Thesis (MS)--Montana State University--Bozeman, 2010. / Typescript. Chairperson, Graduate Committee: Fabian D. Menalled. Includes bibliographical references (leaves 82-96).

Submitted in complete fulfilment for the Degree of Master of Technology: Biotechnology, Durban University of Technology, 2013. / The continual growth of the global biodiesel industry has resulted in a proportional increase in crude glycerol production. The by-production of glycerol waste during the manufacture of biodiesel has, with recent research, proven to hold use as a feedstock for the production of several commodity chemicals. The conversion of glycerol may be carried out by both chemical as well as biological means. The biological conversion of glycerol surpasses chemical conversion with respect to higher yield and selectivity, normal reaction conditions and the use of cheaper biological catalysts. Many microorganisms are known to convert glycerol to different value added products. This study involved the isolation of bacteria from soil and crude glycerol from a local biodiesel plant. Isolates were then used to convert crude glycerol supplemented with salts and a nitrogen source into commercially viable products. Isolates which successfully degraded glycerol were then identified via 16S PCR. A strain of Klebsiella pneumoniae, which is a known producer of 1,3-propanediol (1,3-PDO), was isolated from soil and two strains of Sphingomonas sp., which is a known gellan producer, was isolated from biodiesel waste. Gellan is an exopolysaccharide used in the food, cosmetic and pharmaceutical industries sold commercially as a product known as Gelrite or Gelzan while 1,3-PDO is an important component of fuels and polyesters (used widely in the petroleum industry) and is currently chemically produced. Using crude glycerol for producing 1,3-PDO is a good solution from an economic as well as ecological point of view. K. pneumoniae, Sphingomonas psueudosanguinis and Sphingomonas yabuuchiae were subjected to a series of shake flask fermentations in order to determine optimal growth conditions. This microoganism was able to successfully produce significant amounts of 1,3-PDO and lactic acid using crude glycerol (80 g/l), without pre-treatment (37 and 6.8 g/l respectively). S psueudosanguinis and S. yabuuchiae were both able to produce two of the highest amounts of gellan gum than that reported by other studies using crude glycerol (80 g/l) as a sole carbon source in a minimal medium (50.9 and 52.6 g/l respectively). / National Research Foundation

Made available in DSpace on 2014-06-11T19:35:41Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-02-18Bitstream added on 2014-06-13T19:25:05Z : No. of bitstreams: 1 moraes_jr_dr_guara.pdf: 858058 bytes, checksum: 9d3737c517e6bd0d7841460e47975a70 (MD5) / A crescente demanda por energia aumenta a busca por fontes energéticas alternativas a fim de se desvencilhar daquelas não renováveis. Todavia, a decisão por uma fonte energética leva em conta fatores técnicos, econômicos, sociais, políticos e ambientais. O termo biodiesel aplica-se ao combustível substituto do óleo diesel, constituído de ésteres obtidos a partir de óleos vegetais, por processo de transesterificação com álcoois em meio ácido ou básico. A utilização de óleos vegetais como combustível apresenta vantagens, principalmente, quanto às emissões de gases nocivos. Contudo, apresenta desvantagens como elevada viscosidade e falta de volatilidade, e seu processo de obtenção gera resíduo não totalmente aproveitável. Sistemas microemulsionados aparecem como um tipo de combustível alternativo, pois se ampliam os limites advindos das propriedades de cada componente da mistura. Pode-se intervir na redução das emissões de poluentes e também em suas características. Permite a utilização de substâncias com menor valor econômico e reaproveitamento de resíduos, constituindo-se como substitutos para os derivados de petróleo, propiciando autossuficiência energética, fortalecimento do agronegócio, desenvolvimento regional sustentável, geração de emprego/renda e melhoria da qualidade do ar / The growing demand for energy increases the search for alternatives to replace fossil sources by renewable energy sources. Nevertheless, the decision for an energy source shall consider technical factors, economic, social and environmental aspects as well. The term biodiesel refers to the substitute fuel for the original diesel, obtained from vegetable oil esters, by means of chemical transesterification with alcohols in acid or basic media. The use of vegetable oils as fuel presents many advantages, mainly concerning lower harmful gas emission. Although, they present disadvantages as high viscosity and lack of volatility, and their production process generates residues not completely usable. Micro-emulsion systems appear as alternatives because it is possible to take better advantage of the properties of each component of the system. It is possible to manipulate the system in order to reduce gas emissions and also their characteristics. It allows the use of components with lower economical value and recovery of residual products, becoming valuable substitutes for petrol derivatives, reducing external energy dependence, strengthen the agro-business, providing sustainable regional development, job and revenue generation and air quality improvement

