Desde 1º de janeiro de 2010, como medida do Programa Nacional de Produção e Uso do Biodiesel (PNPB), é obrigatória a adição de 5% de biodiesel (em volume) a todo óleo diesel comercializado no Brasil. Entretanto, apesar da ideia inicial de apoiar o PNPB na produção de biodiesel a partir da agricultura familiar, atualmente a maior parte do biodiesel produzido no país é a partir de óleo de soja, cuja expansão no país tem impactos ambientais significativos. O uso de óleos residuais, por sua vez, apresenta vantagens interessantes. Por outro lado o uso de metanol na reação de transesterificação faz com que o produto final não seja tão renovável como seria se fosse usado o etanol de cana de açúcar. Neste contexto, o objetivo desta dissertação é estudar a viabilidade técnica e os aspectos ambientais do biodiesel etílico de óleos residuais de fritura como combustível alternativo para substituir parte do óleo diesel consumido no setor de transporte brasileiro no âmbito do PNPB. Do ponto de vista técnico, foi possível constatar que o biodiesel etílico, assim como o biodiesel metílico, é um combustível adequado para substituir parte do óleo diesel consumido no setor de transporte brasileiro, pois as suas propriedades como combustível são semelhantes às do óleo diesel mineral. Do ponto de vista do processo de produção, o uso do etanol para a produção de biodiesel apresenta algumas dificuldades técnicas com relação ao uso do metanol, relacionadas, sobretudo, à maior dificuldade na separação de fases entre o biodiesel e o glicerol e à recuperação e purificação do etanol, que forma mistura azeotrópica com a água. Além disso, o uso de etanol eleva o custo de produção do biodiesel quando comparado com o uso do metanol, devido ao preço mais elevado do etanol, do menor rendimento da reação de transesterificação e da maior complexidade do processo. Ambientalmente, o biodiesel etílico apresenta vantagens com relação ao metílico, visto que o etanol é um insumo renovável, menos tóxico do que o metanol e produzido no Brasil em larga escala a partir de processos sustentáveis e eficientes. Apesar dessas vantagens, o PNPB não apresenta medidas especiais de incentivo à produção de biodiesel pela rota etílica, e praticamente todo o biodiesel produzido no país utiliza a rota metílica de produção. O uso de óleos residuais de fritura também se mostra uma alternativa ambientalmente vantajosa para a produção de biodiesel, apesar de não estarem disponíveis em grande escala, tendo em vista a magnitude do consumo de óleo diesel no Brasil, estes óleos constituem uma matéria prima de baixo custo que pode ser utilizada para complementar a produção de biodiesel, oferecendo uma aplicação energética sustentável a um resíduo potencialmente poluidor e que muitas vezes é disposto de forma inadequada no meio ambiente. Entretanto, do ponto de vista técnico, os óleos residuais de fritura constituem uma matéria prima heterogênea, e a presença de alguns compostos resultantes do processo de degradação dos triacilgliceróis pode ocasionar problemas como a formação de depósitos e gomas nos componentes do motor e do sistema de injeção. Do ponto de vista do processo de produção, os elevados teores de ácidos graxos livres presentes nos óleos residuais de fritura podem impedir a sua conversão em biodiesel através do processo convencional de transesterificação com o uso de catalisadores alcalinos, exigindo o uso de tecnologias alternativas como, por exemplo, o uso de catalisadores ácidos ou a hidroesterificação. Adicionalmente, o uso dessa matéria prima em escala comercial ainda enfrenta problemas relacionados à logística de coleta e armazenamento do óleo descartado. / Since January 1, 2010, the addition of 5% biodiesel (by volume) for all diesel fuel sold in Brazil is mandatory by the Brazilian Biodiesel Programme. However, despite the initial idea of supporting biodiesel production from family farms, currently most of the biodiesel produced in the Brazil is derived from soybean oil, whose expansion in the country has significant environmental impacts. The use of residual oils, in turn, has interesting advantages. Moreover, the use of methanol in the transesterification reaction makes the final product not as renewable as it would be using bioethanol from sugar cane. In this context, the aim of this dissertation is to study the technical feasibility and environmental aspects of ethylic biodiesel from waste cooking oils as an alternative fuel to replace part of the diesel oil consumed in the brazilian transportation sector. From the technical point of view, it was found that ethylic biodiesel, like the methylic biodiesel, is a suitable fuel to partially replace the diesel fuel consumed in the transportation sector in Brazil, because its fuel properties are similar to those of fossil diesel .From the point of view of the production process, the use of bioethanol to produce biodiesel presents technical difficulties in comparison with the use of methanol, mainly related to the greater difficulty in separation between the biodiesel phase and the glycerol phase, and the recovery and purification ethanol, which form an azeotropic mixture with water. Furthermore, the use of ethanol increases the cost of production of biodiesel compared to the use of methanol, due to the higher prices of ethanol, the lower yields of the transesterification reaction and the greater complexity of the process. Environmentally, ethylic biodiesel presents advantages over the methylic, since bioethanol is a renewable raw material, is less toxic than methanol and is produced in Brazil in large scale through sustainable and efficient processes. Despite these advantages, the PNPB presents no special measures to encourage the production of biodiesel through the ethylic route, and virtually all biodiesel produced in the country uses the methylic route. The use of waste cooking oils is also an environmentally advantageous alternative for the production of biodiesel, although not available on a large scale in view of the magnitude of the diesel fuel consumption in Brazil, these oils are a matter low cost material that can be used to supplement the production of biodiesel, providing a sustainable energy application to a potentially polluting waste that is often disposed improperly in the environment. However, from the technical point of view, the waste cooking oils are a heterogeneous raw material, and the presence of compounds resulting from the degradation of the triacylglycerol may cause problems as the formation of gum and deposits in the components of the engine and injection system. From the point of view of the production process, the high levels of free fatty acids in the waste cooking oils can inhibit its conversion in biodiesel trough the conventional transesterification process with the use of alkaline catalysts, requiring the use of alternative technologies such as, for example, the use of acid catalysts or the hydroesterification. Additionally, the use of this raw material on a commercial scale is still facing problems related to the logistics of collection and storage of waste oils.

