| 引用本文: | 庞素艳,鲁雪婷,江进,袁立鹏,马军.KMnO4氧化降解雌酮反应动力学与氧化产物[J].哈尔滨工业大学学报,2016,48(2):38.DOI:10.11918/j.issn.0367-6234.2016.02.007 |
| PANG Suyan,LU Xueting,JIANG Jin,YUAN Lipeng,MA Jun.Oxidation of estrone by aqueous permanganate:reaction kinetics and oxidation products[J].Journal of Harbin Institute of Technology,2016,48(2):38.DOI:10.11918/j.issn.0367-6234.2016.02.007 |
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| KMnO4氧化降解雌酮反应动力学与氧化产物 |
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庞素艳1,鲁雪婷1,江进2,3,袁立鹏1,马军2,3
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(1.哈尔滨理工大学 化学与环境工程学院,绿色化工技术黑龙江省高校重点实验室,150040哈尔滨; 2.城市水资源与水环境 国家重点实验室(哈尔滨工业大学),150090 哈尔滨; 3.哈尔滨工业大学 市政环境工程学院,150090哈尔滨)
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| 摘要: |
| 为探讨KMnO4氧化降解雌酮（E1）的效能和反应机理，在假一级条件下，研究KMnO4氧化降解E1的动力学规律，利用三重四级杆串联线性离子阱液相-质谱联用仪（LC-MS/MS）对KMnO4氧化降解E1的产物进行分析.结果表明，KMnO4氧化降解E1符合假一级动力学规律，且假一级动力学常数Kobs（s-1）随着KMnO4浓度的增加呈线性增加，二级反应动力学常数k（L·mol-1·s-1）随着pH的升高而增大.通过与HOCl和O3氧化E1对比，在中性pH附近，KMnO4氧化E1的二级反应动力学常数与HOCl相当，但远低于O3.然而，实际水体中KMnO4的除污染效能明显高于HOCl和O3，主要是由于HOCl和O3在实际水体中的消耗速度比较快，有效剩余浓度低，而KMnO4在实际水体中的消耗速度比较慢.LC-MS/MS测定KMnO4氧化降解E1产物的结果表明，KMnO4易氧化进攻E1苯环上的活性位酚羟基，形成一系列羟基化、醌型、羧酸化芳香开环产物，并且有效降低其内分泌干扰活性.
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| 关键词: KMnO4 雌酮 反应动力学 LC-MS/MS 氧化产物 |
| DOI：10.11918/j.issn.0367-6234.2016.02.007 |
| 分类号:X703 |
| 文献标识码:A |
| 基金项目:黑龙江省教育厅科学技术研究项目(12531111). |
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| Oxidation of estrone by aqueous permanganate:reaction kinetics and oxidation products |
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PANG Suyan1, LU Xueting1, JIANG Jin2,3, YUAN Lipeng1, MA Jun2,3
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(1.Key Laboratory of Green Chemical Engineering and Technology of College of Heilongjiang Province, College of Chemical and Environmental Engineering, Harbin University of Science and Technology, 150040 Harbin, China; 2. State Key Laboratory of Urban Water Resource and Environment (Harbin Institute of Technology), 150090 Harbin, China; 3. School of Municipal and Environmental Engineering, Harbin Institute of Technology, 150090 Harbin, China)
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| Abstract: |
| The purpose of this article was to investigate the effectiveness and mechanism for the oxidation of estrone by aqueous potassium permanganate. Experiments were conducted to examine the reaction kinetics of potassium permanganate with estrone under the condition with potassium permanganate in excess over a wide pH range. Then, reaction products of estrone with potassium permanganate were identified with liquid chromatography tandem mass spectrometry (LC-MS/MS). The results showed that the loss of estrone followed the pseudo-first-order kinetics with potassium permanganate, suggesting that the reaction is first-order with respect to estrone. The pseudo-first-order rate constant (Kobs, s-1) increased linearly with the increase of potassium permanganate concentration. The degradation of estrone of the second-order rate constants (k, L·mol-1·s-1) increased with the increase of pH. Estrone was shown to exhibit similarly appreciable reactivity toward potassium permanganate with the second-order rate constant at near neutral pH comparable to chlorine but much lower than that of ozone. In comparison with these oxidants, however, potassium permanganate was much more effective for the oxidative removal of estrone in real waters, mainly due to the relatively high stability of potassium permanganate therein. Identification of oxidation products suggested the initial attack of potassium permanganate at the hydroxyl group in the aromatic ring of estrone, leading to the formation of a series of quinone-like and aromatic ring-opening products and thus the elimination of its estrogenic activity.
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| Key words: potassium permanganate estrone reaction kinetics LC-MS/MS mass spectrometry oxidation products |
