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The glycerol has been identified as a main platform product in biorefineries and its use as a renewable raw material has gained the great attention of the scientific community. Thanks to its unique structure, bioavailability, properties and renewability, scientists consider glycerol as a non-toxic bio-sourced building block for chemical transformations into higher added-value substances, meeting the objectives of minimizing the environmental impact and economic risk and giving a value to the production of biodiesel. In this chapter, we highlighted the important progress by summarizing; the representative achievements for the different promising reactions focusing on glycerol valorization and reactional mechanisms proposed for some processes.

A new and mild method of glycerol acetalization reaction with various carbonyl compounds catalyzed by the cheap and simple iron catalyst FeCl3·6H2O has been developed. This method which consists in the transformation of glycerol to cyclic acetals under mild conditions, with or without solvent, allowed interesting results: glycerol acetalization using ketones leads to the corresponding 1,3-dioxolanes with a very good selectivity (97–100%), whereas mixture of 1,3-dioxolanes and 1,3-dioxanes was formed when using aldehydes, with a good selectivity toward 1,3-dioxanes up to 76%.