Este estudo tem como objetivo analisar os comportamentos hidráulico, mecânico e microestrutural de misturas compostas, por solo residual arenito Botucatu e bentonita sódica, com e sem adição de cimento, quando permeadas por água (H2O), soda cáustica (NaOH), na concentração de 5% e ácido sulfúrico (H2SO4) na mesma concentração para sua possível utilização em barreiras de contenção de contaminantes do tipo slurry wall. O arenito, solo areno-siltoso característico da região de São Leopoldo/ RS, compõe a matriz das misturas, sendo que a bentonita sódica confere a estas características impermeabilizantes, imprescindíveis às barreiras hidráulicas de contenção. O cimento, além de fazer com que a mistura adquira resistência, interfere na reatividade da barreira, mediante os contaminantes utilizados. A estimativa da eficiência destas misturas baseou-se na comparação entre os valores do coeficiente de condutividade hidráulica, resistência à compressão simples e parâmetros de compressibilidade determinados através dos ensaios de compressão confinada, apresentados nos ensaios com e sem contaminação, conjuntamente com a análise microestrutural das misturas nas mesmas situações. Foram feitas análises químicas por Difração de Raios-x, Microscopia Eletrônica de Varredura (SEM) e Análise Química Elementar (EDS) visando à explicação ordinária das causas microestruturais que levam as misturas a determinado comportamento sob percolação de contaminantes. Na busca do efeito de cada componente sobre o comportamento final de determinada mistura, houve a necessidade de realizar análises químicas e microscópicas individuais, também sob interferência ou não de substâncias agressivas. A partir deste estudo foi possível inferir que a mistura solo-cimentobentonita, é adequada à utilização como barreira vertical quando o contaminante for ácido sulfúrico, por no mínimo 20 semanas, já que a eficiência da mesma foi comprovada pela realização de ensaios no permeâmetro de parede rígida, considerado adequado para este tipo. O uso da mistura solo bentonita para barreiras verticais pode ser emergencial visto que quando o contaminante for soda cáustica a mistura resiste por 4 dias. / The objective of this study is to analyze the hydraulic, mechanical and micro-structural conduct of composite mixtures of Botucatu residual soil and sodic bentonite, with and without cement addition, when permeated by water (H2O), caustic soda (NaOH) in a concentration of 5% and sulfuric acid in the same concentration to their possible utilization in contention of contaminant barriers of the slurry walls type. The sandy soil constitutes part of the matrix of the mixtures. The sodic bentonite confers to these mixture essential waterproof characteristics of hydraulic barriers of containment. The cement interferes on the barrier reactivity moreover add resistance to the mixture by the contaminants that were utilized. The efficiency estimation of these mixtures was established by comparison between hydraulic conductive coefficient, unconfined compression strength and one dimensional compressibility presented on the tests with or without contamination, with the mixture micro-structural and chemical analysis on the same situations: X-ray diffraction, scanning electronic microscopy, Elemental Chemical Analysis (EDS), they want to explain the micro-structural causes that make the mixtures to determinate behavior by percolating of contaminants. Searching the effect of all components about the final behavior of determined mixture there was the necessity to carry out chemical and microscopically individual analysis also by aggressive or non-aggressive substances interference. After completed the study, it is possible to affirm that the soil-cement-bentonite mixture, is good for using as a vertical barrier when the contaminant is sulfuric acid, based on the results of rigid wall permeameter, adequate for this kind of mixture. The use of soilbentonite mixture as vertical barrier for caustic soda could be done just in emergency cases and for a short period of time, once that after some time the barrier reduces drastically its efficiency.

A presença de tonsteins e bentonitas dentro da Supersequência Gondwana I no setor sul da Bacia do Paraná não são incomuns e suas ocorrências estão documentadas, especialmente nas unidades Rio Bonito e Rio do Rasto. Embora fosse esperada a identificação de bentonita na Formação Irati devido ao seu posicionamento estratigráfico dentro do Permiano e por estar vinculada a um ambiente que preenche os requisitos para acumular e preservar os eventos de deposição de cinza vulcânica, não são conhecidos trabalhos sistemáticos voltados para a identificação da bentonita na Formação Irati do Rio Grande do Sul. A presença de níveis de bentonita na Formação Irati foi demonstrada a partir de trabalhos realizados no setor norte da Bacia do Paraná. Este artigo tem como objetivo identificar e apresentar argumentos mineralógicos e químicos que demonstram a existência de níveis de bentonitas inseridos na Formação Irati em afloramentos desta unidade situados a leste da cidade de Aceguá, sul do Rio Grande do Sul. Tratam-se de níveis com pequena espessura (em média 4 cm) e grande extensão lateral constituídos de argilitos maciços, com cores branco acinzentadas que em campo contrastam com os folhelhos que compõem a Formação Irati. Para o reconhecimento da bentonita, a técnica empregada na preparação das amostras viabilizou a realização de um estudo detalhado do comportamento mineralógico a partir da divisão das amostras numa fração fina (menor que 2μm) e numa fração maior que 0,025mm. As bentonitas do Irati se caracterizam por serem rochas bimodais compostas predominantemente por Camontmorilonita que formam a matriz fina da rocha onde estão dispersos cristais primários ou magmáticos com tamanho não superior a areia muito fina. Uma característica comum destes cristais e que atestam a origem vulcânica é o hábito idiomórfico, sem indícios de alteração ou de terem sido submetidos a processos de transporte sedimentar, em discordância ao que é observado com os minerais formadores da rocha encaixante representada pelo folhelho Irati. Entre os principais minerais primários identificados e representativos do ambiente vulcânico encontramse paramorfos de quartzo beta, feldspatos tipo sanidina, biotita, zircão, apatita e ilmenita. Baseando-se na geoquímica da rocha e na cristaloquímica da montmorilonita neoformada nos níveis de bentonita infere-se sobre a natureza do vulcanismo precursor. Ambas as metodologias apontam que neste período as cinzas vulcânicas que alcançaram a Bacia do Paraná foram oriundas de um vulcanismo com composição intermediária (andesítica) em concordância ao que é conhecido sobre as manifestações da Província Vulcânica Choiyoi Inferior, sincrônica com a sedimentação da Formação Irati na Bacia do Paraná. A comprovação obtida de que os níveis de argilitos identificados na seção estudada são bentonitas abre a perspectiva de novos estudos em outros campos da geologia, como a