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Ethanolysis of vegetal oils by enzymatic catalysis accelerated by microwave irradiation

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Author(s):
Patrícia Caroline Molgero da Rós
Total Authors: 1
Document type: Master's Dissertation
Press: Lorena.
Institution: Universidade de São Paulo (USP). Escola de Engenharia de Lorena (EEL/ASDI)
Defense date:
Examining board members:
Heizir Ferreira de Castro; Ernandes Benedito Pereira; Júlio César dos Santos
Advisor: Heizir Ferreira de Castro
Abstract

The objective of this project was to study the application of electromagnetic fields of high frequency (microwave) in enzymatic process, especially in the synthesis of biodiesel by the ethanolysis of vegetal oils in a solvent free system. The indicated enzyme for this process - lipase (EC 3.1.1.3) was used in an immobilized form and the assays were carried out using low cost vegetal oils (babassu oil and palm oil) and ethanol as raw material sources. For each vegetal oil a specific lipase preparation was used based on previous results. For babassu oil lipase from Burkholderia cepacia-PS was used while for palm oil lipase from Pseudomonas fluorescens-AK. The experimental work was developed in three steps. In the first, lipase from Burkholderia cepacia-PS was immobilized on two non-commercial matrixes, as inorganic matrix (niobium oxide, Nb2O5) and hybrid matrix (polysiloxane-polyvinyl alcohol, SiO2- PVA) aiming to determine the most suitable matrix to immobilize this specific preparation of lipase. The resulting immobilized derivatives were analyzed regarding their biochemical properties (pH and temperature), kinetic properties (Km and Vmax) and thermal stability (60oC) following their applications in the reaction proposed. The results obtained indicated that the immobilized derivate on hybrid matrix (SiO2-PVA) was more thermally stable and efficient to mediate the ethanolysis reaction of babassu oil, reaching a yield of 90.1% in 24 h. This matrix was also used to immobilize lipase from Pseudomonas fluorescens-AK. In the second stage of work, thermal stability tests of the immobilized lipases on SiO2-PVA under microwave irradiation were performed using a microwave reactor (Discover/University-Wave, Cem Corporation). The tests were performed at 60oC in organic medium, revealing half-life times in the order of 5.65 and 8.22h, respectively for Burkholderia cepacia and Pseudomonas fluorescens. In the last stage, conditions to carry out the transesterification for each vegetable oil were determined, using a statistic method. This stage was conducted by a factorial design matrix, attaining the influence of temperature and molar ratio in biodiesel synthesis. For the ethanolysis of babassu oil, the formation of ethyl esters was strongly influenced by quadratic variables (X12, X22), molar ratio and temperature, respectively. The statistical model allowed predicting the adequate conditions that could reach high yields of biodiesel production, maximizing the reaction (100%) in 10h for reaction media consisting of a molar ratio of 1:12 (oil/ethanol) at 50oC. For ethanolysis of palm oil, the formation of ethyl ester was highly influenced by linear variables (X1, X2), molar ratio and temperature, respectively. The proposed statistic model indicated that the low levels of temperature (43oC) and ratio molar 1:8 (oil/ethanol) conduct to 97% conversion of fatty acid present on palm oil in ethyl esters in 12h of reaction. The obtained results indicated that the development of enzymatic reactions conducted by microwaves constitutes a potential procedure for the production of biodiesel in view that it was possible to reduce the reaction time, demonstrating the viability of the considered enzymatic process for both vegetal oils, with advantages adds in relation to the submitted process to the conventional heating. (AU)