Alkaline modification of ZSM-5 catalysts for methanol aromatization: The effect of the alkaline concentration

doi:10.1007/s11705-015-1542-2

Front. Chem. Sci. Eng.

2015, Vol. 9

Issue (4) : 450-460 https://doi.org/10.1007/s11705-015-1542-2

RESEARCH ARTICLE

Alkaline modification of ZSM-5 catalysts for methanol aromatization: The effect of the alkaline concentration

Zhenhao Wei¹,Tengfei Xia¹,Minghui Liu¹,Qingsheng Cao¹,Yarong Xu^1,²,Kake Zhu¹,Xuedong Zhu^1,^*(

)

1. State Key Laboratory of Chemical Engineering, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
2. Research Institute of Urumchi Petrochemical Company, PetroChina Company Limited, Urumchi 830019, China

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Abstract

The effects of alkaline treatment on the physical properties of ZSM-5 catalysts and on their activities for methanol to aromatics conversion have been investigated. A mild alkaline treatment (0.2 and 0.3 mol/L NaOH) created mesopores in the parent zeolite with no obvious effect on acidity. The presence of mesopores gives the catalyst a longer lifetime and higher selectivity for aromatics. Treatment with 0.4 mol/L NaOH decreased the number of Brønsted acid sites due to dealumination and desilication, which resulted in a lower deactivation rate. In addition, more mesopores were produced than with the mild alkaline treatment. As a result, the lifetime of the sample treated with 0.4 mol/L NaOH was almost five times that of the parent ZSM-5. Treatment with a higher alkaline concentration (0.5 mol/L) greatly reduced the number of Brønsted acid sites and the number of micropores resulting in incomplete methanol conversion. When the alkaline-treated catalysts were washed with acid, some of the porosity was restored and a slight increase in selectivity for aromatics was obtained.

Keywords aromatics ZSM-5 alkaline treatment dealumination desilication mesopores methanol

Corresponding Author(s): Xuedong Zhu

Online First Date: 16 November 2015 Issue Date: 26 November 2015

Cite this article:

Kake Zhu,Xuedong Zhu,Zhenhao Wei, et al. Alkaline modification of ZSM-5 catalysts for methanol aromatization: The effect of the alkaline concentration[J]. Front. Chem. Sci. Eng., 2015, 9(4): 450-460.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-015-1542-2
https://academic.hep.com.cn/fcse/EN/Y2015/V9/I4/450

Fig.1 XRD patterns of the parent and modified ZSM-5 samples

Fig.2 SEM of the parent and modified HZSM-5 samples. (a and b): R; (c) AT0.2; (d and e): AT0.5 (the scale bar of Fig. 2(e) is 2 µm)

Tab.1 Chemical composition and textural properties of the parent and modified ZSM-5 samples

Fig.3 N₂ adsorption-desorption isotherms of (a) R, AT0.2, AT0.3, and AT0.4 and (b) AT0.5 and AT0.5-AW0.1

Fig.4 BJH mesopore distributions derived from the isotherm adsorption branches for the parent and alkaline-treated zeolites

Fig.5 NH₃-TPD patterns of (a) R, AT0.2, AT0.3, and AT0.4 and (b) AT0.5 and AT0.5-AW0.1

Tab.2 Acidic properties of the parent and modified ZSM-5 samples

Fig.6 Pyridine infrared spectra for samples R, AT0.3, AT0.4 and AT0.5

Tab.3 Product distribution of MTA reactions with different catalysts^a)

Fig.7 (a) Methanol conversion and (b) selectivity for BTX versus time on stream (reaction conditions: 400 °C, 1 atm, WHSV=1.0 h⁻¹)

Fig.8 TGA profiles of used catalysts after 8 h on stream

Fig.9 (a) Methanol conversion and (b) selectivity for BTX versus time on stream for two reaction-regeneration cycles (reaction conditions: 400 °C, 1atm, WHSV= 1.0 h⁻¹)

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