calibração da seção estratigráfica e de biozonas através de técnicas de datação absoluta com o uso de minerais, em especial os zircões. Os múltiplos níveis de bentonita identificados ao longo da seção também viabilizam estudos de avaliação do estilo e da história explosiva do vulcanismo, bem como permitirão melhorar as correlações entre diferentes exposições da formação Irati ao longo da Bacia do Paraná. / The presence of tonsteins and bentonite within Supersequence I in the southern sector of the Paraná Basin are not uncommon, and their occurrences have been documented, especially in the Rio Bonito and Rio do Rasto units. Although the identification of bentonite in the Irati Formation was expected, due to its stratigraphic position within the Permian and because it is linked to an environment that meets the requirements to accumulate and preserve volcanic ash deposition events, systematic studies aimed at identifying bentonite in the Irati Formation in Rio Grande do Sul are not known. The presence of bentonite levels in the Irati Formation was demonstrated from studies carried out in the northern sector of the Paraná Basin. This article aims to identify and present mineralogical and chemical arguments about the existence of bentonite levels included in the Irati Formation in outcrops of this unit located east of the city of Aceguá, southern Rio Grande do Sul. They are thin levels (on average 4 cm in thickness) and large lateral extension made up of massive claystones, of grayish white colors, which on the field stand out from the shales that compose the Irati Formation. In order to recognize the bentonite, the technique used in preparing the samples made it possible to conduct a detailed study of the mineralogical behavior based on the division of the samples into a fine fraction (less than 2 μm) and a fraction above 0.025 mm. The Irati bentonites are characterized by being bimodal rocks composed predominantly of Ca-montmorillonite which form the fine matrix of the rock where primary or magmatic crystals are dispersed, not larger than very fine sand. A common feature of these crystals that attest to the volcanic origin is the idiomorphic habit, with no signs of alteration or of having undergone sediment transport processes, unlike what is observed with the minerals forming the host rocks represented by the Irati shale. Among the main primary minerals identified and representative of the volcanic environment are the beta-quartz paramorphs, sanidine feldspars, biotite, zircon, apatite and ilmenite. Based on the rock geochemistry and the crystal chemistry of the neoformed montmorillonite in the bentonite levels, the nature of the precursor volcanism is inferred. Both methodologies indicate that in this period the volcanic ashes that reached the Paraná Basin were derived from volcanism of intermediate composition (andesitic) in agreement with what is known about the manifestations of the Lower Choiyoi Volcanic Province, synchronous with the sedimentation of the Irati Formation in the Paraná Basin. The obtained evidence that the claystones identified in the studied section are bentonites unfolds the perspective of new studies in other geology fields, such as the calibration of the stratigraphic section and biozones through absolute dating techniques with the use of minerals, especially zircons. The multiple levels of bentonite identified throughout the section also enable assessment studies of the explosive style and history of the volcanism, and will also improve the correlations between different exposures of the Irati Formation along the Paraná Basin.

O presente trabalho investigou o comportamento mecânico e hidráulico de novos materiais geotécnicos compósitos para a utilização em barreiras verticais do tipo Slurry Walls. Fundamentalmente, o objetivo do programa experimental foi analisar o comportamento tensão-deformação e a influência da poro-pressão, através de ensaios triaxiais e ensaios de compressão não-confinada em misturas solo-cimento-bentonita (SCB) e solo-cimentobentonita- fibra (SCBF) e também a condutividade hidráulica em misturas solo-bentonita-fibra (SBF) e solo-cimento-bentonita-fibra. As misturas testadas nos ensaios triaxiais, cisalhadas na condição não-drenada (CIU) com tensões efetivas entre 50 e 470 kPa, foram rompidas após um período de 7 dias de cura. Nestes ensaios, foram medidas as condutividades hidráulicas antes e após o cisalhamento dos corpos de prova, a fim de comparar e identificar o comportamento da condutividade quando as barreiras verticais são solicitadas.A condutividade hidráulica avaliada em permeâmetro de parede rígida para as misturas SBF e SCBF foram comparadas com resultados de misturas SB e SCB obtidos na literatura. Os resultados dos ensaios realizados indicaram uma mudança dos padrões de comportamento dos materiais compósitos em relação à situação sem reforço, como o aumento dos parâmetros de resistência ao cisalhamento e a diminuição das deformações volumétricas sob carregamento isotrópico. Os ensaios de condutividade hidráulica confirmaram que o comportamento do material não foi afetado pela adição das fibras. Já os ensaios de condutividade hidráulica realizados no equipamento triaxial demonstraram que a condutividade hidráulica aumenta após o cisalhamento do corpo de prova. / The present work aimed the investigation of the mechanical and hydraulic behavior of new geotechnical composite materials for use in vertical barrier walls (Slurry Walls). Fundamentally, the objective of the experimental program was to analyze the stress-strain behavior as well as the pore-pressure influence by means of triaxial tests, unconfined compression tests on mixtures of soil-cement-bentonite (SCB) and soil-cement-bentonitefiber (SCBF), and hydraulic conductivity tests on soil-bentonite-fiber (SBF) and soil-cementbentonite- fiber mixtures. The speciments formatted by the different mixtures were tested in the triaxial equipment, and sheared under consolidated isotropically undrained conditions (CIU) and efective stresses ranging from 50 to 470 kPa, after 7 days of curing. In these tests, the hydraulic conductivities were measured previously and after shearing the samples, in order to compare and identify the conductivity behavior at the moment in which the vertical barriers are requested. The hydraulic conductivity coefficients of SBF and SCBF mixtures obtained from rigid wall permeameter tests were compared with results existent in the literature for SB and SCB mixtures. The results indicated changes of the behavior standards for composite materials if compared with the unreinforced situation, such as increases of shear strength parameters and decreases of volumetric deformations under isotropic loading. The results of hydraulic conductivity tests confirmed that the behavior of the material is not affected by the addition of fibers. The results of hydraulic conductivity tests conducted in the triaxial equipment showed increases of the hydraulic conductivity coefficient after the shearing of the samples.

