石油炼制与化工 ›› 2025, Vol. 56 ›› Issue (3): 90-98.

• 基础研究 • 上一篇    下一篇

MFI分子筛中质子酸位点对C4组分反应路径的影响

侯轶膑,张榕芯,王子健,陆斌,王杰广   

  1. 中石化石油化工科学研究院有限公司
  • 收稿日期:2024-02-29 修回日期:2024-09-02 出版日期:2025-03-12 发布日期:2025-02-25
  • 通讯作者: 王杰广 E-mail:wangjg.ripp@sinopec.com
  • 基金资助:
    中国石油化工股份有限公司课题

EFFECT OF BRONSTED ACID SITES IN MFI ZEOLITE ON REACTION PATHWAYS OF C4 COMPONENT

  • Received:2024-02-29 Revised:2024-09-02 Online:2025-03-12 Published:2025-02-25
  • Contact: Wang Jieguang E-mail:wangjg.ripp@sinopec.com

摘要: 为系统研究MFI分子筛质子酸位点对异丁烷和1-丁烯转化的作用,采用硅铝原子比为20~150的ZSM-5系列分子筛为催化材料,考察了反应温度400~600 ℃范围内质子酸位点数量对异丁烷、1-丁烯以及二者不同比例混合物转化反应的产物分布及反应路径的影响。试验结果表明:以异丁烷为反应物时,质子酸位点数量会影响二次反应的深度,反应由烷烃单分子质子化裂解引发;以1-丁烯为反应物时,反应由烯烃异构-叠合-氢转移的双分子路径引发;以异丁烷与1-丁烯混合物为反应物时,反应仍以双分子路径为主,产物组成介于以纯异丁烷和纯1-丁烯作为反应物之间。进一步说明,只有合理匹配质子酸位点和反应条件,才能实现对C4组分反应路径与产物分布的调控。

关键词: C4组分, ZSM-5分子筛, 质子酸, 单分子裂解, 双分子路径

Abstract: A series ZSM-5 zeolites with a silicon-to-aluminum atomic ratio of 20 - 150 were applied to systematically study the effects of proton acid sites on the catalytic performance of i-butane and 1-butene. The relationships between the quantity of proton acid site and product distributions and reaction pathways of i-butane, 1-butene, and their mixtures with different ratios were investigated in the temperature range of 400–600 oC, respectively. In the case of long residence time of reactants, the number of proton acid sites affects the depth of the secondary reaction. For i-butane, the reaction is initiated by the protonation and monomolecular cracking, and whereas for 1-butene, the reaction is initiated by the tandem bimolecular pathway of olefin isomerization, polymerization, and hydrogen transfer. For the mixture of i-butane and 1-butene, the reaction still follows the bimolecular pathway, and the product composition is distributed between that of i-butane and 1-butene. This work demonstrates that a reasonable combination of proton acid sites and reaction conditions is necessary to adjust the reaction pathways and product distributions of the C4 component.

Key words: C4 component, ZSM-5 zeolite, Br?nsted acid site, monomolecular cracking, bimolecular pathway