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Previous issue date: 2013-02-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (Capes) / Neste trabalho est? descrito uma nova metodologia para a produ??o de biodiesel (?steres met?licos ou et?licos de ?cidos graxos) a partir do emprego de diversos ?leos vegetais na sua forma ?bruta?, assim como ?leos residuais oriundos de processo de fritura e tamb?m gordura animal (sebo) como material de partida. Al?m deste desafio, procurou-se realizar as rea??es de transesterifica??es em um processo acelerado por irradia??o das micro-ondas obtidas a partir de um forno de micro-ondas dom?stico, o qual n?o sofreu adapta??es, tais como: inser??o de um sistema de agita??o e tamb?m de refluxo, para ser utilizado em rea??es qu?micas. O primeiro passo do trabalho incluiu a utiliza??o dos diferentes ?leos vegetais brutos, isto ?, desprovidos de processo de refino e de degomagem, para a produ??o de biodiesel. Para tanto foi necess?rio o desenvolvimento de uma metodologia que permitisse a purifica??o desses ?leos vegetais brutos, pois estes podem conter subst?ncias, como a ?gua, os ?cidos graxos livres (AGL) e os ?steres de f?sforos (fosfat?dicos) que s?o inibidoras do processo de transesterifica??o. Na busca por uma t?cnica que permitisse a pr?via purifica??o desses ?leos vegetais, foram testados e obtidos excelentes resultados, quando foi realizada a sua filtra??o em s?lica gel 60 Mesh. A polaridade dessa s?lica oriunda dos grupos silan?is permitiu com grande ?xito a reten??o de AGL e dos ?steres de f?sforo, al?m do seu alto poder de adsor??o, reduzindo de maneira significativa o teor de ?gua presente nesses ?leos vegetais. O fator limitante para o emprego da s?lica gel comercial nos processos de purifica??o das diversas oleaginosas foi o seu alto custo, o que tornava invi?vel o processo de purifica??o. Ap?s diversos estudos e tentativas de encontrar um processo que substitu?sse a s?lica gel comercial anteriormente empregada, foi realizado a s?ntese de uma nova s?lica gel a partir do emprego de areia de constru??o e de carbonatos, sendo um processo simples e de baixo custo. Os resultados obtidos no processo de purifica??o dos ?leos vegetais brutos empregando s?lica gel ?sint?tica? foram similares aos da s?lica gel ?comercial?, o que levou o emprego desse processo de purifica??o de maneira sistem?tica no preparo de mat?ria-prima (reagentes) para posterior transesterifica??o. Os bons resultados permitiram testes dessa nova metodologia de purifica??o em ?leos e gorduras residuais (OGR) oriundos de processos de fritura. Nesses ?leos foram encontrados um n?mero bem maior de subprodutos (impurezas) que podem inibiriooooooo65t\azs NM de maneira parcial ou total o processo de transesterifica??o. Dessa forma, a purifica??o dos OGR tornou-se um grande desafio para a s?lica gel ?sint?tica?. Entre as impurezas contidas nesses ?leos residuais, podemos destacar os AGL, ?gua e os produtos oriundos da degrada??o oxidativa e t?rmica (per?xidos, alde?dos, cetonas, furanos, mon?meros c?clicos e n?o c?clicos) dos ?leos vegetais. Os OGR foram purificados com excelentes resultados por filtra??o sob s?lica gel ?sint?tica? em um processo realizado a temperatura ambiente. Al?m dos ?leos residuais puros, nesse processo foi obtida a gordura animal, a qual ficou retida sobre a s?lica sint?tica dentro do funil de filtra??o. Essa gordura animal foi posteriormente purificada por filtra??o a 60 ?C tamb?m em s?lica gel sint?tica e assim como o ?leo residual utilizada como material de partida na s?ntese de biodiesel. Vale ressaltar que os bons resultados alcan?ados no processo de purifica??o sob s?lica gel sint?tica e a necessidade crescente de mat?ria-prima (?leos vegetais), incentivou a amplia??o do programa de coleta de ?leo e gorduras residuais (OGR) na cidade de Diamantina/MG, intitulado como ?Doe Energia? e implantado em 2006. Tanto os ?leos vegetais brutos, como os ?leos residuais e a gordura animal purificados em s?lica gel sint?tica foram transesterificados a biodiesel (met?lico ou et?lico) em alcoolatos (metanolatos e etanolatos) previamente preparados ?in situ? a partir da solubiliza??o de NaOH ou KOH em metanol ou etanol. Neste processo ocorreu a adi??o do alcoolato sobre o material de partida, sendo a rea??o conduzida sob irradia??o de micro-ondas dom?stica a 240 W durante dez minutos e acompanhada por cromatografia em camada delgada (CCD). Os produtos da rea??o (biodiesel e glicerina) foram separados por decanta??o em funil de separa??o, sendo o biodiesel (et?lico ou met?lico) posteriormente lavado at? pH neutro, seco em Na2SO4 e purificados por destila??o a press?o reduzida. A caracteriza??o do biodiesel produzido foi realizada por m?todos