Orientador: Ana Rita Morales / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-14T07:32:02Z (GMT). No. of bitstreams: 1 Paiva_LucileneBetegade_D.pdf: 25147063 bytes, checksum: a98b5c9f475d3fb0e39af5793bb3acee (MD5) Previous issue date: 2009 / Resumo: Sete bentonitas foram avaliadas quanto ao potencial na obtenção de formas organofílicas, através da caracterização por difração de raios-X para avaliar os espaçamentos basais, pelo teste de inchamento, em água e em xileno, para avaliar o caráter a hidrofílico e organofóbico, por energia dispersiva de raios-X para identificar os elementos presentes, e da capacidade de troca de cátions pelo método de adsorção do azul de metileno. Somente uma não apresentou potencial para organofilização e foi descartada. As bentonitas que apresentaram potencial para serem organofilizadas, foram tratadas com um sal quaternário de amônio por troca de cátions em dispersão aquosa, metodologia convencionalmente usada, e intercalação em meio semi-sólido, como metodologia alternativa. Posteriormente, as bentonitas foram caracterizadas por difração de raios-X, para avaliar intercalação dos cátions orgânicos, pelo teste de inchamento, em água e em xileno, para avaliar o caráter organofílico e hidrofóbico adquirido, por energia dispersiva de raios-X para identificação dos elementos presentes. Adicionalmente, ambas bentonitas sódicas e organofilizadas, foram caracterizadas por análise termogravimétrica para avaliar a estabilidade térmica e o teor de cátions orgânicos incorporado, por microscopia eletrônica de varredura para avaliar a morfologia das partículas e por medida da área específica baseada na adsorção de nitrogênio. Todas as bentonitas adquiriram caráter organofílico. Foram preparados nanocompósitos com polipropileno e as bentonitas organofílicas obtidas. Após o processamento, foi feita uma caracterização por difração de raios-X e por microscopia eletrônica de transmissão para avaliar a dispersão das bentonitas organofílicas na matriz polimérica e o tipo de estrutura formada. Foram obtidos nanocompósitos com estruturas esfoliadas, parcialmente esfoliadas e intercaladas, e intercaladas. O estudo mostra uma grande potencialidade das bentonitas em estudo na obtenção de bentonitas organofílicas para nanocompósitos poliméricos, bem como a eficiência da metodologia de organofilização em meio semi-sólido. / Abstract: Seven bentonites were evaluated to verify the potential to obtain the organophilic clay. The characterization by X-ray diffraction to evaluate the basal spacings was made, as well as the characterization by swelling capacity test, in water and in xylene, to evaluate the hydrophilic and organophobic character, by X-ray dispersive energy to indentify the present elements, and by cations exchange capacity using the method of blue methylene adsorption. Only one bentonite didn't show potential to be organophilized and was rejected. The bentonites that showed potential to be organophilized, were treated with a quaternary ammonium salt by cation exchange in aqueous dispersion, the conventional methodology used, and by intercalation in semi-solid medium, as an alternative methodology. Subsequently, they were characterized by X-ray diffraction, to evaluate the intercalation of the organic cations, by the swelling capacity test, in water and in xylene, to evaluate the organophilic and hidrophobic acquired, by X-ray dispersive energy to identify the present elements. Furthermore, both sodium and organophilized bentonites were characterized by thermogravimetric analysis to evaluate the thermal stability and the tenor of organic cations incorporated, by scanning electronic microscopy to evaluate the morphology of the particles, and by measurement of specific area based on the adsorption of nitrogen. All bentonites acquired organophilic character. Nanocomposites with polypropylene as matrix and the organophilic bentonites obtained were prepared. After the processing, a characterization by X-ray diffraction and by transmission electronic microscopy to evaluate the dispersion of the organophilic bentonites in the polymeric matrix and the type of structure formed were made. Nanocomposites with exfoliated, or partially exfoliated and intercalated, and intercalated structures were obtained. The study shows a large potential of the bentonites in study in obtaining organophilic bentonites for polymeric nanocomposites, as well as the efficiency of the methodology of organophilization in semi-solid medium. / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Orientadores: Meuris Gurgel Carlos da Silva, Ronia Marques Oisiovici / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-08T06:52:13Z (GMT). No. of bitstreams: 1 Melo_Cristiane_M.pdf: 1461718 bytes, checksum: a4ff5e71772cb30781695b61478427af (MD5) Previous issue date: 2007 / Resumo: A indústria têxtil possui um dos processos de maior geração de efluentes líquidos, contribuindo quantitativa e qualitativamente com a carga poluidora descartada em corpos hídricos. Em particular, seus efluentes coloridos geram grandes danos ambientais, impedindo a luz solar de chegar até o ecossistema aquático, prejudicando o desenvolvimento da biota e a qualidade da água para consumo. Dentre os tratamentos existentes para a eliminação de cor de efluentes, a aplicação da adsorção em materiais residuais de outros processos e de baixo custo tem se mostrado uma opção eficiente e viável. Neste trabalho foi estudada a remoção de cor de um efluente sintético, constituído pelo corante Solophenyl azul marinho BLE 250%, utilizando a técnica de adsorção em argila calcinada proveniente de Pernambuco. Inicialmente foram realizados ensaios preliminares em banho finito para verificar a melhor temperatura de calcinação da argila em relação à remoção de cor e para determinar os parâmetros cinéticos e de equilíbrio. Após, foram realizados ensaios em coluna, empregando argila calcinada a 300°C e as cinéticas de remoção de cor foram avaliadas por meio de um planejamento fatorial 23 com ponto central. Os fatores estudados foram: concentração inicial de corante, diâmetro médio de partícula e vazão volumétrica, tendo como resposta a quantidade removida Qt (mg corante/g argila). A melhor condição de remoção foi obtida para o nível superior de concentração e níveis inferiores de diâmetro