Vous êtes sur la page 1sur 8

ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

ELECTROCHEMICAL RECOVERY OF RARE EARTH ELEMENTS FROM


MAGNETSCRAPSATHEORETICALANALYSIS
V.PRAKASH*,Z.H.I.SUN,J.SIETSMA,Y.YANG
Department of Materials Science and Engineering, Delft University of Technology
Mekelweg2,2628CD,Delft,TheNetherlands

*P.Venkatesan@tudelft.nl

Abstract
Recoveryofrareearthelements(REEs)fromsecondaryresourcesisofgreatenvironmental
and economic importance. In the case of magnet scraps, multistep hydrometallurgy and
liquid metal extraction with high energy consumption are usually applied to accomplish
acceptable recovery rate of REEs from the scrap. This paper aims to provide theoretical
framework for using electrochemistry to selectively extract REEs into aqueous solution.
Thermodynamic and electrochemical behaviour of different components in the alloy are
theoretically predicted and correlated with available data from the literature. The role of
microstructure and different elements in dissolution mechanism of the REE magnet is
reviewed. Through understanding various factors involved in dissolution behaviour of the
alloy, an electrochemical process with enhanced selectivity to recover REEs can be
established.

Introduction
Rare earth elements are of great importance in modern industry for producing various
functional materials like permanent magnets, rechargeable batteries, catalysts, lamp
phosphorsbecauseoftheiruniquemagneticandelectronicproperties.Duetotheincreased
demandandsupplyshortage,REEsarelistedascriticalrawmaterialsofstrategicimportance
inmanycountriesintheworld1,2.ThishaspromotedresearchforrecoveringREEsfromend
oflife (EOL) products and the scrap created during production. Neodymium iron boron
magnet(Nd2Fe14B)isoneofthemajorusagesforrareearthelementsandhas62%3ofthe
marketshareofpermanentmagneticmaterial.Apartfromneodymium,REEslikedysprosium
and praseodymium are used in varying amounts (in total 2530%) for obtaining required
magneticproperties4.Cobalt(010%)isoftenaddedtoincreasetheCurietemperatureand
otherelementslikevanadium,oxygenandnitrogencanbeaddedintraceamountstoreduce
corrosion5a,5b.
The complex composition of EOL magnets and magnet scrap makes the recovery of REEs
rather difficult and demands a range of metallurgical and chemical techniques Various
methods have been reported in the past for recovering neodymium and other rare earth
elementsfromthemagnets.Lymanetal.6usedtheleachingmethodandhaveobtainedhigh
recoveryofneodymium(98%)bydissolvingthescrapinsulfuricacidfollowedbyusingalkali
hydroxidestoprecipitatedoublesaltsofneodymiumwhichcanbefurthertreatedtoobtain
neodymiumoxide.Otherresearchgroupshavealsotriedselectiveleaching 7,ultrasound
assistedleaching8andacombinationofpreroastingthescrapalongwithselectiveleaching

PAGE|163
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

andsolventextraction9torecovertheREEsfromthescrap.Althoughtheabovementioned
hydrometallurgical methods have achieved appreciable recovery of REEs, they require
multiple steps to enhance leaching selectivity, expensive pretreatment techniques and
consumptionoflargeamountsofchemicals.Henceforanaqueouschemicalmethodtobe
economicallyviableforrecycling,enhancedselectivityofREEsrecoverycombinedwithlow
consumption of chemicals and reduced number of steps involved is of paramount
importance.
In this paper, the thermodynamics and the corresponding electrochemical behaviour of
variouselementspresentinwastemagnetsarediscussedandcomparedduringdissolution
into an aqueous solution. With improved understanding of these behaviour, a process to
selectivelyextractREEsfromwastemagnetcanbeestablished.

Thermodynamicevaluations
Atypicalcompositionofcommercialmagnetandmagnetscrapsobtainedfromliterature9,10,11
islistedinTable1.

Table1:Typicalcompositionofmagnetscraps
Elements Nd Dy Pr Fe B Co C N Others
Wt% 2325 3.55 0.055 6269 1 010 00.14 00.1 12
*OthersCu,Al,Ga,Si,Gd,Mo.

ThestandardGibbsenergyofformationfordifferentrareearthspeciesarecalculatedfrom
theliterature12,13andtheircorrespondingNernstequationaresummarizedinTable2.Itcan
benoticedthatthestandardelectrodepotentials(ERE3+/RE=2.2to2.4VvsSHE)ofthe
rareearthelementsareverycloseowingtotheirsimilarchemicalnature.