The petroleum fuels are nonrenewable, are finites resources and its combustion produces many pollutants into the atmosphere. So, researches aiming alternative sources of energy have been increased. Vegetable oils seem to be a great alternative to produce biodiesel - a renewable fuel, non-toxic and releases fewer pollutants. The sunflower is a great oilseed for biodiesel production, because it can be planted in northeastern of Brazil during the rainy season. Biodiesel can be obtained by transesterification: reaction between vegetable and/or animal fat with shot chain alcohol in presence of catalyst. The aim of this work is to study the effect of the process variable in the production of biodiesel – agitation speed - and even equipment configuration, as characteristic impeller and presence or absence of chicanery in the reactor. For this, full factorial design 2 ³ was performed a resulting in eight experiments. The biodiesel was produced by the transesterification reaction from refined sunflower oil and anhydrous ethanol, and sodium hydroxide P.A. as catalyst. The following operating conditions were used: temperature of the thermostatic bath maintained at 70 °C; weight of catalyst of 1.5% by weight of oil; ratio between number of moles of oil ans ethanol of 1:10; and reaction time of 30 min. Prior to reaction, was performed to characterize the oil, as well as the characterization of biodiesel obtained after the reaction. It was observed that the presence of baffle contributed to obtain lower yields throughout the reaction. When used impeller 2 (turbine impeller with dimensions greater than those reported in the literature), higher yields were obtained at the beginning of the reaction. The stirring speed of 35o rpm contributed to higher yields were obtained at the beginning of the reaction. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Os combustíveis derivados do petróleo são não-renováveis, são fontes finitas e sua combustão emite muitos poluentes para a atmosfera. Com isso, têm aumentado as pesquisas por fontes alternativas de energia. Os óleos vegetais parecem ser uma ótima alternativa para obtenção de biodiesel - um combustível renovável, não-tóxico e que libera menos poluentes. O girassol é uma oleaginosa com potencial utilização para produção de biodiesel, podendo ser plantada no Nordeste brasileiro no período chuvoso. O biodiesel pode ser obtido através da transesterificação: reação entre gordura vegetal e/ou animal com álcool de cadeia curta, na presença de catalisador. O objetivo do presente trabalho é estudar o efeito da variável de processo na produção do biodiesel – velocidade de agitação - e ainda configuração do equipamento, como: característica do impelidor e presença ou não de chicana no reator. Para isso, foi realizado um planejamento fatorial completo 2³, resultando em 8 experimentos. O biodiesel foi produzido por reação de transesterificação a partir de óleo de girassol refinado e etanol anidro, tendo-se hidróxido de sódio P.A. como catalisador. Foram utilizadas as seguintes condições operacionais: temperatura de reação de 70 ºC; relação entre a massa de catalisador e a massa do óleo de 1,5%; relação entre número de mols óleo/álcool etílico de 1:10; e, tempo total de reação de 30 min. Previamente à reação, foi realizada a caracterização do óleo, bem como, a caracterização do biodiesel obtido após a reação. Foi observado que a presença de chicana contribuiu para a obtenção de menores rendimentos durante toda a reação. Ao ser utilizado o impelidor 2 (impelidor tipo turbina com dimensões maiores que aquelas citadas na literatura) foram obtidos rendimentos mais elevados no início da reação. A velocidade de agitação de 350 rpm contribuiu para que fossem obtidos maiores rendimentos no início da reação.

