以三氯乙烯为供氢剂将四氯化碳转化为氯仿

doi:10.16085/j.issn.1000-6613.2020-0735

摘要/Abstract

摘要：

四氯化碳（CTC）是甲烷氯化物生产的副产品，也是一种消耗臭氧层物质（ODS），将其转化为氯仿，可同时实现ODS的生产淘汰和资源化循环利用。本文开发了一种以四丁基氟化铵（TBAF）为相转移催化剂、K₂CO₃为助催化剂、三氯乙烯为供氢剂将CTC转化为氯仿的新方法，研究了温度、催化剂种类和用量对反应的影响，考察了反应动力学特征及反应放大效应。结果表明：在碱性条件下，三氯乙烯的酸性H原子可与四氯化碳发生取代反应，生成四氯乙烯和氯仿；反应速率随相转移催化剂用量的增加以及助催化剂碱性的增强而提高；循环使用过程中催化剂活性的降低与TBAF中氟离子的取代反应消耗有关；表观反应速率符合拟一级反应动力学模型，过程放大效应不明显。在优化反应条件下（30~60℃，9g CTC，10mmol 三氯乙烯，1mmol TBAF，10mmol K₂CO₃，0.5h），三氯乙烯被完全转化，氯仿选择性大于95%。

关键词: 废物处理, 催化剂, 多相反应, 资源化利用, 消耗臭氧层物质, 加氢脱氯

Abstract:

Carbon tetrachloride (CTC) is a byproduct of chloromethanes industry and an ozone-depleting substance (ODS). Its conversion to chloroform can achieve both ODS production phaseout and recycled resource utilization. A new method for converting CTC to chloroform was developed by using tetrabutylammonium fluoride (TBAF) as phase transfer catalyst, K₂CO₃ as co-catalyst and trichloroethylene as hydrogen donor. The effect of temperature, composition and usage of the catalysts on the reaction was studied, and the reaction kinetics and the scale-up effect were investigated. The results showed that radical substitution took place between CTC and the acidic H-atom of trichloroethylene under basic conditions, forming tetrachloroethene and chloroform. The reaction rate increased with increasing usage and basicity of the catalysts. The catalytic activity of the catalysts declines slightly in the recycled uses due to the partial fluorination of polychlorinated alkanes by TBAF. The overall reaction rate followed the pseudo-first order model with insignificant scale-up effect. Under optimal conditions (30—60℃,9g CTC, 10mmol trichloroethylene, 1 mmol TBAF, 10 mmol K₂CO₃, 0.5 h), trichloroethene can be converted completely with over 95% chloroform selectivity.

Key words: waste treatment, catalyst, multiphase reaction, resource utilization, ozone depleting substance, hydrodechlorination

中图分类号:

TQ209

姜亚光, 王瑞康, 王倩, 李春喜. 以三氯乙烯为供氢剂将四氯化碳转化为氯仿[J]. 化工进展, 2021, 40(2): 1114-1121.

Yaguang JIANG, Ruikang WANG, Qian WANG, Chunxi LI. Converting carbon tetrachloride to chloroform by using trichloroethene as hydrogen donor[J]. Chemical Industry and Engineering Progress, 2021, 40(2): 1114-1121.

图/表 9

图1 反应后溶液的GC-MS图1—一氟三氯甲烷；2—一氟二氯乙烯；3—氯仿；4—一氟三氯乙烯；5—一氯丁烷；6—四氯化碳；7—三氯乙烯；8—四氯乙烯；9—三丁胺

图2 温度对三氯乙烯转化率和产物选择性的影响

图3 TBAF用量对三氯乙烯转化率和产物选择性的影响

图4 K2CO3用量对三氯乙烯转化率和产物选择性影响

表1 碱性物质的碱性及其助催化效果

碱性物质	pH(c=0.1mol·L^-1)	反应时间	转化率/%
KOH	12.63	5min	100
NaAlO₂	12.17	30min	100
K₃PO₄	11.92	2h	100
K₂CO₃	11.14	40min	100
K₂HPO₄	9.08	12h	17.0
KHCO₃	8.34	12h	13.0
K₂SO₃	7.28	12h	0
二氧六环		12h	0
三乙胺（Et₃N）		12h	0
N-甲基咪唑(MIM)		12h	0
AlF₃-KOH		12h	0
CsF-KOH		12h	0
无		12h	0

图5 四氯化碳加氢脱氯的动力学曲线

图6 不同放大倍数下的转化率

图7 K2CO3重复使用次数对三氯乙烯转化率和产物选择性的影响

图8 反应前后固体K2CO3的XRD谱图

A—K2CO3；B—KCl

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