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transcript
2013/3/17
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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, Japantfujita@sys.t.u‐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.
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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)
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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
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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
2θ
IMG150 µm Ce L 50 µm Ba L50 µm
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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
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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
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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
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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)
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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
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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
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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)
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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
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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
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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.
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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%)
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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
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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%
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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.