Selective Conversion of Glycerol into Propylene: Single-Step versus Tandem Process

Dehydration and catalytic cracking reactions can be combined to convert glycerol into light olefins using solid acid catalysts. The combination is suitable for a single-step process to convert glycerol into light olefins at high temperatures (26–36% selectivity at 873 K). However, large quantities of carbon oxides are produced (31–39% CO x selectivity), and catalyst deactivation also occurs. High light olefin selectivity (62–65%) and a smaller quantity of carbon oxides (11–12% CO x selectivity) can be obtained by using a tandem process involving the dehydration of glycerol and subsequent catalytic cracking of the dehydration products (mainly acetol and acrolein). Furthermore, the ratio of propylene to ethylene can be adjusted by changing the dehydration catalysts to favor the production of acetol or acrolein: Acetol forms propylene, and acrolein forms ethylene. To overcome the fast deactivation of acid catalysts in glycerol dehydration, the hydrogenolysis and catalytic cracking reactions can be synchronized to convert glycerol into hydrocarbons using a combination of metal and acid catalysts. The single-step conversion of glycerol over a metal or bifunctional catalyst formed alcohols and paraffin. The highest selectivity for propylene production (approximately 76%) was obtained in a tandem process via the selective hydrogenolysis of glycerol to propanols over Pt/ZSM-5 catalysts followed by the catalytic dehydration/cracking of propanols to propylene over ZSM-5 catalysts at low temperatures (523 K). The selectivity for propylene was improved by increasing the Si/Al ratio of the ZSM-5 catalysts and the reaction time. Under these conditions, economically competitive crude glycerol (mainly mixtures of glycerol and methanol) can be used to synthesize light olefins (approximately 61% selectivity) with a long lifetime (∼500 h) in single-route reactions by increasing the cracking temperature to 773 K, which is suitable for practical methanol to propylene process.