e vazão, correspondendo a um maior tempo de contato entre solução e adsorvente, atingindo o valor de 6,28 mg/g. Ensaios empregando carvão ativado e zeólita clinoptilolita nas melhores condições obtidas no planejamento com argila foram feitos com a finalidade de comparar as cinéticas de remoção dos três adsorventes. Estes adsorventes foram menos adequados que a argila para a remoção do corante estudado. Os resultados obtidos mostraram que a melhor eficiência do processo de adsorção nas condições investigadas ocorreu quando aplicada a argila bentonita calcinada a 300°C, que apresentou capacidade de remoção satisfatória, além de ter vantagens no seu custo por se constituir em resíduo gerado em grande abundância na mineração da gipsita / Abstract: Textile industry processes have one of the greatest wastewater productions, increasing quantitatively and qualitatively polluting load discharge in surface water. Colored water result of their process generate great environment damages once they not only reduce the water quality but also block sun light from penetrating in the aquatic ecosystem harming biota development. Within existing treatments for wastewater color elimination, adsorption with low cost residual materiais is an efficient and feasible option. Color removal from synthetic wastewater composed by Solophenyl Navy BLE 250% direct dye was studied using adsorption in calcined bentonite clay from Pernambuco. Preliminary tests were carried out in finite bath seeking best clay calcination temperature as well as to evaluate kinetic and equilibrium parameters. Then, tests in a porous bed were carried out using the clay that had greater affinity with the pigment which was the calcinedat 300°C. Color removal kineticswas evaluated using a factorial design 23 with central points. The studied factors were initial concentration, average grain size and uptake flow rate. The response variable evaluated was uptake capacity Qt (mg dye/g clay). Best removal was obtained with higher concentration, lower diameter and lower flow rate, which correspond to greater contact time between solution and the adsorbent reaching 6,28 mg dye/g clay uptake. Tests using activated carbon and clinoptilolite zeolite in the best conditions reached with the factorial plan with bentonite were done to compare removal kinetic of the three adsorbents. These adsorbents were less efficient than bentonite for the removal of the studied dye. Therefore, the results proved efficiency on bentonite's clay adsorption process and the bentonite calcined at 300°C was pointed out as a potential adsorbent for dye removal with cost advantages due to its mineral waste characteristic in gypsum extraction / Mestrado / Engenharia de Processos / Mestre em Engenharia Química

Made available in DSpace on 2016-08-19T12:56:35Z (GMT). No. of bitstreams: 1 SINARA DE FATIMA FREIRE DOS SANTOS.pdf: 5017143 bytes, checksum: 47814d067ba298cd245c1c37cd698b95 (MD5) Previous issue date: 2010-10-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The present work has the objective to purify the babassu and soy biodiesel using as adsorbent bentonite clay and talc, under monitoring by measurements of dielectric constant, index of acidity and humidity test. Initially, it was determined the quality of babassu oil and soy through physic-chemical, then was synthesized methylic and ethylic biodiesel. The talc and bentonite adsorbents were characterized for their surface area, pore diameter, MEV, XRD and FTIR. During the purification of biodiesel was used some percentages of adsorbent (0.5, 1, 2, 3 and 4% for 50 g of biodiesel) and adsorption times of 20, 30, 60, 90 and 120 min, under constant agitation and ambient temperature, the results were compared with the process of washing with acidified water, by monitoring with measurements of dielectric constant, acidity index and humidity test. The evaluation of the purification of biodiesel by dry washing, monitored by dielectric constants, got better answers than the process of washing with acidified water, with lower values of dielectric constant around 4.0% of adsorbent and 120 min of adsorption time .In relation to the index of acidity and the humidity test, samples of purified biodiesel with the adsorbent are in accordance with the specifications of the National Agency of Petroleum, Natural Gas and Biofuels (ANP). Therefore, it is considered that the methodology for dry washing, as well as monitoring by dielectric constant, is feasible as a method of purification and monitoring, respectively, using as references the results of conventional purification process. / O presente trabalho tem o objetivo de otimizar as condições do processo de purificação a seco de biodiesel, utilizando como adsorvente a bentonita e o talco, sob monitoramento por medidas de constante dielétrica, índice de acidez e teor de umidade. Inicialmente, foi determinada a qualidade dos óleos de babaçu e soja através de testes físico-químicos, em seguida foi sintetizado o biodiesel metílico e etílico. Os adsorventes foram caracterizados por adsorção de nitrogênio, microscopia eletrônica de varredura, difração de raios-X e infravermelho. Durante a purificação do biodiesel utilizou-se várias percentagens de adsorventes (0,5, 1, 2, 3 e 4% por 50 g de biodiesel) e tempos de adsorção de 20, 30, 60, 90 e 120 min, sob agitação constante e temperatura ambiente, os resultados foram comparados com o processo de lavagem com água acidificada, através do monitoramento com medidas de constante dielétrica, índice de acidez e teor de umidade. A avaliação da purificação do biodiesel por lavagem a seco, monitorada por constantes dielétricas, obteve respostas melhores que o processo de lavagem com água acidificada, com menores valores de constante dielétrica em torno de 4,0 % de adsorvente e 120 min de tempo de adsorção. Em relação ao índice de acidez e o teor de umidade, as amostras de biodiesel purificadas com os adsorventes, estão de acordo com as especificações da Agência Nacional do Petróleo, Gás Natural e Biocombustíveis (ANP). Portanto, considera-se que a metodologia por lavagem a seco, bem como, o monitoramento por constante dielétrica, é viável como método de purificação e monitoramento, respectivamente, usando como referências os resultados obtidos do processo de purificação convencional.

