Pressure-volume-temperature data for n-butanol have been determined from 117.5°C and 14.7 psi to 268°C. and 480 psi. The apparatus, designed to reach 1100 psi, was modeled after Kay⁴⁰ and used a dead weight gauge tester for pressure readings and a glass capillary tube as the sample container. Pressures were obtained to ± 0.1 per cent. Nitrogen manometers were also used for pressure measurement in some cases but much less successfully. Temperatures were maintained constant within a vacuum jacketed column, and measured by a copper-constantan thermocouple calibrated against a standard platinum resistance thermometer to ± 0.05°C. Trial runs were made on purified water and pure (research grade) n-hexane. The results for water checked with Keyes'⁵⁵ data within 0.5 per cent, and for n-hexane checked with Kay's²³ vapor pressure equation within 3 per cent. The latter deviation was possibly due to contamination while filling the capillary, and a modified filling procedure was introduced for the n-butanol. Vapor pressure results fell on smooth curves and checked within 0.5 per cent of Stull's critical collection of vapor pressure data at lower pressures, but at higher pressures (400 psi) deviations as much as 7 per cent were found. The saturated and superheated specific volume data also fell on smooth curves. Saturated values were shown to be accurate for heats of vaporization calculations. The superheated values compared favorably with values calculated from the reduced compressibility charts for hydrocarbons. Available thermodynamic data were compiled for n-butanol. A pressure-enthalpy diagram was constructed using only Cp data and heats of vaporization as calculated by the correlative methods of Othmer³⁰ and Thomas²⁹. Heats of vaporization were also calculated from the vapor-pressure and specific volume data using the Clausius-Clapeyron equation agreeing within 3 per cent of the Othmer and Thomas correlations. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate

