活性炭负载吡啶氯化铜催化乙炔氢氯化反应

摘要/Abstract

摘要： 采用浸渍法制备活性炭负载的吡啶氯化铜催化剂，测试吡啶氯化铜催化剂在乙炔氢氯化反应中的催化性能，并与活性炭负载的氯化铜催化剂进行比较。在反应温度为330 ℃、乙炔体积空速为100 h^-1、氯化氢与乙炔物质的量比为1.05、吡啶氯化铜表观负载量（w）为15%的条件下，乙炔转化率可达64%，氯乙烯选择性大于95%。通过扫描电镜（SEM）、X射线衍射（XRD）、X射线光电子能谱分析（XPS）等表征手段，证实吡啶氯化铜催化剂对氯化氢的强吸附及良好的Cu²⁺稳定性是其具有较高活性的关键，揭示吡啶氯化铜催化剂失活的主要原因为催化剂表面积炭，而氯化铜催化剂失活的主要原因为积炭和Cu²⁺被还原。利用分子模拟软件对吡啶氯化铜分子进行计算，探讨吡啶氯化铜催化乙炔氢氯化反应的机理。

关键词: 乙炔氢氯化, 催化剂, 吡啶氯化铜, 氯乙烯, 活性炭

Abstract: The copper pyridinium chloride catalyst supported on activated carbon was prepared by the impregnation method. The catalytic performance of the catalyst in the acetylene hydrochlorination reaction was tested and compared with that of the catalyst of copper chloride supported on activated carbon. Under the conditions of reaction temperature of 330 ℃, the volume space velocity of C₂H₂ of 100 h^-1, the molar ratio of HCl to C₂H₂of 1.05, and the content of copper pyridinium chloride of 15%, the conversion rate of acetylene reached 64%, and the selectivity of vinyl chloride was more than 95%. By means of SEM, XRD, XPS, TG, BET and TPD, It was found that the strong adsorption of hydrogen chloride and the good stability of Cu²⁺ were the key factors for the high activity of the catalyst, and the main reason for the deactivation of the copper pyridinium chloride catalyst was the deposition of carbon on its surface, the main reasons for deactivation of copper chloride catalyst were coke deposition and Cu²⁺ reduction. The mechanism of acetylene hydrochlorination catalyzed by copper pyridinium chloride was studied by using molecular simulation software.

Key words: acetylene hydrochlorination, catalyst, copper pyridinium chloride, vinyl chloride, activated carbon

王金雨张莹陈超群张丽刘红郭廷会. 活性炭负载吡啶氯化铜催化乙炔氢氯化反应[J]. 石油炼制与化工, 2023, 54(2): 27-34.

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