Tobias Wesselborg , Siiri Asumalahti , Sami Virolainen , Tuomo Sainio
{"title":"设计电池金属回收中的连续离子交换工艺:从单柱实验到模拟移动床配置","authors":"Tobias Wesselborg , Siiri Asumalahti , Sami Virolainen , Tuomo Sainio","doi":"10.1016/j.hydromet.2024.106361","DOIUrl":null,"url":null,"abstract":"<div><p>In hydrometallurgical recovery of LIB metals, ion exchange (IX) has hitherto played only a minor role. Separation experiments were conducted in single laboratory-scale IX columns with the aim of laying the foundation for a continuously operated multicolumn IX process similar to a simulated moving bed (SMB) configuration. In this study, the initial process developed earlier was improved by reducing the number of process steps and external streams. The desorption step with oxalate solution was examined in single-column batch experiments to ensure complete desorption of iron in the proposed continuous multicolumn IX process. Additionally, the volume flowrates were adjusted to achieve acceptable switch times of 25 min in an SMB configuration. It was found that the bead size of the resin is a critical factor in IX recovery of battery metals. The raffinate purity for the case of processing 2.5 BV lithium-ion battery waste leachate (LIBWL) improved from 97.2 % to 99.8 % when the resin bead size was reduced from 0.55 ± 0.05 mm to 0.4 ± 0.04 mm and a narrower bead size distribution. The LIBWL feed concentration was varied to mimic the dilution of fresh feed in an SMB set-up. The percentage recovery of Co and Ni decreased from 93.7 % and 96.6 % to 80.8 % and 89.4 %, respectively, when the LIBWL was diluted. This was a result of the decrease in concentration of impurity metals in the feed. Less impurity metals were sorbed and consequently, more ion exchange sites were available for the sorption of the target metals, which enhanced the retention of Co and Ni. The results were used to develop an IX column operation strategy and to suggest an initial SMB design. 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引用次数: 0
摘要
在惰性金属的湿法冶金回收中,离子交换(IX)迄今为止只发挥了次要作用。在单个实验室规模的 IX 柱中进行了分离实验,目的是为类似于模拟移动床(SMB)配置的连续运行多柱 IX 工艺奠定基础。在这项研究中,通过减少工艺步骤和外部流的数量,对之前开发的初始工艺进行了改进。在单柱间歇实验中对草酸盐溶液的解吸步骤进行了检验,以确保在拟议的连续多柱 IX 工艺中完全解吸铁。此外,还调整了体积流量,以便在 SMB 配置中实现可接受的 25 分钟切换时间。实验发现,树脂珠的大小是 IX 回收电池金属的关键因素。在处理 2.5 BV 锂离子电池废浸出液(LIBWL)时,当树脂珠粒径从 0.55 ± 0.05 mm 减小到 0.4 ± 0.04 mm 且珠粒径分布更窄时,浸出液纯度从 97.2% 提高到 99.8%。改变 LIBWL 进料浓度是为了模拟 SMB 装置中新鲜进料的稀释。稀释 LIBWL 后,钴和镍的回收率分别从 93.7% 和 96.6% 降至 80.8% 和 89.4%。这是进料中杂质金属浓度降低的结果。吸附的杂质金属减少,因此有更多的离子交换位点可用于吸附目标金属,从而提高了钴和镍的保留率。研究结果被用于制定 IX 塔操作策略,并提出了初步的 SMB 设计建议。这项工作中提出的多柱配置为连续生产高纯度含锂、镍和钴的废渣(> 99.5 %)提供了巨大的潜力。
Design of a continuous ion exchange process in battery metals recycling: From single column experiments towards a simulated moving bed configuration
In hydrometallurgical recovery of LIB metals, ion exchange (IX) has hitherto played only a minor role. Separation experiments were conducted in single laboratory-scale IX columns with the aim of laying the foundation for a continuously operated multicolumn IX process similar to a simulated moving bed (SMB) configuration. In this study, the initial process developed earlier was improved by reducing the number of process steps and external streams. The desorption step with oxalate solution was examined in single-column batch experiments to ensure complete desorption of iron in the proposed continuous multicolumn IX process. Additionally, the volume flowrates were adjusted to achieve acceptable switch times of 25 min in an SMB configuration. It was found that the bead size of the resin is a critical factor in IX recovery of battery metals. The raffinate purity for the case of processing 2.5 BV lithium-ion battery waste leachate (LIBWL) improved from 97.2 % to 99.8 % when the resin bead size was reduced from 0.55 ± 0.05 mm to 0.4 ± 0.04 mm and a narrower bead size distribution. The LIBWL feed concentration was varied to mimic the dilution of fresh feed in an SMB set-up. The percentage recovery of Co and Ni decreased from 93.7 % and 96.6 % to 80.8 % and 89.4 %, respectively, when the LIBWL was diluted. This was a result of the decrease in concentration of impurity metals in the feed. Less impurity metals were sorbed and consequently, more ion exchange sites were available for the sorption of the target metals, which enhanced the retention of Co and Ni. The results were used to develop an IX column operation strategy and to suggest an initial SMB design. The multicolumn configuration presented in this work offers great potential for continuous production of high-purity Li, Ni and Co-containing raffinate (> 99.5 %).
期刊介绍:
Hydrometallurgy aims to compile studies on novel processes, process design, chemistry, modelling, control, economics and interfaces between unit operations, and to provide a forum for discussions on case histories and operational difficulties.
Topics covered include: leaching of metal values by chemical reagents or bacterial action at ambient or elevated pressures and temperatures; separation of solids from leach liquors; removal of impurities and recovery of metal values by precipitation, ion exchange, solvent extraction, gaseous reduction, cementation, electro-winning and electro-refining; pre-treatment of ores by roasting or chemical treatments such as halogenation or reduction; recycling of reagents and treatment of effluents.