Produção de biohidrogénio por bactérias a partir de resíduos fermentescíveis

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia Química e Bioquímica

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Obtenção de álcool alílico (PROP-2-EN-1-OL) a partir da glicerina derivada do biodiesel de óleo de mamona

In this work, biodiesel was produced from castor oil that was a byproduct glycerin. The molar ratio between oil and alcohol, as well as the use of (KOH) catalyst to provide the chemical reaction is based on literature. The best results were obtained using 1 mol of castor oil (260g) to 3 moles of methyl alcohol (138g), using 1.0% KOH as catalyst at a temperature of 260 ° C and shaken at 120 rpm. The oil used was commercially available, the process involves the reaction of transesterification of a vegetable oil with methyl alcohol. The product of this reaction is an ester, biodiesel being the main product and the glycerin by-product which has undergone treatment for use as raw material for the production of allyl alcohol. The great advantage of the use of glycerin to obtain allyl alcohol is that its use eliminates the large amount of waste of the biodiesel and various forms of insult to the environment. The reactions for the formation of allyl alcohol was conducted from formic acid and glycerin in a ratio 1/1, at a temperature of 260oC in a heater blanket, being sprayed by a spiral condenser for a period of 2 hours and the product obtained contains mostly the allylic alcohol .. The monitoring of reactions was performed by UV-Visible Spectrophotometer: FTIR Fourier transform, the analysis showed that these changes occur spectrometer indicating the formation of the product allylic alcohol (prop-2-en-1-ol) in the presence of water, This alcohol was appointed Alcohol GL. The absorption bands confirms that the reaction was observed in (υ C = C) 1470 -1600 cm -1 and (υ CO), 3610-3670 attributed to C = C groups and OH respectively. The thermal analysis was carried out in a thermogravimetric analyzer SDT Q600, where the mass and temperature are displayed against time, that allows checking the approximate rate of heating. The innovative methodology developed in the laboratory (LABTAM, UFRN), was able to treat the glycerine produced by transesterification of castor oil and used as raw material for production of allyl alcohol, with a yield of 80%, of alcohol, the same is of great importance in the manufacture of polymers, pharmaceuticals, organic compounds, herbicides, pesticides and other chemicals

Aproveitamento e valorização de resíduos provenientes da produção de Biodiesel

Com o desenvolvimento económico das últimas décadas, a gestão de recursos energéticos é um desafio que a sociedade moderna enfrenta. Assim, actualmente há a necessidade da procura de novas fontes de energia, fontes de energia renováveis. Sendo o biodiesel uma fonte de energia renovável, a sua crescente produção irá trazer um aumento da produção de resíduos, como o glicerol e ácidos gordos. É pois importante reduzir/valorizar estes resíduos de forma a impedir a sua acumulação ao longo do tempo. A valorização destes resíduos é o objectivo principal deste trabalho. A primeira parte consistiu na esterificação de ácidos gordos livres com glicerol, na presença de um catalisador ácido, para a produção de monoglicerídeos. Foram utilizados diferentes tipos de matérias-primas: glicerol (76,3%) e resíduo de ácidos gordos (20,8%), fornecidos pela empresa SOCIPOLE SA, glicerol puro (92,2%) e ácido oleico puro (93,1%). Os catalisadores usados foram o cloreto de zinco comercial e o ácido p-tolueonossulfónico comercial. Não foram efectuadas análises específicas aos monoglicerídeos, o produto foi caracterizado pelo índice de acidez. Aparentemente, a maior conversão de ácidos gordos foi obtida no ensaio de esterificação de ácidos gordos com glicerol, ambos da SOCIPOLE SA. No entanto, este não serviu como termo de comparação com os outros devido à formação de uma fase sólida (polímero). Relativamente aos outros ensaios, com razão molar glicerol/ácidos gordos de 1:3, o melhor resultado foi obtido na reacção de glicerol da SOCIPOLE SA com ácido oleico puro, na presença do catalisador ácido p-toluenossulfónico, à temperatura de 106,3ºC e tempo de reacção de 4h30min, sendo a conversão final de ácido oleico 80,7%. Na segunda parte foi feito o estudo da esterificação de ácidos gordos livres com metanol, na presença de ácido sulfúrico, para a produção de biodiesel utilizando ácidos gordos fornecidos pela empresa SOCIPOLE SA, ácidos gordos derivados dos sabões de um resíduo de glicerol fornecido pelo Laboratório de Tecnologia Química, Professora Doutora Lídia Vasconcelos do ISEP e ácidos gordos derivados dos sabões do glicerol bruto, fornecido pela empresa SOCIPOLE SA. Os ensaios foram efectuados a 65ºC, com uma agitação de 120rpm e uma razão molar ácidos gordos/metanol de 1:3. Verificou-se que o índice de acidez do produto, depois de lavado e seco, diminuía com o tempo de reacção e na generalidade a percentagem de ésteres aumentava, observando-se que a partir das seis horas, a reacção se tornava muito lenta. O estudo da razão ácidos gordos/metanol, não permitiu tirar conclusões. O melhor resultado obtido correspondeu a um produto com 96,2% de ésteres metílicos e 8,54mgKOH/gamostra de índice de acidez, pelo que não pode ainda ser designado de biodiesel.

