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儿茶酚螯合剂作为基于芬顿反应的氧化还原试剂对木质素模型底物降解及从无元素氯硫酸盐法制浆厂废水中去除化学需氧量的影响。

The effect of a catecholate chelator as a redox agent in Fenton-based reactions on degradation of lignin-model substrates and on COD removal from effluent of an ECF kraft pulp mill.

作者信息

Arantes Valdeir, Milagres Adriane Maria Ferreira

机构信息

Department of Biotechnology, Faculdade de Engenharia Química de Lorena, FAENQUIL, CP 116-12.600-970 Lorena, SP, Brazil.

出版信息

J Hazard Mater. 2007 Mar 6;141(1):273-9. doi: 10.1016/j.jhazmat.2006.06.134. Epub 2006 Jul 7.

Abstract

We evaluated the effect of a catecholate chelator as a redox agent in Fenton-based reactions (known as chelator-mediated Fenton reaction-CMFR), in the presence of three different transition metals ions (Fe(2+), Fe(3+) and Cu(2+)) by determining the oxidative capability of CMFR towards lignin-model substrates. The potential application of mediated Fenton-based reactions as a novel process to treat pulp mill effluent was evaluated and monitored by chemical oxygen demand (COD) and total phenol removals from a combination of the effluents generated during an ECF bleaching stage. The catecholate chelator 3,4-dihydroxiphenilacetic acid (DOPAC) reduced both Fe(3+) and Cu(2+), in addition, the maximum Cu(2+) reduction activity was reached in a shorter time than for Fe(3+) reduction, however, the highest metal reduction activity was observed with Fe(3+). When DOPAC was added to Fenton-based reactions (Fe(3+)/H(2)O(2), Fe(2+)/H(2)O(2), Cu(2+)/H(2)O(2)) an increase in oxidative activities of these reactions were found as they resulted in great degradation improvement of the lignin-model substrates azure B, phenol red and syringaldazine. The same increase in oxidative capability of Fenton-based reactions in the presence of DOPAC was observed after effluent treatment, expressed by the increase in COD removal, namely, an increase in the range of about 70% in COD removal when Fe(2+) or Fe(3+) was the catalytic metal and about 25% for Cu(2+). However CMFR lead to an increase in total phenol content. As COD removal by CMFR system using Fe(3+) and Fe(2+) was not significantly different and that Fe(3+) ions promoted lesser increase in total phenol content, Fe(3+) was chosen for experimental optimization. At optimum conditions, 75% of COD and 30% of total phenol removal were achieved.

摘要

我们通过测定螯合剂介导的芬顿反应(CMFR)对木质素模型底物的氧化能力,评估了一种儿茶酚螯合剂作为氧化还原剂在基于芬顿反应(称为螯合剂介导的芬顿反应 - CMFR)中,在三种不同过渡金属离子(Fe(2+)、Fe(3+)和Cu(2+))存在下的效果。通过化学需氧量(COD)以及从无元素氯(ECF)漂白阶段产生的混合废水中去除总酚,评估并监测了基于芬顿反应的介导反应作为处理制浆厂废水的新工艺的潜在应用。儿茶酚螯合剂3,4 - 二羟基苯乙酸(DOPAC)能还原Fe(3+)和Cu(2+),此外,达到最大Cu(2+)还原活性的时间比Fe(3+)还原的时间短,然而,观察到Fe(3+)具有最高的金属还原活性。当将DOPAC添加到基于芬顿的反应(Fe(3+)/H₂O₂、Fe(2+)/H₂O₂、Cu(2+)/H₂O₂)中时,发现这些反应的氧化活性增加,因为它们使木质素模型底物天青B、酚红和丁香醛连氮的降解有了很大改善。在废水处理后,观察到在DOPAC存在下基于芬顿反应的氧化能力有相同程度的增加,这表现为COD去除率的提高,即当Fe(2+)或Fe(3+)作为催化金属时,COD去除率提高约70%,而对于Cu(2+)约为25%。然而,CMFR导致总酚含量增加。由于使用Fe(3+)和Fe(2+)的CMFR系统对COD的去除没有显著差异,并且Fe(3+)离子促进的总酚含量增加较少,因此选择Fe(3+)进行实验优化。在最佳条件下,实现了75%的COD去除率和30%的总酚去除率

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