Co-production of butyrate methyl ester and triacetylglycerol from tributyrin and methyl acetate

Abstract

a b s t r a c tThe simultaneous synthesis of butyric acid methyl ester, the shortest component of the FAME (fatty acid methyl esters) family, and glycerol triacetate (TAG) from glycerol tributyrate (tributyrin) and methyl acetate was studied as a function of several reaction parameters, such as type of catalyst, temperature and products distribution. The reaction is an interesterification, a multistep consecutive ester interchange catalyzed by either acid or base catalyst. Under optimized conditions, a complete tributyrin conversion and an almost quantitative butyric acid methyl ester accumulation were achieved. The other reaction product, TAG, formed by the complete acetylation of the glycerol moiety, reached almost 70% yield, whereas the mono-and di-acetylated intermediates accumulated in the order of 5-8% and 24-27%, respectively. Similar final conversions and products yields were obtained with either acid or base homogeneous catalysts, suggesting that the final products mixture did not depend on the type of catalysis but might be limited by equilibrium conditions. In spite of similar final yields, base catalysis needed shorter reaction times (minutes instead of hours) and lower temperature (60 • C instead of 130 • C) with respect to the best acid catalyst. On the other hand, unlike heterogeneous basic catalysts, which showed low activity, a heterogeneous acid catalyst almost as active as the homogenous counterpart was found.

Sulfonic acid-functionalized mesoporous silicas: Microcalorimetric characterization and catalytic performance toward biodiesel synthesis

“…To the best of our knowledge the interesterification of triglycerides with methyl acetate or ethyl acetate has mostly been studied in the presence of an enzyme biocatalyst [46][47][48][49], or under supercritical conditions without any catalyst [50][51][52]. Only few papers reported the use of inorganic acid and alkaline catalysts [53][54][55].…”

Continuous ion-exchange resin catalysed esterification of eugenol for the optimized production of eugenyl acetate using a packed bed microreactor

“…In recent years, a great deal of attention has been focused towards the use of supported catalysts 19,20 that not only can be easily recovered and reused but have also favoured the development of continuous ow processes for a number of industrially important productions. 21,22 Most of the articles or patents describing the esterication of natural products promoted by heterogeneous catalysts, falls in the eld of biofuels production [23][24][25][26] and, in several cases, ion-exchange resins have been successfully employed as acid 27,28 or basic catalysts. 29 Based on all these promising features, the aim of this work was to set up an optimized continuous-ow process for eugenyl acetate production based on the use of an ion-exchange resin as catalyst and acetic anhydride as acylating agent.…”

Interesterification of Glyceryl Trioctanoate Catalyzed by Sulfonic Silica-Based Materials: Insight into the Role of Catalysts on the Reaction Mechanism

“…For the evaluation of DGs and MAMGs, an empirical calibration coefficient was determined, considering the instrumental response factor as a function of TA and GTO concentration [ 35 ]. Then, the yield of each intermediate was calculated by Equation (3).…”

“…Nevertheless, the research was principally focused on heterogeneous catalysts that can be easily removed and reused. Battistel et al [ 35 ] carried out a wide screening of acids and bases, both in the homogeneous and heterogeneous phase, for the interesterification of tributyrin with methyl acetate. In the homogeneous phase, base catalysts (CH 3 Ona, (CH 3 ) 3 COK, TBD, DBU) had the best activity, with reaction times in the order of minutes and temperature of 60–80 °C, whereas acid catalysts (methanesulfonic acid, sulphuric acid, trifluoro-acetic acid, trifluoro-methanesulfonic acid) required high temperature (130–140 °C) and longer reaction time (20 h) to obtain comparable conversions and yields.…”

“…Among the heterogeneous catalysts investigated for the interesterification reactions, Nafion SAC-13, a commercial perfluoro-sulfonic acid polymer on porous silica, has shown the best catalytic performance [ 35 ]. This catalyst after 20 h at 130 °C gave 98% conversion of tributyrin, methyl butyrate yield of 83%, and triacetin selectivity of 60%, using 1:20 tributyrin to methyl acetate molar ratio and 5–15 wt% of catalyst [ 42 ].…”