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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 firstname.lastname@example.org‐tokyo.ac.jp
• USA: 1954 Rare metals handbook (C. A. Hampel) 1. Small amount in the crust 2. Difficulty of extraction even if large amount in the crust 2 Diffi l f i if l i h 3. Minor utilization after extraction Now 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
Ⅰ. Introduction Rare metal definition
Mineral Resources and materials
Base metals for infrastructure
is studied in our laboratory.
Metal production quantity
Many rare metals produce with base metals. Base metal production also reduces.
Price increases as the decrease of production amount. By T.Nishiyama: Rare metal resource （2009）
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
Total rare metal number in Japan is 31 as rare earth group is one.
Relationship between the energy to get 1 ton of metal copper from copper mine. = deep metal deposit and low grade
Energy/1t cu 103kw/hr
Oligopoly of rare metal
Metal Ni Cr 1st production Russia S. Africa S. Africa S Africa Congo China 米国 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
Rare metal production in２０００
by JOGMEC 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. China７, 2.South Africa, ６、3. Australia ６、4. Russia ５、5. Canada ５
Mn Co W Mo V Nb Ta
Cu grade Year
Sb Pt group Zr In
Rare earth China
Cu grade of ore、％
Existence amount of elements in the earth crust 地殻存在量の他元素との比較
Rare earth distribution in the world
Rare earth Atomic number
(Handbook of extractive metallurgy, Vol.3, Wiley‐VCH, 1997 より）
Metal extraction→Large amount of gangue・・・Necessary for environmental burden Many kinds of metals contain in many kinds of wastes・・Necessary for recycling
Waste to get 1 ton of metal (Eco rucksack) 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 metal amount in electric tools, etc., Ton in Japan Japan/world % ton 16.36 6,800
Price of rare earth elements, Oct. 2010
（by Hirokawa in ＪＯＧＭＥＣ） Dy，Tb prices are high. Nd,Sm,Pr,La,Ce,Y increased rapidly in 2010. May 2011/April 2010 Ce2O3：30 La2O3: 20 Nd metal:8 Dy metal :5 In August 2011, many rare earth elements showed th l t h d maximum price.
3 1 2
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
Rare earth minerals
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
Importance deep sea deposit （from JOGMEC）
Th の含有 Th content
Chemical composition 化学組成
( 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*
○ ○ ○ ○
Metal is still Metal is still producing in seafloor hydrothermal ore deposit Cu10‐20％、 Au10‐20g/t １０ times grade comparing in land deposit
hydrothermal ore deposit
Cobalt rich crust
Radioactive Th or U is included in some rare earth minerals .
From Y. Nishikawa
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)
Ⅱ. Possibility of Mineral separation
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 elements in the mud.
- Synchysite Xenotime YPO4
Cerite 2(Ca,Fe)O3・Ce2O3・6SiO23H2O Ion adsorption ore
Small amout of radioactive elements
Rare earth ore deposit in Vietnam
XRD pattern and SEM-EDS photos
4500 4000 3500 3000 2500 2000 1500 1000 500 0
C : Cerium flouoride carbonate / Bastnaesite B : Barium sulfate / Barite Q : Silicon oxide / Quartz
Barite BaSO4、 Quartz SiO2
Q B Q C B B
B B Q QB B Q C
Density of minerals fore density separation
Laboratory scale of centrifugal gravity concentrator (100 to 1 μm size)
4 3 2 1 0
Hematite Synchysite Monazite Bastnaesite
Zeta-potential to find the flotation possibility
-25 -20 -15 -10
Z Zeta-potential, (mV)
-5 0 5 10 15 20 25 30 35 2 3 4 5 6 7 8
Hydrophobic particles are attached with air bubble and floated Air bubble in the water
Bastnaesite Monazite Flourite Synchysite Barite pH
Denver Sub‐A type Hydrophilic particles are circulated in the water Mechanical agitation for blowing air
Electrical properties of minerals
650000000 640000000 630000000 620000000
Particle feed Corona discharge High voltage
relative dielectric constant
Electric conductivity ( Ω /m)
0.00E+000 Synchysite Monazite Bastnaesite
CaF2 Barite 0.00 Synchysite Monazite Bastnaesite CaF2 Barite
Insulator middling conductor HV Insulator Conductor
Electric conductivity Relative dielectric constant
Conductor Humidity, %
Magnetization curve of pure rare earth minerals
0.0011 0.0010 0.0009 0 0009 0.0008
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 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
0.0007 0.0006 0.0005 0.0004 0.0003 0.0002 0.0001
Applied magnetic field, H0
Paramagnetic capture area
Magnetic field H0
A B A B
Diamagnetic capture area
0.2 0.4 0.6 0.8 1.0 1.2
Matrix: expanded steel (25×20mm)
Paramagnetic capture area
Magnetic field strength, (T)
If rare earth elements are distributed to very finer size in Leaching minerals, the leaching method is utilized.
