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Microfiltration is one of the most important processes in membrane sciences that can be used for separating drops/particles above 1 ??m. Depth microfiltration membranes retain drops/particles inside the surface of the membrane, the process is expensive and membranes quickly become fouled. On the other hand, surface microfiltration membranes stop drops/particles on the surface of the membrane and the process is less fouling. Higher permeate flux and lower trans-membrane pressure is obtained with a shear enhanced microfiltration technique. Production of specific size of drops and stability of the drops are very important in testing the microfiltration of crude oil drops/water emulsions. Oil drops from 1-15 ??m were produced with a food blender, operated at its highest speed for the duration of 12 mins. In addition, vegetable oil drops were stabilised with 1% polyvinyl alcohol (PVA), Tween 20 and gum Arabic, stability was assessed on the basis of consistency in the size distribution and number of drops in each sample analysed at 30 mins interval. A slotted pore Nickel membrane with the slot width and slot length of 4 and 400 ??m respectively has been used in the filtration experiments. The slot width to the slot length ratio (aspect ratio) of the used membrane is 100. Vibrating the membrane at various frequencies created shear rates of different intensities on the surface of the membrane. Membrane with a tubular configuration is preferred over the flat sheet because it is easy to control in-case of membrane oscillations both at lab and industrial scale. Besides this, a tubular membrane configuration provides a smaller footprint as compared to the flat sheet. The influence of applied shear rate on slots/pore blocking has been studied. Applying shear rate to the membrane reduced the blocking of the slots of the membrane; and reduction of slots blocking is a function of the applied shear rate. At higher shear rate, lower blocking of the slots of the membrane was verified by obtaining lower trans-membrane pressure for constant rate filtration. The experiments are in reasonable agreement with the theoretical blocking model. Divergence of the experimental data from the theory may be due to involvement of deforming drops in the process. During microfiltration of oil drops, the drops deform when passing through the slots or pores of the membrane. Different surfactants provided different interfacial tensions between the oil and water interface. The influence of interfacial tension on deformation of drops through the slots was studied. The higher the interfacial tension then the lower would be the deformation of drops through the slots. A mathematical model was developed based on static and drag forces acting on the drops while passing the membrane. The model predicts 100% cut-off of drops through the membrane. Satisfactory agreement of the model with the experiments shows that the concept of static and drag force can be successfully applied to the filtration of deformable drops through the slotted pore membranes. Due to the applied shear rate, inertial lift migration velocities of the drops away from the surface of the membrane were created. Inertial lift velocities are linear functions of the applied shear rate. A mathematical model was modified based on inertial lift migration velocities. The critical radius of the drops is the one above which drops cannot pass through the surface of the membrane into the permeate due to the applied shear rate and back transport. The model is used as a starting point and is an acceptable agreement with the experiment. The model can be used to predict the 100% cut-off value for oil drops filtration and a linear fit between this value and the origin on a graph of grade (or rejection) efficiency and drop size to slot width ratio was used to predict the total concentration of dispersed oil left after filtration. Hence, it is shown how it is possible to predict oil discharge concentrations when using slotted filters.

Accurate predictions of macroscopic multiphase flow properties, such as relative permeability and capillary pressure, are necessary for making key decisions in reservoir engineering. These properties are usually measured experimentally, but pore-scale network modeling has become an efficient alternative for understanding fundamental flow behavior and prediction of macroscopic properties. In many cases network modeling gives excellent agreement with experiment by using models physically representative of real media. Void space within a rock sample can be extracted from high resolution images and converted to a topologically equivalent network of pores and throats. Multiphase fluid transport is then modeled by imposing mass conservation at each pore and implementing the Young-Laplace equation in pore throats; the resulting pressure field and phase distributions are used to extract macroscopic properties. Advancements continue to be made in making network modeling predictive, but one limitation is that artificial (e.g. constant pressure gradient) boundary conditions are usually assumed; they do not reflect the local saturations and pressure distributions that are affected by flow and transport in the surrounding media. In this work we demonstrate that flow behavior at the pore scale, and therefore macroscopic properties, is directly affected by the boundary conditions. Pore-scale drainage is modeled here by direct coupling to other pore-scale models so that the boundary conditions reflect flow behavior in the surrounding media. Saturation couples are used as the mathematical tool to ensure continuity of saturations between adjacent models. Network simulations obtained using the accurate, coupled boundary conditions are compared to traditional approach and the resulting macroscopic petrophysical properties are shown to be largely dependent upon the specified boundary conditions. The predictive ability of network simulations is improved using the novel network coupling scheme. Our results give important insight into upscaling as well as approaches for including pore-scale models directly into reservoir simulators. / text

