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2013/3/17 1 No.2 Importance of rare metals and new development and advances in development and advances in purification and recycling technologies for rare metals March, 2013 Toyohisa Fujita, Energy and Environmental course, Graduate school of Engineering, RACE The University of Tokyo, Japan [email protected]tokyo.ac.jp . Introduction Rare metal definition USA: 1954 Rare metals handbook (C. A. Hampel) 1. Small amount in the crust 2 Diffi l f i if l i h 2. Difficulty of extraction even if large amount inthe crust 3. Minor utilization after extraction Now USA utilize the word of Critical metal ・・・ http://www.investmentu.com/2011/September/cobaltcriticalmetalcleanenergy.html or Critical / rare metal・・・ http://www.criticalmetals.com/ Japan: 1984 METI, Japan made a definition of rare metal. Europe: utilize the word of Minor metal (Germany)・・・ http://www.mmta.co.uk/home/ China: Journal ・・・ Rare metal, from Springer http://www.springerlink.com/content/10010521 Mineral Resources and materials Base metals for infrastructure Rare metals By T.Nishiyama: Rare metal resource 2009Price increases as the decrease of production amount. Many rare metals produce with base metals. Base metal production also reduces. Metal production quantity Metal price Rare metal is studied in our laboratory. La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb,Lu Rare earth Total rare metal number in Japan is 31 as rare earth group is one.

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Page 1: o②Vietnams lecture 2, 2013.3-20

2013/3/17

1

No.2「 Importance of rare metals and new

development and advances indevelopment and advances in purification and recycling technologies

for rare metals 」March, 2013

Toyohisa Fujita, Energy and Environmental course,

Graduate school of Engineering, RACEThe University of Tokyo, [email protected]‐tokyo.ac.jp

Ⅰ. Introduction Rare metal definition

• USA: 1954 Rare metals handbook (C. A. Hampel)

1. Small amount in the crust2 Diffi l f i if l i h2. Difficulty of extraction even if large amount in the crust3. Minor utilization after extractionNow USA utilize the word of Critical metal ・・・http://www.investmentu.com/2011/September/cobalt‐critical‐metal‐clean‐energy.html

or Critical / rare metal・・・ http://www.criticalmetals.com/・Japan: 1984 METI, Japan made a definition of rare metal.・Europe: utilize the word of Minor metal (Germany)・・・http://www.mmta.co.uk/home/

・China: Journal ・・・ Rare metal, from Springer http://www.springerlink.com/content/1001‐0521

Mineral Resources and materials Base metals

for infrastructure

Rare metals

By T.Nishiyama: Rare metal resource (2009)

Price increases as the decrease of production amount.Many rare metals produce with base

metals. Base metal production also reduces.

Metal production quantity Metal price

Rare metal

is studied in our laboratory.

La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, LuRare earth

Total rare metal number in Japan is 31 as rare earth group is one.

Page 2: o②Vietnams lecture 2, 2013.3-20

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2

Relationship between the energy to get 1 ton of metal copper from copper mine.

= deep metal deposit and low gradeEnergy/1t cu

103kw/hr MineChile

Year

Cu grade

Cu grade of ore、%

Oligopoly of rare metal Rare metal production in2000

Metal 1st production 2nd production 3rd production TotalNi Russia 23% Canada 17% Australia 14% 54%

Cr S. Africa 51 Kazafstan 20 India 16 87

Mn S Africa 20 China 15 Gabon 13 48

by JOGMEC1. China7, 2.South Africa, 6、3. Australia 6、4. Russia 5、5. Canada 5

Mn S. Africa 20 China 15 Gabon 13 48Co Congo 22 Australia 18 Canada 16 56

W China 76 Russia 12 Australia 5 93Mo 米国 41 China 25 Chili 24 90V S. Africa 38 China 38 Russia 21 97Nb Brazil 89 Canada 10 Australia 1 99Ta Australia 72 Brazil 18 Canada 9 99Sb China 58 Russia 21 S. Africa 5 84Pt group S. Africa 58 Russia 32 USA 3 93Zr Australia 42 S. Africa 42 USA 10 94In France 20 China 18 Canada 16 54Rare earth China 86 USA 6 India 3 95

地殻存在量の他元素との比較Existence amount of elements in the earth crust

1ppm=1g/t

sten

ce

Rare earth

Exis

Atomic number

Rare earth distribution in the world

(Handbook of extractive metallurgy, Vol.3, Wiley‐VCH, 1997 より)

Page 3: o②Vietnams lecture 2, 2013.3-20

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3

Metal extraction→Large amount of gangue・・・Necessary for environmental burdenMany kinds of metals contain in many kinds of wastes・・Necessary for recycling

Waste to get 1 ton of metal(Eco rucksack)

Accumulated metal amount in electric tools, etc.,

waste , Ton in Japan Japan/world

AuPd PtDyTaAgInNd

ton1,100,000810,000520,0009,0006,8004,8004,5003 000

Au

Ta AgIn

ton6,800

4,40060,0001,700

%16.36

10.4122.4215.50

NdLiCuWZnPbFe

3,0001,50036019036288

LiCuWZnPbFe

150,00038,000,000

57,00013,000,0005,600,000

1,200,000,000

3.838.061.976.369.851.62

Price of rare earth elements, Oct. 2010(by Hirokawa in JOGMEC)

31

Dy,Tb prices are high.Nd,Sm,Pr,La,Ce,Yincreased rapidly in 2010.

2

3

1

2May 2011/April 2010Ce2O3:30La2O3: 20Nd metal:8Dy metal :5

In August 2011, many rare th l t h d3

1earth elements showed maximum price.

