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氢气替代原位生成 H2O2:在芬顿反应中的应用。

Hydrogen substitutes for the in situ generation of H2O2: an application in the Fenton reaction.

机构信息

Departament d'Enginyeria Química, Universitat Rovira i Virgili, Av. Països Catalans 26, 43007 Tarragona, Spain.

出版信息

J Hazard Mater. 2011 Aug 15;192(1):340-6. doi: 10.1016/j.jhazmat.2011.05.029. Epub 2011 May 17.

DOI:10.1016/j.jhazmat.2011.05.029
PMID:21641717
Abstract

This study investigates the ability of formic acid, hydrazine and hydroxylamine to act as H(2) substitutes in conducting phenol degradation by Fenton reaction using in situ generated hydrogen peroxide. The processes were performed with semi-heterogeneous (Pd/Al(2)O(3)+soluble Fe(2+)) and fully heterogeneous (FePd/Al(2)O(3)) catalytic systems under ambient conditions. In contrast to bulk H(2)O(2) production conditions, hydrazine is able to produce H(2)O(2)in situ followed by phenol degradation using Pd/Al(2)O(3)+Fe(2+) at pH 3 without the need for halide ions. However, a degree of mineralization exceeding 37% could not be achieved. The significant production of in situ H(2)O(2) at the inherent acidic pH of hydroxylammonium sulfate in the presence of Pd/Al(2)O(3)+Fe(2+) was also found to differ from the bulk production of H(2)O(2), in which no H(2)O(2) was detected. A remarkable degree of mineralization (ca. 65%) as well as fast phenol degradation during the reaction started at pH 7 over FePd/Al(2)O(3) may be an advantage of using hydroxylamine. On the other hand, using formic acid, H(2)O(2) was produced at a moderate rate, thereby achieving higher efficiency in the mineralization of phenol. Most importantly, the catalysts were more stable in the presence of formic acid than hydrazine or hydroxylamine.

摘要

本研究考察了甲酸、肼和羟胺在芬顿反应中替代原位生成的过氧化氢作为 H2 时的能力,以促进苯酚降解。在环境条件下,使用半均相(Pd/Al2O3+可溶性 Fe2+)和全均相(FePd/Al2O3)催化体系进行了这些过程。与大量 H2O2 生成条件相比,肼能够在 pH 3 下用 Pd/Al2O3+Fe2+原位产生 H2O2,随后降解苯酚,而无需卤化物离子。然而,无法达到超过 37%的矿化程度。在 Pd/Al2O3+Fe2+存在下,硫酸羟胺固有酸性 pH 下原位产生大量 H2O2 的情况也与大量 H2O2 生成不同,在后者中未检测到 H2O2。在 pH 7 下开始反应时,FePd/Al2O3 上使用羟胺可实现显著的矿化程度(约 65%)和快速苯酚降解,这可能是其优势。另一方面,使用甲酸以适度的速率产生 H2O2,从而提高了苯酚矿化的效率。最重要的是,与肼或羟胺相比,甲酸的存在使催化剂更稳定。

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