Aqueous extraction of yellow mustard seed recovers oil in the form of oil-in-water emulsion. In this study, the ternary phase diagram of IPA, oil and water was developed to design an effective oil extraction process of oil-in-water emulsion. A 4-stage extraction process recovered 92.3% of oil from the emulsion into virtually anhydrous IPA-oil miscella. The oil and water separation and IPA usage efficiency was improved by using recycled solvent, but the oil recovery was decreased to 86.0%. The obtained IPA-oil miscella can be used directly in biodiesel production. The use of IPA as a reactant and a co-solvent in transesterification was investigated in this study. Isopropanolysis at 1.2% KOH resulted in 54% ester content in the product. When IPA was used as a co-solvent in methanolysis, the transesterification was drastically improved. The product met the total glycerol limit of the ASTM biodiesel standard within 10 minutes, with over 99% ester content.

Aqueous extraction of yellow mustard seed recovers oil in the form of oil-in-water emulsion. In this study, the ternary phase diagram of IPA, oil and water was developed to design an effective oil extraction process of oil-in-water emulsion. A 4-stage extraction process recovered 92.3% of oil from the emulsion into virtually anhydrous IPA-oil miscella. The oil and water separation and IPA usage efficiency was improved by using recycled solvent, but the oil recovery was decreased to 86.0%. The obtained IPA-oil miscella can be used directly in biodiesel production. The use of IPA as a reactant and a co-solvent in transesterification was investigated in this study. Isopropanolysis at 1.2% KOH resulted in 54% ester content in the product. When IPA was used as a co-solvent in methanolysis, the transesterification was drastically improved. The product met the total glycerol limit of the ASTM biodiesel standard within 10 minutes, with over 99% ester content.

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

No Brasil, a matriz energética nacional obteve um ganho incremental, a partir da institucionalização do Programa Nacional de Produção e Uso do Biodiesel (PNPB), em 2005. Este programa coloca o país na condição de segundo maior produtor e primeiro maior consumidor mundial deste biocombustível, a partir do ano de 2011. Dentre os seus Estados produtores, o Rio Grande do Sul é o que possui a maior concentração industrial de produção de biodiesel, responsável por 32% de todo o biodiesel produzido no país, no ano de 2011. A criação do Selo Combustível Social (SCS), associado ao PNPB, impõe à indústria detentora deste componente, a condição de promotora de inclusão social, uma identidade inédita, no plano internacional. A execução das regras do selo, pela indústria gaúcha, fez com que 53.839 propriedades familiares tivessem a oportunidade de acessar o mercado do biodiesel, pela venda de matéria-prima, com condições diferenciadas, de forma individual ou por meio de cooperativas agropecuárias, no ano de 2011. Esta política tem possibilitado, por um lado, mais renda aos agricultores familiares, às cooperativas e às indústrias de biodiesel, inclusive, melhorias na assistência técnica, na venda de maiores volumes de matéria-prima de origem familiar, na organização da cadeia produtiva e de suprimentos para este mercado, entre outros benefícios. Por outro lado, a conduta do SCS tem implicado uma série de custos de transação, que ocorrem na indústria, nas cooperativas, e, em menor escala, nas organizações sindicais e governamentais, que participam e coordenam respectivamente o programa. Neste sentido, o presente estudo procura entender a institucionalização do PNPB no Brasil e, os direcionadores de custos de transação na contratação de matéria-prima familiar, vinculada ao Selo Combustível Social, no biodiesel gaúcho. O referencial teórico procurou analisar as contribuições da Nova Economia Institucional, onde está situada a Economia dos Custos de Transação, complementado pelas visões sobre Cadeia de Produção e Suprimentos e demais conceitos associados a