The reversion of weather alterations constitutes one of the main challenges in conjunction faced by human societies worldwide. Its facing has developed the transition from fossil energetic matrixes to renewable ones and contributed to global warming be treated as a theme of geopolitics security and a human and feeding matter. Some countries have had expectations to become the most supreme nations from biomass energetic production in the world scene. In Brazil, the dominance of strategic knowledge, the use of advanced techniques and the availability of natural resources are good advantages to be in charge of energetic integration competition in a remarkable geopolitics position. The national Biodiesel Production and Usage Program (PNPB) since 2005 has been an ambitious bet to conciliate economical, social and environment agendas to face such matters. However, the lack of clearness of methods to avoid environment resources pressure, the growing of country conflicts, the food security and the phenomenon of desterritorialization have become limitations, as national or local questions, the program accomplishes its established directions. In Sergipe State, there´s the worry with the sustentability of bioenergetic production, the absence of data of obtained results up to the moment, suggesting deficiency in supervision and evaluation of its actions. This view contributes in order to take a look at the suggested institutional arranged government model on a empirical way of the Sergipe Biodiesel Program (Probiose). In this direction, the chosen main aim social sustentability and also the environment, economical and institutional matters of the program, in the questions of sustentability. The told evaluation was made by the formulation of a system of indicators (SiaspBio) since which biogrames were created. The reading of the graphic models revealed that is Sergipe´s study the growing of sunflowers hasn`t had impact on incomes of familiar farming or on life quality. The analysis was made under a systematic focus. / A reversão das alterações climáticas se constitui um dos principais desafios conjuntos com os quais se deparam as sociedades humanas em escala planetária. Seu enfrentamento tem impulsionado a transição de matrizes energéticas fósseis pelas renováveis e contribuído para que o aquecimento global passe a ser tratado como tema de segurança geopolítica, humana e alimentar. Alguns países têm nutrido a expectativa de a partir da produção de energia proveniente da biomassa, virem a se destacar no cenário mundial como nação soberana. No caso do Brasil, o domínio de conhecimentos estratégicos, a utilização de técnicas avançadas e a disponibilidade de estoques naturais se revelam como vantagem competitiva para que o país venha assumir o comando da integração energética e passe a ocupar posição de destaque no cenário geopolítico. O Programa Nacional de Produção e Uso de Biodiesel (PNPB), regulamentado desde o ano de 2005, surge como uma pretensiosa aposta de conciliar as agendas econômicas, sociais e ambientais para o enfrentamento de tais questões. Contudo, a falta de clareza em relação às estratégias que serão adotadas para evitar as pressões aos bens ambientais, ao alargamento dos conflitos no meio rural, à segurança alimentar e ao fenômeno da desterritorialização tem se revelado como limitação para que, tanto na esfera nacional como no âmbito local, o Programa cumpra com as diretrizes estabelecidas em seu escopo. No estado de Sergipe, reforça a preocupação com a sustentabilidade da produção bioenergética a ausência de dados que revelem os resultados alcançados até o momento, sugerindo deficiência no monitoramento e na avaliação do Programa. Esse entendimento contribuiu para que se lançasse um olhar empírico sobre o arranjo institucional proposto no modelo de governança do Programa de Biodiesel de Sergipe (Probiose). Nessa direção, elegeu-se como objetivo geral do estudo avaliar o grau de sustentabilidade social, ambiental, econômica e institucional do Programa. A referida avaliação se deu mediante a formulação de um sistema de indicadores (SiaspBio), a partir dos quais foram gerados biogramas. A leitura dos modelos gráficos revelou que no estado de Sergipe o cultivo de girassol não tem refletido na renda dos agricultores familiares, tampouco servido para melhorar a qualidade de vida. A análise foi conduzida sob o enfoque sistêmico.

