Oxidative leaching mechanism and kinetics of Se, Te and Cu for selenium distillation slag by H₂SO₄ and H₂O₂

Abstract

Selenium distillation slag (SDS) is a high-value-added secondary resource with a high recovery value. This paper aims to investigate the leaching behavior and kinetics of selenium, tellurium, and copper in the SDS acid oxidation leaching process with H₂SO₄ and H₂O₂. The experimental results showed that under the optimum conditions, the contents of selenium, tellurium, and copper in the SDS were reduced from 22.13 wt%, 3.58 wt%, and 6.42 wt% to 3.06 wt%, 0.27 wt%, and 0.33 wt%, respectively. Correspondingly, the recovery rates are 87.08%, 97.15% and 99.7%. The leaching processes of selenium and tellurium were controlled by diffusion and chemical reactions, and the leaching behavior of copper was controlled by chemical reactions. Below 45 °C, the activation energies for selenium, tellurium, and copper were found to be 26.47, 62.18 and 19.67 kJ/mol, respectively. In addition, the contents of lead, silver and gold in the leaching residue are increased to 46.8 wt%, 8.35 wt% and 0.27 wt%, respectively. These substances can be utilized as raw materials for the recovery of these valuable metals. Importantly, the entire process does not generate toxic or harmful waste, making it a green and environmentally friendly method for resource recovery.

Keywords

selenium / acid leaching / oxidation leaching / leaching kinetics

References

[1] Qiu G, Charnas A, Niu C, et al.. The resurrection of tellurium as an elemental two-dimensional semiconductor [J]. npj ∣ 2D Materials and Applications, 2022, 6: 17

[2] Li J-f, Liu M, Yang K, et al.. Selenium substitution in bithiophene imide polymer semiconductors enables high-performance n-type organic thermoelectric [J]. Advanced Functional Materials, 2023, 33(23): 2213911

[3] Hadar I, Song T B, Ke W-j, et al.. Modern processing and insights on selenium solar cells: The world’s first photovoltaic device [J]. Advanced Energy Materials, 2019, 9(161802766

[4] Mishra P K, Babu P D, Ravikumar G, et al.. Possible room temperature ferromagnetism in silicon doped tellurium semiconductor [J]. Journal of Alloys and Compounds, 2015, 639: 5-8

[5] Zhu M-h, Niu G-d, Tang J. Elemental Se: Fundamentals and its optoelectronic applications [J]. Journal of Materials Chemistry C, 2019, 7(82199-2206

[6] Naumov A V. Selenium and tellurium: State of the markets, the crisis, and its consequences [J]. Metallurgist, 2010, 54(3): 197-200

[7] Vernigora A S. Analysis of the current situation of global production and use of rare-earth metals [J]. Russian Journal of Industrial Economics, 2015, 4: 7

[8] Krivovichev V G, Krivovichev S V, Charykova M V. Tellurium minerals: Structural and chemical diversity and complexity [J]. Minerals, 2020, 10(7): 623

[9] XIAO Peng, WANG Hong-jun, YE Feng-chun, et al. Current status and prospects of selenium and tellurium recycling process for scattered metals [J]. Metal Mine, 2020(4): 52–60. DOI: https://doi.org/10.19614/j.cnki.jsks.202004009.

[10] Elshkaki A, Graedel T E, Ciacci L, et al.. Copper demand, supply, and associated energy use to 2050 [J]. Global Environmental Change, 2016, 39: 305-315

[11] Wang S-x, Cui W, Zhang G-w, et al.. Ultra fast ultrasound-assisted decopperization from copper anode slime [J]. Ultrasonics Sonochemistry, 2017, 36: 20-26

[12] Liu G-q, Wu Y-f, Tang A-j, et al.. Recovery of scattered and precious metals from copper anode slime by hydrometallurgy: A review [J]. Hydrometallurgy, 2020, 197: 105460

[13] Zha G-z, Kong X-f, Jiang W-l, et al.. Sustainable chemical reaction-free vacuum separation process to extract selenium from high-value-added hazardous selenium sludge [J]. Journal of Cleaner Production, 2020, 275: 124083

[14] Li Z-d, Qiu F-x, Tian Q, et al.. Production and recovery of tellurium from metallurgical intermediates and electronic waste—A comprehensive review [J]. Journal of Cleaner Production, 2022, 366: 132796

[15] Zha G-z, Wang Y-k, Cheng M-q, et al.. Purification of crude selenium by vacuum distillation and analysis [J]. Journal of Materials Research and Technology, 2020, 9(32926-2933

[16] Zhen T-t, Luo H, Liu L, et al.. Selective recovery of valuable metals (Se, Te, Cu) from the selenium distillation residue by sulfuric acid oxidative leaching [J]. Journal of Sustainable Metallurgy, 2022, 8(31191-1203

[17] Liu L, He J-l, Shi T-t, et al.. Sustainable and effective extraction of Se and recovery of valuable metals from selenium filter residue by vacuum volatilization [J]. Vacuum, 2024, 230: 113652

