Este trabalho apresenta o desenvolvimento da tese intitulada: Estudo, em escala de laboratório, do uso de argilas do tipo Bofe na obtenção de argilas organofílicas e ativadas. Argilas do tipo esmectítico são as de maior utilização industrial, sendo considerada a mais interessante das argilas industriais. Todavia em diversos casos faz-se necessário submetê-las a tratamentos químicos para desenvolver suas potencialidades. Para o desenvolvimento da tese foram utilizadas quatro amostras de argilas do tipo Bofe, provenientes de jazidas localizadas no município de Boa Vista, PB. Esse tipo de argila, apesar de ser bastante abundante, possui baixo valor econômico dada a dificuldade de obter produtos com propriedades adequadas a partir delas. Neste estudo utilizamos dois tipos de tratamentos, para verificar a potencialidade destas argilas, que foram: ativação ácida e organofilização. Para ativação ácida, foi utilizado o ácido clorídrico com diferentes tempos de reação, variando de uma hora até sete dias e com estas amostras avaliou-se o poder descorante em óleo de soja. Para a organofilização foram utilizados três sais quaternários de amônio e com as argilas organofílicas obtidas realizou-se teste de sorção em solventes orgânicos. Os resultados obtidos indicam que o tratamento ácido em argilas, com tempos de reação muito longos, promove destruição significativa da estrutura do argilomineral esmectítico. As argilas na sua forma natural apresentaram, no descoramento de óleo de soja, comportamento superior ao de argilas industriais ativadas de alto desempenho o que potencializa o uso das argilas tipo Bofe como materiais descorantes naturais (terras fuller). Em relação à organofilização, observou-se a eficiência no tratamento aplicado, visto o aumento do espaçamento interplanar, medido por difração de raios-X e da alta capacidade de sorção de óleo Diesel e Tolueno dos materiais organofílicos obtidos. / This work present the development of the entitled thesis: Study, at laboratory scale, of the use of the Bofe type clay to obtain organophillic and activated clays. Clays of the smectite type are of the bigger industrial use, being considered most interesting of the clay minerals. However, becomes necessary to submit it to chemical treatments for develop its potentialities. For the development of the research four samples of clay from the Bofe type had been used, proceeding from deposits located in areas near to the city of Boa Vista, PB. This type of clays, in spite of they be quite abundant, possess low economic value because the difficulty to obtain products with adequate properties starting from them. In this study to verify the potentiality of these clays we used two types of treatments. Those treatments were: acid activation and organophillic modification. For the acid activation treatment, hydrochloric acid was used with different times of reaction, varying from one hour up to seven days and with the obtained samples the fade power was evaluated in soy oil. To the organophillic modification treatment three quaternary ammonium salts were used. With the samples of the treated clays were made sorption in organic solvents tests. The obtained results indicate that the acid treatment in clays, with very long times of reaction, promotes significant destruction of the structure of the smectite clay mineral. Clays in its natural form presented, in the soy oil fade, superior behavior to the one of industrial activated clays of high performance, that indicates the potential of use of the type Bofe clays as natural bleacher material (fuller\'s earth). In relation to the organophillic modification, it was observed efficiency in the applied treatment, seen the increase of the interplane spacing, measured by X ray diffraction and the high capacity of sorption of Diesel oil and Toluene of the gotten organophillic materials indicating its potential of use in the sorption of hydrocarbons.

