Co-conversion of methanol and <i>n</i>-hexane into aromatics using intergrown ZSM-5/ZSM-11 as a catalyst

doi:10.1007/s11705-019-1868-2

Front. Chem. Sci. Eng.

2020, Vol. 14

Issue (5) : 783-792 https://doi.org/10.1007/s11705-019-1868-2

RESEARCH ARTICLE

Co-conversion of methanol and n-hexane into aromatics using intergrown ZSM-5/ZSM-11 as a catalyst

Shumei Wei^1,², Yarong Xu²(

), Zhaoyang Jin¹, Xuedong Zhu¹(

)

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

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Abstract

The conversion of n-hexane and methanol into value-added aromatic compounds is a promising method for their industrially relevant utilization. In this study, intergrown ZSM-5/ZSM-11 crystals were synthesized and their resulting catalytic performance was investigated and compared to those of the isolated ZSM-5 and ZSM-11 zeolites. The physicochemical properties of ZSM-5/ZSM-11 intergrown zeolite were analyzed using X-ray diffraction, N₂ isothermal adsorption-desorption, the temperature-programmed desorption of ammonium, scanning electron microscopy, Fourier transform infrared spectra of adsorbed pyridine, and nuclear magnetic resonance of ²⁷Al , and compared with those of the ZSM-5 and ZSM-11 zeolites. The catalytic performances of the materials were evaluated during the co-feeding reaction of methanol and n-hexane under the fixed bed conditions of 400°C, 0.5 MPa (N₂), methanol:꞉n-hexane=7꞉:3 (mass ratio), and weight hourly space velocity=1 h^–1 (methanol). Compared to the ZSM-5 and ZSM-11 zeolites, the ZSM-5/ZSM-11 zeolite exhibited the largest specific surface area, a unique crystal structure, moderate acidity, and suitable Brønsted/Lewis acid ratio. The evaluation results showed that ZSM-5/ZSM-11 catalyst exhibited better catalytic reactivity than the ZSM-5 and ZSM-11 catalysts in terms of methanol conversion rate, n-hexane conversion rate, and aromatic selectivity. The outstanding catalytic property of the intergrown ZSM-5/ZSM-11 was attributed to the enhanced diffusion associated with its unique crystal structure. The benefit of using zeolite intergrowth in the co-conversion of methanol and alkanes offers a novel route for future catalyst development.

Keywords ZSM-5/ZSM-11 methanol n-hexane cofeeding aromatics

Corresponding Author(s): Yarong Xu,Xuedong Zhu

Just Accepted Date: 19 November 2019 Online First Date: 30 December 2019 Issue Date: 25 May 2020

Cite this article:

Shumei Wei,Yarong Xu,Zhaoyang Jin, et al. Co-conversion of methanol and n-hexane into aromatics using intergrown ZSM-5/ZSM-11 as a catalyst[J]. Front. Chem. Sci. Eng., 2020, 14(5): 783-792.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-019-1868-2
https://academic.hep.com.cn/fcse/EN/Y2020/V14/I5/783

Fig.1 XRD patterns of the prepared samples: (a) 5°?50°, (b) 20°?25°, and (c) 44°?47°.

Tab.1 Physical properties of the prepared ZSM-5, ZSM-5/ZSM-11, and ZSM-11 zeolites.

Fig.2 N₂ adsorption isotherms of the prepared ZSM-5, ZSM-5/ZSM-11, and ZSM-11 zeolites.

Tab.2 Acid properties of the prepared ZSM-5, ZSM-5/ZSM-11 and ZSM-11 zeolites.

Fig.3 (a) NH₃-TPD profiles and (b) Py-IR profiles of the prepared ZSM-5, ZSM-5/ZSM-11 and ZSM-11 zeolites.

Fig.4 The ²⁷Al NMR patterns of the prepared ZSM-5, ZSM-5/ZSM-11, and ZSM-5 zeolite.

Tab.3 Relative amounts of Al species in the prepared ZSM-5, ZSM-5/ZSM-11, and ZSM-5 zeolites.

Fig.5 SEM images of (a1 and a2) ZSM-5, (b1 and b2) ZSM-5/ZSM-11, and (c1 and c2) ZSM-11.

Fig.6 TEM images of the prepared (a) ZSM-5, (b) ZSM-5/ZSM-11, and (c) ZSM-11 zeolites.

Fig.7 Time course of methanol conversion over the ZSM-5, ZSM-5/ZSM-11, and ZSM-11 catalysts.

Fig.8 Time course of n-hexane conversion over the ZSM-5, ZSM-5/ZSM-11, and ZSM-11 catalysts.

Fig.9 Time course of the selectivity for aromatics over the ZSM-5, ZSM-5/ZSM-11, and ZSM-11 catalysts.

Fig.10 Aromatic distribution as a function of time on stream over the ZSM-5, ZSM-5/ZSM-11, and ZSM-11 catalysts.

Fig.11 Gas production distribution in the cofeeding reaction of methanol with n-hexane over the ZSM-5, ZSM-5/ZSM-11, and ZSM-11 catalysts at TOS= 8 h (400°C, methanol?n-hexane= 7?3, WHSV= 1 h^?¹ (methanol) and 0.5 MPa (N₂)).

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