Neste trabalho foram sintetizados ésteres etílicos do óleo de babaçu através da catálise alcalina em meio homogêneo. O planejamento de experimentos foi utilizado como ferramenta de otimização e também na identificação dos principais fatores que influenciam nas conversões em ésteres etílicos. As reações de transesterificação foram realizadas através de duas metodologias de processo - a tradicional com agitação mecânica e a promovida por ondas ultrassônicas. A espectrometria de ressonância magnética nuclear foi utilizada na quantificação das conversões de todos os experimentos e a análise termogravimétrica foi empregada na determinação da pureza dos ésteres etílicos e do principal subproduto da reação - o glicerol. Matrizes ortogonais de Taguchi foram utilizadas para o desenvolvimento deste estudo. Os fatores independentes avaliados na transesterificação tradicional foram: razão molar etanol/óleo, temperatura, turbulência, razão ponderal catalisador/óleo, tempo e os tipos de catalisadores mais comumente empregados (NaOH e KOH). Os ensaios envolvendo a transesterificação clássica foram realizados sob atmosfera de nitrogênio e também sob atmosfera normal. Com o método sonoquímico foram avaliados os fatores: razão molar, tempo, razão ponderal catalisador/óleo e tipo de catalisador. O delineamento experimental mostrou que o principal fator a influenciar nas conversões em ésteres etílicos com ambos os métodos é a razão molar. Destaca-se ainda na transesterificação alcalina tradicional, a influência das interações entre a temperatura e o tempo, mostrando que melhores conversões são obtidas com temperaturas próximas a ambiente (27 a 30ºC). De acordo com o modelo obtido através do delineamento experimental, conversões superiores a 99% são obtidas quando a razão estequiométrica é ajustada em 6:1, utilizando-se 1,0% de KOH, sob agitação mecânica a 400rpm durante 60min. A influência da atmosfera de nitrogênio mostrou-se pouco significativa para a reação e conversões semelhantes foram obtidas com atmosfera normal. A transesterificação alcalina assistida por ondas ultrassônicas apresentou os melhores resultados em relação ao tempo de reação e de separação entre as fases glicerínica e de ésteres etílicos. O modelo experimental mostrou que conversões superiores a 99% podem ser obtidas em 10 minutos ajustando as variáveis independentes nos seguintes valores: razão estequiométrica em 6:1 com 1,0% de KOH. Em ambos os métodos o catalisador KOH mostrou-se superior ao NaOH, especialmente durante as etapas de purificação. A estratégia de purificação dos ésteres etílicos adotada consistiu na utilização de um solvente (hexano) e lavagens com HCl 0,1 mol.L-1 que foi otimizada para 12,5% de solução em relação ao peso de ésteres obtidos, coletados logo após a separação de fases. O rendimento mássico obtido com o modelo experimental, após procedimentos de lavagens mencionados, foi de 94,59%. O trabalho demonstrou que o processo de obtenção de biodiesel de babaçu apresenta ótimos rendimentos desde que os parâmetros de reação sejam otimizados. A sonoquímica mostrou-se potencialmente promissora para obtenção de elevadas conversões em curtos intervalos de tempo. / In this work ethyl esters of babassu oil were synthesized by alkaline catalysis in homogeneous medium. The experimental design was used as a tool for optimization of the transesterification reaction and also in identifying key factors influencing the conversion into ethyl esters. The transesterification reactions were performed using two methods of process - the traditional mechanical agitation and agitation promoted by sound waves. The nuclear magnetic resonance spectroscopy was used to quantify the conversion of all reactions of transesterification and thermogravimetric analysis was used to determine the purity of ethyl esters and the main byproduct of the reaction - the glycerol. Taguchi orthogonal arrays were used to develop this study. The independent factors evaluated in the transesterification traditional were: molar ratio ethanol / oil, temperature, stirring speed, weight ratio catalyst / oil, time and the types of most commonly used catalysts (NaOH and KOH). The classical experiments involving the transesterification were performed under nitrogen atmosphere and also under normal atmosphere. With the sonochemical method were evaluated the following factors: molar ratio, time, weight ratio catalyst / oil and type of catalyst. The experiment showed that the main factor influencing the conversion into ethyl esters in both methods is the molar ratio. The best conversion results were obtained with twice the stoichiometric quantity. Also noteworthy in the traditional alkaline transesterification is the influence of interactions between temperature and time, showing that the best conversions are obtained with temperatures close to ambient (30°C) in 60 minutes. According to the model obtained by the experimental design, conversions above 99% are obtained when the stoichiometric ratio is set at 6:1, with 1.0% KOH, under stirring at 400 rpm. The influence of nitrogen atmosphere was less significant for the reaction and similar conversions were obtained with normal atmosphere. Alkaline transesterification assisted by sound waves produced the best results with respect to time of reaction and phase separation of glycerin and ethyl esters. The experimental model showed that conversions above 99% can be obtained in 10 minutes by adjusting the independent variables in the following values: in the stoichiometric ratio 6:1 with 1.0% KOH. In both methods the KOH catalyst was superior to NaOH, influence also noted during the purification steps. Experimentally it was found that the formation of emulsions and gels are more frequent with the use of the sodium hydroxide catalyst. The strategy for purification of ethyl esters adopted was the use of a solvent (hexane) and washing with HCl 0.1 mol.L- 1 that was optimized for 12.5% solution by weight of esters obtained, collected just after phase separation. The mass yield obtained with the experimental model, after washing procedures mentioned, was 94.59%. The study showed that the process of obtaining babassu biodiesel has good yields since the reaction parameters are optimized. The sonochemical proved to be potentially promising for achieving high yields in short time, which might be an excellent route for production aiming to meet the high market demands.

