Thesis (M.S.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xx, 159 p. : ill. (some col.), map. Includes abstract. Includes bibliographical references (p. 64-65).

Solids-stabilized water-in-oil emulsions have been suggested as a drive fluid to recover viscous oil through a piston-like displacement pattern. While crude heavy oil was initially suggested as the base oil, an alternative oil ? used engine oil was proposed for emulsion generation because of several key advantages: more favorable viscosity that results in better emulsion injectivity, soot particles within the oil that readily promote stable emulsions, almost no cost of the oil itself and relatively large supply, and potential solution of used engine oil disposal. In this research, different types of used engine oil (mineral based, synthetic) were tested to make W/O emulsions simply by blending in brine. A series of stable emulsions was prepared with varied water contents from 40~70%. Viscosities of these emulsions were measured, ranging from 102~104 cp at low shear rates and ambient temperature. Then an emulsion made of 40% used engine oil and 60% brine was chosen for a series of coreflood experiments, to test the stability of this emulsion while flowing through porous media. Limited breakdown of the effluent was observed at ambient injection rates, indicating a stability of the emulsion in porous media. Pressure drops leveled off and remained constant at constant rate of injection, indicating steady-state flows under the experimental conditions. No plug off effect was observed after a large volume of emulsion passed through the cores. Reservoir scale simulations were conducted for the emulsion flooding process based on the emulsion properties tested from the experiments. Results showed significant improvement in both displacement pattern and oil recovery especially compared to water flooding. Economics calculations of emulsion flooding were also performed, suggesting this process to be highly profitable.

Vegetable oil is one of the most widely available renewable sources of energy that can be used to meet the world’s demands. Many vegetable oils also have the advantage of containing little to no detectable amounts of nitrogen. Recently, research studies have revealed that when two liquids with different vapor pressure values are formed into droplet-like emulsions, a micro-explosion effect can happen under specific environmental conditions. Understanding the micro-explosion phenomena can help increase the efficiency of bio-emulsion combustion as well as reduce pollution levels. Many researchers have conducted experiments to find the optimal condition that induces microexplosion effects. Microexplosion is also associated with the formation of shock waves characteristic of explosions at larger scales. However, little is known about how emulsion composition and droplet size affect the micro-explosion process. Through this research, methanol-in-vegetable oil emulsion has been studied from the microexplosion point of view using custom made electric furnace equipment with a high speed camera system and an acoustic sensor system. The main goal of this study is to understand the effect of emulsion compositions, chamber temperatures, and droplet sizes on the characteristics of microexplosion. First, an n-hexadecane-in-water emulsion was prepared to validate the performance of the custom-made experimental apparatus using previous published data. Methanol-in-canola oil emulsions with different compositions were also prepared and used to compare the micro-explosion phenomena with water as a volatile compound. Microexplosion events of the blended fuels were captured using a high speed camera and an acoustic sensor. The wave signals generated by the microexplosion were analyzed after converting the signals using a Fast Fourier Transform coded in Matlab. One of the major findings of this research work was that higher temperatures and higher concentrations of high vapor pressure fluids such as methanol and water in emulsions causes a high probability of microexplosion event due to the sudden expansion of the emulsified fluid. Also, the effect of size on microexplosion was evident in the greater probability of explosion. Methanol-in-canola oil emulsion with 15 % methanol with droplets size of 200 m placed in a furnace chamber heated to 980 ˚C showed optimal microexplosion behavior based on the formation of fine droplets. Also, smaller droplets produced higher frequencies, which could be used to detect microexplosion without high speed imaging. When large droplets microexploded, lower frequencies were detected in all the blends.

The effects of partial or total replacement of fish oil with linseed oil or corn oil or both in diets of cobia were valuated. Basal diet was isonitrogenous and isoenergetic and contained 15% crude lipid. Results of the 8-wk feeding trial show that fish fed diet containing only fish oil grew significant better than fish fed other replacement diets (replacement level 33-100%). Fish fed diet containing only plant oil grew the least and had the lowest liver weight, condition factor and body lipid concentration. Oil replacement did not significantly change liver mRNA gene expression of fatty acid desaturase and elongase. As levels of replacement increased, tissue PUFA increased while HUFA decreased. Fish fed all fish oil diet had the highest respiratory burst activities of head kidney phagocytes. Serum of the fish fed the all vegetable oil diets had the lowest lysozyme activities. Fish fed all linseed oil diet had the highest SOD activities. Serum alternative complement pathway activity, aspartate transaminase and alanine transaminase activity did not vary among treatments. The results show that cobia juveniles had relatively high need for fish oil in their diets, and the ability to synthesized HUFA from PUFA was limited. Partial or total replacement (33-100%) of fish oil with linseed oil or corn oil or both were detrimental to fish growth and immune responses.

Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references (leaves 237-240). Available also in a digital version from Dissertation Abstracts.

Thesis (Ph. D.)--University of Missouri-Columbia, 2003. / Typescript. Vita. Includes bibliographical references (leaves 420-424). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 2003. / Typescript. Vita. Includes bibliographical references (leaves 420-424). Also available on the Internet.

