Novel recovery of a low-concentration gold thiosulfate complex through electroreduction via a walnut shell charcoal electrode

Abstract

Low-concentration Au(S₂O₃)₂³⁻ recovery is an urgent issue to facilitate the application of thiosulfate leaching instead of cyanide leaching in factories. Herein, this work presents a novel recovery of low-concentration Au(S₂O₃)₂³⁻ combining adsorption and electrodeposition (electroreduction) to realize high Au(S₂O₃)₂³⁻ recovery in the form of gold particles (Au⁰). Walnut shells were used as the raw material for the successful preparation of charcoal with porous structure and rich oxygen-containing functional groups. Walnut shell charcoal (WSC) as the electrode achieved efficient recovery of low-concentration Au(S₂O₃)₂³⁻. The recovery under low-concentration conditions was higher than 90%, with the highest reduction of 46.97 mg·g⁻¹. Applying a suitable low voltage (0.8 V) facilitated low-concentration Au(S₂O₃)₂³⁻ recovery, which was immensely improved than that without voltage. Au(S₂O₃)₂³⁻ recovery performances under applied voltage via the WSC electrode were related to electrochemical abilities, including reaction intensity and charge transfer. More reactive sites containing suitable pores and oxygen functional groups were beneficial for the reduction reaction. This work offers a new way to recover low-concentration Au(S₂O₃)₂³⁻ via cheap charcoal electrodes from solutions for application in the cyanide-free leaching method in industry.

Keywords

Electroreduction / Low concentration / Au(S2O3)2 3− / Au0 / Walnut shell charcoal electrode

References

[1] C. Wang, G. Lin, J.L. Zhao, S.X. Wang, L.B. Zhang, Y.H. Xi, X.T. Li, Y. Ying, Highly selective recovery of Au(III) from wastewater by thioctic acid modified Zr-MOF: experiment and DFT calculation, Chem. Eng. J. 380 (2020) 122511.

[2] Z. Lu, T. Li, S.R. Mudshinge, B. Xu, G.B. Hammond, Optimization of catalysts and conditions in gold(I) catalysis-counterion and additive effects, Chem. Rev. 121 (14) (2021) 8452-8477.

[3] S. Choi, S.I. Han, D. Jung, H.J. Hwang, C. Lim, S. Bae, O.K. Park, C.M. Tschabrunn, M. Lee, S.Y. Bae, J.W. Yu, J.H. Ryu, S.W. Lee, K. Park, P.M. Kang, W.B. Lee, R. Nezafat, T. Hyeon, D.H. Kim, Highly conductive, stretchable and biocompatible Ag-Au core-sheath nanowire composite for wearable and implantable bioelectronics, Nat. Nanotechnol. 13 (2018) 1048-1056.

[4] H.L. Qian, F.L. Meng, C.X. Yang, X.P. Yan, Irreversible amide-linked covalent organic framework for selective and ultrafast gold recovery, Angew. Chem. Int. Ed Engl. 59 (40) (2020) 17607-17613.

[5] X.E. Dang, W.S. Ke, C. Tang, J. Lv, X. Zhou, C.P. Liu, Increasing leaching rate of gold cyanide of two-stage calcination generated from refractory ore containing arsenopyrite and pyrrhotite, Rare Met 35 (10) (2016) 804-810.

[6] J.S. Xia, R. Marthi, J. Twinney, A. Ghahreman, A review on adsorption mechanism of gold cyanide complex onto activation carbon, J. Ind. Eng. Chem 111 (2022) 35-42.

[7] H.Q. Niu, H.Y. Yang, L.L. Tong, Research on gold leaching of carbonaceous pressure-oxidized gold ore via a highly effective, green and low toxic agent trichloroisocyanuric acid, J. Clean. Prod 419 (2023) 138062.

[8] S.S. Konyratbekova, A. Baikonurova, A. Akcil, Non-cyanide leaching processes in gold hydrometallurgy and iodine-iodide applications: a review, Miner. Process. Extr. Metall. Rev. 36 (3) (2015) 198-212.

[9] C.B. Sun, X.L. Zhang, J. Kou, Y. Xing, A review of gold extraction using noncyanide lixiviants: Fundamentals, advancements, and challenges toward alkaline sulfur-containing leaching agents, Int. J. Miner. Metall. Mater. 27 (4) (2020) 417-431.