A pesquisa foi desenvolvida no Setor de Avicultura do Departamento de Zootecnia do Centro de CiÃncias AgrÃrias da Universidade Federal do Cearà (UFC), objetivando avaliar o desempenho zootÃcnico e a qualidade dos ovos de poedeiras comerciais, submetidas Ãs dietas com diferentes Ãleos vegetais. O procedimento experimental envolveu 224 poedeiras comerciais da linhagem Hy-line W-36, com 23 semanas de idade, dividido em 5 ciclos de 28 dias, durante os quais foram coletados dados para estudo. O delineamento estatÃstico foi em blocos ao acaso, com 7 tratamentos, sendo a unidade experimental representada por 1 parcela com 8 aves, e 4 repetiÃÃes por tratamento. Os tratamentos constaram de 7 raÃÃes, com nÃvel de energia de 2.850 Kcal EM/kg e proteÃna de 18%, sendo: T1 - dieta basal (sem Ãleo); T2 - dieta basal + 2% de Ãleo de soja; T3 - dieta basal + 4% de Ãleo de soja; T4 - dieta basal + 2% de Ãleo de linhaÃa; T5 - dieta basal + 4% de Ãleo de linhaÃa; T6 - dieta basal + 2% de Ãleo de algodÃo e T7 - dieta basal + 4% Ãleo de algodÃo. A inclusÃo do Ãleo vegetal nas dietas nÃo possibilitou uma melhora absoluta (P>0,05) na percentagem de ovos, conversÃo alimentar, massa de ovo, ganho de peso corporal, peso dos ovos, percentagens da gema, clara e casca, e na reduÃÃo do nÃvel de colesterol dos ovos, em relaÃÃo à dieta controle (sem Ãleo). De acordo com a idade das aves, observou-se aumento significativo (P<0,05) do peso dos ovos e da percentagem da gema, e reduÃÃo na percentagem da clara e na coloraÃÃo da gema crua, porÃm nÃo houve alteraÃÃo significativa (P>0,05) na percentagem da casca. O nÃvel de 4% de adiÃÃo do Ãleo vegetal nas dietas promoveu uma melhora efetiva (P<0,05) na coloraÃÃo da gema crua dos ovos. Os ovos conservados em temperatura de refrigeraÃÃo apresentaram menor (P<0,05) perda de peso e melhores (P<0,05) Ãndices de percentagem da clara, gravidade especÃfica, unidades Haugh e coloraÃÃo da gema crua, quando comparados aos ovos conservados em temperatura ambiente. Constatou-se que a qualidade dos ovos à alterada significativamente (P>0,05) em funÃÃo da temperatura de conservaÃÃo e do perÃodo de estocagem, notadamente para os parÃmetros perda de peso, percentagens da gema e clara, gravidade especÃfica e unidades Haugh. Em relaÃÃo à anÃlise sensorial, a inclusÃo de 4% de adiÃÃo de Ãleo de linhaÃa nas dietas alterou (P<0,05) efetivamente o sabor e a textura da gema e da clara dos ovos. Na anÃlise econÃmica, observou-se que a margem bruta e o lucro operacional efetivo foram maiores na dieta com 2% Ãleo de soja e menores na dieta com 4% Ãleo de linhaÃa. A melhor resposta econÃmica da produÃÃo de ovos foi obtida pelas aves que consumiram dieta com 2% Ãleo de soja / The research was developed in the Sector of Poultry of the Department of Zootecnical Center of Agrarian Sciences of the Federal University of Cearà (UFC), objectifying to evaluate the zootecnical performance and the quality of eggs of commercial laying hens, submitted to the diets with different vegetal oils. The experimental procedure involved 224 commercial laying hens of the Hy-line W-36 line, with 23 weeks of age, divided in 5 cycles of 28 days, during which were collected data for study The experiment followed a randomized blocks, distributed in seven treatments, each experimental unit was a box with 8 hens and 4 repetitions per treatment. The treatments consisted of 7 rations, with level of energy of 2850 kcal ME/kg and protein of 18%, being: T1 - basal diet (without oil); T2 - basal diet + 2% of soy oil; T3 - basal diet + 4% of soy oil; T4 - basal diet + 2% of flax oil; T5 - basal diet + 4% of flax oil; T6 - basal diet + 2% of cotton oil and T7 - basal diet + 4% cotton oil. The inclusion of the vegetal oil in the diets did not make possible an absolute improvement (P>0,05) in the egg percentage, feed conversion, egg mass, body weight, egg weight, percentages of the yolk, egg white and shell and did not reduce cholesterol level of eggs, in relation to the basal diet (without oil). In accordance with the age of the birds, significant increase (P<0,05) of the weight of eggs and the percentage of the egg yolk was observed, and reduction in the percentage of the yolk and the coloration of the raw egg yolk, however it does not to have significant alteration (P>0,05) in the percentage of the shell. The level of 4% of addition of the vegetal oil in the diets promoted an effective improvement (P<0,05) in the coloration of the raw egg yolk. The eggs conserved in temperature of refrigeration presented (P<0,05) smaller loss of weight and better (P<0,05) percentage of the yolk, specific gravity, Haugh units and coloration of the raw egg yolk, when compared with eggs conserved in ambient temperature. It was evidenced that the quality of eggs is modified significantly (P>0,05) in function of the temperature of conservation and the period of storage, mainly for the parameters weight loss, percentages of the yolk and, specific gravity and Haugh units. In relation to the sensorial analysis, the inclusion of 4% of oil addition of flax oil in the diets effectively modified (P<0,05) the flavor and the texture of the yolk and the white egg. Economic analysis suggested that the rude edge and the effective operational profit were bigger in the diet with 2% oil of soy and smaller in the diet with 4% flax oil. The best economic reply of the egg production was gotten by the birds that consumed diet with 2% soy oil

