Marszałek Marta, Piotrowski Marcin, Druzgała Bożena, Wzorek Zbigniew
Cracow University of Technology, Faculty of Chemical Engineering and Technology, Warszawska 24, 31-155 Krakow, Poland.
Materials (Basel). 2025 May 16;18(10):2333. doi: 10.3390/ma18102333.
Copper removal from wastewater is a major challenge in the treatment of both hydrometallurgical copper recycling effluents and mining wastewater. The use of sorbents is considered the most efficient and environmentally friendly method for this purpose. Zirconium aminotris(methylenephosphonates) exhibit excellent sorption properties towards many metal ions. Therefore, the goal of this research was to synthesize amorphous zirconium phosphonate materials with a wide range of P:Zr molar ratios (0.5-100) in the reaction mixture and under mild conditions. The obtained sorbents were characterized using ATR-FTIR, XRD, SEM-EDS, CHN analysis, and pH titration. The sorption properties of the zirconium aminotris(methylenephosphonates) were studied in pure copper solutions and in the complex acidic solutions (pH 1.6-3.2). The results were compared with those for the commercially available resins designed to capture copper containing iminodiacetic acid and bispicolylamine as surface groups. Zirconium aminotris(methylenephosphonate) synthesized at a P:Zr molar ratio of 50:1 shows fast sorption kinetics and the best sorption properties. The maximum sorption capacity in pure copper solutions is 62.3 mg/g, and its affinity for copper ions is comparable to that of reference resins = 2.7-3.9). Moreover, this sorbent can be easily regenerated with 1 M solutions of HCl, HNO, or HSO (Cu recovery up to 95%).
从废水中去除铜是湿法冶金铜回收废水和采矿废水处理中的一项重大挑战。为此，使用吸附剂被认为是最有效且环保的方法。氨基三亚甲基膦酸锆对许多金属离子表现出优异的吸附性能。因此，本研究的目标是在温和条件下，在反应混合物中合成具有广泛P:Zr摩尔比（0.5 - 100）的无定形膦酸锆材料。使用ATR - FTIR、XRD、SEM - EDS、CHN分析和pH滴定对所得吸附剂进行表征。在纯铜溶液和复杂酸性溶液（pH 1.6 - 3.2）中研究了氨基三亚甲基膦酸锆的吸附性能。将结果与用于捕获含亚氨基二乙酸和双吡啶甲胺作为表面基团的铜的市售树脂的结果进行比较。以50:1的P:Zr摩尔比合成的氨基三亚甲基膦酸锆表现出快速的吸附动力学和最佳的吸附性能。在纯铜溶液中的最大吸附容量为62.3 mg/g，其对铜离子的亲和力与参考树脂相当（β = 2.7 - 3.9）。此外，这种吸附剂可以很容易地用1 M的HCl、HNO₃或H₂SO₄溶液再生（铜回收率高达95%）。