A utilização de solo natural misturado com bentonita empregado em camadas impermeáveis para retenção de contaminante é bastante comum em aterros sanitários. Neste trabalho, serão apresentados os resultados de ensaios com misturas de solo-bentonita nos teores de 3%, 5% e 7%, utilizando-se um solo arenoso proveniente da região de Pindorama (SP). Os ensaios de condutividade hidráulica para o solo-bentonita foram realizados em permeâmetros de parede flexível. Os resultados obtidos indicam que para os teores de 5% e 7% de bentonita a condutividade hidráulica apresenta-se com valores adequados para a construção de barreiras impermeáveis. A resistência ao cisalhamento do solo compactado puro e das misturas compactadas foi avaliada através de ensaios triaxiais do tipo consolidado não drenado (CU) e ensaios de compressão simples. A coesão efetiva e o ângulo de atrito efetivo do solo aumentou e diminuiu, respectivamente, com a adição de bentonita. Os ensaios de resistência à compressão simples para as misturas com 5% de bentonita atingiram valores aceitáveis para o emprego em camadas impermeabilizantes. / It is becoming very common the use of soil-bentonite mixtures for building sanitary landfill liners with the purpose of retaining pollutants. This work shows the results of hydraulic conductivity and shear strength tests performed with soil-bentonite mixtures with 3%, 5% and 7% bentonite content. The natural soil was gathered in the Pindorama area, which is located in the northeast of Sao Paulo state. The hydraulic conductivity tests were performed in a flexible wall permeameter. Test results show that mixtures with 5% and 7% bentonite content are suitable, in terms of hydraulic conductivity, for construction of sanitary landfill liners. The shear strength parameters of natural soil and mixtures have been assessed performing undrained triaxial compression tests and unconfined compression tests. The effective cohesion and the effective friction angle increased and decreased with the increase of the bentonite content, respectively. The unconfined compression test results have shown that mixtures with 5% bentonite content are suitable, in terms of shear strength, for construction of sanitary landfill liners.

Orientador: Rosângela Barros Zanoni Lopes Moreno / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T08:17:10Z (GMT). No. of bitstreams: 1 Lopes_LeandroFreitas_M.pdf: 2721752 bytes, checksum: 3eff0862fda0329e774f1b5e9dbeaf25 (MD5) Previous issue date: 2012 / Resumo: A perfuração de poços de petróleo pode danificar fortemente a formação, incluindo a região de interesse: o reservatório. Perfurar sem que se danifique o reservatório caracteriza-se como um grande desafio, e por isso, tem sido estimulado o desenvolvimento de tecnologias de fluidos e otimização de processos de perfuração, incluindo, por exemplo, o projeto de fluidos com vistas à minimização de dano. Tem sido relatado que, um planejamento detalhado desde o projeto do fluido pode ajudar a minimizar o dano de formação e contribuir para uma melhor restauração da produtividade do poço. Este trabalho é focado na análise do dano de formação causado pela invasão de fluidos de perfuração de base água em reservatórios de petróleo areníticos. Os fluidos foram preparados com os seguintes componentes: sal, polímero e argila. O sal utilizado foi o iodeto de sódio (NaI) na concentração de 150000 ppm; o polímero foi, ora a poliacrilamida parcialmente hidrolisada (PHPA), ora a Goma Xantana (GX), e a argila utilizada foi a bentonita. Para simular o reservatório foram utilizadas amostras pequenas de arenito Botucatu de alta permeabilidade. As amostras, inicialmente 100% saturadas com óleo mineral (~ 24 cp @23º C), foram submetidas a um processo de invasão, simulando-se uma perfuração sobrebalanceada, e a um fluxo reverso de óleo, simulando-se o início de produção de petróleo, aplicando-se para ambos um diferencial de pressão manométrica de 20 psi (~ 138 kPa). A concentração de polímero foi de 3,5 lb/bbl (10 g/l ou 10000 ppm) quando preparados com PHPA, e de 3,0 lb/bbl (8,6 g/l ou 8600 ppm) quando preparados com GX. A concentração de bentonita variou de 2,5%, 2,0%, 1,5% e 0,0% em massa para ambos os polímeros, resultando em um total de oito fluidos preparados. Foram avaliadas a redução da permeabilidade e da razão de produtividade das amostras durante a invasão dos fluidos, bem como o retorno destas quando aplicado um fluxo reverso de óleo. Os resultados obtidos mostraram que os fluidos que continham argila resultaram em uma menor invasão ou perda de fluido para a formação do que os fluidos que continham somente polímero. Além disso, a concentração de argila influenciou nos resultados obtidos de redução de permeabilidade e do retorno da razão de produtividade. Quanto maior a concentração de argila, menor a invasão de filtrado, porém, o retorno da razão de produtividade também foi menor, evidenciando o potencial de dano da mesma. Os fluidos preparados com PHPA, quando injetados, resultaram em uma maior invasão de filtrado do que os fluidos preparados com GX, porém o retorno da razão de produtividade também foi maior, mostrando que estes fluidos, apesar de invadirem mais, danificaram menos as amostras. Os fluidos preparados com GX tamponaram as gargantas de poro mais rapidamente, e em alguns casos, por completo. O fato de tamponar ou não os poros das amostras teve influência no retorno da razão de produtividade, sendo observado maior retorno nas amostras não tamponadas em relação àquelas tamponadas por completo. Os resultados apresentados aqui podem contribuir para a tecnologia de fluidos de perfuração e avaliação do projeto do fluido, com vistas à minimização de dano à formação e manutenção da produtividade do reservatório o mais próximo da original / Abstract: Oil well drilling can strongly damage the formation, including the interest region: the reservoir. Drilling without damaging the reservoir is characterized as a hard challenge, and therefore, the development of technologies and optimization process has been stimulated, including, for example, the fluid design in order to minimize damage. It has been reported that a detailed fluid management plan addressing fluid design can help to minimize formation damage and contribute to a better well productivity restoration. This work is focused on formation damage analysis caused by water-based drilling fluids invasion in sandstone oil reservoirs. Fluids were prepared including the following components: salt, polymer and clay. It was used a 150,000 ppm concentration of sodium iodide (NaI) as salt, either a partially hydrolyzed polyacrylamide (HPAM) or a xanthan gum (XG) as polymer, and bentonite as clay. To simulate the reservoir, small samples of high permeability Botucatu sandstone were used. The samples, 100% initially saturated with mineral oil (~ 24 cp @ 23 ° C), were submitted to an invasion process, simulating an overbalanced drilling, and to an oil reverse flow, simulating the oil production beginning, applying to both a 20 psi (~ 138 kPa) gauge pressure