SCI和EI收录∣中国化工学会会刊

›› 2017, Vol. 25 ›› Issue (9): 1217-1221.DOI: 10.1016/j.cjche.2016.12.003

• Catalysis, kinetics and reaction engineering • 上一篇    下一篇

The ligand coordination approach for improving the stability of low-mercury catalyst in the hydrochlorination of acetylene

Xiaolong Xu, Haihua He, Jia Zhao, Bailin Wang, Shanchuan Gu, Xiaonian Li   

  1. Institute of Industrial Catalysis of Zhejiang University of Technology, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Hangzhou 310032, China
  • 收稿日期:2016-09-12 修回日期:2016-12-05 出版日期:2017-09-28 发布日期:2017-10-11
  • 通讯作者: Xiaonian Li,E-mail:xnli@zjut.edu.cn
  • 基金资助:
    Supported by the National Natural Science Foundation of China (21476207) and the China Postdoctoral Science Foundation (2016M592015).

The ligand coordination approach for improving the stability of low-mercury catalyst in the hydrochlorination of acetylene

Xiaolong Xu, Haihua He, Jia Zhao, Bailin Wang, Shanchuan Gu, Xiaonian Li   

  1. Institute of Industrial Catalysis of Zhejiang University of Technology, State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Hangzhou 310032, China
  • Received:2016-09-12 Revised:2016-12-05 Online:2017-09-28 Published:2017-10-11
  • Supported by:
    Supported by the National Natural Science Foundation of China (21476207) and the China Postdoctoral Science Foundation (2016M592015).

摘要: Mercuric chloride supported on activated carbon (HgCl2/AC) is used as an industrial catalyst for the hydrochlorination of acetylene. Loss of HgCl2 by sublimating from the surface of activated carbon causes the irreversible deactivation of mercury catalyst and environmental pollution. In this work, a ligand coordination approach based on the Principle of Hard and Soft Acids and Bases (HSAB) was employed to design more stable lowmercury catalyst. The low-mercury catalysts (4% HgCl2 loading) were prepared by using HgCl2 and potassium halides (KX, X=Cl, I) as precursors. The HgCl2-4KI/AC catalyst showed best catalytic stability than HgCl2/AC and HgCl2-4KCl/AC in the hydrochloriantion of acetylene. HgCl2 could form more stable complex with KI, K2HgI4 as the main active component of the HgCl2-4KI/AC catalyst. The characterizations of XRD and EDX analysis illustrated that the active component of HgCl2-4KI/AC was highly dispersed on the surface of activated carbon. The sublimation rates of HgCl2 from the catalysts verified that the active component with larger stability constant had better thermal stability. Using Hg(Ⅱ) complexes with high stability constant as the active component may be the research direction of developing highly stable low-mercury catalyst for the hydrochlorination of acetylene.

关键词: Low-mercury catalyst, Sublimation, K2HgI4, Ligand coordination, Acetylene hydrochlorination

Abstract: Mercuric chloride supported on activated carbon (HgCl2/AC) is used as an industrial catalyst for the hydrochlorination of acetylene. Loss of HgCl2 by sublimating from the surface of activated carbon causes the irreversible deactivation of mercury catalyst and environmental pollution. In this work, a ligand coordination approach based on the Principle of Hard and Soft Acids and Bases (HSAB) was employed to design more stable lowmercury catalyst. The low-mercury catalysts (4% HgCl2 loading) were prepared by using HgCl2 and potassium halides (KX, X=Cl, I) as precursors. The HgCl2-4KI/AC catalyst showed best catalytic stability than HgCl2/AC and HgCl2-4KCl/AC in the hydrochloriantion of acetylene. HgCl2 could form more stable complex with KI, K2HgI4 as the main active component of the HgCl2-4KI/AC catalyst. The characterizations of XRD and EDX analysis illustrated that the active component of HgCl2-4KI/AC was highly dispersed on the surface of activated carbon. The sublimation rates of HgCl2 from the catalysts verified that the active component with larger stability constant had better thermal stability. Using Hg(Ⅱ) complexes with high stability constant as the active component may be the research direction of developing highly stable low-mercury catalyst for the hydrochlorination of acetylene.

Key words: Low-mercury catalyst, Sublimation, K2HgI4, Ligand coordination, Acetylene hydrochlorination