An energy saving and fluorine-free electrorefining process for ultrahigh purity lead refining
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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(HClO_4-Pb(ClO_4)_2) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO_4 is very stable, and there is no any reduction reaction of HClO_4 during the electrolytic process. The redox reactions of lead ions in HClO_4 solution are very reversible with an ultrahigh capacity efficiency, so the HClO_4 acts as a stable support electrolyte with higher ionic conductivity than the traditional H_2SiF_6 electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L~(-1) HClO_4, 0.4 mol·L~(-1) Pb(ClO_4)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).
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(HClO_4-Pb(ClO_4)_2) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO_4 is very stable, and there is no any reduction reaction of HClO_4 during the electrolytic process. The redox reactions of lead ions in HClO_4 solution are very reversible with an ultrahigh capacity efficiency, so the HClO_4 acts as a stable support electrolyte with higher ionic conductivity than the traditional H_2SiF_6 electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L~(-1) HClO_4, 0.4 mol·L~(-1) Pb(ClO_4)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).
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(HClO_4-Pb(ClO_4)_2) with the additives of gelatin and sodium lignin sulfonate is employed as the new electrolyte. The cathodic polarization curves show that HClO_4 is very stable, and there is no any reduction reaction of HClO_4 during the electrolytic process. The redox reactions of lead ions in HClO_4 solution are very reversible with an ultrahigh capacity efficiency, so the HClO_4 acts as a stable support electrolyte with higher ionic conductivity than the traditional H_2SiF_6 electrolyte. The results of the scale-up experiments show that under the optimal conditions of 2.8 mol·L~(-1) HClO_4, 0.4 mol·L~(-1) Pb(ClO_4)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).
引文
[1]M.W.Stevensona,C.S.Lakshmia,J.E.Manders,L.T.Lamb,VRLA refined?lead-Amust for VRLA batteries specification and performance,J.Power Sources 95(2001)264-270.
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[4]S.Matteson,E.Williams,Residual learning rates in lead-ACID batteries:Effects on emerging technologies,Energy Policy 85(2015)71-79.
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[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.
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[10]F.Ojebuoboh,S.Wang,M.Maccagni,Refining primary lead by granulationleaching-electrowinning,J.Miner.Met.Mater.Soc.55(2003)19-23.
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[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 H2Si F6,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 Chemistry70th 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.
[2]H.Y.Chen,A.J.Li,D.E.Finlow,The lead and lead-acid battery industries during 2002and 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 granulationleaching-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 H2Si F6,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 Chemistry70th 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.