A review on catalytic role of heterogeneous acidic catalysts during glycerol acetylation to yield acetins

Glycerol is a colorless, odorless, and non-toxic compound and has application in food, paint, and pharmaceutical industries. At an industrial scale, glycerol (GL) commonly forms as a by-product of soap and biodiesel producing industries. To utilize the excess GL of biodiesel industry, former has been employed as a building block to manufacture value added products such as acetins by fine chemical manufacturers. Acetins, including monoacertin (MA), diacetin (DA) and triacetin (TA), has diverse application such as in cosmetics, fuel additives, pharmaceuticals, leather, and food processing. Specifically, TA is employed as an additive to improve the anti-knocking property of gasoline and viscosity and cold flow properties of biofuel. The acetins are frequently produced at an industrial scale via a homogeneous Brønsted acid catalysed process employing acetic acid or acetic anhydride as an acetylating agent. Homogeneous acid catalysts are corrosive, non-reusable, difficult to separate from the reaction mixture, and sensitive to water, which is formed as a by-product during the glycerol acetylation. To address the issues, Brønsted or Lewis acidic group have been immobilized over various matrices (e.g., mixed metal oxides, mesoporous silica, ion exchange resins, carbon, zeolites, and magnetic nanoparticles) to prepare the heterogeneous acidic catalysts for the glycerol acetylation. Both the sites assisted the carbocation mediated esterification of glycerol with acetic acid or acetic anhydride. The ease of catalyst separation from the reaction mixture and reusability are the major advantages of their usage. However, lower conversion levels with low product selectivity, catalysts deactivation, and partial dissolution in the reaction mixture are the concerns related to the catalysts. To address these issues, novel catalyst preparation techniques to incorporate the variety of active sites over the matrix surface have been employed in the literature, which will be highlighted in detail in the present review article.