School of Urban Construction, Wuhan University of Science and Technology, Wuhan 430065, PR China.
State Key Laboratory of Environmental Geochemistry, Institute of Geochemistry, Chinese Academy of Sciences, Guiyang 550081, PR China.
J Hazard Mater. 2023 Jan 15;442:130069. doi: 10.1016/j.jhazmat.2022.130069. Epub 2022 Sep 26.
Fe-based replacement and precipitation are promising methods for removal of copper ethylenediaminetetraacetic acid (Cu(II)-EDTA) but are limited by the necessity of controlling pH and dissolved oxygen. The details of the decomplexation mechanism also remain unclear. The present work investigated an anoxic iron electrocoagulation process capable of automatically modulating anoxic conditions and solution pH during exposure to air and thus promoting the rapid and thorough decomplexation of Cu(II)-EDTA. Dissolved Fe (II), rather than Fe(II)-bearing minerals, was found to be primarily responsible for the reduction of Cu(II)-EDTA to Cu(I)-EDTA and for the subsequent replacement reaction to generate free Cu(I) ions within the initial pH range of 2-7. The Cu(I) was primarily precipitated as CuO on the surface of green rust and magnetite as the pH was increased. The aeration of these Fe-containing precipitates released free Cu(I) ions instead of chelated Cu into solution, allowing for recycling of the Cu. This release of Cu(I) was likely induced by the pH decrease during aeration. This study provides important insights regarding the reductive decomplexation of chelated Cu(II) and the recovery of Cu via anoxic iron electrocoagulation, which is a promising green approach to recycling Cu from wastewater.
基于铁的取代和沉淀是去除铜乙二胺四乙酸(Cu(II)-EDTA)的有前途的方法,但受到需要控制 pH 值和溶解氧的限制。去络合机制的细节也不清楚。本研究考察了一种缺氧铁电凝过程,能够在暴露于空气时自动调节缺氧条件和溶液 pH 值,从而促进 Cu(II)-EDTA 的快速彻底去络合。发现溶解的 Fe(II),而不是含 Fe(II)的矿物,主要负责将 Cu(II)-EDTA 还原为 Cu(I)-EDTA,并在初始 pH 值为 2-7 的范围内进行随后的取代反应,生成游离的 Cu(I)离子。随着 pH 值的升高,Cu(I)主要以 CuO 的形式沉淀在绿色锈和磁铁矿的表面。这些含铁沉淀物的曝气将游离的 Cu(I)离子而不是螯合的 Cu 释放到溶液中,从而实现了 Cu 的回收。Cu(I)的这种释放可能是由于曝气过程中 pH 值下降引起的。本研究提供了有关络合 Cu(II)的还原去络合以及通过缺氧铁电凝回收 Cu 的重要见解,这是从废水中回收 Cu 的一种很有前途的绿色方法。