estes temas. Do ponto de vista metodológico, esta pesquisa ancora-se, sob enfoques, qualitativo e quantitativo, em um caráter de complementaridade. Para tanto, envolveu 35 dirigentes ligados a oito (8) cooperativas agropecuárias e a oito (8) indústrias, além de 10 atores vinculados a organizações governamentais, sindicais e demais experts, no RS. Os resultados conclusivos apontam para a ocorrência de um conjunto de custos de transação no processo de contratação de matéria-prima familiar, os quais foram elencados como custos ex-ante e ex-post aos contratos, sendo os principais e de maior impacto, os custos com o bônus (prêmio) e a Assistência Técnica e Extensão Rural (ATER), vinculados à venda de produção familiar. Ainda, qualifica-se a especificidade dos ativos envolvidos, a freqüência e as incertezas nas transações e os comportamentos de oportunismo e confiança, relacionados à aquisição de matérias-primas familiares, entre indústrias e cooperativas, no Estado do Rio Grande do Sul. Por fim, pondera-se acerca de limitações e sugestões para trabalhos futuros. / In Brazil, the national energy matrix obtained an incremental gain from the institutionalization of the National Program for Production and Use of Biodiesel (PNPB) in 2005. This program places the country as the second largest producer and largest consumer of this first biofuel from the year 2011. Among his producing states, Rio Grande do Sul is what has the greatest concentration of industrial production of biodiesel, accounting for 32% of all biodiesel produced in the year 2011 in the country. The creation of the Social Fuel Seal (SCS), associated with PNPB, requires the owner of this component industry, the condition promotes social inclusion, identity unprecedented internationally. The implementation of the rules of the seal, the industry of the state, made 53,839 family farms had the opportunity to access the biodiesel market, the sale of raw materials, with different conditions, either individually or through agricultural cooperatives in the year, 2011. This policy has allowed, on the one hand, more income to farmers, cooperatives and biodiesel industries, including improvements in technical assistance in selling larger volumes of raw material source familiar organization in the supply chain and supplies to this market, among other benefits. Moreover, the conduct of the SCS has implicated a number of additional costs to the process, called transaction costs, which occur in industry, cooperatives, and to a lesser extent, the unions and government, involved and coordinate respectively the program. In this sense, this study seeks to understand the institutionalization of PNPB in Brazil, and the drivers of transaction costs in hiring feedstock family, linked to the Social Fuel Seal, the gaucho biodiesel. The theoretical sought to analyze the contributions of the New Institutional Economics, which is situated the Transaction Cost Economics, complemented by views of Production and Supply Chain, and other concepts related to these themes. From the methodological point of view, this research is anchored under approaches, qualitative and quantitative, in a complementary character. For both, involved 35 officers linked to eight (8) agricultural cooperatives and eight (8) industries, in addition to 10 players linked to government organizations, unions and other experts in the RS. The conclusive results point to the occurrence of a set of transaction costs in the hiring process feedstock family, which were listed as costs ex-ante and ex-post procurement, the main and largest impact, costs with the bonus (premium) and the Technical Assistance and Rural Extension (ATER), linked to the sale of household production. Still, qualifies the specificity of the assets involved, the frequency and uncertainty in transactions and behaviors of opportunism and trust related to the acquisition of raw materials relatives, between industries and cooperatives in the state of Rio Grande do Sul. Finally, weighs up about limitations and suggestions for future work.

