湖北农业科学 ›› 2022, Vol. 61 ›› Issue (4): 61-65.doi: 10.14088/j.cnki.issn0439-8114.2022.04.010

• 资源·环境 • 上一篇    下一篇

球磨机械化学法处理2,4-二氯苯酚污染土壤产物表征及降解机理分析

王嘉1, 朱雷鸣2, 尹勇3, 蒋鹏3, 陈冬1,3, 张文艺1   

  1. 1.常州大学环境与安全工程学院,江苏 常州 213164;
    2.中石化广州工程有限公司,广州 510000;
    3.江苏龙环环境科技有限公司,江苏 常州 213022
  • 收稿日期:2021-09-08 出版日期:2022-02-25 发布日期:2022-03-18
  • 通讯作者: 张文艺(1968-),男,安徽池州人,教授,主要从事污染控制与生态修复的研究,(电话)13915046002(电子信箱)zhangwenyi888@sina.com。
  • 作者简介:王 嘉(1994-),男,江苏常州人,在读硕士研究生,研究方向为土壤修复。
  • 基金资助:
    中国石油化工股份有限公司科技计划项目(319005-7)

Characterization and degradation mechanism of 2,4-dichlorophenol contaminated soil by ball milling mechanochemical method

WANG Jia1, ZHU Lei-ming2, YIN Yong3, JIANG Peng3, CHEN Dong1,3, ZHANG Wen-yi1   

  1. 1. School of Environmental and Safety Engineering,Changzhou University,Changzhou 213164,Jiangsu,China;
    2. Sinopec Guangzhou Engineering Co. Ltd.,Guangzhou 510000,China;
    3. Jiangsu Longhuan Enviromental Science Co. Ltd.,Changzhou 213022,Jiangsu,China
  • Received:2021-09-08 Online:2022-02-25 Published:2022-03-18

摘要: 应用球磨机械化学法对2,4-二氯苯酚污染土壤进行处理试验,通过粒径分析、扫描电镜、XRD、IR和GC-MS等表征手段对球磨前后的2,4-二氯苯酚污染土壤进行表征,深入研究球磨机械化学法处理有机污染土壤机理,解析2,4-二氯苯酚的可能降解路径。结果表明,转速400 r/min、球磨4 h,其对土壤中2,4-二氯苯酚含量由9 009.0 mg/kg降解至70.7 mg/kg,降解率达99%。同时,土壤中的苯酚、邻苯二甲酸二甲酯、苯并(b)荧蒽等也同步得到了降解。球磨机械化学法对土壤进行球磨处理过程中,随着球磨时间的增加,土壤粒径减小,反应面面积增加,加快了反应速度,同时改变了土壤颗粒的形状与结构,激发了化学能的增加;球磨过程中C-Cl键断裂,出现了C-H、C=C键,H和C取代2,4-二氯苯酚上的Cl,把Cl从2,4-二氯苯酚上脱除下来,此过程中SiO2没有参与反应。推测2,4-二氯苯酚的降解路径为随着化学能的增加,2,4-二氯苯酚与氧化钙碰撞,发生电子转移,产生自由基氢,C-Cl键断裂,生成低毒的 2-氯酚,2-氯酚进一步降解为小分子的有机物,逐级进行降解,最终成为无定形碳和无机氯。

关键词: 机械化学法, 土壤, 球磨, 2,4-二氯苯酚, 降解

Abstract: 2,4-dichlorophenol contaminated soil was treated by ball milling mechanochemical method. Particle size analysis, scanning electron microscopy, XRD, IR and GC-MS were used to characterize the 2,4-dichlorophenol contaminated soil before and after ball milling. The mechanism of ball milling mechanochemical treatment of organic contaminated soil was studied, and the possible degradation path of 2,4-dichlorophenol was analyzed. The results showed that the content of 2,4-dichlorophenol in the soil was degraded from 9 009.0 mg/kg to 70.7 mg/kg after ball milling at 400 r/min for 4 h, and the degradation rate reached 99%. At the same time, the concentrations of phenol, dimethyl phthalate and benzo (b) fluoranthene were also degraded simultaneously. In the process of ball milling, with the increase of milling time, the particle size of soil decreased, the area of reaction surface increased, the reaction speed was accelerated, the shape and structure of soil particles were changed, and the chemical energy was increased; meanwhile, C-Cl bond broke, C-H and C=C bonds appeared, H and C replaced the Cl on 2, 4-dichlorophenol and Cl was removed from 2, 4-dichlorophenol. In this process, SiO2 did not participate in the reaction. It was speculated that the degradation path of 2,4-dichlorophenol was as follows: With the increase of chemical energy, 2,4-dichlorophenol collided with calcium oxide, electron transfer occurred, free radical hydrogen was generated, C-Cl bond was broken, and 2-chlorophenol was further degraded into small molecule organic matter, which was gradually degraded to amorphous carbon and inorganic chlorine.

Key words: mechanochemical method, soil, ball milling, 2,4-dichlorophenol, degradation

中图分类号: