In the poultry industry, further processed meat products have the highest share in the market, and because there is a growing demand of food products with enriched amounts of unsaturated fatty acids, the objectives of this research were to assess lipid oxidation development and quality characteristics of chicken meat as affected by dietary fat and vitamin E levels. Broilers were fed during six weeks with diets containing animal/vegetable, lard, palm kernel, soybean, conjugated linoleic acid, flaxseed, or menhaden oil. Each lipid diet was supplemented with either a control (33 or 42 mg/kg) or a supranutritional level (200-400 or 200 mg/kg) of vitamin E. Breast and thigh meat, or skin, were processed, packaged, and refrigerated as raw meat, cooked patties, or cooked sous vide meat. The results showed that the chicken meat fatty acid composition reflected those from the dietary fats. In the meat or skin there was a higher lipid oxidation susceptibility as the proportion of unsaturated fatty acids increased, shown as malonaldehyde values, particularly in the treatments with low supplemented level of vitamin E (P<0.05). The relative lipid oxidative stability of the meat decreased in consecutive order from raw, cooked sous vide, and cooked meat patties. Sous vide cooked meat developed lipid oxidation at a slow rate and showed not to be affected by nonheme iron values. Dietary fat and vitamin E level affected breast meat lightness (L* color space) values (P<0.05), but not muscle pH, Allo-Kramer shear force, or water holding capacity. In conclusion, the increment in the proportion of unsaturated fatty acids increases the susceptibility to lipid oxidation in the meat. Supranutritional supplementation levels of vitamin E are more effective at inhibiting the lipid oxidation development in chicken meat than some current levels used by the poultry industry. Neither dietary fat nor vitamin E level seems to affect the development of pale, soft, and exudative meat condition in chicken meat.

In the poultry industry, further processed meat products have the highest share in the market, and because there is a growing demand of food products with enriched amounts of unsaturated fatty acids, the objectives of this research were to assess lipid oxidation development and quality characteristics of chicken meat as affected by dietary fat and vitamin E levels. Broilers were fed during six weeks with diets containing animal/vegetable, lard, palm kernel, soybean, conjugated linoleic acid, flaxseed, or menhaden oil. Each lipid diet was supplemented with either a control (33 or 42 mg/kg) or a supranutritional level (200-400 or 200 mg/kg) of vitamin E. Breast and thigh meat, or skin, were processed, packaged, and refrigerated as raw meat, cooked patties, or cooked sous vide meat. The results showed that the chicken meat fatty acid composition reflected those from the dietary fats. In the meat or skin there was a higher lipid oxidation susceptibility as the proportion of unsaturated fatty acids increased, shown as malonaldehyde values, particularly in the treatments with low supplemented level of vitamin E (P<0.05). The relative lipid oxidative stability of the meat decreased in consecutive order from raw, cooked sous vide, and cooked meat patties. Sous vide cooked meat developed lipid oxidation at a slow rate and showed not to be affected by nonheme iron values. Dietary fat and vitamin E level affected breast meat lightness (L* color space) values (P<0.05), but not muscle pH, Allo-Kramer shear force, or water holding capacity. In conclusion, the increment in the proportion of unsaturated fatty acids increases the susceptibility to lipid oxidation in the meat. Supranutritional supplementation levels of vitamin E are more effective at inhibiting the lipid oxidation development in chicken meat than some current levels used by the poultry industry. Neither dietary fat nor vitamin E level seems to affect the development of pale, soft, and exudative meat condition in chicken meat.