Rare earth minerals

鉱物名 化学組成 REO wt% Thの含有

Aeschyn ite (La , Ca, Fe , Th)(Ti , Nb)2 (O, OH)6 36

Ancylite S rLa(CO 3)2 (OH)・ H2O 46

Mineral Chemical composition Th content

Apat ite    Ca5(PO4)3 (F , Cl , OH) 19

Bastnasite LaCO 3F 76

Ce r ian ite    (Ce , Th)O2 81

Cheralite  (La , Ca, Th)(PS i )O4 5

Chevkin ite (Ce , Ca, Th)4 (Fe , M g)(Ti , Fe , M g)4 n .a.

Church iite  YPO 4・ 2H2O 44

Euxen ite (La , Ca, U, Th)(Nb, Ta , Ti ) 2 O6 <40*

Ferguson ite La(Nb, Ti )O 4 47Fe rguson ite   , 4 47

Lopar ite    (La , Na, Ca)(Ti , Nb)O 3 36

Monazite    (La , Th)PO 4 71

Thale n ite     Y3S i 3O 10 (OH)  63*

Xenot ime    YPO 4 61 *

*理論値.n.a.:not available 

From Y. NishikawaRadioactive Th or U is included in some rare earth minerals .

Importance deep sea deposit (from JOGMEC)

Metal is still

Cu10‐20%、

Metal is still producing in seafloor hydrothermal ore deposit

Depth Depth Depth

Au10‐20g/t

10 times grade comparing in land deposit

Cobalt rich crustMn nodulehydrothermal ore deposit

Page 4: o②Vietnams lecture 2, 2013.3-20

2013/3/17

4

High rare earth concentration mud is found under 0 to 2m of bottom in pacific ocean(Dr. Kato, The U. of Tokyo in July 4th, 2011)

No radioactive elements in the mud.

Minerals including rare earth- Monazite (Ce,La,Nd)PO4

B t it (C L )(CO )F

Ⅱ. Possibility of Mineral separation

-Bastnaesite (Ce,La)(CO3)F

- Synchysite CaCe(CO3)2F

Xenotime YPO4

Cerite 2(Ca,Fe)O3・Ce2O3・6SiO23H2O

Ion adsorption ore

Smallamoutof radioactive elementsOthers

Rare earth ore deposit in VietnamXRD pattern and SEM-EDS photos

3000

3500

4000

4500

5000C : Cerium flouoride carbonate / BastnaesiteB : Barium sulfate / BariteQ : Silicon oxide / Quartz

試料 2

Bastnaesite (Ce,La)(CO3)F、

Fiber type

20 30 40 50 60 70 800

500

1000

1500

2000

2500

3000

BC

C

B

B

B

BB BBB

BB

BB

QQQQQQQQ

Q

Q

Inte

nsity

Fiber type

Barite BaSO4、

Quartz SiO2

IMG150 µm Ce L 50 µm Ba L50 µm

Page 5: o②Vietnams lecture 2, 2013.3-20

2013/3/17

5

Density of minerals fore density separation

6

7

Specific gravity

2

3

4

5

Spec

ific

grav

ity

Hematite Synchysite Monazite Bastnaesite CaF2 Barite Silica0

1

Laboratory scale of centrifugal gravity concentrator(100 to 1 μm size)

20cm

Zeta-potential to find the flotation possibility

-15

-20

-25

15

10

5

0

-5

-10

Zet

a-po

tent

ial,

(mV

)

BastnaesiteMonazite

2 3 4 5 6 7 8 9 1035

30

25

20

pH

Z Monazite Flourite Synchysite Barite

Floatation

Air

Air bubble in the water

Hydrophobic particles are attached with air bubble and floated

Mechanical agitation for blowing air

Hydrophilic particles are circulated in the

water

Denver Sub‐A type

Page 6: o②Vietnams lecture 2, 2013.3-20

2013/3/17

6

630000000640000000650000000

0.10

Electrical properties of minerals

6.4E8

1.00E+008

600000000610000000620000000630000000

Ele

ctri

c co

nduc

tivity

(

/m)

0.02

0.04

0.06

0.08

rela

tive

diel

ectr

ic c

onst

ant

Ω

3.8E6

1.0E8

1.8E6

1.1E8

Synchysite Monazite Bastnaesite CaF2 Barite0.00E+000

Synchysite Monazite Bastnaesite CaF2 Barite0.00

Electric conductivity Relative dielectric constant

Electrostatic separatorParticle feed

Corona dischargedischarge

High voltage

Insulator middling conductor

HV

ConductorInsulator

Humidity, %

Conductor

Magnetization curve of pure rare earth minerals

0 0009

0.0010

0.0011

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

0.0004

0.0005

0.0006

0.0007

0.0008

0.0009

Synchysite (0.5 x 10 SI) Monazite (8.7 x 10-4 SI)

M

agne

tizat

ion,

(T)

Reference material: Ni(): magnetic susceptibility

0.0 0.2 0.4 0.6 0.8 1.0 1.20.0000

0.0001

0.0002

0.0003

Magnetic field strength, (T)

Schematic diagram of the wet high gradient magnetic separator (HGMS) and schematic diagram of particle capture areas (cross section) in a magnetic field around a cylindrical wire

Sample andSolution

N

Applied magnetic field, H0

Superconducting coil

160mm

Paramagnetic capture area

Magnetic field H0

Flow Vf

ABB

Diamagnetic capture area

Diamagnetic capture area

Matrix: expanded steel

(25×20mm)

S Paramagnetic capture area

Acapture area capture area

Page 7: o②Vietnams lecture 2, 2013.3-20

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7

Leaching

90

100 La Ce Pr Nd

concentration of (NH4)2SO4concentration of (NH4)2SO4 S/L ratioS/L ratio

90

100 La Pr Nd

If rare earth elements are distributed to very finer size in minerals, the leaching method is utilized.

