Chinese Journal of Catalysis ›› 2016, Vol. 37 ›› Issue (12): 2134-2141.DOI: 10.1016/S1872-2067(16)62587-1

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Alkylation of toluene with tert-butyl alcohol over HPW-modified Hβ zeolite

Yuanyuan Wanga, Hua Songa, Xinglong Sunb   

  1. a Northeastern Petroleum University, Chemistry and Chemical Engineering, Daqing 163318, Heilongjiang, China;
    b Daqing Petrochemical Engineering Co., Ltd., Daqing 163714, Heilongjiang, China
  • Received:2016-09-29 Revised:2016-10-27 Online:2016-12-27 Published:2016-12-27
  • Contact: Hua Song

Abstract:

An Hβ-supported heteropoly acid (H3PW12O40 (HPW)/Hβ) catalyst was successfully prepared by wetness impregnation, and investigated in the alkylation of toluene with tert-butyl alcohol for the synthesis of 4-tert-butyltoluene (PTBT). X-ray diffraction, scanning electron microscopy, transmission electron microscopy, fourier-transform infrared spectroscopy, inductively coupled plasma-optical emission spectrometry, the brunauer emmett teller (BET) method, temperature-programmed NH3 desorption, and pyridine adsorption infrared spectroscopy were used to characterize the catalyst. The results showed that loading HPW on Hβ effectively increased the B acidity and decreased the pore size of Hβ. The B acidity of HPW/Hβ was 142.97 μmol/g, which is 69.74% higher than that of Hβ (84.23 μmol/g). The catalytic activity of the HPW/Hβ catalyst was much better than that of the parent Hβ zeolite because of its high B acidity. The toluene conversion over HPW/Hβ reached 73.1%, which is much higher than that achieved with Hβ (54.0%). When HPW was loaded on Hβ, the BET surface area of Hβ decreased from 492.5 to 379.6 m2/g, accompanied by a significant decrease in the pore size from 3.90 to 3.17 nm. Shape selectivity can therefore play an important role and increase the product selectivity of the HPW/Hβ catalyst compared with that of the parent Hβ. PTBT (kinetic diameter 0.58 nm) can easily diffuse through the narrowed pores of HPW/Hβ, but 3-tert-butyltoluene (kinetic diameter 0.65 nm) diffusion is restricted because of steric hindrance in these narrow pores. This results in high PTBT selectivity over HPW/Hβ (around 81%). The HPW/Hβ catalyst gave a stable catalytic performance in reusability tests.

Key words: Alkylation, Toluene, tert-Butyl alcohol, H3PW12O40, B acidity, H&beta, zeolite