Neste trabalho foram sintetizados ésteres etílicos do óleo de babaçu através da catálise alcalina em meio homogêneo. O planejamento de experimentos foi utilizado como ferramenta de otimização e também na identificação dos principais fatores que influenciam nas conversões em ésteres etílicos. As reações de transesterificação foram realizadas através de duas metodologias de processo - a tradicional com agitação mecânica e a promovida por ondas ultrassônicas. A espectrometria de ressonância magnética nuclear foi utilizada na quantificação das conversões de todos os experimentos e a análise termogravimétrica foi empregada na determinação da pureza dos ésteres etílicos e do principal subproduto da reação - o glicerol. Matrizes ortogonais de Taguchi foram utilizadas para o desenvolvimento deste estudo. Os fatores independentes avaliados na transesterificação tradicional foram: razão molar etanol/óleo, temperatura, turbulência, razão ponderal catalisador/óleo, tempo e os tipos de catalisadores mais comumente empregados (NaOH e KOH). Os ensaios envolvendo a transesterificação clássica foram realizados sob atmosfera de nitrogênio e também sob atmosfera normal. Com o método sonoquímico foram avaliados os fatores: razão molar, tempo, razão ponderal catalisador/óleo e tipo de catalisador. O delineamento experimental mostrou que o principal fator a influenciar nas conversões em ésteres etílicos com ambos os métodos é a razão molar. Destaca-se ainda na transesterificação alcalina tradicional, a influência das interações entre a temperatura e o tempo, mostrando que melhores conversões são obtidas com temperaturas próximas a ambiente (27 a 30ºC). De acordo com o modelo obtido através do delineamento experimental, conversões superiores a 99% são obtidas quando a razão estequiométrica é ajustada em 6:1, utilizando-se 1,0% de KOH, sob agitação mecânica a 400rpm durante 60min. A influência da atmosfera de nitrogênio mostrou-se pouco significativa para a reação e conversões semelhantes foram obtidas com atmosfera normal. A transesterificação alcalina assistida por ondas ultrassônicas apresentou os melhores resultados em relação ao tempo de reação e de separação entre as fases glicerínica e de ésteres etílicos. O modelo experimental mostrou que conversões superiores a 99% podem ser obtidas em 10 minutos ajustando as variáveis independentes nos seguintes valores: razão estequiométrica em 6:1 com 1,0% de KOH. Em ambos os métodos o catalisador KOH mostrou-se superior ao NaOH, especialmente durante as etapas de purificação. A estratégia de purificação dos ésteres etílicos adotada consistiu na utilização de um solvente (hexano) e lavagens com HCl 0,1 mol.L-1 que foi otimizada para 12,5% de solução em relação ao peso de ésteres obtidos, coletados logo após a separação de fases. O rendimento mássico obtido com o modelo experimental, após procedimentos de lavagens mencionados, foi de 94,59%. O trabalho demonstrou que o processo de obtenção de biodiesel de babaçu apresenta ótimos rendimentos desde que os parâmetros de reação sejam otimizados. A sonoquímica mostrou-se potencialmente promissora para obtenção de elevadas conversões em curtos intervalos de tempo. / In this work ethyl esters of babassu oil were synthesized by alkaline catalysis in homogeneous medium. The experimental design was used as a tool for optimization of the transesterification reaction and also in identifying key factors influencing the conversion into ethyl esters. The transesterification reactions were performed using two methods of process - the traditional mechanical agitation and agitation promoted by sound waves. The nuclear magnetic resonance spectroscopy was used to quantify the conversion of all reactions of transesterification and thermogravimetric analysis was used to determine the purity of ethyl esters and the main byproduct of the reaction - the glycerol. Taguchi orthogonal arrays were used to develop this study. The independent factors evaluated in the transesterification traditional were: molar ratio ethanol / oil, temperature, stirring speed, weight ratio catalyst / oil, time and the types of most commonly used catalysts (NaOH and KOH). The classical experiments involving the transesterification were performed under nitrogen atmosphere and also under normal atmosphere. With the sonochemical method were evaluated the following factors: molar ratio, time, weight ratio catalyst / oil and type of catalyst. The experiment showed that the main factor influencing the conversion