催化学报 ›› 2013, Vol. 34 ›› Issue (8): 1576-1582.DOI: 10.1016/S1872-2067(12)60621-4

• 研究论文 • 上一篇    下一篇

多级孔ZSM-5分子筛的合成及其在甲醇脱水制二甲醚反应中的应用

杨琦a, 张海涛b, 孔猛a, 包秀秀a, 费金华a, 郑小明a   

  1. a 浙江大学催化研究所, 浙江省应用化学重点实验室, 浙江杭州310028;
    b 中国石油兰州化工研究中心, 甘肃兰州730060
  • 收稿日期:2013-03-05 修回日期:2013-05-13 出版日期:2013-08-16 发布日期:2013-07-30
  • 通讯作者: 费金华
  • 基金资助:

    国家重点基础研究发展计划(973计划,2007CB210207和2013CB228104); 国家高技术研究发展计划(863计划, 2007AA05Z415).

Hierarchical mesoporous ZSM-5 for the dehydration of methanol to dimethyl ether

Qi Yanga, Haitao Zhangb, Meng Konga, Xiuxiu Baoa, Jinhua Feia, Xiaoming Zhenga   

  1. a Institute of Catalysis, Key Laboratory of Applied Chemistry of Zhejiang Province, Zhejiang University, Hangzhou 310028, Zhejiang, China;
    b Petrochina Lanzhou Chemical Research Centre, Lanzhou 730060, Gansu, China
  • Received:2013-03-05 Revised:2013-05-13 Online:2013-08-16 Published:2013-07-30
  • Supported by:

    This work was supported by the National Basic Research Program of China (973 Program, 2007CB210207, 2013CB228104) and the High Technology Research and Development Program of China (863 Program, 2007AA05Z415).

摘要: 以四丙基氨为微孔模版剂,阳离子高分子聚合物为介孔模版剂,合成了具有多级介孔的ZSM-5分子筛,并用于甲醇气相脱水合成二甲醚.结果表明,加入阳离子高分子聚合物后,合成的HZSM-5分子筛样品既保持了其MFI典型结构,又呈现了多级介孔特征;随着阳离子高分子聚合物模板剂加入量的增加,其多级介孔特征更为明显.具有多级介孔的HZSM-5分子筛表现出比常规微孔HZSM-5分子筛高的反应稳定性和二甲醚选择性,这主要是由于其织构和酸性的双重作用.

关键词: 多级孔, HZSM-5分子筛, 表面酸性, 甲醇脱水, 二甲醚

Abstract: Hierarchical mesoporous ZSM-5 zeolites were synthesized using small organic cations of tetrapropylammonium and meso-sized cationic polymers of dimethyldiallyl ammonium chloride acrylamide copolymer as templates. The zeolites were used for the dehydration of methanol to dimethyl ether (DME). Characterization results showed that the basic MFI-type structure was still obtained after adding the cationic polymers, while their nitrogen isotherms exhibited a broad hysteresis loop at relative pressures higher than 0.4, which proved the presence of mesopores. The mesoporosity of the hierarchical mesoporous ZSM-5 can be adjusted simply by adding different amounts of the cationic polymer. Catalytic tests showed that the hierarchical mesoporous HZSM-5 zeolites exhibited better stability than conventional HZSM-5 and excellent DME selectivity. The activity for methanol dehydration strongly depended on the textural property and acidity of the catalyst.

Key words: Hierarchical mesopore, HZSM-5 zeolite, Surface acidity, Methanol dehydration, Dimethyl ether