O manto litosférico é depletado em elementos incompatíveis como potássio, rubídio e estrôncio, confinado sob altas condições de pressão e caracterizado por uma composição e mineralogia específicas: espinélios anidros e/ou granada lherzolitos e harzburgitos. Esta região pode ser hidratada e enriquecida em elementos incompatíveis (ex. potássio) através de processos de subducção, onde a placa oceânica subductada leva consigo material pelágico composto de argilominerais e filossilicatos. A transferência de massa entre a placa subductada com os sedimentos e a cunha mantélica ocorre primeiramente através da liberação de fluidos aquosos gerados pela devolatilização de minerais hidratados. Neste contexto, a esmectita destaca-se como um dos mais importantes minerias responsáveis pelo enriquecimento do manto litosférico em água e elementos incompatíveis, quando sua estrutura é desestabilizada. Com o aumento da pressão e temperatura, esmectitas perdem sua água interlamelar, ao mesmo tempo em que se transformam em camadas mistas esmectita-ilita. Nestas condições de desidratação, e com o aumento da pressão, mudanças estruturais ocorrem e, havendo potássio disponível no sistema, o argilomineral evolui para uma mica muscovita. Considerando este contexto, o presente trabalho tem como objetivo verificar o comportamento estrutural da esmectita saturada em potássio modificando as variáveis pressão e temperatura: (1) sob pressão atmosférica em diferentes temperaturas (100º a 700ºC); (2) sob pressão de até 11.5 GPa sem temperatura - Diamond Anvil Cell (DAC); (3) sob diferentes pressões com aplicação de temperatura: 2.5GPa (400º a 700ºC) e 4.0GPa (200º a 700ºC). Os resultados das técnicas de análise de Difração de raios X, Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão (MET) e Espectroscopia por Infravermelho (FTIR) sugerem que, sob uma pressão de 2.5 GPa, que é cerca de 75km de profundidade no manto, e a aproximadamente 500ºC, a esmectita transforma-se em muscovita, enquanto sob a pressão de 4.0 Gpa, equivalente a cerca de 120 km de profundidade, a mesma transformação ocorre a 400ºC. Estes resultados contribuem significativamente para o entendimento de como a desidratação do sedimento pelágico ocorre em um processo de subducção, bem como o comportamento da esmectita sob a influência do aumento de pressão e temperatura. / The lithospheric mantle is depleted regarding to incompatible elements as potassium, rubidium and strontium, confined under pressure conditions and characterized by a specific mineralogy and composition, basically as anhydrous spinel and/or garnet lherzolite and harzburgite. This region can be hydrated and enriched in incompatible elements (e.g. potassium) through subduction processes that bring pelagic material, composed of clay minerals and other phyllosilicates, together with the hydrated subducted oceanic slab. A mass transfer from the subducted slab plus sediments into the mantle wedge occurs primarily through the release of aqueous fluids produced by devolatilization of hydrated minerals. In this context, smectite stands out as one of the most important minerals responsible for enriching the lithospheric mantle with water and incompatible elements when its structure is destabilized. By pressure and temperature increasing smectite lose its interlayer water, at the same time that it transforms into a mixed-layer illite-smectite. In this condition of dehydration and with increasing pressure, structural changes occur and, having potassium available on the system, the clay mineral evolves into a muscovite mica. Considering this context, we verified the structural behavior of potassium saturated smectite modifying variables pressure and temperature: (1) under atmospheric pressure at different temperatures (100º to 700º C); (2) under pressure up 11.5 GPa without temperature - Diamond Anvil Cell (DAC); (3) under different pressures with temperature application: 2.5 GPa (400º to 700º C) and 4.0 GPa (200º to 700º C). The results of the analysis techniques of X-ray diffraction, Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and Infrared Spectroscopy (FTIR), suggest that under the pressure of 2.5 GPa, which is about 75km depth in the mantle, and at around 500ºC smectite transforms into muscovite, while under the pressure of 4.0 GPa, equivalent to around 120km depth, the same transformation occurs at 400ºC. These results contribute significantly to understanding how pelagic sediment dehydration occurs in a subduction process, as well as the behavior of smectite under the influence of increasing pressure and temperature.