into ethyl esters in both methods is the molar ratio. The best conversion results were obtained with twice the stoichiometric quantity. Also noteworthy in the traditional alkaline transesterification is the influence of interactions between temperature and time, showing that the best conversions are obtained with temperatures close to ambient (30°C) in 60 minutes. According to the model obtained by the experimental design, conversions above 99% are obtained when the stoichiometric ratio is set at 6:1, with 1.0% KOH, under stirring at 400 rpm. The influence of nitrogen atmosphere was less significant for the reaction and similar conversions were obtained with normal atmosphere. Alkaline transesterification assisted by sound waves produced the best results with respect to time of reaction and phase separation of glycerin and ethyl esters. The experimental model showed that conversions above 99% can be obtained in 10 minutes by adjusting the independent variables in the following values: in the stoichiometric ratio 6:1 with 1.0% KOH. In both methods the KOH catalyst was superior to NaOH, influence also noted during the purification steps. Experimentally it was found that the formation of emulsions and gels are more frequent with the use of the sodium hydroxide catalyst. The strategy for purification of ethyl esters adopted was the use of a solvent (hexane) and washing with HCl 0.1 mol.L- 1 that was optimized for 12.5% solution by weight of esters obtained, collected just after phase separation. The mass yield obtained with the experimental model, after washing procedures mentioned, was 94.59%. The study showed that the process of obtaining babassu biodiesel has good yields since the reaction parameters are optimized. The sonochemical proved to be potentially promising for achieving high yields in short time, which might be an excellent route for production aiming to meet the high market demands.

CAPES / As emissões de gases de efeito estufa (GEE) vêm gerando graves mudanças no clima mundial. Uma das soluções propostas para mitigar o problema é a substituição dos combustíveis fósseis por biocombustíveis. A eficácia dessa medida tem sido questionada, tendo em vista as possíveis consequências indiretas da produção agrícola. A Avaliação Consequencial do Ciclo de Vida é um método de avaliação ambiental de produtos que inclui efeitos indiretos. Diante disso, o objetivo do presente trabalho é aplicar o método para obtenção de um inventário do uso agrícola do solo necessário para incrementar a produção de óleo vegetal visando atender a mudança na demanda de biodiesel no Brasil prevista para o período 2010-2030. Das matérias-primas consideradas (soja, amendoim, algodão, dendê, girassol e canola), o estudo mostra que o óleo de dendê é a matéria-prima marginal e apenas 5% da área potencial para plantio de dendê seria utilizada para atender ao incremento na demanda de biodiesel. A área necessária diretamente pelo dendê seria de 2,1 milhões de hectares na região Norte do Brasil. A torta de amêndoa, co-produto dependente do processo multifuncional do dendê, pode substituir o farelo de soja usado como ração, evitando o plantio de 0,6 milhões de hectares de soja. Assim, o inventário final do uso do solo é um incremento 1,5 milhões de hectares para produção agrícola na região Norte do Brasil. Foram desenvolvidos cenários alternativos: produtividade do dendê constante, mudança no horizonte temporal (2010-2020) e mudança na taxa de crescimento do co-produto determinante. Não houve alteração no resultado do estudo para os cenários considerados. / Greenhouse gas emission has several negative consequences on worldwide climate. Biofuels have been considered one of the solutions to mitigate this problem by substitution of fossil fuel. However, indirect effects should be included in order to produce more reliable results in environmental assessment. In this context, Consequential Life Cycle Assessment is a method that can fill this gap. The objective of this work is to use the method to obtain the agricultural land use inventory to meet the biodiesel demand change in Brazil, considering the period 2010-2030. Only the main feedstock were included (soybean, peanut, cottonseed, palm, sunflower and canola). From these, the study found the palm oil as the marginal one. Around 5% of the potential area for palm would be used to meet the biodiesel demand change. The increased area would be 2,1 million hectares in North region of Brazil. The palm meal, which is a dependent co-product from multifunctional process, can substitute soybean meal as animal feed. The substitution avoids 0,6 million hectares of soybean in North region. Finally, the net land use inventory is 1,5 million hectares in North region of Brazil. Three alternative cenarios were developed: palm productivity unchanged, a different time horizon (2010-2020) and a different increasing rate for the determinant co-product. The same result was found for all cenarios.