No Brasil, a matriz energética nacional obteve um ganho incremental, a partir da institucionalização do Programa Nacional de Produção e Uso do Biodiesel (PNPB), em 2005. Este programa coloca o país na condição de segundo maior produtor e primeiro maior consumidor mundial deste biocombustível, a partir do ano de 2011. Dentre os seus Estados produtores, o Rio Grande do Sul é o que possui a maior concentração industrial de produção de biodiesel, responsável por 32% de todo o biodiesel produzido no país, no ano de 2011. A criação do Selo Combustível Social (SCS), associado ao PNPB, impõe à indústria detentora deste componente, a condição de promotora de inclusão social, uma identidade inédita, no plano internacional. A execução das regras do selo, pela indústria gaúcha, fez com que 53.839 propriedades familiares tivessem a oportunidade de acessar o mercado do biodiesel, pela venda de matéria-prima, com condições diferenciadas, de forma individual ou por meio de cooperativas agropecuárias, no ano de 2011. Esta política tem possibilitado, por um lado, mais renda aos agricultores familiares, às cooperativas e às indústrias de biodiesel, inclusive, melhorias na assistência técnica, na venda de maiores volumes de matéria-prima de origem familiar, na organização da cadeia produtiva e de suprimentos para este mercado, entre outros benefícios. Por outro lado, a conduta do SCS tem implicado uma série de custos de transação, que ocorrem na indústria, nas cooperativas, e, em menor escala, nas organizações sindicais e governamentais, que participam e coordenam respectivamente o programa. Neste sentido, o presente estudo procura entender a institucionalização do PNPB no Brasil e, os direcionadores de custos de transação na contratação de matéria-prima familiar, vinculada ao Selo Combustível Social, no biodiesel gaúcho. O referencial teórico procurou analisar as contribuições da Nova Economia Institucional, onde está situada a Economia dos Custos de Transação, complementado pelas visões sobre Cadeia de Produção e Suprimentos e demais conceitos associados a estes temas. Do ponto de vista metodológico, esta pesquisa ancora-se, sob enfoques, qualitativo e quantitativo, em um caráter de complementaridade. Para tanto, envolveu 35 dirigentes ligados a oito (8) cooperativas agropecuárias e a oito (8) indústrias, além de 10 atores vinculados a organizações governamentais, sindicais e demais experts, no RS. Os resultados conclusivos apontam para a ocorrência de um conjunto de custos de transação no processo de contratação de matéria-prima familiar, os quais foram elencados como custos ex-ante e ex-post aos contratos, sendo os principais e de maior impacto, os custos com o bônus (prêmio) e a Assistência Técnica e Extensão Rural (ATER), vinculados à venda de produção familiar. Ainda, qualifica-se a especificidade dos ativos envolvidos, a freqüência e as incertezas nas transações e os comportamentos de oportunismo e confiança, relacionados à aquisição de matérias-primas familiares, entre indústrias e cooperativas, no Estado do Rio Grande do Sul. Por fim, pondera-se acerca de limitações e sugestões para trabalhos futuros. / In Brazil, the national energy matrix obtained an incremental gain from the institutionalization of the National Program for Production and Use of Biodiesel (PNPB) in 2005. This program places the country as the second largest producer and largest consumer of this first biofuel from the year 2011. Among his producing states, Rio Grande do Sul is what has the greatest concentration of industrial production of biodiesel, accounting for 32% of all biodiesel produced in the year 2011 in the country. The creation of the Social Fuel Seal (SCS), associated with PNPB, requires the owner of this component industry, the condition promotes social inclusion, identity unprecedented internationally. The implementation of the rules of the seal, the industry of the state, made 53,839 family farms had the opportunity to access the biodiesel market, the sale of raw materials, with different conditions, either individually or through agricultural cooperatives in the year, 2011. This policy has allowed, on the one hand, more income to farmers, cooperatives and biodiesel industries, including improvements in technical assistance in selling larger volumes of raw material source familiar organization in the supply chain and supplies to this market, among other benefits. Moreover, the conduct of the SCS has implicated a number of additional costs to the process, called transaction costs, which occur in industry, cooperatives, and to a lesser extent, the unions and government, involved and coordinate respectively the program. In this sense, this study seeks to understand the institutionalization of PNPB in Brazil, and the drivers of transaction costs in hiring feedstock family, linked to the Social Fuel Seal, the gaucho biodiesel. The theoretical sought to analyze the contributions of the New Institutional Economics, which is situated the Transaction Cost Economics, complemented by views of Production and Supply Chain, and other concepts related to these themes. From the methodological point of view, this research is anchored under approaches, qualitative and quantitative, in a complementary character. For both, involved 35 officers linked to eight (8) agricultural cooperatives and eight (8) industries, in addition to 10 players linked to government organizations, unions and other experts in the RS. The conclusive results point to the occurrence of a set of transaction costs in the hiring process feedstock family, which were listed as costs ex-ante and ex-post procurement, the main and largest impact, costs with the bonus (premium) and the Technical Assistance and Rural Extension (ATER), linked to the sale of household production. Still, qualifies the specificity of the assets involved, the frequency and uncertainty in transactions and behaviors of opportunism and trust related to the acquisition of raw materials relatives, between industries and cooperatives in the state of Rio Grande do Sul. Finally, weighs up about limitations and suggestions for future work.

