Thesis--Göttingen. / In Periodical Room.

Orientador: Renato Sprung / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-26T18:52:24Z (GMT). No. of bitstreams: 1 Villanueva_SandraBizarriaLopes_M.pdf: 2903045 bytes, checksum: db594687be29d4cac9565af2f790f98f (MD5) Previous issue date: 2000 / Resumo: Materiais do tipo hidrotalcita MgI-xAlx(OH)2(COl)x/2.Y H20 foram sintetizados, calcinados, caracterizados e testados cataliticamente na conversão do etanol. As sínteses foram realizadas com proporções de alumínio correspondentes a valores de x variando de 0,25 e 0,33. Ambos os materiais mostraram diftatogramas típicos de hidrotalcitas, áreas superficiais BET de cerca de 50 m2g-1 e 60 m2g-I, e volumes de mesoporos de 0,16cm3g-1 e 0,38 cm3g- / Abstract: Hydrotalcite-like compounds, Mg1-xAlx(OH)2(Col")xl2.y H20, were synthesized, calcined, characterized, and tested as catalysts for the vapor phase conversion of ethanol. Two hydrotalcite-like compounds were synthesized by varying the fraction x of aluminum in the starting solutions from 0,25 to 0,33. Both materiaIs yielded X-ray diffraction pattems typical ofhydrotalcites, with BET surface areas ofabout 50 and 60 m2g1 and mesopore volumes of 0,16 and 0,38 cm3g-1, respectively. Micropore volumes were negligible. When calcined at temperatures ranging from 500 to 1000°C, the materiaIs flrst yielded aluminum and magnesium double hydroxides for temperatures up to 800°C. By increasing the calcination temperature, the double hydroxides were progressively decomposed into magnesium hydroxide and a magnesium aluminate spinelic phase. The BET surface areas were increased up to about 200 m2g-1 and the mesopores volumes, to 0,68 cm3g-1. Catalytic tests were performed at 350°C and atmospheric pressure by passing 1,96 gIh ethanol diluted in nitrogen at a molar ratio of 1:2 through a fixed bed of calcined hydrotalcite partieles. Ethylene, acetaldehyde, ethyl ether and n-butanol were identifled as the reaction products. The ratio of ether to n-butanol was elose to one for alI the hydrotalcite samples utilized. The global yield of the condensation products, ether and nbutanol, was maximum for materiaIs calcined at 650°C, about 80%, and decreased continuously with increasing calcination temperatures. Acetaldehyde yield was maximum for materiaIs calcined at 1000°C. Total conversions of ethanol were slightly higher when using samples with higher aluminum content (x=0,33); samples calcined at 650°C yielded the highest ethanol conversion, about 14%. No conversion changes were detected over 150 minutes of reactor operation. Catalytic tests performed with magnesium oxide, obtained by calcination of synthesized magnesium hydroxide, yielded acetaldehyde and traces of ethylene. Total conversion of ethanol was typically 1 % after strong catalyst deactivation / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Bibliography: pages 154-195. / The production of acetone and butanol by Clostridium acetobutylicum P 262 was studied in continuous culture under conditions where the nutrients were present in excess of the requirements and the cell growth was limited by the products formed during the fermentation. This system differs from most continuous culture systems used to obtain solvent production where the limitation of a specific nutrient was utilised to limit the cell growth.

The aim of this work was to map out the theoretical basics of acetone-butanol fermentation. In addition, it is to find available data for possibility of the industrial use of this process and to make conclusion for next procedure. The microorganisms producing butanol, conditions of fermentation and usable raw material were described. Batch, Fed-batch and Continuous fermentation processes are described in more detail from the point of view of productivity of process and yield. Available data was evaluated, but there was a lack of technological data to construct an operational system. Therefore, an experimental pilot plant system was constructed that allowed different types of microorganisms and substrates to be tested. The pilot plant system is for single stage Continuous fermentation with gas stripping product recovery with possibility of expansion to two-stage Continuous fermentation. As well the balance of this process was done.

