石油炼制与化工 ›› 2016, Vol. 47 ›› Issue (2): 53-59.

• 催化剂 • 上一篇    下一篇

Ag 改性ZSM-11分子筛催化剂的制备及其重油催化裂解性能评价

陈璐1,刘诗哲1,韩东敏2,李春义1   

  1. 1. 中国石油大学(华东)重质油国家重点实验室

    2. 中国石油大学胜利学院
  • 收稿日期:2015-06-30 修回日期:2015-08-10 出版日期:2016-02-12 发布日期:2016-01-29
  • 通讯作者: 李春义 E-mail:chyli@upc.edu.cn

PREPARATION OF ZSM-11 ZEOLITE CATALYST MODIFIED BY SILVER AND ITS CATALYTIC CRACKING PERFORMANCE FOR HEAVY OIL

  • Received:2015-06-30 Revised:2015-08-10 Online:2016-02-12 Published:2016-01-29

摘要:

以具有微介复合结构的ZSM-11分子筛为活性组分,采用初湿浸渍法对分子筛进行Ag改性,并将其制备成催化剂。采用X射线衍射(XRD)、氮气吸附-脱附、Py-FT-IR光谱、NH3-TPD技术和UV-Vis光谱对样品进行表征,结果表明:少量Ag物种对ZSM-11的结构影响较小,其在ZSM-11中的主要存在形式为Ag+、Agn+或Agm;此外,Ag物种还可调变酸性,增加强L酸量。在固定床重油微反装置上对Ag改性催化剂进行评价,结果表明:ZSM-11分子筛中少量Ag物种的引入可显著增强其水热稳定性,提高催化剂的裂解活性;而引入大量Ag时,强L酸量增加,会促进干气和焦炭的生成,降低低碳烯烃的选择性,对反应不利。

关键词: ZSM-11分子筛, Ag改性, 催化裂解, 水热稳定性

Abstract:

The ZSM-11 zeolites with micro-meso porous were modified by Ag species, followed by incipient impregnation to prepare catalysts. The modified zeolites and catalysts were characterized by XRD, FT-IR, NH3-TPD, UV-Vis and N2 adsorption-desorption. The results indicated that small amounts of Ag had little influence on the structure of ZSM-11. Ag+, Agn+ and Agm were the main states of Ag on modified ZSM-11 zeolites. Besides, Ag species affect the acidity of the samples and increase the strong Lewis acidity. The heavy oil catalytic cracking performance of the catalysts was investigated in a fixed micro-reactor. The results indicated that the addition of small amount of Ag can enhance greatly the hydrothermal stability and the catalytic activity. However, larger Ag loadings favore the formation of dry gas and coke due to more strong Lewis acidity formed, resulting in the decrease of selectivity to light olefins.

Key words: ZSM-11, silver modification, catalytic cracking, hydrothermal stability