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第21138号 / 農博第2264号 / 新制||農||1057(附属図書館) / 学位論文||H30||N5112(農学部図書室) / 京都大学大学院農学研究科食品生物科学専攻 / (主査)教授 谷 史人, 教授 保川 清, 教授 橋本 渉 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Biodiesel is a renewable and biodegradable fuel that has the possibility to replace conventional diesel fuel and reduce the environmental pollution. Despite its environmental benefits, it has been shown to cause damage to the vehicle engines, due to its oxidative properties. Different metals, such as copper, zinc and aluminium are present in the vehicle fuel system and have been shown to catalyse the oxidation of biodiesel. Several studies have been performed to investigate the interaction between these metals and fuel. However, some reports concluded contradicting results when it comes to the oxidation of biodiesel in contact with aluminium alloys. This project aimed therefore to investigate and create a simple method for comparing the catalytic effect on oxidation for metals, and use this method to evaluate the degradation rate of biodiesel in contact with aluminium alloys. Different heating methods and coating materials were tested using the biodiesel RME to develop the testing procedure. When a test procedure was established, three filter houses made from cast aluminium alloy and three aluminium ingots with different amount of copper were immersed in RME and the stability was evaluated. The results showed that using an oven at 80 °C to investigate the stability provided the most repeatable results, and the spray paint Auto K billack spray Universal appeared to be compatible to use with RME. The inner untreated surface of the fuel filter houses did not seem to increase the oxidation rate of biodiesel. Aluminium alloys with higher copper content degraded RME more than aluminium alloys with little/no copper, if the surface had been treated mechanically, but not to a large extent. This concludes that aluminium alloys may reduce the stability of biodiesel if it contains much copper and if the surface of the alloy has been treated. However, the detected reduction on oxidation stability could depend on other factors, and therefore it is recommended to conduct further experiments on test the aluminium alloys. / Biodiesel är ett förnybart och biologiskt nedbrytbart bränsle som har möjligheten att ersätta konventionell diesel och minska föroreningen av miljön. Trots dess fördelar så har det visats att bränslet skadar motorerna i fordon, vilket beror på dess oxidativa egenskaper. Olika metaller, såsom koppar, zink och aluminium förekommer i fordons bränslesystem, och dessa har påvisats katalysera oxidationen av biodiesel. Flera studier har genomförts där interaktionen mellan de tidigare nämnda metallerna och biodiesel har undersökts. En del av dessa studier har fått motsägelsefulla resultat när det kommer till interaktionen mellan aluminium legeringar ochbiodiesel. Detta projekt har därför haft som syfte att ta fram en enkelt metod att jämföra metallers katalystiska effekt på biodieslets oxidations stabilitet, samt använda denna metod för att bedöma nedbrytningen av biodiesel i kontakt med aluminium legeringar. Olika uppvärmningsmetoder och täckningsmaterial undersöktes med hjälp av biodiesel gjord på rapsolja, RME, för att ta fram mätmetoden. När ett tillvägagångssätt hade fastlagts, så sänktes bitar av tre olika bränslefilterhus tillverkade av aluminium legeringar, och tre olika aluminium tackor med olika kopparhalter i RME och bränslets stabilitet mättes. Användning av ugn vid 80 °C för att testa biodieslets oxidations stabilitet gav de mest upprepbara resultaten, och sprejfärgen Auto K billack spray Universal var mest kompatibel att använda som täckningsmaterial. Den inre, obehandlade ytan av bränslefilterhusen visade sig inte påverka oxidations stabiliteten på biodieslet. Aluminijm legeringar med en högre koppar halt bröt ned RME lite mer än aluminium legeringar med lite/ingen koppas, men endast om ytan hade blivit mekaniskt behandlad. Detta ger slutsatsen att aluminium legeringar kan minska biodieslets stabilitet om det innehåller mycket koppar och om legeringens yta har blivit behandlad. Däremot så kan den reduktionen av oxidations stabiliteten bero på andra faktorer och det rekommenderas därför att genomföra fler experiment med aluminum legeringar och biodiesel.

