Pt/TiO2/ZSM-5催化剂的制备及其催化转化正丁烷

doi:10.11949/j.issn.0438-1157.20160464

化工学报 ›› 2016, Vol. 67 ›› Issue (8): 3363-3373.DOI: 10.11949/j.issn.0438-1157.20160464

• 催化、动力学与反应器 • 上一篇下一篇

Pt/TiO₂/ZSM-5催化剂的制备及其催化转化正丁烷

刘佳, 姜桂元, 赵震, 韩善磊, 张耀远, 杨庆鑫, 孙乾耀, 王雅君

中国石油大学(北京)重质油国家重点实验室, 北京 102249

收稿日期:2016-04-11 修回日期:2016-07-01 出版日期:2016-08-05 发布日期:2016-08-05
通讯作者: 赵震
基金资助:
国家重点基础研究发展计划项目（2012CB215001）；国家自然科学基金石油化工联合基金项目（U1162117）；北京高等学校青年英才计划项目（YETP0696）；教育部新世纪优秀人才计划项目（NCET-11-0732）；中国石油大学（北京）前瞻导向项目（QZDX-2014-02）。

Preparation of Pt/TiO₂/ZSM-5 catalyst for catalytic conversion of n-butane

LIU Jia, JIANG Guiyuan, ZHAO Zhen, HAN Shanlei, ZHANG Yaoyuan, YANG Qingxin, SUN Qianyao, WANG Yajun

State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249, China

Received:2016-04-11 Revised:2016-07-01 Online:2016-08-05 Published:2016-08-05
Supported by:
supported by the National Basic Research Program of China (2012CB215001), the National Natural Science Foundation of China (U1162117), the Beijing Higher Education Young Elite Teacher Project (YETP0696), the Program for New Century Excellent Talents in University (NCET-11-0732) and the Prospect Oriented Foundation of China University of Petroleum, Beijing (QZDX-2014-02).

摘要/Abstract

摘要：

采用溶胶-凝胶法和等体积浸渍法，分别对ZSM-5分子筛进行TiO₂改性和Pt负载，获得了具有脱氢-裂解双功能的Pt/TiO₂/ZSM-5催化剂，采用XRD、N₂吸附-脱附、TEM、XPS和NH₃-TPD对样品的晶体结构，孔结构、形貌、活性金属价态和酸性质等进行了表征，并研究了正丁烷在此催化剂上催化转化制备低碳烯烃的反应规律。研究结果表明，TiO₂的引入，一方面使得改性后的ZSM-5分子筛获得了额外的酸性中心，特别是强酸性位含量的增加，有助于促进正丁烷的活化；另一方面Pt与TiO₂之间存在“金属-载体”强相互作用（SMSI），在H₂还原气氛下，Pt能够促进TiO₂的还原，生成Ti³⁺物种，而Ti³⁺的存在增加了Pt周围的电荷密度,降低了Pt对低碳烯烃（C₂⁼～C₃⁼）的吸附能力，抑制了深度脱氢和生焦反应，从而提高双功能催化剂对烯烃的选择性。当H₂还原温度为450℃时,Pt/10TiO₂/ZSM-5催化剂在625℃下的正丁烷转化率为76.1%，低碳烯烃（C₂⁼～C₃⁼）收率为50.9%，分别比Pt/ZSM-5催化剂提高了16.7%和12.6%。

关键词: Pt/TiO₂/ZSM-5, 催化剂, ", 金属-载体", 强相互作用, 分子筛, 低碳烯烃

Abstract:

Pt/TiO₂/ZSM-5 catalyst with dehydrogenation-cracking bifunctionality catalytic activity was prepared by modifying ZSM-5 zeolite with titanium dioxide (TiO₂) via sol-gel method and then loading Pt to the titanium modified ZSM-5 zeolite by incipient impregnation method. The as-prepared catalyst was characterized by means of XRD, N₂ adsorption-desorption, TEM, XPS and NH₃-TPD to analyze crystal structure, pore properties, morphology, valence states of active metal and acid properties of the catalyst, and the catalytic performance for the cracking of n-butane into light olefins was investigated. The results showed that the introduction of titanium dioxide provided additional acid sites to ZSM-5 zeolite, especially increasing the strong acid centers and enhancing the activation of n-butane. In addition, after reduction in hydrogen atmosphere, the partially reduced Ti³⁺ species was generated which was catalyzed by platinum due to the strong metal-support interaction (SMSI) between Pt and TiO₂. The formation of appropriate amount of Ti³⁺ species enhanced the electron density around Pt, and thus weakened the adsorption of ethene and propene on Pt atoms. After reduction by hydrogen at 450℃,n-butane conversion of 76.1% and yield of light olefins (C₂⁼-C₃⁼) of 50.9% were achieved at the reaction temperature of 625℃ over Pt/10TiO₂/ZSM-5 catalyst, which was 16.7% and 12.6% higher than those of Pt/ZSM-5 catalyst, respectively.

Key words: Pt/TiO₂/ZSM-5, catalyst, strong metal-support interaction, molecular sieves, light olefins

中图分类号:

O643.3

刘佳, 姜桂元, 赵震, 韩善磊, 张耀远, 杨庆鑫, 孙乾耀, 王雅君. Pt/TiO₂/ZSM-5催化剂的制备及其催化转化正丁烷[J]. 化工学报, 2016, 67(8): 3363-3373.

LIU Jia, JIANG Guiyuan, ZHAO Zhen, HAN Shanlei, ZHANG Yaoyuan, YANG Qingxin, SUN Qianyao, WANG Yajun. Preparation of Pt/TiO₂/ZSM-5 catalyst for catalytic conversion of n-butane[J]. CIESC Journal, 2016, 67(8): 3363-3373.

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Pt/TiO₂/ZSM-5催化剂的制备及其催化转化正丁烷

Preparation of Pt/TiO₂/ZSM-5 catalyst for catalytic conversion of n-butane

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