Submitted by Rosangela Silva (rosangela.silva3@unioeste.br) on 2018-02-21T20:17:45Z No. of bitstreams: 2 Vinicius Thomas Back.pdf: 1753274 bytes, checksum: af1e13acb3f88c2e0ce98d9ed828073a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-02-21T20:17:45Z (GMT). No. of bitstreams: 2 Vinicius Thomas Back.pdf: 1753274 bytes, checksum: af1e13acb3f88c2e0ce98d9ed828073a (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-02-23 / Technological advance requires an increase in the consumption of fuels, mainly of fossil fuels, that besides being exhaustible, are highly harmful to the environment, therefore, there is inherent need of the production of alternative fuels. The present study aims to verify the financial and commercial feasibility of producing biodiesel using the residual chicken oil from slaughterhouses located in the region of Cascavel in the state of Paraná, and to identify the consumer's perception regarding this energy source. A literature review was carried out regarding the themes addressed in the study. To verify financial viability, an adaptation of the model of Bertolini et al. (2012), which was applied to a cooperative located in the region of the city of rattlesnake and for the analysis of consumer perception regarding biodiesel production an adaptation of the VAPERCOM model of Brandalise (2008) was used, applied to the potential users of the Biodiesel, ie owners of diesel-powered vehicles, trucks and vans. The results indicate that there is no financial and commercial feasibility for the cooperative under study to produce biodiesel, because if it uses the fat and oil of viscera to produce biodiesel, it must acquire soybean oil for the production of animal feed, currently Soybean oil is R $ 1.33 more expensive than the value to produce biodiesel. Regarding the analysis of the environmental perception of the potential consumers of biodiesel, it was verified that they have a low concern regarding the characteristics of the life cycle of the fuel they consume. / O avanço tecnológico exige um aumento no consumo de combustíveis, principalmente de combustíveis fósseis, que além de serem esgotáveis, são altamente prejudiciais ao meio ambiente, portanto, existe a inerente necessidade da produção de combustíveis alternativos. O presente estudo tem por objetivo verificar a viabilidade financeira e comercial de produzir biodiesel utilizando o óleo de frango residual de abatedouros localizados na região de Cascavel no estado do Paraná, e identificar a percepção do consumidor em relação a esta fonte de energia. Foi realizada uma revisão de literatura com relação aos temas abordados no estudo. Para verificação da viabilidade financeira foi realizada uma adaptação do modelo de Bertolini et al. (2012), o qual foi aplicado à uma cooperativa localizada na região da cidade de cascavel e para a análise da percepção dos consumidores com relação à produção de biodiesel foi utilizada uma adaptação do modelo VAPERCOM de Brandalise (2008), aplicada aos potenciais usuários do biodiesel, ou seja, proprietários de veículos movidos a diesel, caminhões e caminhonetes. Os resultados, apontam que não existe viabilidade financeira e comercial para a cooperativa em estudo produzir o biodiesel, pois caso a mesma utilize a gordura e óleo de vísceras para produção do biodiesel, a mesma deve adquirir óleo de soja para produção de ração animal, atualmente o óleo de soja é R$ 1,33 mais caro do que o valor para produzir o biodiesel. Com relação à análise da percepção ambiental dos possíveis consumidores do biodiesel, constatou-se que os mesmo possuem fraca preocupação com relação às características do ciclo de vida do combustível que consomem

Submitted by Vicente Alves Pimenta Junior (vicente.pimenta@delphi.com) on 2013-07-11T11:15:40Z No. of bitstreams: 1 Dissertação Vicente_final.pdf: 3937663 bytes, checksum: ce1db3ebf0d9f877a578d1520cb3083c (MD5) / Approved for entry into archive by Suzinei Teles Garcia Garcia (suzinei.garcia@fgv.br) on 2013-07-11T12:47:06Z (GMT) No. of bitstreams: 1 Dissertação Vicente_final.pdf: 3937663 bytes, checksum: ce1db3ebf0d9f877a578d1520cb3083c (MD5) / Made available in DSpace on 2013-07-11T12:57:26Z (GMT). No. of bitstreams: 1 Dissertação Vicente_final.pdf: 3937663 bytes, checksum: ce1db3ebf0d9f877a578d1520cb3083c (MD5) Previous issue date: 2013-06-18 / This study shows the special condition that the standby equipment (equipment that stays for long periods with no running) is submitted to, with biodiesel blends in its interior. It is shown that the validation tests to introduce the biodiesel in Brazil, made under the coordination of the Brazilian Government, were basically constituted of tests that generated mileage, as if the diesel universe were only composed of trucks, vans and buses. The off highway equipment in all forms of presentation and types of use, were not adequately covered in the validation study. The result is that a new fuel was introduced in the country (diesel and biodiesel blend), with the property of degradation a lot higher when compared to pure diesel. This paper presents the quality parameters required for a fuel in order to be considered appropriated; presents the main effects of oxidative degradation; makes a survey of best practices by the manufacturers of engines and diesel vehicles in the world, and finally enquire the fuel systems, engines and vehicles manufacturers in Brazil to understand if they warn their consumers and recommend to them preventive actions that are adapted to Brazilian conditions. In light of the problems observed in Brazil, few new procedures have to be made by the owners in order to have their equipment preserved. Among the recommendation the following stand out: a) the specification of the blend must be rigorously obeyed; b) wherever possible, when it is possible to forecast the stoppage of a machine, its tank has to be emptied; c) When the tank cannot be depleted, the fuel must be used