difference. The polymer concentration was 3.5 lb/bbl (10 g/l or 10,000 ppm) when prepared with HPAM, and 3.0 lb/bbl (8.6 g/l or 8,600 ppm) when prepared with XG. The bentonite concentration ranged from 2.5%, 2.0%, 1.5% and 0.0% weight for both polymers, resulting in eight tested fluids. During fluids invasion, the permeability impairment and productivity ratio of the samples were evaluated, as well as their return when applied to an oil reverse flow. Obtained results pointed that fluids containing clay resulted in a lower fluid loss to the formation than fluids containing only polymer. Moreover, clay concentration influenced on permeability impairment and on obtained results for the productivity ratio return. The higher is clay concentration, the less is fluid invasion, however, productivity ratio return was also lower, highlighting the clay damage potential. HPAM fluids, when injected, resulted in a higher fluid invasion than XG fluids, but productivity ratio return was also higher, pointing that HPAM fluids, even though had invaded more, the damage was lower. XG fluids blocked pore throats faster and, in some cases, completely. The blocking effect on samples pores influenced on productivity ratio return, i. e., higher return was obtained for samples that weren't blocked. Results presented here may contribute to drilling fluids technology, fluid design evaluation and formation damage minimization aiming to keep the reservoir productivity closer to the original / Mestrado / Reservatórios e Gestão / Mestre em Ciências e Engenharia de Petróleo

The use of lime for soil stabilization has greatly increased since the second half of the 20th century. A lot of research has been conducted to understand the mechanisms of stabilization. These mechanisms are caused by pozzolanic reactions between lime and clay minerals. However, it has not yet been possible to quantify the factors affecting the evolution of these reactions. The variety of soils and the disruptive elements do not allow comparing these soils with each other and giving any quantitative and generalized conclusions in terms of mechanical improvement. The goal of this study is to build a progressive understanding of this phenomenon by avoiding any disruptive elements and controlling most of the parameters. Consequently, the choice is made to study a synthetic soil by controlling its particle size distribution and composition. This soil is a mixture of sand and bentonite taken at different compositions. An analysis of the evolution of lime treatment on such model soils is carried out on two scales: the macroscopic scale and the microscopic scale. The macroscopic scale studies the evolution through unconfined compressive strength, lime consumption, electrical resistivity as well as complementary studies such as sonic and triaxial tests. Results from macroscopic tests show that sand takes an important part into soil stabilization, meaning that a soil containing a lot of clay does not necessary give the best long term mechanical characteristics. Tests that allow a much more detailed comprehension of stabilization are also presented. Microscopic evolution is studied through X-Ray Computed Tomography and Mercury Intrusion Porosimetry. A study on tomographic image treatment has also been carried out to segment the images from its different constituents. / L'utilisation de la chaux pour stabiliser le sol s'est considérablement déve-lop-pée depuis la seconde moitié du 20e siècle. De nombreuses recherches ont vu le jour pour comprendre les mécanis-mes de cette stabilisation. Ces mé-ca-nis-mes sont causés par les réactions pouzzolaniques entre la chaux et les minéraux argileux. Cependant, il n'a pas encore été possible de quantifier totalement les facteurs influençant le déroulement de ces réactions. La diversité des sols et la présence d'éléments perturbateurs ne permettent pas de les comparer et d'en tirer des conclusions quantitatives et généralisables en termes d'amélioration des paramètres mécaniques. Cette étude envisage donc de construire une compréhension progressive du phénomène en ne prenant pas en compte les éléments perturbateurs et en contrôlant à priori un maximum de paramètres. Pour ce faire, il est proposé d'étudier un sol synthétique dont la granulométrie et la composition peuvent être contrôlées. Ce sol est un mélange de sable et de bentonite pris à différentes compositions. Une analyse sur l'évolution du traitement à la chaux est alors effectuée sur ces mélanges sur deux échelles :l'échelle macroscopique et l'échelle microscopique. L'échelle macroscopique envisage des essais de compression simple, de consommation de chaux, de résistivité électrique ainsi que des essais complémentaires tels que les essais soniques et triaxiaux. Les résultats macroscopiques montrent que le sable joue un rôle important dans la stabilisation, le sol présentant la fraction argileuse la plus importante n'ayant pas les meilleures caractéristiques mécaniques à long terme. Les tests permettant une compréhension plus fine de cette stabilisation sont également présentés. L'échelle microscopique est étudiée via la tomographie aux rayons-X et la porosimétrie au mercure. Une étude sur le traitement des images tomographiques est aussi mise en oeuvre pour segmenter de manière adéquate les images de ses différents constituants. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

Clays are used for long for the control of soil and water pollution as they are inexpensive natural materials with a high adsorption capacity for a wide range of pollutants. However their use as components in engineered waste containment systems is often limited when it comes to the control of organic contaminants as the clays are organophobic in nature. Organic modification of the natural clays, by replacing the exchangeable inorganic cations of clay with organic cations, can facilitate to overcome this limitation. On modification the clays become organophilic which can enhance their sorption capacities for organic contaminants. There are several ways by which natural clays can be modified with organic cations. The type of clay, the type of modifier, and the extent of modification play an important role in enhancing the organic sorption capacity. Sorption of organics by the organo clays depends on a large extent on the specific interactions that occur between modified clay and the organic contaminants. The interaction between the clay and the contaminants depend on the physico-chemical properties of modified clay and nature of organic contaminants. Since the properties of natural clays are likely to be altered by the modification a detailed study has been taken up to understand the physico chemical characteristics of organo clays which essentially control their organic sorption efficiency. Apart from bentonite which is widely used as a component of barrier systems, the characteristics of other types of clays on organic modification also needs to be assessed as they can also form part of the containment system frequently. Further the modification