2013/3/17

No.2

Importanceofraremetalsandnew developmentandadvancesin development and advances in purificationand recyclingtechnologies forraremetals

March,2013 Toyohisa Fujita, EnergyandEnvironmentalcourse, GraduateschoolofEngineering,RACE TheUniversityofTokyo,Japan tfujita@sys.t.utokyo.ac.jp

USA: 1954Raremetalshandbook(C.A.Hampel) 1. Smallamountinthecrust 2. Difficultyofextractioneveniflargeamountinthecrust 2 Diffi l f i if l i h 3. Minorutilizationafterextraction NowUSAutilizethewordofCriticalmetal http://www.investmentu.com/2011/September/cobalt criticalmetalcleanenergy.html or Critical/raremetal http://www.criticalmetals.com/ Japan:1984METI,Japanmadeadefinitionofraremetal. Europe: utilizethewordofMinor metal(Germany) http://www.mmta.co.uk/home/ China:Journal Raremetal,fromSpringer http://www.springerlink.com/content/10010521

.Introduction Raremetaldefinition

Raremetal

MineralResourcesandmaterials
Basemetals forinfrastructure

isstudiedinour laboratory.

Raremetals

Metalproductionquantity

Metalprice

Manyraremetalsproducewithbase metals.Basemetalproductionalso reduces.

Priceincreasesas thedecreaseof production amount. ByT.Nishiyama:Raremetal resource 2009

La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu
Rareearth

TotalraremetalnumberinJapanis31asrareearthgroupisone.

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Relationshipbetweentheenergytoget1tonofmetal copperfromcoppermine. =deepmetaldepositandlowgrade

Energy/1tcu 103kw/hr
Mine

Oligopolyofraremetal
Metal Ni Cr 1st production Russia S.Africa S.Africa S Africa Congo China S.Africa Brazil Australia China S.Africa Australia France 23 51 20 22 76 41 38 89 72 58 58 42 20 86 2nd production Canada Kazafstan China Australia Russia China China Canada Brazil Russia Russia S.Africa China USA

Raremetalproductionin
byJOGMEC Total 54 87 48 56 93 90 97 99 99 84 93 94 54 95 3rd production 17 20 15 18 12 25 38 10 18 21 32 42 18 6 Australia India Gabon Canada Australia Chili Russia Australia Canada S.Africa USA USA Canada India 14 16 13 16 5 24 21 1 9 5 3 10 16 3

1.China,2.SouthAfrica,3.Australia 4.Russia5.Canada

Chile

Mn Co W Mo V Nb Ta

Cu grade Year

Sb Pt group Zr In

Rare earth China

Cugradeofore

Existenceamountofelementsintheearthcrust
1ppm=1g/t

Rareearthdistributionintheworld

Rareearth Atomicnumber
(Handbookofextractivemetallurgy,Vol.3,WileyVCH,1997

Exis stence

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MetalextractionLargeamountofgangueNecessaryforenvironmentalburden ManykindsofmetalscontaininmanykindsofwastesNecessaryforrecycling
Waste toget1tonofmetal (Ecorucksack) waste , ton 1,100,000 Au 810,000 Pd 520,000 Pt 9,000 Dy 6,800 Ta 4,800 Ag 4,500 In Nd 3,000 3 000 Li 1,500 Cu 360 W 190 Zn 36 Pb 28 Fe 8 Accumulated metalamountinelectrictools, etc., ToninJapan Japan/world % ton 16.36 6,800

Priceofrareearthelements,Oct.2010
byHirokawa in DyTb pricesarehigh. Nd,Sm,Pr,La,Ce,Y increasedrapidlyin2010. May2011/April2010 Ce2O330 La2O3:20 Nd metal:8 Dy metal:5 InAugust2011,manyrare earthelementsshowed th l t h d maximumprice.

3 1 2

Au

Ta Ag In Li Cu W Zn Pb Fe

4,400 60,000 1,700 150,000 38,000,000 57,000 13,000,000 5,600,000 1,200,000,000

10.41 22.42 15.50 3.83 8.06 1.97 6.36 9.85 1.62

2 3 1

Rareearthminerals
Mineral
Ae sc h yn it e An c ylit e Apat it e Bast n asit e Ce r ian it e Ch e r alit e Ch e vkin it e Ch u r c h iit e Eu xe n it e Fe r gu so n it e Lo par it e Mo n azit e Th ale n it e X e n o t ime
*.n.a.not available

ImportancedeepseadepositfromJOGMEC
Th Th content

Chemicalcomposition
( L a , Ca , F e , T h) ( T i , Nb ) 2 ( O , O H) 6 S r L a ( CO 3 ) 2 ( O H) H 2 O Ca 5 ( P O 4 ) 3 ( F , Cl , O H) L a CO 3 F ( Ce , T h) O 2 ( L a , Ca , T h) ( P S i ) O 4 ( Ce , Ca , T h) 4 ( F e , M g ) ( T i , F e , M g ) 4 YP O 4 2 H 2 O ( L a , Ca , U, T h) ( Nb , T a , T i ) 2 O 6 L a ( Nb , T i ) O 4 ( L a , Na , Ca ) ( T i , Nb ) O 3 ( L a , T h) P O 4 Y 3 S i 3 O 1 0 ( O H) YP O 4

R EO wt% 36 46 19 76 81 5 n .a. 44 <40* 47 36 71 6 3 * 61*

Metalisstill Metal is still producingin seafloor hydrothermal oredeposit Cu1020 Au1020g/t timesgrade comparingin landdeposit

Depth

Depth

Depth

hydrothermal oredeposit

Mnnodule

Cobaltrichcrust

RadioactiveTh orUisincludedinsomerareearthminerals.

