Synthesis of Hierarchical ZSM-22 Zeolite and its Catalytic Performance for Hydrogenation Isomerization of n-Dodecane

doi:10.11901/1005.3093.2025.096

Chinese Journal of Materials Research

2026, Vol. 40

Issue (1): 1-12 DOI: 10.11901/1005.3093.2025.096

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Synthesis of Hierarchical ZSM-22 Zeolite and its Catalytic Performance for Hydrogenation Isomerization of n-Dodecane

HAN Yang¹^,², LI Mengchen³^,⁴, YU Hongyue³, QIAO Liang³, SHEN Yuge³, GAO Shanbin³, JIAO Yilai²(

), CHI Kebin³(

)

^1.School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
^2.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
^3.Petrochemical Research Institute, PetroChina Company Limited, Beijing 102206, China
^4.Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

Cite this article:

HAN Yang, LI Mengchen, YU Hongyue, QIAO Liang, SHEN Yuge, GAO Shanbin, JIAO Yilai, CHI Kebin. Synthesis of Hierarchical ZSM-22 Zeolite and its Catalytic Performance for Hydrogenation Isomerization of n-Dodecane. Chinese Journal of Materials Research, 2026, 40(1): 1-12.

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Abstract

The zeolite ZSM-22 with different grain length and pore structure was synthesized by hydrothermal synthesis with TDPA as mesoporous template agent. The synthesized material was characterized using XRD, XRF, SEM, TEM, NH₃-TPD, N₂ adsorption/desorption, solid-state NMR, and Py-IR. The results indicated that the incorporation of TDPA is beneficial for the formation of the mesoporous structure and the optimization of the acidity distribution for the prepared ZSM-22 zeolite. Then, a novel bifunctional noble metal catalyst was prepared with the acquired hierarchical ZSM-22 zeolite as support, meanwhile the performance of catalyst in the hydrogenation isomerization of n-dodecane was evaluated. The results revealed that with a molar ratio of nTDPA/SiO₂ of 0.0170, the synthesized ZSM-22 zeolite presented proper pore structure and acidic performance, with an average crystal grain length lowered to 200 nm and an optimal distribution of acid strength and acid sites. For the n-dodecane conversion rate of 83%, the isomer selectivity increased to 68%, representing a 10-percentage-point improvement compared to the conventional blank ZSM-22 catalyst (58%). This study provides a new approach for developing highly efficient hydroisomerization catalyst through the in-situ synthesis of ZSM-22 zeolites with mesoporous structures.

Key words: inorganic non-metallic materials molecular sieves hydroisomerization mesoporous porous structure acidity ZSM-22

Received: 04 March 2025

ZTFLH:

TE65

Fund: National Key Research and Development Program of China(2023YFB3810600);National Natural Science Foundation of China(22378407)

Corresponding Authors: JIAO Yilai, Tel: (024)23971936, E-mail: yljiao@imr.ac.cn;
CHI Kebin, Tel: (010)80165536, E-mail: ckb459@petrochina.com.cn

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	HAN Yang
	LI Mengchen
	YU Hongyue
	QIAO Liang
	SHEN Yuge
	GAO Shanbin
	JIAO Yilai
	CHI Kebin

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https://www.cjmr.org/EN/10.11901/1005.3093.2025.096 OR https://www.cjmr.org/EN/Y2026/V40/I1/1

Fig.1 Fixed-bed catalyst evaluation apparatus

Fig.2 XRD patterns and relative crystallinity of ZSM-22 zeolite with different TDPA additive amounts

Table 1 Results of synthetic products with different TDPA additive amounts by BET analysis

Fig.3 Texture properties of synthetic products (a) N₂ adsorption-desorption isotherm curves of products synthesized with different TDPA addition, (b) BJH aperture distribution, (c) H-K micropore size distribution, (d) H-K cumulative pore size distribution

Fig.4 SEM images of the synthesized products with different TDPA addition amounts and its grain length frequency distribution (a) Z22-0, (b) Z22-0.0068, (c) Z22-0.0119, (d) Z22-0.0170, (e) Z22-0.0221, (f) Z22-0.0272

Fig.5 TEM images (a) Z22-0, (b) Z22-0.0170

Fig.6 NMR spectra of the synthesized products with different TDPA addition amounts (a) ²⁷Al NMR spectra, (b) ²⁹Si NMR spectra

Table 2 Concentration of acid sites determined by NH₃-TPD and SiO₂/Al₂O₃ determined by XRF

Fig.7 Acidity characterization of products synthesized with different TDPA addition (a) NH₃-TPD, (b) Py-IR spectra at 200 ^oC

Table 3 Py-IR analysis results of the synthesized products with different TDPA addition amounts

Fig.8 Comprehensive electron microscopy analysis results of Pt/Z22-0.0170-5L (a) SEM-EDS surface scanning mapping, (b) TEM image, (c) STEM image

Fig.9 Evaluation results of n-dodecane hydroisomerization (a) iso-hexadecane yield, (b) iso-hexadecane selectivity

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