Butyl-ester type biodiesels

Biodiesel is typically synthesized from triacylglycerides derived from vegetable oils and an alcohol with base catalysis, yielding the fatty acid ester type biodiesel. Wahlen et al. determined conditions that allowed rapid and high yield conversion of oil feedstocks containing significant concentrations of free fatty acids into biodiesel using an acid-cata­lyzed reaction with longer chain alcohols such as n-butanol at a slight molar excess. Bio­diesel yields >98% were achieved in <40 min. Key properties of the resulting butyl-diesel were determined, including cetane number, pour point, and viscosity [229]. The batch and continuous-flow preparation of biodiesel derived from vegetable oil and 1-butanol using a microwave apparatus has been reported. The methodology allows for the reac­tion to be run under atmospheric conditions and in continuous-flow mode. It can be uti­lized with new or used vegetable oil with 1-butanol and a 1:6 molar ratio of oil to alcohol. Sulfuric acid or potassium hydroxide can be used as catalyst [230]. High conver­sion could be reached when the transesterification of triglycerides with 1-butanol was performed under near-critical or supercritical conditions with microwave heating [231].

Biodiesel synthesis by butanolysis of vegetable oils (soybean, sunflower, and rice bran) catalyzed by Lipozyme RM-IM), and the optimization of the enzyme stability over repeated batches has been described. The enzyme showed the highest activity at a 9:1 BuOH:oil molar ratio and in the 30-35 °C temperature range [232]. Transesterification reaction using sunflower oil and butanol catalyzed by immobilized lipases can be carried out without auxiliary solvent. Immobilized porcine pancreatic lipase (PPL) and Candida rugosa lipase (CRL) showed satisfactory activity in these reactions. Activities of immobilized lipases were highly increased in comparison with free lipases because its activity sites became more effective. Immobilized enzyme could be repeatedly used without difficult method of separation and the decrease in its activity was not largely observed [233].