Recycling of Secondary Rear Earth Metal
Transcript of Recycling of Secondary Rear Earth Metal
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Recycling of Secondary Rare
Earth and Precious Metals
in China
Hao Du
Institute of Process Engineering
Chinese Academy of Sciences
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Outline
Rear Earth Metal Resources
Recovery of Secondary Rare Earth Metals
Recovery of Precious Metal from PCBs
Closing Remark
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1. Rare Earth Metal Resources-Overview
Position of rear earth metal andprecious metal on the periodic table
La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, andYtotally 17 elements. 3
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Rare Earth Metal Resources-Application
Rare earth metals (REMs) have
unique electric, magnetic, optical,and biological properties, and
are important materials for
information, biology, and energy
technologies-Vitaminsformodern industries.
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La Atomic number:57
High refractive index glass, hydrogen storage materials, battery-
electrodes, camera lenses, cracking catalysts
Application of REMs -Lanthanum
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Ce Atomic number:58
Application of REMs - Cerium
Glass additives, high temperature alloys, catalysts, laser materials6
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Pr Atomic number:59
Magnets, laser materials, carbon arc lighting, glasses additives, alloys
Application of REMs - Praseodymium
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Nd Atomic number:60
Rare-earth magnets, laser materials, glass and ceramics
Application of REMs - Neodymium
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Application of REMs Summary
Application Area REM Used Products
Magnetic material Nd, Pr, Dy, Tb, SmHard discs, Permanent magnet,
Electronic Driving device
hydrogen storage
material
La, Ce, Pr, Nd Battery
Automobile emission
purification material Ce, La, Nd Catalysts
Petrochemical Area La, Ce, Pr, Nd Catalysts
Luminescent materialEu, Gd,Tb, Dy, La, Ce, Pr,
GdLCD Panel, Monitor, Lamps
Polishing powder Ce, La, Pr, mixed metals LCD Panel, Silicon Chips
Glass additives Ce, La, Nd, Gd, Yb, Er Optical glass, Optical Fibers
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Advanced Materials
Agriculture andlight industry
Glass and
ceramics
Petrochemical
industry
Metallurgical and
Mechanical industry
Application of REMs -Trend
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Current application:
Japan: 90% for high technology application
U.S.A: 70% for high technology application
China: In 2008, 54.8% for advanced material application.
Application of REMs - Current and Future
China, Japan, and the USA are three of major countries for REM
consumption, accounting for 85% of consumption globally
Future application:
Traditional area: Metallurgy, Catalysts, Polishing Powder,
Ceramics5.3% increase annually
High technology area: Magnetic materials, Hydrogen Storage
Materials, Optical Materials, Catalysts28% increase annually.
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Rare Earth Mineral Distribution - Global
China, Australia, Russia, America, Brazil, and Canada12
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China
AmericaRussia
Australia
Brazil
IndonesiaIndia
Rest
China: 36 million tons, Russia: 19 million tons, America: 13 million tons
22.83%
5.48%5.48%
13.19%
19.27%
36.52%
Rare Earth Mineral Distribution - Global
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ChinaAmerica
India
Rest
94.23%
2.56%
1.97%1.24%
Rare Earth Mineral Production - Global
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Rare Earth Mineral Distribution - China
Largest countryin terms of REMs reserves, production amount, sales
volume, and consumption amount.Only countrythat can provides all category of RE products.
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Baotou
Shandong
Sichuan
Southern China
Rest83%
8%
3%3%
3%
Baotou
Shandong
Sichuan
Southern China
Rest83%
8%
3%3%
3%
83%
8%
3%3%
3%
Baiyunerbo RE minerals are mainly located in northern China, total reserve
43.5 million tons, accounting for 83%percent of total reserve in China.
RE minerals in southern China is mainly ionic medium and heavy RE minerals,which is only foundin China.
