| Summary: | Fossil additives are a primary energy source and their contribution is around 80% in the world. Therefore, bioadditives that reduce their impact are each very important. This article discusses the chemical transformation of glycerol to carbonate, ethers, esters, ketals, and acetals, compounds with high technological applications, especially in the fuel sector as bioadditives. Mainly, heterogeneous catalysts are important in the production of more than 80% of chemicals in the word. The focus is on demonstrating how the Keggin heteropolyacids (HPAs) are efficient catalysts in the reactions of syntheses of glycerol-derived bioadditives, either in homogeneous or heterogeneous phases. Although solid, HPAs have a low surface area and are soluble in polar solvents, hampering their use as heterogeneous catalysts. Alternatively, they have been successfully used supported on solid matrixes with a high surface area. Another option is converting the Keggin HPAs to insoluble salts simply by exchanging their protons with large cations like potassium, cesium, or ammonium-derivatives. Therefore, solid heteropoly salts have reduced the cost and the environmental impact of bioadditive synthesis processes, being an alternative to traditional mineral acids or solid-supported catalysts. This review describes the most recent advances achieved in the processes of synthesis of glycerol-derived bioadditives over solid-supported HPAs or their solid heteropoly salts.
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