催化学报

催化学报 ›› 2013, Vol. 34 ›› Issue (6): 1148-1158.DOI: 10.1016/S1872-2067(12)60579-8

• 研究论文 • 上一篇    下一篇

四丙基氢氧化铵改性纳米HZSM-5分子筛及其在甲醇制汽油中的催化性能

何英萍a, 刘民a, 代成义a, 徐舒涛b, 魏迎旭b, 刘中民b, 郭新闻a   

  1. a 大连理工大学化工学院催化化学与工程系, 精细化工国家重点实验室, 辽宁大连116024;
    b 中国科学院大连化学物理研究所, 辽宁大连116023
  • 收稿日期:2012-11-30 修回日期:2013-03-18 出版日期:2013-06-07 发布日期:2013-06-09
  • 通讯作者: 刘民,郭新闻
  • 基金资助:

    新世纪优秀人才支持计划(NCET-04-0268); 教育部111计划工程.

Modification of nanocrystalline HZSM-5 zeolite with tetrapropylammonium hydroxide and its catalytic performance in methanol to gasoline reaction

HE Yingpinga, LIU Mina, DAI Chengyia, XU Shutaob, WEI Yingxub, LIU Zhongminb, GUO Xinwena   

  1. a State Key Laboratory of Fine Chemicals, Department of Catalysis Chemistry and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, Liaoning, China;
    b Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China
  • Received:2012-11-30 Revised:2013-03-18 Online:2013-06-07 Published:2013-06-09
  • Supported by:

    This work was supported by the New Century Excellent Talent in University, China (NCET-04-0268) and the Plan 111 Project of the Ministry of Education of China.

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被引次数

65

摘要：

采用四丙基氢氧化铵(TPAOH)溶液对纳米ZSM-5分子筛进行改性, 运用X射线衍射、扫描电镜、27Al和29Si固体核磁、X射线光电子能谱、N2物理吸附脱附法和NH3程序升温脱附等手段对所制样品进行了表征, 并评价了其催化甲醇制汽油反应性能. 结果表明, 改性后的HZSM-5相对结晶度增加, 晶体形貌更加规整, 表面硅铝比增加, 比表面积和微孔表面积增大, 强酸位酸量增多. 同时, TPAOH改性不仅可以使分子筛脱硅脱铝, 而且伴有二次晶化补硅补铝, 改变了分子筛的硅铝分布. 改性的HZSM-5在甲醇制汽油反应中的稳定性大幅度提高, 其寿命由70h增至170h以上, 随着TPAOH处理时间的增加, 催化剂寿命增加, 氢转移反应加快, 导致油相产品中异构烷烃增多, 烯烃减少.

关键词: 纳米HZSM-5, 分子筛, 四丙基氢氧化铵, 甲醇制汽油

Abstract:

Nanocrystalline ZSM-5 zeolite was modified with tetrapropylammonium hydroxide (TPAOH) solution. The effect of the TPAOH treatment time on the catalytic performance of HZSM-5 was investigated in methanol to gasoline (MTG) reaction. The modified samples were characterized using X-ray diffraction, scanning electron microscopy, 27Al and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy, X-ray photoelectron spectroscopy, N2 adsorption, and NH3 temperature-programmed desorption. The HZSM-5 structure was basically unchanged after modification, but the relative crystallinity increased and the crystal morphology was more regular. The Brunauer-Emmett-Teller surface area, the micropore surface area, the surface Si/Al ratio, and the amount of strong acid sites increased; this might be caused by desilication and dealumination, and secondary crystallization of the zeolite during the treatment. The stability of the catalyst was significantly improved after modification, as reflected by the increased lifetime from 70 h to above 170 h in MTG reaction. The catalyst lifetime increased with increasing TPAOH treatment time. Hydrogen transfer reactions became faster and led to more isoparaffins and less olefins in the liquid products.

Key words: Nanocrystalline HZSM-5, Zeolite, Tetrapropylammonium hydroxide, Methanol to gasoline