Complete recovery of valuable metals from chlorinated titanium-white waste acids: Focus on solvent extraction for recovery and preparation of battery-grade manganese sulfate (MnSO4·H2O) from lab to pilot scale

• Published in: Chemical engineering journal (Lausanne, Switzerland : 1996) Switzerland : 1996), 2024-07, Vol.491, p.151766, Article 151766
• Main Authors: Han, Zhejie, Li, Jia, Guan, Wenjuan, Cao, Zuoying, Li, Qinggang, Wang, Mingyu, Wu, Shengxi, Zhang, Guiqing
• Format: Article
• Language: English
• Subjects: Battery materials; Battery-grade MnSO4·H2O; Chlorination titanium-white waste acid; Pollution reduction; Resource recovery; Solvent extraction
• ISSN: 1385-8947; 1873-3212
• DOI: 10.1016/j.cej.2024.151766

[Display omitted] •Green, comprehensive and novel process for metals recovery form chlorination titanium-white waste acid.•Deep separation of Mn from Ca, Mg in a chlorination system by D2EHPA/4PC synergistic solvent extraction system and extraction mechanism.•Preparation of battery-grade MnSO4·H2O from complex waste acid and stepwise metals recovery.•Pilot test of extraction was conducted to detect the purity of the product and the stability of the organic phase cycle. Chlorination titanium-white waste acid (CTWA) is known to contain a substantial number of valuable metals, including Mn, which can be utilized in the manufacturing of high-value battery cathode materials. Based on the concept of complete resource recovery and zero pollution, a novel process for metal recovery from CTWA has been developed. D2EHPA was used to extract Sc, V from CTWA. Al was completely removed by slowly adding 1.5 mol/L NaOH until the solution pH reached 4.20 and stabilized for 0.5 h. This process resulted in a limited loss of 11 % for Fe and 5 % for Mn. An oxidative precipitation method was proposed to process the Al-free solution to preparate a pure and easily filterable FePO4 product, which can be used in the production of battery materials. Additionally, the loss of Mn in this process was less than 0.5 %. After removing Fe and Al, the pre-extraction feed has an O/A ratio of 2.5:1, a temperature of 40 °C, and an equilibrium pH of 4.5 ∼ 5.0, it is possible to extract Mn at over 99.50 % using a 5-stage extraction. The loaded phase is scrubbed with 5 g/L H2SO4, O/A = 5:1. It is then cyclically stripped with 75 g/L H2SO4, O/A = 8:1, to obtain a battery-grade MnSO4 solution. The stripped solution can be 100 % crystallized to obtain battery-grade MnSO4·H2O products after removing heavy metals using BaS and removing oil with activated carbon. The recovery of Mn in the extraction process was 97.59 %. The pilot test was conducted to demonstrate that the extraction process can be efficiently and continuously produced. The process achieved the recovery of valuable metals from CTWA and the preparation of corresponding products. This process is comprehensive and environmentally friendly, which has an industrial foundation.