Toxicity of organic solvents to microbial hosts is a major consideration in the economical production of biofuels such as ethanol and especially butanol, with low product concentrations leading to high recovery costs. The key to rational engineering of solvent tolerant microorganisms for such processes lies in obtaining appropriate tolerance genes (modules) suited for different compounds. In this project, a synthetic biology approach was adopted to generate a library of standardised BioBrick parts involved in different stress responses. Using a multiple-assay approach, including a bioluminescence assay, these stress response genes were tested individually and in combination to determine their effects on survival in ethanol, nbutanol, acetone and fermentation inhibitors produced by biomass pre-treatment. A set of tolerance modules was obtained for ethanol and n-butanol. Proof-of-concept tests suggested that ethanol and n-butanol toxicity was mainly due to damage to membrane, cellular proteins and DNA possibly by oxidative stress. No synergistic interactions were observed from a combination of different tolerance genes. Further tests carried out using enzyme and fluorescence-based assays to elucidate the effect of n-butanol on the cell envelope showed that the solvent released lipopolysaccharides from the outer membrane of E. coli and also caused both outer and inner membranes to be leaky. Very high n-butanol concentrations resulted in an altered cell shape and bleb formation suggesting an impairment in cell division and peptidoglycan biosynthesis. The cell membrane was modified by cis-trans isomerisation of unsaturated fatty acids in the phospholipids resulting in a reduction of membrane leakage which in effect, increased n-butanol tolerance in E. coli. In conclusion, results from this research suggest that strategies to protect the membrane and cellular proteins should be included in rational engineering of n-butanol tolerant bacteria.

Butane-grown Pseudomonas butanovora oxidized butane by a soluble butane monooxygenase through the terminal pathway yielding 1 -butanol as the predominant product. Alcohol dehydrogenases (ADHs) involved in butane oxidation in P. butanovora were purified and characterized at the biochemical, genetic and physiological levels. Butane-grown P. butanovora expressed a type I soluble quinoprotein 1 -butanol dehydrogenase (BOH), a soluble type II quinohemoprotein 1 -butanol dehydrogenase (BDH) and an NAD���-dependent secondary ADH. Two additional NAD���-dependent secondary ADHs were also detected in cells grown on 2-butanol and lactate. BDH was purified to near homogeneity and characterized. BDH is a monomer of 66 kDa consisting of one mole of pyrroloquinoline quinone (PQQ) and 0.25 mole of heme c as the prosthetic groups. BOH was partially purified and its deduced amino acid sequence suggests a 67-kDa ADH containing a PQQ as a cofactor. BOH and BDH exhibited high activities and preference towards I -butanol and fair preference towards butyraldehyde. While BDH could not oxidize 2-butanol, BOH is capable of 2-butanol oxidation and has a broader substrate range than that of BDH. Genes encoding BOH and BDH and their deduced amino acid sequences were identified. BOH and BDH mRNAs and 1-butanol oxidation activity were induced when cells were exposed to butane. Primary C��� and C��� alcohols were the most effective inducers for boh and bdh. Some secondary alcohols, such as 2-butanol, were also inducers for BOH mRNA, but not for BDH mRNA. Insertional inactivation of boh or bdh affected unfavorably, but did not eliminate, butane utilization in P. butanovora. The P. butanovora mutant strain with both boh and bdh genes disrupted was unable to grow on butane and 1-butanol. This result confirmed the involvement of BOH and BDH in butane and 1-butanol metabolism in P. butanovora. Roles of B011 and BDH in butane and 1-butanol metabolism were further studied at the physiological level. There are no substantial differences between BOH and BDH in the mRNA expressions in response to three different 1- butanol levels tested and in their abilities to respond to 1-butanol toxicity. Different bioenergetic roles of BOH and BDH in butane and 1-butanol metabolism were suggested. A model of 1 -butanol- dependent respiratory systems was proposed where the electrons from 1 -butanol oxidation follow a branched electron transport chain. The role of BOH was suggested to function primarily in energy generation because B011 may couple to ubiquinone with the electrons being transported to a cyanide-sensitive terminal oxidase. BDH may be more important in the detoxification of 1 -butanol because the electrons from BDH may be transferred to a terminal oxidase system that is less sensitive to cyanide, which is not capable of energy generation. / Graduation date: 2003

Thesis (M.S.)--Youngstown State University, 2009. / Includes bibliographical references (leaves 50-52). Also available via the World Wide Web in PDF format.

