Techn. Hochsch., Diss., 2004--Aachen.

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

Η παρούσα ερευνητική αυτή εργασία που αφορά στην οπτική παρατήρηση των αποθέσεων των αλάτων ανθρακικού ασβεστίου σε πορώδη μέσα εκπονήθηκε με στόχο την διερεύνηση του μηχανισμού σχηματισμού αποθέσεων ανθρακικού ασβεστίουσε πορώδη μέσα. Τα πειράματα έγιναν σε υάλινα και πλαστικά πορώδη υλικά και εξετάσθηκαν οι παράγοντες του υπερκορεσμού, της θερμοκρασίας, του pH, της παροχής και πως αυτοί επιδρούν στο σχηματισμό των κρυστάλλων ανθρακικού ασβεστίου και στον τρόπο απόθεσης του άλατος στα διάφορα τμήματα του πορώδους μέσου. / This present inquiring work that concerns in the optical observation of depositions of calcium carbonate salts in poroys media it was worked out amining at the investigation of mechanism of shaping of calcium carbonate depositions in porous media. The experiments were made and plastic porous materials and were examined the factors of supersaturation, temperature, pH and the benefit of its effect in the shaping of calcium carbonate crystals and in the way of deposition of salt in the various departments of porous means.

abstract: Emission of CO2 into the atmosphere has become an increasingly concerning issue as we progress into the 21st century Flue gas from coal-burning power plants accounts for 40% of all carbon dioxide emissions. The key to successful separation and sequestration is to separate CO2 directly from flue gas (10-15% CO2, 70% N2), which can range from a few hundred to as high as 1000°C. Conventional microporous membranes (carbons/silicas/zeolites) are capable of separating CO2 from N2 at low temperatures, but cannot achieve separation above 200°C. To overcome the limitations of microporous membranes, a novel ceramic-carbonate dual-phase membrane for high temperature CO2 separation was proposed. The membrane was synthesized from porous La0.6Sr0.4Co0.8Fe0.2O3-d (LSCF) supports and infiltrated with molten carbonate (Li2CO3/Na2CO3/K2CO3). The CO2 permeation mechanism involves a reaction between CO2 (gas phase) and O= (solid phase) to form CO3=, which is then transported through the molten carbonate (liquid phase) to achieve separation. The effects of membrane thickness, temperature and CO2 partial pressure were studied. Decreasing thickness from 3.0 to 0.375 mm led to higher fluxes at 900°C, ranging from 0.186 to 0.322 mL.min-1.cm-2 respectively. CO2 flux increased with temperature from 700 to 900°C. Activation energy for permeation was similar to that for oxygen ion conduction in LSCF. For partial pressures above 0.05 atm, the membrane exhibited a nearly constant flux. From these observations, it was determined that oxygen ion conductivity limits CO2 permeation and that the equilibrium oxygen vacancy concentration in LSCF is dependent on the partial pressure of CO2 in the gas phase. Finally, the dual-phase membrane was used as a membrane reactor. Separation at high temperatures can produce warm, highly concentrated streams of CO2 that could be used as a chemical feedstock for the synthesis of syngas (H2 + CO). Towards this, three different membrane reactor configurations were examined: 1) blank system, 2) LSCF catalyst and 3) 10% Ni/y-alumina catalyst. Performance increased in the order of blank system < LSCF catalyst < Ni/y-alumina catalyst. Favorable conditions for syngas production were high temperature (850°C), low sweep gas flow rate (10 mL.min-1) and high methane concentration (50%) using the Ni/y-alumina catalyst. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

