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

doi:10.11949/j.issn.0438-1157.20160464

Abstract

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

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

CLC Number:

O643.3

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.

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.

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

Pt/TiO₂/ZSM-5催化剂的制备及其催化转化正丁烷

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