State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, 210023, China.
State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, 210023, China; Research Center for Environmental Nanotechnology (ReCENT), Nanjing University, Nanjing, 210023, China.
Water Res. 2017 Dec 1;126:172-178. doi: 10.1016/j.watres.2017.09.021. Epub 2017 Sep 13.
Most available processes are incapable of removing Cr(III)-organic complexes from water due to their high solubility, extremely slow decomplexation rate, and possible formation of more toxic Cr(VI) during oxidation. Herein, we proposed a new combined process, i.e., UV/Fe(III) followed by alkaline precipitation (namely UV/Fe(III)+OH), to achieve highly efficient and environmentally benign removal of Cr(III)-organic complexes from water. The combined process could remove Cr(III)-citrate from 10.4 mg Cr/L to 0.36 mg Cr/L and ∼60% total organic carbon as well. More attractively, negligible Cr(VI) (<0.06 mg/L) was formed during the process. In the viewpoint of mechanism, the added Fe(III) generates ·OH radicals to transform Cr(III) into Cr(VI) and simultaneously released the citrate ligand to form Fe(III)-citrate simultaneously. Then, the photolysis of Fe(III)-citrate under UV irradiation involved the citrate degradation and the production of massive Fe(II) species, which in turn transformed the formed Cr(VI) back to Cr(III). The free metal ions, including Cr(III), Fe(II) and Fe(III) were removed by the subsequent alkaline precipitation. Also, the combined process is applicable to other Cr(III) complexes with EDTA, tartrate, oxalate, acetate. The applicability of the combined process was further demonstrated by treating two real tanning effluents, resulting in the residual Cr(III) below 1.5 mg/L (the discharge standard of China) and negligible formation of Cr(VI) (<0.004 mg/L) as well. In general, the combined process has a great potential for efficient removal of Cr(III) complexes from contaminated waters.
大多数现有工艺由于其高溶解度、极慢的解络合速率以及氧化过程中可能形成更具毒性的 Cr(VI),而无法将 Cr(III)-有机络合物从水中去除。在此,我们提出了一种新的联合工艺,即 UV/Fe(III) 后接碱性沉淀(即 UV/Fe(III)+OH),以实现高效、环境友好地去除水中的 Cr(III)-有机络合物。该联合工艺可将 10.4mg Cr/L 的 Cr(III)-柠檬酸盐去除至 0.36mg Cr/L,同时去除约 60%的总有机碳。更具吸引力的是,该过程中几乎没有形成 Cr(VI)(<0.06mg/L)。从机理角度来看,加入的 Fe(III) 生成·OH 自由基将 Cr(III)转化为 Cr(VI),同时释放出柠檬酸盐配体,同时形成 Fe(III)-柠檬酸盐。然后,在 UV 照射下,Fe(III)-柠檬酸盐的光解涉及到柠檬酸盐的降解和大量 Fe(II)物种的生成,这些物质反过来又将形成的 Cr(VI)还原回 Cr(III)。随后的碱性沉淀去除了游离的金属离子,包括 Cr(III)、Fe(II)和 Fe(III)。该联合工艺还适用于 EDTA、酒石酸、草酸盐、乙酸盐等其他 Cr(III)络合物。该联合工艺通过处理两种实际的制革废水进一步证明了其适用性,处理后残余 Cr(III)低于 1.5mg/L(中国排放标准),几乎没有形成 Cr(VI)(<0.004mg/L)。总的来说,该联合工艺具有从受污染的水中高效去除 Cr(III)络合物的巨大潜力。