FromY.Nishikawa

2013/3/17

Highrareearthconcentrationmudisfoundunder0to 2mofbottominpacificocean
Dr.Kato,TheU.ofTokyoinJuly4th,2011)

.PossibilityofMineralseparation
Minerals including rare earth
- Monazite (Ce,La,Nd)PO4 CaCe(CO3)2F -Bastnaesite (C L )(CO3)F B t it (Ce,La)(CO

No radioactive elementsin themud.

- Synchysite Xenotime YPO4

Cerite 2(Ca,Fe)O3Ce2O36SiO23H2O Ion adsorption ore

Others

Small amout of radioactive elements

RareearthoredepositinVietnam

XRD pattern and SEM-EDS photos

5000

2
Bastnaesite (Ce,La)(CO3)F
Intensity

4500 4000 3500 3000 2500 2000 1500 1000 500 0

C : Cerium flouoride carbonate / Bastnaesite B : Barium sulfate / Barite Q : Silicon oxide / Quartz

Fiber type

Barite BaSO4 Quartz SiO2

Q B Q C B B
20

B BB
30

B B Q QB B Q C
40

Q B
50

Q
60

QQ
70

B
80

50 m

IMG1

50 m

Ce L

50 m

Ba L

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Density of minerals fore density separation

7

Specific gravity
6 5

Laboratoryscaleofcentrifugal gravityconcentrator (100 to1msize)

Specific gravity

4 3 2 1 0

Hematite Synchysite Monazite Bastnaesite

CaF2

Barite

Silica

20cm

Zeta-potential to find the flotation possibility

-25 -20 -15 -10

Floatation
Air

Z Zeta-potential, (mV)

-5 0 5 10 15 20 25 30 35 2 3 4 5 6 7 8

Hydrophobicparticles areattachedwithair bubbleandfloated Airbubblein thewater

Bastnaesite Monazite Flourite Synchysite Barite pH

9 10

DenverSubAtype Hydrophilicparticles arecirculatedinthe water Mechanicalagitationfor blowingair

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Electricalpropertiesofminerals
650000000 640000000 630000000 620000000

Electrostaticseparator
Particlefeed Corona discharge High voltage

6.4E8
relative dielectric constant

0.10

Electric conductivity ( /m)

610000000 600000000

0.08

1.0E8
1.00E+008

1.1E8

0.06

0.04

0.02

3.8E6
0.00E+000 Synchysite Monazite Bastnaesite

1.8E6
CaF2 Barite 0.00 Synchysite Monazite Bastnaesite CaF2 Barite

Insulatormiddlingconductor HV Insulator Conductor

ElectricconductivityRelativedielectricconstant

Conductor Humidity,%

Magnetizationcurveofpurerareearthminerals
0.0011 0.0010 0.0009 0 0009 0.0008

Schematicdiagramofthewethighgradientmagneticseparator (HGMS)andschematicdiagramofparticlecaptureareas (crosssection)inamagneticfieldaroundacylindricalwire

Sample and Solution Superconducting coil

Bastnaesite (7.0 x 10 4 SI) -4 Synchysite (0 5 x 10 SI) (0.5 -4 Monazite (8.7 x 10 SI)

(): magnetic susceptibility
Reference material: Ni

Magnetization, (T)

0.0007 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001

N
Applied magnetic field, H0

Flow Vf

Paramagnetic capture area

Magnetic field H0

160mm

Diamagnetic
capture area

A B A B

Diamagnetic capture area

0.0000 0.0

S
0.2 0.4 0.6 0.8 1.0 1.2

Matrix: expanded steel (2520mm)

Paramagnetic capture area

Magnetic field strength, (T)

2013/3/17

Ifrareearthelementsaredistributedtoveryfinersizein Leaching minerals,theleachingmethodisutilized.

concentrationof(NH4)2SO4
100 90 80 L Leaching ratio, (%) 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 16 18 20 Concentration of ammoniumsulfate, (mass% )

.Systemtoconstructenvironmentalfriendly
materialcirculationsociety

S/Lratio
100

La Sm

Ce Gd

Pr Dy

Nd

90 80 L Leaching ratio, (%) 70 60 50 40 30 20 10

La Sm

Pr Gd

Nd Dy

leachingratioofCeby(NH4)2SO4 is about2.5%.

0 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22 S/L ratio, (-) (Experimentalconditions:ammoniumsulfate concentration:1%;Leachingtime:3h; Temperature:293K)

La,Pr,Nd,Smhadequilibrated La Pr Nd Sm had equilibrated inspiteofincreasingS/Lratio. GdandDyincreasedwithincreasing S/Lratioupto0.09.

(Experimentalconditions:Leachingtime:24h;S/L ratio:0.1;Temperature:293K)

Itisnecessaryfor energyand technological innovationtochange fromsolidlinetothe brokenline. b k l

Importanceofraremetalsforcompetitionofindustries(likeVitamin) Medicalappliances(MRIetc.)DigitalcameraCellphoneDigitalplayer TelevisionPersonalcomputer Robot Automobiles Highfunctionalmaterials Steel Display Electric parts Small,light,energysaving,environment Small motor Secondary battery Hard metal Catalyst forair

Ni,Cr,W, Mo, Mn,V

Ga,Ta Ni,Ti Zr,Nb In Pt,etc. Rareearth (Nd,Dy,Sm) Coetc.

Li,Co,Ni Rareearth etc.