Orientadores: Ariovaldo José da Silva, Bruna de Souza Moraes / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Agrícola / Made available in DSpace on 2018-08-30T07:46:17Z (GMT). No. of bitstreams: 1 Santos_GracieteMarydos_M.pdf: 3271887 bytes, checksum: 539f68130eb11eac441d2bca07c2e7da (MD5) Previous issue date: 2015 / Resumo: No Brasil, o efluente industrial produzido em maior quantidade é a vinhaça, caracterizada por altos níveis de ácidos orgânicos, fósforo, cálcio, potássio e magnésio. O reaproveitamento energético da vinhaça mostra-se como uma alternativa interessante para produção de biocombustíveis ou sub-produtos. Este trabalho avaliou o potencial da vinhaça como fonte de substrato e nutrientes para produção de álcoois e ácidos orgânicos voláteis (AOV) por meio fermentação em batelada utilizando consórcio anaeróbio (lodo de bovinocultura) pré-tratados com choque térmico (TT) e choque ácido-térmico (AT). Foram utilizados dois meios diferentes, de sacarose (S) e de vinhaça (V), sendo a sacarose a principal fonte de carbono. A vinhaça provou ser uma excelente fonte de nutrientes para os microrganismos envolvidos na fermentação butírica, uma vez que a adição de vinhaça melhora significativamente a produção de ácido butírico em comparação com meio de cultura sintético. As máximas concentrações de ácido butírico, iso-butírico e acético foram de 14,13 ± 0,77 g L-1 na amostra ATV B3; 10,34 ± 0,43 g L-1na amostra ATV B2 e; 4,13 ± 0,06 g L-1na amostra TTV B3, respectivamente. O rendimento dos AOV acético, iso-butírico e butírico e de etanol foi mais elevado nas amostras ATV B3 e TTV B3, atingindo valores máximos de 0,14; 0,28; 0,69 e; 0,26 g g-1 carboidratos totais, respectivamente. Não foram encontradas diferenças significativas entre métodos de pré-tratamento e enriquecimento de inóculo, AT e TT no que diz respeito a produção de ácido butírico e etanol. Em escala maior, operando em reator de 1,5 L, a fermentação de vinhaça bruta e melado de cana por consórcio microbiano AU mostrou potencial para produção de solventes como o butanol, uma vez que concentrações elevadas de ácido butírico foram produzidas, com concentração máxima, rendimento e produtividade de 13,85 g L-1; 0,64 g g-1 e; 199,98 mg L h-1, respectivamente. A caracterização microbiológica, pirosequenciamento, revelou a ocorrência em maior abundância de bactérias do gênero Clostridium, principalmente no consórcio AU e Lactobacillus mais abundante nos consórcios TT e AT. Foi identificada uma espécie conhecida pela produção de butanol, o C. pasteurianum no consórcio AU. Contudo, o presente trabalho representa um passo importante no desenvolvimento de um processo industrial para reutilização da vinhaça. A exploração de novos microrganismos e estudo dos fatores que interferem no processo de fermentação como pH, temperatura, nutrientes, densidade da cultura, cargas aplicadas e características do substrato, são fundamentais para o entendimento dos efeitos sinérgicos e antagônicos da associação de culturas / Abstract: In Brazil, industrial waste produced in the greatest amount is vinasse, characterized by high levels of organic acids, phosphorus, calcium, potassium and magnesium. The energy reuse of vinasse shows up as an interesting alternative for the production of biofuels or byproducts. This study evaluated the potential of vinasse as a source of substrate and nutrients for the production of alcohols and volatile fatty acids (VFA) through fermentation batch using anaerobic consortium (cattle sludge) pre-treated with heat shock (TT) and acid-shock thermal (AT). We used two different media, sucrose (S) and vinasse (V), with sucrose being the main source of carbon. The vinasse proved to be an excellent source of nutrients for microorganisms involved in the butyric fermentation, since the addition of vinasse significantly improves the production of butyric acid as compared to synthetic culture medium. The maximum concentrations of butyric acid, iso-butyric and acetic acid were 14.13 ± 0.77 g L-1 in the sample ATV B3; 10.34 ± 0.43 g L-1 in ATV B2 and 4.13 ± 0.06 g L-1 in TTV B3, respectively. The yield of acetate, iso-butyric acid, butyrate and ethanol was higher in ATV B3 and TTV B3 samples, reaching maximum values of 0.14; 0.28; And 0.69; 0.26 g g-1 total carbohydrates, respectively. There were no significant differences between pretreatment and enrichment methods inoculum, TA and TT as regards the production of butyric acid and ethanol. On a larger scale, operating at 1.5 L reactor, crude fermentation vinasse and molasses of sugar cane from AU microbial consortium showed potential for producing butanol as the solvent, since high concentrations of butyric acid was produced, with maximum concentration, yield and productivity of 13.85 g L-1 0.64 g g-1 and 199.98 mg h L-1, respectively. Microbiological characterization, pyrosequencing, revealed the occurrence in greater abundance of the genus Clostridium bacteria, particularly the AU and most abundant Lactobacillus in consortium TT and AT consortia. C. pasteurianum, known for the production of butanol was identified in AU consortium. However, this study represents an important step in the development of an industrial process for reuse of vinasse. The exploration of new microorganisms and study of the factors that interfere in fermentation process such as pH, temperature, nutrients, cultures, applied loads and characteristics of the substrate are critical for understanding the synergistic and antagonistic effects of culture associatio / Mestrado / Agua e Solo / Mestra em Engenharia Agrícola