30

40

50

60

70

80

90Sm Gd Dy

Lea

chin

g ra

tio, (

%)

La Pr Nd Sm had equilibrated30

40

50

60

70

80

90 Sm Gd Dy

Lea

chin

g ra

tio, (

%)

(Experimental conditions: ammonium sulfate concentration: 1%; Leaching time: 3 h; Temperature: 293 K)

0 2 4 6 8 10 12 14 16 18 200

10

20

L

Concentration of ammonium sulfate, (mass%)

(Experimental conditions: Leaching time: 24 h; S/L ratio: 0.1; Temperature: 293 K)

leaching ratio of Ce by (NH4)2SO4 is about 2.5 %.

La, Pr, Nd, Sm had equilibrated in spite of increasing S/L ratio.

Gd and Dy increased with increasing S/L ratio up to 0.09.

0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.220

10

20

L

S/L ratio, (-)

Ⅲ. System to construct environmental friendly material circulation society

It is necessary for energy and technological

innovation to change from solid line to the

b k lbroken line.

Fig.6 Relationship between grade and recovery for recycling technology (from Delft Univ. of Tech)

Importance of rare metals for competition of industries (like Vitamin)

Medical appliances (MRI etc.) Digital camera Cell phone Digital player

Television Personal computerRobot

Automobiles

High functional materials Small, light, energy saving, environment

Steel Display Electric

parts

Small

motor

Secondary

battery

Hard

metalCatalyst

for air

Pt PdNi,Cr,W,Mo,

Mn,V

etc. In

Ga, Ta

Ni, Ti

Zr, Nb

Pt, etc.

Rare earth

(Nd,Dy,Sm)

Co etc.

Li, Co,Ni

Rare earth

etc.

W, Co

Mn, V

Etc.

Pt, Pd

Rh

Page 8: o②Vietnams lecture 2, 2013.3-20

2013/3/17

8

Rare metal amounts in small home appliances

Au 2.9%, Ag 2.3%m Cu 0.2%, La 4.4%, Nd 0.2%, W 0.1%, Co 0.02% in Japanese demandUnit: t

Cell phoneGame machine (small)Gamemachine (large)Game machine (large)Portable CD,MD playerPortable digital audioDigital cameraCar navigationVideo cameraDVD playerAudioCar audio

(from METI)

Car audioHair drierElectric ovenVacuum cleaner‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐Total‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐Domestic demand (2010)

1 Liquid display recycling, (In)

Economical crushing methods as pretreatment for recycle and pyrometallurgical process to recover small

Liberation of the liquid crystal display‐panel by the electrical disintegration and recovery of each component,pp. 490‐496A. Shibayama, S. Yamagata, Y. Yamamoto, K. Abe, T. Miyazaki, T. Fujita, J. MMIJ, Vol.118, p.490‐496, 2002

pyrometallurgical process to recover small amount of indium in used display panel

Recovering Indium from the Liquid Crystal Display of the Discarded Cellular Phones by Means of Chloride‐induced Vaporization at Relatively Low Temperature, K. Takahashi, A. Sasaki, G. Dodbiba, J. Sadaki, N. Sato and T. Fujita, Metallurgical and Materials Transactions A, 2009, Vol.40A, April, pp.891‐900

Electrical disintegration method

Without heating, the LCD panel can be rapidly separated with the electrical disintegration ofseparated with the electrical disintegration of high voltage pulse in water.

Here, a LCD of cellular phone is tested. A setting of LCD in water by the electrical disintegration apparatus is shown .

LCD of cellular phone

Ground

High voltage pulse electrode60kV

LCD panel is separated completely into two glass panels.

Some liquid crystal floats in water and some are attached on the glass surface. Content of indium in LCD of a cellar phone is about 1100g/t.

2. Liquid crystal recycling

Liquid crystal can be recovered by organic solvent extraction. The evaporation of liquid crystal on glass by heating in vacuum is also possible.

Photo. LCD of cellular phone before separation (a) and separated LCD panels (b).

(a) (b)

Page 9: o②Vietnams lecture 2, 2013.3-20

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9

The separated glasses are put into hydrochloric acid aqueous solution and ITO on the glass surface is dissolved. The flow sheet for LCD recycling is proposed.

Used LCD

Recycling of indium and tin from LCD by hydrorometallurgy process

Used LCD↓・・Electrical disintegration in water

Separated glass panel↓・・Recover of LC by organic solvent →LC↓・・Acid leaching by heating →In, Sn solution

Glass, filter ↓・・pH controlIn, Sn hydroxide

Proposed flow sheet of LCD recycling process

The hydrometallurgical process using Leaching and recovery method of ITO is suitable for large size of LCD recycling.

Recycling of indium and tin from LCD by pyrometallurgical process

If the used LCD was mechanically crushed, the crushed grass attached metal ions should be washed and this process includes the costly ion exchange method.

In the crushing process the suitable recycling process is pyrometallurgical process.

If the metal exists on the particle surface and the indium content is small of less than 1000ppm pporder, the evaporation method by heating at low temperature is more economical.

To evaporate indium at low temperature, ITO is chlorinated by soaking with small amout of HClsolution.

The other pretreatment

Separation of LCD panel

Parts (Explosion in water)

Electrical disintegration in water

Fig. Flow sheet of a pyrometallurgical process for chloride‐induced vaporization of indium compound to prior to its refining for recycling.

2. Li ion battery recycling, (Li, Co)

Effect crushing of battery, physical separation of LiCoO2 etc. and recovery of Li ion by d i f d b

A novel flow sheet for processing of used lithium‐ion batteries for recycling, Y.Yamajji, G.Dodbiba, S.Matsuo, K.Okaya, A Shib T F ji R

adsorption from used battery

A.Shibayama, T.Fujita, Resources Processing,2011, Vol.58, pp.9‐13

Page 10: o②Vietnams lecture 2, 2013.3-20

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10

etc.

Al foil

7%

PVC

6%Separator

6%

Steel case28%

Cu foil

10%

Carbon

10%

Composition of lithium‐ion battery used in theexperiment and photographs of two types (cylindrical and rectangular) of lithium –ion battery.