Biodiesel is a renewable and biodegradable fuel that has the possibility to replace conventional diesel fuel and reduce the environmental pollution. Despite its environmental benefits, it has been shown to cause damage to the vehicle engines, due to its oxidative properties. Different metals, such as copper, zinc and aluminium are present in the vehicle fuel system and have been shown to catalyse the oxidation of biodiesel. Several studies have been performed to investigate the interaction between these metals and fuel. However, some reports concluded contradicting results when it comes to the oxidation of biodiesel in contact with aluminium alloys. This project aimed therefore to investigate and create a simple method for comparing the catalytic effect on oxidation for metals, and use this method to evaluate the degradation rate of biodiesel in contact with aluminium alloys. Different heating methods and coating materials were tested using the biodiesel RME to develop the testing procedure. When a test procedure was established, three filter houses made from cast aluminium alloy and three aluminium ingots with different amount of copper were immersed in RME and the stability was evaluated. The results showed that using an oven at 80 °C to investigate the stability provided the most repeatable results, and the spray paint Auto K billack spray Universal appeared to be compatible to use with RME. The inner untreated surface of the fuel filter houses did not seem to increase the oxidation rate of biodiesel. Aluminium alloys with higher copper content degraded RME more than aluminium alloys with little/no copper, if the surface had been treated mechanically, but not to a large extent. This concludes that aluminium alloys may reduce the stability of biodiesel if it contains much copper and if the surface of the alloy has been treated. However, the detected reduction on oxidation stability could depend on other factors, and therefore it is recommended to conduct further experiments on test the aluminium alloys. / Biodiesel är ett förnybart och biologiskt nedbrytbart bränsle som har möjligheten att ersätta konventionell diesel och minska föroreningen av miljön. Trots dess fördelar så har det visats att bränslet skadar motorerna i fordon, vilket beror på dess oxidativa egenskaper. Olika metaller, såsom koppar, zink och aluminium förekommer i fordons bränslesystem, och dessa har påvisats katalysera oxidationen av biodiesel. Flera studier har genomförts där interaktionen mellan de tidigare nämnda metallerna och biodiesel har undersökts. En del av dessa studier har fått motsägelsefulla resultat när det kommer till interaktionen mellan aluminium legeringar ochbiodiesel. Detta projekt har därför haft som syfte att ta fram en enkelt metod att jämföra metallers katalystiska effekt på biodieslets oxidations stabilitet, samt använda denna metod för att bedöma nedbrytningen av biodiesel i kontakt med aluminium legeringar. Olika uppvärmningsmetoder och täckningsmaterial undersöktes med hjälp av biodiesel gjord på rapsolja, RME, för att ta fram mätmetoden. När ett tillvägagångssätt hade fastlagts, så sänktes bitar av tre olika bränslefilterhus tillverkade av aluminium legeringar, och tre olika aluminium tackor med olika kopparhalter i RME och bränslets stabilitet mättes. Användning av ugn vid 80 °C för att testa biodieslets oxidations stabilitet gav de mest upprepbara resultaten, och sprejfärgen Auto K billack spray Universal var mest kompatibel att använda som täckningsmaterial. Den inre, obehandlade ytan av bränslefilterhusen visade sig inte påverka oxidations stabiliteten på biodieslet. Aluminijm legeringar med en högre koppar halt bröt ned RME lite mer än aluminium legeringar med lite/ingen koppas, men endast om ytan hade blivit mekaniskt behandlad. Detta ger slutsatsen att aluminium legeringar kan minska biodieslets stabilitet om det innehåller mycket koppar och om legeringens yta har blivit behandlad. Däremot så kan den reduktionen av oxidations stabiliteten bero på andra faktorer och det rekommenderas därför att genomföra fler experiment med aluminum legeringar och biodiesel.