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-07-26T23:02:54Z No. of bitstreams: 1 ANTÓNIO BENJAMIM MAPOSSA – DISSERTAÇÃO (UAEMa) 2016.pdf: 2373040 bytes, checksum: 0e1d7bfeaa96324742cc4cc77ef98a30 (MD5) / Made available in DSpace on 2018-07-26T23:02:54Z (GMT). No. of bitstreams: 1 ANTÓNIO BENJAMIM MAPOSSA – DISSERTAÇÃO (UAEMa) 2016.pdf: 2373040 bytes, checksum: 0e1d7bfeaa96324742cc4cc77ef98a30 (MD5) Previous issue date: 2016-01-29 / CNPq / A busca por combustíveis limpos tem resultado no desenvolvimento de pesquisas para o beneficiamento de óleos e gorduras, constituídos principalmente por ácidos graxos, com alto poder energético e passível de conversão em ésteres (biodiesel), mediante reações de transesterificação e esterificação com catálise homogênea, heterogênea e enzimática. Os problemas identificados no uso de esterificação com catálise homogênea podem ser minimizados pela esterificação com catálise heterogênea, que busca melhorar a efetividade da produção do biodiesel. Nesse estudo o catalisador heterogêneo desenvolvido é conhecido por ferritas, que são materiais ferrimagnéticos que vem sendo alvo de inúmeras pesquisas científicas em virtude das suas propriedades magnéticas, estabilidade química e térmica. Assim, uma aplicação que tem apresentado promissora para esses materiais é a área de catálise para o biodiesel. Com base neste contexto, esta pesquisa propôs sintetizar nanoferritas Ni1-xZnxFe2O4 (x = 0,0; 0,3; 0,5; 0,7 e 1,0 mol de Zn2+) por reação de combustão e avaliar a influência da substituição dos íons Ni2+por íons Zn2+na estrutura, morfologia e atividade catalítica em reação de esterificação do óleo de soja em presença de metanol. Durante a síntese foi realizada a medição do tempo e temperatura de chama e os produtos resultantes foram caracterizados por difração de raios X, fluorescência de raios X por energia dispersiva, análise textural por adsorção de N2, espectroscopia na região do infravermelho com transformada de Fourier, distribuição granulométrica, densidade, microscopia eletrônica de varredura, análise termogravimétrica e medidas magnéticas. O biodiesel obtido foi analisado por um cromatógrafo a gás. Para esse fim, uma investigação da dependência da morfologia, magnetismo, acidez e atividade catalítica dos nanocatalisadores foram avaliados em função do teor de Zn2+. O aumento do teor de Zn2+causou alterações na estrutura, morfologia, magnetismo, acidez e potencial zeta das amostras, o que contribuiu significativamente para o aumento na conversão catalítica, a qual variou de 49,08% a 99,06%. Os resultados indicam que os nanocatalisadores Ni1-xZnxFe2O4 são materiais promissores para uso em reações de esterificação para produção de biodiesel. / The search for clean fuels has resulted in the development of research for the processing of fats and oils mainly consisting of fatty acids, high-energy power which can be converted to esters (biodiesel) by trans-esterification reactions and esterification with homogeneous catalysis, heterogeneous and enzyme. The problems identified with the use of esterification with homogeneous catalysis can be minimized by esterification with heterogeneous catalysis that seeks to improve the effectiveness of the production of biodiesel. In this study the heterogeneous catalyst developed it is itself known as ferrites which are ferromagnetic materials that have been the subject of numerous scientific studies due to their magnetic properties, chemical and thermal stability. Therefore, an application that has shown promise for these materials is the catalysis for biodiesel. Based on this background the present study concerns itself to synthesize nanoferrites Ni1-xZnxFe2O4 (x = 0.0; 0.3; 0.5; 0.7 and 1.0 mol of Zn2+) by combustion reaction to evaluate the influence of replacement of the Ni2+ions by Zn2+ions in the structure, morphology, and catalytic activity in soybean oil esterification reactions in the presence of methanol. In order to find out what was really happening, during the research the time measurement and flame temperature and the resulting product was characterized by X-ray diffraction, X-ray fluorescence energy dispersive, textural analysis by N2 adsorption spectroscopy in the infrared Fourier transform, particle size distribution, density, scanning electron microscopy, thermal analysis and magnetic measurements. The biodiesel obtained was analysed by a gas chromatograph. It was noticed that, an investigation of the dependence of morphology, magnetism, acidity and catalytic activity of the nanocatalyst were evaluated according to the Zn2+content. The findings reflected that, the increase of the Zn2+content caused changes in the structure, morphology, magnetism, acidity and zeta potential of the samples, which contributed significantly to the increase in the catalytic conversion, which ranged from 49.08% to 99.06%. It was found out that Ni1-xZnxFe2O4 nanocatalysts are promising materials for use in the esterification reaction for biodiesel production.