+1 00 1 00

Lithium-ion battery

Explosion in water

Cutter mill

Experiment

Carbon

+1.00mm -1.00mm

FeLiCoO2, etc.

PVC, Film

磁着

Sieving

FlotationMagnetic separation

Eddy current separation

Dissolution by acid

Precipitation by alkaline

Flow sheet for recovering the lithium‐ion battery

Co3O4Cu Al Li2CO3

Air table Precipitation by alkaline Heating

Removal of salts, Adsorption and desorption

Non crushed materials

m

Underwater explosion of lithium ion battery

1.7m

1.5

m

LiPF6 + H2O →LiF + POF3 + 2HFelectrolyte

Experimental setup of explosion of lithium‐ion battery in water and photograph of decomposed batteries by explosion.

(Emulsion explosive 10g, water 1.45t, lithium‐ion battery 5kg)

6 2 3

CaCl2 + 2HF →CaF2 + 2HCl

Page 11: o②Vietnams lecture 2, 2013.3-20

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11

ion,

%D

istri

but

Crushing time, s

Cutter mill to crush the lithium‐ion battery decomposed by explosion and the crushed size distribution depending on the crushing time.

←0.1m→

+4.8 -4.8+1.0 -1.0 mmCrushed size

+1mm

Nonmagnetic materials

Rare earth roll magnetic separator 0.3m

Magnetic

materials

(Eriez Magnetics Japan Co.,Ltd.)

0.3m

+1mm

Eddy current separator

(Eriez Magnetics Japan Co.,Ltd.)

Feed zone

Side slope, β

End slope, α

Higher side Air

Porous deck

Inlet endHigher end

+1mm

Sideslope , β En d slope, αDischargeendLower sideRiffle sInlete nd

Lowe r end

Higherend

Left-h and compartmentRight-h and compartment

Collecting b inAir(Lo w-density fraction)(High -densityfraction)

End slope, αDischarge end

Lower side

Riffles

Lower end Left-hand compartment

Right-hand compartment

Collecting bin

Air

(Low-density fraction)

(High-density fraction)

Air table as pneumatic separation(TRIPLE/S DYNAMICS, Inc., USA)

Page 12: o②Vietnams lecture 2, 2013.3-20

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12

Flotation result for ‐1mm size of crushed lithium ion battery.

Grade ,% Recovery, %

FlotationLi Co Graphite Li Co Graphite

Feed(About 60% LiCoO2)

about 30%

100 100 100

Float 0.7 3.3 90 15 12 95

Sink 3.8 24 5 85 88 5

(Pulp density 10%, MIBC 0.14kg/t, kerosene 3kg/t、

500oC 2 hours heated)

3. Capacitor recycling, (Ta, Ni)

3 1 T it

Ta and Ni recovery using heat treatment and physical separation3.1 Ta capacitor・Copper and tantalum recovery from printed circuit board, T.Fujita, H. Ono, G. Dodbiba, K. Okaya, S.Matsuo, J. Sadaki, S. Murakami,

Conference of metallurgists, Oct. 2‐5,2011 Montreal, QC

・Tantalum recovery from printed circuit board by heat treatment, H. Ono, T. Fujita, J. of MMIJ, vol.127, pp.519‐525 (2011)

35%9%

11%

China

Japan Ref.) Fuji Chimera Research

World Printed Circuit Board (PCB) production

13%

12%

Taiwan

South Korea

North America

others

Research Institute, Inc.

•47

21%

13%

Total $44 billion (in 2009)

47

Mechanical separation method of mounted parts on printed circuit board

Heating with steem and hitting to seaparetemounted parts

Inclined drum type crusher to separate mounted parts

Patent2009‐195901

48

Page 13: o②Vietnams lecture 2, 2013.3-20

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13

L d t

Example of tantalum capacitor

Tantalum recovery from liberated capacitor by thermal treatment

Lead type Chip type7.0x4.5mm 6.0x3.2x2.6mm

About 5g

Schematic illustration of tip type tantalum capacitor

Silver Paste

Graphite

Molded Epoxy ResinSilver Paste

Graphite

Molded Epoxy Resin

Anode Terminal Cathode Terminal

Tantalum Sintered Body Tantalum wire

Anode Terminal Cathode Terminal

Tantalum Sintered Body Tantalum wire

Sintered tantalum body and wire exists in the center of epoxy resin mold. The capacitor size is about several mm. 50

3035404550

s (m

ass%

)

TGDTA

exo

ther

mic

05

10152025

273 373 473 573 673 773 873 973 1073

Wei

ght l

osss

← e

ndot

herm

ic

0

Figure TG‐DTA thermograph of tip type tantalum capacitor in the air atmosphere.

273 373 473 573 673 773 873 973 1073

Temparature (K)

51

Heat treatment of tantalum capacitors

+0.5mm sieving after sintering: mainly tantalum oxides and Steel

After heat treatment

‐0.5mm sieving after sinteringi l ld d SiO

773K 1hour in an air atmosphere

―0.5mm

873K 1hourIn an air atmosphere

52

:mainly mold powder SiO2

+0.5mm lead frame, metal wire10mm

Tantalum oxide powders

Page 14: o②Vietnams lecture 2, 2013.3-20

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14

Steel

Figure Flow sheet to recover tantalum from mounted parts of PCB.