Pt,Pd Pt Pd W,Co Mn,V Etc. Rh

Fig.6 Relationshipbetweengradeandrecoveryfor recyclingtechnology(fromDelftUniv.ofTech)

etc.

2013/3/17

Raremetalamountsinsmallhomeappliances

Au2.9%,Ag2.3%mCu0.2%,La4.4%,Nd 0.2%,W0.1%,Co0.02%inJapanesedemand
Unit:t
Cellphone Gamemachine(small) Gamemachine(large) Game machine (large) PortableCD,MDplayer Portabledigitalaudio Digitalcamera Carnavigation Videocamera DVDplayer Audio Caraudio Car audio Hairdrier Electricoven Vacuumcleaner Total Domesticdemand(2010)

1Liquiddisplayrecycling,(In) Economicalcrushingmethodsas pretreatmentforrecycleand pyrometallurgical process to recover small processtorecoversmall amountofindium inuseddisplaypanel
Liberationoftheliquidcrystaldisplaypanelbytheelectrical disintegrationandrecoveryofeachcomponent, pp.490496A.Shibayama,S.Yamagata,Y.Yamamoto,K.Abe,T. Miyazaki,T.Fujita,J.MMIJ,Vol.118,p.490496,2002 RecoveringIndiumfromtheLiquidCrystalDisplayoftheDiscarded CellularPhonesbyMeansofChlorideinducedVaporizationat RelativelyLowTemperature,K.Takahashi,A.Sasaki,G.Dodbiba,J. Sadaki,N.SatoandT.Fujita,MetallurgicalandMaterials TransactionsA,2009,Vol.40A,April,pp.891900

(fromMETI

LCDpanelisseparatedcompletelyintotwoglasspanels.

Electricaldisintegration method
Withoutheating,theLCDpanelcanberapidly separatedwiththeelectricaldisintegrationof separated with the electrical disintegration of highvoltagepulseinwater. Here,aLCDofcellularphoneistested.A setting ofLCDinwaterbytheelectricaldisintegration apparatusisshown.
Highvoltagepulseelectrode LCDofcellularphone Ground
60kV

Someliquidcrystalfloatsinwaterandsomeareattachedonthe glasssurface. ContentofindiuminLCDofacellarphoneisabout 1100g/t. 2. Liquidcrystalrecycling Liquidcrystalcanberecoveredbyorganicsolventextraction.The evaporationofliquidcrystalonglassbyheatinginvacuumisalso possible.

(a)(b)
Photo.LCDofcellularphonebeforeseparation(a)and separatedLCDpanels(b).

2013/3/17

Theseparatedglassesareputintohydrochloricacidaqueous solutionandITOontheglasssurfaceisdissolved. TheflowsheetforLCDrecyclingisproposed.

RecyclingofindiumandtinfromLCDby hydrorometallurgy process

RecyclingofindiumandtinfromLCDby pyrometallurgical process

IftheusedLCDwasmechanicallycrushed,the crushedgrassattachedmetalionsshouldbe washedandthisprocessincludesthecostlyion exchangemethod. Inthecrushingprocessthesuitablerecycling processispyrometallurgical process. Ifthemetalexistsontheparticlesurfaceandthe pp indiumcontentissmalloflessthan1000ppm order,theevaporationmethodbyheatingatlow temperatureismoreeconomical. Toevaporateindiumatlowtemperature,ITOis chlorinatedbysoakingwithsmallamout ofHCl solution.

UsedLCD Used LCD Electricaldisintegrationinwater Separatedglasspanel RecoverofLCbyorganicsolventLC Acidleachingbyheating In,Sn solution Glass,filterpHcontrol In,Sn hydroxide ProposedflowsheetofLCDrecyclingprocess
ThehydrometallurgicalprocessusingLeachingandrecovery methodofITOissuitableforlarge sizeofLCDrecycling.

Theotherpretreatment

2. Liionbatteryrecycling,(Li,Co)
Effectcrushingofbattery,physicalseparation ofLiCoO2 etc.andrecoveryofLi ionby adsorption f d i fromusedbattery db Anovelflowsheetforprocessingofused lithiumionbatteriesforrecycling, Y.Yamajji,G.Dodbiba,S.Matsuo,K.Okaya, A.Shibayama,T.Fujita,Resources A Shib T F ji R Processing,2011,Vol.58,pp.913

SeparationofLCDpanel Parts(Explosioninwater)

Electricaldisintegrationin water

Fig.Flowsheetofapyrometallurgicalprocessforchlorideinduced vaporizationofindiumcompoundtopriortoitsrefiningforrecycling.

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Experiment
PVC 6% Al foil 7% Carbon 10% Cu foil 10% Separator 6%

Lithium-ion battery

Explosion in water Cutter mill

etc.

Sieving

Flotation Magnetic separation

LiCoO2,etc. Fe
Carbon Dissolution by acid

Steelcase 28%

Eddy current separation Air table

PVC,Film Precipitation by alkaline Removal of salts, Adsorption and desorption Heating

Compositionoflithiumionbatteryusedinthe experimentandphotographsoftwotypes(cylindrical andrectangular)oflithiumionbattery.

Cu

Al
Non crushed materials

Li2CO3

Co3O4

Flowsheetforrecoveringthelithiumionbattery

Underwaterexplosionoflithiumionbattery

1.7m

1.5m m

electrolyte

LiPF6 +H2OLiF+POF3 +2HF CaCl2 +2HFCaF2+2HCl

Experimentalsetupofexplosionoflithiumionbatteryinwater andphotographofdecomposedbatteriesbyexplosion. (Emulsionexplosive10g,water1.45t,lithiumionbattery5kg)

10

2013/3/17

+1mm

Distribution, %

Crushing time, s Crushed size 0.1m +4.8 -4.8+1.0 -1.0 mm

Nonmagnetic materials

Magnetic

Cuttermilltocrushthelithiumionbatterydecomposedby explosionandthecrushedsizedistributiondependingonthe crushingtime.

