Citation: Xue-Feng SHEN, Jia-Jia DING, Hong-Xing LIU. Hierarchical SAPO-34 templated by amphiphilic single-quaternary-ammonium surfactants[J]. Chinese Journal of Inorganic Chemistry, ;2023, 39(11): 2065-2073. doi: 10.11862/CJIC.2023.180 shu

Hierarchical SAPO-34 templated by amphiphilic single-quaternary-ammonium surfactants

Xue-Feng SHEN ^{1, 2} ,
Jia-Jia DING ^{1, 2} ,
Hong-Xing LIU ^{1, 2,,}

1.
SINOPEC Shanghai Research Institute of Petrochemical Technology Co., Ltd, Shanghai 201208, China
2.
State Key Laboratory of Green Chemical Engineering and Industrial Catalysis, Shanghai 201208, China

Corresponding author: Hong-Xing LIU, liuhx.sshy@sinopec.com
Received Date: 31 May 2023
Revised Date: 11 October 2023

Figures(7)

The introduction of mesopores and downsizing of the crystals of SAPO-34 can enhance its diffusion efficiency, leading to high catalytic activity in methanol-to-olefin (MTO) reactions. Amphiphilic single-quaternary-ammonium molecules with different lengths of carbon chains ([N⁺(CH₂CH₃)₃-C_nH_2n+1] [Br^-], Cn-1N (n=4, 6, 8)) were designed and synthesized as co-structure directing agents. Due to the electrostatic interaction, amphiphilic molecules acted as crystal growth inhibitors or pore-forming agents, which resulted in the formation of hierarchical SAPO-34 (HS) zeolite with a smaller crystal size. When the carbon chain length was four (C4-1N), the hierarchical SAPO-34 zeolite (HS-4) was synthesized with a smaller crystal size and without other crystal phases. SAPO-34 zeolites with high mesopore volume (HS-6 and HS-8) were synthesized with C6-1N and C8-1N as co-structure directing agents. Without adding a co-structure directing agent, conventional SAPO-34 (CS) was synthesized. There were many tetrahedral particles in CS, which is the early morphology of the cubic particles. The results of the X-ray fluorescence spectrometer (XRF) and ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS NMR) indicated that Cn-1N molecules restrain Si atoms from incorporating into the AlPO₄ framework. The results of NH₃-temperature-programmed desorption (NH₃-TPD) proved the strong acid gradually decreases in the order of CS > HS-8 > HS-6 > HS-4. The diffusion behaviors of methanol molecules in HS-4, HS-6, and HS-8 were better than in CS. HS-4 showed excellent catalytic performance in MTO reaction: the selectivity of ethylene (C₂H₄) and propylene (C₃H₆) (84.4%) has improved by about 4% compared to that of CS (80.5%), and the catalyst lifetime of HS-4 was about two times the lifetime of CS. HS-6 also exhibited high selectivity of C₂H₄ and C₃H₆ (83.5%), and its lifetime was almost the same as HS-4. HS-8 had a high mesopore volume, but the higher strong acidity promoted hydrogen transfer reactions, leading to alkanes, aromatics, and coke, so the lifetime of HS-8 in MTO reaction was slightly prolonged.
- SAPO-34,
- amphiphilic molecules,
- hierarchical pores,
- methanol-to-olefin reaction
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