Journal of Catalysis, Vol.307, 305-315, 2013
Continuous production of the renewable rho-cymene from alpha-pinene
The aim of this work was to demonstrate the feasibility to produce rho-cymene, an important commodity chemical, in a continuous, one-pot reaction system from abundant alpha-pinene, available e.g. as a by-product of pulping industry. The isomerization reactions of alpha-pinene over bimetallic heterogeneous catalysts, 3 and 5 wt% Pd-Zn (1:1, 1:4, 4:1, 1:0, and 0:1), supported on Al-SBA15 were studied. The principal reaction products were identified as rho- and m-cymenes, limonene, camphene, and rho-menthene, respectively. The highest concentration of rho-cymene reached 77 wt% under the optimized reaction conditions: 300 degrees C and alpha-pinene feed of 0.03 mL/min. Two main reaction pathways toward rho- and m-cymenes were described, and a mechanistic kinetic model, based on a plausible reaction network in line with Langmuir-Hinshelwood approach, was developed. The catalyst characterization revealed the reduction in Pd(II) sites, catalyst coking, and decline of surface area over the course of time. The catalyst recovery and reuse was addressed. (C) 2013 Elsevier Inc. All rights reserved.