一种高效稳定的低负载量的氯化-2-羟乙基三甲胺改性钌基催化剂用于乙炔氢氯化反应

doi:10.1016/S1872-2067(18)63121-3

催化学报 ›› 2018, Vol. 39 ›› Issue (11): 1770-1781.DOI: 10.1016/S1872-2067(18)63121-3

一种高效稳定的低负载量的氯化-2-羟乙基三甲胺改性钌基催化剂用于乙炔氢氯化反应

李航^a, 吴博韬^a, 王建辉^b, 王富民^a, 张旭斌^a, 王刚^c, 李海朝^c

a 天津大学化工学院, 天津化学化工协同创新中心, 天津 300350;
b 天津大学理学院化学系, 天津 300072;
c 青海民族大学化学化工学院, 青海西宁 810007

收稿日期:2018-05-16 修回日期:2018-06-06 出版日期:2018-11-18 发布日期:2018-09-01
通讯作者: 王富民, 张旭斌
基金资助:
国家重点基础研究发展计划（2012CB720302）；国家重点研发计划（2016YFF0102503）.

Efficient and stable Ru(III)-choline chloride catalyst system with low Ru content for non-mercury acetylene hydrochlorination

Hang Li^a, Botao Wu^a, Jianhui Wang^b, Fumin Wang^a, Xubin Zhang^a, Gang Wang^c, Haichao Li^c

a School of Chemical Engineering & Technology, Collaborative Innovation Center of Chemical Science and Chemical Engineering(Tianjin), Tianjin University, Tianjin 300350, China;
b Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China;
c College of Chemistry and Chemical Engineering, Qinghai Nationalities University, Xining 810007, Qinghai, China

Received:2018-05-16 Revised:2018-06-06 Online:2018-11-18 Published:2018-09-01
Contact: 10.1016/S1872-2067(18)63121-3
Supported by:
This work was supported by the National Basic Research Program of China (2012CB720302) and the National Key R&D Program of China (2016YFF0102503).

摘要/Abstract

摘要：

来自煤化工的乙炔氢氯化生产氯乙烯的工艺由于其经济优势成为我国生产PVC的主要路线.为了降低该工艺中汞触媒催化剂对环境的毒害，开发高效环保的乙炔氢氯化无汞催化剂刻不容缓.但已有研究表明，稳定性差和价格高昂成为制约乙炔氢氯化非汞催化剂工业化的瓶颈.由此，我们选用价格低廉、催化活性良好的RuCl₃作为催化剂的前驱体，采用浸渍法制备了低负载量的氯化-2-羟乙基三甲胺改性RuCl₃的催化剂，其中活性组分在ESI-MS中观测到是一种离子型配合物，其阴阳离子分别为RuCl₄^-和C₅H₁₄NO⁺.该催化剂在乙炔氢氯化反应中的测试结果表明，氯化-2-羟乙基三甲胺的加入可以显著提高催化活性和稳定性.通过透射电镜（TEM）和扫描-透射电镜（STEM）表征表明，该催化体系的活性组分具有良好的分散性，季铵盐[Me₃NCH₂CH₂OH]Cl不仅与RuCl₃形成配合物为活性组分，其过量时也提供了一个溶剂环境，能够稳定活性组分不团聚.透射电镜和X射线光电子能谱（XPS）结果共同表明，相比于单一负载的RuCl₃催化剂，该催化体系中Ru物种基本保持在+3氧化态，不易在制备过程中被氧化或在反应过程中被还原性气体乙炔还原为金属颗粒，表现出了良好的稳定性.程序升温脱附（TPD）结果表明，氯化-2-羟乙基三甲胺这一季铵盐的加入能够大幅度提升体系对氯化氢的吸附，降低体系对乙炔和产物氯乙烯的吸附，从而促进乙炔氢氯化反应的进行，减少体系吸附乙炔或氯乙烯过强导致的积炭现象.另一方面，本工作中采用密度泛函理论方法研究了乙炔氢氯化非汞催化剂的性质、催化剂与反应物的吸附和相互作用模式.其中吸附能的计算结果表明，活性组分和季铵盐都能够提升对氯化氢的吸附，季铵盐还能够抑制体系对乙炔的吸附，计算结果与TPD的结果基本一致.对反应物和催化剂之间的相互作用进行了考察，发现该体系对氯化氢存在一个协同活化的作用，能够促进H-Cl共价键的异裂，有利于跨越传统催化剂对氯化氢吸附和活化的障碍.此外，该催化体系对乙炔氢氯化过程也展现了一个协同催化的模式，为乙炔氢氯化无汞非均相催化剂的设计提供了参考.

关键词: 乙炔氢氯化, 高活性, 非均相催化, 离子型配合物, 钌

Abstract:

Herein, we report an excellent, supported Ru(Ⅲ)-ChCl/AC catalyst with lower Ru content, where the ionic complex ChRuCl₄ serves as the active component for acetylene hydrochlorination. The prepared heterogeneous Ru-10%ChCl/AC catalyst shows excellent activity and long-term stability. In this system, ChCl provides an environment for the ChRuCl₄ to be stabilized as Ru(Ⅲ), thus suppressing the reduction of the active species and the aggregation of ruthenium species during the reaction. The interaction between reactants and catalyst species was investigated by catalyst characterizations in combination with DFT calculations to disclose the effect of the ChRuCl₄ complex and ChCl on the catalytic performance. This inexpensive, efficient, and long-term catalyst is a competitive candidate for application in the hydrochlorination industry.

Key words: Acetylene hydrochlorination, Catalytic activity, Heterogeneous catalysis, Ionic complex, Ruthenium

李航, 吴博韬, 王建辉, 王富民, 张旭斌, 王刚, 李海朝. 一种高效稳定的低负载量的氯化-2-羟乙基三甲胺改性钌基催化剂用于乙炔氢氯化反应[J]. 催化学报, 2018, 39(11): 1770-1781.

Hang Li, Botao Wu, Jianhui Wang, Fumin Wang, Xubin Zhang, Gang Wang, Haichao Li. Efficient and stable Ru(III)-choline chloride catalyst system with low Ru content for non-mercury acetylene hydrochlorination[J]. Chinese Journal of Catalysis, 2018, 39(11): 1770-1781.

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一种高效稳定的低负载量的氯化-2-羟乙基三甲胺改性钌基催化剂用于乙炔氢氯化反应

Efficient and stable Ru(III)-choline chloride catalyst system with low Ru content for non-mercury acetylene hydrochlorination

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