concentration of (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% )
Ⅲ. System to construct environmental friendly
material circulation society
90 80 L Leaching ratio, (%) 70 60 50 40 30 20 10
leaching ratio of Ce by (NH4)2SO4 is about 2.5 %.
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, (-) (Experimental conditions: ammonium sulfate concentration: 1%; Leaching time: 3 h; Temperature: 293 K)
La, Pr, Nd, Sm had equilibrated 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.
(Experimental conditions: Leaching time: 24 h; S/L ratio: 0.1; Temperature: 293 K)
It is necessary for energy and technological innovation to change from solid line to the broken line. b k l
Importance of rare metals for competition of industries (like Vitamin) Medical appliances (MRI etc.) Digital camera Cell phone Digital player Television Personal computer Robot Automobiles High functional materials Steel Display Electric parts Small, light, energy saving, environment Small motor Secondary battery Hard metal Catalyst for air
Ni,Cr,W, Mo, Mn,V
Ga, Ta Ni, Ti Zr, Nb In Pt, etc. Rare earth (Nd,Dy,Sm) Co etc.
Li, Co,Ni Rare earth etc.
Pt, Pd Pt Pd W, Co Mn, V Etc. Rh
Fig.6 Relationship between grade and recovery for recycling technology (from Delft Univ. of Tech)
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 demand
Cell phone Game machine (small) Game machine (large) Game machine (large) Portable CD,MD player Portable digital audio Digital camera Car navigation Video camera DVD player Audio Car audio Car audio Hair drier Electric oven Vacuum cleaner ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐ Total ‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐‐ Domestic demand (2010)
1 Liquid display recycling, (In) Economical crushing methods as pretreatment for recycle and pyrometallurgical process to recover small process to recover small amount of indium in used display panel
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 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
LCD panel is separated completely into two glass panels.
Electrical disintegration method
Without heating, the LCD panel can be rapidly separated with the electrical disintegration of separated 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 .
High voltage pulse electrode LCD of cellular phone Ground
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).
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.
Recycling of indium and tin from LCD by hydrorometallurgy process
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 pp indium content is small of less than 1000ppm order, 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 HCl solution.
Used LCD 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 control In, 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.
The other pretreatment
2. Li ion battery recycling, (Li, Co)
Effect crushing of battery, physical separation of LiCoO2 etc. and recovery of Li ion by adsorption f d i from used battery db A novel flow sheet for processing of used lithium‐ion batteries for recycling, Y.Yamajji, G.Dodbiba, S.Matsuo, K.Okaya, A.Shibayama, T.Fujita, Resources A Shib T F ji R Processing,2011, Vol.58, pp.9‐13
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.
