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响应面法优化除草剂 4-氯-2-甲基苯氧乙酸的光电芬顿降解。

Solar photoelectro-Fenton degradation of the herbicide 4-chloro-2-methylphenoxyacetic acid optimized by response surface methodology.

机构信息

Laboratori d'Electroquímica dels Materials i del Medi Ambient, Departament de Química Física, Facultat de Química, Universitat de Barcelona, Martí i Franquès 1-11, 08028 Barcelona, Spain.

出版信息

J Hazard Mater. 2011 Oct 30;194:109-18. doi: 10.1016/j.jhazmat.2011.07.089. Epub 2011 Aug 5.

Abstract

A central composite rotatable design and response surface methodology (RSM) were used to optimize the experimental variables of the solar photoelectro-Fenton (SPEF) treatment of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA). The experiments were made with a flow plant containing a Pt/air-diffusion reactor coupled to a solar compound parabolic collector (CPC) under recirculation of 10 L of 186 mg L(-1) MCPA solutions in 0.05 M Na(2)SO(4) at a liquid flow rate of 180 L h(-1) with an average UV irradiation intensity of about 32 Wm(-2). The optimum variables found for the SPEF process were 5.0 A, 1.0mM Fe(2+) and pH 3.0 after 120 min of electrolysis. Under these conditions, 75% of mineralization with 71% of current efficiency and 87.7 k Wh kg(-1) TOC of energy consumption were obtained. MCPA decayed under the attack of generated hydroxyl radicals following a pseudo-first-order kinetics. Hydroxyl radicals also destroyed 4-chloro-2-methylphenol, methylhydroquinone and methyl-p-benzoquinone detected as aromatic by-products. Glycolic, maleic, fumaric, malic, succinic, tartronic, oxalic and formic acids were identified as generated carboxylic acids, which form Fe(III) complexes that are quickly photodecarboxylated by the UV irradiation of sunlight at the CPC photoreactor. A reaction sequence for the SPEF degradation of MCPA was proposed.

摘要

采用中心复合旋转设计和响应面法(RSM)优化太阳能光电芬顿(SPEF)处理除草剂 4-氯-2-甲基苯氧乙酸(MCPA)的实验变量。实验在一个流动装置中进行,该装置包含一个 Pt/空气扩散反应器,与太阳能复合抛物面收集器(CPC)耦合,在 180 L h(-1) 的液体流速下,以 10 L 的 186 mg L(-1) MCPA 溶液在 0.05 M Na(2)SO(4)中循环,平均紫外辐照强度约为 32 Wm(-2)。SPEF 过程的最佳变量为 5.0 A、1.0mM Fe(2+)和 pH 3.0,电解 120 min 后。在此条件下,获得 75%的矿化度、71%的电流效率和 87.7 k Wh kg(-1) TOC 的能耗。MCPA 在生成的羟基自由基的攻击下降解,遵循准一级动力学。羟基自由基还破坏了检测到的作为芳香族副产物的 4-氯-2-甲基苯酚、甲基氢醌和甲基对苯醌。鉴定出生成的羧酸为乙二醇酸、马来酸、富马酸、苹果酸、琥珀酸、酒石酸、草酸和甲酸,它们形成 Fe(III)配合物,这些配合物在 CPC 光反应器中的阳光紫外辐射下迅速光解羧基。提出了 SPEF 降解 MCPA 的反应序列。

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