Table2:CalculatedvaluesofG0(kJ/mol)andstandardreductionpotentialat298Kandthe
correspondingNernstequation.Solublespeciesconcentrations(exceptH+)is101.0M
Reaction G0 (KJ/mol) E0 (V) Nernstequation
Nd 3e Nd 671.6 2.32 E=2.32+0.020log[Nd3+]
Nd+3H2 ONd OH 3+3H+ +3e 563.3 1.94 E=1.94 +0.059pH
Nd3+ +3H2 ONd OH 3+3H+ 108.3 3pH=19log[Nd3+]
Dy 3e Dy 664.0 2.29 E=2.29+0.020log[Nd3+]
Dy+3H2 ODy OH 3+3H+ +3e 564.4 1.95 E=1.95+0.059pH
Dy +3H2 ODy OH 3+3H+ 98.6 3pH=17.3log[Dy3+]
Pr 3e Pr 680.3 2.35 E=2.35+0.020log[Pr3+]
Pr+3H2 OPr OH 3+3H+ +3e 568.0 1.96 E=1.96 +0.059pH
Pr +3H2 OPr OH 3+3H+ 111.9 3pH=19.68log[Pr3+]

Theirverynegativepotentialvalueswhichfallbelowthehydrogenevolutionlineindicatea
strongreactivityinaqueoussolutions.Experimentalobservationofcorrosionandpassivity
behaviour of neodymium in different conditions have also confirmed rigorous hydrogen
evolution14.Inparticular,comparisonofthebehaviourofironandREEsinaqueoussolution
atdifferentpHcanbeofimportance.Koyamaetal.15usedaPourbaixdiagram(Fig.1)tosee

PAGE|164
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

stability of different species of neodymium and iron in different pH and they selectively
leachedoutNd3+byleavingoutironasFe2O3inthesolution.
In contrast to selective leaching where pH plays a vital role, using scrap magnets in an
electrochemicalcelloffersanadditionaladvantageofcontrollingparameterslikepotential
and current density to manipulate and selectively dissolve REEs. Fig. 2 shows standard
electrodepotentialsofdifferentcomponentsofscrapmagnetsvsAg/AgClelectrode(0.25V
vs SHE). The other major elements present in the waste magnets in terms of weight
percentageareironandcobalt.Thestandardreductionpotentialsofironandcobaltare0.44
Vand0.28VvsSHErespectively.EOLmagnetsalsocontaincopper,asaminoradditiveorin
thecoatingalongwithnickeltopreventcorrosion.

Fig.1:PourbaixdiagramofFeH2OandNdH2Osystem9

Itcanbenotedthat,whenmagnetsaredeployedasanodesina3electrodeelectrochemical
cell(Ag/AgClreferenceelectrode),selectivedissolutioncanbeacceleratedbycontrollingthe
potentialandmaintainingitintheregionbetweendissolutionofrareearthsandtheregion
inwhichmetalliciron,cobaltandotherelementsarestable.Furtheranodicpolarizationof
thescrapmagnetscanacceleratethedissolutionprocess.

PAGE|165
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014


Fig.2:Standardreductionpotential(VvsAg/AgCl)ofdifferentelementsinscrapmagnet9a

Analyzing elements individually can theoretically form a basis for selective dissolution but
dissolution of individual components from an alloy is governed by their partial
thermodynamicproperties.Partialpotentialofanindividualcomponentinanalloycanbe
writtenas16

ln N (1)

