石油学报(石油加工) ›› 2019, Vol. 35 ›› Issue (5): 1025-1032.doi: 10.3969/j.issn.1001-8719.2019.05.026

• 综述 • 上一篇    下一篇

SAPO-34催化甲醇制烯烃反应积炭机理及改性研究进展

黄芳涛1,2, 曹建新1,2,3, 刘飞1,2,3   

  1. 1.贵州大学 化学与化工学院,贵州 贵阳 550025;2.贵州省绿色化工与清洁能源技术重点实验室,贵州 贵阳 550025;
    3.贵州省矿产资源高效利用与绿色化工技术特色重点实验室,贵州 贵阳 550025
  • 收稿日期:2018-07-23 修回日期:2019-04-03 出版日期:2019-09-25 发布日期:2020-04-01
  • 通讯作者: 曹建新,男,教授,博士,从事资源能源转化催化技术研究,E-mail:jxcao@gzu.edu.cn;刘飞,男,教授,博士,从事资源能源转化催化技术研究,E-mail:ce.feiliu@gzu.edu.cn E-mail:jxcao@gzu.edu.cn
  • 作者简介:黄芳涛,男,硕士研究生,从事资源能源转化催化技术研究,E-mail:15185057923@163.com
  • 基金资助:
    国家自然科学基金项目(21666007)、贵州省百层次创新型人才专项(黔科合平台人才[2016]5655)、贵州省科技创新人才团队(黔科合平台人才[2018]5607)和贵州省科技计划项目(黔科合平台人才[2017]5788号)资助

Research Progress on Coke Formation Mechanism and Modification of SAPO-34 in Methanol to Olefins Reaction

HUANG Fangtao1,2, CAO Jianxin1,2,3, LIU Fei1,2,3   

  1. 1School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China;
    2Guizhou Key Laboratory for Green Chemical and Clean Energy Technology, Guiyang 550025, China;
    3.Guizhou Key Laboratory for Efficient Utilization of Mineral and Green Chemical Technology, Guiyang 550025, China
  • Received:2018-07-23 Revised:2019-04-03 Online:2019-09-25 Published:2020-04-01

摘要: SAPO34分子筛被认为是最有应用前景的甲醇制烯烃(MTO)反应催化剂。目前影响SAPO34分子筛工业化应用的主要问题是易积炭失活,单程寿命极短。SAPO34催化MTO反应过程中积炭主要来源于活性中间体的转化和烯烃的二次反应,且反应温度对积炭反应具有重要影响。现有的SAPO34分子筛改性调变以延长寿命的手段主要从其表面酸性质和结构性质入手,但效果不明显,主要原因是SAPO34特有的拓扑结构没有改变,积炭前驱体的扩散限制没有得到显著缓解。基于积炭形成机理以及目前延长SAPO34反应寿命的主要改性手段,笔者针对SAPO34反应寿命延长效果不明显的瓶颈问题,提出了制备具有微介孔结构的金属氧化物/分子筛复合结构催化剂的新思路,同时通过适当降低反应温度,以进一步抑制积炭生成,延长催化剂寿命。

关键词: SAPO-34, MTO, 积炭机理, 改性, 寿命, 复合结构, 拓扑结构

Abstract: SAPO34 molecular sieve is the most promising MTO catalyst. However, SAPO34 suffers from rapid deactivation with short lifetime in MTO due to coke deposition, which seriously affects the industrial application. The coke species mainly derive from the conversion of active intermediates, as well as the secondary reaction of olefins. The reaction temperature also has an important impact on the coke reaction. Generally, SAPO34 is mainly modulated by changing the surface acid property and structural property, and the lifetime of modified SAPO34 is slightly prolonged. The reason is that the special topology of SAPO34 has not been changed, and the diffusion limit of coke precursor has not been significantly alleviated. In this paper, based on the coke formation mechanism and the modified methods for prolonging lifetime of SAPO34 in existing researches, a new method is proposed to prepare the metal oxide/molecular sieve composite catalyst with new active centers and a micromeso porous structure. Moreover, reducing the reaction temperature appropriately inhibits the formation of coke, thus extending of catalyst lifetime.

Key words: SAPO-34, MTO, coking mechanism, modification, lifetime, composite structure, topology