[10] L. Liao, Y.H. Song, P.P. Zhang, Y.F. Li, J. Bao, J.M. Zhou, Treatment of actual cyanide gold extraction wastewater by persulfate oxidation and its reaction mechanism, Res. Chem. Intermed. 49 (8) (2023) 3705-3721.

[11] S.J. Zhou, W.C. Li, W.G. Liu, J.B. Zhai, Removal of metal ions from cyanide gold extraction wastewater by alkaline ion-exchange fibers, Hydrometallurgy 215 (2023) 105992.

[12] I. Birloaga, I. De Michelis, F. Ferella, M. Buzatu, F. Vegliò, Study on the influence of various factors in the hydrometallurgical processing of waste printed circuit boards for copper and gold recovery, Waste Manag 33 (4) (2013) 935-941.

[13] Y.B. Yang, Z.H. Xie, B. Xu, Q. Li, T. Jiang, Gold extraction from a high carbon low-grade refractory gold ore by flotation-roasting-leaching process, in: N.R. Neelameggham, S. Alam, H. Oosterhof, A. Jha, D. Dreisinger, S. Wang (Eds.), Rare Metal Technology, 2015 Springer, Cham, 2015, pp. 63-70.

[14] L. Zhang, T. Jiang, X.Y. Guo, Q.H. Tian, S.P. Zhong, L. Dong, H. Qin, Z.W. Liu, B. Makuza, Sustainable processing of gold cyanide tailings: reduction roasting, mechanical activation, non-cyanide leaching, and magnetic separation, Hydrometallurgy 217 (2023) 106028.

[15] L. Jones, R.P. Hackl, Sources of high cyanide consumption for a biooxidized refractory gold concentrate, Process. Metall. 9 (C) (1999) 337-346.

[16] W.Q. Zhan, Y. Yuan, X. Yao, B.Q. Yang, F.F. Jia, C.S. Lin, J.L. Arauz-Lara, S.X. Song, Efficient recovery of gold(I) from thiosulfate solutions through photocatalytic reduction with Mn(II)-doped MoS₂ , ACS Sustain. Chem. Eng 9 (35) (2021) 11681-11690.

[17] A. Filcenco Olteanu, T. Dobre, E. Panturu, A.D. Radu, A. Akcil, Experimental process analysis and mathematical modeling for selective gold leaching from slag through wet chlorination, Hydrometallurgy 144-145 (2014) 170-185.

[18] K. Li, Q. Li, Y. Zhang, X.L. Liu, Y.B. Yang, T. Jiang, Improved thiourea leaching of gold from a gold ore using additives, Hydrometallurgy 222 (2023) 106204.

[19] M.R. Ahmed, H.S. Mohammed, M.G. El-Feky, Y.K. Abdel-Monem, Gold leaching using thiourea from uranium tailing material, Gabal El-Missikat, Central Eastern Desert, Egypt, J. Sustain. Metall 6 (4) (2020) 599-611.

[20] G. Le, W.J. Li, K. Song, Y.S. Song, Y. Chen, A.P. Bai, Y. Cheng, Electrochemical dissolution behavior of gold and its main coexistent sulfide minerals in acid thiocyanate solutions, Rare Met 41 (1) (2022) 254-261.

[21] H. Wu, Y.L. Feng, W.F. Huang, H.R. Li, S.D. Liao, The role of glycine in the ammonium thiocyanate leaching of gold, Hydrometallurgy 185 (2019) 111-116.

[22] B. Xu, W.H. Kong, Q. Li, Y.B. Yang, T. Jiang, X.L. Liu, A review of thiosulfate leaching of gold: Focus on thiosulfate consumption and gold recovery from pregnant solution, Metals 7 (6) (2017) 222.

[23] P.Z. Xiang, Y.M. Zhang, Q. Liu, Gold leaching from printed circuit board scrap with thiosulfate, IOP Conf. Ser.: Mater. Sci. Eng 394 (2018) 022001.

[24] S. Ubaldini, D. Guglietta, F. Vegliò, V. Giuliano, Valorization of mining waste by application of innovative thiosulphate leaching for gold recovery, Metals 9 (3) (2019) 274.