Orientador: Maria Alvina Krahenbuhl / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-25T16:32:43Z (GMT). No. of bitstreams: 1 LopezMunoz_LauraAlicia_M.pdf: 2311093 bytes, checksum: 2b4ab867e0a31b54e9ac583e8cf2da5d (MD5) Previous issue date: 1999 / Resumo: Este trabalho de pesquisa apresenta contribuições para o equilíbrio líquido ¿ vapor (ELV) dos sistemas binários butanol ¿ácido butírico e butanol ¿ ácido acético. Dados isobáricos P-T-x-y de ELV foram medidos em duas faixas de pressão, 200 e 400 mmHg. O equipamento empregado foi um ebuliômetro de fluxo, ideal para sistemas que, ao longo do tempo, venham a reagir entre si. O princípio básico para a determinação do ELV neste tipo de equipamento consiste em promover o equilíbrio e a separação quase que imediata das fases, evitando-se assim a formação de produtos de ração indesejáveis. A qualidade dos dados P-T-x-y medidos foi verificada pela aplicação do teste de consistência termodinâmica de Van Ness ¿ Fredenslund. Os parâmetros de interação binária para os modelos de coeficientes de atividade da fase líquida. Representados pelos modelos, Wilson, UNIQUAC e NRTL, foram ajustados para os sistemas estudados pelo método da máxima verossimilhança. Foi considerada a não idealidade da fase vapor, empregando-se a teoria química com a correlação de Hayden & O¿Connell para o cálculo do segundo coeficiente Virial, e predição da constante de equilíbrio químico de dimerização / Abstract: This research work presents contributions for the vapor ¿ liquid equilibria (VLE) of the binary systems Butanol ¿ Butyric acid and Butanol ¿ Acetic acid. Isobaric data P-T-x-y of VLE were measured in two pressure, 200 and 400 mmHg. The used equipment was a flow ebuliometerm ideal for systems that, along the time, come to react to each other. The basic principle for the determination of VLE in this equipment type consists of almost promoting the equilibrium and the immediate separation of the phases, being avoided the formation of undesirable reaction products. The quality of the measured data P-T-x-y ws verified on applying the thermodynamic consistency test of Van Ness ¿ Fredenslund. The binary interaction parameters for models of activity coefficients of the liquid phase, represented by the models, Wilson, UNIQUAC and NRTL, were adjusted for the studied systems by the maximum likelihood method. The non-ideality of the vapor phase was considered by using the chemical theory with the correlation of hayden & O¿Connell for the calculation of the second Virial coefficient, and prediction of the chemical equilibrium dimerization constant / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

Orientador: Maria Regina Wolf Maciel / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-07-19T19:58:51Z (GMT). No. of bitstreams: 1 Westphalen_DenisLibert_M.pdf: 3649815 bytes, checksum: cb7d3824a100a56ccbea071f5c27dd07 (MD5) Previous issue date: 1993 / Resumo: Síntese de processos é uma área de pesquisa da engenharia química relativamente recente que se preocupa com a sistematização do projeto conceituaI de processos químicos. Neste trabalho, um fluxograma para fabricação de 2-butanol foi concebido utilizando-se técnicas de síntese de processos. A rota de reação escolhida foi a hidratação de butenos lineares sobre resina de troca iônica fortemente ácida. Seguindo uma hierarquia de decisões, o trabalho foi dividido em três etapas: projeto do reator, sistema de separação e reciclos; e rede de trocadores de calor e utilidades. Na etapa projeto do reator, um projeto simplificado do reator foi elaborado de modo a se identificar suas variáveis de projeto e uma estimativa do custo do equipamento. No estudo do sistema de separação, foi realizada a escolha dos equipamentos de separação apropriados, seu sequenciamento e projeto preliminar. O sistema de separação concebido é composto por três colunas de destilação: Coluna de Separação de Butenos, Coluna de Separação de 2-butanol e Coluna de Separação de di-sec-butil-éter. Para o cálculo do custo da rede de trocadores de calor e do consumo de utilidades, recorreu-se à Tecnologia PINCH, que permite a obtenção destes dados sem o projeto da rede de trocadores. Desta forma, o custo de fabricação do 2-butanol considerando-se os principais equipamentos, foi calculado e chegou-se à conclusão que os valores ótimos das variáveis de projeto: conversão de butenos no reator e concentração de butenos na corrente de purga estão em tomo de 60% e 40%, respectivamente / Abstract: Not informed. / Mestrado / Desenvolvimento de Processos Químicos / Mestre em Engenharia Química

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