where isthedifferencebetweenequilibriumelectrodepotentialofthecomponentiin
thealloyandthecorrespondingpotentialofthesamecomponentintheindividualphase.R,
T, F ,Zi, Ni are molar gas constant, temperature, Faradays constant, number of electrons
transferredandmolarfractionofthecomponentrespectively.Bydefinitionmolefractionis
lessthanoneandhencethepartialpotentialofacomponentinthealloywillalwaysbemore
positivethantheindividualcomponentpotential.Henceexperimentaldeterminationofthe
extentofpositiveshiftforindividualcomponentsintheNd2Fe14Balloyindifferentelectrolytic
environmentsisvital.
Anelectrolyteenvironmentwhichisnoninhibitingandencouragingfreecorrosionprocessis
essential. Passivity is in principle possible in highly alkaline solutions and Song et al.17
observed that NdFeB magnets form passive hydroxide layers in sodium hydroxide and in
oxalicacid.Jingwuetal.18observedsimilartypeofpassivebehaviourinphosphoricacidwith
lowcorrosioncurrent.Howeverthealloyfreelydissolvesinotheracidssuchassulfuricacid,
nitricacidandhydrochloricacidwithhighcurrentdensityandisalsosusceptibletoattackby
chlorideandotherionseveninthesolutionsinwhichtheyexhibitpassivity.Henceforactive
dissolutionofthemagnetsitispreferredtohaveanacidicconditionswithstrongacidshaving
highcorrosioncurrent.

PAGE|166
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

Microstructureofthemagnetanddissolutionmechanism
Another crucial aspect of selective dissolution is to understand the correlation between
microstructureofthealloyandthecorrespondingdissolutionmechanism.NdFeBmagnets
haveamatrixferromagneticphase()ofNd2Fe14Btetragonalcompoundandissurrounded
byintergranularregionscontaininganeodymiumrichphase(n)andaboronrichphase()19.
Thecomplexityoftheintergranularregioninthemicrostructureoftheneodymiummagnets
depend upon the additional elements such as cobalt, aluminum and gallium . In order to
selectively dissolve rare earths, an understanding of dissolution mechanism in different
environmentsisthusnecessary.Severalauthors19,20,23haveproposedthatneodymiumrich
phases(n)corrodepreferentiallyduetotheformationofagalvaniccoupleowingtonegative
standardpotentialofrareearths.Thisisfollowedbytheboronrichphasedissolutionandthis
rendersthematrixloosefinallycreatingdisruptionofthematrixphase.CorrosioninNdFeB
alloyisanaturalprocessandcanevenresultinthepulverizationofthemagnet.Thescheme
ofstepbystepdissolutionprocesspresentedbySchlutz19etal.isgiveninFig.3.


Fig.3:SchematicillustrationofdissolutionprocessofNdFeBmagnetsbycorrosion19

20
Mao et al. observed the dissolution process of individual phases by synthesizing them
separatelyandsubjectingthemtodifferentcorrosiontests.TheNdrichphasehadthemost
negativeopencircuitpotentialfollowedbymatrixphaseandtheboronrichphase,indicating
that the Nd rich phase has the highest electrochemical reactivity. These results further
strengthentheconclusionthatselectivedissolutionofrareearthsarefeasibleandisinfacta
naturallyoccurringcorrosionprocess.
Thecompositionofdifferentcomponentsinthealloyalsoplayacrucialroleindissolution
process.Corrosionstudiesofmagnetswithhigherweightpercentofironinphthalatebuffer
showed reduced current density, indicating formation of passive layers like iron oxide
preventingcorrosion21.Aluminum,galliumandcopperhavereducedthecorrosionasthey
reduce the strength of galvanic coupling among magnetic phases22 and cobalt has been
observedtoimprovecorrosionresistanceasitpreventsmagneticpulverisation23.Highrateof
dissolutionisobservedinlowcarbonandoxygenalloywhenthenitrogencontentexceeds

PAGE|167
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

0.1wt%.Oxygenimpedescorrosionwhenitisaddedbetween0.61.2wt%andtheoptimum
amount of carbon was found to be 0.1wt% as anything above that facilitates corrosion5a.
Dysprosiumandniobiumhavebeensaidtohaveformedstableintermetallicphaseswhich
retards corrosion24 but also high amount of dysprosium (16 %) has been deemed as
disadvantageous 25. On the whole, it is important to know the nature of the scrap to
acceleratethedissolutionprocessbyvariousmeansandbyalteringtheenvironment.