[25] Y. Lin, X.Z. Hu, F.T. Zi, Y.L. Chen, S.L. Chen, X.R. Li, L. Zhao, Y.F. Li, Synergistical thiourea and thiosulfate leaching gold from a gold concentrate calcine with copper-ammonia catalysis, Sep. Purif. Technol. 327 (2023) 124928.

[26] Y. Zhang, Q. Li, X.L. Liu, T. Jiang, A thermodynamic analysis on thiosulfate leaching of gold under the catalysis of Fe³⁺/Fe²⁺ complexes , Miner. Eng. 180 (2022) 107511.

[27] Y. Ou, Y.B. Yang, K. Li, W. Gao, L. Wang, Q. Li, T. Jiang, Eco-friendly and low-energy innovative scheme of self-generated thiosulfate by atmospheric oxidation for green gold extraction, J. Clean. Prod 387 (2023) 135818.

[28] Q. Wang, X.Z. Hu, F.T. Zi, P. Yang, Y.L. Chen, S.L. Chen, Environmentally friendly extraction of gold from refractory concentrate using a copper-ethylenediamine-thiosulfate solution, J. Clean. Prod 214 (2019) 860-872.

[29] A. Behnamfard, M.M. Salarirad, F. Veglio, Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation, Waste Manag 33 (11) (2013) 2354-2363.

[30] X.R. Li, L. Zhao, S.L. Chen, Y. Lin, X.Z. Hu, F.T. Zi, Highly efficient and selective extraction of Au(I) from thiosulfate gold-leaching solution using diphenylphosphine, J. Environ. Chem. Eng 12 (1) (2024) 111750.

[31] F. Xie, J.N. Chen, X.Z. Zhang, B. Xu, W. Wang, Adsorption mechanism of copper and gold thiosulfates onto activated carbon, Trans. Nonferrous Met. Soc. China 33 (10) (2023) 3210-3221.

[32] Z.L. Dong, T. Jiang, B. Xu, J.T. Wu, Q. Li, Y.B. Yang, A comparative study of electrodeposition and sodium dithionite reduction for recovering gold in gold-rich solution from the adsorption of thiosulfate solution by ion exchange resin, Sep. Purif. Technol. 328 (2024) 125053.

[33] S. Raiguel, L. Gijsemans, A. Van den Bossche, B. Onghena, K. Binnemans, Solvent extraction of gold(III) with diethyl carbonate, ACS Sustainable Chem. Eng 8 (36) (2020) 13713-13723.

[34] L.L. Zhao, Q.S. Zhou, Y. Yang, Y. Zhang, Y.W. Qiu, Y.J. Chen, X. Jin, X.J. Yang, S.X. Wang, Ultra-high adsorption capacity and selectivity of photo-enhanced sulfur-rich M₂S₃ (M = Bi and Sb) for gold recovery from electronic wastewater , J. Water Process. Eng 57 (2024) 104572.

[35] Y. Xiang, C.Y. Cheng, M.H. Liu, W.C. Bai, Z.X. Zang, L. Xu, Y. Yu, G.J. Liu, Efficient recovery of gold using Macroporous Metal-Organic framework prepared by the ‘MOF in MOF’ method, Sep. Purif. Technol. 335 (2024) 126131.

[36] Z.L. Dong, T. Jiang, B. Xu, Y.B. Yang, Q. Li, An eco-friendly and efficient process of low potential thiosulfate leaching-resin adsorption recovery for extracting gold from a roasted gold concentrate, J. Clean. Prod 229 (2019) 387-398.

[37] T. Ouchi, S. Wu, T.H. Okabe, Recycling of gold using anodic electrochemical deposition from molten salt electrolyte, J. Electrochem. Soc 167 (12) (2020) 123501.

[38] M. Matsumiya, R. Kinoshita, Y. Sasaki, Recovery of gold by solvent extraction and direct electrodeposition using phosphonium-based ionic liquids, J. Electrochem. Soc 169 (8) (2022) 082513.

[39] D.Y. Hou, F.N. Bai, P. Dong, J. Chen, Y.T. Zhang, F.M. Meng, Z.H. Zhang, C.X. Zhang, Y.J. Zhang, J. Hu, Recent development of low temperature plasma technology for lithium-ion battery materials, J. Power Sources 584 (2023) 233599.