No Brasil, a matriz energética nacional obteve um ganho incremental, a partir da institucionalização do Programa Nacional de Produção e Uso do Biodiesel (PNPB), em 2005. Este programa coloca o país na condição de segundo maior produtor e primeiro maior consumidor mundial deste biocombustível, a partir do ano de 2011. Dentre os seus Estados produtores, o Rio Grande do Sul é o que possui a maior concentração industrial de produção de biodiesel, responsável por 32% de todo o biodiesel produzido no país, no ano de 2011. A criação do Selo Combustível Social (SCS), associado ao PNPB, impõe à indústria detentora deste componente, a condição de promotora de inclusão social, uma identidade inédita, no plano internacional. A execução das regras do selo, pela indústria gaúcha, fez com que 53.839 propriedades familiares tivessem a oportunidade de acessar o mercado do biodiesel, pela venda de matéria-prima, com condições diferenciadas, de forma individual ou por meio de cooperativas agropecuárias, no ano de 2011. Esta política tem possibilitado, por um lado, mais renda aos agricultores familiares, às cooperativas e às indústrias de biodiesel, inclusive, melhorias na assistência técnica, na venda de maiores volumes de matéria-prima de origem familiar, na organização da cadeia produtiva e de suprimentos para este mercado, entre outros benefícios. Por outro lado, a conduta do SCS tem implicado uma série de custos de transação, que ocorrem na indústria, nas cooperativas, e, em menor escala, nas organizações sindicais e governamentais, que participam e coordenam respectivamente o programa. Neste sentido, o presente estudo procura entender a institucionalização do PNPB no Brasil e, os direcionadores de custos de transação na contratação de matéria-prima familiar, vinculada ao Selo Combustível Social, no biodiesel gaúcho. O referencial teórico procurou analisar as contribuições da Nova Economia Institucional, onde está situada a Economia dos Custos de Transação, complementado pelas visões sobre Cadeia de Produção e Suprimentos e demais conceitos associados a estes temas. Do ponto de vista metodológico, esta pesquisa ancora-se, sob enfoques, qualitativo e quantitativo, em um caráter de complementaridade. Para tanto, envolveu 35 dirigentes ligados a oito (8) cooperativas agropecuárias e a oito (8) indústrias, além de 10 atores vinculados a organizações governamentais, sindicais e demais experts, no RS. Os resultados conclusivos apontam para a ocorrência de um conjunto de custos de transação no processo de contratação de matéria-prima familiar, os quais foram elencados como custos ex-ante e ex-post aos contratos, sendo os principais e de maior impacto, os custos com o bônus (prêmio) e a Assistência Técnica e Extensão Rural (ATER), vinculados à venda de produção familiar. Ainda, qualifica-se a especificidade dos ativos envolvidos, a freqüência e as incertezas nas transações e os comportamentos de oportunismo e confiança, relacionados à aquisição de matérias-primas familiares, entre indústrias e cooperativas, no Estado do Rio Grande do Sul. Por fim, pondera-se acerca de limitações e sugestões para trabalhos futuros. / In Brazil, the national energy matrix obtained an incremental gain from the institutionalization of the National Program for Production and Use of Biodiesel (PNPB) in 2005. This program places the country as the second largest producer and largest consumer of this first biofuel from the year 2011. Among his producing states, Rio Grande do Sul is what has the greatest concentration of industrial production of biodiesel, accounting for 32% of all biodiesel produced in the year 2011 in the country. The creation of the Social Fuel Seal (SCS), associated with PNPB, requires the owner of this component industry, the condition promotes social inclusion, identity unprecedented internationally. The implementation of the rules of the seal, the industry of the state, made 53,839 family farms had the opportunity to access the biodiesel market, the sale of raw materials, with different conditions, either individually or through agricultural cooperatives in the year, 2011. This policy has allowed, on the one hand, more income to farmers, cooperatives and biodiesel industries, including improvements in technical assistance in selling larger volumes of raw material source familiar organization in the supply chain and supplies to this market, among other benefits. Moreover, the conduct of the SCS has implicated a number of additional costs to the process, called transaction costs, which