The role of mesoporosity and Si/Al ratio in the catalytic etherification of glycerol with benzyl alcohol using ZSM-5 zeolites

• Zeolites as solid acid catalysts for glycerol etherification.
• Glycerol etherification reaction conducted with benzyl alcohol.
• Mesoporous vs microporous zeolites provide different selectivity.
• Catalysts highly active and reusable under investigated conditions.

A comparative study of the influence of three different acid solids as catalysts (conventional zeolites Z15c with Si/Al = 19.5 and Z40c with Si/Al = 48.2, and a hierarchical zeolite Z40c-H with Si/Al = 50.0) for the etherification of glycerol with benzyl alcohol was performed. The catalytic activity and selectivity of these zeolites was elucidated at different catalyst contents. Three different ethers (3-benzyloxy-1,2-propanediol, which is a mono-benzyl-glycerol ether (MBG) and 1,3-dibenzyloxy-2-propanol, which is a di-benzyl-glycerol ether (DBG) and dibenzyl ether (DBz) were identified as the main products. MBG was the major product of the reaction catalyzed by the microporous Z15c zeolite with low Si/Al molar ratio, whereas DBG was formed in higher yield with the use of microporous Z40c and hierarchical Z40c-H zeolites, both of them having a similar high Si/Al molar ratio (≈50). MBG is a value-added product and it is obtained with good yield and selectivity when using the conventional zeolite Z15c as a catalyst. Under the best conditions tested, i.e., 25 mg of catalyst for 8 h at 120 °C, a 62% of conversion was obtained without the need of solvent, with an excellent 84% selectivity toward the MBG and no formation of DBz.

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