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超声波对苯酚氧化过程中水体浊度的影响。(氢)过氧络合物的形成。

Effect of ultrasonic waves on the water turbidity during the oxidation of phenol. Formation of (hydro)peroxo complexes.

作者信息

Villota Natalia, Lomas Jose M, Camarero Luis M

机构信息

Department of Chemical and Environmental Engineering, Escuela Universitaria de Ingeniería Vitoria-Gasteiz, University of the Basque Country, UPV/EHU, Vitoria-Gasteiz, Spain.

Department of Chemical and Environmental Engineering, Escuela Universitaria de Ingeniería Vitoria-Gasteiz, University of the Basque Country, UPV/EHU, Vitoria-Gasteiz, Spain.

出版信息

Ultrason Sonochem. 2017 Nov;39:439-445. doi: 10.1016/j.ultsonch.2017.05.024. Epub 2017 May 16.

DOI:10.1016/j.ultsonch.2017.05.024
PMID:28732966
Abstract

Analysis of the kinetics of aqueous phenol oxidation by a sono-Fenton process reveals that the via involving ortho-substituted intermediates prevails: catechol (25.0%), hydroquinone (7.7%) and resorcinol (0.6%). During the oxidation, water rapidly acquires color that reaches its maximum intensity at the maximum concentration of p-benzoquinone. Turbidity formation occurs at a slower rate. Oxidant dosage determines the nature of the intermediates, being trihydroxylated benzenes (pyrogallol, hydroxyhydroquinone) and muconic acid the main precursors causing turbidity. It is found that the concentration of iron species and ultrasonic waves affects the intensity of the turbidity. The pathway of (hydro)peroxo-iron(II) complexes formation is proposed. Operating with 20.0-27.8mgFe/kW rates leads to formation of (hydro)peroxo-iron(II) complexes, which induce high turbidity levels. These species would dissociate into ZZ-muconic acid and ferrous ions. Applying relationships around 13.9mgFe/kW, the formation of (hydro)peroxo-iron(III) complexes would occur, which could react with carboxylic acids (2,5-dioxo-3-hexenedioic acid). That reaction induces turbidity slower. This is due to the organic substrate reacting with two molecules of the (hydro)peroxo complex. Therefore, it is necessary to accelerate the iron regeneration, intensifying the ultrasonic irradiation. Afterwards, this complex would dissociate into maleic acid and ferric ions.

摘要

通过声-芬顿法对苯酚在水溶液中的氧化动力学分析表明,涉及邻位取代中间体的途径占主导:儿茶酚(25.0%)、对苯二酚(7.7%)和间苯二酚(0.6%)。在氧化过程中,水迅速变色,在对苯醌浓度达到最大值时颜色强度达到最大。浊度形成的速率较慢。氧化剂用量决定了中间体的性质,三羟基苯(连苯三酚、羟基对苯二酚)和粘康酸是导致浊度的主要前体。研究发现,铁物种的浓度和超声波会影响浊度的强度。提出了(氢)过氧铁(II)配合物的形成途径。以20.0 - 27.8mgFe/kW的速率运行会导致(氢)过氧铁(II)配合物的形成,从而导致高浊度水平。这些物种会分解为粘康酸和亚铁离子。以约13.9mgFe/kW的比例运行时,会形成(氢)过氧铁(III)配合物,它可以与羧酸(2,5 - 二氧代 - 3 - 己烯二酸)反应。该反应导致浊度的速度较慢。这是由于有机底物与两分子的(氢)过氧配合物发生反应。因此,有必要加速铁的再生,增强超声辐照。之后,该配合物会分解为马来酸和铁离子。

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