采用配位稳定策略制备的炭负载钌催化剂乙炔氢氯化反应性能

doi:10.1016/S1872-2067(20)63616-6

摘要/Abstract

摘要： 聚氯乙烯（PVC）广泛用于建材、电器、日常用具等各个领域，全球使用量在高分子材料中位居第二，其中有70%左右的产能来自中国.基于我国"富煤、贫油、少气"的资源特征，以汞催化剂催化的乙炔氢氯化生产氯乙烯单体的工艺在我国占主导地位.随着环保需求的提高和2017年8月国际限汞公约在中国正式生效，无汞催化剂的开发迫在眉睫.在无汞催化剂中，钌催化剂制备成本低，具有优异的乙炔氢氯化性能，是非常有竞争潜力的无汞催化剂体系之一.由于乙炔氢氯化反应是路易斯酸催化的反应，无论是汞催化剂还是非汞体系的金属催化剂的活性组分均为氯化物.如果活性中心的酸性太强，会引起乙炔的裂解或聚合造成催化剂积炭失活.因此对负载氯化物的酸性中心结构调控是研发的重点.本文通过配体（硫脲、菲咯啉和L-乳酸）与钌配位来调控钌催化剂的电子结构，研究催化剂活性中心的电子结构对催化剂活性及稳定性的影响.
采用氮气吸附、X射线衍射、高分辨透射电镜等对配体修饰的Ru/C催化剂结构进行了表征，结果显示，催化剂的比表面积没有明显下降，且没有发现堵孔现象，也未检测到钌纳米粒子的形成，说明钌物种高度分散.其中以硫脲为配体制备的Ru-Thi/AC催化剂在乙炔氢氯化反应表现了最高的TOF值和稳定性.X光电子能谱及紫外可见吸收光谱表征结果显示，配体的配位原子通过取代RuCl₃中的Cl^-与钌离子配位，配位后的钌离子的结合能比未配位的RuCl₃/AC均有一定程度的偏移，说明通过配体修饰钌催化剂可以调控钌离子的电子结构.进一步关联以后，发现配体修饰的钌催化剂在乙炔氢氯化反应的TOF值和表观活化能与钌催化剂的Ru离子的结合能位置呈线性关系，说明钌催化剂的活性中心的结构和活性中心钌电子结构有关.采用C₂H₂-TPD表征了C₂H₂在钌催化剂表面的吸附行为，发现钌催化剂上有两个乙炔吸附物种，且乙炔吸附峰面积随钌离子的结合能增加而逐渐减少.通过C₂H₂-HCl-TPSR表征证明只有低温脱附的乙炔物种才能发生乙炔氢氯化反应，高温脱附的乙炔物种则易造成积碳.通过NH₃-TPD表征了钌催化剂的酸性，验证了催化剂的酸性和失活速率之间的关系，催化剂的酸性越强，催化剂失活越严重.由于NH₃的碱性较强，催化剂表面只有一个NH₃脱附峰.采用HCl-TPD表征HCl在钌催化剂上的吸附，发现部分配体如硫脲及菲咯啉的氮物种可吸附活化HCl，和钌离子之间存在一定的协同作用，进一步提高了催化剂的性能.本工作提出的配体修饰的方法对高活性高稳定性无汞催化剂的设计合成提供了一个新的思路和简单有效的方法.

关键词: 钌催化剂, 配体, 电子结构, 协同作用, 乙炔氢氯化反应

Abstract: The development of efficient and stable non-mercury catalysts for the chlor-alkali industry is desirable but remains a great challenge. Herein, we design a series of ruthenium catalysts for acetylene hydrochlorination by regulating the electronic structure of ruthenium ions through coordination with various ligands (thiourea, phenanthroline, and L-lactic). The turnover frequencies (TOFs) and apparent activation energies for the acetylene hydrochlorination have a linear relationship with the binding energy of Ru³⁺ in the ruthenium catalysts. The synergetic effect of the ruthenium ion and ligands plays an important role in acetylene hydrochlorination. The Ru-Thi/AC catalyst with thiourea as the ligand shows the highest TOF and stability in acetylene hydrochlorination. The present study provides a rational method to regulate the electronic structure of supported metal catalysts with high catalytic performance exhibited by the carbon-supported heterogeneous catalysts.

Key words: Ruthenium catalyst, Ligand, Electronic structure, Synergetic effect, Acetylene hydrochlorination

王小龙, 蓝国钧, 程载哲, 韩文锋, 唐浩东, 刘化章, 李瑛. 采用配位稳定策略制备的炭负载钌催化剂乙炔氢氯化反应性能[J]. 催化学报, 2020, 41(11): 1683-1691.

Xiaolong Wang, Guojun Lan, Zaizhe Cheng, Wenfeng Han, Haodong Tang, Huazhang Liu, Ying Li. Carbon-supported ruthenium catalysts prepared by a coordination strategy for acetylene hydrochlorination[J]. Chinese Journal of Catalysis, 2020, 41(11): 1683-1691.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63616-6

https://www.cjcatal.com/CN/Y2020/V41/I11/1683

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