The kinetics of propylene epoxidation over Au supported on titanium silicalite-1 (Au/TS-1) catalysts were measured in a continuous stirred tank reactor (CSTR) free from temperature and concentration gradients. Apparent reaction orders measured at 473 K for H2 (0.7 order), O2 (0.2), and propylene (0.2) for a series of Au/TS-1 with varied Au (0.02–0.09 wt%) and Ti (Si/Ti: 75–143) contents were consistent with those reported previously. Co-feeding propylene oxide enabled measurement of the apparent reaction order in propylene oxide (−0.4 to −0.8 order) and the determination that relevant pressures of propylene oxide reversibly inhibit propylene epoxidation over Au/TS-1, while co-feeding carbon dioxide and water had no effect on the propylene epoxidation rate. Analysis of previously proposed two-site reaction mechanisms in light of reaction orders for O2 (0.4), H2 (1), and C3H6 (0.4), corrected to account for propylene oxide inhibition, provides further evidence that propylene epoxidation over Au/TS-1 occurs via a simultaneous mechanism requiring two distinct, but adjacent, types of sites, and not a sequential mechanism that invokes migration of H2O2 formed on Au sites to PO forming Ti sites. H2 oxidation rates are not inhibited by propylene oxide, implying that the sites required for hydrogen oxidation are distinct from those required for propylene epoxidation.
Bibliographical noteFunding Information:
The authors acknowledge funding from the U.S. Department of Energy, Office of Basic Energy Sciences, Chemical Sciences, under Grant DE-FG02-03ER15408. Garrett Mitchell acknowledges Purdue University for funding from an Andrews fellowship. We thank Jason Bates, Michael Cordon, Dr. Viktor Cybulskis, and Dr. Wen-Sheng Lee (Dow Chemical) for many useful discussions, and also thank Dr. Yury Zvinevich for assistance constructing the CSTR reactor unit.
- Product inhibition