Mixing of miscible gas with oil in a reservoir decreases the effective strength of the gas, which can adversely affect miscibility and recovery efficiency. The mixing that occurs in a reservoir, however, is widely debated and often ignored in reservoir simulation, where very large grid blocks are used. Large grid blocks create artificially large mixing that can cause errors in predicted oil recovery. Reservoir mixing, or dispersion, is caused by diffusion of particles across streamlines of varying velocities. Mixing is enhanced by any mechanism that increases the area of contact between the gas and the oil, thereby allowing the effects of diffusion to be magnified. This is, in essence, the cause of scale-dependent dispersion. The contact area grows primarily because of variations in streamlines and their velocities around grains and through layers of various permeabilities (heterogeneity). Mixing can also be enhanced by crossflow, such as that caused by gravity and by the effects of other neighboring wells. This dissertation focuses on estimation of the level of effective local mixing at the field scale and its impact on oil recovery from miscible gas floods. Pore-level simulation was performed using the Navier-Stokes and convection-diffusion equations to examine the origin of scale dependent dispersion. We then estimated dispersivity at the macro scale as a function of key scaling groups in heterogeneous reservoirs. Lastly, we upscaled grid blocks to match the level of mixing at the pattern scale. Once the contact area ceases to grow with distance traveled, dispersion has reached its asymptotic limit. This generally occurs when the fluids are well mixed in transverse direction. We investigated a variety of pore-scale models to understand the nature of scale dependency. From the pore-scale study, we found that reservoir mixing or dispersion is caused by diffusion of particles across streamlines. Diffusion can be significantly enhanced if the surface area of contact between the reservoir and injected fluid are increased as fluids propagate through the reservoir. Echo and transmission dispersivities are scale dependent. They may or may not reach an asymptotic limit depending on the scale of heterogeneities encountered. The scale dependence results from an increase in the contact area between solute (gas) and resident fluid (oil) as heterogeneities are encountered, either at the pore or pattern-scale. The key scaling groups for first-contact miscible (FCM) flow are derived and their impact on mixing is analyzed. We examine only local mixing, not apparent mixing caused by variations in streamline path lengths (convective spreading). Local mixing is important because it affects the strength of the injected fluid, and can cause an otherwise multicontact miscible (MCM) flood to become immiscible. We then showed how to upscale miscible floods considering reservoir mixing. The sum of numerical dispersion and physical dispersion associated with the reservoir heterogeneities, geometry and fluid properties must be equal at both the fine- and large-scales. The maximum grid-block size allowed in both the x- and z-directions is determined from the scaling groups. Small grid-blocks must be used for reservoirs with uncorrelated permeabilities, while larger grid blocks can be used for more layered reservoirs. The predicted level of mixing for first-contact miscible floods can be extended with good accuracy to multicontact miscible (MCM) gas floods. / text

Pore-scale network modeling has become an effective method for accurate prediction and upscaling of macroscopic properties, such as permeability. Networks are either mapped directly from real media or stochastic methods are used that simulate their heterogeneous pore structure. Flow is then modeled by enforcing conservation of mass in each pore and approximations to the momentum equations are solved in the connecting throats. In many cases network modeling compares favorably to experimental measurements of permeability. However, computational and imaging restrictions generally limit the network size to the order of 1 mm3 (few thousand pores). For extremely heterogeneous media these models are not large enough in capturing the petrophysical properties of the entire heterogeneous media and inaccurate results can be obtained when upscaling to the continuum scale. Moreover, the boundary conditions imposed are artificial; a pressure gradient is imposed in one dimension so the influence of flow behavior in the surrounding media is not included. In this work we upscale permeability in large, heterogeneous media using physically-representative pore-scale network models (domain ~106 pores). High-performance computing is used to obtain accurate results in these models, but a more efficient, novel domain decomposition method is introduced for upscaling the permeability of pore-scale models. The medium is decomposed into hundreds of smaller networks (sub-domains) and then coupled with the surrounding models to determine accurate boundary conditions. Finite element mortars are used as a mathematical tool to ensure interfacial pressures and fluxes are matched at the interfaces of the networks boundaries. The results compare favorably to the more computationally intensive (and impractical) approach of upscaling the media as a single model. Moreover, the results are much more accurate than traditional hierarchal upscaling methods. This upscaling technique has important implications for using pore-scale models directly in reservoir simulators in a multiscale setting. The upscaling techniques introduced here on single phase flow can also be easily extended to other flow phenomena, such as multiphase and non-Newtonian behavior. / text