[40] K.G. Sun, M. Tebyetekerwa, C. Wang, X.F. Wang, X.W. Zhang, X.S. Zhao, Electro capacitive deionization: Mechanisms, electrodes, and cell designs, Adv. Funct. Mater. 33 (18) (2023) 2213578.

[41] M.L. Sall, A.K.D. Diaw, D. Gningue-Sall, A. Chevillot-Biraud, N. Oturan, M. Ali Oturan, J.J. Aaron, Removal of Cr(VI) from aqueous solution using electrosynthesized 4-amino-3-hydroxynaphthalene-1-sulfonic acid doped polypyrrole as adsorbent, Environ. Sci. Pollut. Res. 24 (26) (2017) 21111-21127.

[42] A. Nosal-Wiercińska, M. Martyna, M. Wiśniewska, Influence of mixed 2-thiocytosine-ionic surfactants adsorption layers on kinetics and mechanism of Bi(III) ions electro reduction: use of the nanostructured R-AgLAFE, Appl. Nanosci. 13 (7) (2023) 4737-4745.

[43] Y. Yin, Y. Peng, M. Zhou, P. Zhang, Y. Cheng, P. Chen, X. Xing, X. Ma, Q. Zhu, X. Sun, Q. Qian, X. Kang, B. Han, Highly efficient zinc electrode prepared by electrodeposition in a salt-induced pre-phase separation region solution, Sci. Bull. 68 (20) (2023) 2362-2369.

[44] Z.W. Hu, R.T. Wu, X.M. Pang, C.H. Yu, X.M. Jian, Adsorption of phosphorus in water by metal-modified large-size biochar: Realizing the recovery and recycling of phosphorus, Sustain. Chem. Pharm. 36 (2023) 101279.

[45] Z. Alimohamadi, H. Younesi, N. Bahramifar, Desorption of Reactive Red 198 from activated carbon prepared from walnut shells: effects of temperature, sodium carbonate concentration and organic solvent dose, Adv. Environ. Technol. 2 (3) (2017) 137-141.

[46] A. Mansoor, S. Anjum, Z. Mustafa, R. Khurram, M. Sattar, T. Ilayas, Erbium substituted baddeleyites (Er_xZr(1−x)O₂): Structural, ferroelectric, magnetic and electrochemical analysis for supercapacitors electrodes using walnut shells charcoal , Ceram. Int. 49 (24) (2023) 39825-39842.

[47] K.Y. Zhu, J. Ma, J.Z. Cong, T. Zhang, H.J. Lei, H.D. Xu, Z.S. Luo, M. Li, The road to reuse of walnut by-products: a comprehensive review of bioactive compounds, extraction and identification methods, biomedical and industrial applications, Trends Food Sci. Technol 143 (2024) 104264.

[48] L. Lu, R. Shan, Y. Shi, S. Wang, H. Yuan, A novel TiO₂/biochar composite catalysts for photocatalytic degradation of methyl orange , Chemosphere 222 (2019) 391-398.

[49] F. Terzi, N. Dossi, Ti as an electrode material. How to make the future better than the present, Anal. Bioanal. Chem 407 (24) (2015) 7257-7261.

[50] W.Q. Zhan, X. Zhang, Y. Yuan, Q.Z. Weng, S.X. Song, M. de Jesús Martínez-López, J.L. Arauz-Lara, F.F. Jia, Regulating chemisorption and electrosorption activity for efficient uptake of rare earth elements in low concentration on oxygen-doped molybdenum disulfide, ACS Nano 18 (9) (2024) 7298-7310.

[51] A. Zeriouh, L. Belkbir, Thermal decomposition of a Moroccan wood under a nitrogen atmosphere, Thermochim. Acta 258 (1995) 243-248.

[52] R.K. Sharma, J.B. Wooten, V.L. Baliga, X.H. Lin, W.G. Chan, M.R. Hajaligol, Characterization of chars from pyrolysis of lignin, Fuel 83 (11-12) (2004) 1469-1482.

[53] D.Y. Chen, K.H. Cen, X.Z. Zhuang, Z.Y. Gan, J.B. Zhou, Y.M. Zhang, H. Zhang, Insight into biomass pyrolysis mechanism based on cellulose, hemicellulose, and lignin: evolution of volatiles and kinetics, elucidation of reaction pathways, and characterization of gas, biochar and bio-oil, Combust. Flame 242 (2022) 112142.

