有序介孔Sn-SBA-15负载铂催化剂上丙烷脱氢性能的提高

doi:10.1016/S1872-2067(17)62805-5

催化学报 ›› 2017, Vol. 38 ›› Issue (4): 726-735.DOI: 10.1016/S1872-2067(17)62805-5

有序介孔Sn-SBA-15负载铂催化剂上丙烷脱氢性能的提高

李冰^a, 徐振新^b, 储伟^a, 罗仕忠^a, 敬方梨^a

a 四川大学化学工程学院, 四川成都 610065;
b 斯特拉斯堡大学能源、环境与健康化学过程研究所, 斯特拉斯堡市, 法国

收稿日期:2017-01-11 修回日期:2017-03-03 出版日期:2017-04-18 发布日期:2017-04-12
通讯作者: 罗仕忠, 敬方梨
基金资助:
四川省科技支撑计划（2016GZ0371）；国家自然科学基金（21476145，21506111）.

Ordered mesoporous Sn-SBA-15 as support for Pt catalyst with enhanced performance in propane dehydrogenation

Bing Li^a, Zhenxin Xu^b, Wei Chu^a, Shizhong Luo^a, Fangli Jing^a

a School of Chemical Engineering, Sichuan University, Chengdu 610065, Sichuan, China;
b Institut de Chimie et Procédés pour l'Energie, l'Environnement et la Santé(ICPEES), UMR 7515 CNRS-Université de Strasbourg(UdS), 25, rue Becquerel, 67087 Strasbourg Cedex 08, France

Received:2017-01-11 Revised:2017-03-03 Online:2017-04-18 Published:2017-04-12
Supported by:
This work was supported by the Science & Technology Support Plan Projects of Sichuan Province (2016GZ0371) and National Natural Science Foundation of China (NNSFC, 21476145, 21506111).

摘要/Abstract

摘要：

丙烷脱氢制丙烯能够将低级烷烃转变成烯烃，是有效扩大丙烯来源的生产工艺.铂锡催化剂用于丙烷催化脱氢的主要缺点是稳定性差、选择性低，通过稳定锡的氧化态可以大大改善催化剂的脱氢性能及稳定性.本文采用一锅水热合成法制备了一系列高比表面积具有高度有序介孔结构的Sn掺杂的Sn-SBA-15材料，并作为载体负载铂催化剂用于丙烷脱氢反应.同时利用传统浸渍法（IM）合成了Sn/SBA-15-IM材料作为对比.结合X射线衍射（XRD）、BET比表面积和孔体积测试、红外光谱（FT-IR）、X射线光电子能谱、H₂程序升温脱附（H₂-TPD）、热重分析（TGA）、扫描电镜和透射电镜等多种物理化学表征手段研究了Sn-SBA-15材料和催化剂的结构性质及其丙烷脱氢反应性能.XRD和BET比表面积和孔体积测试结果表明，水热合成法原位引入助剂Sn不影响载体SBA-15的有序孔道结构，同时能够保持较大的比表面积.传统浸渍法引入Sn会堵塞载体孔道，载体比表面积及孔道有序度下降.Sn掺杂进入SBA-15骨架能够增强Sn物种与载体的相互作用，有利于Sn物种在反应过程中保持氧化态，提高催化剂丙烷脱氢反应的活性及选择性.当Sn掺杂量增至2.0 wt%时，Pt，Sn组分与载体之间的相互作用减弱，催化剂中Sn⁰物种所占比例增多，导致催化剂丙烷脱氢性能下降.在丙烷脱氢反应过程中，一锅法引入Sn的催化剂上反应活性和稳定性明显优于浸渍法引入Sn的催化剂.其中，Pt/0.5Sn-SBA-15催化剂表现出最优的丙烷脱氢性能，丙烷转化率为43.8%，丙烯选择性为98.5%.

关键词: 丙烷脱氢, 一锅水热合成, Sn掺杂SBA-15, 铂基催化剂, 构效关系

Abstract:

A series of Sn-incorporated SBA-15 materials with high specific surface areas and highly ordered mesoporous structures were synthesized by a facile one-pot method and used as catalyst supports. A reference sample was also prepared using a conventional impregnation method. The catalysts were characterized using various methods, and their activities in propane dehydrogenation were investigated. The incorporation of Sn into the SBA-15 matrix led to strong interactions between Sn species and the support, and these helped to maintain the oxidation states of Sn species during the reaction. Substitution with Sn changed the interfacial properties of the Pt species and improved the function and effect of the Sn promoter. The catalytic activities and stabilities of the Pt catalysts supported on Sn-incorporated SBA-15 were better than those of the impregnated sample. However, the catalytic performance deteriorated when an excessive amount of Sn was introduced and the interactions among Pt, Sn species, and the support became weaker. The Pt/0.5Sn-SBA-15 catalyst gave the best propene selectivity, i.e., 98.5%, with a corresponding propane conversion of about 43.8%.

Key words: Propane dehydrogenation, One-pot hydrothermal synthesis, Sn-incorporated SBA-15, Pt-based catalyst, Structure activity relationship

李冰, 徐振新, 储伟, 罗仕忠, 敬方梨. 有序介孔Sn-SBA-15负载铂催化剂上丙烷脱氢性能的提高[J]. 催化学报, 2017, 38(4): 726-735.

Bing Li, Zhenxin Xu, Wei Chu, Shizhong Luo, Fangli Jing. Ordered mesoporous Sn-SBA-15 as support for Pt catalyst with enhanced performance in propane dehydrogenation[J]. Chinese Journal of Catalysis, 2017, 38(4): 726-735.

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有序介孔Sn-SBA-15负载铂催化剂上丙烷脱氢性能的提高

Ordered mesoporous Sn-SBA-15 as support for Pt catalyst with enhanced performance in propane dehydrogenation

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