Rareearthrollmagneticseparator
(EriezMagneticsJapanCo.,Ltd.)

materials 0.3m

+1mm 0.3m

+1mm
Feed zone Inlet end S slope, ide End slope, Discharge end Air
Left-hand compartment
(Low-density fraction)
t n I p o l s e d i S , d n d n r e h g i H l f i R r e w o L e i s d A r n E
H ( t h g i R

P orous dec k Air Hig her sid e Hig her end

Lower side Riffles Lower end

Right-hand compartment
(High-density fraction)

, e p ls d o ) f y i s e t r p m o c d n a n g r a h c i D

e w o L

d n e r o ( h t f e L

b iig t c o e t r p m o c d n a ) f y w n l-s e

i n

Co lle

c ting

b in

Eddycurrentseparator (EriezMagneticsJapanCo.,Ltd.)

Airtable aspneumaticseparation
TRIPLE/SDYNAMICS,Inc.,USA)

11

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Flotationresultfor1mmsizeofcrushed lithiumionbattery.
Grade ,% Flotation Li Co Recovery, % Graphite Li about 30% 3.3 24 90 5 100 15 85 Co 100 12 88 Graphite 100 95 5

3.Capacitorrecycling,(Ta,Ni)
Taand Nirecoveryusingheattreatmentand physicalseparation 3.1Tacapacitor 31T it Copperandtantalumrecoveryfromprinted circuitboard,T.Fujita,H.Ono,G.Dodbiba,K. Okaya,S.Matsuo,J.Sadaki,S.Murakami, Conferenceofmetallurgists,Oct.25,2011 Montreal,QC Tantalumrecoveryfromprintedcircuitboardby heattreatment,H.Ono,T.Fujita,J.ofMMIJ, vol.127,pp.519525(2011)

Feed Float Sink

(About 60% LiCoO2) 0.7 3.8

(Pulp density 10%, MIBC 0.14kg/t, kerosene 3kg/t 500oC 2 hours heated)

WorldPrintedCircuitBoard(PCB)production
11% 9% China 35% Japan Taiwan 12% South Korea North America others 13% 21%
Total $44 billionin2009

Mechanicalseparationmethodofmountedpartson printedcircuitboard
Inclineddrumtypecrusherto separatemountedparts Heatingwithsteem andhittingtoseaparete mountedparts

Ref.)FujiChimera
Research Research Institute,Inc.

Patent2009195901

47

47

48

12

2013/3/17

Tantalumrecoveryfromliberated capacitorbythermaltreatment
Exampleoftantalumcapacitor

Schematicillustrationoftiptypetantalum capacitor
Graphite Silver Paste Molded Epoxy Resin

Leadtype L dt

Chiptype
Anode Terminal Tantalum wire Tantalum Sintered Body Cathode Terminal

7.0x4.5mm6.0x3.2x2.6mm

About5g

Sinteredtantalumbodyandwireexistsinthecenterof epoxyresinmold. Thecapacitorsizeisaboutseveralmm.

50

50 endothermic 0 exothermic 45 Weight losss (mass ) s 40 35 30 25 20 15 10 5 0 273 373 473 573 673 773 873 973 1073 Temparature(K) TG DTA

Heattreatmentoftantalumcapacitors
Afterheattreatment +0.5mmsievingaftersintering :mainlytantalumoxidesandSteel

773K 1hourinanairatmosphere 0.5mmsievingaftersintering mainlymoldpowderSiO2 i l ld d SiO

873K 1hour Inanair atmosphere

0.5mm Tantalum oxidepowders

FigureTGDTAthermographoftiptypetantalumcapacitorin theairatmosphere.
+0.5mmleadframe,metalwire
51

10mm

52

13

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3.2Nicapacitor
Nickel recoveryfromprintedcircuitboardand distributionofotherelementsbyheattreatmentand g p , , , , magneticseparation,H.Ono,G.Dodbiba,J.Sadaki, T.Fujita,TheU.ofTokyo,J.ofMMIJ,Vol.127,pp.584 591(2011) Recoveryofnickelparticlesfromwastedelectronicparts byflotation,M.Matsuda,E.Yuze,A.Shibayama,T.Fujita, ResourcesProcessing,Vol.50,No.1,pp.39(2003) TheRecoveryandLifeCycleAssessmentofNickel Th R d Lif C l A t f Ni k l ParticlesinaMultiSolenoidOpenGradientMagnetic Separator,A.Shibayama,M.Matsuda,A.Otsuki,G. Dodbiba,T.Fujita,B.Jeyadevan,K.Takahashi,Magnteic andElectricalSeparation,Vol.11,pp.127139,(2002)
53

Steel

Leadframe,metalwire Cu,Au,Ag,PGM

FigureFlowsheettorecovertantalumfrom mountedpartsofPCB.

Multilayerceramiccapacitor
B
L

C A

Ba Ti Ni Cu Sn Si Al Zn Fe Pb Br B Sb Ag Mn

MLCC 45.4 45 4 17.2 10.5 4.2 2.3 0.8 0.2 0.1 0.1

unit: mass% Lead Type 13.2 13 2 6.1 2.9 12.1 9.1 6.5 0.1 0.1 9.8 7.7 2.0 20 0.7 0.3 0.1

(a)(b)

(a) ObversesideofPrintedCircuitBoardwithMLCC. (b) ReversesideofPrintedCircuitBoardwithMLCC.

