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

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

The scope of work can be divided into; the measurement of the rheological properties of a new emulsified acid system that can be suitable for high temperature applications, a study of the performance of the new emulsified acid in stimulating both calcite and dolomite formations, measuring the reaction rate and diffusion coefficient when the new emulsified acid systems react with both calcite and dolomite, and testing the new emulsified acid using core samples obtained from carbonate reservoirs. The droplet size has a practical impact on the performance of emulsified acid. A good understanding and characterization of the emulsified acid by its size distribution will lead to better understanding of its stability, rheology and how it reacts with carbonate rocks. The influence of the concentration of the new emulsifier on the droplet size, droplet size distribution and upon the rheology of emulsified acids is studied in detail. The emulsified acid reaction kinetics with calcite rocks was studied before in few studies, and very little work was done with dolomite. One of the main objectives of the present work is to study in detail the reaction of the emulsified acid with both calcite and dolomite rocks using the rotating disk apparatus. Most of the previous studies on the emulsified acid were done using core samples that were saturated with brine or deionized water. One of the main objectives of the present work is to study in detail the effect of the presence of crude oil in the reservoir rock on the performance of emulsified acids. Lastly, an innovative technique of emulsifying the chelating agents is evaluated for high temperature applications. The rheology of the emulsified chelating agent is measured using an HPHT rheometer. Also, the reaction of the new emulsified chelating agent with calcite is studied using the rotating disk apparatus, and coreflood experiments were performed using chelating agents and calcite core samples.

This study geochemically characterized a proposed Carbon Capture and Storage project in northeast British Columbia, and presents new dissolution kinetics data for the proposed saline aquifer storage reservoir, the Keg River Formation. The Keg River Formation is a carbonate reservoir (89-93% Dolomite, 5-8% Calcite) at approximately 2200 m depth, at a pressure of 190 bar, and temperature of 105 °C. The Keg River brine is composed of Na, Cl, Ca, K, Mg, S, Si, and HCO3 and is of approximately 0.4 M ionic strength. Fluid analysis found the Keg River brine to be relatively fresh compared with waters of the Keg River formation in Alberta, and to also be distinct from waters in overlying units. These findings along with the physical conditions of the reservoir make the Keg River Formation a strong candidate for CO2 storage. Further work measured the dissolution rates of Keg River rock that will occur within the Keg River formation. This was performed in a new experimental apparatus at 105 °C, and 50 bar pCO2 with brine and rock sampled directly from the reservoir. Dissolution rate constants (mol!m-2s-1) for Keg River rock were found to be Log KMg 9.80 ±.02 and Log KCa -9.29 ±.04 for the Keg River formation. These values were found to be significantly lower compared to rate constants generated from experiments involving synthetic brines with values of Log KMg -9.43 ±.09, and Log KCa -9.23 ±.21. Differences in rates were posited as due to influences of other element interactions with the >MgOH hydration site, which was tested through experiments with brines spiked with SrCl2 and ZnCl2. Results for the SrCl2 spiked solution showed little impact on dissolution rates with rate constants of Log KMg -9.43 ±.09, and Log KCa -9.15 ±.21, however the ZnCl2 spiked solution did show some inhibition with rate constants of Log KMg -9.67 ±.04, and Log KCa -9.30 ±.04. Rate constants generated in this work are among the first presented which can actually be tested by full-scale injection of CO2. / Graduate

Geochemical processes involving the interaction of fluids and minerals occur in nearly every environment on the surface and in the crust of the Earth. The variety of fluid–mineral processes on the Earth is quite diverse, and these various processes can occur under a large range of geochemical conditions. Aqueous dissolution and alteration, hydration, protonation, solution–precipitation, diffusion, and fluid and isotope exchange are among the many fluid–mineral interaction processes that contribute to the overall cycling of elements on Earth. This dissertation uses analog experiments to examine fluid­–mineral interaction processes found in different geological environments and under a range of environmental conditions. The first part of this dissertation examines the reactive and diffusive exchange of oxygen isotopes that results from performing a dolomite breakdown experiment under a temperature, pressure, and fluid condition analogous to a contact metamorphic environment. The second two parts of the dissertation involve the development of new methods for the growth of nanocrystalline fayalite and intermediate composition olivine. The final two parts of this dissertation focus on the interaction of olivine with either H2O or acidic solutions (0.005 M H2SO4 or 0.01 M HCl) at low temperature and pressure. The first of these two parts experimentally uses different surface area olivine powders that are reacted with low pH fluids in non-buffered, closed system experiments where pH and solution composition are allowed to change. The second of these two parts uses various analytical techniques that can examines changes to the surfaces of olivine single crystals at the nanoscale resulting from experiments performed under environmental conditions where the fluid–mineral interaction transitions from dissolution at low temperature and pressure to alteration at moderate temperature and pressure. Though the individual projects contained within this dissertation are varied, they share the common theme of using experiments to examine fluid­–mineral interaction processes.

