OH自由基引发的甲烷光化学氧化体系中有机过氧化物的研究  

STUDIES ON THE FORMATION OF ORGANIC PEROXIDES IN THE OH-INITIATED OXIDATION OF CH_4

作　　者：陈忠明[1] 邵可声[1] 唐孝炎[1] 胡敏[1] 张远航[1] 齐斌 

机构地区：[1]环境模拟与污染控制国家重点联合实验室北京大学环境科学中心,北京100871 [2]环境模拟与污染控制国家重点联合实验室

出　　处：《环境化学》1998年第4期309-314,共6页Environmental Chemistry

基　　金：国家科委中法科技促进合作项目

摘　　要：在１．０１３２５×１０＾５Ｐａ，２９８Ｋ，Ｏ２－Ｎ２气氛下，采用长光路付立叶红外光谱仪跟踪反应进程，高压液相色谱仪测定反应产物中有机过氧化物，研究了ＯＨ自由基基引发的甲烷光化学反应体系，证实反应产物中有Ｈ２Ｏ２、甲基过氧化氢（ＣＨ３Ｏ２Ｈ，ＭＨＰ）和过氧甲醚（ＣＨ３Ｏ２ＣＨ３），并发现羟甲基过氧化氢（ＨＯＣＨ２ＯＯＨ，ＨＭＨＰ）和一未知有机过氧化物。Formation of Organic peroxides in the OH-initiated photooxidation of CH4 in O2-N2 mixtures at 1. 01325×105 Pa and 298K was studied with HPLC and FT-IR methods. The results of HPLC analysis showed that five peaks were found in the chromatogram .and the four of them were identified as H2O2, HOCH2OOH(HMHP), CH3O2H(MHP) and CH3OZCH3 based on their retention times,among which HMHP was first reported, while the other unknown peak of 8. OSmin was assigned tentatively to HC(O)OOH. The formation of HMHP in the reaction system indicated that there was a probable path for CH3O2 radicals to produce Criegee biradical·CH2OO·. The formation mechanism of organic peroxides in the photooxidation of CH4 was more complicated than it had been assumed before. Photooxidation of CH4 probably was an important source of organic peroxides in the troposphere.

关 键 词：甲烷 光化学 有机过氧化物 大气污染 污染物质 

分 类 号：X132[环境科学与工程—环境科学]