PVC 6% Al foil 7% Carbon 10% Cu foil 10% Separator 6%
Explosion in water Cutter mill
＋１．００ｍｍ ＋１ ００
－１．００ｍｍ １ ００
Flotation Magnetic separation
LiCoO2, etc. Fe
Carbon Dissolution by acid
Steel case 28%
Eddy current separation Air table
PVC, Film Precipitation by alkaline Removal of salts, Adsorption and desorption Heating
Composition of lithium‐ion battery used in the experiment and photographs of two types (cylindrical and rectangular) of lithium –ion battery.
Non crushed materials
Flow sheet for recovering the lithium‐ion battery
Underwater explosion of lithium ion battery
LiPF6 + H2O →LiF + POF3 + 2HF CaCl2 + 2HF →CaF2 + 2HCl
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)
Crushing time, s Crushed size ←0.1m→ +4.8 -4.8+1.0 -1.0 mm
Cutter mill to crush the lithium‐ion battery decomposed by explosion and the crushed size distribution depending on the crushing time.
Rare earth roll magnetic separator
(Eriez Magnetics Japan Co.,Ltd.)
Feed zone Inlet end S slope, β ide End slope, α Discharge end Air
t n I p o l s e d i S , d n β 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
α , 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
Eddy current separator (Eriez Magnetics Japan Co.,Ltd.)
Air table as pneumatic separation
（TRIPLE/S DYNAMICS, Inc., USA)
Flotation result for ‐1mm size of crushed lithium ion battery.
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. Capacitor recycling, (Ta, Ni)
Ta and Ni recovery using heat treatment and physical separation 3.1 Ta capacitor 31T it ・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)
Feed Float Sink
(About 60% LiCoO2) 0.7 3.8
(Pulp density 10%, MIBC 0.14kg/t, kerosene 3kg/t、 500oC 2 hours heated)
World Printed Circuit Board (PCB) production
11% 9% China 35% Japan Taiwan 12% South Korea North America others 13% 21%
Total $44 billion （in 2009）
Mechanical separation method of mounted parts on printed circuit board
Inclined drum type crusher to separate mounted parts Heating with steem and hitting to seaparete mounted parts
Ref.) Fuji Chimera
Research Research Institute, Inc.
Tantalum recovery from liberated capacitor by thermal treatment
Example of tantalum capacitor
Schematic illustration of tip type tantalum capacitor
Graphite Silver Paste Molded Epoxy Resin
Lead type L dt
Anode Terminal Tantalum wire Tantalum Sintered Body Cathode Terminal
Sintered tantalum body and wire exists in the center of epoxy resin mold. The capacitor size is about several mm.
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
Heat treatment of tantalum capacitors
After heat treatment +0.5mm sieving after sintering : mainly tantalum oxides and Steel
773K 1hour in an air atmosphere ‐0.5mm sieving after sintering ：mainly mold powder SiO2 i l ld d SiO
873K 1hour In an air atmosphere
―0.5mm Tantalum oxide powders
Figure TG‐DTA thermograph of tip type tantalum capacitor in the air atmosphere.
+0.5mm lead frame, metal wire
3.2 Ni capacitor
・Nickel recovery from printed circuit board and distribution of other elements by heat treatment and g p , , , , magnetic separation, H. Ono, G. Dodbiba, J. Sadaki, 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) ・The Recovery and Life Cycle Assessment of Nickel Th R d Lif C l A t f Ni k l Particles in a Multi‐Solenoid Open‐Gradient Magnetic Separator, A. Shibayama, M. Matsuda, A. Otsuki, G. Dodbiba, T. Fujita, B. Jeyadevan, K. Takahashi, Magnteic and Electrical Separation, Vol. 11, pp. 127‐139, (2002)
Lead frame, metal wire Cu, Au, Ag, PGM
Figure Flow sheet to recover tantalum from mounted parts of PCB.
Multilayer ceramic capacitor
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) Obverse side of Printed Circuit Board with MLCC. (b) Reverse side of Printed Circuit Board with MLCC.
Schematic illustration of multi‐layer ceramic capacitor.