Utilização de resíduos do sector avícola para a produção de biodiesel

Dissertação para obtenção do Grau de Mestre em Energia e Bioenergia

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Estudo térmico dos resíduos gerados da destilação atmosférica das misturas diesel/biodiesel de dendê

The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 °C.min-1, nitrogen atmosphere and heating to 600 ° C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance

Utilização do óleo extraído dos resíduos da filetagem de tilápia (Oreochromis niloticus) para produção de biodiesel

The aims of this study were to evaluate the potential of the oil extracted from tilapia residues filleting for biodiesel production, select the one that presents the greatest potential for this purpose and characterize the obtained biodiesel to be neutralized or refined and analyzed according to their physicochemical and yield characteristics. For this, the crude heads, carcasses and offal which have undergone physical and chemical analysis and yield were extracted. For this, the crude oil was extracted from the heads, carcasses and guts, which have passed through physicochemical and yield analysis.For the statistical analysis, a completely randomized design was used with 3 treatments (head, carcass and viscera) and 5 replications.It was observed significant differences in the oils (P <0.05) being the viscera oil the one that showed higher yield although it presented the worst values for all evaluated indices. For this reason this oil was selected for further studies. In this new stage of the study the treatments were: neutralized crude oil and viscera refined oil with different volumes of NaOH 16%.It was adopted a completely randomized design, with a 2x3 factorial (types of oil x soda volumes) with 3 replications. The analyzed variables were acid value, saponification index, peroxide value and iodine value. It was also evaluated the performance of all the obtained biodiesel. It can be concluded that: among the filleting residues oil of tilapias, the one which is more suitable for biodiesel production, due to its high yield, was the viscera oil. The use of all stages of refining is indispensable, once the obtained index and the yield were greater in the biodiesel refined oil; the produced biodiesel from tilapia’s viscera oil meets the ANP standards and, therefore, it is adequate for use.

Desenvolvimento de biodiesel microemulsionado com reaproveitamento de resíduos de óleos vegetais

Pós-graduação em Engenharia Mecânica - FEG

Produção biológica integrada de hidrogénio e metano a partir de resíduos da indústria do biodiesel

Dissertação de Mestrado Integrado em Engenharia da Energia e do Ambiente

Produção enzimática de biodiesel a partir de resíduos agro-industriais usando a lipase imobilizada de origem microbiana

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica

Avaliação térmica dos resíduos da destilação atmosférica das blendas - biodiesel/diesel

The worldwide concern regarding the use of sustainable energy and preserving the environment are determining factors in the search for resources and alternative sources of energy and therefore fuel less aggressive nature. In response to these difficulties Biodiesel has emerged as a good solution because it is produced from renewable sources, produces burns cleaner and is easily reproducible. This work was synthesized with biodiesel oil, sunflower via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the blends BX (a proportion of biodiesel X = 5, 10, 15 and 20 %). Atmospheric distillation of the analysis, performed in blends with and without BHT were collected residue generated by each sample and performed a study heat from the thermogravimetric analysis at a heating rate of 10 °C*min-1, nitrogen atmosphere and heating to 600 °C. According to the specifications of Resolution N 7/2008 for biodiesel, it was found that the synthesized material was in accordance with the specifications. For blends showed that the samples are in accordance with the Resolution of ANP N 42/2009. From the TG / DTG curves of the samples of biodiesel, blends and waste can be seen that these show a single loss of thermal decomposition concerning constituents present in each sample. The blends without BHT with ratios of 5%, 10% and 15% biodiesel showed a lower amount of waste (1,07%; 1,09% e 1,10%) to mineral diesel (1,15%). Therefore, it is concluded that the addition of biodiesel with diesel mineral can improve some physico-chemical parameters, but also, depending on the added amount, decreasing the amount of waste generated. This fact is of great importance because the carbonaceous residue can cause problems in mechanical equipment and parts for vehicles, causing more frequent maintenance, and this is not desirable