[18] Liu L, He J-l, Shi T-t, et al.. An innovative green method for efficient extraction of selenium by melt filtration-vacuum distillation [J]. Separation and Purification Technology, 2025, 357: 129969

[19] Zeng Y-l, Zou J-b, Liao C-f, et al.. Selective separation and recovery of selenium from copper anode slime by compound leaching followed by sulfate roasting [J]. Minerals Engineering, 2022, 186: 107749

[20] Khanlarian M, Rashchi F, Saba M. A modified sulfation-roasting-leaching process for recovering Se, Cu, and Ag from copper anode slimes at a lower temperature [J]. Journal of Environmental Management, 2019, 235: 303-309

[21] Hait J, Jana R K, Sanyal S K. Processing of copper electrorefining anode slime: A review [J]. Mineral Processing and Extractive Metallurgy, 2009, 118(4): 240-252

[22] Lee J C, Kurniawan K, Chung K W, et al.. Metallurgical process for total recovery of all constituent metals from copper anode slimes: A review of established technologies and current progress [J]. Metals and Materials International, 2021, 27(7): 2160-2187

[23] Guo X-y, Xu Z-p, Li D, et al.. Recovery of tellurium from high tellurium-bearing materials by alkaline sulfide leaching followed by sodium sulfite precipitation [J]. Hydrometallurgy, 2017, 171: 355-361

[24] XU Zhi-peng, GUO Xue-yi, LI Dong, et al. Leaching kinetics of tellurium-bearing materials in alkaline sulfide solutions [J]. Mineral Processing and Extractive Metallurgy Review, 2020. DOI: https://doi.org/10.1080/08827508.2018.1506981.

[25] Hait J, Jana R K, Sanyal S K. Mineralogical characteristics of copper electrorefining anode slime and its leached residues [J]. Industrial & Engineering Chemistry Research, 2004, 43(9): 2079-2087

[26] Abdollahi M, Shafaei S. Optimized leaching conditions for selenium from Sar-Cheshmeh copper anode slimes [J]. Iranian Journal of Chemistry and Chemical Engineering, 2004, 23(2): 101-108

[27] Rao S, Wang D-x, Cao H-y, et al.. Hydrothermal oxidative leaching of Cu and Se from copper anode slime in a diluted H₂SO₄ solution [J]. Separation and Purification Technology, 2022, 300: 121696

[28] Fan Y-q, Yang Y-x, Xiao Y-p, et al.. Recovery of tellurium from high tellurium-bearing materials by alkaline pressure leaching process: Thermodynamic evaluation and experimental study [J]. Hydrometallurgy, 2013, 139: 95-99

[29] Rao S, Liu Y, Wang D-x, et al.. Pressure leaching of selenium and tellurium from scrap copper anode slimes in sulfuric acid-oxygen media [J]. Journal of Cleaner Production, 2021, 278: 123989

[30] Zha G-z, Yang B, Luo H, et al.. Innovative green approach for the selective extraction of high-purity selenium from hazardous selenium sludge [J]. Separation and Purification Technology, 2021, 266: 118536

[31] Liu Q-s, Tu T, Guo H, et al.. High-efficiency simultaneous extraction of rare earth elements and iron from NdFeB waste by oxalic acid leaching [J]. Journal of Rare Earths, 2021, 39(3): 323-330

[32] Xin C-f, Xia H-y, Jiang G-y, et al.. Mechanism and kinetics study on ultrasonic combined with oxygen enhanced leaching of zinc and germanium from germanium-containing slag dust [J]. Separation and Purification Technology, 2022, 302: 122167

[33] Hulett J R. Deviations from the Arrhenius equation [J]. Quarterly Reviews, Chemical Society, 1964, 18(3227-242

[34] Youssef A A, Salas A H, Al-Harbi N, et al.. Determination of chemical kinetic parameters in Arrhenius equation of constant heating rate: Theoretical method [J]. Alexandria Engineering Journal, 2023, 67: 461-472

[35] Zheng Y-j, Chen K-K. Leaching kinetics of selenium from selenium–tellurium-rich materials in sodium sulfite solutions [J]. Transactions of Nonferrous Metals Society of China, 2014, 24(2536-543

[36] Xu L, Xiong Y-h, Zhang G-g, et al.. An environmental-friendly process for recovery of tellurium and copper from copper telluride [J]. Journal of Cleaner Production, 2020, 272: 122723

[37] Wang S-jie. Tellurium recovery: Development of a novel hydrometallurgical process [C]. Rare Metal Technology 2022, 2022, Cham, Springer International Publishing225-235

[38] Xu B, Ma Y-p, Gao W, et al.. A review of the comprehensive recovery of valuable elements from copper smelting open-circuit dust and arsenic treatment [J]. JOM, 2020, 72(11): 3860-3875

[39] Davenport W G, King M J, Schlesinger M E, et al.. Extractive metallurgy of copper [M], 2002

RIGHTS & PERMISSIONS

Central South University