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电过氧协同作用可实现废水中 Cr(III)络合物的高效去除和回收,并抑制中间产物 Cr(VI)的生成:性能与机理。

Electro-peroxone enables efficient Cr removal and recovery from Cr(III) complexes and inhibits intermediate Cr(VI) generation in wastewater: Performance and mechanism.

机构信息

National and Local Joint Engineering Research Center for Ecological Treatment Technology of Urban Water Pollution, College of Life and Environmental Science, Wenzhou University, Wenzhou 325035, China.

State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023, China.

出版信息

Water Res. 2022 Jun 30;218:118502. doi: 10.1016/j.watres.2022.118502. Epub 2022 Apr 25.

Abstract

Available oxidation processes for removing Cr(III) complexes from water/wastewater usually encounter the formation of highly toxic Cr(VI) and the generation of Cr enriched waste sludge, posing challenges on the subsequent disposal. Herein, we achieve efficient removal of Cr(III)-organic complexes and simultaneous recovery of Cr from wastewater with enhanced curtailment of intermediate Cr(VI), by using an electrochemically driven peroxone (i.e., electro-peroxone) process with activated carbon fiber (ACF) electrodes. For Cr(III)-EDTA, electro-peroxone could remove ∼90% total Cr from 11.50 mg/L to 1.20 mg/L and ∼80% total organic carbon, with a strong curtailment of Cr(VI) to less than 0.2 mg/L. Additionally, the process could obtain a complete recovery of the removable Cr, of which 78.3% are enriched at ACF cathode as amorphous Cr(OH) deposits and the remaining 21.7% are adsorbed at the anode, thus avoiding the generation of Cr laden sludge. Mechanism studies show the electro-generated HO reacts with O to generate abundant HO· for decomplexation, which sequentially oxidizes Cr(III) to Cr(VI), and degrades the released EDTA via stepwise decarboxylated process, as confirmed by HPLC analysis. Multiple pathways including electro-reduction, HO reduction and electro-adsorption synergistically curtail and immobilize the formed intermediate Cr(VI). ACF characterizations and continuous 5-cycle experiments substantiate the excellent reusability of the ACF electrodes. Moreover, this process exhibits satisfactory effectiveness to Cr(III) complexed with other ligands (e.g., citrate and oxalate), and complexed Cr(III) in the real electroplating wastewater. We believe this study would provide an efficient and eco-friendly alternative for Cr(III) complexes removal from wastewater.

摘要

从水/废水中去除 Cr(III) 络合物的常用氧化方法通常会遇到形成剧毒 Cr(VI) 和产生富含 Cr 的废污泥的问题,这对后续处理构成了挑战。在此,我们通过使用带有活性炭纤维 (ACF) 电极的电化学驱动过氧单硫酸盐 (即电过氧单硫酸盐) 工艺,实现了从废水中高效去除 Cr(III)-有机络合物并同时回收 Cr,同时极大地减少了中间 Cr(VI) 的生成。对于 Cr(III)-EDTA,电过氧单硫酸盐可以将浓度为 11.50mg/L 的 Cr(III)-EDTA 去除到 1.20mg/L,总去除率约为 90%,总有机碳去除率约为 80%,同时 Cr(VI) 的生成量被严格控制在 0.2mg/L 以下。此外,该工艺还可以完全回收可去除的 Cr,其中 78.3%以无定形 Cr(OH)3 的形式富积在 ACF 阴极上,其余 21.7%则被吸附在阳极上,从而避免了含 Cr 污泥的生成。机理研究表明,电生成的 HO 与 O 反应生成大量 HO·用于去络合,HO·随后将 Cr(III)氧化为 Cr(VI),并通过逐步脱羧过程降解释放的 EDTA,这一点通过 HPLC 分析得到了证实。包括电还原、HO 还原和电吸附在内的多种途径协同作用,极大地减少并固定了形成的中间 Cr(VI)。ACF 的特性和连续的 5 个循环实验证实了 ACF 电极的优异可重复使用性。此外,该工艺对与其他配体(如柠檬酸和草酸盐)络合的 Cr(III)以及实际电镀废水中的络合 Cr(III)均具有良好的处理效果。我们相信,本研究为从废水中去除 Cr(III) 络合物提供了一种高效且环保的替代方法。

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