Uniaxial consolidation tests of resedimented mudrocks from the offshore Gulf of Mexico reveal compression and permeability behavior that is in many ways similar to those of intact core specimens and field measurements. Porosity (n) of the resedimented mudrock also falls between field porosity estimates obtained from sonic and bulk density well logs at comparable effective stresses. Laboratory-prepared mudrocks are used as testing analogs because accurate in-situ measurements and intact cores are difficult to obtain. However, few direct comparisons between laboratory-prepared mudrocks, field behavior, and intact core behavior have been made. In this thesis, I compare permeability and compressibility of laboratory-prepared specimens from Gulf of Mexico material to intact core and field analysis of this material. I resediment high plasticity silty claystone obtained from Plio-Pleistocene-aged mudrocks in the Eugene Island Block 330 oilfield, offshore Louisiana, and characterize its compression and permeability behavior through constant rate of strain consolidation tests. The resedimented mudrocks decrease in void ratio (e) from 1.4 (61% porosity) at 100 kPa of effective stress to 0.34 (26% porosity) at 20.4 MPa. I model the compression behavior using a power function between specific volume (v=1+e) and effective stress ([sigma]'v): v=1.85[sigma]'v-⁰̇¹⁰⁸. Vertical permeability (k) decreases from 2.5·10-¹⁶ m² to 4.5·10-²⁰ m² over this range, and I model the permeability as a log-linear function of porosity (n): log₁₀ k=10.83n - 23.21. Field porosity estimates are calculated from well logs using two approaches; an empirical correlation based on sonic velocities, and a calculation using the bulk density. Porosity of the resedimented mudrock falls above the sonic-derived porosity and below the density porosity at all effective stresses. Measurements on intact core specimens display similar compression and permeability behavior to the resedimented specimens. Similar compression behavior is also observed in Ursa Basin mudrocks. Based on these similarities, resedimented Gulf of Mexico mudrock is a reasonable analog for field behavior. / text

Current study of separation mechanism in chromatography heavily relies on the measurement of macroscopic properties, such as retention time and peak width. This dissertation describes the vibrational spectroscopy characterization of separation processes.Raman Spectroscopic characterization of a silica-based, strong anion exchange stationary phase in concentrated aqueous solutions is presented. Spectral response of stationary phase quaternary amine is closely related to changes in interaction between counter anions and the amine functional groups as the result of anion hydration. The molecular-level information obtained will provide useful guidance for control of stationary phase selectivity.To study the effects of stationary phase pore size on separations processes, monodisperse silica particles in the sub-100 nm range are prepared and self-assembled to well-ordered, three-dimensional colloidal arrays. A modified LaMer model is proposed and demonstrated for optimization of reaction conditions that lead to uniform and spherical silica particles. This approach greatly reduces the number of training experiments required for optimization. Fast Fourier transformation of colloidal array scanning electron microscopy images indicates closely-packed hexagonal packing patterns.Using these arrays, a novel system for the measurement of molecular diffusion coefficients in nanopores is reported. This system consists of an ordered colloidal array with well-defined pore structure deposited onto an internal reflection element for in-sit collection of kinetic information by attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR). A mathematical model is established to extract diffusion coefficients from these data. A decrease of approximately eight orders of magnitude in molecular diffusion coefficients is observed for molecular transport in nanopores.Finally, by using this colloidal array-ATR-FTIR system and the corresponding mathematical models that describe absorption in the colloidal array, the distribution in the nanopores of the acetonitrile organic modifier in an aqueous mobile phase solvent system is determined. Based on the results of 50 nm colloidal arrays, pore surface properties have a strong effect on the distribution of organic molecules from bulk solution to the pores.