Global energetic and environmental concerns have generated interest in the biological systems for the production liquid biofuels. Butanol is one such biofuel, which can be naturally produced by some Clostridia species. However, possible limitations in Clostridial engineering and large-scale fermentation have led to an examination of other potential organisms that might house this pathway for butanol production. As a robust industrial host and key model organism in the study of fundamental biological processes, the yeast Saccharomyces cerevisiae has been used to house the Clostridial ABE-butanol pathway. However, butanol yields and titres in this yeast are relatively low. Therefore, in this thesis, three distinct strategies were carried out with the goal of optimising butanol production in the strain of yeast (previously constructed in the Ashe lab) bearing the ABE-butanol pathway: 1. Mutation of genes involved in the regulation of carbon source usage. 2. Deletion of genes where the product is involved in the consumption of cytosolic acetyl-CoA (the starting precursor for the butanol synthetic pathway). 3. Targeted mutagenesis to improve the efficiency of the thiolase enzyme, which catalyses the condensation of 2x acetyl-CoA to initiate the ABE-butanol synthesis pathway. The results showed the first two strategies did not lead to improvements in butanol yields. However, increases of intracellular acetyl-CoA were observed in some mutant strains, even though butanol production did not increase in these strains. In order to make maximum use of the accumulating cytosolic acetyl-CoA, thiolase engineering in the butanol production yeast strain was pursued. The introduced changes caused an increase in butanol (about two fold). Overall, this project has used a minimal engineering approach by modulation of associated pathways or optimisation of the heterologous enzyme with a view to improve butanol production in yeast. To achieve high and scalable butanol production in yeast, a robust approach involving whole synthetic biology - Design, Build Test, and Learn will need to be adopted to create a more efficient yeast-butanol system.

Catalytic Distillation for the synthesis of tertiary butyl alcohol (TBA) is investigated in this thesis. The solvent, ethylene glycol, is proposed as a means of overcoming challenges, which limit the potential benefits of the application of reactive separation for TBA. The proposed action of the solvent is that of extractive distillation entrainer, thus a new unit operation of Catalytic Extractive Distillation (CED) is suggested. The solubility of isobutylene in water, TBA, and ethylene glycol and their binary and ternary mixtures, at different temperatures, is measured and correlated. The solubility is found to be highly non-linear in solutions containing TBA. The kinetics of isobutylene hydration over Amberlyst 15 is characterised in the presence of ethylene glycol. The solvent is found to promote reaction rate, however it is also found to compete for reaction with isobutylene. Water is found to strongly inhibit the reaction of ethylene glycol and isobutylene. The selectivity ratio of TBA to by products is determined and found to improve with increased temperature and lower solvent concentration. Bale packing is chosen as catalytic distillation hardware for the containment of Amberlyst 15 and its two-phase fluid dynamics characterised for the first time. Raschig rings are used as a benchmark for the study. Bale packing is found to exhibit two ranges of backmixing behaviour in the pre-loading regime. This behaviour is attributed to the three levels of porosity of the hardware and indicative of low rates of catalyst/liquid renewal. The effectiveness of ethylene glycol as extractive distillation entrainer for the separation of the TBA/water azeotrope over Bale packing is investigated and the solvent found to be highly effective. The mass transfer resistances to isobutylene transport are determined for countercurrent fixed bed reactor (CFBR) application of Bale packing. It is found that ethylene glycol improves mass transfer coefficients attainable. Catalytic Extractive Distillation is implemented over Bale packing and the ability of the solvent to improve reaction rates and purity of TBA demonstrated. However, the reaction rates achieved have much scope for improvement through increased isobutylene availability. In response to poor liquid renewal of static packing such as Bale packing and the necessity of improved isobutylene transport a new form of catalytic distillation reactor design is proposed, the Basket Impeller Column (BIC). The BIC combines the mass transfer benefits of a rotating basket reactor with that of a dual flow column. Capacity of the new hardware is determined and correlated. Separation and reactive separation are demonstrated to be feasible. It is found that Damk??hler number can be varied directly using the additional process variable of speed of rotation.