A indústria da construção civil é conhecida como umas das atividades econômicas que causam os maiores impactos ambientais desde o processo de extração da matéria prima até a produção dos produtos, incluindo o transporte e manutenção do ambiente construído. A produção de um dos seus principais componentes, o cimento, é o maior contribuinte para a emissão de gases de efeito estufa, principalmente devido a queima de combustíveis fósseis. Por este motivo, pesquisas na área de biotecnologia sustentável são conduzidas para diminuir e até mitigar os efeitos danosos provocados pelos fatores que compõem a construção civil. Dentre estas pesquisas destacam-se as que se baseiam na Biomimética, que é uma ciência que busca na Natureza as soluções tecnológicas para os problemas que os desenvolvimentos humanos geralmente apresentam: a geração de resíduos poluentes, uso de produtos químicos tóxicos e processos que operam com energia e pressão elevadas. Com base nos conceitos biomiméticos, este trabalho se propôs a estudar a biomineralização, que é um processo que ocorre na Natureza a milhares de anos e é responsável pela formação de muitas estruturas biomineralizadas tanto no ambiente terrestre como aquático. A biomineralização é um fenômeno provocado pela ação de diversas espécies de microrganismos que durante o processo de obtenção de energia reciclam minerais presentes no solo e na água e os precipitam na forma de sais inorgânicos. Este material precipitado age como agente ligante de partículas como no caso de formações geológicas (estromatólitos) ou exoesqueletos de animais marinhos, por exemplo. Neste estudo foi avaliado a biomineralização por biodeposição de carbonato de cálcio precipitado na presença da espécie de bactéria ureolítica (Bacillus subtilis) em ensaios em escala laboratorial utilizando corpos de prova de areia, argamassa e concreto. Os corpos de prova em areia e argamassa foram observados em MEV e EDS permitindo a identificação de células de microrganismos, formação de biofilme e provável formação de cristais de carbonato de cálcio na região de biofilme. Os corpos de prova de concreto foram utilizados para avaliar as consequências da biodeposição na absorção de água por capilaridade do material. Resultados indicam redução de 20% na absorção de água por capilaridade. Com os resultados obtidos é possível concluir que a técnica de biodeposição pode ser uma alternativa ao tratamento superficial de estruturas de concreto, contudo requer estudos posteriores de aplicação técnica e viabilidade econômica. / The construction industry has been known as one of the economic activities that cause the major environment impacts since the process of raw material extraction until the products manufacturing including transport and maintenance of the built environment. The production of one of the main compounds, the cement, is the largest contributor to the greenhouse gas emissions, mainly due to burn fossil fuels. For this reason, researches in sustainable biotechnological area are conducted to minimize and even mitigate the damaging effects either promoted by construction industry factors. Among these ones, it stands out researches based on Biomimetic, which is a science that seeks in Nature the technological solutions for problems that human’s development usually presents: the generation of pollutant residues, the use of toxic chemicals and process that operates in high pressure and energy. Based on biomimetic concepts this research proposes to study the biomineralization, which is a process that has occurred in the Nature for thousands of years and it is responsible for the formation of many structures either in soil and water environments. The biomineralization is a phenomenon caused by several specimens of microorganisms that during the process of obtaining energy, they recycle minerals presents at soil and water inducing precipitation as inorganic salts. This precipitated material works as a binder of particles similar to geologic formations (stromatolites) or exoskeleton of sea animal for example. In this study the biomineralization was evaluated through biodeposition of precipitated calcium carbonate by specimen of ureolytic bacteria (Bacillus subtilis). Essays were held using samples made by sand, mortar and concrete. The samples made by sand and mortar were observed at MEV and EDS, allowing the identification of microorganism cells, biofilm formation and probable formation of calcium carbonate crystals at biofilm region. The concrete samples were used to evaluate the consequences of biodeposition on water absorption by capillarity of the material. The results show reduction of 20% on water absorption by capillarity. According the results achieved it possible to conclude that the biodeposition technique can be an alternative to superficial treatment for concrete structures. However, it will be required more studies to evaluate technical application and economical availability.