A: internal electrode, B: dielectric, C: external electrode
Metal distributions of carbonization treatment and magnetic separation for PCB with MLCC.
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
Magnetics at 0.1T after carbonization treatment for PCB with MLCC.
g/kg 15 23 49 686 18 26 62 650 16 23 72 611
4. Hard metal recycling (W,V)
Physical separation for recycling in hard metal production process and effective crushing and production process and effective crushing and hydrometallurgy process for recycling tungsten alloy 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 NISHIMURA and 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. The elemental composition of the steel sludge analyzed by XRF is h l l f h l l d l db 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 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
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
4.2 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
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%.
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 particles zircon 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, H. L 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.
Single sample extraction
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
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)
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)
Actual sample of alumina and zircon mixture
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. Bottom ash recycling (Ti, Cr)
Novel magnetic separation method to recover fine titanium oxide and chrome oxide particles
• Superconducting high gradient magnetic 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 Recovery of heavy metals by flotation from fh t l b fl t ti f incinerated automobile shredder residues, R. Ito, G. Dodbiba, J. Sadaki, J. W. Ahn, T. Fujita, Resources Processing, Vol.54, p.152‐157 (2007)
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)
Chemical composition of the bottom ash by 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
Magnetization curve measured by VSM and Captured 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)
α-Fe2O3 Cr2O3 FeCl3・6H2O MnSO4・5H2O
Materials containing in ash. Magnetic Magnetic susceptibility and median particle diameter
Reagent TiO2 (Rutile) CaTiO3 (Perovskite) Cr2O3 α-Fe2O3 Al2O3 SiO2 CaCO3 FeCl3・6H2O MnSO4・5H2O
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 (μm)
100% 80% 60% 40% 20%
αFe2O3 Cr2O3 TiO2 CaTiO3 Al2O3 SiO2 CaCO3 0 1 2 3 4 5 6 Magnetic flux density (T)
0.5 1 1.5 Magnetic flux density (T)
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)
90% 80% C Captured (wt%) 70% 60% 50% 40% 30% 20% 10% 0% 0 10 20 30 40 FeCl3・6H2O 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 α-Fe2O3. (fluid velocity: 10mm/sec., feed: 1g of TiO2 and 1g of α-Fe2O3 mixed with 1L of solution, magnetic flux density: 1T)
7. Fluorescent lump recycling (Rare earth)
Physical separation for rare earth elements including powder reuse
・Separation of Rare Earth Fluorescent Poewders by Two Liquid 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)
Grade（％） TiO2 48.7
(1) Blank (2) FeCl3 1g/L
Mag. Non Mag M Mag. Non Mag
αFe2O3 92.4 43.1 56.9 7.6 51.3 74.4 20.8
Recovery （％） αTiO2 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
Production, Consumption and Waste of Fluorescent Lamp (Recovery process of mercury and glass from fluorescent lamps) Fluorescent
Fluorescent lamps Cutting off the edge
End cap Glass tube Electron powder UV light Mercury atom Visible light Filament (Electrode)
Separation of fine particles by liquid‐liquid 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
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/μm 2.6 26
Density, ρF /kg m-3 5120
Glass Blowing Mercury
Flow sheet Design
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)
(Hydrophobic organic liquid ‐ hydrophilic organic liquid)
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
Grade > 90% Recovery > 90% R 90%