Schematicillustrationofmultilayerceramiccapacitor.
A:internalelectrode,B:dielectric,C:externalelectrode

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2013/3/17

Metaldistributionsofcarbonizationtreatmentandmagnetic separationforPCBwithMLCC.
Carbonization. Temp. (K) 773 Weight (g/kg-PCB) -4mm Mag. at 0.1T Mag. t 0.8T M at 0 8T Non-mag. at 0.8T +4mm Mag. at 0.1T Mag. at 0.8T Non-mag. at 0.8T +4mm -4mm Mag. at 0.1T Mag. at 0.8T g Non-mag. at 0.8T +4mm Distribution of metal (%) Cu Pb Sn Ni 0.2 3.2 2.9 67.5 0.4 6.1 6.3 73.0 0 4 6 1 6 3 73 0 4.1 13.0 21.4 27.0 95.5 80.9 72.3 0.0 0.2 1.7 2.2 73.9 0.4 2.8 3.5 79.3 5.4 47.3 61.2 9.3 94.2 49.9 35.3 11.5 0.2 20.5 5.2 77.9 0.4 22.3 8.9 81.8 5.7 71.7 58.8 11.1 94.0 6.0 32.3 7.1

873

973

Magneticsat0.1Taftercarbonizationtreatment forPCBwithMLCC.

g/kg 15 23 49 686 18 26 62 650 16 23 72 611

4. Hardmetalrecycling(W,V)
Physicalseparationforrecyclinginhardmetal productionprocessandeffectivecrushingand production process and effective crushing and hydrometallurgyprocessforrecyclingtungsten alloyscraps
4.1FundamentalstudyonRecoveryofWCfromhardmetal sludgeby usingmineralprocessing JungAhKIM,GjergjDODBIBA,KatsunoriOKAYA,SeijiMATSUO,Kenji NISHIMURA andToyohisaFUJITA MaterialsTransactions,Vol.52,No.7(2011)pp.14711476

Hardmetalsludgeproducedfromprocessingofhardmetaltools containswateroroilanddiatomaceousearthwasaddedasa filtrationassistanttofilteroutthewateroroil.Diatomaceous earthcontainsover90mass%SiO2. TheelementalcompositionofthesteelsludgeanalyzedbyXRFis h l l f h l l d l db giveninthetable.Theresultoftheanalysisshowedthatthe steelsludgecontainedabout69.9mass%tungsten[W],17.6 mass%silicon[Si],6.8mass%cobalt[Co]and2.4mass%iron [Fe]. l ii f C l d l db ( i %) Element composition of WC sludge, analyzed by XRF (Unit : mass%) Na Mg Al Si S Cl K Ca Cr Fe Co W

Dried 0.1 0.1 0.7 17.6 0.3 0.1 1.0 0.5 0.5 2.4 6.8 69.9 sample

15

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100 90 Grade in suspen nsion (mass%) 80 70 60 50 40 30 20 10 0 500 1000 Rotational speed (rpm) 1500
Tungsten carbide (WC) grade Silica (SiO2) grade Tungsten carbide (WC) recovery

100 80 70 60 50 40 30 20 10 0 Recovery in suspension (mass%) 90

4.2Crushingandhydrometallurgyprocessfor recyclingtungstenalloyscraps
Theeffectofunderwaterexplosiononthekineticsofalkaline leachingofroastedtungstencarbidescrapsforrecycling, S.W.Baik,A.Shibayama,K.Murata,T.Fujita,Int.J.Soc.Mater.Eng. Resour.Vol.12,No.2,pp.5559(2004) Anovelprocessforrecoveryoftungstenandvanadiumfroma leachsolutionoftungstenalloyscrap L.Luo,L.Kejun,A.Shibayama,E.T.Yen,T.Fujita,O.Shindo, A.KataiHydrometallurgy 72,2004,pp.18 Anovelprocessforrecovry oftungstenandvanadiumfroma leachsolutionoftungstenalloyscrap L.Luo,T.Miyazaki,A.Shibayama,W.T.Yen,T.Fujita,Minearal Eng.,16, 2003,pp.665670

Towermillgrinding

Fig.WC()andSiO2 ()gradesandrecoveryofWC()in suspensionasafunctionofrotationspeed.(millingtime:3h, sinkingtime:3h,pH6.9)

ExperimentalresultsindicatedthatWCgradewasincreasedtoabout80.5mass%andSiO2 grade wasdecreasedtoabout9.6mass%whenrotationalspeedwas1500rpm.Moreover,WC recoverywasincreasedtoabout9.79mass%.

Theunderwaterexplosioncrushedfineparticlescanbewell oxidizedbyroastingandthenleachedmuchfaster.

5.Polishingpowderrecycling(Zr)
Liquidliquidseparationtoseparatefineparticles zirconmixtureforrecycling SeparationofUltrafineParticlesofAluminaandZircon byLiquidLiquidExtractionUsingKeroseneasthe OrganicPhaseandSodiumDodecylsulfate asthe SurfactantCollector L.P.Wang,Y.Kanemitsu,G.Dodbiba,T.Fujita,Y.Oya,H. L P Wang Y Kanemitsu G Dodbiba T Fujita Y Oya H Yokoyama,TheUniversityofTokyo, The11th Int.SymposiumonEastAsiaResources RecyclingTechnology,2011
ThisseparationmethodissimilartoCe2O3 separationofpolishedpowder.IfCe2O3 recoveryisnecessaryinTaiwan,wearehappytocooperatetheresearch.