[pt] A seleção de materiais para o transporte de óleo e gás não é feita pela sua resistência à corrosão, mas sim pelas suas boas propriedades mecânicas, facilidade de fabricação e baixos custos. Devido às taxas de perda de material, causado pela corrosão interna, existe necessidade em se conhecer o comportamento dos aços de mais alta resistência, utilizados especialmente em gasodutos e oleodutos tais como API 5L X70 e API 5L X80. Um dos elementos responsáveis pela corrosão interna é o dióxido de carbono (CO2). O principal produto de corrosão da reação deste gás com o aço é um precipitado de carbonato de ferro que em determinada temperatura se acredita poder retardar o processo de corrosão, agindo como uma barreira à difusão das espécies. Neste trabalho foi estudado o comportamento destes aços numa solução de 1% NaCl contendo CO2, e a estabilidade do filme formado (FeCO3) à diferentes temperaturas. Técnicas de análise eletroquímicas como: curvas de polarização, resistência à polarização linear e de impedância eletroquímica foram usadas para estudar a formação do filme de carbonato de ferro sobre a superfície dos aços. O filme também foi observado e caracterizado por microscópio eletrônico de varredura (MEV) e difração de raios-X. / [en] The selection of materials for the transport of oil and gas, is not always made sufficiently emphasizing corrosion resistance, but rather good mechanical properties, ease of fabrication and low cost. Due to the material loss rates resulting from internal corrosion, it becomes necessary to thoroughly characterize the behaviour of the high strength steels which are used for oil and gas pipelines, such as API 5L X70 and API 5L X80. One the contributing factors responsible for internal corrosion is carbon dioxide (CO2). The main corrosion product resulting from the action of this gas, in solution, on the steel is an iron carbonate precipitate which is believed to retard further corrosion at some temperatures, acting as a diffusion barrier to the chemical species involved. The current work studies the behaviour of the above steels in a 1% NaCl solution containing CO2, and the stability of the FeCO3 film formed at different temperatures. Electrochemical analysis techniques, such as polarization curves, linear polarization resistance and impedance measurements were used to study the formation of the iron carbonate film on the surface of the steels. The film was also observed and characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD).

The ~5.6-4.8 Ma Bouse Formation, exposed along the lower Colorado River, contains a well exposed but debated record of river integration. Sedimentologic and stratigraphic analysis aid interpretation of depositional processes, relative water depth, depositional environments, stratal architecture, and basin-filling history. Data collected include detailed measured sections, facies descriptions, and fault measurements. Seven lithologically distinct units have been identified along with numerous marine sedimentary structures and fossils. The Bouse Formation preserves a systematic sequence-stratigraphic architecture that records two cycles of base level rise and fall. Lacustrine versus estuarine interpretation remains elusive, though new isotope and micropaleontology data suggest a shift from marine to lacustrine. Constructed stratigraphic facies panels reveal a wedging geometry indicative of syn- to post-depostional tilting, leading us to propose a "sag basin" model during deposition of the Bouse. Finally, the newly described Bouse upper limestone unit resolves a long-standing debate over the age of the first through-going river.