RE minerals in China - Characteristics
(Ce,La)PO4
(Ce,Na,Ca)(Ti,Nb)O3
Light REM
ores
Loparite
MonaziteBastnasite
(Ce,La,Y)CO3F(Ce,La)PO4
(Ce,Na,Ca)(Ti,Nb)O3
Light REM
ores
Loparite
MonaziteBastnasite
(Ce,La,Y)CO3F
Heavy REM
ores
Ion
adsorption
type
Xenotime
YPO4
Heavy REM
ores
Ion
adsorption
type
Xenotime
YPO4
RE2O3
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2 R f REM f S d R
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2. Recovery of REMs from Secondary Resources
1. RE permanent magnet materials;
2. Hydrogen storage materials
3. Catalysts
4. luminescent materials
5. Polishing powders
Secondary REMs resources include:
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R f REM f d
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Species
Waste utilization rate during production
and application
Secondary material recovery
rate
Permanent magnets > 80% < 20%
Nickel-hydrogen battery 2050%Ni >5080% < 20%
Luminescent powder 2050% 2050%
catalysts < 20%Precious metal >80% < 20%
Recovery of REMs in Japan
Species
Waste utilization rate during production
and application
Secondary material recovery
rate
Permanent magnets > 90% < 20%
Nickel-hydrogen battery 80% < 10%
Recovery of REMs in China
Recovery of REMs from secondary resources
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R f REM P t M t
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Globally, 68 kilo tons of Nd-Fe-B permanent magnetic materials annually
and50 kilo tons in China.Total REMs recovery >90%.
Recovery of REMs -Permanent Magnets
Acid
Treatment
Alkaline
Treatment
RE
Hydroxides
Spent NdFeB
Materials
H2SO4
NaOH
Acid
Treatment
HCl
Solvent
Extraction
Sedimentation
& calcination
Nd2O3, Dy2O3
H2
C2
O2
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Recovery of REMs Hydrogen Storage Materials
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Dissemble
Leaching
Alkalization
Acidification
Leaching Cake
RECl3
Leaching liquor
Solvent
Extraction
Zn, Mn, Fe
Solvent
Extraction II
CoSO4
Ni(OH)2
Recovery of REMs -Hydrogen Storage Materials
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Reco er of REMs Catal sts
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Flocculation and
Sedimentation
S/L
Acidification
Extraction
Liquor
Strip Liquor with
Concentrated REMs
Filtrate of
Molecular Sieves
Flocculants
HCl
Striping
Recovery of REMs - Catalysts
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Recovery of REMs Luminescent Materials
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Recovery of REMs - Luminescent Materials
Recovery of REMs from fluorescent lamp
Supercritical fluid extraction of rare earth elements from luminescent material in waste fluorescent lampsJ.
of Supercritical fluid, 332005 235-241
Schematic diagram of the fluorescent lamp and
photograph of the luminescent material
Schematic diagram of SFE experimental system
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3 Recovery of Precious Metals from PCBs
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3. Recovery of Precious Metals from PCBs
Where are the E-wastes from?
Internally: 350 million TVs, 13 million refrigerators, 17 million
washing machines, 18 million PCs, 19 million cell phones
Externally: Around 4000 tons of electronic wastes are produc
ed every hour, and about 70% of them are imported into China
through different channels
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Properties of E-wastes
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Cons
Contains heavy metals including Pb, Cd, Hg, Cr (VI) .
Contains organic pollutants including PBB and PBDE.
A pollution of one Ni-H battery to the soil will last 50 years.
Properties of E-wastes
Pros
Contains precious metals including: Au, Ag, Cu, Pt.
For each tonnage of PCBs, 450 grams of Au can be recovered
For each tonnage of wasted PCs treated, 128 kg Cu, 58 kg Pb,
and 40 kg Sn can be recovered.
Why to recycle them?
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Recovery of E wastes: Existing Condition
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Recovery of E-wastes: Existing Condition
Collect Dissemble Recycle
How to recycle them?
