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类芬顿降解 MTBE:铁抗衡阴离子和自由基清除剂的影响。

Fenton-like degradation of MTBE: Effects of iron counter anion and radical scavengers.

机构信息

University of Puerto Rico at Mayaguez, Department of Civil Engineering and Surveying, USA.

出版信息

Chemosphere. 2010 Jan;78(5):563-8. doi: 10.1016/j.chemosphere.2009.11.005. Epub 2009 Dec 2.

DOI:10.1016/j.chemosphere.2009.11.005
PMID:19959205
Abstract

Fenton-driven oxidation of methyl tert-butyl ether (MTBE) (0.11-0.16mM) in batch reactors containing ferric iron (5mM) and hydrogen peroxide (H(2)O(2)) (6mM) (pH=3) was performed to investigate MTBE transformation mechanisms. Independent variables included the forms of iron (Fe) (Fe(2)(SO(4))(3).9H(2)O and Fe(NO(3))(3).9H(2)O), H(2)O(2) (6, 60mM), chloroform (CF) (0.2-2.4mM), isopropyl alcohol (IPA) (25, 50mM), and sulfate (7.5mM). MTBE, tert-butyl alcohol and acetone transformation were significantly greater when oxidation was carried out with Fe(NO(3))(3).9H(2)O than with Fe(2)(SO(4))(3).9H(2)O. Sulfate interfered in the formation of the ferro-peroxy intermediate species, inhibited H(2)O(2) reaction, hydroxyl radical (()OH) formation, and MTBE transformation. Transformation was faster and more complete at a higher [H(2)O(2)] (60mM), but resulted in lower oxidation efficiency which was attributed to ()OH scavenging by H(2)O(2). CF scavenging of the superoxide radical (()O(2)(-)) in the ferric nitrate system resulted in lower rates of ()O(2)(-) reduction of Fe(III) to Fe(II), ()OH production, and consequently lower rates of MTBE transformation. IPA, an excellent scavenger of ()OH, completely inhibited MTBE transformation in the ferric nitrate system indicating oxidation was predominantly by ()OH. ()OH scavenging by HSO(4)(-), formation of the sulfate radical (()SO(4)(-)), and oxidation of MTBE by ()SO(4)(-) was estimated to be negligible. The form of Fe (i.e., counter anion) selected for use in Fenton treatment systems impacts oxidative mechanisms, treatment efficiency, and post-oxidation treatment of residuals which may require additional handling and cost.

摘要

在含有铁(5mM)和过氧化氢(H(2)O(2))(6mM)(pH=3)的间歇式反应器中,对甲基叔丁基醚(MTBE)(0.11-0.16mM)进行芬顿驱动氧化,以研究 MTBE 转化机制。自变量包括铁(Fe)的形式(Fe(2)(SO(4))(3).9H(2)O 和 Fe(NO(3))(3).9H(2)O)、H(2)O(2)(6、60mM)、氯仿(CF)(0.2-2.4mM)、异丙醇(IPA)(25、50mM)和硫酸盐(7.5mM)。与使用 Fe(2)(SO(4))(3).9H(2)O 相比,使用 Fe(NO(3))(3).9H(2)O 进行氧化时,MTBE、叔丁醇和丙酮的转化明显更大。硫酸盐干扰亚铁过氧中间物种的形成,抑制 H(2)O(2)反应、羟基自由基(()OH)形成和 MTBE 转化。在较高的[H(2)O(2)](60mM)下,转化更快、更完全,但氧化效率较低,这归因于 H(2)O(2)对()OH 的清除。在硝酸铁体系中,CF 清除超氧自由基(()O(2)(-))导致 Fe(III)还原为 Fe(II)、()OH 生成和 MTBE 转化的()O(2)(-)还原率降低。IPA 是()OH 的优秀清除剂,完全抑制了硝酸铁体系中 MTBE 的转化,表明氧化主要是由()OH 引起的。HSO(4)(-)对()OH 的清除、硫酸根自由基(()SO(4)(-))的形成以及()SO(4)(-)对 MTBE 的氧化估计可以忽略不计。芬顿处理系统中选择的铁形式(即抗衡阴离子)会影响氧化机制、处理效率以及可能需要额外处理和成本的残余物的后氧化处理。

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