A urolitíase é um problema recorrente na clínica veterinária considerada como causa de morbidade. As urolitíases são estreitamente associadas ao pH urinário e a nutrição exerce um papel fundamental no controle desta afecção, pois através da manipulação da dieta, pode-se modificar o pH urinário. A dieta possui cátions e ânions na sua composição mineral e a diferença entre íons é medida em miliequivalentes (mEq/kg) e denominado excesso de bases (EB) da dieta, calculado através da equação: (49,9 x Ca) + (82,3 x Mg) + (43,5 x Na) + (25,6 x K) – (64,6 x P) – (62,4 x S) – (28,2 x Cl), sendo a concentração dos elementos em g/kg de MS. A finalidade deste estudo, dividido em dois experimentos, foi avaliar o efeito da adição de fontes de enxofre (S) e cálcio nas dietas de felinos sobre o pH urinário e equilíbrio ácido-básico. A adição de fontes de enxofre objetivou demonstrar a eficácia na acidificação urinária. No primeiro experimento avaliaram-se três diferentes fontes de enxofre: sulfato de cálcio (CaSO4), DL-metionina (DLM) e Metionina hidróxi análoga (MHA) adicionados a uma dieta controle em dois níveis cada um. No tratamento controle não houve adição de acidificantes. No primeiro nível adicionou-se 1,28 g de S/kg e no segundo 2,56 g de S/kg, resultando em sete tratamentos. No segundo experimento duas fontes de cálcio foram avaliadas com o objetivo de pesquisar a eficácia destes sais na alcalinização da urina. No tratamento controle não houve adição de fontes de cálcio. Nos tratamentos 2 e 3 foram adicionados à dieta controle carbonato de cálcio e gluconato de cálcio, respectivamente, nas doses de +160 mEq/kg, resultando em três tratamentos. A urina produzida em cada período de 24 horas teve aferida seu volume, densidade e pH. No segundo experimento foi também medida a excreção urinária de cálcio no período de 72h. O equilíbrio ácido-básico foi avaliado pela hemogasometria de sangue venoso. A DLM no maior nível e o MHA diferiram da dieta controle em relação ao pH urinário (p<0,001) e seu poder acidificante foi maior que o do sulfato de cálcio (p<0,05). As duas fontes de cálcio alcalinizaram a urina, mas o carbonato de cálcio atingiu um pH urinário mais alto que o gluconato de cálcio. Concluiu-se que o efeito diferenciado das fontes de S e cálcio sobre o pH urinário é um indicador de que a participação do cálcio é dependente dos ânions a que está associado, o que leva ao questionamento sobre qual a melhor forma de avaliar sua participação no cálculo do EB. / Urolithiasis is a commom problem in the veterinary clinic considered as a cause of morbidity. The urolithiasis are closely associated with urinary pH and nutrition plays a key role in the control of this disease, because through dietary manipulation, it´s possible modify the urinary pH. The diet has cations and anions in their mineral composition and the difference between ions is measured in milliequivalents (mEq/kg) and called base excess (BE) of the diet, calculated by the equation: (49.9 x Ca) + (82, Mg x 3) + (43.5 x Na) + (25.6 x K) - (64.6 x P) - (62.4 x S) - (28.2 x Cl), being the concentration of elements in g/kg DM. The purpose of this study, divided in two experiments, was to evaluate the effect of addition of sources of sulfur (S) and calcium in the diets of cats on the urinary pH and acid-base balance. The addition of sulfur sources aimed to demonstrate the efficacy in urinary acidification. In the first experiment were evaluated three different sources of sulfur, calcium sulfate (CaSO4), DLMethionine (DLM) and Methionine hydroxy analogue (MHA) added to a control diet at two levels each. In the control treatment there was no addition of acidifying. At the first level was added 1.28 g S/kg and in the second 2.56 g S/kg, resulting in seven treatments. In the second experiment two calcium sources were evaluated in order to research the effectiveness of these salts in alkalinize urine. In the control treatment there was no addition of calcium sources. In treatments 2 and 3 were added to the control diet calcium carbonate and calcium gluconate, respectively, at doses of +160 mEq/kg, resulting in three treatments. The urine produced in each period of 24 hours had measured its volume, density and pH. The second experiment also measured the urinary excretion of calcium in the period of 72 hours. The acid-base balance was evaluated by blood gas analysis of venous blood. The DLM at the highest level and MHA differed of the control diet in relation to urinary pH (p<0.001) and their acidifying power was greater than the calcium sulfate (p<0.05). The two sources of calcium alkalinized the urine, but the calcium carbonate reached a urine pH higher than calcium gluconate. It was concluded that the effect of different sources of S and calcium on urinary pH is an indicator that the participation of calcium is dependent of the anions that is associated, which leads to questions about how is the best way to evaluate its participation in calculation of BE.