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This research addresses a number of fundamental issues concerning convective mass transfer across fluid-fluid interfaces in porous media. Mass transfer to/from distributed sinks/sources is considered for i) the slow dissolution of liquid filaments of a wetting non-aqueous phase liquid (NAPL) held in the corners of angular pores or throats and ii) the fate of gas bubbles generated during the flow of a supersaturated aqueous phase in porous media. 1. Effects of the stability of NAPL films on wetting NAPL dissolution Wettability profoundly affects the distribution of residual NAPL contaminants in natural soils. Under conditions of preferential NAPL wettability, NAPL is retained within small pores and in the form of thick films (liquid filaments) along the corners and crevices of the pore walls. NAPL films in pore corners provide capillary continuity between NAPL-filled pores, dramatically influencing the behaviour of NAPL dissolution to the flowing aqueous phase by convection and diffusion. A pore network model is developed to explore the dissolution behaviour of wetting NAPL in porous media. The effects of initial NAPL distribution and NAPL film stability on dissolution behaviour are studied using the simulator. NAPL phase loses continuity and splits into disconnected clusters of NAPL-filled pores due to rupture of NAPL films. Quasi-state drainage and fingering of the aqueous phase into NAPL-filled pores is treated as an invasion percolation process and a stepwise procedure is adopted for the solution of flow and solute concentration fields. NAPL film stability is shown to critically affect the rate of mass transfer as such that stable NAPL films provide for more rapid dissolution. The network simulator reproduces the essential physics of wetting NAPL dissolution in porous media and explains the concentration-tailing behaviour observed in experiments, suggesting also new possibilities for experimental investigation. 2. Convective Mass Transfer across Fluid Interfaces in Straight Angular Pores Steady convective mass transfer to or from fluid interfaces in pores of angular cross-section is theoretically investigated. The model incorporates the essential physics of capillarity and solute mass transfer by convection and diffusion in corner fluid filaments. The geometry of the corner filaments, characterized by the fluid-fluid contact angle, the corner half-angle and the interface meniscus curvature, is accounted for. Boundary conditions of zero surface shear (???perfect-slip???) and infinite surface shear (???no-slip???) at the fluid-fluid interface are considered. The governing equations for laminar flow within the corner filament and convective diffusion to or from the fluid-fluid interface are solved using finite-element methods. Flow computations are verified by comparing the dimensionless resistance factor and hydraulic conductance of corner filaments against recent numerical solutions by Patzek and Kristensen [2001]. Novel results are obtained for the average effluent concentration as a function of flow geometry and pore-scale Peclet number. These results are correlated to a characteristic corner length and local pore-scale Peclet number using empirical equations appropriate for implementation in pore network models. Finally, a previously published ???2D-slit??? approximation to the problem at hand is checked and found to be in considerable error. 3. Bubble evolution driven by solute diffusion during the process of supersaturated carbonated water flooding In situ bubble growth in porous media is simulated using a pore network model that idealizes the pore space as a lattice of cubic chambers connected by square tubes. Evolution of the gas phase from nucleation sites is driven by the solute mass transfer from the flowing supersaturated water solution to the bubble clusters. Effects of viscous aqueous phase flow and convective diffusion in pore corners are explicitly accounted for. Growth of bubble clusters is characterised by a pattern of quasi-static drainage and fingering in the gas phase, an invasion percolation process controlled by capillary and gravitational forces. A stepwise solution procedure is followed to determine the aqueous flow field and the solute concentration field in the model by solving the conservation equations. Mobilization of bubbles driven by buoyancy forces is also studied. Results of bubble growth pattern, relative permeability and macroscopic mass transfer coefficient are obtained under different gas saturations and aqueous flow conditions.

The main objective of this research was to model the airflow paths through grain bulks and predict the resistance to airflow. The discrete element method (DEM) was used to simulate the pore structures of grain bulks. A commercial software package PFC3D (Particle Flow Code in Three Dimension) was used to develop the DEM model. In the model, soybeans kernels were considered as spherical particles. Based on simulated positions (coordinates) and radii of individual particles, the characteristics of airflow paths (path width, tortuosity, turning angles, etc.) in the vertical and horizontal directions of the grain bed were calculated and compared. The discrete element method was also used to simulate particle packing in porous beds subjected to vertical vibration. Based on the simulated spatial arrangement of particles, the effect of vibration on critical pore structure parameters (porosity, tortuosity, pore throat width) was quantified. A pore-scale flow branching model was developed to predict the resistance to airflow through the grain bulks. Delaunay tessellation was also used to develop a pore network model to predict airflow resistance. Experiments were conducted to measure the resistance to airflow to validate the models. It was found that the discrete element models developed using PFC3D was capable of predicting the pore structures of grain bulks, which provided a base for geometrically constructing airflow paths through the pore space between particles. The tortuosity for the widest and narrowest airflow paths predicted based on the discrete element model was in good agreement with the experimental data reported in the literature. Both pore-scale models (branched path and network) proposed in this study for predicting airflow resistance (pressure drop) through grain bulks appeared promising. The predicted pressure drop by the branched path model was slightly (<12%) lower than the experimental value, but almost identical to that recommended by ASABE Standard. The predicted pressure drop by the network model was also lower than the measured value (2.20 vs. 2.44 Pa), but very close to that recommended by ASABE Standard (2.20 vs. 2.28Pa). / February 2017