Les séquences argileuses peu perméables telles que les argilites callovo-oxfordiennes du bassin de<br />Paris ou les siltites vraconiennes du Gard, ont été choisies pour l'implantation éventuelle d'un<br />laboratoire souterrain destiné à tester les propriétés physico-chimiques de ces formations dans<br />l'éventualité d'un stockage profond de déchets nucléaires. La connaissance et la compréhension des<br />modifications post-sédimentaires sont fondamentales dans la définition de ces propriétés. Le but du<br />présent travail visait donc à évaluer et quantifier ces changements par l'étude de ces roches, en<br />particulier des minéraux argileux.<br />Les échantillons proviennent de deux forages (HTM102 et MAR501). Les principaux minéraux<br />argileux dans le forage HTM102 sont l'illite et les interstratifiés illite/smectite. Les observations au<br />MET et au MEB couplées aux analyses isotopiques K-Ar et Rb-Sr mettent en évidence la néoformation de carbonates (calcite, dolomite) et d'argiles. Celles-ci apparaissent au MET comme des particules authigènes lattées en croissance sur des particules détritiques. La durée et l'extension de ces événements diagénétiques sont difficiles à évaluer du fait d'une contamination systématique des<br />échantillons par une contribution détritique, et ce même dans les fractions les plus fines. Cependant,<br />l'étude d'un niveau de bentonite dans la séquence permet de caler l'époque et la durée de la<br />diagenèse. En assimilant cette bentonite à un pôle authigène, il a été possible de reconstruire les<br />variations des valeurs K-Ar de chaque fraction argileuse dans la séquence. Ainsi, la corrélation<br />observée entre les variations du niveau marin relatif et la formation d'un matériel argileux riche en<br />smectite d'une part, et des chimies de fluides différentes d'autre part, sont autant d'arguments en<br />faveur de réactions diagénétiques en système sinon clos du moins restreint.<br />Les travaux sur le forage MAR501 sont comparables à ceux réalisés sur le forage HTM102, avec<br />également un mélange entre deux populations argileuses d'âge différent. Les glauconites<br />diagénétiques ont permis de caler le Vraconien au voisinage de 93,7 ± 0,3 Ma, en accord avec les<br />données stratigraphiques. L'étude d'une fracture colmatée par une matrice essentiellement argileuse<br />confirme le caractère confiné de cette séquence. Aucune migration d'éléments, et en particulier de<br />TR, n'a été mise en évidence lors de la circulation de paléofluides, indiquant que les minéraux<br />argileux ont conservé leurs propriétés géochimiques.<br />L'ensemble de ces résultats est en faveur de propriétés de confinement fiables dans le cas des deux séquences argileuses.

Chlorite and corrensite are very common secondary minerals in very low-grade metamorphic or hydrothermally altered mafic rocks. Corrensite, although defined as a 1:1 regularly mixed-layered chlorite/smectite or chlorite/vermiculite, has been considered as a unique mineral phase and might thus be a potential index mineral for evaluating very low metamorphic grade. Many lenticular basaltic rocks, which are intercalated with unmetamorphosed to low-grade metamorphosed Tertiary sedimentary rocks, occur sporadically in the Western foothills and the Central Range in Taiwan. The lenticular basaltic rocks in the Western foothills (diagenetic zone) and the western flank of the Central Range (anchizone to epizone) were subjected to different degrees of hydrothermal alteration and/or metamorphism. However, only few occurrences of corrensite in these basaltic rocks were reported. In the present study, the occurrences and mixed-layering features of corrensite and coexisting chloritic minerals in the basaltic rocks were characterized by utilizing optical microscopy, X-ray diffraction, scanning electron microscopy with energy dispersive spectrometry, and transmission electron microscopy (TEM). The results showed that most of these basaltic rocks contain abundant chloritic minerals occurring as replacements of mafic minerals or interstitial glass, or as vein- or vesicle-filling materials. The chloritic minerals include smectite, corrensite, chlorite, mixed-layered chlorite/smectite, or mixed-layered chlorite/corrensite. The compositions of chlorite, corrensite, and smectite are distinctive in terms of their Si/Al ratios, interlayer cations, and total cation numbers. Corrensite, chlorite, and mixed-layered chlorite/corrensite are common secondary mineral assemblages in the anchizone basaltic rocks, whereas only discrete chlorite occur in the epizone. The basaltic rocks in the diagenetic zone contain different assemblages, such as smectite only, chlorite + smectite + mixed-layered chlorite/smectite + mixed-layered chlorite/corrensite, or chlorite + corrensite + mixed-layered chlorite/corrensite. These different assemblages of chloritic minerals and other secondary mineral assemblages might reflect different stages of hydrothermal alteration. Corrensite was positively identified with TEM lattice-fringe imaging in the diagenetic rocks collected from Nangang, Poneikeng, Shanzijiao, Nanshihjiao, Hsiungkong, Shihsiouping, Fusing, and Northern Shihmen Reservoir areas, and in the studied anchizone rocks from Junghua, Kaopo and Baolai areas. The disappearance of corrensite clearly marks the boundary between the anchizone and epizone basaltic rocks. Corrensite, as a chemically and structurally unique mineral phase, is therefore a potential index mineral in very low-grade metamorphic rocks.