Estudo térmico dos resíduos gerados da destilação atmosférica das misturas diesel/biodiesel de dendê

The growing world demand for energy supplied by fossil fuels, a major contributor to the emission of pollutants into the atmosphere and causing environmental problems, has been encouraging governments and international organizations to reflect and encourage the use of alternative renewable sources. Among these new possibilities deserves attention biodiesel, fuel cleaner and easy to reproduce. The study of new technologies involving that source is necessary. From this context, the paper aims at analyzing the thermal stability by thermogravimetric analysis, of the waste generated from atmospheric distillation of mixtures with ratios of 5, 10, 15 and 20% palm biodiesel in diesel with and without addition of BHT antioxidant. It was synthesized biodiesel through palm oil, via homogeneous catalysis in the presence of KOH, with and without the use of BHT and subsequently added to the diesel common indoor type (S1800) from a gas station BR. The diesel was already added with 5% biodiesel, and thus the proportions used for these blends were subtracted from the existing ratio in diesel fuel, resulting in the following proportions palm oil biodiesel: 0% (B5), 5% (B10), 10 % (B15) and 15% (B20). From atmospheric distillation analysis, performed in mixtures with and without BHT were collected residue generated by each sample and performed a thermal study from the thermogravimetric analysis at a heating rate of 10 °C.min-1, nitrogen atmosphere and heating to 600 ° C. According to the specifications of Resolution No. 7/2008 for biodiesel, it was found that the material was synthesized in accordance with the specifications. For mixtures, it was noted that the samples were in accordance with the ANP Resolution No. 42/2009. Given the TG / DTG curves of the samples of waste mixtures with and without BHT antioxidant was able to observe that they showed a single stage of thermal decomposition attributed to decomposition of heavy hydrocarbons and esters and other heavier constituents of the waste sample weighed. The thermal behavior of residues from atmospheric distillation of mixtures of diesel / biodiesel is very important to understand how this affects the proper functioning of the engine. A large amount of waste can generate a high content of particulate material, coke formation and carbonaceous deposits in engine valves, compromising their performance

Utilização de co-solventes na produção de biodiesel a partir de óleo residual e etanol por catálise enzimática