CNPq; FAPESB / O uso de combustíveis adulterados acarreta danos aos veículos, desgaste de peças, aumento do consumo de combustível, bem como da emissão de material particulado e de gases de exaustão. Os métodos usados para determinação da adulteração do diesel, em geral, não são rápidos, incluem diversas etapas de preparação de amostras, apresentam alto custo de análises e requerem equipamentos complexos com necessidades constantes de calibração e aferição. Além de demandar tempo para coleta e logística das amostras. Com o propósito de avaliar possíveis adulterações de óleo diesel, com óleo vegetal in natura ou residual, em vez de biodiesel, foi usada a espectrofluorimetria como técnica analítica para este fim. Inicialmente foram preparadas misturas individuais de óleo diesel (S1800), contendo 2, 4, 6, 8, 10, 15 e 20 % de óleo e de biodiesel de soja, de canola e residual de fritura. Esses combustíveis foram analisados por Infravermelho e por espectrofluorimetria, usando espectrofluorímetro da marca Varian e da marca Quimis (protótipo), que utiliza LEDs como fontes de luz de excitação ao invés de lâmpada de xenônio. Apenas com os espectros resultantes dessas análises não se obteve diferenciação entre as amostras desejadas, tornando necessário o uso da análise de componentes principais (PCA). Com base na PCA realizada a partir dos resultados obtidos no protótipo, foram diferenciadas com nitidez diesel de biodiesel ou de óleo vegetal, bem como, discriminadas as misturas de diesel/óleo e diesel/biodiesel de soja e de fritura. Já os resultados obtidos no Varian apresentaram distinção nítida apenas para as misturas contendo óleo e biodiesel de fritura. Os resultados do Infravermelho apresentaram notável diferenciação entre as misturas diesel/biodiesel e diesel/óleo para todas as amostras na região de 1700 a 1800 cm-¹. No entanto, esta técnica não foi efetiva em distinguir biodiesel e/ou óleo vegetal adicionado ao diesel, sem aplicação da PCA. Por outro lado, com o propósito de evidenciar sinais específicos de fluorescência nos combustíveis em questão, como por exemplo, a presença de sinais de clorofila nos óleos vegetais e/ou monoésteres, foi utilizada substâncias (aditivos), como a Floroglucina, Fluoresceína, Stains All, p-Anisaldeído, Dimetilaminobenzaldeído, Sudan III, Rodamina B e Nile, Red. As quais foram adicionadas às amostras puras de diesel, óleo vegetal e biodiesel. As amostras foram analisadas em espectrofluorímetro Varian, onde se verificou que o Sudan III foi o único a apresentar resultado eficaz, nas condições testadas. Usando esse composto a fluorescência da clorofila presente em óleos e monoésteres foi realçada (675 nm), inclusive no óleo e biodiesel de fritura. Estes resultados possibilitaram a discriminação de diesel, óleo vegetal e biodiesel, bem como, a caracterização rápida da adição de óleo vegetal in natura ou residual ao diesel. / The use of adulterated fuels causes damage in vehicles, wear parts, increase in fuel consumption, as well as emission of particulate material and exhaust gas. The methods used for determination of diesel adulteration, in general, are not fast, they include various stages of sample preparation, at high cost and require complex equipment that needs constant calibration and measurement, besides involving time consuming to collect and logistics of samples. In order to evaluate possible adulteration of diesel with fresh vegetable oil or waste, rather than biodiesel, spectrofluorimetry was used as analytical technique for this purpose. Initially, Individual mixtures of diesel (S1800) were prepared containing 2, 4, 6, 8, 10, 15 and 20 % of oil and soybean biodiesel, canola and residual frying oil. These fuels were analyzed by Infrared and spectrofluorimetry, using spectrofluorimeter from brands Varian and Quimis (prototype), which use LEDs as excitation light source instead of the xenon lamp. Only with the spectra resulting from this analysis any distinction was obtained among the desired samples, making necessary the usage of the principal component analysis (PCA). Based on the PCA carried out from the results obtained in the prototype, it was clearly distinguished diesel from biodiesel or vegetable oil, as well as, separated mixtures of diesel/oil and diesel/biodiesel of soybean and frying. The results obtained from Varian showed clear distinction for mixtures containing oil and biodiesel frying only. The infrared results showed remarkable difference between mixtures of diesel/oil and diesel/biodiesel for all the samples in the region 1700-1800 cm-¹. However, this technique was not effective in distinguishing biodiesel and/or vegetable oil added to diesel, without application of the PCA. Moreover, for the purpose of putting evidence in specific fluorescence signals in fuels, for example, the presence of chlorophyll signals in vegetable oils and / or monoesters,some substances (additives) were used, such as Phoroglucine, Fluorescein, Stains All, p-anisaldehyde, Dimethylaminobenzaldehyde, Sudan III, Nile Red and Rhodamine B. Which were added to samples of pure diesel, vegetable oil and biodiesel. The samples were analyzed in Varian spectrofluorimeter, where it was found that the Sudan III was the only one to show effective results under the conditions tested. Using this compound, the fluorescence of chlorophyll present in oils and monoesters is highlighted (675 nm), including the frying oil and biodiesel. These results allowed discrimination of diesel, vegetable oil and biodiesel, as well as the rapid characterization of fresh vegetable oil addition or residual to diesel. / 5000