Neste trabalho foram realizados estudos para avaliaÃÃo e modificaÃÃo de derivados de petrÃleo e de bioderivados. Na primeira parte deste estudo foi avaliada a seletividade de adsorÃÃo de C8 aromÃticos em peneiras moleculares comerciais. A separaÃÃo dos isÃmeros de xilenos à um importante processo na indÃstria petroquÃmica. As tÃcnicas de cromatografia em headspace e pulsos cromatogrÃficos foram utilizadas para obtenÃÃo de dados experimentais de equilÃbrio de adsorÃÃo. Esta abordagem pode ser muito Ãtil para a seleÃÃo de adsorventes, bem como para investigar a variaÃÃo na seletividade em relaÃÃo à composiÃÃo e temperatura do processo. As seletividades de adsorÃÃo de misturas multicomponentes determinadas atravÃs do mÃtodo de pulsos cromatogrÃficos confirmaram os valores obtidos utilizando os experimentos de cromatografia em headspace. Os valores indicaram o carÃter de para-seletividade dos zeolitos Y (&#945;px/ox ~ 4) e beta (&#945;px/ox ~ 2) e de orto-seletividade para os zeolitos mordenita (&#945;ox/px ~ 1,5). Na segunda parte deste trabalho foi estudado o processo de adsorÃÃo de poliaromÃticos com misturas modelo e com amostras de Ãleos naftÃnicos pesados (ONP). Os experimentos com as misturas modelo serviram para estudar a capacidade de adsorÃÃo de poliaromÃticos dos materiais, avaliar os parÃmetros de processo e selecionar os materiais mais promissores (Norit 830W e Norit 1240 plus) para avaliaÃÃo com amostras de ONP. As amostras de ONP foram caracterizadas e apresentaram altos teores de poliaromÃticos (8,2% m/m). AtravÃs dos experimentos em coluna, foi possÃvel avaliar a capacidade de adsorÃÃo dos carbonos ativados, estimar parÃmetros de transferÃncia de massa e simular o comportamento breakthrough dos sistemas estudados. Foram avaliadas as propriedades fÃsico-quÃmicas e o teor de poliaromÃticos apÃs o tratamento. Os resultados confirmaram a eficiÃncia dos carbonos ativados para utilizaÃÃo em processos de reduÃÃo do teor de compostos poliaromÃticos de ONP. Na terceira e Ãltima parte deste trabalho foram estudadas as propriedades fÃsico-quÃmicas e resistÃncia oxidativa de bioderivados (biodiesel e biolubrificantes) do Ãleo de mamona. O uso de antioxidantes aumentou de 6 a 15 vezes a estabilidade das amostras de biodiesel. Os estudos de estabilidade dos biolubrificantes hidrogenados com os melhores antioxidantes mostraram elevaÃÃo do perÃodo de induÃÃo em 10 vezes. / In this work, the methods for evaluation and modification of petroleum-based and bio-based products were studied. In the first part of this study, the adsorption of C8 aromatics in commercial molecular sieves was evaluated. The separation of xylene isomers is an important issue in the petrochemical industry. Headspace and chromatographic pulse techniques were used to measure experimental equilibrium data. This approach is very useful for the selection of adsorbents, as well as in the investigation of selectivity variation, with respect to composition and process temperature. The adsorption selectivities of multicomponent mixtures determined by the chromatographic pulse method were in agreement with the values obtained using headspace technique. The aforementioned values indicate the character of para-selectivity in zeolites Y (&#945;px/ox ~ 4) and beta (&#945;px/ox ~ 2), as well as the ortho-selectivity for the mordenite zeolites (&#945;ox/px ~ 1.5). In the second part of this study, we studied the adsorption of polyaromatics using model samples and heavy naphthenic oils (HNO). The experiments with model solutions were used to study the capacity of polycyclic aromatic adsorption to evaluate the process parameters and to select the most promising adsorbents (Norit 830W and Norit 1240 Plus), with samples for the evaluation of the HNO. Therefore, the samples were characterized and the HNO had a high content of polyaromatics hydrocarbons (8.2% m/m). Through column experiments, it was possible to evaluate the adsorption capacity of activated carbons, estimating parameters and mass transfers to simulate the breakthrough behavior of the above systems. We evaluated the physicochemical properties and the content of polyaromatics after treatment. The results confirmed the efficiency of activated carbons as an alternative process to reduce polyaromatics content of a HNO. In the third part of this study, we analyzed the physicochemical properties and the oxidation resistance of bio-based products (biodiesel and biolubricants) of the castor oil. Hence, the use of antioxidants increased from 6 to 15 times the stability of castor oil biodiesel. Stability studies of hydrogenated biolubricants with the best antioxidants showed an elevation of the induction period by 10 times.

