O_3/H_2O_2去除水中硝基苯效果与机理

Effect and Mechanism of Degradation of Nitrobenzene in Aqueous Solution by O_3/H_2O_2

以硝基苯为目标反应物,对O3/H2O2体系氧化去除水中硝基苯的效果和机理进行了研究,考察了pH值、H2O2剂量、自由基抑制剂或促进剂对硝基苯的去除效果的影响.研究发现,在pH≤7时,H2O2促进臭氧化去除硝基苯的效果较为明显,当H2O2投加量从1.0 mg/L增加到4.0 mg/L时,在氧化5 min内,硝基苯的去除率明显的升高,但当H2O2投加量由4.0 mg/L提高到20 mg/L时,硝基苯的去除率呈下降趋势;同时发现单独臭氧化硝基苯的过程中能明显产生H2O2;几种有机物的加入,不同程度都降低了硝基苯的去除率.无论单独臭氧化还是催化臭氧化都很难将体系TOC大幅度降低,硝基脱出后几乎完全以NO-3形式存在,反应体系pH随氧化时间的增加而明显的降低.LC-MS和GC-MS的分析表明,硝基苯主要的臭氧化产物为酚类和羧酸类物质.对O3/H2O2与硝基苯反应历程进行推导,认为硝基苯的臭氧化降解分为2个阶段,首先是羟基自由基进攻使苯环羟基化,然后是羟基化的芳环发生开裂,生成各种脂肪族化合物或进一步矿化.

Nitrobenzene （NB） was selected as the model pollutant in water and the efficiency and mechanism of degradation of NB in aqueous solution by O3/H2O2 were investigated. The effects of pH, H2O2 dose and the inhibitor or accelerant of ·OH on the removal rate of NB were studied. H2O2 could obviously improve the ozonation decay rate of NB when the pH value of the solution was below 7. The removal rate of NB was enhanced remarkably while H2O2 dose was increased from 1.0 m g/L to 4.0 mg/L. However, as H2O2 dose increased from 4.0 mg/L to 20 mg/L, the removal efficiency of NB decreased. Different quantities of H2O2 were yielded in different reaction phases of single ozonation system. Both systems of single ozonation and H2O2-catalysed ozonation could not reduce TOC observably. During the NB degradation process, organonitrogen was almost completely converted to nitrate and the pH value of the solution reduced significantly. Results of LC-MS and GC-MS analysis showed that the main intermediate products were phenolic compounds and carbonyl compounds. A possible reaction pathway of the catalytic ozonation of NB was also proposed. It was found that the catalytic ozonation of NB could be divided into two steps. First, hydroxyl radical attacked phenyl ring to form phenolic compounds, then the ring was opened, forming into various aliphatic compounds or being mineralized to inorganic compounds.