espectrom?tricos como a RMN1H e 13C, al?m disso, o controle de qualidade do biodiesel produzido foi realizado empregando t?cnicas anal?ticas seguindo as normas preconizadas pela Ag?ncia Nacional de Petr?leo, G?s Natural e Biocombust?veis (ANP). A glicerina foi purificada, atrav?s de um pr?vio tratamento com adi??o de ?cido sulf?rico ou clor?drico, gerando o AGL, biodiesel e sulfatos ou cloretos de metais alcalinos como co-produtos. Alguns desses sais como o sulfato de s?dio foi posteriormente purificados por recristaliza??o e utilizados como dessecantes para o pr?prio biodiesel. A efici?ncia da metodologia empregando irradia??o de micro-ondas dom?stica, levou ao estudo do seu uso em rea??es in situ, ou seja, transesterifica??o direta das sementes e dos frutos de oleaginosas, tais como a soja e a mamona. Esse processo consiste em uma desidrata??o pr?via dos frutos ou sementes a uma temperatura de 80 ?C durante 8 horas. O alcoolato preparado foi adicionado sobre os frutos ou sementes triturados e secos e a mistura foi agitada com o aux?lio de um agitador mec?nico a 7500 rpm durante 10 minutos a temperatura ambiente, a fim de homogeneizar a mistura reacional. Essa mistura foi levada a um forno de micro-ondas dom?stico e irradiada a 240 W durante 10 minutos em um processo acompanhado por CCD. Ap?s esse per?odo a massa reacional foi filtrada sob v?cuo, a fim de eliminar o res?duo vegetal s?lido (torta). A solu??o resultante foi transferida para um funil de separa??o, onde ocorreu ap?s poucos minutos, a separa??o do biodiesel (fase superior) da glicerina (fase inferior) por simples decanta??o. Os produtos foram separados por decanta??o e tanto a glicerina como o biodiesel (et?lico ou met?lico) foram purificados e caracterizados. O rendimento em biodiesel foi de aproximadamente 96% no emprego de sementes de soja e de 97% empregando sementes de mamona. / Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Qu?mica, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2011. / ABSTRACT
This work described a new methodology for the production of biodiesel (methyl or ethyl esters of fatty acids) from the use of various vegetable oils in its "raw" as well as waste oil from the frying process and also animal fat (tallow) as starting material. In addition to this challenge, we tried to carry out the reactions transesterification in a process accelerated by microwave irradiation obtained from a domestic microwave oven, which has not undergone changes, such as insertion of an agitation system and also reflux for used in chemical reactions. The first step of the work included the use of different crude oils, this is, devoid of the process of refining and degumming, for the production of biodiesel. For this purpose it was necessary to develop a methodology that allows the purification of crude vegetable oils, as they may contain different substances such as water, free fatty acids (FFA) and esters of phosphorus (Phosphatidic) which are inhibitors of the transesterification process. In the search for a technique that allowed the prior purification of vegetable oils have been tested and achieved excellent results when your filtration was performed on silica gel 60 Mesh. The polarity of this coming from the silica silanol groups with great success allowed the retention of FFA and phosphorus esters, in addition to its high adsorption, significantly reducing the water content present in these oils. The limiting factor for the commercial use of silica gel in the purification processes of other crops was the high cost, which made impossible the purification process. After several studies and attempts to find a process to replace the previously used commercial silica gel was carried out the synthesis of a new silica gel from the use of construction sand and carbonates, with a simple and low cost. The results obtained in the purification process of crude vegetable oils using silica gel "synthetic" were similar to those of silica gel "commercial", which led to the use of this purification process in a systematic manner in the preparation of raw materials (reagents) for subsequent transesterification. The good results allowed testing of this new method of purification of waste oils and fats (WOF) from the frying process. These oils have been found a much larger number of products (impurities) in a manner that can inhibit the partial or total transesterification process. Thus, the purification of WOF has become a major challenge for the silica gel "synthetic". Among the residual impurities contained in these oils, we can highlight the FFA, water and products from thermal and oxidative degradation (peroxides, aldehydes, ketones, furans, cyclic and non cyclic monomers) of vegetable oils. The WOF