含AlCa复合除氟剂在含氟硫酸锌溶液中的除氟性能刘争伟

26520165Volume26Number5TheChineseJournalofNonferrousMetalsMay20161004-0609(2016)-05-1151-07AlCa(410083)AlCa100g/LZn2+160g/LH2SO4450mg/LF−pH=3t=90minw=4g/Lθ=25F−20mg/L96%108mg/gCl−800mg/L93%SO42−Zn2+96%5%Langmuir143.3mg/gLangmuirTF813A80%AlAl[1−3]F−[4]50mg/L70%−[5][6][7−8][9][10−11][12][13][14−16][17][18]F−CaF2Ca-FCaF2[12][13]pHZn2+F−ZnF+F−Al-F/[20−21]pH[21]20g/L[6][8][9][10](5120420851374240)[e-mail]:10.19476/j.ysxb.1004.0609.2016.05.025201651152[22][23][18]F−AlCapHtwθSO42−Cl−11.1AlCaCa(NO3)2Al(NO3)3200mLAlCaNaHCO3pH6.51h603001hAlCa1.2100mL(ρ(Zn2+)=100g/Lρ(SO42−)=160g/Lρ(F−)=450mg/L)NaOHH2SO4pHT(PF-1-01)pHTwtηS(mg/g)%1000F0(1)wSF0(2)ρFmg/Lρ0mg/L22.1pH1pH1pH1~3pHpH=396%ρ(F−)450mg/L18mg/L108mg/gpHUpH3pHρ(H+)[14]c(H+)F−H+HF[24]pH3OH−F−pHOH−F−[24]pH31pH(θ=25t=2hw=4g/L)Fig.1EffectofpHondefluoridationefficiencybycompositedefluoridationagent(θ=25,t=2h,w=4g/L)2.22260min265AlCa1153ρ(F−)30mg/L90minρ(F−)(96%)ρ(F−)20mg/L107.5mg/g2ρ(F−)ρ(F−)F−ρ(F−)ρ(F−)90min2t(pH=3w=4g/Lθ=25)Fig.2Effectofreactiontimeondefluoridationefficiencybycompositedefluoridationagent(pH=3,w=4g/L,θ=25)2.3333g/Lρ(F−)30mg/L90%140mg/g(w=3g/L)3g/L3g/L6g/Lρ(F−)30mg/L12mg/L73mg/gρ(F−)3g/L3g/Lρ(F−)[24]ρ(F−)4g/Lρ(F−)450mg/L3~4g/L3(pH=3t=2hθ=25)Fig.3Effectofdoseofadsorbentondefluoridationefficiencybycompositedefluoridationagent(pH=3,t=2h,θ=25)2.4444(pH=3t=2hw=4g/L)Fig.4Effectofreactiontemperatureondefluoridationefficiencybycompositedefluoridationagent(pH=3,t=2h,w=4g/L)2016511542.5ρ(SO42−)ρ(Cl−)5(a)ρ(Cl−)ρ(Cl−)ρ(Cl−)700mg/L95%ρ(F−)18~20mg/L106.8mg/gρ(Cl−)700mg/Lρ(Cl−)800mg/Lρ(F−)25mg/L93%104.6mg/g5(b)ρ(SO42−)ρ(SO42−)160g/L220g/L96%108mg/gρ(SO42−)ρ(Cl−)5Cl−SO42−(pH=3t=2hθ=25w=4g/L)Fig.5Effectofρ(Cl−)(a)andρ(SO42−)(b)ondefluoridationefficiencybycompositedefluoridationagent(pH=3,t=2h,θ=25,w=4g/L)2.6Zn2+1Zn2+1ρ(Zn2+)40~100g/L95%ICP(IRISIntrepidIIXSP)Zn2+11Zn2+(pH=3t=2hθ=25w=4g/L)Table1Efficiencyofdefluoridationatdifferentc(Zn2+)andZnlossratio(pH=3,t=2h,θ=25,w=4g/L)ρ(Zn2+)/(g·L−1)Defluoridationefficiency/%Znlossrate/%4094.92.74595.63.85095.63.65595.63.26095.83.46595.62.87095.43.58095.32.49095.34.010095.34.712.4%~4.7%2.7F-LangmuirFreundlichmaxemaxe1SbSS(3)eFln1lnlncnkS(4)ρemg/LSmg/gSmaxmg/gbkFn(1)ρ(F−)400mg/L500mg/L600mg/L700mg/L800mg/L900mg/L100mL4g/Lt=2h265AlCa1155θ=25pH=3ρ(F−)(2)ρ(F−)SF−ρe66Fig.6Compositedefluoridationagentdefluoridationisotherm7LangmuirFreundlichFig.7Langmuirisothermfittingplot(a)andFreundlichisothermfittingplot(b)ofcompositedefluoridationagentdefluoridationOrigin7(a)(b)22LangmuirR2=0.99804Langmuirb=0.03352LangmuirFreundlichTable2LangmuirandFreundlichisothermparametersofcompositedefluoridationagentIsothermmodelParametersCalculatevalueLangmuirR20.99804Smax/(mg·g−1)143.3b/(L·mg−1)0.0335FreundlichR20.88132kF/(mg·g−1)(L/mg)1/n51.04n631)AlCapH=3t=90minw=4g/Lθ=25ρ(F−)450mg/L20mg/L96%108mg/g2)AlCaSO42−Zn2+Cl−Cl−(800mg/L)Cl−F−3)AlCaLangmuir143.3mg/g4)AlCaREFERENCES[1]XUET,COOPERWC,PASCUALR,SAMOTOS.Effectoffluorideionsonthecorrosionofaluminiuminsulphuricacidandzincelectrolyte[J].JournalofAppliedElectrochemistry,1991,20165115621(3):238−246.[2]MACKINNONDJ,BRANNENJM.Aluminiumcathodeeffectsinzincelectrowinningfromindustrialacidsulphateelectrolyte[J].JournalofAppliedElectrochemistry,1986,16(1):127−133.[3]HANJS,O’KEEFETJ.Thedegradationofaluminiumcathodesbyfluorideionduringzincelectrowinning[J].JournalofAppliedElectrochemistry,1992,22(7):606−612.[4]ZHONGXiao-cong,YUXiao-ying,JIANGLang-xing,LÜXiao-jun,LIUFang-yang,LAIYan-qing,LIJie.InfluenceoffluorideionontheperformanceofPb-Aganodeduringlong-termgalvanostaticelectrolysis[J].JOM,2015,9(67):2022−2027.[5],.[J].,2013,29(1):40−43.SUSha,CHENHai-qing.Researchonremovaloffluorideandchlorideinzinchydrometallurgy[J].HunanNonferrousMetals,2013,29(1):40−43.[6],.[J].,1999,18(2):36−40.ZHANGYuan-Fu,HUANGGuang-yu.InvestigationonFluorideremovalfromzincoxidedustleachingsolutionbyGoethiteMethod.HydrometallurgyofChina,1999,18(2):36−40.[7],,,.:,201010584552.3[P].2011−04−20.WEIXu,LICun-xiong,DENGZhi-gan,LIXing-bin.MethodtoSeparatezincwithF,Clfromzincsulfatesolution:China,201010584552.3[P].2011−04−20.[8],,,,.:,201210159097.1[P].2012−05−21.WANGZhi-bin,WEIGuo-long,YUTan,LIShi-pin,NIChang-kai.AmethodofzinchydrometallurgytoremovalFluoride,chloridebyextraction:China,201210159097.1[P].2012−05−21.[9].:,200910042770.1[P].2009−07−29.SONGZhi-hong.ZinchydrometallurgyindustrializeionsexchangemethodtoremovalF,Cl:China,200910042770.1[P].2009−07−29.[10],.,[J].,1986,4:8.WANGHeng-quan,SHIAn-quan.RemovalF,CltechnologyrevolutionexperimentinZincproduction[J].YunNanMetallurgy,1986,4:8.[11].:,201210009592.4[P].2012−06−27.LIJian-sheng.AmethodandequipmettoremovalF,Clfromzincelectrolyte:China,201210009592.4[P].2012−06−27.[12].:,201110182683.3[P].2011−01−02.ZENGYong.AmethodtouseactivatedAl2O3toremovalFfromzincsulfate:China,201110182683.3[P].2011−01−02.[13].[J].(),1996,2:26−30.XIEWei-xin.StudyontheremovalofF−fromelectrolyticZincsolutionusedforzinc-makinginwetmethod[J].JournalofGuangXiUniversityf