16

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Singlesampleextraction
40 Zeta potential (mV) ( 30

100 Extraction fraction in n kerosene phase (%) (

Al2O3 ZrSiO Z SiO4

20 10 0 -10 -20 -30 -40 0 2 4 6 pH 8 10

80 60 40 20 0

Alumina Zircon Zi

Al2O3 Zr(SiO4)

12

14

10

12 pH

Zetapotentialof alumina/zirconasa functionofpH

Effect of pH on the extraction fraction of alumina and zircon by using kerosene as the organic phase without the addition of surfactant collector (Experimental conditions: alumina/zircon powder c.a. 1g, kerosene 20mL/water 80mL)

Photographofthereparatoryfunnelsafteralumina(left)andzircon (right)areextractedbykerosenewiththeadditionof0.1kg/ton SDSatpH7 (Experimentalconditions:alumina/zirconpowderc.a.1g,kerosene 20mL/water80mL)

Actualsampleofaluminaandzirconmixture
100 Grade or Recovery (%) R 80 60 40 20 0 7.72 9.01 9.54 10.1 10.7 pH
Recovery of zircon in water phase Grade of zircon in water phase p Recovery of alumina in kerosene phase Grade of alumina in kerosene phae p

6.Bottomashrecycling(Ti,Cr)
Novelmagneticseparationmethodtorecover finetitanium oxideandchrome oxideparticles
Superconducting high gradient magnetic Superconductinghighgradientmagnetic separationoftitaniumandchromiumcompounds forrecyclingraremetalsintheincineratedash,R. Ito,T.Fujita,H.Tanno,A.Okada,J.ofMMIJ, Vol.123,p.342350(2007) R Recoveryofheavymetalsbyflotationfrom fh t l b fl t ti f incineratedautomobileshredderresidues,R.Ito, G.Dodbiba,J.Sadaki,J.W.Ahn,T.Fujita, ResourcesProcessing,Vol.54,p.152157(2007)

Thegradeandrecoveryofzirconinwaterphaseaswellas aluminainkerosenephaseatvariouspHafterliquidliquid extractionisconductedfortheabrasivemanufacturewaste (Experimentalconditions:abrasivemanufacturewaste c.a.2g, SDSaddition1.25kg/ton,kerosene20mL/water80mL)

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Chemicalcompositionofthebottomashby XRF(unit:wt%)
Na2O 9.9 MgO Al2O3 SiO2 2.0 6.2 15.2 SO3 5.4 Cl 7.1 K2O 1.4 CaO TiO2 Fe2O3 13.2 10.2 18.5

MagnetizationcurvemeasuredbyVSMand Capturedmagneticfractionofreagentsbywet HGMSasafunctionofmagneticfluxdensity(fluid velocity:10mm/sec.,feed:1gofeachreagent mixedwithlL ofwater)

0.002
-Fe2O3 Cr2O3 FeCl36H2O MnSO45H2O

Materials containingin ash. Magnetic Magnetic susceptibility andmedian particle diameter

Reagent TiO2 (Rutile) CaTiO3 (Perovskite) Cr2O3 -Fe2O3 Al2O3 SiO2 CaCO3 FeCl36H2O MnSO45H2O

Ca aptured (wt%)

0.32 0.55 0.41 0.54 1.98 12.9 0.14 -

Ma agnetization (T)

Magnetic susceptibility (10-6, SI unit) 11.1 38.5 1070 2040 -18.1 a -16.3 a -13.0 a 1520 1570

Median particle diameter (m)

100% 80% 60% 40% 20%

Fe2O3 Cr2O3 TiO2 CaTiO3 Al2O3 SiO2 CaCO3 0 1 2 3 4 5 6 Magnetic flux density (T)

0.0015

0.001

0.0005
CaTiO3

0 0

TiO2

0%

0.5 1 1.5 Magnetic flux density (T)

CapturedmagneticfractionofTiO2 andCaTiO3 particlesasafunctionof FeCl36H2Oconcentrationinwater bywetHGMSatmagneticflux density4T(fluidvelocity:10mm/sec., feed:1gofeachreagentmixedwith 1Lofsolution)

90% 80% C Captured (wt%) 70% 60% 50% 40% 30% 20% 10% 0% 0 10 20 30 40 FeCl36H2O concentration in water (g/L) TiO2 CaTiO3

Effect of the addition of FeCl3 in water on the wet HGMS results using a mixture of TiO2 and -Fe2O3. (fluid velocity: 10mm/sec., feed: 1g of TiO2 and 1g of -Fe2O3 mixed with 1L of solution, magnetic flux density: 1T)

7.Fluorescentlumprecycling(Rareearth)
Physicalseparationforrareearthelements includingpowderreuse
Separation of Rare Earth Fluorescent Poewders by Two Liquid SeparationofRareEarthFluorescentPoewders byTwoLiquid FlotationusingOrganicSolvent,A.Otsuki,G.Dodbiba,A.Shibayama, J.Sadaki,G.Mei,T.Fujita,J.J.AppliedPhysics,Vol.47,No.6, pp.50935099(2008) TwoLiquidFlotation:Heterocoagulation ofFineParticlesinPolar OrganicSolvent,A.Otsuki,G.Dodbiba&T.Fujita,Materials Transactions,Vol.48,No.5,pp.1095 1104(2007) Transactions, Vol.48,No.5, pp.10951104 (2007) Solidsolidseparationoffluorescentpowdersbyliquidliquid extractionusingaqueousandorganicphases,A.Otsuki,G.Mei,Y. Jiang,M.Matsuda,A.Shibayama,J.Sadaki &T.Fujita,Resources Processing,Vol.53,No.3,pp.121133(2006)

