Sun Jing-Mei, Shang Chii, Huang Ju-Chang
Department of Civil Engineering, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong.
Environ Sci Technol. 2003 Sep 15;37(18):4281-7. doi: 10.1021/es030316h.
The mechanisms of hexavalent chromium [Cr(VI)] co-removal with copper [Cu(II)] during homogeneous precipitation were studied with batch tests using a synthetic solution containing Cr(VI) and Cu(II). Metal precipitation was induced by adding Na2CO3 stepwise to different pH, and the respective removals of Cu(II) and Cr(VI) were measured. At the same time, the relative quantities of Cu(II) and Cr(VI) in the precipitates were also analyzed to establish their stoichiometric relationship. The results indicated that, in a solution containing 150 mg/L Cu(II) and 60 mg/L Cr(VI), the initial co-removal of Cr(VII with Cu(II) began at pH 5.0 and completed at pH 6.2. At pH 5.0-5.2, coprecipitation took place through the formation of copper-chromium-bearing solids [such as CuCrO4 and/or CuCrO4 x 2Cu(OH)2]. Thereafter, the remaining soluble copper started to react with carbonate in a heterogeneous environment to form the negatively charged basic copper carbonate precipitates [CuCO3 x Cu(OH)2], which subsequently adsorbed additional Cr(VI) (or HCrO4-) at pH 5.2-6.2. The maximum Cr(VI) co-removal took place at pH 6.2. Between the two mechanisms, co-precipitation accounted for about 29% of the total chromium's co-removal while the remaining 71% was attributed to surface adsorption, mainly through electrostatic attraction and ligand exchange. When the solution pH was increased to beyond 7.5, a surface charge reversal took place on the basic copper carbonate solids, and this led to some Cr(VI) desorption. Thus, the extent of Cr(VI) adsorption is highly pH dependent.
采用含有六价铬(Cr(VI))和铜(Cu(II))的合成溶液进行批次试验,研究了均相沉淀过程中六价铬与铜(Cu(II))共去除的机制。通过逐步向不同pH值的溶液中添加碳酸钠来诱导金属沉淀,并测定Cu(II)和Cr(VI)各自的去除率。同时,还分析了沉淀物中Cu(II)和Cr(VI)的相对含量,以确定它们的化学计量关系。结果表明,在含有150 mg/L Cu(II)和60 mg/L Cr(VI)的溶液中,Cr(VI)与Cu(II)的初始共去除在pH 5.0时开始,在pH 6.2时完成。在pH 5.0 - 5.2时,通过形成含铜铬的固体(如CuCrO4和/或CuCrO4·2Cu(OH)2)发生共沉淀。此后,剩余的可溶性铜开始在非均相环境中与碳酸盐反应,形成带负电荷的碱式碳酸铜沉淀(CuCO3·Cu(OH)2),随后在pH 5.2 - 6.2时吸附额外的Cr(VI)(或HCrO4-)。Cr(VI)的最大共去除发生在pH 6.2时。在这两种机制中,共沉淀约占总铬共去除量的29%,其余71%归因于表面吸附,主要通过静电吸引和配体交换。当溶液pH值增加到7.5以上时,碱式碳酸铜固体发生表面电荷反转,这导致一些Cr(VI)解吸。因此,Cr(VI)的吸附程度高度依赖于pH值。