物理化学学报 >> 2014, Vol. 30 >> Issue (3): 535535-543.doi: 10.3866/PKU.WHXB201401032

催化和表面科学 上一篇    下一篇

纳米薄层HZSM-5分子筛催化甲醇制丙烯

张少龙, 张兰兰, 王务刚, 闵媛媛, 马通, 宋宇, 巩雁军, 窦涛   

  1. 中国石油大学(北京)化学工程学院, 重质油国家重点实验室, 中国石油天然气集团公司催化重点实验室, 北京102249
  • 收稿日期:2013-11-29 修回日期:2014-01-02 发布日期:2014-02-27
  • 通讯作者: 巩雁军 E-mail:gongyj@cup.edu.cn
  • 基金资助:

    国家重点基础研究发展规划项目(973) (2012CB215002),国家自然科学基金(21276278,21176255)及中国石油股份公司(2011A-2101)资助

Methanol to Propylene over Nanosheets of HZSM-5 Zeolite

ZHANG Shao-Long, ZHANG Lan-Lan, WANG Wu-Gang, MIN Yuan-Yuan, MATong, SONG Yu, GONG Yan-Jun, DOU Tao   

  1. State Key Laboratory of Heavy Oil Processing, The Key Laboratory of Catalysis, China National Petroleum Corporation, College of Chemistry Engineering, China University of Petroleum-Beijing, Beijing 102249, P. R. China
  • Received:2013-11-29 Revised:2014-01-02 Published:2014-02-27
  • Contact: GONG Yan-Jun E-mail:gongyj@cup.edu.cn
  • Supported by:

    The project was supported by the National Key Basic Research Program of China (973) (2012CB215002), National Natural Science Foundation of China (21276278, 21176255), and China National Petroleum Corporation (CNPC) Program (2011A-2101).

摘要:

在合成系列硅铝比纳米薄层HZSM-5分子筛的基础上,研究了纳米薄层HZSM-5分子筛催化甲醇制丙烯(MTP)的反应性能. 在固定床微反装置上详细考察了工艺条件对纳米薄层HZSM-5 分子筛催化性能的影响,同时与纳米HZSM-5 分子筛对MTP反应的催化性能进行了比较. 结果表明,纳米薄层HZSM-5 分子筛具有较高的目的产物选择性和较长的催化寿命. 在适宜硅铝比(n(SiO2)/n(Al2O3)=213)和反应条件下(温度470 ℃,甲醇质量空速为3 h-1),丙烯的选择性达到46.7%,三烯(乙烯、丙烯和C4烯烃)选择性达到78.7%. 其中,丙烯/乙烯的质量比可达到6.5,是纳米HZSM-5分子筛的2倍,而芳烃的选择性比纳米分子筛明显降低. 这是因为纳米薄层HZSM-5分子筛比纳米HZSM-5分子筛具有较宽的(010)晶面、较大的外比表面积和介孔孔容.

关键词: 纳米薄层, HZSM-5分子筛, 甲醇, 丙烯

Abstract:

Nanosheets of HZSM-5 zeolite with different SiO2/Al2O3 molar ratios were synthesized, and their catalytic behavior in the methanol-to-propylene (MTP) reaction was evaluated in a fixed bed reactor. The effect of reaction conditions on catalytic performance was studied in detail. The catalytic performance of nanosheets of HZSM-5 zeolites in the MTP reaction was compared with that of the nanosized HZSM-5 zeolite. The nanosheets of HZSM-5 zeolite had higher propylene selectivity, total three olefins' selectivity (ethylene, propylene, C4 alkenes) , and a longer catalytic lifetime than the nanosized HZSM-5 zeolite. The nanosheets of HZSM-5 zeolite with a SiO2/Al2O3 molar ratio of 213 yielded a propylene selectivity of 46.7%, total three olefins' selectivity of 78.7% at 470 ℃, and a methanol weight hourly space velocity (WHSV) of 3 h-1. It also yielded a propylene/ethylene mass ratio of 6.5, which was double that of the nanosized HZSM-5 zeolite. The nanosheets of HZSM-5 zeolite had a lower aromatic selectivity than the nanosized HZSM-5 zeolite. The good MTP catalytic performance of the nanosheets of HZSM-5 zeolite was attributed to their wide (010) surface, high external surface area, and large mesoporous volume.

Key words: Nanosheet, HZSM-5 zeolite, Methanol, Propylene

MSC2000: 

  • O643