Product

Weight

Grade TiO2 48.7

(1) Blank (2) FeCl3 1g/L

Mag. Non Mag M Mag. Non Mag

Fe2O3 92.4 43.1 56.9 7.6 51.3 74.4 20.8

Recovery TiO2 Fe2O3 91.5 93.1 8.5 27.9 72.1 6.9 81.1 18.9

54.5 25.6 45.5 79.2

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Production,ConsumptionandWasteofFluorescent Lamp(Recoveryprocessofmercuryandglassfrom fluorescentlamps) Fluorescent

Fluorescentlamps Cuttingofftheedge
Endcap Glasstube Electron powder UVlight Mercuryatom Visiblelight Filament (Electrode)

Separationoffineparticlesbyliquidliquid extraction(Material)
Fluorescent Powder, (Formula) Red (Y2O3:Eu3+) Green (LaPO4:Tb3+,Ce3+) Components Y2 O3 Eu2O3 P2O5 La2O3 Ce2O3 Tb2O3 P2O5 Al2O3 Cl CaO Fe2O3 SrO BaO
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Content, (wt %) 91.6 7.8 29.8 39.7 17.9 10.1 25.0 1.3 1.1 1.8 0.014 41.2 27.0 1.0

Average particle size, D/m 2.6 26

Density, F /kg m-3 5120

1.1

5060

Glass Blowing Mercury

Endcap

Fluorescent powder

The Target

Blue ((Sr,Ca,Ba)10(PO4)6Cl2

:Eu2+)

2.1

4270

EuO

74

FlowsheetDesign
Mixture of fluorescent powders (red, green and blue) Mixed solvent: Non-polar (n-heptane) and polar (DMF) Surfactant (DAA) DMF phase p Filtering Washing by ethanol Drying The remaining component of mixture (blue and red powders) Second extraction n Surfactant (sodium 1-octansulfonate) Interface of two phases Filtering Drying Second product (blue) Shake and rest DMF phase Filtering Drying Third product (red) Mixed solvent: Non-polar (n-heptane) and polar (DMF)

SeparationResults
(Hydrophobicorganicliquid hydrophilicorganicliquid)
First product (Green) Grade (%) 90.0 Recovery (%) 95.2 Second product (Blue) Grade (%) 92.2 Recovery (%) 91.8 Third product (Red) Grade (%) 95.3 Recovery (%) 90.9 Overall efficiency (%) 62.8

First ext traction

Interface of two phases Filtering Drying First product (green)

Shake and rest

Experimental conditions:

Grade>90% Recovery>90% R 90%

mixing ratio of red, green and blue was 1:1:1; DAA concentration at 1st stage: 2x104 mol L1; sodium 1octanesulfonate concentration at 2nd stage: 20x104 mol L1; mixing ratio of solvent DMF: nheptane: 1:1; solid concentration at 1st stage 30 g L1, solid concentration at 2nd stage 15 g L1); process time: 4min
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8.Opticalglassrecycling(Rareearth)
Hydrometallurgicalrecoveryprocessofrare earthfromusedglass

Exampleofcompositionofopticalglasses
LaflintglassTaflintglassHeavyTaflintglassHeavyNb flintglass

Recoveryofrareearthfromwasteopticalglassby precipitationandsolventextraction,M.Matsuda, A.Shibayama,K.Matsushima,Y.Jiang,T.Fujita,T. Kikukawa,ShigentoSozai,Vol.119,p.668674 (2003) Recoveryofrareearthfromthespentoptical glassbyhydrometallurgicalprocess,Y.Jiang,A. Shibayama,K.Liu,T.Fujita,CanadianMetallurgical Quarterly,Vol.43,No.4,pp.431438(2004)

Rare earth La2O3 Gd2O3 Y2O3

Compositionsoftwoglasssamples

Conditionof Extraction, Scrubbing, Striping

Methodto recover A: Crystallization B:Solvent extraction Result La99.95% Y98.65% Gd 95.18%

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9.Magnetrecycling(Rareearth)
Pretreatmenttocrush rotorusingrareearth magnetandintroductionofusedrareearth t d i t d ti f d th magnetrecycling
L.Wang,G.Dodbiba,K.Okaya,T.Fujita, K.Murata,M.Kawano,Y.Fujigaki

Rotorinmotor aircompressorofairconditioner
Rareearthmagnets includedparts included parts

AnnualmeetingofMMIJ, C37,pp.119120 (2011)

Asieve(1mm)atthebottomofexplosiontank

Separatedrareearthmagnetpowder(a) andsteelplate(b)

(a)(b)

heatedat400 for demagnetization Sievingof5mm

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Hydrometallurgicalrecyclingmagnet
NdFeBmagnetscrap Crushing(+Oxidizingroasting) Fe2O3,Nd2O3,NdFeO3byroasting. AcidleachingSelectiveIronleaching Nd2O3andNdFeO3 canbeleached. Solidliquidseparation Solventextractionoffiltrate Extractant ,forexample,PC88A Nd richsolution,Dy richsolution ROH PrecipitationPrecipitaion P (byOxalicacid)(byOxalicacid) (by Oxalic acid) (by Oxalic acid) ROO BakingBaking Nd2O3 Dy2O3

