SEPARATION AND PURIFICATION TECHNOLOGY
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2025
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IF 9
Yaoyu Yan,Shuchen Sun,A. Shubo,Jing Wei,Faxin Xiao,Ganfeng Tu
Electrolytic manganese residue (EMR), a highly acidic solid waste generated during electrolytic manganese metal (EMM) production, is produced in massive quantities and contains recoverable manganese. However, due to its encapsulation within a dense silicate–gypsum framework, conventional leaching methods often suffer from low efficiency. Long-term stockpiling also poses serious environmental risks such as toxic metal leaching. To address these challenges, an integrated process chain combining wet high-intensity magnetic separation and H₂SO₄/H₂O₂ synergistic leaching was developed. Under optimized grinding conditions (5 min, −74 μm accounting for 84.68 %) and a magnetic field strength of 1.6 T, the manganese grade increased from 5.86 wt% to 18.24 wt%, with a recovery rate of 83.3 % and tailings Mn content reduced to 0.98 wt%. Subsequently, leaching under 2.5 mol L −1 H₂SO₄, twice the stoichiometric amount of H₂O₂, at 60 °C for 2 h yielded a Mn leaching efficiency of 92.87 %. Kinetic analysis indicated that leaching was jointly controlled by interfacial reaction and product layer diffusion during the first 100 min, then shifted to diffusion-dominated behavior between 100 and 180 min. XRD, FTIR, and SEM–EDS characterization revealed that H₂O₂ not only reduces MnO₂ to soluble Mn 2+ , but also induces the formation of rod-like CaSO₄·0.5H₂O and colloidal SiO₂ via exothermic reactions and bubble agitation, resulting in a loose filter cake structure and improved filtration performance. After stepwise impurity removal via neutralization and MnF₂ precipitation, the final MnSO₄·H₂O crystals meet Grade I metallic-impurity limits of HG/T 4823–2023. This study presents a technically feasible and environmentally friendly approach for the efficient recovery of manganese from EMR, offering valuable insights into the integrated resource utilization of metallurgical solid waste and the production of battery-grade manganese sulfate. This process offers a scalable and cost-effective route for the green recovery of Mn and aligns with circular economy goals.
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高影响因子
Separations
·
2026
·Vol. 13
·期 9
·239
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IF 3.5
Zhengwu Peng,Ruili Zheng,Xiangyu Wang,Zhen Wan,Xiaolin Pan,Zhi Wang,Zongliang Zhang,Dong Wang,Guoyu Qian
The increasing generation of spent Ni-rich layered cathodes creates an urgent demand for efficient lithium recovery and value-added reutilisation of transition-metal components. An MnSO4·H2O-assisted rapid thermal reconstruction route coupled with water leaching was developed for selective lithium recovery from spent NCM811 cathodes. At an MnSO4·H2O-to-NCM811 mass ratio of 0.9:1, an applied current of 30 A, and a treatment duration of 20 s, the layered structure was converted into water-soluble lithium sulfates and transition-metal-rich oxides. Water leaching at 20 °C for 20 min achieved a stage lithium-leaching recovery of 99.12%, with limited dissolution of Ni, Co, and Mn. The combined aqueous stream contained 0.42 g L−1Li. After concentration and CO2carbonation, Li2CO3was obtained with a precipitation efficiency of 90.6% and a purity of 99.52 wt.%, corresponding to an overall lithium recovery of 88.7%. Elemental-balance closures were 98.6–99.6% for Li, Ni, Co, Mn, and S. The regenerated cathode LiNi0.54Co0.07Mn0.39O2delivered 95.2 mAh g−1after 150 cycles at 0.2 C. These results demonstrate integrated lithium recovery and transition-metal reutilisation from spent Ni-rich cathodes.
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高影响因子
JOURNAL OF CHEMICAL AND ENGINEERING DATA
·
2023
·
IF 2.6
Qiongqiong Luo,Shaoheng Wang,Dehua Cai,Ning Zhang,Dewen Zeng
A ZnSO4 electrolyte solution with impurity salts such as MnSO4 and MgSO4 is often used in zinc hydrometallurgical processes over a wide temperature range. CaSO4·2H2O(s) scaling and fluorine corrosion are two encountered problems in the process. Understanding the CaF2(s) solubility behavior in MSO4 (M = Zn, Mn, Mg) aqueous solutions at various temperatures helps remove Ca2+ and F– ions from the solution. However, CaF2(s) solubility data, especially at temperatures >298 K, have not been published yet. In this work, CaF2(s) solubilities in the CaF2–CaSO4–MSO4–H2O (M = Zn, Mn, Mg) quaternary systems and its subsystems of the CaF2–MSO4–H2O (M = Zn, Mn, Mg) at 348.15 K and the CaF2–CaSO4–MSO4–H2O (M = Zn, Mg) quaternary systems and the CaF2–MgSO4–H2O ternary system at 298.15 K are systematically measured. The results show that the CaF2(s) solubility in the MSO4 (M = Zn, Mn, Mg) aqueous solution of a certain concentration at 348.15 K is considerably higher than that at 298.15 K. At 298.15 and 348.15 K, the salting-in effect of MSO4 (M = Zn, Mn, Mg) on CaF2(s) solubility is enhanced with the order ZnSO4 < MnSO4 < MgSO4. At both temperatures, CaF2(s) solubilities in CaSO4·2H2O(s)- or CaSO4(s)-saturated MSO4 (M = Zn, Mn, Mg) aqueous solutions are generally lower than those in pure MSO4 (M = Zn, Mn, Mg) aqueous solutions. Particularly, the salting-in effect of MgSO4 on CaF2 is so strong that CaF2(s) dissolves completely and is converted to CaSO4·2H2O(s) and MgF2(s) in a concentrated MgSO4 aqueous solution. Hence, this study indicates that high temperatures and high salt concentrations increase the CaF2(s) solubility, making the removal of Ca2+ and F– ions from the system challenging. Further, the existence of impurity salts MnSO4 and MgSO4 makes it more difficult.