CAPES / As emissões de gases de efeito estufa (GEE) vêm gerando graves mudanças no clima mundial. Uma das soluções propostas para mitigar o problema é a substituição dos combustíveis fósseis por biocombustíveis. A eficácia dessa medida tem sido questionada, tendo em vista as possíveis consequências indiretas da produção agrícola. A Avaliação Consequencial do Ciclo de Vida é um método de avaliação ambiental de produtos que inclui efeitos indiretos. Diante disso, o objetivo do presente trabalho é aplicar o método para obtenção de um inventário do uso agrícola do solo necessário para incrementar a produção de óleo vegetal visando atender a mudança na demanda de biodiesel no Brasil prevista para o período 2010-2030. Das matérias-primas consideradas (soja, amendoim, algodão, dendê, girassol e canola), o estudo mostra que o óleo de dendê é a matéria-prima marginal e apenas 5% da área potencial para plantio de dendê seria utilizada para atender ao incremento na demanda de biodiesel. A área necessária diretamente pelo dendê seria de 2,1 milhões de hectares na região Norte do Brasil. A torta de amêndoa, co-produto dependente do processo multifuncional do dendê, pode substituir o farelo de soja usado como ração, evitando o plantio de 0,6 milhões de hectares de soja. Assim, o inventário final do uso do solo é um incremento 1,5 milhões de hectares para produção agrícola na região Norte do Brasil. Foram desenvolvidos cenários alternativos: produtividade do dendê constante, mudança no horizonte temporal (2010-2020) e mudança na taxa de crescimento do co-produto determinante. Não houve alteração no resultado do estudo para os cenários considerados. / Greenhouse gas emission has several negative consequences on worldwide climate. Biofuels have been considered one of the solutions to mitigate this problem by substitution of fossil fuel. However, indirect effects should be included in order to produce more reliable results in environmental assessment. In this context, Consequential Life Cycle Assessment is a method that can fill this gap. The objective of this work is to use the method to obtain the agricultural land use inventory to meet the biodiesel demand change in Brazil, considering the period 2010-2030. Only the main feedstock were included (soybean, peanut, cottonseed, palm, sunflower and canola). From these, the study found the palm oil as the marginal one. Around 5% of the potential area for palm would be used to meet the biodiesel demand change. The increased area would be 2,1 million hectares in North region of Brazil. The palm meal, which is a dependent co-product from multifunctional process, can substitute soybean meal as animal feed. The substitution avoids 0,6 million hectares of soybean in North region. Finally, the net land use inventory is 1,5 million hectares in North region of Brazil. Three alternative cenarios were developed: palm productivity unchanged, a different time horizon (2010-2020) and a different increasing rate for the determinant co-product. The same result was found for all cenarios.

Bien que thermodynamiquement et cinétiquement stable, le dioxyde de carbone est une molécule qui peut être convertie en carbonates cycliques à cinq ou six atomes respectivement au départ d’époxydes ou d’oxétanes moyennant l’utilisation d’un catalyseur approprié. Ces carbonates cycliques sont utilisés comme solvants verts, électrolytes pour les batteries au lithium ou comme intermédiaires pour la synthèse de polymères. Cependant, les performances catalytiques doivent être améliorées en particulier pour lecouplage du CO2 avec les huiles végétales époxydées ou les oxétanes. Dans ce contexte, nous avons développé un nouveau catalyseur homogène bicomposant organique composé d’un sel d’ammonium jouant le rôle de catalyseur et d’un co-catalyseur fluoré simple ou double donneur de liaison hydrogène. Dans un premier temps, l’efficacité de ces nouveaux catalyseurs a été évaluée et optimisée pour le couplage entre un époxyde terminal et le CO2 via des études cinétiques par spectroscopie FTIR ou Raman in-situ sous pression. Ces études ont démontré que l’utilisation combinée de sels d’ammonium et d’alcools fluorés induit un effet synergique permettant la fixation rapide et sélective du CO2 sur les époxydes modèles et les huiles végétales époxydées dans des conditions douces et sans solvant. L’utilisation de cette plateforme catalytique performante a ensuite été exploitée pour la synthèse d’oligocarbonates hydroxyles téléchéliques au départ d’oxétanes nettement moins réactifs que les époxydes. Ces oligocarbonates ont finalement été valorisés pour la synthèse de polyuréthanes CO2-sourcés par extension de chaines en présence de diisocyanates. En complément de ces travaux, une compréhension fine des mécanismes réactionnels a été réalisée via calculs DFT qui ont mis en évidence que l’efficacité catalytique de ces catalyseurs était liée à la stabilisation multiple des intermédiaires et états de transition par liaisons hydrogènes. A ce jour, via une étude comparative, nous avons mis en évidence que ce système catalytique bicomposant constitue un des catalyseurs organiques les plus performants pour le couplage du CO2 et d’époxydes et le seul système organique permettant la conversion d’oxétanes en synthons d’intérêt. / Although it is a thermodynamically and kinetically stable molecule, carbon dioxide can beconverted into five- and six-membered cyclic carbonates by coupling with epoxides or oxetanes, respectively, using appropriate catalysts. Cyclic carbonates are used as green solvents, electrolytes for Liion batteries or intermediates for the synthesis of polymers. However, the catalytic performance must be further enhanced in particular for the coupling of CO2 with epoxidized vegetable oils or oxetanes. In this context, we developed a new highly efficient bicomponent homogeneous organocatalyst composed of anammonium salt as the catalyst and fluorinated single or double hydrogen bond donors as co-catalysts. First,a screening of onium-based catalysts and hydrogen-bond donors was performed. Performances of thecatalysts and optimization of the reaction was realized through detailed kinetics studies using in-situ FTIR/Raman spectroscopy under pressure. We demonstrated that fluorinated alcohols showed unexpected co-catalytic activity due to synergisms between the onium salt and fluorinated co-catalysts enabling the fast and selective addition of CO2 on to model epoxides and epoxidized vegetable oils under solvent-free and mild experimental conditions. The use of this powerful dual catalyst was then extended to the first organocatalytic coupling of CO2 with less reactive oxetanes to produce hydroxyl telechelic oligocarbonates that were used asprecursor of CO2-based polyurethanes by chain-extension with a diisocyanate. In addition, a fine comprehension of the mechanisms was investigated by DFT calculations highlighting that the co-catalytic performance of the onium salt/fluorinated alcohol binary catalyst arose from the strong stabilization of the intermediates and transitions states by hydrogen-bonding. To date, through comparative studies, we evidenced that this new catalyst is one