or replaced within 30 days; d) Maybe re introduce, under special condition, pure diesel. This new reality that has been established with the introduction of biodiesel into the Brazilian energy matrix was not properly informed to the population. Emergency power generators that do not follow these recommendations may find problems to work due to fuel degradation in its interior and worst, people may realize this fact when the equipment is needed. / Este estudo apresenta a condição especial a que estão submetidos os equipamentos que ficam por longos períodos sem funcionar, sobretudo os chamados standby com misturas de biodiesel em seu interior. Mostra que os ensaios de validação para a introdução do biodiesel no Brasil, realizados sob o comando do governo brasileiro, foram basicamente constituídos por testes para acúmulo de quilometragem, como se o universo do diesel se resumisse a caminhões, vans e ônibus. Os equipamentos fora de estrada, em todas as suas formas de apresentação e uso, não foram adequadamente cobertos. O resultado é que um novo combustível foi introduzido no país (mescla de diesel mineral com biodiesel), com característica de degradabilidade muito maior do que o diesel puro. Este trabalho apresenta os parâmetros de qualidade necessários para que um combustível seja considerado adequado; apresenta os efeitos principais da degradação oxidativa; faz um levantamento das melhores práticas recomendadas pelos fabricantes de motores e veículos a diesel no mundo e, finalmente, consulta os fabricantes de sistema de injeção, motores e veículos no Brasil para saber se, em função das condições brasileiras, os fabricantes recomendam ações de prevenção distintas de suas matrizes. Em função dos problemas observados no país, algumas medidas adicionais precisam ser tomadas pelos proprietários de equipamentos a diesel para preservá-los. Dentre as medidas, destacam-se as seguintes: a) a especificação da mistura precisa ser obedecida com rigor; b) sempre que possível, quando o equipamento tiver de ser parado de modo previsível, o combustível deve ser esgotado do tanque; c) quando não for possível esgotar o tanque, o combustível tem de ser usado ou substituído em no máximo 30 dias; d) talvez reintroduzir sob condições especiais o diesel puro. Essa realidade nova que se instaurou com a introdução do biodiesel na matriz energética brasileira não foi devidamente informada à comunidade. Geradores de emergência que não seguem esses cuidados podem ter problemas para funcionar devido à degradação do combustível em seu interior e, pior, pode-se vir a descobrir esse fato apenas no momento da necessidade.

This study investigated In situ biodiesel production with supercritical methanol. A micro-algae based feedstock was used and obtained from a local water treatment plant situated just outside of Bethal, South Africa (S 26° 29’ 19.362” E 29° 27’ 11.552”). The wet feedstock was used as harvested with only the excess moisture being removed. Characterisation of the feedstock showed that a wide variety of macro-algae, micro-algae, cyanobacteria and bacterial species were present in the feedstock. The main algal species isolated from the feedstock were Nostoc sp. and Chlamydomonas. The feedstock was found to have a higher heating value (HHV) of 22 MJ.kg-1 and a lower heating value (LHV) of 16.03 MJ.kg-1 with an inherent moisture content of 270g.kg-1 feedstock. The protein and fat content of the feedstock was determined by the Agricultural Research Council (ARC) and found to be 370.1 g.kg-1 and 61.6 g.kg-1 on a moisture free basis respectively. The high protein and fat content gives a theoretical bio-yield of 430 wt%. The low lignin content and high cellulose and hemi-cellulose content indicated that the feedstock would be suitable for energy production. Three experimental sets were performed to determine the effect certain reaction parameters will have on the bio-char, bio-oil and biodiesel yields. The first set entailed hydrothermal liquefaction without the addition of methanol. The second set involved in situ biodiesel production with supercritical methanol, while both supercritical methanol and an acid catalyst were used during in situ biodiesel in the third set. For the first set of experiments the effect of temperature (240°C to 340°C in intervals of 20°C) on the crude bio-oil and bio-char yields were investigated. The highest bio-char yield was found to be 336g g char.kg-1 biomass at 280°C, while the highest crude bio-oil yield was 470.7 g crude bio-oil per kg biomass at 340°C. In the second set of experiments the dry biomass loading was kept constant at 500 g.kg-1 and the temperature varied (240°C to 300°C in intervals of 20°C) along with methanol to dry biomass ratio (1:1, 3:1 and 6:1). The optimum bio-oil yield of 597.1 g bio-oil per kg biomass for this set was found at 500 g.kg-1 biomass loading, 300°C and 3:1 methanol to dry biomass ratio. The highest bio-char yield was found to be 382.6 g bio-char.kg-1 biomass for a 1:1 methanol to dry biomass weight ratio set with 500 g.kg-1 biomass loading at 280°C. An increase in methanol ratio also led to an increase in crude bio-oil yields however the 3:1 methanol to dry biomass mass ratio was found to give the highest bio-oil yield and the purest biodiesel, with less unsaturated FAME. The 6:1 methanol to dry biomass mass ratio did however increase the FAME yield, which tends to show completion of the in situ production of biodiesel. This was also seen in the amount fatty acid methyl esters (FAME) present in the crude bio-oil as the degree of transesterification starts to increase with an increase in methanol. The FAME content was determined using gas chromatography (GC) and gas chromatography coupled to mass spectrometry (GC-MS). During the last set of experiments the temperature (260°C to 300°C in intervals of 20°C) and methanol to dry biomass ratio (1:1, 3:1 and 6:1) was varied at a constant catalyst loading of 1 