Made available in DSpace on 2015-01-26T13:21:17Z (GMT). No. of bitstreams: 0 Previous issue date: 2013-02-28Bitstream added on 2015-01-26T13:30:47Z : No. of bitstreams: 1 000802134.pdf: 2331571 bytes, checksum: 3098cbb9aa3c5c25a9cc346814de9c95 (MD5) / Na produção de biodiesel em pequena escala são comumente empregados os decantadores para separar o glicerol do biodiesel após a reação química de transesterificação do óleo com um álcool e um catalisador. Na maioria das vezes, esse processo de separação é realizado de forma manual e subjetiva por um operador que está sujeito a erros de interpretação, podendo, com isso, aumentar o custo de produção e/ou comprometer a qualidade do combustível produzido. Neste trabalho é proposta uma metodologia para o desenvolvimento e teste de um sistema eletrônico micro controlado, capaz de distinguir as fases formadas após o processo de decantação por meio de um sensor de condutividade elétrica, o qual permite o acionamento de válvulas para controle automático do direcionamento do biodiesel e do glicerol para reservatórios distintos. Essa metodologia contém a técnica de desenvolvimento abrangendo modelagem, simulação computacional, seleção de materiais, usinagem, projeto eletrônico, calibração e obtenção das características do desempenho do sensor. O sistema é composto por um painel elétrico que permite observar características do processo, através de um visor de LCD, e permite alterar as configurações do micro controlador, através da comunicação USB do equipamento com um computador. O sistema se mostrou eficiente nos testes com o biodiesel e glicerol, em processos produtivos com óleo de soja refinado, sendo que o glicerol apresentou valor de condutividade superior ao biodiesel, conforme esperado / In the production of biodiesel on a small scale decanters are commonly utilized to separate the glycerol from biodiesel produced after a chemical reaction of oil with some alcohol and a catalyst. In most cases, this separation process is done manually and subjectively by an operator that can make mistakes in interpretation, increasing the cost of production and/or compromising the quality of the fuel produced. This work presents a methodology for developing and testing of a micro controlled electronic system, capable of distinguishing the phases formed after the decanting process by means of an electrical conductivity sensor, which permits the actuation of valves in order to have an automatic control of the direction of biodiesel and glycerol for different reservoirs. This methodology contains the technical development including modeling, computer simulation, materials selection, manufacturing, electronic project, calibration and obtains the performance characteristics of the sensor. The system consists of an electrical panel, which allows to observe the process through features an LCD display and permits change the settings of microcontroller through the USB communication device with a computer. The system proved effective in tests with biodiesel and glycerol production processes with refined soybean oil, and glycerin showed conductivity value higher than biodiesel as expected

