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New Additives Assisted Green Tin Electrorefining in Methanesulfonic Acid System AITranslate

Yuantao Yang1; Junli Wang2; Linjing Yang1; Xuanbing Wang1; Jinlong Wei1; Xiaoning Tong1; Ruidong Xu1;
1.Faculty of Metallurgical and Energy Engineering，Kunming University of Science and Technology，Kunming 650093，China
2.Researcher Center for Analysis and Measurement，Kunming University of Science and Technology，Kunming 650093，China
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Abstract AITranslate

Metallurgical processes of tin are pyrometallurgical refining and electrorefining. Compared with pyrometallurgical refining，although the tin produced by electrorefining accounts for less total tin production，it has the advantages of short process and high product purity. At present，the electrorefining of tin is generally carried out in the fluorosilicic acid system with the assistance of bone glue and β-naphthol. The high saturated vapor pressure and low stability of fluorosilicic acid will cause a certain burden on the environment，which is contrary to the purpose of green and sustainable development of metallurgy. According to research reports，methanesulfonic acid （MSA）is a strong organic acid，which is very stable for chemical oxidation and reduction. In addition，it does not tend to hydrolyze in water and has the advantages of low toxicity，low volatility，high stability and conductivity，and easy treatment of waste liquid. It is an ideal acid in hydrometallurgy. In addition，in terms of additives，bone glue，lignosulfonate，and other ingredients from natural animal bones and plant additives are unstable，resulting in variability of relative molecular mass and structural uncertainty and complexity of actual production. With the technology development trend of green，energy-saving and sustainable metallurgical construction becoming more and more obvious，it is urgent to develop a green method for tin production. Therefore，the chemical synthesis additive assisted MSA electrolyte for tin electrorefining，with high stability and designability，has a greener application prospect. The rectifier was used to provide direct current for the electrolysis system，and the circulation system of the electrolyte with a constant temperature control system and a peristaltic pump was used to carry out the electrorefining test. The energy consumption and morphology were adjusted，and the simulation and verification of electrorefining were carried out. The electrochemical behavior of Lugalvan BNO12 on tin electrodeposition in methanesulfonic acid system was studied by cyclic voltammetry，and the effect of Lugalvan BNO12 on tin deposition was analyzed. The effects of additive content，cathode current density，tin ion concentration，methanesulfonic acid concentration，electrode spacing and electrolyte temperature on power consumption and current efficiency were studied by electrorefining simulation experiments. The energy consumption was calculated by recording the cell voltage data at regular intervals. The cathode sample mass was weighed before and after electrorefining to calculate the cathode current efficiency. The surface morphology of the cathode tin was observed by macroscopic photography，scanning electron microscope （SEM），and optical profilometer. The effect of additives on the surface of the cathode was analyzed by comparing the effects of different additive concentrations on the surface of the cathode. The composition changes of electrolyte before and after electrolysis were analyzed by inductively coupled plasma （ICP）. The changes of peak position and intensity of functional groups before and after electrolyte electrolysis were analyzed by infrared spectroscopy. The crude tin raw materials and final products were tested by ICP and compared with the national standard. The results of electrochemical experiments showed that the addition of Lugalvan BNO12 to MSA electrolyte could enhance the polarization of the cathode process and inhibit the electrodeposition of Sn，which was beneficial to inhibit the dendrite growth of Sn during the deposition process and achieve the densification effect. Through the macroscopic observation and SEM analysis of the cathode plate，the surface additive Lugalvan BNO12 could reduce the dendrites and nodules of the cathode tin，and make the cathode tin smooth and dense. When the concentration of Lugalvan BNO12 was 3 g·L−1，the best dense and smooth cathode tin could be obtained. The optimal process conditions were as follows：Sn2+ concentration was 100 g·L−1，methanesulfonic acid concentration was 100 g·L−1，Lugalvan BNO12 concentration was 3 g·L−1，cathode current density was 100 A·m−2，electrode spacing was 2 cm，and electrolysis temperature was 35 ℃. Under the optimal process conditions，the cathode tin was dense and flat without dendrites. The final product was tested by ICP. The results showed that the purity of the cathode tin could reach 99.98%，which reached the national standard of 99.95 grade and AA grade tin ingot. Infrared spectroscopy analysis showed that the peak position and intensity of the electrolyte did not change，indicating that the MSA system was stable. The methanesulfonic acid system had excellent stability，and the solution after electrorefining could be recycled. However，after multiple electrolytic cycles，it was necessary to remove impurity ions，supplement additives and acid，and Sn2+ in the solution. In future experiments，online detection and adaptive addition of components in the electrolyte should be increased，expanded production experiments should be carried out，and the influence of electrolyte circulation on electrorefining should be explored.