Na costa do leste do Brasil, destacam-se importantes acumulações de carbonatos lacustres do Cretáceo (Aptiano) relacionadas à fase de rift que precede a abertura do Oceano Atlântico, estes carbonatos consistem principalmente em espessos pacotes de bivalves associados a sedimentos siliciclásticos finos. Na bacia de Campos este intervalo equivale a Formação Coqueiros e é portador de hidrocarbonetos sendo reservatório nos campos de Badejo, Linguado, Pampo e Trilha. Estes reservatórios são o foco deste estudo, que teve como objetivo aprofundar o conhecimento desses depósitos através da análise das fácies e associações de fácies para definição de sequências seguindo a compreensão atual dos conceitos de estratigrafia de sequência. Foram descritos testemunhos de poços associados a análise de dados de perfil e sísmica através das quais foram definidas dezesseis fácies. A classificação das fácies utilizou critérios sedimentológicos associados a conceitos tafonômicos o que permitiu a intepretação dos processos sedimentares envolvidos em sua deposição Estas fácies foram agrupadas em associações de acordo com gradiente hidrodinâmico de uma plataforma dominada por ondas o que permitiu a interpretação dos padrões de empilhamento e definição de tratos de sistema transgressivos e regressivos. Foi proposto um ciclo ideal de alta frequência com a sucessão esperada de fácies para cada trato que serviu de base para interpretação de sequências de alta e média frequência. Esta análise permitiu a definição de três sequências internas no intervalo conhecido como Coquina Inferior, correlacionadas entre os poços que possuíam a melhor amostragem do intervalo permitindo assim analisar a variação vertical e lateral de fácies. A metodologia proposta permite a intepretação da estratigrafia em uma escala de maior detalhe auxiliando a interpretação da ocorrência de fácies e sua distribuição espacial na escala de dezenas a centenas de metros. Este tipo de análise é importante para desenvolvimento da produção de campos de hidrocarbonetos sendo útil na construção de modelos geológicos. Pode ser aplicável a ambientes análogos com similaridades quanto à composição das rochas e os processos envolvidos em sua deposição, como a Formação Itapema análoga na Bacia de Santos. / On the eastern Brazilian coast there is an important accumulation of Cretaceous lacustrine carbonates linked to the rift phase, which precedes the opening of the Atlantic Ocean. These carbonates consist mainly of bivalve packages associated with fine siliciclastic sediments. In the Campos Basin this interval is denominated Coqueiros Formation and constitutes a hydrocarbon reservoir in the fields of Badejo, Linguado, Pampo and Trilha. These reservoirs are the focus of this study, which aimed to detail the knowledge of these deposits through the analysis of facies and their associations in order to define sequences according to the present understanding of sequence stratigraphy concepts. Core samples description, well logs and seismic data analyses have been carried out, allowing the definition of sixteen facies. The facies classification was based on sedimentary characteristics associated with taphonomic concepts that allowed the interpretation of sedimentary processes involved in the deposition. These facies were grouped in associations according to a hydrodynamic gradient of a wave-dominated platform, which allowed the interpretation of stacking patterns and the definition of both transgressive and regressive system tracts It was proposed an ideal high frequency cycle with the facies succession from each tract which was used for the interpretation of high and medium frequency sequences. This analysis allowed the definition of three internal sequences in the so-called Lower Coquina Interval correlated among the best sampled wells, and the analysis of vertical and lateral variation of facies. The proposed methodology allows the interpretation of the stratigraphy in a small scale contributing to the interpretation of the occurrence of facies and their spatial distribution in a scale of tens to hundreds of meters. This type of analysis is important for the development of production in a hydrocarbon field and is useful for the construction of geological models and is applicable to similar environments with same composition of the rocks and similarities in the processes involved in their deposition, such as the Itapema Formation in the Santos Basin.

Master of Science / Geology / Matthew W. Totten / The Mississippian-aged St. Louis Limestone of Western Kansas is a carbonate resource play that has been producing oil, gas, and natural gas liquids (NGL) for over 50 years. The Mississippian Limestone is made up of heterogeneous limestones with interbedded layers of porous and non-porous units, abrupt facies changes, and diagenetic alterations. These factors combine to characterize the St. Louis Limestone's internal complexity, which complicates hydrocarbon exploration. This study focuses on improving the understanding of the geometry, distribution, and continuity of depositional facies within Kearny County, Kansas. Petrophysical analysis of a suite of geophysical logs integrated with core provided the basis for establishing facies successions, determining vertical stacking patterns within a sequence stratigraphic framework, and correlating areas of high porosity with a respective facies. The following depositional facies were identified; 1) porous ooid grainstone, 2) highly-cemented ooid grainstone, 3) quartz-carbonate grainstone, 4) peloidal grainstone, 5) micritic mudstone, and the 6) skeletal wackestone/packstone. The porous ooid grainstone is the chief reservoir facies, with log-derived porosity measurements between four and eighteen percent. In areas without available core, depositional facies were predicted and modeled using a neural network analysis tool (Kipling2.xla). Values derived from the evaluated core intervals and their respective geophysical logs served as the framework for the neural network model. This study illustrates the advantages of correlating depositional facies with reservoir quality and correlating those specific facies to geophysical logs, ultimately to create a greater understanding of the reservoir quality and potential within the St. Louis Limestone of western Kansas.