with excellent results were purified by filtration on silica gel "synthetic" in a process performed at room temperature. Besides the pure residual oils, this process was obtained animal fat, which was held on the synthetic silica into the filter funnel. This fat was then purified by filtration at 60 ?C also on silica gel and synthetic as well as the residual oil is also used as starting material in the synthesis of biodiesel. It is noteworthy that the good results achieved in the purification process in synthetic silica gel and the increasing need of raw material (vegetable oils) has encouraged the expansion of the program to collect waste oil and fats (WOF) in the Diamantina / MG city, titled as "Energy Donate" and implemented in 2006. Both crude vegetable oils, such as waste oils and animal fat purified on silica gel synthesis was transesterified biodiesel (methyl or ethyl) in alcoholates (metanolatos and ethanolate) previously prepared "in situ" from the solubilization of NaOH or KOH in methanol or ethanol. This process was the addition of alcoholates on the starting material, and the reaction was conducted under microwave irradiation of a 240 W home for ten minutes and accompanied by thin layer chromatography (TLC). The reaction products (biodiesel and glycerol) were separated by decanting funnel separation, and biodiesel (methyl or ethyl) subsequently washed until neutral, dried on Na2SO4 and purified by distillation at reduced pressure. The characterization of the biodiesel produced was performed by spectrometric methods such as RMN 1H and 13C, in addition, the quality control of biodiesel was carried out using analytical techniques following the standards recommended by the National Petroleum, Natural Gas and Biofuels Agency (ANP). The glycerin was purified through a previous treatment with sulfuric acid or hydrochloric acid, generating the FFA, biodiesel or chlorides and sulfates of alkali metals as co-product. Some of these salts such as sodium sulfate was further purified by recrystallization and used as desiccants for their own biodiesel. The efficiency of the methodology using a household microwave irradiation, led to the study of their use in reactions in situ, that is, direct transesterification of seeds and fruits of oilseeds such as soybeans and castor beans. This process consists of a prior dehydration of fruits or seeds at a temperature of 80 ?C for 8 hours. The alcoholates prepared was added on the fruits or seeds crushed and dried mixture was stirred with the aid of a mechanical stirrer at 7500 rpm for 10 minutes at room temperature in order to homogenize the reaction mixture. This mixture was brought to a domestic microwave oven and irradiated at 240 W for 10 minutes in a process monitored by TLC. After this time the reaction mass was filtered under vacuum to remove the solid waste plant (cake). The resulting solution was transferred to a separatory funnel, which occurred a few minutes, after the separation of biodiesel (upper phase) of glycerin (lower phase) by simple decantation. The products were separated by decantation and glycerin as much biodiesel (methyl or ethyl) have been purified and characterized. The yield of biodiesel was approximately 96% in the use of soybean and 97% employing castor beans.
| Identifer | oai:union.ndltd.org:IBICT/oai:acervo.ufvjm.edu.br/jspui:1/520 |
| Date | 29 October 2011 |
| Creators | Miranda, S?vio Eduardo Oliveira |
| Contributors | Santos, Sandro Luiz Barbosa dos, Hurtado, Gabriela Ramos, Klein, Stanlei Ivair, Archanjo, Fernando Costa, Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM), Santos, Sandro Luiz Barbosa dos |
| Publisher | UFVJM |
| Source Sets | IBICT Brazilian ETDs |
| Language | Portuguese |
| Detected Language | Portuguese |
| Type | info:eu-repo/semantics/publishedVersion, info:eu-repo/semantics/masterThesis |
| Source | reponame:Repositório Institucional da UFVJM, instname:Universidade Federal dos Vales do Jequitinhonha e Mucuri, instacron:UFVJM |
| Rights | A concess?o da licen?a deste item refere-se ao ? termo de autoriza??o impresso assinado pelo autor, assim como na licen?a Creative Commons, com as seguintes condi??es: Na qualidade de titular dos direitos de autor da publica??o, autorizo a Universidade Federal dos Vales do Jequitinhonha e Mucuri e o IBICT a disponibilizar por meio de seus reposit?rios, sem ressarcimento dos direitos autorais, de acordo com a Lei n? 9610/98, o texto integral da obra disponibilizada, conforme permiss?es assinaladas, para fins de leitura, impress?o e/ou download, a t?tulo de divulga??o da produ??o cient?fica brasileira, e preserva??o, a partir desta data., info:eu-repo/semantics/openAccess |
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