An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining

doi:10.1016/j.cjche.2018.09.005

中国化学工程学报 ›› 2019, Vol. 27 ›› Issue (5): 1191-1199.DOI: 10.1016/j.cjche.2018.09.005

• Energy, Resources and Environmental Technology • 上一篇下一篇

An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining

Xuan Zhang, Junqing Pan, Yanzhi Sun, Yongjun Feng, Huixia Niu

State Key Laboratory of Chemical Resource Engineering, Beijing Engineering Center for Hierarchical Catalysts, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

收稿日期:2018-06-27 修回日期:2018-08-28 出版日期:2019-05-28 发布日期:2019-06-27
通讯作者: Junqing Pan
基金资助:
Supported by the National Natural Science Foundation of China (21676022) and the Fundamental Research Funds for the Central Universities (BHYC170A & JD701).

An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining

Xuan Zhang, Junqing Pan, Yanzhi Sun, Yongjun Feng, Huixia Niu

State Key Laboratory of Chemical Resource Engineering, Beijing Engineering Center for Hierarchical Catalysts, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Received:2018-06-27 Revised:2018-08-28 Online:2019-05-28 Published:2019-06-27
Contact: Junqing Pan
Supported by:
Supported by the National Natural Science Foundation of China (21676022) and the Fundamental Research Funds for the Central Universities (BHYC170A & JD701).

摘要/Abstract

摘要： The present paper reports a new fluoride-free and energy-saving lead electrolytic refining process in order to solve the serious problems of the existing Betts lead electrorefining process, such as low production efficiency, high energy consumption and fluorine pollution. In the process, a mixed solution of perchloric acid and lead perchlorate (HClO₄-Pb(ClO₄)₂) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO₄ is very stable, and there is no any reduction reaction of HClO₄ during the electrolytic process. The redox reactions of lead ions in HClO₄ solution are very reversible with an ultrahigh capacity efficiency, so the HClO₄ acts as a stable support electrolyte with higher ionic conductivity than the traditional H₂SiF₆ electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L^-1 HClO₄, 0.4 mol·L^-1 Pb(ClO₄)₂ and electrolysis temperature of 45℃, the energy consumption is as low as 24.5 kW·h·(t Pb)^-1, only about 20% of that by Betts method at the same current density of 20 mA·cm^-2, and the purity of the refined lead is up to 99.9992%, much higher than that specified by Chinese national standard (99.994%, GB/T 469-2013) and European standard (99.99%, EN 12659-1999).

关键词: Lead refining, Perchloric acid, Fluoride-free, Electrorefining process

Abstract: The present paper reports a new fluoride-free and energy-saving lead electrolytic refining process in order to solve the serious problems of the existing Betts lead electrorefining process, such as low production efficiency, high energy consumption and fluorine pollution. In the process, a mixed solution of perchloric acid and lead perchlorate (HClO₄-Pb(ClO₄)₂) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO₄ is very stable, and there is no any reduction reaction of HClO₄ during the electrolytic process. The redox reactions of lead ions in HClO₄ solution are very reversible with an ultrahigh capacity efficiency, so the HClO₄ acts as a stable support electrolyte with higher ionic conductivity than the traditional H₂SiF₆ electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L^-1 HClO₄, 0.4 mol·L^-1 Pb(ClO₄)₂ and electrolysis temperature of 45℃, the energy consumption is as low as 24.5 kW·h·(t Pb)^-1, only about 20% of that by Betts method at the same current density of 20 mA·cm^-2, and the purity of the refined lead is up to 99.9992%, much higher than that specified by Chinese national standard (99.994%, GB/T 469-2013) and European standard (99.99%, EN 12659-1999).

Key words: Lead refining, Perchloric acid, Fluoride-free, Electrorefining process

Xuan Zhang, Junqing Pan, Yanzhi Sun, Yongjun Feng, Huixia Niu. An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining[J]. 中国化学工程学报, 2019, 27(5): 1191-1199.

Xuan Zhang, Junqing Pan, Yanzhi Sun, Yongjun Feng, Huixia Niu. An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining[J]. Chinese Journal of Chemical Engineering, 2019, 27(5): 1191-1199.