Electrochemicalcell:cathodeproductsandanodeslime
Table2liststhepossibleanodicreactionsintheelectrochemicalcell.Besidesdissolutionof
rareearthmetals,codissolutionofironandcobaltbychemicalorelectrochemicalmeansis
alsopossiblealthoughnotdesirable.
Rareearths,duetotheirverynegativepotentialliberatehydrogenonthecathodeinaqueous
solutions from an electrochemical process. Due to the same, the rate determining step
becomesmasstransportasthechargetransferisrelativelyfast.Thecathodicreactionsin
suchcaseare

2H 2e H (2)

M ne M(3)

2H 0 2e H 2 OH (4)

Hydrogenevolutionreactionthoughinevitable,canbekineticallysloweddownwithproper
choiceofacathodeasitwillhinderdepositionofnonREEsaswellasmodifythepH.Schlutz
etal.14observedwaterreductiontobetheprominentcathodicreactionforpureneodymium
at lower concentrations (0.01 M) and at higher concentrations they observed hydrogen
evolution.Inadditiontojustactingascounterelectrode,thecathodecanalsobechosenin
suchawaythatitallowsdepositionofcodissolvednonREEs.Inordertohaveacathodeto
allow deposition of nonREEs, it should a) be inexpensive b) have slow kinetics and low
exchangecurrentdensityforhydrogenevolutionreactionc)favorthedepositionofnonREEs
likeiron,nickelorcobalt.Besidesifsuchadepositfromscrapscanalsobeattractiveinterms
ofcommercialapplications(suchasFeNialloys)itcanbeanaddedbenefit.
AsimpleschematicisillustratedinFig.4fortheconceptualframeworkoftheelectrochemical
celldescribedinthepaper.Fig.4a)showsthescrapmagnetsplacedasanodesinasimple2
electrode electrochemical cell. Fig. 4 b) shows an inprogress dissolution. Although it is
preferredtoselectivelydissolveonlyrareearthions,chemicaldissolutionandthecomplex
microstructure of the alloy might also encourage codissolution of nonREEs. These co
dissolvednonREEscanbefurtherdepositedbackonthecathodewhichresultsinapartially
purifiedsolutionenrichedinrareearthswhichissuitableforfurtherelementalrecoveryand
the rest of undissolved elements can be collected as anode slime. The proof of principle
experimentsarecurrentlyinpreparation.

PAGE|168
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

Fig..4SimpleschematicoftheproposedelectrochemicalmethodforREErecovery

Conclusion
This paper establishes the theoretical framework required to perform an electrochemical
recyclingofendoflifescrapNdFeBmagnets.Bydrawingideasfromdifferentfieldssuchas
electrodeposition, selective dissolution, corrosion and also by projecting thermodynamic
predictionsfordifferentrareearthsofourinterest,itcanbeobservedthatnotonlyenhanced
selectiverecoveryofrareearthsispossiblebutalsoitis,toanextent,anaturallyfavored
process.Thenextstepofthisresearchwillbetobuildupa3electrodeelectrochemicalcell
whichcanhelpestablishtheproofofconceptdescribedinthepaper.
Amoredetailedlookintothedissolutionmechanismandkineticsofscrapmagnetsbyusing
complimentarytoolssuchaselectroanalyticaltechniquesandmicroscopywillbeessential.
Oncethedissolutionmechanismisunderstood,influenceofdifferentparameterssuchaspH,
temperature, potential difference and electrolyte composition can be analyzed and
optimized.Thefurthergoalwillbetobuildupalabscalecellwhichcanhandlefewhundreds
ofgramsofscrapinanefficientmanner.

Acknowledgment
TheauthorswishtoacknowledgetheEUFP7MarieCurieprojectEREAN(ProjectID607411)
forfinancialsupport.