Made available in DSpace on 2018-07-27T18:26:12Z (GMT). No. of bitstreams: 0 Previous issue date: 2015-05-06. Added 1 bitstream(s) on 2018-07-27T18:30:32Z : No. of bitstreams: 1 000870856.pdf: 2297678 bytes, checksum: 6aad44cf33b94a5bdcb65780e40fc4fe (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A modificação química do biodiesel tem sido uma proposta interessante para obtenção de diversos compostos oleoquímicos com propriedades e aplicações semelhantes aos derivados do petróleo, com o diferencial de serem obtidos através de rotas limpas e ambientalmente benigmas, utilizando insumos naturais como óleo vegetal e dióxido de carbono, atendendo diversos princípios da Química Verde. Este trabalho têm como proposta realizar uma série de modificações químicas do biodiesel de linhaça, partindo de sua síntese, epoxidação e cicloadição de CO2 para obtenção de epóxidos e carbonatos cíclicos biodegradáveis. O biodiesel de linhaça foi produzido através de catálise com ácido de Lewis (NbCl5) e teve seu teor de insaturação concentrado via purificação com uréia. A epoxidação do biodiesel concentrado teve sua cinética acompanhada pelo progresso do valor de oxigênio oxirano além de ser estudada via GC-FID e GC-MS. Os carbonatos cíclicos foram obtidos pela cicloadiação de CO2 supercrítico nos epóxidos catalisada por TEAB sem solvente e mostraram-se bons reagentes frente a diversas aminas para formação de carbamatos (uretanos). Espectros de FT-IR e RMN (1H e 13C) identificaram as transformações de todos os principais grupos funcionais comprovando êxito nas modificacões químicas propostas / The chemical modification of biodiesel has been an interesting proposal for obtaining various oleochemical compounds with similar porperties and aplications to petroleum derivates, with the difference of being obtained through clean and environmentally benign routes, using natural feedstock as vegetables oil and carbon dioxide, according to several principles of Green Chemistry. This work proposes to conduct a series of chemical modifications of flaxseed biodiesel, from its synthesis, epoxidation and cycloaddtion of CO2 to obtain biodegradable epoxides and cyclic carbonates. The flaxseed biodiesel was produced through Lewis acid catalysis (NbCl5) and had its unsaturation content concentrated by urea purification. The epoxidation of the concentrated biodiesel had its kinetics monitored by the evolution of oxygen oxirane value and studied by GC-FID and GC-MS. The cyclic carbonates were obtained from the solventless cycloaddition of supercritical CO2 in the opoxides catalyzed by TEAB, and have shown good reactants for a wide range of amines to from its respective carbamates (urethanes). FT-IR and NMR (1H and 13C) spectra identified the transformatios of all maior functional groups proving successful in the proposed chemical modifications

Orientador: Luiz Roberto Carrocci / Coorientador: Edgard Paz Perez / Banca: Celso Eduardo Tuna / Banca: Eliana Vieira Canettieri / Banca: Daniele Camargo Vernilli / Banca: Valesca Alves Corrêa / Resumo: A crescente demanda por energia aumenta a busca por fontes energéticas alternativas a fim de se desvencilhar daquelas não renováveis. Todavia, a decisão por uma fonte energética leva em conta fatores técnicos, econômicos, sociais, políticos e ambientais. O termo biodiesel aplica-se ao combustível substituto do óleo diesel, constituído de ésteres obtidos a partir de óleos vegetais, por processo de transesterificação com álcoois em meio ácido ou básico. A utilização de óleos vegetais como combustível apresenta vantagens, principalmente, quanto às emissões de gases nocivos. Contudo, apresenta desvantagens como elevada viscosidade e falta de volatilidade, e seu processo de obtenção gera resíduo não totalmente aproveitável. Sistemas microemulsionados aparecem como um tipo de combustível alternativo, pois se ampliam os limites advindos das propriedades de cada componente da mistura. Pode-se intervir na redução das emissões de poluentes e também em suas características. Permite a utilização de substâncias com menor valor econômico e reaproveitamento de resíduos, constituindo-se como substitutos para os derivados de petróleo, propiciando autossuficiência energética, fortalecimento do agronegócio, desenvolvimento regional sustentável, geração de emprego/renda e melhoria da qualidade do ar / Abstract: The growing demand for energy increases the search for alternatives to replace fossil sources by renewable energy sources. Nevertheless, the decision for an energy source shall consider technical factors, economic, social and environmental aspects as well. The term biodiesel refers to the substitute fuel for the original diesel, obtained from vegetable oil esters, by means of chemical transesterification with alcohols in acid or basic media. The use of vegetable oils as fuel presents many advantages, mainly concerning lower harmful gas emission. Although, they present disadvantages as high viscosity and lack of volatility, and their production process generates residues not completely usable. Micro-emulsion systems appear as alternatives because it is possible to take better advantage of the properties of each component of the system. It is possible to manipulate the system in order to reduce gas emissions and also their characteristics. It allows the use of components with lower economical value and recovery of residual products, becoming valuable substitutes for petrol derivatives, reducing external energy dependence, strengthen the agro-business, providing sustainable regional development, job and revenue generation and air quality improvement / Doutor