Cette étude a porté sur le développement de procédés continus performants de production d’esters à partir de l’huile de tournesol hautement oléique vierge ou raffinée en réacteurs enzymatiques à lit fixe, très productifs et stables dans le temps. Un procédé de transestérification continue en réacteur à lit fixe utilisant Novozyme 435 (lipase B de candida antarctica immobilisée sur Lewatit VP OC 1600), biocatalyseur non régio-spécifique, a été optimisé pour transformer de l’huile vierge de tournesol hautement oléique en esters butyliques. Les phénomènes de partition des composés polaires (phospholipides présents initialement dans l’huile, du glycérol co-produits etc.) entre milieu réactionnel et support enzymatique ont été gérés grâce à l’utilisation de tert-butanol, un solvant polaire. Les conditions assurant le meilleur compromis entre stabilité, productivité et rendements de production d’esters ont été obtenues pour une concentration initiale en huile de 500mM et un rapport molaire entre substrats de 5. De telles conditions permettent une productivité de 13,8 tonnes.an-1.kg de Novozyme 435-1. Le réacteur ainsi dimensionné s’est avéré stable pendant 50 jours consécutifs sans aucune perte d’activité, permettant de minimiser le coût élevé de l’enzyme. L’originalité du procédé est l’utilisation d’huiles vierges contenant des antioxydants naturels (phospholipides, tocophérols etc.). Nous avons démontré que ces composés mineurs sont préservés au cours du procédé de transestérification. Cela confère aux esters formés de remarquables propriétés de résistances à l’oxydation.La pertinence économique du procédé a été améliorée grâce au développement d’un nouveau biocatalyseur sur support hydrophobe (l’Accurel MP) permettant d’éviter toute adsorption de composés polaires. Une analyse économique du procédé (maximisation de la valeur nette actualisée) a permis de rationaliser les conditions optimales d’immobilisation. Une économie de l’ordre de 50% sur les coûts générés tout au long du temps de vie du procédé a pu ainsi être obtenue. En conditions de transestérification continue, aucune différence dans le profil de produits par rapport à Novozyme 435 n’a été observée. Finalement, une alternative à la transestérification directe de l‘huile a été envisagée. Une première phase d’hydrolyse de l’huile est suivie d’un procédé de récupération des acides gras qui sont dans un second temps estérifiés enzymatiquement. Pour réaliser cette dernière étape, le meilleur système réactionnel s’est avéré être le milieu sans solvant. Un réacteur continu d’estérification de l’acide oléique avec l’isobutanol a été optimisé. Cela a permis un réacteur stable pendant 54 jours consécutifs et respectant les critères des biotechnologies blanches. Une productivité annuelle de 126 tonnes.kg de Novozyme 435-1 a été atteinte. Cela représente une amélioration de la productivité d’un facteur 9,2 par rapport au procédé de transestérification développée précédemment / This work focused on the development of efficient continuous processes for the production of esters from crude or refined high oleic sunflower oil with enzymatic packed bed reactor presenting high levels of productivity and stability. A process of continuous transesterification in packed bed reactor using Novozyme 435 (lipase B from Candida antarctica immobilized onto Lewatit VP OC 1600), a non-specific biocatalyst, was optimized to transformation of high-oleic sunflower oil into butylic esters. The phenomena of partition of polar compounds (phospholipids found in crude oils, produced glycerol etc.) between the reaction medium and the enzymatic support were managed using tert-butanol, a polar solvent. The conditions that enabled the best compromise between stability, productivity and production yields were obtained with an initial oil concentration of 500 mM and a molar ratio between co-substrates of 5. Such conditions enabled a productivity of 13.8 tons.kg-1.kg of Novozyme 435-1 to be reached. The reactor exhibited great stability for 50 consecutive days without any loss of activity. That enabled to minimize the high costs of the enzyme. The novelty of the process was the use of crude oils, containing high levels of natural antioxidants (phospholipids, tocopherols etc.). We demonstrated that these minor components of oils were preserved during the transesterification process. It conferred the synthesized esters some remarkable properties of oxidative resistance.The economic relevance of the process was improved thanks to the development of a new biocatalyst onto a very hydrophobic support (Accurel MP) in order to avoid any adsorptions of polar compounds. An economic analysis (maximisation of the net present value) enabled to rationalize the optimal immobilisation conditions. Over the whole process, it enabled a 50% saving on the global expenses.__ In continuous transesterification conditions, no difference in the product profile was noticed between the new biocatalyst and Novozyme 435.Finally, an alternative to direct transesterification of oil was considered. A first stage of oil hydrolysis is followed by a process of fatty acid recovery and a stage of enzymatic esterification into esters. In order to realize/complete this last stage, the best reaction system was a solvent-free medium. A continuous reactor for the esterification of oleic acid with isobutanol was optimized. It enabled a reactor stable/a stable reactor for 54 consecutive days, respecting the conditions of white biotechnologies. An annual productivity of 126 tons.year-1.kg of Novozyme 435-1 was reached. That represented a productivity improvement by a factor of 9.2 in comparison with the transesterification process.