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 mol L‐1; mixing ratio of solvent DMF: n‐heptane: 1:1; solid concentration at 1st stage 30 g L‐1, solid concentration at 2nd stage 15 g L‐1); process time: 4min
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8. Optical glass recycling (Rare earth)
Hydrometallurgical recovery process of rare earth from used glass
Example of composition of optical glasses
La flint glass Ta flint glass Heavy Ta flint glass Heavy Nb flint 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)
Rare earth La2O3 Gd2O3 Y2O3
Compositions of two glass samples
Condition of Extraction, Scrubbing, Striping
Method to recover A: Crystallization B: Solvent extraction Result La 99.95% Y 98.65% Gd 95.18%
9.Magnet recycling (Rare earth)
Pretreatment to crush rotor using rare earth magnet and introduction of used rare earth t d i t d ti f d th magnet recycling
L. Wang, G. Dodbiba, K. Okaya, T. Fujita, K. Murata, M. Kawano, Y. Fujigaki
Rotor in motor （ air compressor of air‐conditioner ）
Rare earth magnets included parts included parts
Annual meeting of MMIJ, C3‐7, pp.119‐120 (2011)
A sieve (1mm) at the bottom of explosion tank
Separated rare earth magnet powder (a) and steel plate (b)
heated at 400℃ for demagnetization →Sieving of 5mm
Hydrometallurgical recycling magnet
Nd‐Fe‐B magnet scrap ↓ Crushing ( + Oxidizing roasting) Fe2O3, Nd2O3, NdFeO3 by roasting. ↓ Acid leaching・・・・Selective Iron leaching Nd2O3 and NdFeO3 can be leached. ↓ Solid liquid separation ↓ Solvent extraction of filtrate Extractant , for example, PC88A ↓ ↓ Nd rich solution, Dy rich solution R OH ↓ ↓ Precipitation Precipitaion P (by Oxalic acid) (by Oxalic acid) (by Oxalic acid) (by Oxalic acid) RO O ↓ ↓ Baking Baking Nd2O3 Dy2O3
10. Automobile catalyst recycling, (Pt, Rh, Pd)
Leaching method of platinum group metals from automobile catalyst
• Leaching of Pt, Pd and Rh from automotive catalyst residue in g y various 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)
K. Koyama, AIST Japan, Technical Information Center, 2010, Oct. ,pp.78‐99
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)
Consumption and products of the leaching in the various chloride based leaching solution.
11. Dentistry waste recycling (Pt, Pd)
Selective leaching of Pt and Pd in dentistry wastes
• Selective leaching of platinum and palladium by sodium chlorade and sodium hypochlorite sodium chlorade and sodium hypochlorite K. 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 applications as an elemental and various kinds of alloys. li ti l t l d i ki d f ll 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
Primary components of density waste samples
Elements Au Grade % Grade % 0.15 0.23 0.01 1.1 0.22 0.37 0.04 97.8
Leaching result of Pd and Pt with NaClO and NaClO3
Pd Pt Cu Zn Fe Ni Others
Separation flow sheet of Density waste by using different leaching solution (NaClO3 and HCl)
12. Precious metals recovery from waste water (Au, Ag, Pt, Pd)
Hydrometallurgical and pyrometallurgical methods to recover precious metals from water
• Recovery of precious metal ions from wastewater generated during the refining 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
Conventional copper smelting process
High frequency induction furnace
Metallic fraction and slag, recovered by fusion →Anode
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 Zn ‐：Ｚｎ、Ｃｄ Ｉ Ｇ Ｇ Ｚ Ｃｄ、Ｉｎ、Ｇａ、Ｇｅ Ni‐：Ｎｉ、Ｃｏ、PGM Ａｌ‐：Ａｌ、Ｇａ Sn‐：Ｓｎ、Ｔａ Hg‐：Ｈｇ only Fe ：Ｆｅ Fe‐：Ｆｅ only Rare‐earth‐：rare earth only Ｔｉ‐：Ｔｉ、Ｚｒ、Ｈｆ Ｍｏ、Ｗ‐：Ｍｏ、Ｗ
Recycling technology innovation is important.
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
Liquid, Liquid Air, Liquid Solid, Air, Liquid Solid, Liquid, Liquid
Blue letters：rare metal
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 y p recycled wasted metals in municipal wastes. 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. Importance of inverse manufacturing and eco‐design 4 I t fi f t i d d i It 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.
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