过氧化氢催化活化体系及其在危化品消毒中的应用

doi:10.16085/j.issn.1000-6613.2021-0184

摘要/Abstract

摘要：

随着我国化工行业的飞速发展，危险化学品事故时有发生，洗消成为化学应急处置的关键技术环节之一。本文综合考虑化学品的毒性、产销量、洗消的必要性等因素，初步建立了潜在危化品洗消污染物谱系；同时，在论述洗消原理及洗消剂的基础上，重点探讨了无机催化剂和有机活化剂对过氧化氢的催化活化原理。无机催化体系主要包含金属离子、金属盐和金属配位体，活性成分为·OH、¹O₂等；有机活化剂主要有酯类、酰胺类、脒类、胍类和腈类等，活性成分为过氧酸或过氧亚酰胺酸。各类体系在危化品消毒处置和漂白印染等领域都有研究和应用，有望成为未来危化品消毒剂的发展主体。本文可为过氧化物类消毒剂产品的研发提供一定的理论依据，为应对危化品事故应急救援洗消需求奠定技术基础。

关键词: 危化品, 洗消, 过氧化氢, 催化剂活化, 氧化, 污染

Abstract:

Hazardous chemical accidents occur frequently as the chemical industry is rapidly developed in China. During the emergency disposal process of hazardous chemical accidents, the decontamination technology has been one of the most important technical part. In this paper, a preliminary decontamination spectrum of potential hazardous chemicals was established as considering the toxicity of chemicals, production and sales, the necessity of decontamination and other factors. Meanwhile, on the basis of discussing the decontamination principle and decontamination agent, the catalytic activation mechanism and the application of hydrogen peroxide combined with the inorganic catalysts and organic activators had been mainly elaborated. The inorganic catalytic system mainly includes metal ions, metal salts and metal ligands. The active ingredient of the compound is ·OH, ¹O₂ and so on. Organic activators mainly include esters, amides, amidines, guanidine and nitriles. The active components are peroxyacid or peroxyimino acid. All kinds of systems have been studied and applied in the fields of disinfection and disposal of hazardous chemicals, bleaching and dyeing, and are expected to become the main body of the development of disinfectants for hazardous chemicals in the future. This paper can provide a theoretical basis for the research and development of peroxide disinfectants, and lay a technical foundation for emergency rescue and decontamination of hazardous chemical accidents.

Key words: hazardous chemicals, decontamination, hydrogen peroxide, catalyst activation, oxidation, pollution

中图分类号:

E929.8

肖博仁, 杨金星, 刘海鹏, 齐丽红, 左国民. 过氧化氢催化活化体系及其在危化品消毒中的应用[J]. 化工进展, 2021, 40(S1): 426-433.

XIAO Boren, YANG Jinxing, LIU Haipeng, QI Lihong, ZUO Guomin. Application of the catalysis and activation system based on hydrogen peroxide on the decontamination of hazardous chemicals[J]. Chemical Industry and Engineering Progress, 2021, 40(S1): 426-433.

图/表 6

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分类	名称	典型化合物
第一类	无机剧毒危化品	氰化钠、氰化钾、氰化镉、氰化氢、氰化银钾、三氧化二砷、亚砷酸钙、亚硒酸钠、亚硒酸氢钠
第二类	卤代烃及其卤化物有机剧毒危化品	鼠甘伏、氟乙酸钠、氟乙酰胺、毒鼠硅、狄氏剂、艾氏剂、氟乙酸甲酯、碳氯灵、氯甲酸甲酯、氯甲酸乙酯、氯乙醇、全氯甲硫醇、三氯硝基甲烷、毒鼠磷、溴敌隆（3-［3-（4-溴联苯-4-基）-3-羟基-1-苯丙基］-4-羟基香豆素）
第三类	有机磷、硫、砷及腈、胺等有机剧毒危化品	八甲磷、速灭磷、甲硫磷、百治磷、效磷、甲基对氧磷、胺吸磷、硫环磷、丁硫环磷、内吸磷、对氧磷、对硫磷、乙拌磷、治螟磷、发硫磷、特丁硫磷、甲胺磷、涕灭威、苯硫酚、甲拌磷、氮丙啶、2-硝基-4-甲氧基苯胺、三丁胺、乙基氰、2-羟基丙腈、地虫硫膦、久效威
第四类	有机芳香环、稠环及杂环化合物	灭鼠优、克百威（2, 3-二氢-2, 2-二甲基苯并呋喃-7-基-N-甲基氨基甲酸酯）、敌鼠、异氰酸苯酯、毒鼠强、杀鼠醚
第五类	化学战剂	沙林、梭曼、维埃克斯（VX）、芥子气、路易氏剂、光气、氢氰酸、氯化氰、苯氯乙酮、毕兹
第六类	其它有毒品	硫酸二甲酯、正硅酸甲酯

