation.

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Amy R. Betz / Boiling is a very effective way of heat transfer due to the latent heat of vaporization. Large amount of heat can be removed as bubbles form and leave the heated surface. Boiling heat transfer has lots of applications both in our daily lives and in the industry. The performance of boiling can be described with two important parameters, i.e. the heat transfer coefficient (HTC) and the critical heat flux (CHF). Enhancing the performance of boiling will greatly increase the efficiency of thermal systems, decrease the size of heat exchangers, and improve the safety of thermal facilities. Boiling heat transfer is an extremely complex process. After over a century of research, the mechanism for the HTC and CHF enhancement is still elusive. Previous research has demonstrated that fluid properties, system pressures, surface properties, and heater properties etc. have huge impact on the performance of boiling. Numerous methods, both active and passive, have been developed to enhance boiling heat transfer. In this work, the effect of pressure was investigated on a plain copper substrate from atmospheric pressure to 45 psig. Boiling heat transfer performance enhancement was then investigated on Teflon© coated copper surfaces, and graphene oxide coated copper surfaces under various system pressures. It was found that both HTC and CHF increases with the system pressure on all three types of surfaces. Enhancement of HTC on the Teflon© coated copper surface is contributed by the decrease in wettability. It is also hypothesized that the enhancement in both HTC and CHF on the graphene oxide coated surface is due to pinning from micro and nanostructures in the graphene oxide coating or non-homogeneous wettability. Condensation and freezing experiments were conducted on engineered surfaces in order to further characterize the pinning effect of non-homogeneous wettability and micro/nano structure of the surface.

Orientador: Rosângela Barros Zanoni Lopes Moreno / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica e Instituto de Geociências / Made available in DSpace on 2018-08-22T07:30:06Z (GMT). No. of bitstreams: 1 EspinosaLeon_Carlos_M.pdf: 5382010 bytes, checksum: fdf960a158541b21f9deb9c7f4593f44 (MD5) Previous issue date: 2013 / Resumo: A molhabilidade tem sido reconhecida como um fator importante controlando a localização microscópica, distribuição e escoamento de fluidos em um meio poroso. Afeta a saturação de água irredutível e de óleo residual assim como as curvas de permeabilidade relativa e pressão capilar do meio poroso, impactando significativamente na recuperação final de óleo. Evidencias de estudos de laboratório têm mostrado que as rochas carbonáticas são de molhabilidade mista a preferencialmente molhadas por óleo. Estas condições são desfavoráveis para a embebição espontânea da água e, portanto, para projetos de injeção de água como método de recuperação. Conforme estudos sobre interações óleo/água/rocha, a composição e propriedades da água injetada podem alterar as propriedades de molhabilidade das rochas durante processos de injeção de água, melhorando a recuperação de petróleo. O principal objetivo deste trabalho é caracterizar a molhabilidade de um bloco de coquinas de afloramento provenientes da Formação Coqueiro Seco - Bacia Sergipe-Alagoas, que são equivalentes às rochas dos reservatórios do pré sal. As medidas do índice de molhabilidade foram realizadas pelo método de Amott, que combina a embebição espontânea e forçada de fluidos para determinar a molhabilidade média das amostras carbonáticas. Óleo mineral e soluções aquosas com salinidade variando de 10000 a 140000 ppm de NaCl foram usadas para representar o óleo e a água de injeção, respectivamente. Os resultados obtidos dos testes realizados neste estudo evidenciam que este tipo de rocha é de molhabilidade mista a preferencialmente molhadas por óleo / Abstract: Wettability has been recognized as an important factor controlling the microscopic location, distribution and fluid flow through a porous medium. It affects the irreducible water saturation and residual oil saturation as well as the relative permeability curves and capillary pressure impacting the ultimate recovery oil. Evidence from laboratory studies have shown that carbonate rocks are mixed wettability to preferentially oil wet which are unfavorable conditions for spontaneous imbibition of water and therefore in the design of a waterflooding process as a recovery method. As studies on oil/water/rock interactions the composition and properties of the injected water can alter the wetting properties of rocks during a waterflooding improving oil recovery. The main objective of this work is to measure the wettability of coquina outcrops from the Coqueiro Seco Formation - Sergipe-Alagoas Basin, which are equivalent to pre-salt reservoir rocks. Wettability index measurements were carried out with the Amott method which combines spontaneous and forced imbibition of fluids to determine the average wettability of carbonate cores. Mineral oil and brines with salinity ranging from 10.000 to 140.000 ppm of NaCl were used to represent crude oil and the injection brine respectively. The results of the tests addressed in this study provided evidences that these rocks are mixed-wet to preferentially oil-wet / Mestrado / Reservatórios e Gestão / Mestre em Ciências e Engenharia de Petróleo