Thesis (M.S.)--University of Missouri-Columbia, 2004. / Typescript. Includes bibliographical references (leaves 24-25). Also available on the Internet.

Thesis (Ph. D.)--West Virginia University, 2007. / Title from document title page. Document formatted into pages; contains xvii, 189 p. : ill. (some col.). Vita. Includes abstract. Includes bibliographical references (p. 150-162).

O Campo de Camorim é um dos principais produtores de hidrocarbonetos da Bacia de Sergipe (SE), situada na porção nordeste da margem continental brasileira. Foram estudados quatro poços com testemunhagem no Membro Carmópolis (da Formação Muribeca) que é considerado como o melhor reservatório do Campo. Os poços posicionamse em dois blocos estruturais (aqui denominados de Área Leste e Área Oeste) que apresentam comportamentos distintos em relação à recuperação de hidrocarbonetos. O Membro Carmópolis caracteriza-se pelo predomínio de conglomerados e litoarenitos de granulometria média a grossa (Área Oeste) e também fina a muito fina (Área Leste). Estas rochas se depositaram sob condições climáticas de semi-aridez, na fase transicional de evolução da margem continental brasileira. A cimentação dolomítica teve um importante papel na qualidade destes reservatórios principalmente pela sustentação do arcabouço. Normalmente, a porosidade é reduzida pela compactação e deformação de fragmentos líticos originando uma pseudomatriz. Em função da evolução diagenética observada na área de estudo, foram identificados três tipos de cimento dolomítico. O Tipo I (dolomita romboédrica microcristalina, intergranular, eogenética) apresenta-se livre de ferro. A dolomita Tipo II, com óxido de ferro (“aspecto sujo”), é caracterizada pela forma de mosaicos (anédricos). No estágio mesodiagenético, caracteriza-se o Tipo III identificado pelos romboedros com zoneamento entre dolomita, dolomita ferrosa e anquerita, pois há com maior disponibilidade do íon ferro no ambiente. Em relação aos valores δ18O e δ13C observa-se que para a Área Oeste, considerando-se o predomínio da influência de águas meteóricas, podem ser calculados valores de 54,9oC a 70,0oC para a precipitação da dolomítica (Tipos I e II). Este intervalo de temperatura associa-se aos arenitos cimentados próximo da superfície e de soterramento raso. Para as amostras da Área Leste propõe-se a atuação de fluidos marinhos e, neste caso, o range da temperatura de precipitação variou de 78,8oC a 102,8oC. Este intervalo de temperatura corresponderia os cimentos de precipitação pós-compactacional associados às maiores profundidades. / The Camorim Field is one of the principal producers of hydrocarbon in the Sergipe Basin (SE), situated in the northeastern portion of the eastern Brazilian continental shore. Four well cores were studied in the Carmópolis Member (from the Muribeca Formation), which is considered the best reservoir in the Field. The wells are positioned in two structural blocks (here denominated as East Area and West Area) that present distinct behavior relating to hydrocarbon recuperation. The Carmópolis Member is characterized by a predominance of conglomerates and lithoarenites with medium and thick granulometry (West Area) and also fine and very fine (East Area). These rocks were deposited under semi-arid conditions, in the transitional phase of the Brazilian continental coast evolution. Dolomitic cementation had an important role in the quality of these reservoirs principally due to supporting the framework. Normally, the porosity is reduced by the compacting and deformity of lithic fragments from a pseudomatrix. Due to the diagentic evolution observed in the studied area, three types of dolomotic cement were found. Type I (microcrystalline romboedric dolomite, intergranular, eogenetic) is free of iron. The Type II dolomite, with iron oxide (“dirty look”), is characterized by it mosaic form (anedric). In the mesodiagenetic phase, Type III is characterized, identified by romboedros with zoning between dolomite, iron dolomite, and anquerite, since there are more iron ions in the environment. In relation to the values δ18O e δ13C, it was observed that for the West Area, considering the predominance of meteoric water influence, the values 54.9oC to 70.0oC can be calculated for dolomite precipitation (Types I and II). This temperature interval is associated to the cemented arenites close to the surface. For the samples from the East Area, marine fluid action is proposed, and in this case, the precipitation temperature range varied from 78.8oC to 102.8oC. This temperature interval would correspond to the post-compact precipitation cements associated to greater depths.