wt% of the dry biomass. The optimum yields achieved were 627 g crude bio-oil per kg biomass and 376 g bio-char per kg biomass at 300°C and 280°C, respectively. These yields were achieved at 500 g.kg-1 biomass loading and 6:1 methanol ratio. Compared to the experiments where no catalyst was used, a slight increase in the yield was observed with the addition of an acid catalyst. This might be due to the base metals present in the feedstock that can lead to saponification during transesterification without the addition of an acid catalyst. An overall improvement in the extraction of crude bio-oil was observed with in situ production compared to hydrothermal liquefaction. During in situ liquefaction, the bio-oil yield increased by 150 g crude bio-oil per kg biomass higher, while the bio-char yields did not significantly vary at the optimum point of 280°C this finding has a significant value for green coal research. The highest HHV for the bio-char of 27 MJ.kg-1 +/- 0.17 MJ.kg-1 was found at 280°C and a 3:1 methanol ratio. The HHV of the bio-char decreases with an increase in temperature as more of the hydrocarbons are dissolved and form part of the bio-crude make-up. The highest HHV recorded for the crude bio-oil was 42 MJ.kg-1 at a 6:1 methanol ratio, a temperature of 300°C and an acid catalyst. The crude bio-oil HHV, which increased with an increase in temperature, is well within the specifications of the biodiesel standard (SANS, 1935). The highest FAME yield of 39.0 g.kg-1 was obtained using a 6:1 methanol ratio and a temperature of 300°C in the presence of an acid catalyst. The crude oil contained 49.0 g.kg-1 triglycerides with alkenes (C13, C15 and C17) making up the balance. The purest biodiesel yield was achieved at 3:1 methanol to dry biomass mass ratio, as it had the lowest yield unsaturated methyl esters. The overall FAME yield increased with an increase in methanol ratio. The derivatised FAME yields were the highest during hydrothermal liquefaction (55.0 g.kg-1 biomass). The in situ production of biodiesel from waste water clarifier effluent stream was found to be possible. Further investigation is needed into sufficient harvesting methods, including the optimum harvesting location, as this will result in fewer impurities in the stream and subsequent higher yields. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

This study investigated In situ biodiesel production with supercritical methanol. A micro-algae based feedstock was used and obtained from a local water treatment plant situated just outside of Bethal, South Africa (S 26° 29’ 19.362” E 29° 27’ 11.552”). The wet feedstock was used as harvested with only the excess moisture being removed. Characterisation of the feedstock showed that a wide variety of macro-algae, micro-algae, cyanobacteria and bacterial species were present in the feedstock. The main algal species isolated from the feedstock were Nostoc sp. and Chlamydomonas. The feedstock was found to have a higher heating value (HHV) of 22 MJ.kg-1 and a lower heating value (LHV) of 16.03 MJ.kg-1 with an inherent moisture content of 270g.kg-1 feedstock. The protein and fat content of the feedstock was determined by the Agricultural Research Council (ARC) and found to be 370.1 g.kg-1 and 61.6 g.kg-1 on a moisture free basis respectively. The high protein and fat content gives a theoretical bio-yield of 430 wt%. The low lignin content and high cellulose and hemi-cellulose content indicated that the feedstock would be suitable for energy production. Three experimental sets were performed to determine the effect certain reaction parameters will have on the bio-char, bio-oil and biodiesel yields. The first set entailed hydrothermal liquefaction without the addition of methanol. The second set involved in situ biodiesel production with supercritical methanol, while both supercritical methanol and an acid catalyst were used during in situ biodiesel in the third set. For the first set of experiments the effect of temperature (240°C to 340°C in intervals of 20°C) on the crude bio-oil and bio-char yields were investigated. The highest bio-char yield was found to be 336g g char.kg-1 biomass at 280°C, while the highest crude bio-oil yield was 470.7 g crude bio-oil per kg biomass at 340°C. In the second set of experiments the dry biomass loading was kept constant at 500 g.kg-1 and the temperature varied (240°C to 300°C in intervals of 20°C) along with methanol to dry biomass ratio (1:1, 3:1 and 6:1). The optimum bio-oil yield of 597.1 g bio-oil per kg biomass for this set was found at 500 g.kg-1 biomass loading, 300°C and 3:1 methanol to dry biomass ratio. The highest bio-char yield was found to be 382.6 g bio-char.kg-1 biomass for a 1:1 methanol to dry biomass weight ratio set with 500 g.kg-1 biomass loading at 280°C. An increase in methanol ratio also led to an increase in crude bio-oil yields however the 3:1 methanol to dry biomass mass ratio was found to give the highest bio-oil yield and the purest biodiesel, with less unsaturated FAME. The 6:1 methanol to dry biomass mass ratio did however increase the FAME yield, which tends to show completion of the in situ production of biodiesel. This was also seen in the amount fatty acid methyl esters (FAME) present in the crude bio-oil as the degree of transesterification starts to increase with an increase in methanol. The FAME content was determined using gas chromatography (GC) and gas chromatography coupled to mass spectrometry (GC-MS). During the last set of experiments the temperature (260°C to 300°C in intervals of 20°C) and methanol to dry biomass ratio (1:1, 3:1 and 6:1) was varied at a constant catalyst loading of 1 wt% of the dry biomass. The optimum yields achieved were 627 g crude bio-oil per kg biomass and 376 g bio-char per kg biomass at 300°C and 280°C, respectively. These yields were achieved at 500 g.kg-1 biomass loading and 6:1 methanol ratio. Compared to the experiments where