Thesis (M.S.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xiii, 172 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 123-125).

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Resumo: O presente trabalho tem como objetivo a obtenção de óxidos de molibdênio e de tungstênio com propriedades texturais controladas, particularmente com elevadas áreas específicas. Tais óxidos serão posteriormente empregados como precursores nas sínteses de nitretos e carbetos de molibdênio e de tungstênio, materiais potencialmente promissores na decomposição catalítica da hidrazina em sistemas micropopulsivos de satélites. Sabe-se da literatura que uma rede inorgânica de óxidos pode ser proveniente de vários precursores. Visando alcançar o objetivo do trabalho proposto, procurou-se primeiramente obter os óxidos, via processo sol-gel, a partir da decomposição térmica dos alcóxidos de molibdênio e de tungstênio. No decorrer do desenvolvimento do projeto de pesquisa achou-se também conveniente testar a decomposição térmica de outros precursores. Estas novas rotas exigem as sínteses de complexos de molibdênio (VI) e de tungstênio (VI) com ácidos a-hidroxicarboxílicos, de ácidos molíbdico e túngstico e dos saia de amônio dos referidos metais. Os materiais sintetizados foram, sempre que possível, analisados por espectroscopia na região infravermelho, difração de raios X e medidas de adsorção de nitrogênio na sua temperatura de condensação. Algumas amostras foram submetidas à análise elementar para a determinação dos teores de C, N e H. Efetuou-se a decomposição térmica de todos os precursores, sendo os óxidos obtidos analisados pelas mesmas técnicas utilizadas anteriormente. Os óxidos de molibdênio apresentaram uma fase cristalina ortorrômbica, exceto em algumas amostras onde se observou além desta fase, a presença de uma pequena quantidade de material amorfo.Com relação ao óxido de molibdênio, o maior valor de área específica de um foi de 8m2/g para uma amostra proveniente da hidrólise controlada de um alcóxido metálico... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work hás a objective the obtaining of molibdenum and tungsten oxides with texturais controlled properties, particularly with high specific areas. Such oxides will be used later on as precursors in the nitrides and carbides synthesis of molibdenium and tungsten, materials potentially promissing in the catalytic decomposition of the hydrazine in micropopulsives system of satellites. It's known about the literature that an inorganic net of oxide can come from several precursors. Seeking to reach the objective of the proposed work, it was firstly tried to obtain the oxides through sol-gel process, starting from the thermal decomposition of the molybdenum and tungsten alcoxides. In elapsing of the development in the research project it was also convenient to test the thermal decomposition of others precursors. These new routes demand the syntheses of molibdenium(VI) and tungsten(VI) complexes with the a-hidroxycarboxylic acids, of molybdic and tungstic acids and of the ammonium salts of the referred metals.The synthesized materials were, whenever possible, analysed by spectroscopy in the infrared region, of X-rays diffraction and measures of adsorption of nitrogen in its condensation temperature. Some samples were submitted the elementary analysis for the determination of texts of C, N and H. The thermal decomposition of all precursors was made, being the obtained oxides analysed same techniques previously used. The molibdenium oxides presented crystalline orthorhombic phase, except in some samples where it was observed besides this phase, the presence of a small amount of amorphous material. With relationship to molibdenium oxide, the largest value of specific area went of 8m2/g to a coming sample of the controlled hydrolysis of a metallic alcoxide. It was also obtained of area around 8m2/g for the ocide, coming from a of molybdic acid sample... (Complete abstract, click electronic address below) / Orientador: Antonio Carlos Massabni / Coorientador: Sandra Helena Pulcinelli / Banca: Elizabeth Berwerth Stucchi / Banca: Carlos de Oliveira Paiva Santos / Banca: José Augusto Jorge Rodrigues / Banca: Ariovaldo de Oliveira Florentino / Doutor

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-10-19T12:37:38Z No. of bitstreams: 1 MARIA ROSIANE DE ALMEIDA ANDRADE - DISSERTAÇÃO (PPGEQ) 2017.pdf: 4020246 bytes, checksum: 96bceac541ee13322a3c142ca97018a6 (MD5) / Made available in DSpace on 2018-10-19T12:37:38Z (GMT). No. of bitstreams: 1 MARIA ROSIANE DE ALMEIDA ANDRADE - DISSERTAÇÃO (PPGEQ) 2017.pdf: 4020246 bytes, checksum: 96bceac541ee13322a3c142ca97018a6 (MD5) Previous issue date: 2017-10-26 / Capes / A diminuição das reservas de combustíveis fósseis devido a grande demanda por energia e as alterações climáticas causadas pela emissão de gases do efeito estufa têm incentivado o desenvolvimento de novas fontes de energia, como o biodiesel. O biodiesel é um combustível biodegradável derivado de fontes renováveis, que pode ser produzido a partir de óleos vegetais, resíduos de óleos e gorduras animais. A principal rota de produção do biodiesel é a transesterificação