分类	名称	典型化合物
第一类	无机剧毒危化品	氰化钠、氰化钾、氰化镉、氰化氢、氰化银钾、三氧化二砷、亚砷酸钙、亚硒酸钠、亚硒酸氢钠
第二类	卤代烃及其卤化物有机剧毒危化品	鼠甘伏、氟乙酸钠、氟乙酰胺、毒鼠硅、狄氏剂、艾氏剂、氟乙酸甲酯、碳氯灵、氯甲酸甲酯、氯甲酸乙酯、氯乙醇、全氯甲硫醇、三氯硝基甲烷、毒鼠磷、溴敌隆（3-［3-（4-溴联苯-4-基）-3-羟基-1-苯丙基］-4-羟基香豆素）
第三类	有机磷、硫、砷及腈、胺等有机剧毒危化品	八甲磷、速灭磷、甲硫磷、百治磷、效磷、甲基对氧磷、胺吸磷、硫环磷、丁硫环磷、内吸磷、对氧磷、对硫磷、乙拌磷、治螟磷、发硫磷、特丁硫磷、甲胺磷、涕灭威、苯硫酚、甲拌磷、氮丙啶、2-硝基-4-甲氧基苯胺、三丁胺、乙基氰、2-羟基丙腈、地虫硫膦、久效威
第四类	有机芳香环、稠环及杂环化合物	灭鼠优、克百威（2, 3-二氢-2, 2-二甲基苯并呋喃-7-基-N-甲基氨基甲酸酯）、敌鼠、异氰酸苯酯、毒鼠强、杀鼠醚
第五类	化学战剂	沙林、梭曼、维埃克斯（VX）、芥子气、路易氏剂、光气、氢氰酸、氯化氰、苯氯乙酮、毕兹
第六类	其它有毒品	硫酸二甲酯、正硅酸甲酯

类别	具体物质
有机磷	敌敌畏、胺吸磷、甲拌磷、对氧磷、对硫磷等
有机硫	硫酸二甲酯、苯硫酚、硫化氢、乙硫醇、乙硫醚等
有机胺	涕灭威、克百威、灭鼠安、灭多虫、异索威、杀线威等
氰化物	氰化钠、氰化钾、羟基乙腈、异氰酸甲酯等
砷化物	三氧化二砷、砒霜、二氯苯胂、氯化亚胂、砷化氯等
卤化物	氯乙醇、全氯甲硫醇、全氟异丁烯、毒鼠磷等

类别	具体物质
有机磷	敌敌畏、胺吸磷、甲拌磷、对氧磷、对硫磷等
有机硫	硫酸二甲酯、苯硫酚、硫化氢、乙硫醇、乙硫醚等
有机胺	涕灭威、克百威、灭鼠安、灭多虫、异索威、杀线威等
氰化物	氰化钠、氰化钾、羟基乙腈、异氰酸甲酯等
砷化物	三氧化二砷、砒霜、二氯苯胂、氯化亚胂、砷化氯等
卤化物	氯乙醇、全氯甲硫醇、全氟异丁烯、毒鼠磷等

活化剂类型	结构式	典型代表物	代表物结构
酯类		NOBS
		戊乙酰葡萄糖（PAG）
		1，2-丙二醇二乙酸酯（PGDA）
		阿司匹林（Aspirin）
酰胺类		四乙酰乙二胺（TAED）
		四乙酰基甘脲（TAGU）
		十八烷基己内酰胺乙基二甲基氯化铵（PAP）
脒类		乙酸甲脒
脒类		盐酸乙脒
胍类		乙酰胍（ACG）
		1，1-二甲基胍硫酸盐（DGA）
		氨基胍硫酸盐
腈类		乙腈（CH₃CN）