This research has been directed at furthering the utilization of crude glycerol oversupply formed as a by-product from the biodiesel manufacturing process. Phosphorylation of hydroxyl groups is a synthetic route that was investigated for the conversion of glycerol into a glycerol-phosphate (GPE) ester mixture. The process investigated for the synthesis of a GPE product was based on phosphorylation reaction procedures that were previously reported in the literature. The reaction to convert glycerol into a GPE mixture has been thoroughly investigated and the hydrogen chloride gas formed as a reaction by-product has been optimized. The chemical properties of GPE have been studied and discussed together with a mass balance of the overall glycerol phosphorylation process. The phosphate groups contained in polyhydric phosphate molecules have a potential chelating effect on cations. There are several cations that may be chelated by the phosphate ester group of polyhydric phosphate molecules. These cations include ammonium (NH4+), Potassium (K+), Calcium (Ca2+) etc, which are essential as nutrients in plant fertilizer formulations. This research has investigated the use of a GPE synthesized from glycerol in the laboratory and the use thereof as a phosphorus containing base in the formulation and evaluation of Nitrogen, Phosphorus and Potassium (NPK) containing fertilizer solution, Ammonium-Potassium-Glycerol-Phosphate (APGP) fertilizer solution. The APGP fertilizer solution has further been evaluated by growing two week old tomato seedlings under controlled conditions. The performance of the APGP fertiliser solution has been evaluated using design of experiments by comparison with traditionally used liquidAmmonium-Potassium-Phosphate inorganic fertilizer. This fertilizer solution has been prepared in similar manner as APGP formulation with the difference between them being the source of phosphorus. The results have been evaluated using statistic analysis where a significant difference between the evaluated fertilizer formulations was found. The comparative study of these formulations was monitored by the observed plant weights. A blank treatment was used as a control to determine if a significant difference among these formulations was observed. Anova single factor and t-Test methods (Two-Samples assumed of equal variances) are statistical models that were applied to interpret the observed experimental data with respect to wet and dry weighed masses of tomato seedlings. These methods indicated a confirmed conclusion that there was a significant difference between APPO4 solution and APGP solution. The observed data have shown that the APPO4 solution provided significantly better fertigation performance than APGP solution. Consequently, further investigation has been conducted to determine the cause of the poorer performance of the APGP solution. The further study of the APGP fertilizer solution included nutrient stability testing, biological analysis and other observed physical changes of the APGP solution over time. Biological results have revealed the presence of a Fusarium fungus species that has grown and is suspended in APGP fertilizer solution. This microbe species has been observed to play a vital role in consuming fertilizer nutrients. In addition, the observed abnormal plant growth and nutrient decomposition of the APGP formulation has been proposed to be mostly a result of the pathogenicity of the fusarium fungi species that was suspended in the APGP solution. Further work has been proposed in which the effect of such biological contamination is eliminated through adequate sterilization procedures and the APGP formulation re-evaluated.