metílica de triglicerídeos na presença de um catalisador básico homogêneo, mas este tipo de catalisador produz sabão e não é recuperado. Nesse sentido, estudos têm sidos desenvolvidos para produzir um catalisador heterogêneo capaz de obter elevadas conversões em ésteres e que seja facilmente recuperado e reutilizado. Dentre os catalisadores heterogêneos destacam-se os catalisadores de molibdênio devido a sua acidez de Lewis e Brønsted-Lowry, suportados em sílicas mesoporosas, como a peneira molecular MCM-41 que apresenta alta estabilidade térmica, elevada área superficial, grande volume de poros e distribuição de mesoporos ordenados que possibilitam a incorporação de metais em sua estrutura. Dessa forma o objetivo do presente trabalho é sintetizar o catalisador MoO3/MCM-41 e avaliar seu potencial catalítico na reação de transesterificação metílica do óleo de soja e testar sua atividade no seu reprocessamento. Para isso, inicialmente a peneira molecular MCM-41 foi obtida por um processo hidrotérmico a 30 °C por 24 h, utilizando o ortossilicato de tetraetila (TEOS), o brometo de cetiltrimetilamônio (CTABr), o hidróxido de amônio (NH4OH) e a água, e em seguida, passou por um processo de ativação por calcinação para remoção do direcionador estrutural. Posteriormente, foi incorporado na estrutura da MCM-41 o precursor heptamolibdato de amônio, por saturação de volume de poro, nas porcentagens (em massa) de 10, 20, 30, 40 e 45 %. A obtenção do MoO3 sob a peneira molecular MCM-41 se deu através do processo de ativação por calcinação. A partir dos resultados obtidos nos difratogramas de raios X foi possível confirmar a formação da peneira molecular MCM-41, bem como identificar os picos referentes ao MoO3. Os óleos obtidos nas reações de transesterificação apresentaram densidade e viscosidade dentro dos padrões estabelecidos pela resolução da Agencia Nacional de Petróleo, Gás Natural e Biocombustíveis (ANP) N° 51 de 25/11/2015, porém o índice de acidez não ficou dentro do limite máximo permissível e apenas os catalisadores com 10, 20 e 30 % de MoO3 conseguiram converter ao valor mínimo de ésteres. Os catalisadores de 30, 40 e 45% de trióxido de molibdênio apresentaram uma boa estabilidade catalítica nos dois ciclos de reuso, com uma redução máxima da atividade catalítica de 2,38%. Os óleos obtidos com a reutilização destes catalisadores apresentaram densidade e viscosidade dentro dos limites estabelecidos pela ANP. / The decline in fossil fuel reserves due to high demand for energy and climate change caused by greenhouse gas emissions has encouraged the development of new energy sources such as biodiesel. Biodiesel is a biodegradable fuel derived from renewable sources, which can be produced from vegetable oils, waste oils and animal fats. The main production route of biodiesel is the methyl transesterification of triglycerides in the presence of a homogeneous basic catalyst, but this type of catalyst produce soap and are not recovered. In this sense, studies have been developed to produce a heterogeneous catalyst capable of obtaining high conversions into esters and that is easily recovered and reused. Among the heterogeneous catalysts, there is one that stands out the molybdenum catalysts due to their acidity of Lewis and Brønsted-Lowry, supported in mesoporous silicas, such as the MCM-41 molecular sieve, which presents high thermal stability, high surface area, large pore volume and distribution of ordered mesopores that allow the incorporation of metals in its structure. Thus the objective of the present work is to synthesize the MoO3/MCM-41 catalyst and to evaluate its catalytic potential in the reaction of methyl transesterification of soybean oil and to test its activity in its reprocessing. For this purpose, the molecular sieve MCM-41 was initially obtained by a hydrothermal process at 30 °C for 24 hours using tetraethyl orthosilicate (TEOS), cetyltrimethylammonium bromide (CTABr), ammonium hydroxide (NH4OH) and water and then passed by a calcination activation process to remove the structural driver. Subsequently, the ammonium heptamolybdate precursor was incorporated into the MCM-41 structure by pore volume saturation, in the percentages (in mass) of 10, 20, 30, 40 and 45%. The MoO3 under the MCM-41 molecular sieve was obtained by the calcination activation process. From the results obtained in the X-ray diffractograms it was possible to confirm the formation of the molecular sieve MCM-41, as well as to identify the peaks related to MoO3. The oils obtained in the transesterification reactions presented density and viscosity within the standards established by the Resolution of the National Agency of Petroleum Natural Gas and Biofuels. (ANP) N°. 51 of 11/25/2015, but the acidity index was not within the maximum allowable limit and only the Catalysts with 10, 20 and 30% MoO3 were able to convert to the minimum value of esters. The catalysts of 30, 40 and 45% of molybdenum trioxide showed good catalytic stability in the two cycles of reuse, with a maximum reduction of catalytic activity of 2.38%. The oils obtained with the reuse of these catalysts showed density and viscosity within the limits established by the ANP.