of clays is bound to bring in significant changes on their geotechnical properties which may affect their performance when used as barrier material. Only limited research has been conducted in the past on the geotechnical characteristics of organo clay. Therefore extensive studies have been carried out on the evaluation of the geotechnical characteristics of organo clays and the effect of organic modification on important geotechnical properties. Since very often inorganic and organic contaminants can occur simultaneously, admixtures of bentonite and organically modified clays needs to be employed as a part of clay barrier system. Moreover clay alone is very rarely used as component of barrier systems and significant portion of barrier material usually include non clay fraction. Hence studies have been carried out on mixtures containing different proportions of organo clay and bentonite and sand – organo clay / bentonite to evaluate their geotechnical behavior. Important geotechnical properties considered for detailed studies are swelling, compressibility and permeability. Detailed studies on the organic sorption capacities of different organically modified and unmodified clays, mixtures of bentonite and organo clays have also been conducted. The results of studies conducted are presented in 9 chapters. The organization of the thesis is as follows: Chapter 1 gives detailed background information on the sources and hazards of organic contaminants, inadequacy of conventional barriers to contain organic contaminants, the need for modification of natural clays, and the methods for organic modification of clays. Extensive review of literature has highlighted the need to study the effect of organic modification on the physico chemical and geotechnical properties of clay in different pore fluids. Organo clays were prepared using a wide range of clays viz., two types of bentonites of different regions, black cotton clay and commercially available kaolinite with a long chain organic cation. The extent of organic modification was varied by varying the amount of organic cation exchanged as function of total cation exchange capacity of the clays. Detailed physico chemical characterization of these modified and unmodified clays has been carried out with the help of different state of art techniques. The Chapter 2 brings out the effect of modification, role of type of clay and type of modifiers on the characteristics of organo clays by comparing the physico chemical characteristics of different modified and unmodified clays. The organic modification of montmorillonitc clays with long chain organic cation is found to increase their lattice spacing with the amount of modification whereas no such increase was observed on modification of kaolinitic clays even when all the exchangeable inorganic cations were replaced with the organic cations. The XRD studies revealed that the intercalated organic cations of the modified montmorillonite clays assumed mono, bi, or pseudo tri layer depending on the extent of organic modification. Irrespective of the type of clay modified or the modifier used all the organo clays tend to become e hydrophobic, and the surface area of the clays was found to decrease. A comparison of the characteristics of clays modified in laboratory with organo clay obtained commercially revealed that the organic modification was more effective for the organo clay prepared in the laboratory. As the index properties of all clays are generally correlated with their geotechnical characteristics, the effect of organic modification on the index properties of clays was studied. Chapter 3 presents the effect of organic modification on the plasticity and free swell behavior of clays. The index properties of commercially available organo clay and the unmodified clay used for its preparation were evaluated with pore fluids of different dielectric constants. Fluids of varied dielectric constants were chosen as it is one of the important characteristics to understand the behavior of clays. It was observed that the organic modification of clays reduced the plasticity of the clays in water and increased the plasticity in less polar liquids like ethanol. As the organo clays are more hydrophobic, the water holding capacity and plasticity in water is decreased to a large extent. The free swell behavior of clays in different pore fluids were assessed in terms of the modified free swell index. It was found that trend of variation of free swell index with dielectric constant for modified and unmodified clays, as in the case of plasticity is quite opposite. The swell volume of the modified clays was observed to be controlled more by surface solvation than by the development of the inter particle repulsive forces and diffused double layer. The effect of incorporating unmodified bentonite with organically modified clay on the index properties of bentonite has also been studied. The results suggested that the effect of organo clay addition to bentonite was always to reduce its plasticity and free swell in water. However in pore fluids of lower dielectric an increase in the plasticity and free swell was observed with increasing organo clay content in the mixture. This owes to the fact that organo clays can interact strongly with organic fluids, changing its fabric arrangement. As reported from literature it is well established that the swell of clays has conflicting role on the stability and permeability of clay barriers. Swelling of clays is liable to cause a reduction in hydraulic conductivity, enhance the retention times of contaminants and attribute self healing capacity to the liners. Even though extensive studies have been carried out on the swell behaviour and mechanism of swell of unmodified clays, no systematic research is reported on the effect of organic modification on swell behavior of clays especially in the presence of different pore fluids. Chapter 4 describes the results of oedometer swell tests carried out on compacted samples of modified, unmodified clays and organo clay –bentonite mixture in the presence of different pore fluids such as water, ethanol, and their mixture and carbon tetra chloride. Swelling ability of the unmodified clays was not completely suppressed even in the presence of low polar miscible organic liquids as they were molded at water contents corresponding to the optimum moisture content (OMC). The order of the swelling for the unmodified bentonites was in the order of the polarity of the pore fluids used, while the order is reversed upon organic modification of clays. The mechanism of swell in the case of organo clays in organic liquids was related to the solvation of the organic liquid by the intercalated organic cations. And unlike in the case of unmodified clays, the organo clays showed “solvent induced swelling”. Both organic modification and addition of organo clay to bentonite resulted in the suppression of the swelling of clays in water irrespective of the type of modifier or the extent of organic modification. The Chapter 5 