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二丁基硫醚通过臭氧化和O3/H2O2高级氧化过程的分解速率。

Rate of dibutylsulfide decomposition by ozonation and the O3/H2O2 advanced oxidation process.

作者信息

Popiel Stanisław, Nalepa Tomasz, Dzierzak Dorota, Stankiewicz Romuald, Witkiewicz Zygfryd

机构信息

Military University of Technology, Institute of Chemistry, Warsaw, Poland.

出版信息

J Hazard Mater. 2009 May 30;164(2-3):1364-71. doi: 10.1016/j.jhazmat.2008.09.049. Epub 2008 Sep 24.

Abstract

A process of dibutylsulfide (DBS) oxidation using advanced methods of oxidation with ozone and hydrogen peroxide was studied. It was demonstrated that depending on pH value there are two mechanisms of DBS oxidation present: ionic and radical. The ionic mechanism predominates in acidic environment and the radical mechanism predominates in alkaline environment. At high pH ozone stability decreases and hydrogen peroxide has a deciding effect on DBS oxidation rate. At pH 9, and at high concentration of hydrogen peroxide (ranging from 0.1 to 1 mol/L), a clear increase in DBS decomposition rate was observed. That was caused by production of hydroperoxide radicals in reaction of hydrogen peroxide and ozone. In solutions pH value of which is close to 2, the rate of DBS oxidation by ozone alone is slower than in a O(3)/H(2)O(2) system, regardless the H(2)O(2) concentration. For higher H(2)O(2) concentrations (ranging from 0.1 to 1 mol/L), regardless the pH value of the solution, oxidation in a O(3)/H(2)O(2) system is faster, compared to a situation in which ozone is a sole oxidizer. For H(2)O(2) concentrations below 0.1 mol/L and when pH>2DBS oxidation in O(3)/H(2)O(2) system is slower compared to the situation in which ozone was the only oxidizer.

摘要

研究了采用臭氧和过氧化氢等先进氧化方法对二丁基硫醚(DBS)进行氧化的过程。结果表明,根据pH值的不同,存在两种DBS氧化机制:离子机制和自由基机制。离子机制在酸性环境中占主导,自由基机制在碱性环境中占主导。在高pH值下,臭氧稳定性降低,过氧化氢对DBS氧化速率起决定性作用。在pH为9且过氧化氢浓度较高(0.1至1 mol/L)时,观察到DBS分解速率明显增加。这是由于过氧化氢与臭氧反应产生了氢过氧自由基。在pH值接近2的溶液中,无论过氧化氢浓度如何,仅用臭氧氧化DBS的速率比在O(3)/H(2)O(2)体系中要慢。对于较高的过氧化氢浓度(0.1至1 mol/L),无论溶液的pH值如何,与仅用臭氧作为氧化剂的情况相比,在O(3)/H(2)O(2)体系中的氧化速度更快。对于过氧化氢浓度低于0.1 mol/L且pH>2时,与仅用臭氧作为氧化剂的情况相比,在O(3)/H(2)O(2)体系中DBS的氧化速度较慢。

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