氯乙烯单体合成催化剂研究进展

doi:10.16085/j.issn.1000-6613.2020-2319

摘要/Abstract

摘要：

氯乙烯（VCM）是应用于高分子化工的重要单体，可以通过乙烯法及乙炔法制得。乙烯氧氯化生产VCM过程中二氯乙烷（EDC）的裂解生成VCM通常需要高温，能耗问题亟待改善。乙炔氢氯化法合成VCM常用氯化汞（HgCl₂）催化剂，其毒性强、挥发性大，对环境和人类健康造成严重污染和危害。替代HgCl₂的贵金属催化剂虽然活性较高，但实现大规模商业化应用还需解决成本昂贵等问题。本文围绕贵金属催化剂、非贵金属催化剂和碳基非金属催化剂在VCM合成方面的最新研究进展，重点介绍了催化剂的活性位点、失活原因以及如何通过合理调控结构来设计催化剂。指出在未来的研究中，探索一种高效、无污染、低成本的催化剂来替代乙炔法HgCl₂催化剂以及开发全新乙烯法催化剂是催化剂设计的重点与难点。

关键词: 氧化, 反应工程, 金属催化剂, 碳基非金属催化剂, 乙烯氧氯化, 乙炔氢氯化, 氯乙烯

Abstract:

Vinyl chloride monomer (VCM) is an important monomer used in polymer chemical industry, which is obtained by ethylene method and acetylene method. VCM is produced by the pyrolysis of dichloroethane (EDC) in the process of ethylene oxychlorination, which usually requires high temperature, and the energy consumption problem needs to be solved urgently. Mercuric chloride catalyst (HgCl₂) is commonly used in acetylene hydrochlorination to synthesize VCM, which has strong toxicity and volatility, causing serious pollution and harm to the environment and human beings. Although the noble metal catalyst substituted for HgCl₂ has high activity, it still needs to solve the problem of high cost to realize large-scale commercial application. This paper focuses on the recent research progress of noble metal catalyst, non-noble metal catalyst and carbon-based metal free catalyst in VCM synthesis, and the active site, deactivation reason of the catalyst and how to design the catalyst through reasonable regulation structure were emphatically introduced. In the future research, explore an efficient, pollution-free and low-cost catalyst to replace mercuric chloride catalyst in acetylene hydrochlorination and to develop a new catalyst in ethylene oxychlorination would be the key issue.

Key words: oxidation, reaction engineering, metal catalysts, carbon-based metal free catalysts, ethylene oxychlorination, acetylene hydrochlorination, vinyl chloride

中图分类号:

O643.3

鲍玉香, 马宏飞, 脱永笑, 祁艳颖, 冯翔, 杨朝合, 陈德. 氯乙烯单体合成催化剂研究进展[J]. 化工进展, 2021, 40(4): 2034-2047.

BAO Yuxiang, MA Hongfei, TUO Yongxiao, QI Yanying, FENG Xiang, YANG Chaohe, CHEN De. Research progress on catalyst for the synthesis of vinyl chloride monomer (VCM)[J]. Chemical Industry and Engineering Progress, 2021, 40(4): 2034-2047.

图/表 11

图1 助剂对Cu5.0催化剂性能的影响[26][还原反应条件：PC2H4=0.1atm，T=230℃，PTotal=1atm;氧化反应条件：PO2=0.1atm，T=230℃，PTotal=1atm(1atm=101.325kPa)]

图2 CuCl2催化剂和双功能CeO2催化剂催化C2H4氧氯化和EDC热裂解生成VCM示意图原子颜色：C—黑色；Cl—绿色；O—红；H—浅灰色；Ce—淡黄色[14]

图3 单金属镧系催化剂催化乙烯氧氯化反应的产物收率（插图是在CeO2、EuOCl和EuOCl-p-973上形成VCM的阿伦尼乌斯图。反应条件：T=450℃，C2H4∶HCl∶O2∶Ar∶He=3∶4.8∶3∶3∶86.2，Wcat∶n0(C2H4)=63g·h/mol[16]）

图4 一步法制备VCM机理示意图[41]

图5 AuCl向AuCl2H的转化及AuCl的再生机制Au—金色；Cl—绿色；H—白色；C—灰色；O—红色

图6 Au纳米团簇在再分散不同阶段的基本步骤[46][包括吸附、碘离子和Au原子之间的相互作用、解体、分离、大小和形状变化(分离和再分散）；图C、D和E代表再分散阶段]

图7 Au纳米颗粒的催化性能[49]

图8 Au基催化剂的C2H2转化率[59][反应条件：T=180℃，GHSV(C2H2)=720h-1，进料比(VHCl/VC2H2)=1.15]

图9 Pt、Ru和Au基催化剂的比较[61]

图10 DFT计算反应机理[71]

图11 VCM生成机理图[76]

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