研究领域:
化学
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材料科学
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冶金学
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高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Qiongqiong Luo,Jinshun Lei,Ziyu Zhuang,Dewen Zeng
The solubility data of the MgF2–MnF2–MnSO4–H2O quaternary system and its subsystems are crucial for the removal of magnesium ions from a MnSO4 aqueous solution as the MgF2 precipitate. However, these data recorded at 298.15 K have not been reported, except for the MnF2–MnSO4–H2O system. In this study, the solubility isotherms of the MgF2–MnF2–H2O, MgF2–MnSO4–H2O, and MgF2–MnF2–MnSO4–H2O systems at 298.15 K and MnF2 solubility in pure water at various temperatures were systematically measured. The results show that MgF2 solubility initially decreases sharply followed by a gradual decrease as the MnF2 concentration increases. MgF2 solubility rises with increasing MnSO4 concentration in pure MnSO4 and the MnF2-saturated MnSO4 aqueous solution. MgF2 solubility in the MnF2-saturated MnSO4 aqueous solution decreases to 2.3–6.5% of its value in the pure MnSO4 aqueous solution at a certain MnSO4 concentration. MnF2 solubility increases with increasing temperatures in the MnF2–H2O system. A Pitzer–Simonson–Clegg model incorporated in the ISLEC software was used to simulate and predict the solubility curves of the MgF2–MnF2–MnSO4–H2O quaternary system and its subsystems. The model satisfactorily represented the solubility data of the subbinary and subternary systems of the MgF2–MnF2–MnSO4–H2O quaternary system within the analysis error, except for the solubility isotherms of the Mg(Mn)SO4·7H2O, Mg(Mn)SO4·4H2O, and Mg(Mn)SO4·H2O solid solutions. The predicted solubility data of the MgF2–MnSO4–H2O system at 298.15 K agree well with the experimental data with a slight deviation of the MgF2–MnF2–MnSO4–H2O system. Based on the established model, the variation of MgF2 solubility curves with the addition of anhydrous MnF2 in MnSO4 aqueous solutions at different concentrations was predicted. The study provides theoretical guidance for removing magnesium ions from a MnSO4 aqueous solution via MgF2 precipitation.
研究领域:
化学工程
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物理化学
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高影响因子
RSC Advances
·
2021
·Vol. 11
·期 40
·24862-24871
·
IF 3.361
Binbin Liu,Yuan Huang,Jiawei Wang,Zixuan Li,Guoshen Yang,Shunyu Jin,Emad Iranmanesh,Pritesh Hiralal,Hang Zhou
Rechargeable aqueous zinc-ion batteries (ZIBs) are promising wearable electronic power sources. However, solid-state electrolytes with high ionic conductivities and long-term stabilities are still challenging to fabricate for high-performance ZIBs. Herein, locust bean gum (LBG) was used as a natural bio-polymer to prepare a free-standing quasi-solid-state ZnSO4/MnSO4 electrolyte. The as-obtained LBG electrolyte showed high ionic conductivity reaching 33.57 mS cm−1 at room temperature. This value is so far the highest among the reported quasi-solid-state electrolytes. Besides, the as-obtained LBG electrolyte displayed excellent long-term stability toward a Zn anode. The application of the optimized LBG electrolyte in Zn–MnO2 batteries achieved a high specific capacity reaching up to 339.4 mA h g−1 at 0.15 A g−1, a superior rate performance of 143.3 mA h g−1 at 6 A g−1, an excellent capacity retention of 100% over 3300 cycles and 93% over 4000 cycles combined with a wide working temperature range (0–40 °C) and good mechanical flexibility (capacity retention of 80.74% after 1000 bending cycles at a bending angle of 90°). In sum, the proposed ZIBs-based LBG electrolyte with high electrochemical performance looks promising for the future development of bio-compatible and environmentally friendly solid-state energy storage devices.
研究领域:
材料科学
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电化学
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储能技术
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电池技术
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可穿戴技术
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高影响因子
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