焦硫化铁氧化生成多聚硫与形成热蓄积关系研究  

On the relation between polysulfide resulted from oxidation of iron sulfide and heat accumulation

作　　者：王增辉[1] 栾和林[2] 周智明[3] 轩小朋[1] 汪鑫[3] 

机构地区：[1]河南师范大学化学与环境科学学院,河南新乡453007 [2]北京矿治研究总院测试所,北京100044 [3]北京理工大学化学与环境学院,北京100081

出　　处：《安全与环境学报》2009年第3期109-112,共4页Journal of Safety and Environment

基　　金：科技部社会公益项目(2005DIB2J222)

摘　　要：采用五氟苄基溴对焦硫化铁在空气中氧化生成的还原性硫S^(2-)、S_2^(2-)、S_3^(2-)、S_8烷基化,对烷基化衍生物进行GC-MS表征,比较检测出的各种还原硫物质的生成量曲线与焦硫化铁的氧化放热曲线。结果表明,多聚硫中S_2^(2-)、S_3^(2-)是焦硫化铁氧化放热过程中的主要还原剂,其迅速生成与氧化是焦硫化铁氧化、放热并引发自燃的主因。根据生成的S_n^(2-)可以标识出焦硫化铁氧化及自燃的孕育程度,这有利于揭示硫铁化物氧化并引发自燃的深层原因。The paper is engaged in searching of the relation between polysulfide resulted from oxidation of iron sulfide and heat accumulation. As we know, in the humid air, hydrogen sulfide tends to react to the iron rust to form iron sulfide whereas the oxidation of iron sulfide is likely to result in the reduced sulfurs（S2^2- ,S2^2- ,S3^2- ,S8） with large amount of heat release. The polysulfides is by nature strong nucleophiles, which may give off some important intermediates in the process of forming dimethylpolysalfides and some other volatile sulfur compounds of environmental significance. Since polysulfides are more reactive than the basic sulfur （S8 ） element, they may play a more significant role in some eco-envirenmentally relevant processes for their redox reactivity and high nucleophilicity. In this paper, we have alkylated polysulfide products with the PFBBr （pentafluorobenzyl bromide）, and detected alkylation products by using GC - MS. Howev- er, the result of our detection of the polysulfides are S^2- , S2^2- , S3^2- , does not mean to detect the long chain of polysulfides （Sn^2- , n ≥4）. On the basis of our study of the change of the reduced sulfur in different cases, we have worked out the changing curve of the polysulfides and Ss. On the other hand, we have also found that the oxidation process of iron sulfide leads to the release of large amount of heat, which may also result in the accumulation or storage of heat as a result of oxidation, and therefore, this heat storage may happen to be the root cause of spontaneous combustion in the process of crude oil storage and transportation. And, consequently, the heat storage and heat dissipation may also lead to the change of temperature. That is why we have also worked the change curve of the temperature simultaneously. For the similar reason, we have developed the change curve about the polysulfides and Ss. In this way, it is highly hypothetic that the change of the polysulfides （ S2^2- ＋ S3^2- ） may lead to the change of the temperatu

关 键 词：应用化学 原油储运 多聚硫 氧化放热 烷基化 

分 类 号：X932[环境科学与工程—安全科学]