Orientador: Eduardo René Pérez González / Banca: Luiz Carlos da Silva Filho / Banca: Gil Valdo José da Silva / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi / Resumo: A modificação química do biodiesel tem sido uma proposta interessante para obtenção de diversos compostos oleoquímicos com propriedades e aplicações semelhantes aos derivados do petróleo, com o diferencial de serem obtidos através de rotas limpas e ambientalmente benigmas, utilizando insumos naturais como óleo vegetal e dióxido de carbono, atendendo diversos princípios da Química Verde. Este trabalho têm como proposta realizar uma série de modificações químicas do biodiesel de linhaça, partindo de sua síntese, epoxidação e cicloadição de CO2 para obtenção de epóxidos e carbonatos cíclicos biodegradáveis. O biodiesel de linhaça foi produzido através de catálise com ácido de Lewis (NbCl5) e teve seu teor de insaturação concentrado via purificação com uréia. A epoxidação do biodiesel concentrado teve sua cinética acompanhada pelo progresso do valor de oxigênio oxirano além de ser estudada via GC-FID e GC-MS. Os carbonatos cíclicos foram obtidos pela cicloadiação de CO2 supercrítico nos epóxidos catalisada por TEAB sem solvente e mostraram-se bons reagentes frente a diversas aminas para formação de carbamatos (uretanos). Espectros de FT-IR e RMN (1H e 13C) identificaram as transformações de todos os principais grupos funcionais comprovando êxito nas modificacões químicas propostas / Abstract: The chemical modification of biodiesel has been an interesting proposal for obtaining various oleochemical compounds with similar porperties and aplications to petroleum derivates, with the difference of being obtained through clean and environmentally benign routes, using natural feedstock as vegetables oil and carbon dioxide, according to several principles of Green Chemistry. This work proposes to conduct a series of chemical modifications of flaxseed biodiesel, from its synthesis, epoxidation and cycloaddtion of CO2 to obtain biodegradable epoxides and cyclic carbonates. The flaxseed biodiesel was produced through Lewis acid catalysis (NbCl5) and had its unsaturation content concentrated by urea purification. The epoxidation of the concentrated biodiesel had its kinetics monitored by the evolution of oxygen oxirane value and studied by GC-FID and GC-MS. The cyclic carbonates were obtained from the solventless cycloaddition of supercritical CO2 in the opoxides catalyzed by TEAB, and have shown good reactants for a wide range of amines to from its respective carbamates (urethanes). FT-IR and NMR (1H and 13C) spectra identified the transformatios of all maior functional groups proving successful in the proposed chemical modifications / Mestre

Among various sources for biofuels, microalgae provide at least three-orders-of-magnitude higher production rate of biodiesel at a given land area than conventional crop-based methods. However, microalgal biodiesel still suffers from significantly lower harvesting efficiency, making such a fuel less competitive. To increase the separation efficiency of microalgae from cultivation solution, an orbital microchannel was utilized that enabled the isolation of biofuel-algae particles from the effluent. The results obtained showed that the separation efficiency in the microfluidic centrifugal separator can be as high as 76% within a quick separation time of 30 seconds. Multiple parameters of algae behaviors and separation techniques such as initial concentration, pH and temperature were studied and manipulated to achieve better efficiencies. It was found that changing these factors altered the separation efficiency by increasing or decreasing flocculation, or “clumping” of the microalgae within the microchannels. The results suggested that an acidic condition would enhance the separation efficiency since in a basic environment, large flocs of microalgae would block and hinder the separation process. Furthermore, a hot temperature solution (around 33 °C) yielded to a higher separation efficiency. The important characteristics of the separator geometry and the infusion rate on algae separation were also very effective in the separation process. This study revealed that there is an opportunity to improve the currently low efficiency of algae separation in centrifugal systems using much smaller designs in size, ensuring a much more efficient algae harvesting. / Includes bibliography. / Thesis (MS)--Florida Atlantic University, 2021. / FAU Electronic Theses and Dissertations Collection

published_or_final_version / abstract / toc / Mechanical Engineering / Master / Master of Philosophy