参考文献

[1] M.W. Stevensona, C.S. Lakshmia, J.E. Manders, L.T. Lamb, VRLA refined^TM lead-A must for VRLA batteries specification and performance, J. Power Sources 95(2001) 264-270.
[2] H.Y. Chen, A.J. Li, D.E. Finlow, The lead and lead-acid battery industries during 2002 and 2007 in China, J. Power Sources 19(2009) 22-27.
[3] N.L.N. Brenda, J.H. Li, B. Wilson, A study of the geographical shifts in global lead production-A possible corresponding shift in potential threats to the environment, J. Clean. Prod. 107(2015) 237-251.
[4] S. Matteson, E. Williams, Residual learning rates in lead-ACID batteries:Effects on emerging technologies, Energy Policy 85(2015) 71-79.
[5] X. Tian, Y.F. Wu, Y. Gong, T.Y. Zuo, The lead-acid battery industry in China:Outlook for production and recycling, Waste Manag. Res. 33(2015) 986-994.
[6] G.B. Lantz, F.C. Mathers, Electrolytic refining of lead, USA Pat., 2664393(1951).
[7] W. Hunter, Electrolytic refining, USA Pat., 3975244(1976).
[8] A. Zabaniotou, E. Kouskoumvekaki, D. Sanopoulos, Recycling of spent lead/acid batteries:The case of Greece, Resour. Conserv. Recycl. 25(1999) 301-317.
[9] M. Volpe, D. Oliveri, G. Ferrara, M. Salvaggio, S. Piazza, S. Italiano, C. Sunseri, Metallic lead recovery from lead-acid battery paste by urea acetate dissolution and cementation on iron, Hydrometallurgy 96(2009) 123-131.
[10] F. Ojebuoboh, S. Wang, M. Maccagni, Refining primary lead by granulation-leaching-electrowinning, J. Miner. Met. Mater. Soc. 55(2003) 19-23.
[11] J.J. Fingland, The Betts electrolytic lead refining in practice, J. Electrochem. Soc. 57(1930) 177-204.
[12] E. Nomura, M. Aramaki, Y. Nishimura, Method for producing electrolylic high purity lead using large-sized electrodes, USA Pat. 3960681(1976).
[13] J.A. González-Domínguez, E. Peters, D.B. Dreisinger, The refining of lead by the Betts process, J. Appl. Electrochem. 21(1991) 189-202.
[14] E. Colton, Fluosilicic acid, J. Chem. Educ. 35(1958) 562-563.
[15] D. Thomas, R. Olivier, C. Roderick, Production of HF from H₂SiF₆, Procedia Eng. 138(2016) 231-239.
[16] H. Kametani, A. Aoki, Method for electrolytic winning of lead, USA Pat., 4115222(1978).
[17] M.M. Wong, F.P. Haver, Method of recovering lead through the direct reduction of leadchloride by aqueous electrolysis, USA Pat., 4181588(1980).
[18] G.U. Ying-Ying, Q.H. Zhou, T.Z. Yang, W. Liu, D.C. Zhang, Lead electrodeposition from alkaline solutions containing xylitol, Trans. Nonferrous Met. Soc. 21(2011) 1407-1413.
[19] J.Q. Pan, C. Zhang, Y.Z. Sun, Z.H. Wang, Y.S. Yang, A new process of lead recovery from waste lead-acid batteries by electrolysis of alkaline lead oxide, Electrochem. Commun. 19(2012) 70-72.
[20] J.Q. Pan, Y.Z. Sun, X.B. Yi, Method of lead recovery by combined electrolysis, CN Pat., 102367578A(2012).
[21] J.Q. Pan, Y.Z. Sun, W. Li, J. Knight, A. Manthiram, A green lead hydrometallurgical process based on a hydrogen-lead oxide fuel cell, Nat. Commun. 4(2013) 2178-2183.
[22] J.Q. Pan, X. Zhang, Y.Z. Sun, S. Song, W. Li, P.Y. Wan, Preparation of high purity lead oxide from spent lead acid batteries via desulfurization and recrystallization in sodium hydroxide, Ind. Eng. Chem. Res. 55(2016) 2059-2068.
[23] W. Liu, T.Z. Yang, Q.H. Zhou, D.C. Zhang, W.F. Liu, A method of crude of electrolytic refining, CN Pat., 102534660A(2012).
[24] L. Li, Y.C. Hu, X.F. Zhu, D.N. Yang, Q. Wang, J.W. Liu, R.V. Kumar, J.K. Yang, Lead citrate precursor route to synthesize nanostructural lead oxide from spent lead acid battery paste, Mater. Res. Bull. 48(2013) 1700-1708.
[25] J.Q. Pan, Y.Z. Sun, X.B. Yi, A Method of preparation of Na₂[Pb(OH)₄] solution and recovery of lead from spent lead paste, CN Pat., 102367577A(2012).
[26] J.Speight, Lange's Handbook of Chemistry 70th Anniversary Edition The Mcgraw-Hill Companies, Chicago, 2005.
[27] Y.Z. Sun, S.C. Guo, Y. Wang, J.Q. Pan, P.Y. Wan, A new lead single flow battery in a composite perchloric acid system with high specific surface capacity for largescale energy storage, J. Solid State Electrochem. 21(12) (2017) 1-11.
[28] Y.Z. Sun, S.C. Guo, Y. Wang, J.Q. Pan, P.Y. Wan, A new lead single flow battery in a composite perchloric acid system with high specific surface capacity for largescale energy storage, J. Solid State Electrochem. 22(12) (2017) 3533-3543.
[29] L.T. Lam, N.P. Haigh, D.A.J. Rand, J.E. Manders, Further demonstration of improved performance from lead-acid batteries manufactured with bismuth-bearing highpurity lead, J. Power Sources 88(2000) 2-10.
[30] L.T. Lam, N.P. Haigh, D.A.J. Rand, Understanding the mechanism by which bismuth improves lead-acid battery capacity, J. Power Sources 88(2000) 11-17.

An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining

An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining

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