gives a detailed account of the compressibility behavior of organically modified clays and its mixtures with bentonite when the samples were molded with water at their respective OMC and later inundated with different fluids. Significant differences were observed on the compressibility of modified and unmodified clay in different fluids. Organic modification of clays reduced their affinity to water and resulted in lowering the compressibility. However there was an increased compressibility for the organo clays when the samples were inundated with non polar liquids and the compression of the organo clay in non polar fluid was not influenced by the nature of clay nor by the type of modifier. The compressibility of the mixtures of organo clay and bentonite in non polar liquids was generally controlled by the organo clay component of the mixture. Organo clays can be recommended as additives in bentonite slurries for construction of slurry walls in order to improve the containment of organics. But the amendment should not compromise the stability and integrity of the slurry walls. Moreover the influence of addition of sorptive material like organo clay on the compressibility behavior of bentonite slurry has received little attention and needs serious consideration as the studies in the previous chapter has brought out that the compressibility of compacted bentonite reduced significantly on organic modification as well as on addition of orgno clay. The Chapter 6 deals with the compressibility behavior of slurries of unmodified bentonite, organo clay, and their mixtures molded with respective liquid limits with water and later inundated with fluids of different dielectric constants as the slurries frequently get in contact with fluids other than water during their operational life. However it was observed that the effect of polarity of the inundating liquid is masked in all the cases by the presence of large amount of initial molding water as the possible specific chemical interactions between organo clay and non polar fluids were restricted in the presence of large amount of molding water. But the slurry samples molded and inundated with non polar carbon tetra chloride showed that the organo clay samples are more compressible when molded with carbon tetrachloride. The chapter also gives a brief discussion on the effect of initial molding water content on the compressibility of organo clays and its mixtures. The compression was found to increase with increase in initial water content irrespective of the type of inundating fluid in agreement with the behavior observed in the case of unmodified clays. However the effect was less pronounced at higher applied pressures. The Chapter 7 brings out the volume change behavior of organo clay amended sand bentonite mixtures (SOB) which form potential barrier to prevent and /or remove contaminants. The compaction behavior of mixtures showed that the degree of compaction achieved was controlled mainly by the sand content and proportion of organo clay in the total fine fraction. The volume change behavior of the SOB mixtures were assessed with the help of oedometer tests conducted on mixtures compacted at OMC conditions and inundated with different fluids same as those used for the swell tests. The samples with higher sand content showed no observable swell when inundated with liquids viz., water, ethanol and their mixture as all the swollen finer particles were accommodated in the voids created by sand particles. However a high swell percentage was measured when samples with high organo clay content were inundated with carbon tetrachloride. Moreover with increased amounts of organo clay in the mix the swelling of bentonite was suppressed and the same trend continued even when the pore fluids were changed to liquids of medium polarity. The organo clays are capable of interacting strongly with non polar liquids like carbon tetra chloride, and hence an appreciable swell was noted when inundated with them especially in the case of mixtures with high organo clay content. The swell behavior of SOB mixtures with lower sand contents were controlled mostly by the interaction of the pore fluid with bentonite and organo clay, interactions between organo clay and bentonite and the polarity of the pore fluid. As the pore fluid polarity was decreased the influence of organo clay component of the mixture was more pronounced. The Chapter 8 explains the hydraulic performance of modified and unmodified clays along with that of the mixtures of organo clay with bentonite and SOB. The coefficient of permeability was calculated from the consolidation data obtained on sample molded at OMC. The permeability variations observed on changing the pore fluids were studied at each applied pressure. The hydraulic conductivity showed a decreasing trend with the increase in applied pressure for all the clays. The specific interactions of the organo clay with the pore fluids and the clay content were found to play a role in controlling the permeability. Limited tests were carried out to simulate a condition where a SOB liner is proposed as a secondary liner below a punctured geo membrane and its hydraulic performance was evaluated with diesel and water as pore fluids. The permeability coefficients with diesel as permeant were observed to decrease with increase in organo clay content of the mixture irrespective of the applied pressure where as the reverse was true when permeated with water. Thus the use of SOB as secondary liner below storage tanks so as to control the transport of contaminants leaking containments systems is established. The organic sorption efficiency of the modified and unmodified clays and the mixture were evaluated in terms of removal of total organic carbon (TOC) and reduction in chemical oxygen demand (COD) of the different leachates including municipal solid waste (MSW) leachate when treated with different types of modified and unmodified clays. All the modified clays irrespective of the type of clay or the type of modifier used showed improved organic sorption capacity. The sorption of TOC was found to follow a linear sorption mechanism in the case of organo clays and the organic contaminants were partitioned on to the organic phase attached to the organo clays. The composition, age and type of leacahte played a major role in controlling the organic sorption efficiency of organo clays in the case of MSW leachates. The studies done with different mixtures of organo clay and bentonite and SOB mixtures clearly proved that the addition of organo clay always enhanced the organic sorption efficiency of the mixtures. The results are discussed in Chapter 9. The Chapter 10 highlights the major conclusions drawn from the study. The study, apart from satisfying the research zeal on understanding the behavior of organo clays, has generated important information useful for the geo environmental engineer to arrive at appropriate design of barrier systems incorporating organically modified clay, based on the characteristics of pore fluid.