Citation: Yuanyuan Wang, Hua Song, Xinglong Sun. Alkylation of toluene with tert-butyl alcohol over HPW-modified Hβ zeolite[J]. Chinese Journal of Catalysis, ;2016, 37(12): 2134-2141. doi: 10.1016/S1872-2067(16)62587-1 shu

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

a Northeastern Petroleum University, Chemistry and Chemical Engineering, Daqing 163318, Heilongjiang, China;
b Daqing Petrochemical Engineering Co., Ltd., Daqing 163714, Heilongjiang, China

Received Date: 29 September 2016
Revised Date: 27 October 2016

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.
- Alkylation,
- Toluene,
- tert-Butyl alcohol,
- H₃PW₁₂O₄₀,
- B acidity,
- Hβ zeolite
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沈阳化工大学材料科学与工程学院沈阳 110142