Ring Opening of Biomass-Derived Cyclic Ethers to Dienes over Silica/Alumina

We show that cyclic ethers, such 2-methylte-trahydrofuran (2-MTHF), can undergo dehydration to produce pentadienes over SiO2/Al2O3. The catalyst exhibited reversible deactivation due to coke deposition, with the yield to pentadienes decreasing from 68% to 52% at 623 K over 58 h time on stream. A reaction network for 2-MTHF dehydration was proposed on the basis of the results of space time studies. Pentadienes can be produced directly by a concerted hydride shift and dehydration of carbenium intermediates or indirectly through dehydration of pentanal and pentenol. Reaction kinetics studies were performed at temperatures ranging from 573 to 653 K and 2-MTHF partial pressures from 0.21 to 2.51 kPa. The apparent activation energy barrier for 2-MTHF conversion to pentadienes and the reaction rate order for ring opening were determined to be 74 kJ mol(-1) and 0.24, respectively, indicating strong interaction between 2-MTHF and the SiO2/Al2O3 surface. Other solid acids such as gamma-Al2O3, H-ZSM-5, and Al-Sn-Beta were found to be active for 2-MTHF dehydration to pentadienes. The rate of ring opening decreased in the order 2,5-dimethyltetrahydrofuran > 2-MTHF > tetrahydropyran > tetrahydrofuran. Over SiO2/Al2O3, the dehydration of 2,5-dimethyltetrahydrofuran resulted in 75% yield to hexadiene isomers.