The Joint Synthesis of 1,2-Propylene Glycol and Isopropyl Alcohol by the Copper-Catalyzed Hydrogenolysis of Solketal

Abstract

A synthetic strategy from glycerol to 1,2-propylene glycol (1,2-PG) via heterogeneously catalyzed hydrogenolysis of solketal (2,2-dimethyl-4-(hydroxymethyl)-dioxolane-1,3) has been proposed for the first time. Upon the hydrogenolysis over 60 wt % Cu/Al2O3 at 200–240 °C, solketal has been converted into mixtures of isopropanol and 1,2-PG with high yield (up to 94 mol %). Under similar conditions, the catalyst specific productivity (a yield of 1,2-PG per unit of mass of the catalyst) was about 2.65 times higher, when solketal was the reaction feed instead of glycerol. The reaction was also performed under atmospheric pressure in the vapor phase, where the solketal hydrogenolysis gave 93 mol % selectivity to 1,2-PG with a conversion of 24%. A plausible reaction mechanism for the solketal hydrogenolysis has been proposed.

Valorisation of glycerol through catalytic hydrogenolysis routes for sustainable production of value-added C3 chemicals: current and future trends

“…113,145 In recent years, many researchers have tried to develop highly uniform, well-dispersed, and stable Cu-based nanoparticle catalysts via tuning the catalytic activity as well as using different preparation methods. 146,147 Notably, Zhu and co-authors (2015) successfully developed a highly stable Cu/SiO 2 (AEH) catalyst using an ammonia evaporation hydrothermal method. 143 The Cu/SiO 2 (AEH) catalyst showed excellent catalytic performance in terms of 1,2-PDO selectivity and was stable up to 300 h. In contrast, the conventional Cu/SiO 2 (IM) prepared by wetness impregnation deactivated after 30 h under the same reaction conditions of 473 K reaction temperature, 5.0 MPa hydrogen pressure and 0.075 h −1 WHSV.…”

Bio-Based Solvents and Gasoline Components from Renewable 2,3-Butanediol and 1,2-Propanediol: Synthesis and Characterization

“…Renewable 1,2-PD could also be transformed into a cyclic ketal via traditional acid-catalyzed ketalization with acetone [25]. It should also be noted that the formation of TMD in the vapor-phase hydrogenolysis of solketal has been recently reported [26]. Some data on 1,2-PD cyclic ketals regarding their diesel fuel blending and physical/solvent properties can be found in the literature [25,27], whereas no data on the gasoline blending properties could be found by us.…”

Non-Porous Sulfonic Acid Catalysts Derived from Vacuum Residue Asphaltenes for Glycerol Valorization via Ketalization with Acetone

“…The industrial use of this compound as a component of green solvents for paints and coatings has been reported [7]. In addition, solketal can be used as a component of biodiesel fuel [8] or automotive gasoline [9][10][11], and also act as an intermediate for the synthesis of higher acetals and glycerol ketals [12], quinolones via Scraup reaction [13], or in the joint synthesis of isopropanol and propylene glycol via solketal destructive hydrogenolysis [14]. Thirdly, when using renewable raw materials, solketal can have a completely renewable nature.…”