Polymer flooding is a commercially proven technology to enhance oil recovery from mature reservoirs. The main mechanism for improving oil recovery is to increase the viscosity of injection water by adding polymer, thereby creating a favorable mobility ratio for improved volumetric sweep efficiency. However, polymer injection brings on several potential problems: a) a high injection pressure with associated pumping cost; b) creation of unwanted injection well fractures; and c) mechanical degradation of polymers due to high shear near wellbore. The high viscosity of polymer solutions and permeability reduction by polymer retention reduce mobility, and simultaneously increase the pressure drop required for the propagation of the polymer bank. The objective of this dissertation is to develop an improved polymer injection process that can minimize the impact of those potential problems in the polymer flooding process, and to extend this application to conformance control. This objective is accomplished by utilizing the pH sensitivity of partially hydrolyzed polyacrylamide (HPAM), which is the most commonly used EOR polymer. The idea of the “low-pH polymer process” is to inject HPAM solution at low-pH conditions into the reservoir. The polymer viscosity is low in that condition, which enables the polymer solution to pass through the near wellbore region with a relatively low pressure drop. This process can save a considerable amount of pump horse power required during injection, and also enables the use of large-molecular-weight polymers without danger of mechanical degradation while injecting below the fracture gradient. Away from the near wellbore region, the polymer solution becomes thickened with an increase in pH, which occurs naturally by a spontaneous reaction between the acid solution and rock minerals. The viscosity increase lowers the brine mobility and increases oil displacement efficiency, as intended. Another potential application of the low-pH polymer injection process is conformance control in a highly heterogeneous reservoir. As a secondary recovery method, water flooding can sweep most oil from the high-permeability zones, but not from the low-permeability zones. The polymer solution under low-pH conditions can be placed deep into such high-permeability sands preferentially, because of its low viscosity. It is then viscosified by a pH increase, caused by geochemical reactions with the rock minerals in the reservoir. With the thickened polymer solution in the high permeability sands, the subsequently injected water is diverted to the low permeability zone, so that the bypassed oil trapped in that zone can be efficiently recovered. To evaluate the low-pH polymer process, extensive laboratory experiments were systematically conducted. As the first step, the rheological properties of HPAM solutions, such as steady-shear viscosity and viscoelastic behavior, were measured as functions of pH. The effects of various process variables, such as polymer concentrations, salinity, polymer molecular weight, and degree of hydrolysis on rheological properties, were investigated for a wide range of pH. A comprehensive rheological model for HPAM solutions was also developed in order to provide polymer viscosity in terms of the above process variables. As the second step, weak acid (citric acid) and strong acid (hydrochloric acid) were evaluated as pH control agents. Citric acid was shown to clearly perform better than hydrochloric acid. A series of acid coreflood experiments for different process variables (injection pH, core length, flow rate, and the presence of shut-ins) were carried out. The effluent pH and five cations (total Ca, Mg, Fe, Al, and K) were measured for qualitative evaluation of the geochemical reactions between the injected acid and the rock minerals; these measurements also provide data for future history matching simulations to accurately characterize these geochemical reactions. Finally, polymer coreflood experiments were carried out with different process variables: injection pH, polymer concentration, polymer molecular weight, salinity, degree of hydrolysis, and flow rate. The transport characteristics of HPAM solutions in Berea sandstone cores were evaluated in terms of permeability reduction and mobility reduction. Adsorption and inaccessible/excluded pore volume were also measured in order to accurately characterize the transport of HPAM solutions under low-pH conditions. The results show that the proposed “low-pH polymer process” can substantially increase injectivity (lower injection pressures) and allow deeper transport of polymer solutions in the reservoir due to the low solution viscosity. The peak pH’s observed in several shut-ins guarantee that spontaneous geochemical reactions can return the polymer solution to its original high viscosity. However, low-pH conditions increase adsorption (polymer-loss) and require additional chemical cost (for citric acid). The optimum injection formulation (polymer concentration, injection pH) will depend on the specific reservoir mineralogy, permeability, salinity and injection conditions. / text

Environmental liability cases involving spilled or released petroleum products into ocean ecosystems require oil identification techniques that are unambiguous and conclusive, even in situations where oils have been subjected to secondary environmental processes, such as, evaporation and dissolution. The ability and functionality of the Compound Specific Isotope Correlation (CSIC) technique is tested to determine its reliability to characterize released petroleum using the carbon isotope ratios (13C/12C) of the individual gasoline-range compounds (C5-C9). In particular, this thesis studies the potential of CSIC as a robust diagnostic tool, to identify and correlate marine releases of oil with their sources, especially those having undergone evaporative weathering. Three crude oils (Alberta Sweet Mixed Blend, Lacula and Louisiana) added to synthetic seawater were exposed to mechanically simulated wave energy and controlled evaporative weathering at 10 oC. Time-series sampling of the gasoline-range vapour fractions from the headspace employed Solid Phase Micro Extraction (SPME). SPME-Continuous Flow-Isotope Ratio Mass Spectrometry (SPME-CF-IRMS) determined the molecular abundances and stable carbon isotope ratios (δ13C) of the gasoline-range compounds of the original and weathered oils. Evaporation rates over the maximum 20 hour period varied for the 3 study oils. Most (74%) of the individual compounds measured in the oils display a δ13C enrichment with progressive evaporation with approximately half of the compounds in all 3 oils showing fractionation of the carbon isotopes ≤ 0.5‰ within measurement precision. The magnitude of carbon isotope shift observed in compounds pre-vs. post-weathering ranges from 0 to 2.8 ±0.6‰. There is no clear relationship identified between the degree of 13C enrichment in the oils and groupings such as chemical class, structure or carbon number. The overall weighted average 13C enrichment for all compounds in the 3 oils is approximately 1‰. Toluene was the only compound consistently exhibiting comparatively high 13C enrichment (1.6‰, 1.8‰ and 2.8‰) in all 3 oils after evaporative weathering. Hierarchical Cluster Analysis (HCA) treatment of the CSIC data set can reliably discriminate between the 3 oils despite evaporative weathering and δ13C changes. HCA is also able to unambiguously relate the three weathered oils back to their respective original unweathered oil. Diagnostic shifts in δ13C of individual compounds in an oil may potentially be used to trace weathered oils back to the source, and possibly give a estimation of time since release. However the typically rapid rate of evaporation for the gasoline-range fractions limits the time that an oil can be successfully identified by CSIC. / Graduate

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