Par rapport aux ressources énergétiques fossiles combustibles, l’énergie solaire présente des caractéristiques inhérentes à la nature même de la ressource. Ce constat met en évidence la nécessité de système de stockage d’énergie. Ce travail de thèse consiste à étudier un stockage thermique pour une centrale solaire à concentration, ainsi que ses deux composants essentiels : le fluide de transfert et les matériaux de garnissage solides. La compréhension du système de stockage thermocline sur lit de roche est réalisée grâce à une approche expérimentale et numérique. Une alternative innovante sur le choix du fluide de transfert consiste à utiliser des huiles végétales. Concernant le garnissage, un matériau à géométrie contrôlée est développé à partir d’un coproduit issu de la sidérurgie. L’originalité de cette association pour le stockage thermique permet d’allier performance, disponibilité des matériaux en quantité industrielle tout en réduisant l’impact environnemental et financier. / Compare to fossil fuel energy resources, solar energy presents the inherent characteristic given by the very nature of the resource (intermittent availability). This observation highlights the need for thermal energy storage system. This doctoral thesis studies thermal energy storage for concentrating solar power plant, as well as its two essential components: the heat transfer fluid and the thermal energy storage materials. The analysis of the thermocline storage system with filler materials is achieved through experimental and numerical approaches. An innovative alternative for the heat transfer fluid consists to use vegetable oils, which offers comparable thermal properties and operating behavior to conventional thermal fluid. Regarding thermal energy storage materials, many natural and recycled materials can be used. A storage material with controlled geometry is developed from steel industry co-product. The originality of this combination for thermal energy storage combines performance, materials availability at industrial scale while reducing environmental and financial impact.

Dans le cadre de cette thèse, les dérivés d’huiles végétales sont utilisés pour la synthèse de bioplastifiants bio-résistants pour le PVC d’une part et la plastification et la réticulation d’un élastomère d’autre part (EPDM). Les huiles ont été choisies comme matières premières renouvelables car elles ont des fonctions esters qui permettent la solubilisation du PVC et des chaines grasses compatibles avec l’EPDM. Les réactions d’ouvertures d’époxydes d’esters gras en di-esters (symétriques et dissymétriques) ont été étudiées et principalement appliquées à la plastification du PVC. L’ouverture des époxydes d’esters gras en éther-esters a aussi été étudiée, principalement pour la plastification de l’EPDM. Les conditions réactionnelles ont été optimisées par l’étude de catalyseurs, homogène (TBACl) et hétérogène (TiO2) pour l’ouverture en hydroxy-ester, et par des résines sulfoniques pour l’ouverture en éther et pour l’estérification des hydroxyles résiduels. Une large variété de réactifs choisis suivant l’application désirée a été utilisée. Le dérivé cyclohexanoate/acétate d’esters méthyliques de colza présente les meilleures propriétés plastifiantes pour le PVC mais il n’est malheureusement pas biorésistant. Les dérivés éther-ester ne sont pas stables thermiquement et ne permettent pas la plastification de l’EPDM. Un dérivé di-insaturé et peu polaire (oléate d’oléyle) a été synthétisé en vue de la plastification et la réticulation de l’EPDM. Plusieurs réactions ont été examinées pour lier l’huile et le polymère (hydrosilylation, ène-réaction et métathèse) mais la réactivité est trop faible pour permettre la réticulation / During this thesis, derivatives of vegetable oils are used to synthesize bio-resistant bio plasticizers for PVC and plasticizer / cross linker for an elastomer (EPDM). The oils possess ester functional groups which allow the solubilization of PVC and fatty chains compatible with EPDM. The reactions of epoxide ring-opening of fatty esters to di esters (symmetrical and asymmetrical) have been studied and applied mainly to the plasticization of PVC. The ring-opening of epoxides of fatty esters to ether-esters has also been studied, primarily for plasticization of EPDM. Optimization of the reaction conditions was carried: homogeneous (TBACl) and heterogeneous (TiO2) catalysts were efficient for the preparation of hydroxy-ester, and sulfonic resins in ether and the esterification of residual hydroxyls. A wide variety of reagents selected according to desired application were used. The derivative cyclohexanoate / acetate rapeseed methyl esters present the best plasticizing properties for PVC but it is unfortunately not bio-resistant. Ether-ester derivatives are not stable thermally and do not allow the plasticization of EPDM. A relatively non-polar di-unsaturated derivative (oleyl oleate) was synthesized for the plasticization and cross linking of EPDM. Several reactions are considered to link the oil and the polymer (hydrosilylation, ene- reaction and metathesis), but the reactivity is too low to allow the cross linking