occur in industry, cooperatives, and to a lesser extent, the unions and government, involved and coordinate respectively the program. In this sense, this study seeks to understand the institutionalization of PNPB in Brazil, and the drivers of transaction costs in hiring feedstock family, linked to the Social Fuel Seal, the gaucho biodiesel. The theoretical sought to analyze the contributions of the New Institutional Economics, which is situated the Transaction Cost Economics, complemented by views of Production and Supply Chain, and other concepts related to these themes. From the methodological point of view, this research is anchored under approaches, qualitative and quantitative, in a complementary character. For both, involved 35 officers linked to eight (8) agricultural cooperatives and eight (8) industries, in addition to 10 players linked to government organizations, unions and other experts in the RS. The conclusive results point to the occurrence of a set of transaction costs in the hiring process feedstock family, which were listed as costs ex-ante and ex-post procurement, the main and largest impact, costs with the bonus (premium) and the Technical Assistance and Rural Extension (ATER), linked to the sale of household production. Still, qualifies the specificity of the assets involved, the frequency and uncertainty in transactions and behaviors of opportunism and trust related to the acquisition of raw materials relatives, between industries and cooperatives in the state of Rio Grande do Sul. Finally, weighs up about limitations and suggestions for future work.

Orientadores: Antonio Batocchio, Kamal Abdel Radi Ismail / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-27T15:04:23Z (GMT). No. of bitstreams: 1 Cunha_LeonardoPassosda_M.pdf: 103899044 bytes, checksum: 5bb4276a2715897ba2b90ad7ce7e9214 (MD5) Previous issue date: 2015 / Resumo: Nesta dissertação, procurou-se investigar, conceber e desenvolver um modelo de negócio para a integração da produção de um catalisador em um complexo de produção de biodiesel em território brasileiro. Esta integração permitiu uma produção mais enxuta e limpa, do ponto de vista ambiental. Dentro deste contexto, foi possível avaliar o impacto econômico de um caso real na sociedade brasileira. Para sua realização, foi necessário investigar e conhecer os possíveis modelos de negócio e tecnologias aplicáveis a este tipo de mercado, bem como as principais ferramentas mais aplicáveis de análise econômica. Durante esta investigação, fez-se necessário inicialmente realizar um estudo sobre o mercado de biodiesel brasileiro, seus modelos de negócio, sistemas de produção e aplicabilidades quanto a análise insumo-produto no estudo econômico de um caso real. Uma vez definido um modelo apropriado de produção para um caso real, elaborou-se uma análise experimental dos seus impactos na geração de empregos e na produção (Produto Interno Bruto - PIB) brasileira. Resultados adicionais mostraram a importância do mercado de biodiesel brasileiro e a relevância de um estudo econômico em projetos de engenharia e de negócios. Os principais resultados desta pesquisa apontam para a importância de futuros estudos econômicos em projetos de engenharia e negócios, tanto no mercado de biocombustíveis quanto em outros domínios de conhecimentos análogos / Abstract: In this master's thesis, it was investigated, designed, and developed a business model for production and integration of a catalyst in a complex of biodiesel production in Brazil. This integration allowed a leaner and cleaner production, regarding an environmental point of view. Within this context, it was possible to assess the economic impact of a real case in the Brazilian society. For its realization, it was necessary to investigate and understand possible business models and technologies applicable to this type of market as well as the main applicable tools of economic analysis. During this investigation, it was necessary to initially conduct a study on the Brazilian biodiesel market, their business models, production systems and applicability of the input-output analysis in the economic study of a real case. Once set an appropriate production model to a real case, it was elaborated an experimental analysis of the impacts on job creation and Brazilian production (Gross Domestic Product - GDP). Additional results show the importance of the Brazilian biodiesel market and the relevance of an economic study in engineering and business. The main results of this research point out to the importance of future economic studies in engineering and business, both in the biofuels market as well as in other fields of analogue knowledge / Mestrado / Materiais e Processos de Fabricação / Mestre em Engenharia Mecânica