PAGE|169
ERES2014:1stEuropeanRareEarthResourcesConference|Milos|0407/09/2014

References
1. CriticalrawmaterialsfortheEU,Reportoftheadhocworkinggroupondefiningcriticalrawmaterials,
(2010).
2. USDepartmentofEnergy,Criticalmaterialsstrategy,(2010).
3. Oliver Gutfleisch , Matthew A. Willard , Ekkes Brck , Christina H. Chen , S. G. Sankar , and J. Ping Liu,
Magnetic Materials and Devices for the 21st Century: Stronger, Lighter, and More Energy Efficient,
Advancedmaterials,23821842(2011).
4. M.Sagawa,S.Fujimura,H.Yamamoto,Y.MatsuuraandK.Hiraga,"PermanentMagnetMaterialsBased
ontheRareEarthIronBoronTetragonalCompound,IEEETrans.Magnetics2015841589(1984).
5. a)A.S.Kim,F.E.CampandE.J.Dulis,Effectofoxygen,carbonandnitrogencontentoncorrosionofNdFe
Bmagnets,IEEETrans.Magnetics,26(5)19361938(1990).
b)M.Sagawa,S.Fujimura,H.Yamamoto,Y.MatsuuraandK.Hiraga,IEEETrans.Magnetics20(5)15841589
(1984)
6. J.WLyman&G.R.Palmer,Reportofinvestigations9481,USbureauofmines,1993.
7. Lee,J.c.,Kim,W.b.,Jeong,J.,Yoon,I.J.,J.KoreanInst.Met.Mater.36,967(1998)
8. Tanaka,Y.,Zhang,Q.W.,Saito,F,Sonochemicalrecoveryofmetalsfromrecordingmedia,J.Chem.Eng.
Jpn.35173177(2002).
9. MikiyaTanaka,TatsuyaOki,KazuyaKoyama,HirokazuNaritaandTetsuoOishi,HandbookonthePhysics
andChemistryofRareEarths,43159255(2013).
9a. StandardPotentialsinAqueousSolution.AllenJ.Bard,RogerParsons,JosephJordan
CRCPress,Aug27,1985(ValuesadjustedtoAg/AgClreferenceelectrodebyresearcher)
10. KojiMiura,MasahiroItoh,KenIchiMachida,ExtractionandrecoverycharacteristicsofFeelementfrom
NdFeB sinteredmagnet powder scrap by carbonylation, JournalofAlloys and Compounds,466 (12)
228232(2008).
11. Amjad Ali, Magnetic properties and corrosion resistance of coated and uncoated rare earth based
permanentmangnets,PhDthesis,UniversityofEngineeringandTechnologyLahore,2011.
12. GeorgeK.Schweitzer,LesterL.Pesterfield,Theaqueouschemistryofelements,Oxforduniversitypress,
2010.
13. AllenJ.Bard,RogerParsons,JosepJordan,Standardpotentialsinaqueoussolution,CRCpress,1985.
14. R. Sueptitz , M. Uhlemann, A. Gebert, L. Schultz, Corrosion, passivation and breakdown of passivity of
neodymium,CorrosionScience52886891(2010)
15. Koyama,K.,Kitajima,A.,Tanaka,M.,RareEarths543637(2009)
16. I.K.Markashov,AnodicDissolutionandSelectiveCorrosionofAlloys,ProtectionofMetalsVol.38(2)139
145(2002)
17. Y.W.Song,H.Zhang,H.X.YangandZ.L.Song,AcomparativestudyonthecorrosionbehaviorofNdFeB
magnetsindifferentelectrolytesolutions,MaterialsandCorrosion200859(10)794801(2008)
18. ZhengJingwu,JiangLiqiang,ChenQiaoling,ElectrochemicalcorrosionbehaviourofNdFeBmagnetin
differentacidsolutions,JournalofRareearths24218222(2006)
19. L.Schultz,A.M.ElAziz,G.Barkleit,K.Mummert,CorrosionbehaviourofNdFeBpermanentmagnetic
alloys,MaterialsScienceandEngineering,A267307(1999)
20. ShoudongMao,HengxiuYang,ZhenlunSong,JinlongLi,HuagenYing,KefeiSun,Corrosionbehaviourof
sinteredNdFeBdepositedwithanaluminiumcoating,CorrosionScience5318871894(2011)
21. M. Rada, J. Lyubina, A. Gebert, O. Gutfleisch, L. Schultz, Corrosion behavior of NdFeB/Fe
nanocompositemagnets,JournalofMagnetismandMagneticMaterials29029112511254(2005)
22. AA.El Moniem, Passivity and its breakdown of sintered NdFeBbased magnets in chloride containing
solution,CorrosionScience4625172532(2004)
23. S.Szymura,H.BalaandG.Pawlowska,Yu.M.Rabinovich,V.V.SergeevandD.V.Pokrovskii,Modification
of the magnetic properties and corrosion resistance of NdFeB permanent magnets with addition of
cobalt,JournaloftheLessCommonMetals,175185198(1991)
24. L.Q.Yu,Y.H.Wen,M.Yan,EffectsofDyandNbonthemagneticpropertiesandcorrosionresistanceof
sinteredNdFeB,JournalofMagnetismandMagneticMaterials283353356(2004)
25. S.Szymura,H.BalaandG.Pawlowska,Yu.M.Rabinovich,Effectofimpuritiesonthecorrosionbehaviour
ofneodymium,JournalofAppliedElectrochemistry,2310171024(1993)

PAGE|170