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.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work presents the use of the oil extracted from seeds and the leaves of Moringa oleifera Lam for the production of biodiesel and ethanol extracts, respectively. The extracted oil was characterized to give yield of 33% (w / w), saponification number of 179 mg KOH g-1, kinematic viscosity of 44.5 mm2s-1, acid value of 13.2 mg KOH g-1, peroxide value of 10.4 meq kg-1, water content of 840 ppm and oxidative stability > 60 hours. This oil was used for biodiesel production in a two-step catalysis, acid (H2SO4) and alkaline (KOH) in methanol, to yield ester 96.8% (w/w) being the predominant ester oleic (81. 6%), kinematic viscosity of 4.5 mm2s-1, acid number of 0.21 mg KOH g-1, density of 882.5 kg m-3, the water content of 257.3 ppm and stability oxidation of 19.3 h, which is the last highlight parameter compared to other biodiesels presenting not greater than 4-6 h. The ethanol extracts of Moringa leaves were evaluated for their antioxidant activity (total phenols, proanthocyanidin content, by the method of DPPH radical sequestration and differential pulse voltammetry) and used as additives to various types of biodiesel, and it was checked the increase in oxidative stability of all biodiesels with superior efficiency in comparison with the synthetic antioxidant tert-butylhydroquinone (TBHQ). Furthermore, it was produced in larger quantity methyl biodiesel from Moringa oleifeira Lam refined oil of Indian origin, which, due to its reduced acidity (0.13 mg KOH g-1), did not require a two-step catalysis (only alkaline reaction). The corrosivity of the biodiesel was assessed by immersion tests (3, 7, 14, 21, 28, 56 and 84 days) with two types of carbon steel (AC1015 and AC4140) in the absence and presence of TBHQ antioxidant in 500 ppm, at room temperature in the dark and without agitation (static testing). The presence of TBHQ led to smaller variations of peroxide index and induction period values and at the same time decreased the corrosion of the metallic coupons (indicated by the low content of iron released to biodiesel in comparison with control experiments). Furthermore, in the absence of TBHQ, the variations of the same parameters were low during the corrosion experiments, which indicated compatibility of Moringa oleifera Lam biodiesel with the evaluated steels. / O presente trabalho apresenta a utilização do óleo vegetal extraído das sementes e das folhas de Moringa oleifera Lam para produção de biodiesel e extratos etanólicos, respectivamente. O óleo vegetal extraído foi caracterizado, obtendo-se rendimento de 33% (m/m), índice de saponificação de 179 mg KOH g-1, viscosidade cinemática de 44,5 mm2 s-1, índice de acidez de 13,2 mg KOH g-1, índice de peróxido de 10,4 meq Kg-1, teor de água de 840 ppm e estabilidade oxidativa > 60 h. Este óleo vegetal foi utilizado para a produção de biodiesel em uma catálise em duas etapas, ácida (H2SO4) e alcalina (KOH) em metanol, com rendimento em ésteres de 96,8% (m/m), sendo predominante o éster oleico (81,6%), viscosidade cinemática de 4,5 mm2 s-1, índice de acidez de 0,21 mg KOH g-1, massa específica de 882,5 Kg m-3, teor de água de 257,3 ppm e estabilidade à oxidação de 19,3 h, sendo este o último parâmetro de grande destaque em comparação a outros biodieseis que apresentam valores não superiores a 4-6 h. Os extratos etanólicos das folhas de Moringa foram avaliados em relação a sua atividade antioxidante (teor de fenóis totais, teor de proantocianidina, pelo método do sequestro do radical DPPH e voltametria por pulso diferencial) e utilizados como aditivos em diferentes tipos de biodiesel, sendo verificado aumento da estabilidade oxidativa de todos os biodieseis com eficiência superior a do antioxidante sintético tert-butilhidroquinona (TBHQ). Adicionalmente, produziu-se em maior quantidade biodiesel metílico a partir de óleo vegetal refinado de Moringa oleifeira Lam de origem indiana, que devido à acidez reduzida (0,13 mg KOH g-1) não exigiu a catálise em duas etapas (apenas a alcalina). A corrosividade deste biodiesel foi avaliada por meio de testes de imersão (3, 7, 14, 21, 28, 56 e 84 dias) com dois tipos de aço carbono (AC1015 e AC4140) na ausência e presença do antioxidante TBHQ em 500 ppm, à temperatura ambiente, na ausência de luz e sem agitação (ensaios estáticos). A presença de TBHQ levou a menores variações dos valores de índice de peróxido e período de indução e ao mesmo tempo retardou a corrosão das peças de aço (indicado pelo baixo teor de ferro liberado ao biodiesel em comparação aos ensaios controle). Mesmo assim, na ausência de TBHQ, as variações dos mesmos parâmetros foram baixas ao longo do experimento de corrosão, o que indicou compatibilidade do biodiesel de Moringa oleifeira Lam com os aços avaliados. / Doutor em Química

Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 PauloRP_TESE.pdf: 5067014 bytes, checksum: b7746014c5447355f701f5568c4dabae (MD5) Previous issue date: 2011-06-28 / Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel / A produ??o de biodiesel aumentou na ?ltima d?cada em fun??o dos benef?cios associados a este combust?vel, incluindo renovabilidade, mat?rias-primas nacionais, menor toxicidade e biodegradabilidade. Desde 2008, o uso do sebo bovino como mat?ria-prima na produ??o de biodiesel no Brasil tem aumentado em import?ncia, representando a segunda fonte de produ??o, depois da soja No entanto, o desempenho do biodiesel em condi??es de clima frio ? pior que do ?leo diesel devido ? ocorr?ncia de materiais insol?veis a baixas temperaturas, acelerando o entupimento de filtros e injetores de motores de ve?culos. Estudos t?m sido realizados acerca do biodiesel de sebo bovino, em sua maioria relacionados ?s propriedades de estabilidade t?rmica e oxidativa; no entanto, poucos abordam a natureza do precipitado formado e sua influ?ncia na qualidade do biodiesel. Pesquisas sugerem que a causa da deposi??o esteja relacionada ? natureza de ?steres saturados, sendo os monoacilglicer?is prov?veis agentes indutores. Este trabalho apresenta os n?veis de mono-, di- e triacilglicer?is, a estabilidade ? oxida??o e o ponto de entupimento de filtro a frio (PEFF) de amostras de biodiesel de sebo bovino de dois produtores comerciais, avaliados por um per?odo de 12 meses. Amostras de precipitados filtrados foram analisadas pelas t?cnicas comparativas de CG-DIC, CLAE-UV/VIS, CLAE-MS-IT-TOF e TG para verificar a composi??o, utilizando monopalmitina e monoestearina como padr?es de refer?ncia. Verificou-se que a forma??o de precipitado reduziu os n?veis de monoacilglicer?is no biodiesel de sebo bovino. Os resultados cromatogr?ficos confirmaram a natureza do precipitado como monoacilglicer?is saturados, com predomin?ncia de monoestearina e monopalmitina como segundo componente majorit?rio. Al?m disso, a an?lise de TG do precipitado resultou perfil de decomposi??o t?rmica semelhante ao dos padr?es de refer?ncia. O dep?sito formado n?o afetou a estabilidade ? oxida??o do biodiesel de sebo bovino e a caracter?stica de PEFF em misturas at? B60. No entanto, a presen?a de ferro reduziu significativamente a estabilidade ? oxida??o do biodiesel

