School of Metallurgy and Environment, Central South University, Changsha 410083, China.
School of Metallurgy and Environment, Central South University, Changsha 410083, China; Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, Changsha 410083, China; State Key Laboratory of Advanced Metallurgy for Non-ferrous Metals, Changsha 410083, China.
J Environ Sci (China). 2025 Mar;149:394-405. doi: 10.1016/j.jes.2023.12.011. Epub 2023 Dec 17.
Heterogeneous crystallization is a common occurrence during the formation of solid wastes. It leads to the encapsulation of valuable/hazardous metals within the primary phase, presenting significant challenges for waste treatment and metal recovery. Herein, we proposed a novel method involving the in-situ formation of a competitive substrate during the precipitation of jarosite waste, which is an essential process for removing iron in zinc hydrometallurgy. We observed that the in-situ-formed competitive substrate effectively inhibits the heterogeneous crystallization of jarosite on the surface of anglesite, a lead-rich phase present in the jarosite waste. As a result, the iron content on the anglesite surface decreases from 34.8% to 1.65%. The competitive substrate was identified as schwertmannite, characterized by its loose structure and large surface area. Furthermore, we have elucidated a novel mechanism underlying this inhibition of heterogeneous crystallization, which involves the local supersaturation of jarosite caused by the release of ferric and sulfate ions from the competitive substrate. The local supersaturation promotes the preferential heterogeneous crystallization of jarosite on the competitive substrate. Interestingly, during the formation of jarosite, the competitive substrate gradually vanished through a dissolution-recrystallization process following the Ostwald rule, where a metastable phase slowly transitions to a stable phase. This effectively precluded the introduction of impurities and reduced waste volume. The goal of this study is to provide fresh insights into the mechanism of heterogeneous crystallization control, and to offer practical crystallization strategies conducive to metal separation and recovery from solid waste in industries.
非均相结晶是固体废物形成过程中的常见现象。它导致有价/有害金属被包裹在主相中,这对废物处理和金属回收带来了重大挑战。在此,我们提出了一种新方法,即在黄钾铁矾沉淀过程中形成原位竞争基质,这是锌湿法冶金中去除铁的关键步骤。我们观察到,原位形成的竞争基质有效地抑制了黄钾铁矾在硫酸铅矿(黄钾铁矾废物中的富铅相)表面的非均相结晶。结果,硫酸铅矿表面的铁含量从 34.8%降低至 1.65%。竞争基质被鉴定为纤铁矿,其具有疏松的结构和较大的表面积。此外,我们阐明了这种抑制非均相结晶的新机制,该机制涉及竞争基质释放的铁离子和硫酸根离子导致的黄钾铁矾局部过饱和度。局部过饱和度促进了黄钾铁矾在竞争基质上的优先非均相结晶。有趣的是,在黄钾铁矾形成过程中,竞争基质通过奥斯特瓦尔德规则的溶解-再结晶过程逐渐消失,其中亚稳相缓慢转变为稳定相。这有效地防止了杂质的引入和废物体积的增加。本研究的目的是为非均相结晶控制机制提供新的见解,并提供有利于从工业固体废物中分离和回收金属的实用结晶策略。