A constante e sistemática subida de preço dos combustíveis fósseis e as contínuas preocupações com o meio ambiente determinaram a procura de soluções ambientalmente sustentáveis. O biodiesel surge, então, como uma alternativa para essa problemática, bem como uma solução para resíduos líquidos e gordurosos produzidos pelo ser humano. A produção de biodiesel tem sido alvo de extensa atenção nos últimos anos, pois trata-se de um combustível biodegradável e não poluente. A produção de biodiesel pelo processo de transesterificação usando álcoois de cadeia curta e catalisadores químicos, nomeadamente alcalinos, tem sido aceite industrialmente devido à sua elevada conversão. Recentemente, a transesterificação enzimática tem ganho adeptos. No entanto, o custo da enzima permanece uma barreira para a sua aplicação em grande escala. O presente trabalho visa a produção de biodiesel por transesterificação enzimática a partir de óleo residual de origem vegetal. O álcool usado foi o etanol, em substituição do metanol usado convencionalmente na catálise homogénea, pois a atividade da enzima é inibida pela presença deste último. As maiores dificuldades apresentadas na etanólise residem na separação das fases (Glicerol e Biodiesel) após a reação bem como na menor velocidade de reação. Para ajudar a colmatar esta desvantagem foi estudada a influência de dois cosolventes: o hexano e o hexanol, na proporção de 20% (v/v). Após a escolha do co-solvente que permite obter melhor rendimento (o hexano), foi elaborado um planeamento fatorial no qual se estudou a influência de três variáveis na produção de biodiesel por catálise enzimática com etanol e co-solventes: a razão molar óleo/álcool (1:8, 1:6 e 1:4), a quantidade de co-solvente adicionado (30, 20 e 10%, v/v) e o tempo de reação (48, 36 e 24h). A avaliação do processo foi inicialmente seguida pelo rendimento da reação, a fim de identificar as melhores condições, sendo substituída posteriormente pela quantificação do teor de ésteres por cromatografia em fase gasosa. O biodiesel com teor de ésteres mais elevado foi produzido nas condições correspondentes a uma razão molar óleo:álcool de 1:4, com 5g de Lipozyme TL IM como catalisador, 10% co-solvente (hexano, v/v), à temperatura de 35 ºC durante 24h. O rendimento do biodiesel produzido sob estas condições foi de 73,3%, traduzido em 64,7% de teor de ésteres etílicos. Contudo o rendimento mais elevado que se obteve foi de 99,7%, para uma razão óleo/álcool de 1:8, 30% de co-solvente (hexano, v/v), reação durante 48h a 35 ºC, obtendo-se apenas 46,1% de ésteres. Por fim, a qualidade do biodiesel foi ainda avaliada, de acordo com as especificações da norma EN 14214, através das determinações de densidade, viscosidade, ponto de inflamação, teor de água, corrosão ao cobre, índice de acidez, índice de iodo, teor de sódio (Na+) e potássio (K+), CFPP e poder calorífico. Na Europa, os ésteres etílicos não têm, neste momento, norma que os regule quanto à classificação da qualidade de biodiesel. Contudo, o biodiesel produzido foi analisado de acordo com a norma europeia EN14214, norma esta que regula a qualidade dos ésteres metílicos, sendo possível concluir que nenhum dos parâmetros avaliados se encontra em conformidade com a mesma.

Avaliação da influência de antioxidantes na estabilização de biodiesel

O biodiesel é uma fonte de energia renovável, que se pode obter pela transformação dos resíduos domésticos, e é ambientalmente inócuo, e fácil de transportar, pois tem um ponto de fulgor elevado. Atualmente tem-se focado a atenção nos efeitos da oxidação do biodiesel causados pelo contato com o ar ambiente durante o seu armazenamento. Os produtores, fornecedores e consumidores, pretendem garantir que a qualidade do biodiesel e das suas misturas com combustíveis destilados do petróleo, mantém-se durante longos períodos de armazenamento. A maioria dos óleos vegetais e das gorduras animais, usados como matéria – prima, são triacilgliceróis com grupos ácido gordos de cadeia longa (C16 – C18) ligados por ligações éster a uma estrutura de glicerol. O objetivo deste estudo foi avaliar a eficiência do ácido gálhico e seus derivados alquilo ésteres aumentando a resistência relativa à oxidação do ácido linoléico, inibindo a peroxidação ácido gordos de cadeia longa insaturados. Outro objetivo foi estudar a taxa de inibição da auto-oxidação do ácido linoleico. Foi, ainda estudado o efeito que a concentração do antioxidante, tinha na estabilidade do ácido linoleico. No caso do ácido gálhico verificou-se que o aumento para o dobro da concentração do antioxidante utilizada, obtinha-se quase o dobro da taxa de inibição da oxidação do ácido linoleico. A auto-oxidação de ácido linoleico é acompanhada pela formação do seu dieno conjugado, o qual foi medido sua absorvância, durante 7 dias, por espetrofotometria de absorção UV a 234 nm. Uma diminuição da taxa de formação de dieno conjugado, indica o aumento da atividade antioxidante do composto adicionado à micela de ácido linoleico. Os resultados obtidos permitem concluir que de todos os antioxidantes testados o galhato de butilo é o que possibilita uma maior inibição da oxidação do ácido linoleico para as duas concentrações de antioxidantes testadas (0,1 mM e 1mM), obteve-se uma percentagem de inibição do ácido linoleico de 54,0% e 63,6%, respetivamente. O estudo comparativo da estabilização do ácido linoleico com o antioxidante de referência, o butil -hidroxitolueno, mostrou que este composto tem um poder de estabilização inferior a qualquer dos antioxidantes estudados. Os resultados deste estudo demonstraram que a utilização de compostos fenólicos, em especial o galhato de butilo, constitui uma boa alternativa para a estabilização de matrizes lipídicas, nomeadamente de combustíveis como o biodiesel.