The objective of this study is to understand the petrographical, mineralogical and geochemical characteristics of Messinian (Upper Miocene) gypsum occurence in Polatli Sazilar region, Ankara and to determine the impurities associated with gypsum. Moreover, it is aimed to interpret the usability of this raw material with impurities in plaster and plasterboard production based on industrial standards. Based on petrographical study, the first variety of gypsum which have different physical properties is white massive, micro crystalline, and translucent gypsum. Prismatic, transparent, idiomorphic and cleavage dominated selenite is the second variety. The gypsum rock is also identified that it is composed of sand sized selenite crystals and gypsum grains in a calcite and clay rich matrix. These impurity minerals also observed in thin beds alternating with gypsum. Scanning electron microscopic (SEM) studies are conducted to determine the relationship between the impurity mineral, gypsum and the selenite. X-ray diffractometry (XRD) studies were used to identify the type of clay minerals. In the samples, Ca-smectite is the essential impurity clay mineral. Rarely, mixed layer of illite-smectite is also identified. Geochemical studies also shows that as the amount of clay impurity increases, MgO, Al2O3, Fe2O3, Na2O, K2O (wt%) increases with decreasing SO3 (wt%). On the other hand, impurity of calcite controls the CaO (wt%) content in varying amounts. Five different groups of samples indicating different abundance of clay and calcite impurities are interpreted. The clay rich samples are enriched, in general, in vanadium, nickel, copper and chromium.

Commonly the thermal maturity of the Late Devonian to Early Mississippian Woodford shale found on the flanks of the Arbuckle Mountains of Oklahoma is determined by vitrinite reflectance, values ranging from 0.3-1.5%. Using phyllosilicate minerals, specifically diagenetic mixed layer illite/smectite and diagenetic illite, an understanding of the extent and processes leading to the thermal maturation may be developed. Analysis by XRD of the clay mineralogy of the Woodford shale found kaolinite and mixed layer illite/smectite with <5% smectite and R≥3 stacking order. Modeling of the Woodford shale also suggests the percentage of smectite present in mixed layer illite/smectite to be <5% and commonly <2.5%. Deconvolution of the illite (001) peak supports the low smectite content and high illite crystallinity. The long range ordered illite, R≥3, and high illite crystallinity values are indicative of diagenesis to anchizone conditions suggesting a higher thermal maturity relative to previously measured values of vitrinite reflectance.

No description available.

Phosphorus (P), a necessary plant and animal nutrient, can also lead to eutrophication of fresh waters when in excess. Appropriate P management is necessary to prevent fresh water pollution. Mineralogy of soil clays has been shown to affect P adsorption, desorption, and movement through soils. Specifically, hydroxy-interlayered minerals have been shown to adsorb and retain inorganic P in soil systems. This study was designed to determine the sorption and desorption characteristics of inorganic, organic, and mixed forms of P interacting with soil hydroxy-interlayered vermiculites (HIV) and smectites (HIS), and compare the findings to sorption and desorption processes of natural aluminum (Al) and Iron (Fe) hydroxide minerals. Results indicate natural Al and Fe hydroxide minerals sorbed and retained P more strongly than hydroxy-interlayered minerals in our samples and inositol hexakisphosphate was more highly sorbed and retained than inorganic P.

The technique of Inverse Gas Chromatography (IGC) was employed for the study of the interactions between various organic solvents with various types of the major inorganic materials (clay minerals and sand) found in Albertas oil sands. Heat of adsorption (-H) was measured for each solvent with respect to each of the four studied inorganic materials. The calculation we used was based on the Infinite Dilution Thermodynamics approach used by Katsanos et. al. [Journal of Chromatography A. 795, 133-184 (1998)]. Retention time data is converted into Retention Volume; H is then obtained by a plot vs. 1/T. The solvents studied were straight chain, branched and cyclic alkanes, alkenes, aromatics, and ketones. The inorganic materials studied were kaolinite, illite, illite-smectite mixed layer, and sand. Our results show that solvents had significantly less affinity for sand when compared to the three types of clay studied. Additionally, solvent affinity to illite had appreciable difference when compared to kaolinite and the mixed layer of illite-smectite. Furthermore, increase in carbon number leads to increased adsorption to the clay. Branched or cyclic alkanes have slightly lower adsorption to clay when compared to straight chain alkane of the same carbon number. Double bonds significantly increase solvent affinity to clay, but have no effect on sand. Lastly, alcohols and ketones have very high affinity to clay that no elution occurred when either solvent was injected into the GC and only ketone eluted when sand was the stationary phase in the GC column. / Chemical Engineering

