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铁/活性炭催化剂上催化湿式过氧化氢氧化(CWPO)中过氧化氢分解对羟基自由基的选择性。

Selectivity of hydrogen peroxide decomposition towards hydroxyl radicals in catalytic wet peroxide oxidation (CWPO) over Fe/AC catalysts.

作者信息

Rey A, Bahamonde A, Casas J A, Rodríguez J J

机构信息

Instituto de Catálisis y Petroleoquímica, CSIC, Marie Curie 2, 28049 Madrid, Spain.

出版信息

Water Sci Technol. 2010;61(11):2769-78. doi: 10.2166/wst.2010.077.

Abstract

Two Fe/AC catalysts prepared with different iron precursors (iron nitrate and iron pentacarbonyl) and the same AC support have been tested in H(2)O(2) decomposition in presence and absence of methanol, a known strong scavenger of hydroxyl radicals, to investigate the selectivity towards .OH formation in this reaction and their behavior in the CWPO of phenol. The catalyst prepared with iron nitrate, with the most oxidized surface and the highest Fe surface content, seems to favor a higher selectivity towards .OH formation in CWPO allowing for complete phenol conversion and a significant TOC removal, with the highest mineralization degree at 50 degrees C and atmospheric pressure. Fe/AC catalysts were more efficient in the CWPO of phenol than in methanol presence due to a better use of the oxidant since adsorbed phenol on catalyst surface minimizes inefficient H(2)O(2) decomposition to H(2)O and O(2)(g). The influence of the initial H(2)O(2) concentration on phenol oxidation with this catalyst was also studied. A theoretical stoichiometric amount of H(2)O(2) for complete oxidation of phenol was chosen as the best starting concentration since auto-scavenging reactions can be minimized and it is sufficient for oxidizing phenol and the aromatic intermediates.

摘要

使用不同铁前驱体(硝酸铁和五羰基铁)和相同活性炭载体制备的两种铁/活性炭催化剂,在有无甲醇(一种已知的强羟基自由基清除剂)存在的情况下,对其在过氧化氢分解反应中羟基自由基生成的选择性以及在苯酚催化湿式过氧化氢氧化(CWPO)中的行为进行了测试。用硝酸铁制备的催化剂,具有最高氧化态的表面和最高的铁表面含量,似乎在催化湿式过氧化氢氧化中对羟基自由基的生成具有更高的选择性,能够实现苯酚的完全转化和显著的总有机碳(TOC)去除,在50℃和常压下具有最高的矿化度。由于催化剂表面吸附的苯酚使过氧化氢分解为水和氧气(g)的无效反应最小化,从而更好地利用了氧化剂,因此铁/活性炭催化剂在苯酚的催化湿式过氧化氢氧化中比在有甲醇存在时更有效。还研究了初始过氧化氢浓度对该催化剂催化苯酚氧化的影响。选择理论化学计量的过氧化氢用于苯酚的完全氧化作为最佳起始浓度,因为自清除反应可以最小化,并且足以氧化苯酚和芳香族中间体。

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