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This study investigated the process by which molybdenum was removed from sea water in Saanich Inlet, an anoxic fjord, whose basin sediments are enriched in molybdenum. Water samples were collected in the inlet from July 1971 to April 1972 at about two month intervals and were analyzed for pH, salinity, temperature, dissolved and suspended molybdenum, suspended manganese and iron, and dissolved oxygen and hydrogen sulphide. A new technique for the determination of dissolved and suspended molybdenum was developed. The data showed a negative correlation between dissolved molybdenum and suspended manganese, and a positive correlation between suspended molybdenum and suspended manganese. This suggested that molybdenum was being scavenged from sea water by suspended manganese oxides. The distribution of molybdenum in the basin surface sediments was qualitatively correlated to the distribution of suspended molybdenum in the overlying basin water. During about September to December, the molybdenum profile was described by a two layer system. In the top 75 m layer the molybdenum followed the salinity profile. Below 75 m the distribution was described by a one dimensional mathematical model. The yearly deposition of molybdenum in the basin sediments was calculated from the estimated sediment deposition rate. This value was not inconsistent with that calculated from the rate molybdenum is scavenged by manganese oxides from the basin water. / Science, Faculty of / Chemistry, Department of / Graduate

A series of three experiments were carried out in order to demonstrate an interaction between molybdenum and selenium in broilers. Trail I investigated the interaction of selenium (0, 0.2, 0.4, and 0.8 ppm) with various toxic and subtoxic dietary levels of molybdenum (0, 0.5, 100, and 330 ppm), supplemented to a wheat based diet to broilers from one to four weeks of age. Results indicated that at 300 ppm molybdenum, increasing selenium levels resulted in progressive decline in weight gain, compared to a non-significant decline across these selenium levels when no molybdenum was supplemented. At these levels of molybdenum, selenium appeared to be acting antagonistically with molybdenum. At lower molybdenum levels, selenium exerted no apparent effects on weight gain. Selenium at toxic levels responded different from selenium at subtoxic dietary levels over molybdenum levels. Trial II, used 480 broiler chicks, assigned in a randomized block (RB) experimental design and 12 treatment combinations of selenium and molybdenum. Although the overall interaction effect was non-significant for weeks 1 to 4 inclusive, there were some definite interaction trends. Results indicated that at either basal or 3 ppm Se over basal 100, 200, or 300 ppm Mo, a non-significant difference in weight gain and feed consumption occurred. Selenium and molybdenum appeared to be interacting reciprocally. At 6 ppm dietary supplementation of selenium, however, combining increasing levels of molybdenum appeared to result in an independent toxic effect on weight gain which was additive for the two mineral toxicities, and not interactive. Using 480 broilers chicks assigned to a 3 x 4x3x3 multifactorial arrangement of 12 treatments an experiment was performed to investigate the effect on weight gain and feed consumption upon feeding toxic levels of molybdenum and selenium. Selenium levies ranged from basal, to 6, 12, and 18 ppm and molybdenum levels from basal, 400, and 800 ppm. Treatments were arranged in a RB experimental design. Results indicated that combining toxic dietary levels of selenium and molybdenum resulted in a measurable interaction in birds based on weight gain to feed consumption from one to four weeks of the experimental period. As the toxic dietary levels of selenium increased from basal to 6, 12, and 18 ppm the adverse effect of molybdenum at basal, 400 and 800 ppm became progressively reduced. At 18 ppm selenium, weight gain and feed consumption were the same irrespective of whether basal, 400, 800 ppm Mo was supplemented to the diet. The presence of toxic levels of selenium appeared to either reduce toxicity of molybdenum, or induce an increased tolerance for increasingly toxic levels of molybdenum. The nature of the interaction between selenium and molybdenum is discussed. / Land and Food Systems, Faculty of / Graduate