Catalytic Distillation for the synthesis of tertiary butyl alcohol (TBA) is investigated in this thesis. The solvent, ethylene glycol, is proposed as a means of overcoming challenges, which limit the potential benefits of the application of reactive separation for TBA. The proposed action of the solvent is that of extractive distillation entrainer, thus a new unit operation of Catalytic Extractive Distillation (CED) is suggested. The solubility of isobutylene in water, TBA, and ethylene glycol and their binary and ternary mixtures, at different temperatures, is measured and correlated. The solubility is found to be highly non-linear in solutions containing TBA. The kinetics of isobutylene hydration over Amberlyst 15 is characterised in the presence of ethylene glycol. The solvent is found to promote reaction rate, however it is also found to compete for reaction with isobutylene. Water is found to strongly inhibit the reaction of ethylene glycol and isobutylene. The selectivity ratio of TBA to by products is determined and found to improve with increased temperature and lower solvent concentration. Bale packing is chosen as catalytic distillation hardware for the containment of Amberlyst 15 and its two-phase fluid dynamics characterised for the first time. Raschig rings are used as a benchmark for the study. Bale packing is found to exhibit two ranges of backmixing behaviour in the pre-loading regime. This behaviour is attributed to the three levels of porosity of the hardware and indicative of low rates of catalyst/liquid renewal. The effectiveness of ethylene glycol as extractive distillation entrainer for the separation of the TBA/water azeotrope over Bale packing is investigated and the solvent found to be highly effective. The mass transfer resistances to isobutylene transport are determined for countercurrent fixed bed reactor (CFBR) application of Bale packing. It is found that ethylene glycol improves mass transfer coefficients attainable. Catalytic Extractive Distillation is implemented over Bale packing and the ability of the solvent to improve reaction rates and purity of TBA demonstrated. However, the reaction rates achieved have much scope for improvement through increased isobutylene availability. In response to poor liquid renewal of static packing such as Bale packing and the necessity of improved isobutylene transport a new form of catalytic distillation reactor design is proposed, the Basket Impeller Column (BIC). The BIC combines the mass transfer benefits of a rotating basket reactor with that of a dual flow column. Capacity of the new hardware is determined and correlated. Separation and reactive separation are demonstrated to be feasible. It is found that Damk??hler number can be varied directly using the additional process variable of speed of rotation.

Dois exemplos de combustíveis renováveis em uso atualmente são bioetanol e biodiesel. Novas alternativas de combustíveis incluem etanol celulósico e biobutanol. Estes apresentam vantagens pois contribuem para uma melhor produtividade e otimização do uso de biomassa. Possuem ainda boas propriedades que garantem o bom desempenho como combustíveis. A pesquisa e interesse industrial têm crescido sobre o biobutanol, com melhorias no processo tradicional de fermentação ABE (Acetona-Butanol-Etanol), desenvolvimento de novos microorganismos para aumentar o rendimento e técnicas de separação para isolar o solvente do meio fermentativo. Algumas companhias anunciaram planos para a introdução de biobutanol em misturas com gasolina no mercado norte-americano. O interesse por biobutanol no Brasil como combustível ainda é limitado, pois a infraestrutura de comercialização já é adaptada ao uso de bioetanol, e a maior parte da frota de carros circulante utiliza motores adaptados ao uso do bioetanol. A cana-de-açúcar pode ser utilizada como matéria prima no processo produtivo do biobutanol, capacitando o Brasil a tornar-se um importante exportador para suprir o biobutanol para outros países. Em curto prazo, o biobutanol poderá ser produzido no Brasil para substituir o petro-butanol como solvente em aplicações industriais ou para o mercado de exportação como combustível. O presente trabalho propõe o uso da técnica technology roadmapping para o planejamento estratégico do desenvolvimento do biobutanol, alinhando os objetivos de longo prazo com os recursos, linhas de financiamento e prioridades para atender as necessidades do processo de desenvolvimento. / Two examples of renewable fuels in use today are bioethanol and biodiesel. New alternatives on biofuels include cellulosic ethanol and biobutanol. They present several advantages over the conventional biofuels, either in terms of better productivity and optimization of the use of biomass, as well as higher performance attributes. The research and industrial interest has grown on biobutanol, with improvements on the traditional ABE fermentation process, on the development of new microorganism strains to improve yield, and separation techniques to isolate the solvent. Companies have announced plans for the introduction of biobutanol in blends with gasoline in the north-american market. The interest on biobutanol as a fuel in Brazil is still limited, since the infrastructure is tailored to bioethanol already, and most of the car fleet uses engines adapted to this fuel. Sugar cane can be used as a potential feedstock in the butanol production process, enabling Brazil to become a key exporter to supply biobutanol to other countries. For the short future biobutanol will be produced in Brazil to replace petro-butanol as a solvent in industrial applications only, or for the export market as a fuel. This work proposes the use of technology roadmapping as a technique for long term strategic planning of the biobutanol development, aligning long term goals with the resources, funding, and priorities to fulfill the needs in the development process.

