Citation: Zhenhao Wen, Daqiang Yang, Fan Yang, Zhenhao Wei, Xuedong Zhu. Methylation of toluene with methanol over HZSM-5: A periodic density functional theory investigation[J]. Chinese Journal of Catalysis, ;2016, 37(11): 1882-1890. doi: 10.1016/S1872-2067(16)62523-8 shu

Methylation of toluene with methanol over HZSM-5: A periodic density functional theory investigation

a Engineering Research Center of Large Scale Reactor Engineering and Technology, East China University of Science and Technology, Shanghai 200237, China;
b State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China

Received Date: 6 May 2016
Revised Date: 27 July 2016

Fund Project: This work was supported by the National Natural Science Foundation of China (21446003) and the Specialized Research Fund for the Doctoral Pro-gram of Higher Education (20130074110018).

Periodic density functional theory was applied to investigate the reaction mechanism for the meth-ylation of toluene with methanol over HZSM-5. The results indicated that toluene could be methyl-ated at its para, meta, ortho and geminal positions via a concerted or stepwise pathway. For the concerted pathway, the calculated free energy barriers for the para, meta, ortho and geminal meth-ylation reactions were 167, 138, 139 and 183 kJ/mol, respectively. For the stepwise pathway, the dehydration of methanol was found to be the rate-determining step with a free energy barrier of 145 kJ/mol, whereas the free energy barriers for the methylation of toluene at its para, meta, ortho and geminal positions were 127, 105, 106 and 114 kJ/mol, respectively. Both pathways led to the formation of C₈H_11⁺ species as important intermediates, which could back-donate a proton to the zeolite framework via a reorientation process or form gaseous products through demethylation. Methane was formed via an intramolecular hydrogen transfer reaction from a ring carbon of the C₈H_11⁺ species to the carbon of the methyl group, with calculated energy barriers of 136, 132 and 134 kJ/mol for the para, meta and ortho C₈H_11⁺ species, respectively. The calculated free energy barriers for the formation of para-, meta-and ortho-xylene indicated that the formation of the pa-ra-xylene had the highest energy barrier for both pathways.
- Toluene,
- Methanol,
- Para-xylene,
- Methylation,
- Density functional theory,
- Hydrocarbon pool mechanism
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