Electrorefining

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Electrorefiningisanageoldprocess.ItwasfirstdemonstratedexperimentallybyvonLeuchtenbergin1847.Elkington,however,patented
theprocessin1865anddevelopedthefirstsuccessfulplantinPembrey,Walesin1869.Thefirstcommercialelectrorefiningplantinthe
UnitedStateswasconstructedbyBalbachSmelting&RefiningCo.in1883.TheNewark,NewJerseyplantproduced23tonsofelectrolytic
copperperdayduringthefirstyear.

Electrorefiningutilizestheelectrochemicaldissolutionofanimpurecopperanodeinanelectrolyticcellcontainingacoppersulfatesulfuric
acidsolution.Copperionsaretransportedtothecathodewheretheyaredepositedwithsuitablepurity.Thebasicelectrochemicalreactions
involvedare:
AnodicReaction:Cu(impure)Cu2+ +2e(Eq.1)
CathodicReaction:Cu2+ +2eCu(pure)(Eq.2)
NetReaction:Cu(impure)Cu(pure)(Eq.3)
Asdissolutionoccurs,impuritiesarereleasedeitherassolidphasesorasaqueousspecies.Purificationresultsfromdifferencesinthe
oxidation/reductionpotentialsoftheindividualions.First,moreelectrochemicallynobleimpurities,suchasgoldandsilver,willremainator
neartheanode.Theelementsthatarelessnoblethancopperwilldissolvealongwithcopperintothebulkelectrolyte.Atthecathode,copper
beingthemostnobleelementinsolutionwilldepositpreferentially.Carefulcontrolofthesystem'svoltage,currentdensity,temperature,
electrolytecontamination,anddepositmorphologyensuresanextremelypurecopperdeposit.
Inanindustrialtankhouse,aconstantcurrentisutilizedtocontroltheproductionrate.Typicalcathodiccurrentdensitiesincommercial
electrorefiningarebetween200300Am2.Highercurrentdensitiescancauseproblemssuchasanodepassivationand/orcathode
contamination.Theoretically,thenetreaction(Eq.3)forcopperelectrorefiningis0.0V.Inpractice,overvoltagesattheanodeandcathode
andtheresistanceintheelectrolyteandelectricalsystemresultintheneedforanappliedvoltageofapproximately0.3V.Tseidlerhas
indicatedthat7080%ofthevoltageisconsumedbyelectrolyteresistance,approximately5%bypolarization,andtheremainderinthe
resistanceoftheelectricalsystemincludingtheelectrodesandelectricalcontacts.Ifthevoltagebecomestoohigh,contaminationcanoccur
bythedepositionofimpuritiessuchastheGroupVBelementsonthecathode.Contaminationcanalsooccurbecauseofdendriticgrowth
whichtrapsimpurityladenelectrolytewithinthedeposit.
Electrolytetemperatureisanotherimportantsystemparameter.Increasedtemperaturereducestheresistanceoftheelectrolyte,whichlowers
thecostofproduction.Thetemperaturealsocontrolsthesolubilityofimpuritiesinthesolution.Adecreaseintemperaturecancause
precipitationofimpurityphases.However,heatingtheelectrolyteaddscosttotheoperation.Thus,mostrefineriescompromiseandhave
electrolytetemperaturesbetween60and65oC.
Electrolyteimpurityconcentrationscanleadtocathodecontamination.Elementsthattypicallyaccumulateintheelectrolytearenickel,
arsenic,antimony,bismuth,andiron.TheGroupVBelementscanbeparticularlyproblematicbecausetheirstandardreductionpotentialsare
veryclosetothatofcopper.Anotherconcernthatmayarisefromtheseelementsistheformationoffloatingslimes.Floatingslimesare
composedofantimonyarsenate,SbAsO4,andbismutharsenate,BiAsO4.Thesephasesformbyprecipitationawayfromtheanodeandcan
floattothecathodecausingcontamination.Impuritiesaretypicallymaintainedatacceptablelevelsintheelectrolytebyremovalinableed
streambyelectrolysisandcrystallization.Recently,ionexchangeandsolventexchangehavebeenimplementedintheremovalofimpurities,
particularlytheGroupVBelements(As,Sb,andBi).
Morphologyisalsoextremelyimportantinmaintainingcathodepurity.Nodulesanddendritesarethemostcommonsurfacedefectsthatlead
toimpuritiesinthecathode.Anoduleformswhenaconductiveparticleremainsonthecathodesurface.Thedepositwillthengrowaround
theparticleencasingit.Thisresultsinabumponthesurface.Thebumpwillthenactasaledgewhichotherparticlescancometoreston.
Thusthenodulebecomeslargerwiththegrowthofthecoppercaseandmorecontaminatedwithslimeparticles.
Uninhibitedgrowthofthecopperelectrodepositwilltypicallyleadtotheformationofdendrites.Thesesurfaceirregularitiescanleadto
entrapmentofelectrolyteorcolloidalparticlesintothedeposit.Additives,suchas,thiourea,glue,andchloride,areaddedtotheelectrolyteto
inhibittheformationofdendrites.Whilethecompletemechanisminwhichtheseadditivesinteractwiththecathodicsurfaceisnotfully
understood,theresultsarereproducible.Thioureaandglue,whichareusuallyaddedtomaintainconcentrationof13mgl1(ppm),actas
levelingagents.Itisbelievedthattheseorganicmoleculesadsorbontohighspotsonthedeposit.Thisblocksthesesites,causingdeposition
tooccuratthelowareas,whichresultinasmoothdeposit.ChlorideiscontainedinthemakeupwateroraddedasNaClwithtypical

concentrationsbeing4060mgl1(ppm).Clactsasagrainrefinerforthedeposit.Properconcentrationsoftheseadditivesresultinasmooth
anddensecathodewithsuitablepurity.
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Recentadvancesandtrendsincopperelectrorefining
Anodepassivationcanbeasignificantprobleminthecommercialelectrorefiningprocess.
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