碳负载Cs和Cu基催化剂用于1，1，2-三氯乙烷的气相脱氯化氢

doi:10.11949/0438-1157.20231104

摘要/Abstract

摘要：

采用浸渍法制备了Cs/AC和Cu/AC催化剂，并在1，1，2-三氯乙烷的气相脱氯化氢反应中进行了评价。在浸渍过程中，活性炭表面产生高度分散的Cs物种和少量结晶的Cu物种。Cs/AC催化剂具有优异的催化性能，在573 K、1000 h^-1的反应条件下，转化率稳定在86.7%。实验和理论计算表明，CsCl物种促进了1，1，2-三氯乙烷的吸附和活化，从而提高了原料转化率。这项工作为探索高效经济地合成偏二氯乙烯提供了一种很有前景的策略。

关键词: 偏二氯乙烯, 活性炭, 催化, 1, 1, 2-三氯乙烷脱氯化氢, 催化剂载体

Abstract:

Cs/AC and Cu/AC catalysts were prepared by impregnation method and evaluated in the gas-phase dehydrochlorination reaction of 1,1,2-trichloroethane. Highly dispersed Cs species and crystalline Cu species are generated on the carbon surface during the impregnation process. Superior catalytic performance is triggered for the Cs/AC catalyst, with an 86.7% stable conversion under reaction conditions of 573 K and a gas hourly space velocity of 1000 h^-1. Experimental and theoretical calculations show that the adsorption and activation 1,1,2-trichloroethane is facilitated over the CsCl species, thereby enhancing the catalytic performance. This work provides a promising strategy to explore highly efficient and economic catalysts for the synthesis of 1,1-dichloroethylene.

Key words: vinylidene chloride, activated carbon, catalysis, dehydrochlorination of 1,1,2-trichloroethane, catalyst support

中图分类号:

TQ 072

盖星宇, 岳玉学, 杨春华, 张子龙, 蔡天姿, 张海丰, 王柏林, 李小年. 碳负载Cs和Cu基催化剂用于1，1，2-三氯乙烷的气相脱氯化氢[J]. 化工学报, 2024, 75(2): 575-583.

Xingyu GAI, Yuxue YUE, Chunhua YANG, Zilong ZHANG, Tianzi CAI, Haifeng ZHANG, Bolin WANG, Xiaonian LI. Carbon supported Cs- and Cu-based catalysts for gas-phase dehydrochlorination of 1,1,2-trichloroethane[J]. CIESC Journal, 2024, 75(2): 575-583.

图/表 9

表1 两种催化剂的ICP值

Table 1 ICP values for two catalysts

Catalyst	Active component loading/%(mass)
Catalyst	Cu/C	Cs/C
Cu/AC	5.03	0
Cs/AC	0	4.98

图1 不同温度对催化剂性能的影响与催化剂活性对比（反应条件：催化剂0.4 g，空速1000 h-1，大气压力0.1 MPa）

Fig.1 Effect of different temperatures on catalyst performance and comparison of catalyst activity (reaction conditions：catalyst 0.4 g, GHSV = 1000 h-1, p = 0.1 MPa)

图2 不同空速对Cu/AC催化活性的影响（反应条件：催化剂0.4 g，大气压力0.1 MPa，温度573 K）

Fig.2 Depicts the effect of testing different GHSV on the catalytic performance of the catalysts (reaction conditions: catalyst 0.4 g, p = 0.1 MPa, T = 573 K)

图3 催化剂的SEM、TEM与Mapping图

Fig.3 SEM, TEM and Mapping images of Cu/AC catalyst and Cs/AC catalyst

图4 两种催化剂的XRD谱图

Fig.4 X-ray diffraction patterns of two catalysts

图5 催化剂的XPS图

Fig.5 XPS spectra of catalysts

图6 两种催化剂的TCE-TPD图

Fig.6 TCE-TPD profiles of Cu/AC and Cs/AC catalysts

图7 催化剂对TCE、VDC和HCl的吸附情况与吸附能

Fig.7 Adsorption structure and adsorption energy of TCE, VDC and HCl over the catalysts

图8 1,1,2-三氯乙烷脱氯化氢可能的反应机理

Fig.8 Possible reaction mechanisms for the dehydrochlorination of 1,1,2-trichloroethane

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