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Green Acetylation of Solketal and Glycerol Formal by Heterogeneous Acid Catalysts to Form a Biodiesel Fuel Additive
Author(s) -
Dodson Jennifer R.,
Leite Thays d C. M.,
S. Pontes Nathália,
Peres Pinto Bianca,
Mota Claudio J. A.
Publication year - 2014
Publication title -
chemsuschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.412
H-Index - 157
eISSN - 1864-564X
pISSN - 1864-5631
DOI - 10.1002/cssc.201402070
Subject(s) - acetic anhydride , chemistry , organic chemistry , catalysis , reagent , glycerol , acetic acid , biodiesel , acylation , heterogeneous catalysis
A glut of glycerol has formed from the increased production of biodiesel, with the potential to integrate the supply chain by using glycerol additives to improve biodiesel properties. Acetylated acetals show interesting cold flow and viscosity effects. Herein, a solventless heterogeneously catalyzed process for the acetylation of both solketal and glycerol formal to new products is demonstrated. The process is optimized by studying the effect of acetylating reagent (acetic acid and acetic anhydride), reagent molar ratios, and a variety of commercial solid acid catalysts (Amberlyst‐15, zeolite Beta, K‐10 Montmorillonite, and niobium phosphate) on the conversion and selectivities. High conversions (72–95 %) and selectivities (86–99 %) to the desired products results from using acetic anhydride as the acetylation reagent and a 1:1 molar ratio with all catalysts. Overall, there is a complex interplay between the solid catalyst, reagent ratio, and acetylating agent on the conversion, selectivities, and byproducts formed. The variations are discussed and explained in terms of reactivity, thermodynamics, and reaction mechanisms. An alternative and efficient approach to the formation of 100 % triacetin involves the ring‐opening, acid‐catalyzed acetylation from solketal or glycerol formal with excesses of acetic anhydride.