no catalyst was used, a slight increase in the yield was observed with the addition of an acid catalyst. This might be due to the base metals present in the feedstock that can lead to saponification during transesterification without the addition of an acid catalyst. An overall improvement in the extraction of crude bio-oil was observed with in situ production compared to hydrothermal liquefaction. During in situ liquefaction, the bio-oil yield increased by 150 g crude bio-oil per kg biomass higher, while the bio-char yields did not significantly vary at the optimum point of 280°C this finding has a significant value for green coal research. The highest HHV for the bio-char of 27 MJ.kg-1 +/- 0.17 MJ.kg-1 was found at 280°C and a 3:1 methanol ratio. The HHV of the bio-char decreases with an increase in temperature as more of the hydrocarbons are dissolved and form part of the bio-crude make-up. The highest HHV recorded for the crude bio-oil was 42 MJ.kg-1 at a 6:1 methanol ratio, a temperature of 300°C and an acid catalyst. The crude bio-oil HHV, which increased with an increase in temperature, is well within the specifications of the biodiesel standard (SANS, 1935). The highest FAME yield of 39.0 g.kg-1 was obtained using a 6:1 methanol ratio and a temperature of 300°C in the presence of an acid catalyst. The crude oil contained 49.0 g.kg-1 triglycerides with alkenes (C13, C15 and C17) making up the balance. The purest biodiesel yield was achieved at 3:1 methanol to dry biomass mass ratio, as it had the lowest yield unsaturated methyl esters. The overall FAME yield increased with an increase in methanol ratio. The derivatised FAME yields were the highest during hydrothermal liquefaction (55.0 g.kg-1 biomass). The in situ production of biodiesel from waste water clarifier effluent stream was found to be possible. Further investigation is needed into sufficient harvesting methods, including the optimum harvesting location, as this will result in fewer impurities in the stream and subsequent higher yields. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2015

Process options to minimise the environmental impact and improve the efficiency of biodiesel production have been investigated. The process options considered include the use of heterogeneous catalysts and used cooking oil (UCO). An esterification pre-treatment reaction was investigated using an ion-exchange resin (Purolite D5082) and an immobilised enzyme (Novozyme 435). Another immobilised enzyme (Amano Lipase PS-IM) was investigated for transesterification. The fresh and used catalysts have been characterised. The catalytic activity of Purolite D5082, Novozyme 435 and Amano Lipase PS-IM have been investigated using a jacketed batch reactor with a reflux condenser. Purolite D5082 has been developed for the esterification pre-treatment process and is not commercially available. Novozyme 435 has been shown to be an effective esterification catalyst for materials with high concentrations of free fatty acid but it has not been investigated for the esterification pre-treatment reaction. It was found that a high conversion was possible with both catalysts. The optimum reaction conditions identified for Purolite D5081 were a temperature of 60 C, a methanol to free fatty acid (FFA) mole ratio of 62:1, a catalyst loading of 5 wt% resulting in a FFAs conversion of 88% after 8 h of reaction time. The optimum conditions identified for Novozyme 435 were a temperature of 50 C, a methanol to FFA mole ratio of 6.2:1 and a catalyst loading of 1 wt% resulting in a conversion of 90% after 8 h of reaction time. These catalysts were compared to previously investigated Purolite D5081 and it was found that the highest conversion of 97% was achieved using Purolite D5081, however there were benefits to using Novozyme 435 because the reaction could be carried out using a much lower mole ratio, at a lower temperature and in much shorter reaction time. During the Novozyme 435 catalysed esterification pre-treatment reactions it was found that the amount of free fatty acid methyl esters (FAME) formed during the reaction was greater than the amount of FFAs consumed. In order to investigate further an ultra-performance liquid chromatography mass spectrometry (UPLC-MS) method was developed to monitor the monogclyeride (MG), diglyceride (DG) and triglyceride (TG) concentrations. This analytical method was used to show that Novozyme 435 would catalyse the esterification of FFAs as well as the transesterification of MGs and DGs typically found in UCO. With the UPLC-MS method it was possible to separate the 1, 2 and 1, 3 DG positional isomers and from this it could be seen that the 1, 3 isomer reacted more readily than the 1, 2 isomer. The results from the UPLC-MS method were combined with a kinetic model to investigate the reaction mechanism. The kinetic model indicated that the reaction progressed with the sequential hydrolysis esterification reactions in parallel with transesterification. Commercially available Amano Lipase PS-IM was investigated for the transesterification reaction. Enzymes are not affected by FFAs and as a result the optimisation was carried out with UCO as the raw material. An optimisation study for the transesterification of UCO with Amano Lipase PS-IM has not previously been reported. The conditions identified for the Amano Lipase PS-IM catalysed transesterification step are addition of 5 vol% water, a temperature of 30 C, a methanol to UCO mole ratio of 3:1 and a catalyst loading of 0.789 wt% resulting in a TG conversion of 43%. An overall enzyme catalysed process was proposed consisting of Amano Lipase PS-IM catalysed transesterification (stage 1) followed by Novozyme 435 catalysed esterification (stage 2). The previously identified optimum conditions identified for each catalyst were used for above stages. It was found that when the oil layer from stage 1 was dried the final TG conversion was 55%.

