Effect of hierarchical ZSM-5 zeolite crystal size on diffusion and catalytic performance of <i>n</i>-heptane cracking

doi:10.1007/s11705-018-1733-8

Front. Chem. Sci. Eng.

2018, Vol. 12

Issue (4) : 780-789 https://doi.org/10.1007/s11705-018-1733-8

RESEARCH ARTICLE

Effect of hierarchical ZSM-5 zeolite crystal size on diffusion and catalytic performance of n-heptane cracking

Shuman Xu¹, Xiaoxiao Zhang¹, Dangguo Cheng¹(

), Fengqiu Chen¹, Xiaohong Ren^2,³

¹. Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
². School of Chemistry and Chemical Engineering, Tianjin University of Technology, Tianjin 300384, China
³. State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China

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Abstract

Hierarchical ZSM-5 zeolite aggregates with different sizes of nanocrystals were synthesized using different amounts of the mesoporogen 3-aminopropyltriethoxysilane. The effect of the crystal size on the catalytic cracking of n-heptane was investigated and the Thiele modulus and effectiveness factor were used to determine the reaction rate-limiting step. The crystal size affected the textual properties of the catalysts but not the acidic properties of the catalysts. The reaction rate was first order with respect to the n-heptane concentration. Cracking over hierarchical zeolites with nanocrystal sizes larger than about 50 nm took place under transition-limiting conditions, whereas the reaction over hierarchical zeolites with nanocrystal sizes of 15 or 30 nm proceeded under reaction control conditions. Hierarchical ZSM-5 zeolite aggregates with smaller nanocrystals had better selectivity for light olefins which can be ascribed to the shorter diffusion path lengths and lower diffusion resistance in these catalysts. Furthermore, these catalysts had lower coking levels which can be attributed to the substantial number of mesopores which prevent the formation of coke precursors.

Keywords hierarchical ZSM-5 crystal size catalytic cracking Thiele modulus effectiveness factor

Corresponding Author(s): Dangguo Cheng

Online First Date: 10 July 2018 Issue Date: 03 January 2019

Cite this article:

Shuman Xu,Xiaoxiao Zhang,Dangguo Cheng, et al. Effect of hierarchical ZSM-5 zeolite crystal size on diffusion and catalytic performance of n-heptane cracking[J]. Front. Chem. Sci. Eng., 2018, 12(4): 780-789.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-018-1733-8
https://academic.hep.com.cn/fcse/EN/Y2018/V12/I4/780

Fig.1 XRD patterns of ZSM-5 zeolites prepared with different amounts of APTES

Fig.2 SEM images of microporous and hierarchical ZSM-5 zeolites. (a) HZ-0, (b) HZ-1, (c) HZ-2, and (d) HZ-3

Fig.3 TEM images with nanocrystal size distribution charts of hierarchical and microporous ZSM-5 zeolites. (a) HZ-0, (b) HZ-1, (c) HZ-2, and (d) HZ-3

Fig.4 N₂ adsorption-desorption isotherms of microporous and hierarchical ZSM-5 zeolites

Tab.1 Textural parameters of the HZ samples

Fig.5 NH₃-TPD profiles of the HZ samples. (a) HZ-0, (b) HZ-1, (c) HZ-2 and (d) HZ-3

Tab.2 NH₃-TPD results for the microporous and hierarchical ZSM-5 zeolites

Fig.6 The relationships between F_A0DX_A/W and C_A0 (1 ? DX_A/2) for n-heptane cracking over the prepared samples. (a) HZ-0, (b) HZ-1, (c) HZ-2 and (d) HZ-3; Reaction conditions: t = 923 K, WHSV= 2–8 h^?¹

Fig.7 Relationship between W/F_A0 and –ln (1 ? X_A)/C_A0 in n-heptane cracking over the prepared samples. (a) HZ-0, (b) HZ-1, (c) HZ-2 and (d) HZ-3; Reaction conditions: t = 923 K, WHSV= 2–8 h^?¹

Tab.3 Activated diffusion parameters for n-heptane in ZSM-5 zeolites

Tab.4 Reaction rate constants, Thiele modulus and effectiveness factors for the n-heptane cracking reactions at 923 K over ZSM-5 zeolites

Fig.8 Relationship between the Thiele modulus and the effectiveness factor for n-heptane cracking at 923 K over the prepared samples

Fig.9 Selectivity of light olefins and conversion of n-heptane over the prepared samples. Reaction conditions: t = 923 K, WHSV= 2.4 h^?¹.

Fig.10 Thermal gravimetric curves of the deactivated catalysts after being subjected to n-heptane cracking

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