Lead frame, metal wire Cu, Au, Ag, PGM

53

3.2 Ni capacitor

・Nickel recovery from printed circuit board and distribution of other elements by heat treatment and magnetic separation, H. Ono, G. Dodbiba, J. Sadaki, g p , , , ,

T. Fujita, The U. of Tokyo, J. of MMIJ, Vol.127, pp.584‐591(2011)

・Recovery of nickel particles from wasted electronic parts by flotation, M. Matsuda, E.Yuze, A.Shibayama, T.Fujita, Resources Processing, Vol.50, No.1, pp.3‐9 (2003)Th R d Lif C l A t f Ni k l・The Recovery and Life Cycle Assessment of Nickel Particles in a Multi‐Solenoid Open‐Gradient Magnetic Separator, A. Shibayama, M. Matsuda, A. Otsuki, G. Dodbiba, T. Fujita, B. Jeyadevan, K. Takahashi, Magnteicand Electrical Separation, Vol. 11, pp. 127‐139, (2002)

Multilayer ceramic capacitor

unit: mass%MLCC Lead Type

Ba 45 4 13 2

WL

BW

L

B

Ba 45.4 13.2Ti 17.2 6.1Ni 10.5 2.9Cu 4.2 12.1Sn 2.3 9.1Si 0.8 6.5Al 0.2 0.1Zn 0.1 0.1Fe 0.1 9.8Pb 7.7B 2 0C

AC

A

Schematic illustration of multi‐layer ceramic capacitor.A: internal electrode, B: dielectric, C: external electrode

Br 2.0Sb 0.7Ag 0.3Mn 0.1

(a) Obverse side of Printed Circuit Board with MLCC.

(a) (b)

(b) Reverse side of Printed Circuit Board with MLCC.

Page 15: o②Vietnams lecture 2, 2013.3-20

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15

Magnetics at 0.1T after carbonization treatment for PCB with MLCC.

Metal distributions of carbonization treatment and magnetic separation for PCB with MLCC.

Carbonization. Temp. Weight Distribution of metal (%)(K) (g/kg-PCB) g/kg Cu Pb Sn Ni773 -4mm Mag. at 0.1T 15 0.2 3.2 2.9 67.5

M t 0 8T 23 0 4 6 1 6 3 73 0Mag. at 0.8T 23 0.4 6.1 6.3 73.0Non-mag. at 0.8T 49 4.1 13.0 21.4 27.0

+4mm 686 95.5 80.9 72.3 0.0873 Mag. at 0.1T 18 0.2 1.7 2.2 73.9

Mag. at 0.8T 26 0.4 2.8 3.5 79.3Non-mag. at 0.8T 62 5.4 47.3 61.2 9.3

+4mm 650 94.2 49.9 35.3 11.5973 -4mm Mag. at 0.1T 16 0.2 20.5 5.2 77.9

Mag. at 0.8T 23 0.4 22.3 8.9 81.8gNon-mag. at 0.8T 72 5.7 71.7 58.8 11.1

+4mm 611 94.0 6.0 32.3 7.1

4. Hard metal recycling (W,V)

Physical separation for recycling in hard metal production process and effective crushing andproduction process and effective crushing and hydrometallurgy process for recycling tungstenalloy scraps

4.1 Fundamental study on Recovery of WC from hardmetal sludge by using mineral processing

Jung‐Ah KIM, Gjergj DODBIBA, Katsunori OKAYA, Seiji MATSUO, Kenji NISHIMURAand Toyohisa FUJITA

Materials Transactions, Vol.52, No.7 (2011)pp.1471‐1476

Hard metal sludge produced from processing of hard metal tools contains water or oil and diatomaceous earth was added as a filtration assistant to filter out the water or oil. Diatomaceous earth contains over 90 mass% SiO2.

h l l f h l l d l d bThe elemental composition of the steel sludge analyzed by XRF is given in the table. The result of the analysis showed that the steel sludge contained about 69.9 mass% tungsten [W], 17.6 mass% silicon [Si], 6.8 mass% cobalt [Co] and 2.4 mass% iron [Fe].

l i i f C l d l d b ( i %)

Na Mg Al Si S Cl K Ca Cr Fe Co W

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

Element composition of WC sludge, analyzed by XRF (Unit : mass%)

Page 16: o②Vietnams lecture 2, 2013.3-20

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16

50

60

70

80

90

100

spen

sion

(mas

s%)

Tungsten carbide (WC) grade Silica (SiO2) gradens

ion

(mas

s%)

50

60

70

80

90

100

500 1000 15000

10

20

30

40

Rec

over

y in

su

2 Tungsten carbide (WC) recovery

Gra

de in

susp

en

Rotational speed (rpm)

0

10

20

30

40

Tower mill grinding

Fig. WC () and SiO2 () grades and recovery of WC () in suspension as a function of rotation speed. (milling time: 3 h, sinking time: 3 h, pH 6.9)

Experimental results indicated that WC grade was increased to about 80.5 mass% and SiO2 grade was decreased to about 9.6 mass% when rotational speed was 1500 rpm. Moreover, WC recovery was increased to about 9.79 mass%.

4.2 Crushing and hydrometallurgy process for recycling tungsten alloy scraps

The effect of underwater explosion on the kinetics of alkaline leaching of roasted tungsten carbide scraps for recycling,

S.W. Baik, A. Shibayama, K. Murata, T. Fujita, Int. J. Soc. Mater. Eng. Resour. Vol.12, No.2,pp.55‐59 (2004)

A novel process for recovery of tungsten and vanadium from a leach solution of tungsten alloy scrap

L. Luo, L. Kejun, A.Shibayama, E.T.Yen, T.Fujita, O.Shindo, A.KataiHydrometallurgy 72,2004, pp.1‐8

A novel process for recovry of tungsten and vanadium from a leach solution of tungsten alloy scrap

L.Luo, T.Miyazaki, A.Shibayama, W.T.Yen, T.Fujita, Minearal Eng., 16, 2003, pp.665‐670

The underwater explosion crushed fine particles can be well oxidized by roasting and then leached much faster. 5. Polishing powder recycling (Zr)

Liquid‐liquid separation to separate fine particleszircon mixture for recycling

Separation of Ultrafine Particles of Alumina and Zircon by Liquid‐Liquid Extraction Using Kerosene as the Organic Phase and Sodium Dodecylsulfate as the Surfactant Collector

L P Wang Y Kanemitsu G Dodbiba T Fujita Y Oya HL.P. Wang, Y. Kanemitsu, G. Dodbiba, T. Fujita, Y. Oya, H. Yokoyama, The University of Tokyo,

The 11th Int. Symposium on East Asia Resources Recycling Technology,2011

This separation method is similar to Ce2O3 separation of polished powder. → If Ce2O3

recovery is necessary in Taiwan, we are happy to cooperate the research.

