Citation: ZHAO Shu-Heng, LANG Lin, YIN Xiu-Li, YANG Wen-Shen, WU Chuang-Zhi. TPAOH Template Removal from High-Silica ZSM-5 by Low-Temperature Hydrocracking[J]. Acta Physico-Chimica Sinica, ;2015, 31(4): 793-799. doi: 10.3866/PKU.WHXB201503021 shu

TPAOH Template Removal from High-Silica ZSM-5 by Low-Temperature Hydrocracking

1.
1 CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, P. R. China;
2 University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Received Date: 28 October 2014
Available Online: 2 March 2015
Fund Project: 国家自然科学基金(51106165, 51202245) (51106165, 51202245)广东省自然科学基金(10251007006000000, S2013010014896)资助项目 (10251007006000000, S2013010014896)

Zeolite membranes, especially the MFI-type zeolite membranes, have attracted significant attention for decades because of their special properties. While organic templates such as tetrapropylammonium hydroxide (TPAOH) have typically been used for the synthesis of ZSM-5 zeolite and zeolite membranes, the templates remain trapped in the as-synthesized zeolite crystals. A common method for removing organic templates and generating porous frameworks is calcination; however, during this process, the channel structure may be affected. In particular, for ZSM-5 membranes, membrane defects may be produced and the separation efficiency therefore may decrease to some extent. In this study, the low-temperature hydrocracking of TPAOH in ZSM-5 zeolite crystals was studied under H₂/N₂, while N₂ adsorption, thermogravimetric (TG) analysis, Fourier transform infrared (FTIR) spectroscopy, temperature-programmed desorption of ammonia (NH₃-TPD), and Raman spectroscopy were used to characterize zeolite samples. The results show that the organic template in the pores of ZSM-5 can be effectively removed below 350 ℃ by low-temperature hydrocracking. Characterization analyses by BET specific surface area, TG, FTIR, and Raman spectroscopy demonstrated that a reducing atmosphere containing H₂ was more conducive to template removal at low temperature than atmospheres of air or N₂. The degree of template removal increased with temperature increasing. The BET surface area of the crystal after hydrocracking at 280 ℃ reached 252 m²·g^-1, although a small amount of organic residue remained. Furthermore, after hydrocracking at 350 ℃, the BET surface area reached 399m2·g^-1, and only trace amount of inorganic carbon residue remained. In addition, the introduction of hydrogen at low temperatures could prevent coke deposits on acid sites and thus ZSM-5 zeolite crystals had greater numbers of acidic sites after low-temperature hydrocracking.
- ZSM-5 zeolite,
- Template removal,
- Low-temperature hydrocracking,
- High Si/Al ratio,
- Tetrapropylammonium hydroxide
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