[54] A.A. Tenimu, Thermogravimetric and dfferential thermal investigation of rice husk cellulose, Bayero J. Pure App. Sci. 12 (1) (2020) 6-11.

[55] Y.B. Tao, S.J. Li, P. Li, Q.L. Wu, Thermogravimetric analyses (TGA) of lignins isolated from the residue of corn stover bioethanol (CSB) production, Holzforschung 70 (12) (2016) 1175-1182.

[56] Y.H. Dou, Q.S. Bai, W.M. Guo, H.F. Wang, S.D. Chen, T.T. Wang, Study on the adsorption characteristics of organic contaminants on alumina surface coated with clean graphene and the influence of amorphous carbon on wetting behavior, Appl. Surf. Sci. 643 (2024) 158658.

[57] K.M. Popov, V.E. Arkhipov, A.G. Kurenya, E.O. Fedorovskaya, K.A. Kovalenko, A.V. Okotrub, L.G. Bulusheva, Supercapacitor performance of binder-free buckypapers from multiwall carbon nanotubes synthesized at different temperatures, Phys. Status Solidi B 253 (12) (2016) 2406-2412.

[58] T. Kesavan, M. Sasidharan, Palm spathe derived N-doped carbon nanosheets as a high performance electrode for Li-ion batteries and supercapacitors, ACS Sustainable Chem. Eng 7 (14) (2019) 12160-12169.

[59] B. Tang, L.P. Zheng, X.C. Dai, H.J. Chen, Nitrogen/oxygen co-doped porous carbons derived from a facilely-synthesized Schiff-base polymer for high-performance supercapacitor, J. Energy Storage 26 (2019) 100961.

[60] Y. Itoh, M.J. Bröcker, S. Sekine, D. Söll, S. Yokoyama, Dimer-dimer interaction of the bacterial selenocysteine synthase SelA promotes functional active-site formation and catalytic specificity, J. Mol. Biol 426 (8) (2014) 1723-1735.

[61] W.Q. Zhan, Y. Yuan, B.Q. Yang, F.F. Jia, S.X. Song, Construction of MoS₂ nano-heterojunction via ZnS doping for enhancing in situ photocatalytic reduction of gold thiosulfate complex , Chem. Eng. J. 394 (2020) 124866.

[62] K. Kiyohara, T. Sugino, K. Asaka, Phase transition in porous electrodes, J. Chem. Phys. 134 (15) (2011) 154710.

[63] D.A. Bograchev, A.D. Davydov, Non-steady-state natural convection in a model electrochemical system with vertical and horizontal plane electrodes, Russ. J. Electrochem 39 (9) (2003) 967-972.

[64] H. Yu, F.T. Zi, X.Z. Hu, Y.H. Nie, P.Z. Xiang, J. Xu, H. Chi, Adsorption of the gold-thiosulfate complex ion onto cupric ferrocyanide (CuFC)-impregnated activated carbon in aqueous solutions, Hydrometallurgy 154 (2015) 111-117.

[65] H. Yu, F.T. Zi, X.Z. Hu, Y.H. Nie, Y.L. Chen, H.L. Cheng, Adsorption of gold from thiosulfate solutions with chemically modified activated carbon, Adsorpt. Sci. Technol. 36 (1-2) (2018) 408-428.

[66] Y.L. Chen, F.T. Zi, X.Z. Hu, Y. Lin, H.H. Du, J. Hu, P. Yang, Y. Zhang, B.M. Yang, The first effective utilization of activated carbon in gold thiosulfate system: A more eco-friendly, easier method for gold recovery and material regeneration, Miner. Eng. 155 (2020) 106441.

[67] C.W. Wang, S.L. Chen, Y.L. Chen, F.T. Zi, X.Z. Hu, X.C. Qin, Y. Zhang, P. Yang, Y. He, P.Q. He, Y. Lin, G.F. Zhang, Modification of activated carbon by chemical vapour deposition through thermal decomposition of thiourea for enhanced adsorption of gold thiosulfate complex, Sep. Purif. Technol. 241 (2020) 116632.