O refratário dolomítico é amplamente utilizado como revestimento de trabalho para panelas no processo de Aciaria, por sua excelente refratariedade em condições de serviço, principalmente em usinas que produzem aços acalmados ao silício. O emprego deste refratário é em virtude de uma formação natural de uma capa protetora, a qual potencializa a vida do refratário, acarretando em um aumento da vida útil do equipamento. O trabalho baseia-se em um estudo comparativo entre dois tijolos dolomíticos nomeados aqui como tijolos A e B. Os testes em escala industrial foram dados pela montagem de seis revestimentos, de cada tijolo, colocados sob as mesmas condições, monitorando-se a temperatura e o grau de oxidação do banho metálico. Ao final da campanha da panela se realizou alguns testes POST MORTEM, onde se destaca as medidas dos residuais. Além disso, para completar este estudo comparativo, separaram-se tijolos novos de cada marca, os quais foram submetidos às análises microestruturais via MEV, análises termogravimétricas, análises químicas por EDS e DRX, entre outros ensaios. Os resultados mostraram que o tijolo A teve um desempenho 20% superior ao tijolo B. O tijolo A tem maior pureza, microestrutura com agregados arredondados, com maior homogeneidade, uma ótima distribuição entre partículas finas e médias, favorecendo o empacotamento o que justifica sua maior tenacidade à fratura e resistência à corrosão. Também foi evidenciada de forma clara a presença de carbono grafite no tijolo A, conferindo-lhe uma maior resistência ao choque térmico e à corrosão. / The refractory dolomite is widely used as coating for ladles work in steelmaking process for its excellent refractoriness in terms of service. The use of this refractory is due to a natural formation of a protective layer, which enhances the life of the refractory, resulting in increased equipment life. This work is based on a comparative study between two bricks dolomite named here as A and B. Tests were given on an industrial scale by assembling six coatings of each brick placed in the same conditions by monitoring the temperature and the degree of oxidation of the metal bath. At the end of the campaign applied some tests POST MORTEM, how measurements of residual stresses. Moreover, to complete this comparative study, separated from each brand new bricks, which were subjected to microstructural analyzes via MEV, thermogravimetric analysis, chemical analysis by EDS and XRD, among other tests. The results showed that the performance of brick A was 20% higher than brick B. The Brick A has a higher purity, microstructure with rounded aggregates with greater homogeneity, optimal distribution between fine and medium particles, favoring the packaging which justifies a higher fracture toughness and corrosion resistance. It was also clearly evidenced the presence of graphitic carbon in the brick A, giving it a higher resistance to thermal shock and corrosion.

O refratário dolomítico é amplamente utilizado como revestimento de trabalho para panelas no processo de Aciaria, por sua excelente refratariedade em condições de serviço, principalmente em usinas que produzem aços acalmados ao silício. O emprego deste refratário é em virtude de uma formação natural de uma capa protetora, a qual potencializa a vida do refratário, acarretando em um aumento da vida útil do equipamento. O trabalho baseia-se em um estudo comparativo entre dois tijolos dolomíticos nomeados aqui como tijolos A e B. Os testes em escala industrial foram dados pela montagem de seis revestimentos, de cada tijolo, colocados sob as mesmas condições, monitorando-se a temperatura e o grau de oxidação do banho metálico. Ao final da campanha da panela se realizou alguns testes POST MORTEM, onde se destaca as medidas dos residuais. Além disso, para completar este estudo comparativo, separaram-se tijolos novos de cada marca, os quais foram submetidos às análises microestruturais via MEV, análises termogravimétricas, análises químicas por EDS e DRX, entre outros ensaios. Os resultados mostraram que o tijolo A teve um desempenho 20% superior ao tijolo B. O tijolo A tem maior pureza, microestrutura com agregados arredondados, com maior homogeneidade, uma ótima distribuição entre partículas finas e médias, favorecendo o empacotamento o que justifica sua maior tenacidade à fratura e resistência à corrosão. Também foi evidenciada de forma clara a presença de carbono grafite no tijolo A, conferindo-lhe uma maior resistência ao choque térmico e à corrosão. / The refractory dolomite is widely used as coating for ladles work in steelmaking process for its excellent refractoriness in terms of service. The use of this refractory is due to a natural formation of a protective layer, which enhances the life of the refractory, resulting in increased equipment life. This work is based on a comparative study between two bricks dolomite named here as A and B. Tests were given on an industrial scale by assembling six coatings of each brick placed in the same conditions by monitoring the temperature and the degree of oxidation of the metal bath. At the end of the campaign applied some tests POST MORTEM, how measurements of residual stresses. Moreover, to complete this comparative study, separated from each brand new bricks, which were subjected to microstructural analyzes via MEV, thermogravimetric analysis, chemical analysis by EDS and XRD, among other tests. The results showed that the performance of brick A was 20% higher than brick B. The Brick A has a higher purity, microstructure with rounded aggregates with greater homogeneity, optimal distribution between fine and medium particles, favoring the packaging which justifies a higher fracture toughness and corrosion resistance. It was also clearly evidenced the presence of graphitic carbon in the brick A, giving it a higher resistance to thermal shock and corrosion.