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-09-25T14:32:33Z No. of bitstreams: 1 ADRIANA ALMEIDA SILVA - TESE (PPGEP) 2008.pdf: 8434650 bytes, checksum: 7ca7e24f622bbd49778d99a13f342587 (MD5) / Made available in DSpace on 2018-09-25T14:32:33Z (GMT). No. of bitstreams: 1 ADRIANA ALMEIDA SILVA - TESE (PPGEP) 2008.pdf: 8434650 bytes, checksum: 7ca7e24f622bbd49778d99a13f342587 (MD5) Previous issue date: 2008-12-19 / Nas últimas décadas uma quantidade substancial de pesquisas foi realizada a fim de encontrar novas fontes de energia renovável e sustentável para substituir o diesel de petróleo. Uma fonte alternativa promissora de energia é o biodiesel, que é um combustível renovável que pode ser produzido a partir dos óleos e gorduras animais/vegetais ou mesmo ácidos graxos reciclados da indústria de alimentos. Os catalisadores heterogêneos podem melhorar os métodos de síntese eliminando os custos adicionais associados aos catalisadores homogêneos e minimizando a produção de poluentes. As argilas ativadas têm atraído atenção como catalisadores para uma variedade de reações ácidas. O comportamento físico-químico dos minerais argilosos tem sido estudado devido a sua relação como adsorvente e/ou propriedades catalíticas. Diante do exposto verifica-se a necessidade de desenvolver estudos sobre a utilização de argilas como catalisador na produção do biodiesel, tornando-se, portanto, fundamental conhecer a estabilidade e propriedades do biodiesel produzido a partir desses catalisadores. Visando avaliar a eficiência das argilas como catalisadores no processo de transesterificação deste combustível, foram estudados nesse trabalho 27 tipos de argilas, fornecidas pela empresa BENTONISA- Bentonita do Nordeste S.A, para produção do biodiesel na rota etílica e metílica, utilizando óleo de soja. Inicialmente foi realizada uma pré-seleção das argilas, utilizando as análises de umidade e pH, onde foram escolhidos 15 tipos de amostras, as mesmas foram submetidas a ensaios nos sistemas reacionais S1 e S2 e utilizando as técnicas de cor do óleo (aspecto visual) e viscosidade, optou-se pelos dois melhores catalisadores argilosos (A23 e A24) a serem testados no sistema padrão para produção do biodiesel, denominado S3. Os catalisadores A23 e A24 foram caracterizados por : fluorescência de raios-X (FRX); difração de raios-X (DRX); espectroscopia de absorção no infravermelho (IV); microscopia eletrônica de varredura (MEV); energia dispersiva de raios-X (EDS) e área específica pelo método BET. O óleo de soja e o biodiesel formado foram caracterizados através das seguintes técnicas: composição química, umidade, acidez, densidade 20ºC, glicerol total e viscosidade 40ºC, teor de éster, teor de álcool e cromatografia gasosa. Os resultados mostraram que é possível obter o biodiesel a partir de catalisadores argilosos. / In the last decades a substantial amount of research has been undertaken to find new sources of renewable and sustainable energy to replace Diesel. A promising alternative energy source is biodiesel, which is a renewable fuel produced from vegetable oils and animal fats or even from recycled fat from the food industry. Heterogeneous catalysts can improve the synthesis methods eliminating additional costs associated with the homogeneous catalysts and minimizing the production of pollutants. Activated clays have attracted attention as catalysts for a variety of acid reactions. The physical and chemical behavior of clay minerals has been studied because of their property as adsorbent and / or catalysts. Therefore the need to develop studies on the use of clays as a catalyst in the production of biodiesel, making it, therefore, necessary to know the stability and properties of biodiesel produced by these catalysts. To evaluate the efficiency of clays as catalysts in the transesterification process of this fuel, 27 types of clay supplied by the company BENTONISA- Bentonite Nordeste SA, were studied in this work. The biodiesel was produced on the ethyl and methyl route, using soybean oil as raw material. The initial preselection for the clays was carried out on moisture and pH analysis, whereby 15 samples were selected. These were submitted to the testing systems in the S1 and S2, using the techniques of oil color (visual aspect) and viscosity. The two best clay catalysts (A23 and A24) were chosen to be tested in the standard system for production of biodiesel called S3. The catalysts A23 and A24 were characterized by: FRX; XRD; IR, SEM, EDS and BET. The soybean oil and biodiesel were characterized by the following techniques: chemical composition, moisture, acidity, density 20ºC, viscosity 40ºC, total glycerol, ester content, alcohol content and gas chromatography. The results showed that it is possible to get biodiesel from clay catalysts.