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20

30

40

(mV

)

Al2O3

Z SiO20

30

40

(mV

)

Al2O3

Z SiO80

100

n in

(%) Alumina

Zi

Single sample extraction

-40

-30

-20

-10

0

10

20

0 2 4 6 8 10 12 14pH

Zeta

pote

ntial

( ZrSiO4

-40

-30

-20

-10

0

10

20

0 2 4 6 8 10 12 14pH

Zeta

pote

ntial

( ZrSiO4

0

20

40

60

80

2 4 6 8 10 12 pH

Ext

ract

ion

fract

ion

kero

sene

pha

se ( Zircon

Zeta potential of alumina/zircon as a function of pH

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)

Al2O3Al2O3

Zr(SiO4)

Photograph of the reparatory funnels after alumina (left) and zircon (right) are extracted by kerosene with the addition of 0.1 kg/ton SDS at pH 7

(Experimental conditions: alumina/zircon powder c.a. 1g, kerosene 20mL/water 80mL)

60

80

100

Rec

over

y (%

)

Actual sample of alumina and zircon mixture

0

20

40

7.72 9.01 9.54 10.1 10.7 pH

Gra

de o

r R

Recovery of zircon in water phase Recovery of alumina in kerosene phaseGrade of zircon in water phase Grade of alumina in kerosene phae

The grade and recovery of zircon in water phase as well as alumina in kerosene phase at various pH after liquid‐liquid extraction is conducted for the abrasive manufacture waste

(Experimental conditions: abrasive manufacture waste c.a. 2g, SDS addition 1.25 kg/ton, kerosene 20mL/water 80mL)

p p

6. Bottom ash recycling (Ti, Cr)

• Superconducting high gradient magnetic

Novel magnetic separation method to recover fine titanium oxide and chrome oxide particles • Superconducting high gradient magnetic separation of titanium and chromium compounds for recycling rare metals in the incinerated ash, R. Ito, T. Fujita, H. Tanno, A. Okada, J. of MMIJ, Vol.123, p.342‐350 (2007)

R f h t l b fl t ti f• Recovery of heavy metals by flotation from incinerated automobile shredder residues, R. Ito, G. Dodbiba, J. Sadaki, J. W. Ahn, T. Fujita, Resources Processing, Vol.54, p.152‐157 (2007)

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Chemical composition of the bottom ash by XRF (unit: wt%)

Na2O MgO Al2O3 SiO2 SO3 Cl K2O CaO TiO2 Fe2O3

9.9 2.0 6.2 15.2 5.4 7.1 1.4 13.2 10.2 18.5

ReagentMagnetic

susceptibility(×10-6, SI unit)

Median particle diameter (μm)

TiO2 (Rutile) 11.1 0.32 CaTiO3 (Perovskite) 38.5 0.55

Cr2O3 1070 0.41

Materials containing in ash.Magnetic

α-Fe2O3 2040 0.54 Al2O3 -18.1 a 1.98

SiO2 -16.3 a 12.9

CaCO3 -13.0 a 0.14

FeCl3・6H2O 1520 -MnSO4・5H2O 1570 -

Magnetic susceptibility and median particle diameter

Magnetization curve measured by VSM andCaptured magnetic fraction of reagents by wet HGMS as a function of magnetic flux density (fluid velocity: 10mm/sec., feed: 1g of each reagent mixed with lL of water)

40%

60%

80%

100%

aptu

red

(wt%

)

αFe2O3

Cr2O3

TiO2

CaTiO30.001

0.0015

0.002

agne

tizat

ion

(T)

α-Fe2O3

Cr2O3FeCl3・6H2O

MnSO4・5H2O

0%

20%

0 1 2 3 4 5 6Magnetic flux density (T)

Ca Al2O3

SiO2

CaCO3

0

0.0005

0 0.5 1 1.5 2Magnetic flux density (T)

Ma

CaTiO3

TiO2

Captured magnetic fraction of TiO2

and CaTiO3 particles as a function of FeCl3・6H2O concentration in water by wet HGMS at magnetic flux density 4T (fluid velocity: 10mm/sec., feed: 1g of each reagent mixed with 1L of solution)

Effect of the addition of FeCl3 in water on the wet HGMS results using a mixture of TiO2 and α-Fe2O3. (fluid velocity: 10mm/sec., feed: 1g of TiO2and 1g of α-Fe2O3 mixed with 1L of solution, magnetic flux density: 1T)

30%40%50%60%70%80%90%

Cap

ture

d (w

t%)

TiO2CaTiO3 Product

Weight

%Grade(%)

Recovery(%)

TiO2α-

Fe2O3TiO2

α-Fe2O3

(1)Blank

Mag. 92.4 43.1 56.9 91.5 93.1NonM 7.6 48.7 51.3 8.5 6.9

0%10%20%

0 10 20 30 40

FeCl3・6H2O concentration in water (g/L)