Made available in DSpace on 2014-12-17T15:42:13Z (GMT). No. of bitstreams: 1 PauloRP_TESE.pdf: 5284084 bytes, checksum: 2ea3c93a4c25ad32fe7fad362cf7de36 (MD5) Previous issue date: 2011-06-28 / Biodiesel production has increased over the last decade because of the benefits associated with this fuel, including renewability, domestic feedstock, lower toxicity, and biodegradability. From 2008, the use of beef tallow as a feedstock for biodiesel production in Brazil has increased in significance, representing the second largest source of biodiesel, after soybeans. However, the performance of biodiesel in cold weather conditions is worse than diesel because of deposition of insoluble at low temperatures, accelerating the plugging of fuel filters and injectors of the vehicle engine. Studies have been conducted on beef tallow biodiesel, mostly related to the properties of thermal and oxidative stability. However, few studies have described the nature of the precipitate formed and its influence on product quality. Research suggests that the cause of deposition is related to the nature of saturated esters and monoacylglycerols as inducing agents. This study monitored the levels of mono-, diand triacylglycerols, the oxidation stability and the cold filter plugging point (CFPP) in beef tallow biodiesel samples from two commercial producers in Brazil for a period of twelve months. Filtered precipitates were analyzed by comparative techniques of GCFID, HPLC-UV/VIS, HPLC-MS-IT-TOF and TG to verify the nature, using monopalmitin and monostearin as reference standards. The formation of precipitate reduced the levels of monoacylglycerols in the beef tallow biodiesel. GC-FID and LCMS- IT-TOF results confirmed the nature of the deposit as saturated monoacylglycerols, predominantly monostearin and monopalmitin as the second major component. Moreover the TG analysis of the residue indicated similar thermal decomposition of the reference standards. The precipitate did not affect the oxidation stability of beef tallow biodiesel and the CFPP characteristic of blends up B60. However, the presence of iron reduced significantly the oxidation stability of biodiesel / A produ??o de biodiesel aumentou na ?ltima d?cada em fun??o dos benef?cios associados a este combust?vel, incluindo renovabilidade, mat?rias-primas nacionais, menor toxicidade e biodegradabilidade. Desde 2008, o uso do sebo bovino como mat?ria-prima na produ??o de biodiesel no Brasil tem aumentado em import?ncia, representando a segunda fonte de produ??o, depois da soja No entanto, o desempenho do biodiesel em condi??es de clima frio ? pior que do ?leo diesel devido ? ocorr?ncia de materiais insol?veis a baixas temperaturas, acelerando o entupimento de filtros e injetores de motores de ve?culos. Estudos t?m sido realizados acerca do biodiesel de sebo bovino, em sua maioria relacionados ?s propriedades de estabilidade t?rmica e oxidativa; no entanto, poucos abordam a natureza do precipitado formado e sua influ?ncia na qualidade do biodiesel. Pesquisas sugerem que a causa da deposi??o esteja relacionada ? natureza de ?steres saturados, sendo os monoacilglicer?is prov?veis agentes indutores. Este trabalho apresenta os n?veis de mono-, di- e triacilglicer?is, a estabilidade ? oxida??o e o ponto de entupimento de filtro a frio (PEFF) de amostras de biodiesel de sebo bovino de dois produtores comerciais, avaliados por um per?odo de 12 meses. Amostras de precipitados filtrados foram analisadas pelas t?cnicas comparativas de CG-DIC, CLAE-UV/VIS, CLAE-MS-IT-TOF e TG para verificar a composi??o, utilizando monopalmitina e monoestearina como padr?es de refer?ncia. Verificou-se que a forma??o de precipitado reduziu os n?veis de monoacilglicer?is no biodiesel de sebo bovino. Os resultados cromatogr?ficos confirmaram a natureza do precipitado como monoacilglicer?is saturados, com predomin?ncia de monoestearina e monopalmitina como segundo componente majorit?rio. Al?m disso, a an?lise de TG do precipitado resultou perfil de decomposi??o t?rmica semelhante ao dos padr?es de refer?ncia. O dep?sito formado n?o afetou a estabilidade ? oxida??o do biodiesel de sebo bovino e a caracter?stica de PEFF em misturas at? B60. No entanto, a presen?a de ferro reduziu significativamente a estabilidade ? oxida??o do biodiesel