Effect of Alcohol Structure on the Kinetics of Etherification and Dehydration over Tungstated Zirconia

Abstract Linear and branched ether molecules have attracted recent interest as diesel additives and lubricants that can be produced from biomass‐derived alcohols. In this study, tungstated zirconia was identified as a selective and green solid acid catalyst for the direct etherification of primary alcohols in the liquid phase, achieving ether selectivities of >94 % for C 6 –C 12 linear alcohol coupling at 393 K. The length of linear primary alcohols (C 6 –C 12 ) was shown to have a negligible effect on apparent activation energies for etherification and dehydration, demonstrating the possibility to produce both symmetrical and asymmetrical linear ethers. Reactions over a series of C 6 alcohols with varying methyl branch positions indicated that substituted alcohols (2°, 3°) and alcohols with branches on the β‐carbon readily undergo dehydration, but alcohols with branches at least three carbons away from the ‐OH group are highly selective to ether. A novel model compound, 4‐hexyl‐1dodecanol, was synthesized and tested to further demonstrate this structure–activity relationship. Trends in the effects of alcohol structure on selectivity were consistent with previously proposed mechanisms for etherification and dehydration, and help to define possible pathways to selectively form ethers from biomass‐derived alcohols.