C Mag 7.6 48.7 51.3 8.5 6.9

(2)FeCl31g/L

Mag. 54.5 25.6 74.4 27.9 81.1NonMag 45.5 79.2 20.8 72.1 18.9

7. Fluorescent lump recycling (Rare earth)

Separation of Rare Earth Fluorescent Poewders by Two Liquid

Physical separation for rare earth elements including powder reuse

・Separation of Rare Earth Fluorescent Poewders by Two‐Liquid Flotation using Organic Solvent, A.Otsuki, G.Dodbiba,A.Shibayama, J. Sadaki, G. Mei, T. Fujita, J.J. Applied Physics, Vol.47,No.6, pp.5093‐5099 (2008)・Two‐Liquid Flotation:Heterocoagulation of Fine Particles in Polar Organic Solvent, A. Otsuki, G. Dodbiba & T. Fujita, Materials Transactions, Vol.48,No.5, pp.1095‐1104 (2007)Transactions, Vol.48,No.5, pp.1095 1104 (2007)・Solid‐solid separation of fluorescent powders by liquid‐liquid extraction using aqueous and organic phases, A.Otsuki, G. Mei, Y. Jiang, M.Matsuda, A.Shibayama, J.Sadaki & T.Fujita, Resources Processing, Vol.53,No.3, pp.121‐133 (2006)

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Production, Consumption and Waste of Fluorescent Lamp (Recovery process of mercury and glass from fluorescent lamps)

Fluorescent lamps Mercury atomUV light

Fluorescent powder

Filament (Electrode)

Visible light

Cutting off the edge

Glass End cap

Blowing

ElectronGlass tubeEnd cap

The Target

Mercury Fluorescent powder

Fluorescent Powder, (Formula) Components Content, (wt %)

Average particle size,

D/μm

Density,ρF /kg m-3

Red Y2O3 91.6 2 6 5120

Separation of fine particles by liquid‐liquid extraction (Material)

(Y2O3:Eu3+) 2.6 5120Eu2O3 7.8

Green(LaPO4:Tb3+,Ce3+)

P2O5 29.8

1.1 5060La2O3 39.7

Ce2O3 17.9

Tb2O3 10.1

P2O5 25.0

Al2O3 1.3

2013/3/17 74

Blue ((Sr,Ca,Ba)10(PO4)6Cl2:Eu2+) 2.1 4270

Cl 1.1

CaO 1.8

Fe2O3 0.014

SrO 41.2

BaO 27.0

EuO 1.0

Flow sheet Design

tract

ion

tract

ion

Mixture of fluorescent powders(red, green and blue)

Interface of two phases DMF phase

Mixed solvent:Non-polar (n-heptane) and polar (DMF)

Surfactant (DAA)

Shake and rest

Firs

t ext

Firs

t ext

First product (green)

Washing by ethanol

Drying

two phases p

Drying

Surfactant

Filtering

Mixed solvent:Non-polar (n-heptane) and polar (DMF)

The remaining component of mixture (blue and red powders)

Filtering

nn

75Third product (red)

Drying Drying

Shake and rest

Second product (blue)

Surfactant(sodium 1-octansulfonate)

Filtering Filtering

DMF phase

Seco

nd e

xtra

ctio

nSe

cond

ext

ract

ion

Interface of two phases

First product (Green)

Second product (Blue)

Third product (Red) Overall

Separation Results(Hydrophobic organic liquid ‐ hydrophilic organic liquid)

efficiency(%)

Grade (%)

Recovery (%)

Grade (%)

Recovery (%)

Grade (%)

Recovery (%)

90.0 95.2 92.2 91.8 95.3 90.9 62.8

Grade > 90%R 90%

2013/3/17 76

Experimental conditions:

mixing ratio of red, green and blue was 1:1:1; DAA concentration at 1st stage:2x10‐4 mol L‐1; sodium 1‐octanesulfonate concentration at 2nd stage: 20x10‐4 molL‐1; mixing ratio of solvent DMF: n‐heptane: 1:1; solid concentration at 1st stage30 g L‐1, solid concentration at 2nd stage 15 g L‐1); process time: 4min

Recovery > 90%

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8. Optical glass recycling (Rare earth)Hydrometallurgical recovery process of rare earth from used glass

・Recovery of rare earth from waste optical glass by precipitation and solvent extraction, M. Matsuda, A. Shibayama, K. Matsushima, Y. Jiang, T. Fujita, T. Kikukawa, Shigen‐to‐Sozai, Vol.119, p.668‐674 (2003)

• Recovery of rare earth from the spent optical glass by hydrometallurgical process, Y.Jiang, A. Shibayama, K.Liu, T. Fujita, Canadian Metallurgical Quarterly, Vol.43, No.4, pp.431‐438 (2004)

Example of composition of optical glassesLa flint glass Ta flint glass Heavy Ta flint glass Heavy Nb flint glass

Rare earth

La2O3Gd2O3Y OY2O3

Compositions of two glass samples

Method to recover

A: CrystallizationCrystallization

B: Solvent extraction

Condition of Extraction,Scrubbing,Striping

ResultLa 99.95%Y 98.65%Gd 95.18%

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9.Magnet recycling (Rare earth)

Pretreatment to crush rotor using rare earth t d i t d ti f d thmagnet and introduction of used rare earth

magnet recycling

L. Wang, G. Dodbiba, K. Okaya, T. Fujita,

K. Murata, M. Kawano, Y. Fujigaki

Annual meeting of MMIJ, C3‐7, pp.119‐120 (2011)

Rotor in motor( air compressor of air‐conditioner )

Rare earth magnets included partsincluded parts

A sieve (1mm) at the bottom of explosion tankSeparated rare earth magnet powder (a)

and steel plate (b)

(a) (b)

heated at 400 for demagnetization→Sieving of 5mm

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Hydrometallurgical recycling magnet Nd‐Fe‐B magnet scrap

↓Crushing ( + Oxidizing roasting)

↓Acid leaching・・・・Selective Iron leaching

Fe2O3, Nd2O3, NdFeO3 by roasting.Nd2O3 and NdFeO3 can be leached.