10.Automobilecatalystrecycling,(Pt,Rh,Pd)
Leachingmethodofplatinumgroupmetals fromautomobilecatalyst
LeachingofPt,PdandRh fromautomotivecatalystresiduein g y variouschloridebasedsolutions,A.Harjanto,Y.Cao,A.Shibayama,I. Naitoh,T.Nanami,K.Kasahara,Y.Okumura,K.Liu,T.Fujita, MaterialsTransactions,vol.47,No.1,pp.129135(2006) KineticstudyontheleachingofPt,PdandRh fromautomotive catalystresiduebyusingchloridesolutions,Y.Cao,S.Harjanto,A. Shibayama,I.Naitoh,T.Nanami,K.Kasahara,Y.Okumura,T.Fujita, MaterialsTransactions,Vol.47,No.8,pp.20152024(2006) Recyclingofpreciousmetalsfromautomobive catalystresidueby leachinginHClH2O2 solution,Y.Cao,A.Shibayama,A.Harjanto,I. Naitoh,T.Nanami,K.Kasahara,Y.Okumura,T.Fujita,International JournalofAutomotiveEngineering(IJAE),Vol.38,No.3,pp.5561 (2007)

K.Koyama,AISTJapan,TechnicalInformationCenter,2010,Oct.,pp.7899

LeachingofPGMfromautomotive catalystresidue

Crushingunder500m Fig.EffectofHCLconcentrationonthe leachingofPGMs (NaClO 15wt%,NaCl1wt%,H2O2 5vol%, S/Lratio100g/L,293K) Fig.Comparisonofleachingsolution fortheleachingofPGMs.HClH2O2 solutionsystemversusaquaregia (Reactiontemperature338K, Time3h,S/L500g/L)

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Consumptionandproductsoftheleachinginthe variouschloridebasedleachingsolution.

11.Dentistrywasterecycling(Pt,Pd)
Selectiveleachingof Ptand Pdindentistrywastes
Selectiveleachingofplatinumandpalladiumby sodiumchlorade andsodiumhypochlorite sodium chlorade and sodium hypochlorite K.Liu,A.Shibayama,W.T.Yen,T.Fujita,ShigentoSozai, Vol.118,pp.745750(2002) Platinumgroupmetals,suchaspalladiumandplatinum, arecommonlyusedinawiderangeofindustrial applicationsasanelementalandvariouskindsofalloys. li ti l t l d i ki d f ll ItisdifficulttorecoverhighgradePdandPtfromthe primaryrawmaterialsandsolidwastes.Theselective leachingofPdandPtfromasecondaryresourceof dentistrywastehasbeeninvestigated.

AFMPtsurface byleaching

Primarycomponents ofdensitywaste samples

Elements Au Grade% Grade % 0.15 0.23 0.01 1.1 0.22 0.37 0.04 97.8

Leachingresultof PdandPtwith NaClO andNaClO3

Pd Pt Cu Zn Fe Ni Others

Separationflowsheetof Densitywastebyusingdifferent leachingsolution(NaClO3 andHCl)

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12.Preciousmetalsrecoveryfrom wastewater(Au,Ag,Pt,Pd)
Hydrometallurgicalandpyrometallurgical methodstorecover preciousmetalsfromwater
Recoveryofpreciousmetalionsfromwastewatergeneratedduringtherefining processofscrapmaterials,K.Takahashi,H.Umeda,A.Shibayamam G.Dodbiba, T.Fujita,ResourcesProcessing,Vol.55,pp.169177(2008)

Flowsheetfor recovering AuPtPdbymeans ofprecipitation

Fusionprocess

Conventional coppersmelting process

Highfrequency inductionfurnace

Metallicfractionandslag, recoveredbyfusion Anode

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Varioussmeltersforelementstorecycle ofmanykindsofmetals
CusmelterPGM Pb Zn NiPGM Sn Hg only Fe Fe only Rareearthrareearthonly

Recyclingtechnologyinnovationisimportant.
Several techniques using multiphase flow to use recycling, mineral processing and environmental cleaning technologies.
Phase Solid, Air Name of separation process Pyrometallurgy, Electrostatic separation, Magnetic separation Insulation, Dust collection, Dry crushing,Gas-solid fluidized bed, Eddy current separation, Cyclone, Color or X-ray sorter Gravity concentration, Heavy media separation, Centrifugal separation, Magnetic separation, Filtration, Leaching, Hydrometallurgy, Adsorption, Classification, Sink and float separation using magnetic fluid, Dielectrophoretic separation Solvent extraction, Emulsion utilization Milli, micro and nano bubble utilization Flotation, Wet grinding, Pyrometallurgy,Wet grinding, Drying Liquid-liquid separation

Solid, Liquid

Italicby-products

Liquid, Liquid Air, Liquid Solid, Air, Liquid Solid, Liquid, Liquid

Blue lettersrare metal

Recycleofraremetalsnow
Recyclerateisinfluencedonmineralsandpurposefor utilization.Recycledependsoneconomics.Thereare followingproblems. SecureofmineralresourcesInvestigationofnon y p recycledwastedmetalsinmunicipalwastes. ProblemforrecyclingtechnologySmallamountofrare metalutilization inproducts.Thistendencycontinuesto reducetheproductioncost.Innovationofrecycling technologyisimportant. RecyclecostproblemDifferenceofrecyclingcost betweencountries.Howtouseandrecycleraremetalsas additivesinproduct. 4.Importanceofinversemanufacturingandecodesign 4 I t fi f t i d d i Itisnecessarytoproduceartifactsandmaterials consideringhowtoreuseandrecycling. 5.Cooperationofrecyclingtechnologyandsystemineast Asianareaconsideringenvironment.

Writeyourname,number,department andUniversityname.
Pleasewriteyourconsiderationforrecycling.

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