Heavy Pollution !!!25
Recovery of Precious Metal from PCB: Example
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Recovery of Precious Metal from PCB: Example
90% of the value of the PCBs is from Au and Pd
Element
Weight Percent Value
Value from
PCBs
Value from
PCBs
/kg /kg
Au 0.025 6500 1.63 59.4
Pd 0.010 8000 0.8 29.2
Ag 0.1 70 0.07
Cu 16 0.8 0.13
Sn 3 3 0.01
Pb 2 0.3
Ni 1 5 0.05
Al 5 0.9 0.05
Fe 5 0.1
Zn 1 0.8
Total 2.74
Composition and valuable elements of PCBs
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Recovery of Precious Metal from PCB- Methods
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Thermal technologies
Pyrometallurgical method
Serious environmental pollution,
thus it was abandoned
gradually
thermolysis method
Low recovery of metals
Mechanical methods
Simple
Little secondary pollution
Complete liberation of
metals could not be
achieves
Biological technologies
Low cost
Clean process
Low leaching rate
Hydrometallurgical technologies
High recovery of metals Large consumption of
chemical solvents
Eroding the equipment
Bright future of commercial
scale application
Recovery of Precious Metal from PCB Methods
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Recovery of Precious Metal from PCB-Physical Separation
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A CrashingMagnetic SeparationElectrostatic Separation
Daimler Benz Ulm Research Centre (Germany) process
CrashingMagnetic
separationCrashing
Nitrogen
freezing
Electrostatic
separation
calcinaitionPrecious metalextraction
Plastics andprecious metal
mixture
Metals
Recovery of Precious Metal from PCB Physical Separation
B CrashingFluidized Bed Separation Ray Chapman (USA) process
Course
CrashingFine
CrashingPCBs
Fluidized
Bed
Separation
Metal
Concentrate
Plastics
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Recovery of Precious Metal from PCB - Physical Separation
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Course
Crashing
Fine
Crashing
Sieving
Flotation
Separation
Shaking Bed
Separation
PCBs
Fine
Particles
Coarse
Particles
Precious
Metal
Concentrate
y y p
C. CrashingShaking
bedFlotationseparation process
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Recovery of Precious Metal from PCB - Chemical Separation
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A Acid Leaching
PCBsStrong
acid
xidant
Precious
metal
precipitateSelective
Reduction
Precious
Metals
liquidRecover Cu
B Dissolution
C Electrolysis
y p
PCBs
Cl containingsolution
dissovlingprecious metal
containing slag
Furthertreatment
precious
metal
l
e
r
o
y
s
i
s
u
o
n
w
i
th
a
d
PCBs
various
metals
Recovery of Precious Metal from PCB - New Technologies
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Manual dissembleUtilization of pneumatic and electric tools
Automatic dissemble
SAT( Australia) Automatic scanning, double laser de-
soldering, and separation under vacuum. 400 kilotons of PCBs
are expected to be dissembled in Europe.
NEC (Japan)utilize infraredto heat and chop PCBs,
advanced thermo shockequipments, and automatic polishing
to remove residue solders.
Advanced dissemble technology is the key for the efficient
recycling of PCBs
y g
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Recovery of Precious Metal from PCB - New Technologies
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Waste PCBs
Separation of metals and nonmetalsby intensified chemical
swelling under extra-fields
Selective metals digestion underchemical catalysis
Poly-metallic
Cu Recovery by SX
Cu SnPb
Polymer based plates
Base plates modification
produced flame-retardantPolyurethane
Flame-retardant
Polyurethane
Separation of
Precious Metals
Ag Au Pd
Medium Cycle
Wastewater
Treatment
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Recovery of E-wastes: Comparison
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China
Physical separation: collect
metal concentrate, followed
by smelting and electrolysis
to recovery precious metals
Chemical leaching: dissolve
precious metals using
strong acid, followed by
reduction to recovery
precious metals
Advanced Countries
Deep bury: Leave the waste
for future treatment
Waste transfer: transfer the
pollution to other countries
Physical separation
Efficient concentrate
previous metals, avoiding
further chemical treatments
Production line transfer:produce electronic products
in other countries
y p
Environmental pollutions Pollution Transfer33
Recovery of E-wastes: Comparison
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Resource of E-waste
No collection system
No stable collection source
Large trading expense
High transportation expense
Stable collection source
Low raw material costs
No trading expense
Low transportation expense
y p
China
Advanced
countries
In China, less than 10% of the E-wastes are collected throughformal channels (with government licenses)34
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Final Exam
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Write a 20 page review about all the metallurgicaltreatment processes discussed in the class.
Inculding Fe Al Ti V Cr Au and Cu.
Review should include main resource main
treatment process and main pollution resource.
Flow sheet for each process is highly suggested.
Major reaction in the process should be clarified.
The review paper is due 15th
Nov.