↓Solid liquid separation

↓Solvent extraction of filtrate Extractant , for example, PC88A

↓ ↓Nd rich solution, Dy rich solution

↓ ↓Precipitation Precipitaion(by Oxalic acid) (by Oxalic acid) P

R OH

(by Oxalic acid) (by Oxalic acid)↓ ↓

Baking BakingNd2O3 Dy2O3

RO O

K. Koyama, AIST Japan, Technical Information Center, 2010, Oct. ,pp.78‐99

10. Automobile catalyst recycling, (Pt, Rh, Pd)

• Leaching of Pt, Pd and Rh from automotive catalyst residue in

Leaching method of platinum group metals from automobile catalyst

g yvarious chloride based solutions, A. Harjanto, Y. Cao, A. Shibayama, I. Naitoh, T. Nanami, K. Kasahara, Y. Okumura, K. Liu, T. Fujita, Materials Transactions, vol.47, No.1, pp.129‐135 (2006)

• Kinetic study on the leaching of Pt, Pd and Rh from automotive catalyst residue by using chloride solutions, Y. Cao, S. Harjanto, A. Shibayama, I. Naitoh, T. Nanami, K. Kasahara, Y. Okumura, T. Fujita, Materials Transactions, Vol.47, No.8, pp.2015‐2024 (2006)

• Recycling of precious metals from automobive catalyst residue by leaching in HCl‐H2O2 solution, Y. Cao, A. Shibayama, A. Harjanto, I. Naitoh, T. Nanami, K. Kasahara, Y. Okumura, T. Fujita, International Journal of Automotive Engineering (IJAE), Vol.38, No.3, pp.55‐61 (2007)

Leaching of PGM from automotive catalyst residue

Crushing under 500 μm

Fig. Effect of HCL concentration on the leaching of PGMs(NaClO 15wt%, NaCl1wt%, H2O2 5vol%,S/L ratio 100g/L, 293K)

Fig. Comparison of leaching solution for the leaching of PGMs. HCl‐H2O2

solution system versus aqua regia(Reaction temperature 338K,Time 3 h, S/L 500g/L)

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Consumption and products of the leaching in the various chloride based leaching solution.

11. Dentistry waste recycling (Pt, Pd)

• Selective leaching of platinum and palladium by sodium chlorade and sodium hypochlorite

Selective leaching of Pt and Pd in dentistry wastes

sodium chlorade and sodium hypochloriteK. Liu, A. Shibayama, W. T. Yen, T.Fujita, Shigen‐to‐Sozai, Vol.118, pp.745‐750 (2002)

Platinum group metals, such as palladium and platinum, are commonly used in a wide range of industrial

li ti l t l d i ki d f llapplications as an elemental and various kinds of alloys. It is difficult to recover high‐grade Pd and Pt from the primary raw materials and solid wastes. The selective leaching of Pd and Pt from a secondary resource of dentistry waste has been investigated.

AFM Pt surface by leaching

Leaching result of Pd and Pt with NaClO and NaClO3

Primary components of density waste samples

Elements Grade %Elements Grade %

Au 0.15

Pd 0.23

Pt 0.01

Cu 1.1

Zn 0.22

Fe 0.37Fe 0.37

Ni 0.04

Others 97.8

Separation flow sheet of Density waste by using different leaching solution (NaClO3 and HCl)

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12. Precious metals recovery from waste water (Au, Ag, Pt, Pd)

• Recovery of precious metal ions from wastewater generated during the refining

Hydrometallurgical and pyrometallurgical methods to recover precious metals from water

process of scrap materials, K. Takahashi, H. Umeda, A. Shibayamam G. Dodbiba, T. Fujita, Resources Processing, Vol.55, pp.169‐177 (2008)

Flow sheet for recovering

Au‐Pt‐Pd by means of precipitation

Fusion process

High frequency induction furnace

Metallic fraction and slag, recovered by fusion→Anode

Conventional copper smelting process

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Various smelters for elements to recycle of many kinds of metals

• Cu smelter:Cu、Au、Ag、Se、Te(Ni、PGM)• Pb ‐:Pb、Bi、Sn、Zn、Sb、Ag、Au

Z Cd I G G• Zn ‐:Zn、Cd、In、Ga、Ge• Ni‐:Ni、Co、PGM• Al‐:Al、Ga• Sn‐:Sn、Ta• Hg‐:Hg only• Fe‐:Fe onlyFe :Fe only• Rare‐earth‐:rare earth only• Ti‐:Ti、Zr、Hf• Mo、W‐:Mo、W

Italic:by-products

Blue letters:rare metal

Several techniques using multiphase flow to use recycling, mineral processing and environmental

cleaning technologies.

Recycling technology innovation is important.

Phase Name of separation processSolid, Air Pyrometallurgy, Electrostatic separation, Magnetic separation 、

Insulation, Dust collection, Dry crushing,Gas-solid fluidized bed, Eddy current separation, Cyclone, Color or X-ray sorter

Solid, Liquid Gravity concentration, Heavy media separation, Centrifugal separation, Magnetic separation, Filtration, Leaching, Hydrometallurgy, Adsorption, Classification, Sink and float separation using magnetic fluid, Dielectrophoretic separation

Liquid, Liquid Solvent extraction, Emulsion utilizationAir, Liquid Milli, micro and nano bubble utilizationSolid, Air, Liquid Flotation, Wet grinding, Pyrometallurgy,Wet grinding, DryingSolid, Liquid, Liquid Liquid-liquid separation

Recycle of rare metals now• Recycle rate is influenced on minerals and purpose for

utilization. Recycle depends on economics. There are following problems.

1.Secure of mineral resources・・・Investigation of non recycled wasted metals in municipal wastes.y p

2.Problem for recycling technology・・・Small amount of rare metal utilization in products. This tendency continues to reduce the production cost. Innovation of recycling technology is important.

3.Recycle cost problem・・・Difference of recycling cost between countries. How to use and recycle rare metals as additives in product.

4 I t f i f t i d d i4. Importance of inverse manufacturing and eco‐designIt is necessary to produce artifacts and materials considering how to reuse and recycling.

5.Co‐operation of recycling technology and system in east Asian area considering environment.

Write your name, number, department and University name.

Please write your consideration for recycling.