Citation: HU Si, ZHANG Qing, XIA Zhi, NG Yan-Jun, XU Jun, DENG Feng, DOU Tao. Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite[J]. Acta Physico-Chimica Sinica, ;2012, 28(11): 2705-2712. doi: 10.3866/PKU.WHXB201207171 shu

Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite

HU Si ¹ ,
ZHANG Qing ¹ ,
XIA Zhi ² ,
NG Yan-Jun ^1, ,
XU Jun ³ ,
DENG Feng ³ ,
DOU Tao ^1,2,

1.
1 The Key Laboratory of Catalysis of CNPC, China University of Petroleum-Beijing, Beijing 102249, P. R. China;
2 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
3 Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071, P. R. China

Received Date: 25 May 2012
Available Online: 17 July 2012
Fund Project: 国家重点基础研究发展计划(973)项目(2012CB215002) (973)项目(2012CB215002) 国家自然科学基金(10979076, 21176255) (10979076, 21176255) 国际科技合作与交流专项项目(2010DFB40440)资助 (2010DFB40440)

(NH₄)₂SiF₆-modified nanosized HZSM-5 zeolite was prepared and investigated as a catalyst formethanol to propylene conversion. The effects of this modification on the framework, textural propertiesand acidity of both the parent and the modified HZSM-5 zeolite were investigated by powder X-raydiffraction (XRD), ²⁷Al magic angle spinning nuclear magnetic resonance (²⁷Al MAS NMR), X-rayfluorescence (XRF), X-ray photoelectron spectroscopy (XPS), N₂ adsorption, transmission electronmicroscopy (TEM), temperature-programmed desorption of ammonia (NH₃-TPD), and infraredspectroscopy of adsorbed pyridine (Py-IR). The catalytic performance of these materials on the methanolto propylene (MTP) conversion process was tested under operating conditions of T=450℃, p=0.1 MPa(p_MeOH=50 KPa) and WHSV=1 h^-1. The results showed that surface aluminum on the nanosized ZSM-5zeolite could be selectively removed by the (NH₄)₂SiF₆ solution and that the number of acidic sites on theHZSM-5 zeolite gradually decreased with increasing (NH₄)₂SiF₆ concentration. Moreover, after modification with an optimally concentrated (NH₄)₂SiF₆ solution, an obvious increase in specific surface area as well asmesopore volume was observed for the nanosized HZSM-5 with a resulting dramatic improvement in thecatalytic performance of this material for the MTP reaction. Both the propylene selectivity and propylene/ethylene (P/E) mass ratio resulting from use of the modified HZSM-5 increased significantly to 45.1% and8.0, as compared to results of 28.8% and 2.6 obtained with the original material. In addition, the catalyticlifespan of the modified zeolite was double that of the original.
- Nanosized ZSM-5,
- Dealumination,
- Pore structure,
- Acidity,
- Propylene selectivity,
- Catalytic lifetime
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Catalytic Conversion of Methanol to Propylene over (NH₄)₂SiF₆-Modified Nanosized HZSM-5 Zeolite