Évaluation de la durabilité de la production de biodiesel est un sujet d'importance croissante en raison de l'intérêt des gouvernements à effectuer des stratégies de souveraineté, diversifier leur matrice énergétique et mis en place l'impact de la production de biocarburants. Dans ce contexte, ce travail propose un modèle dynamique du système pour évaluer la production de biodiesel dans un contexte spécifique, basé sur une structure hiérarchique générale d'évaluation de la durabilité qui intègre les dimensions du développement durable avec les principes, critères et indicateurs (PC & I). Le cadre de l'évaluation de la production de biodiesel a été défini d'après un ample état de la technique, ce qui entraîne une sélection et analyse de 113 documents, y compris les lois, directives et autres documents normatifs, les documents de politique, les certificats et documents publiés dans des revues. Pour définir le cadre final, une stratégie de validation basée sur les consultations d'experts enquête et une analyse statistique descriptive a été réalisée. Ainsi, un cadre composé de cinq dimensions (sociales, économiques, environnementale, politiques et technologiques), 13 principes et 31 critères a été proposé. Par la suite, un modèle de dynamique de système (DS) a été développé et appliqué pour évaluer la durabilité de la production du biodiesel en Colombie. Au départ, le modèle DS a été utilisé pour simuler la production du biodiesel, compte tenu des conditions actuelles en Colombie, ce qui permet de déterminer le niveau de référence (années 2008-2014). Par la suite, certains indicateurs exogènes du scénario de référence ont été modifiés afin de générer une analyse de sensibilité pour définir plusieurs conditions fondamentales vers la production de biodiesel durable dans le contexte colombien. Une fois l'analyse de sensibilité a été réalisée, on a déterminé les conditions qui favorisent ou découragent la production de biodiesel et, par conséquent, des scénarios optimistes et pessimistes ont été proposées. Les résultats de l'analyse des scénarios peuvent aider les institutions, les décideurs et les autres parte prenants associés à établir les conditions à réaliser pour promouvoir une production durable du biodiesel / Sustainability assessment of biodiesel production is a topic of increasing importance due to the interest of governments to stablish sovereignty strategies, diversify their energy matrix and set up the impact of biofuels production. In this context, this work proposes a system dynamic model to assess biodiesel production in a specific context, based on a general hierarchical structure of sustainability assessment that integrates dimensions of sustainable development with principles, criteria and indicators (PC&I). The assessment framework of biodiesel production was defined based on a comprehensive state of the art, resulting in a selection and analysis of 113 documents, including laws, directives and other normative documents, policy documents, certificates and papers published in peer-reviewed journals. To define the final framework, a validation strategy based on expert survey consultations and a descriptive statistical analysis was conducted. As a result, a framework composed of five dimensions (social, economic, environmental, political and technological), 13 principles and 31 criteria was proposed. Subsequently, a System Dynamics (SD) model was developed and applied for assess the sustainability biodiesel production in Colombia. Initially, the SD model was used to simulate the biodiesel production considering the current conditions in Colombia, enabling to determine the baseline (years 2008 to 2014). Subsequently, some exogenous indicators of the baseline scenario were modified in order to generate a sensibility analysis to define several fundamental conditions for the sustainable biodiesel production in the Colombian context. Once the sensibility analysis was conducted, the conditions that promote or discourage biodiesel production were determined and, consequently, optimistic and pessimistic scenarios were proposed. The results of the analysis of the scenarios can help institutions, decision-makers and other agents related to establish the conditions to be carried out to promote a sustainable biodiesel production