KeyWords AITranslate

tin (Sn) methanesulfonic acid （MSA） additives electrochemical behavior electrorefining

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY24040027

Chinese Library Classification Number:TF81

Citation Information:

Metallurgical processes of tin are pyrometallurgical refining and electrorefining. Compared with pyrometallurgical refining，although the tin produced by electrorefining accounts for less total tin production，it has the advantages of short process and high product purity. At present，the electrorefining of tin is generally carried out in the fluorosilicic acid system with the assistance of bone glue and β-naphthol. The high saturated vapor pressure and low stability of fluorosilicic acid will cause a certain burden on the environment，which is contrary to the purpose of green and sustainable development of metallurgy. According to research reports，methanesulfonic acid （MSA）is a strong organic acid，which is very stable for chemical oxidation and reduction. In addition，it does not tend to hydrolyze in water and has the advantages of low toxicity，low volatility，high stability and conductivity，and easy treatment of waste liquid. It is an ideal acid in hydrometallurgy. In addition，in terms of additives，bone glue，lignosulfonate，and other ingredients from natural animal bones and plant additives are unstable，resulting in variability of relative molecular mass and structural uncertainty and complexity of actual production. With the technology development trend of green，energy-saving and sustainable metallurgical construction becoming more and more obvious，it is urgent to develop a green method for tin production. Therefore，the chemical synthesis additive assisted MSA electrolyte for tin electrorefining，with high stability and designability，has a greener application prospect. The rectifier was used to provide direct current for the electrolysis system，and the circulation system of the electrolyte with a constant temperature control system and a peristaltic pump was used to carry out the electrorefining test. The energy consumption and morphology were adjusted，and the simulation and verification of electrorefining were carried out. The electrochemical behavior of Lugalvan BNO12 on tin electrodeposition in methanesulfonic acid system was studied by cyclic voltammetry，and the effect of Lugalvan BNO12 on tin deposition was analyzed. The effects of additive content，cathode current density，tin ion concentration，methanesulfonic acid concentration，electrode spacing and electrolyte temperature on power consumption and current efficiency were studied by electrorefining simulation experiments. The energy consumption was calculated by recording the cell voltage data at regular intervals. The cathode sample mass was weighed before and after electrorefining to calculate the cathode current efficiency. The surface morphology of the cathode tin was observed by macroscopic photography，scanning electron microscope （SEM），and optical profilometer. The effect of additives on the surface of the cathode was analyzed by comparing the effects of different additive concentrations on the surface of the cathode. The composition changes of electrolyte before and after electrolysis were analyzed by inductively coupled plasma （ICP）. The changes of peak position and intensity of functional groups before and after electrolyte electrolysis were analyzed by infrared spectroscopy. The crude tin raw materials and final products were tested by ICP and compared with the national standard. The results of electrochemical experiments showed that the addition of Lugalvan BNO12 to MSA electrolyte could enhance the polarization of the cathode process and inhibit the electrodeposition of Sn，which was beneficial to inhibit the dendrite growth of Sn during the deposition process and achieve the densification effect. Through the macroscopic observation and SEM analysis of the cathode plate，the surface additive Lugalvan BNO12 could reduce the dendrites and nodules of the cathode tin，and make the cathode tin smooth and dense. When the concentration of Lugalvan BNO12 was 3 g·L−1，the best dense and smooth cathode tin could be obtained. The optimal process conditions were as follows：Sn2+ concentration was 100 g·L−1，methanesulfonic acid concentration was 100 g·L−1，Lugalvan BNO12 concentration was 3 g·L−1，cathode current density was 100 A·m−2，electrode spacing was 2 cm，and electrolysis temperature was 35 ℃. Under the optimal process conditions，the cathode tin was dense and flat without dendrites. The final product was tested by ICP. The results showed that the purity of the cathode tin could reach 99.98%，which reached the national standard of 99.95 grade and AA grade tin ingot. Infrared spectroscopy analysis showed that the peak position and intensity of the electrolyte did not change，indicating that the MSA system was stable. The methanesulfonic acid system had excellent stability，and the solution after electrorefining could be recycled. However，after multiple electrolytic cycles，it was necessary to remove impurity ions，supplement additives and acid，and Sn2+ in the solution. In future experiments，online detection and adaptive addition of components in the electrolyte should be increased，expanded production experiments should be carried out，and the influence of electrolyte circulation on electrorefining should be explored.

quote

GB/T 7714-2015 [1] Yuantao Yang, Junli Wang, Linjing Yang, et al. New Additives Assisted Green Tin Electrorefining in Methanesulfonic Acid System[J]. Chinese Journal of Rare Metals, 2025, 49(5): 748-758. DOI:10.13373/j.cnki.cjrm.XY24040027.
MLA [1] Yuantao Yang, et al., "New Additives Assisted Green Tin Electrorefining in Methanesulfonic Acid System." Chinese Journal of Rare Metals, vol. 49, no. 5, 2025, pp. 748-758, https://doi.org/10.13373/j.cnki.cjrm.XY24040027.
APA [1] Yuantao Yang, Junli Wang, Linjing Yang, Xuanbing Wang, Jinlong Wei, Xiaoning Tong, & Ruidong Xu. (2025). New Additives Assisted Green Tin Electrorefining in Methanesulfonic Acid System. Chinese Journal of Rare Metals, 49(5), 748-758. https://doi.org/10.13373/j.cnki.cjrm.XY24040027
IEEE [1] Yuantao Yang, Junli Wang, Linjing Yang, Xuanbing Wang, Jinlong Wei, Xiaoning Tong, and Ruidong Xu, "New Additives Assisted Green Tin Electrorefining in Methanesulfonic Acid System," Chinese Journal of Rare Metals, vol. 49, no. 5, pp. 748-758, 2025, doi: 10.13373/j.cnki.cjrm.XY24040027. keywords: {tin (Sn);methanesulfonic acid （MSA）;additives;electrochemical behavior;electrorefining}