Tuning of diglycerol yield and isomer distribution in oligomerization of glycerol supported by DFT-calculations

► Glycerol can be converted to diglycerols by basic as well as acidic catalysts. ► Higher oligomers are formed in consecutive reactions. ► Basic zeolites dramatically change composition of the diglycerol isomer pool. ► Acidic ionomers used at reduced reaction pressure seem to be applicable catalysts. ► Falling film reactor set-up prevents consecutive reactions of diglycerols.