Dois exemplos de combustíveis renováveis em uso atualmente são bioetanol e biodiesel. Novas alternativas de combustíveis incluem etanol celulósico e biobutanol. Estes apresentam vantagens pois contribuem para uma melhor produtividade e otimização do uso de biomassa. Possuem ainda boas propriedades que garantem o bom desempenho como combustíveis. A pesquisa e interesse industrial têm crescido sobre o biobutanol, com melhorias no processo tradicional de fermentação ABE (Acetona-Butanol-Etanol), desenvolvimento de novos microorganismos para aumentar o rendimento e técnicas de separação para isolar o solvente do meio fermentativo. Algumas companhias anunciaram planos para a introdução de biobutanol em misturas com gasolina no mercado norte-americano. O interesse por biobutanol no Brasil como combustível ainda é limitado, pois a infraestrutura de comercialização já é adaptada ao uso de bioetanol, e a maior parte da frota de carros circulante utiliza motores adaptados ao uso do bioetanol. A cana-de-açúcar pode ser utilizada como matéria prima no processo produtivo do biobutanol, capacitando o Brasil a tornar-se um importante exportador para suprir o biobutanol para outros países. Em curto prazo, o biobutanol poderá ser produzido no Brasil para substituir o petro-butanol como solvente em aplicações industriais ou para o mercado de exportação como combustível. O presente trabalho propõe o uso da técnica technology roadmapping para o planejamento estratégico do desenvolvimento do biobutanol, alinhando os objetivos de longo prazo com os recursos, linhas de financiamento e prioridades para atender as necessidades do processo de desenvolvimento. / Two examples of renewable fuels in use today are bioethanol and biodiesel. New alternatives on biofuels include cellulosic ethanol and biobutanol. They present several advantages over the conventional biofuels, either in terms of better productivity and optimization of the use of biomass, as well as higher performance attributes. The research and industrial interest has grown on biobutanol, with improvements on the traditional ABE fermentation process, on the development of new microorganism strains to improve yield, and separation techniques to isolate the solvent. Companies have announced plans for the introduction of biobutanol in blends with gasoline in the north-american market. The interest on biobutanol as a fuel in Brazil is still limited, since the infrastructure is tailored to bioethanol already, and most of the car fleet uses engines adapted to this fuel. Sugar cane can be used as a potential feedstock in the butanol production process, enabling Brazil to become a key exporter to supply biobutanol to other countries. For the short future biobutanol will be produced in Brazil to replace petro-butanol as a solvent in industrial applications only, or for the export market as a fuel. This work proposes the use of technology roadmapping as a technique for long term strategic planning of the biobutanol development, aligning long term goals with the resources, funding, and priorities to fulfill the needs in the development process.

Thesis (Ph. D.)--University of Chicago, 1933. / "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois."

Thesis (Ph. D.)--University of Wisconsin, 1960. / Includes vita. Includes tabular statistical computations (leaves 265-323). eContent provider-neutral record in process. Description based on print version record. "Literature cited": leaves 260-264. 61

Thesis (Ph. D.)--University of Wisconsin--Madison, 1933. / Typescript. eContent provider-neutral record in process. Description based on print version record.