With its multiple dining halls, close proximity to restaurants, and diesel vehicle fleet, the University of Texas at Austin (UT) has both the supply of raw materials to implement a waste vegetable oil to biodiesel recycling program and the capacity to use it. At face value, implementing a large-scale recycling program provides a source of cheap, low emissions fuel. However, the feasibility of such a program is contingent on its economic cost and environmental impact relative to alternative fuel sources. Thus, this research estimated the greenhouse gas (GHG) inventories and the unit cost associated with 1 megajoule worth of recycled biodiesel derived from three production processes –Alkali Catalyzed, Acid Catalyzed, and Supercritical Methanol–using environmental life cycle assessment and life cycle costing. These GHG inventories and unit costs were then compared to the conventional diesel and oilseed biodiesel sources that make up UT’s current fuel portfolio. This analysis suggested that implementing a recycling program using a Supercritical Methanol biodiesel conversion process would have the lowest combined GHG impact and unit cost, although as an emerging technology, it poses a high investment risk. In general, these findings are encouraging to the success and impact of a large-scale recycling program. / text

El biodiesel es un combustible preparado en base a aceites vegetales, grasas animales, o desperdicios de aceites los cuales se hacen reaccionar con metanol o etanol para convertir las grasas triglicéridos en metil o etil ésteres vía transesterificación. Las características de este combustible lo hacen apropiado para funcionar en motores de ignición por compresión. En la actualidad el biodiesel se plantea como una alternativa o un complemento al diesel para los vehículos pesados, siendo entonces necesario establecer políticas para su producción y utilización en bases a los efectos que pueda tener en los vehículos. La presente investigación tiene como objetivo determinar el efecto de la utilización de distintas mezclas de biodiesel sobre las emisiones de vehículos pesados. Para llevar a cabo la investigación se realizaron mediciones de los niveles de contaminantes críticos: hidrocarburos (HC), óxidos de nitrógeno (NOX), monóxido de carbono (CO), material particulado (MP) y dióxido de carbono (CO2). Estas se efectuaron sobre 2 tipos de camiones (con norma y sin norma de emisiones); con 2 tipos de biodiesel (raps y aceite refrito) y 2 porcentajes de biodiesel en la mezcla (5%, y 10%). Los ensayos se realizaron siguiendo la fase rural y la fase urbana del ciclo transiente de conducción europeo FIGE-ETC, sobre un dinamómetro de chasis para vehículos pesados. Para los dos camiones y los dos tipos de biodiesel, las emisiones de NOX aumentaron entre 4% y 5%, para una mezcla al 10% de biodiesel, siendo este aumento mayor para el biodiesel de aceite refrito. Así mismo, en todos los casos el material particulado presentó reducciones entre un 20% y un 50%. CO presentó reducciones sólo para el camión con norma Euro II, mientras que para el camión sin norma no presentó tendencias definidas. Tanto NOX como MP y CO se comportaron de forma similar a lo reportado en la literatura, mientras que HC ni CO2 mostraron tendencias de cambio en sus emisiones. En conclusión, es posible utilizar una mezcla de diesel hasta con 10% de biodiesel, teniendo únicamente efectos negativos en las emisiones de NOX, las cuales pueden ser tratadas modificando el tiempo de inyección; con efectos positivos en las emisiones de material particulado y en algunos casos en las emisiones de CO; y sin efectos importantes en el resto de los contaminantes.