Abstract

By using 1,3-specific Pig Pancreatic lipase (EC 3.1.1.3 or PPL), covalently immobilized on AlPO4/Sepiolite support as biocatalyst, a new second-generation biodiesel was obtained in the transesterification reaction of sunflower oil with ethanol and other alcohols of low molecular weight. The resulting biofuel is composed of fatty acid ethyl esters and monoglycerides (FAEE/MG) blended in a molar relation 2/1. This novel product, which integrates glycerol as monoacylglycerols (MG) into the biofuel composition, has similar physicochemical properties compared to those of conventional biodiesel and also avoids the removal step of this by-product. The biocatalyst was found to be strongly fixed to the inorganic support (75%). Nevertheless, the efficiency of the immobilized enzyme was reduced to half (49.1%) compared to that of the free PPL. The immobilized enzyme showed a remarkable stability as well as a great reusability (more than 40 successive reuses) without a significant loss of its initial catalytic activity. Immobilized and free enzymes exhibited different reaction mechanisms, according to the different results in the Arrhenius parameters (Ln A and Ea). However, the use of supported PPL was found to be very suitable for the repetitive production of biofuel due to its facile recyclability from the reaction mixture.

Highlights

  • The lipid fraction of biomass has been identified as carbon neutral substitution of fuels from fossil sources in the transportation sector

  • We have recently developed an alternative protocol for the preparation of novel biofuels integrating glycerol into their composition via 1,3-regiospecific enzymatic alcoholysis of sunflower oil using some "1,3" regioespecific low cost lipase, like pig pancreatic lipase, PPL [36,37,38]

  • 1,3-regiospecific PPL can play an advantageous role compared to the conventional base catalyzed processes to prepare new biofuels incorporating glycerin as monoglycerides, obtaining in this way a reduction in the production of waste, an improvement in the reaction conversion (100% theoretical) and greener operating conditions

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Summary

Introduction

The lipid fraction of biomass has been identified as carbon neutral substitution of fuels from fossil sources in the transportation sector. The atom efficiency is improved, as the total number of atoms involved in the reaction is part of the final mixture In this context, we have recently developed an alternative protocol for the preparation of novel biofuels integrating glycerol into their composition via 1,3-regiospecific enzymatic alcoholysis of sunflower oil using some "1,3" regioespecific low cost lipase, like pig pancreatic lipase, PPL [36,37,38]. Taking into account the excellent results obtained in the immobilization of these enzymes, in this study we have extended the possibilities of this methodology to be applied to the covalent attachment of PPL to be applied as an economically viable biocatalyst for the production of a novel biofuel integrating glycerine into its composition

Results and Discussion
Support Synthesis and Support Functionalization
PPL Immobilization and Enzymatic Activity
Alcoholysis Reactions
Compositional Analysis of Reaction Products by Gas Chromatography
Viscosity Measurements
Conclusions
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