Recycling of Secondary Rare

Earth and Precious Metals

in China

Hao Du
Institute of Process Engineering
Chinese Academy of Sciences

Outline
Rear Earth Metal Resources
Recovery of Secondary Rare Earth Metals

Recovery of Precious Metal from PCBs

Closing Remark

1. Rare Earth Metal Resources-Overview

Position of rear earth metal and
precious metal on the periodic table

La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sc, and
Ytotally 17 elements.
3

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-Vitamins for
modern industries.

Application of REMs -Lanthanum

La, Atomic number: 57

High refractive index glass, hydrogen storage materials, batteryelectrodes, camera lenses, cracking catalysts

Application of REMs - Cerium

Ce, Atomic number: 58

Glass additives, high temperature alloys, catalysts, laser materials

Application of REMs - Praseodymium

Pr, Atomic number: 59

Magnets, laser materials, carbon arc lighting, glasses additives, alloys

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Application of REMs - Neodymium

Nd, Atomic number: 60

Rare-earth magnets, laser materials, glass and ceramics

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Application of REMs Summary

Application Area

REM Used

Products

Magnetic material

Nd, Pr, Dy, Tb, Sm

Hard 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 material

Eu, Gd,Tb, Dy, La, Ce, Pr,

Gd

LCD 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

Application of REMs -Trend

Advanced Materials
Agriculture and
light industry
Glass and
ceramics
Petrochemical
industry
Metallurgical and
Mechanical industry

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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

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.
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 Canada

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Rare Earth Mineral Distribution - Global

5.48%
5.48%

22.83%
19.27%
36.52%

13.19%

China
America
Russia
Australia
Brazil
Indonesia
India
Rest

China: 36 million tons, Russia: 19 million tons, America: 13 million tons

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Rare Earth Mineral Production - Global

1.97%

1.24%

2.56%

94.23%

China
America
India
Rest

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Rare Earth Mineral Distribution - China

Largest country in terms of REMs reserves, production amount, sales

volume, and consumption amount.
Only country that can provides all category of RE products.

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RE minerals in China - Characteristics

Xenotime

Monazite

Bastnasite

Heavy REM
ores

Light REM
ores

Ion
adsorption
type

Loparite

3%
(Ce,Na,Ca)(Ti,Nb)O3

YPO4

(Ce,La)PO4

(Ce,La,Y)CO3F

3%

3%

8%
83%

RE2O3

Baotou
Shandong
Sichuan
Southern China
Rest

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 found in China.
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2. Recovery of REMs from Secondary Resources

Secondary REMs resources include:

1. RE permanent magnet materials;

2. Hydrogen storage materials

3. Catalysts

4. luminescent materials
5. Polishing powders

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Recovery of REMs from secondary resources

Recovery of REMs in Japan
Waste utilization rate during production

Secondary material recovery

and application

rate

Permanent magnets

> 80%

< 20%

Nickel-hydrogen battery

2050%Ni >5080%

< 20%

Luminescent powder

2050%

2050%

catalysts

< 20%Precious metal >80%

< 20%

Species

Recovery of REMs in China

Waste utilization rate during production

Secondary material recovery

and application

rate

Permanent magnets

> 90%

< 20%

Nickel-hydrogen battery

<20%Ni <50%

< 10%

Luminescent powder

>70%

< 10%

catalysts

< 10%Precious metal >80%

< 10%

Species

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Recovery of REMs - Permanent Magnets

Spent NdFeB
Materials

H2SO4
Acid
Treatment

H2C2O2

Sedimentation
& calcination

Solvent
Extraction
HCl

NaOH
Alkaline
Treatment

Acid
Treatment

Nd2O3, Dy2O3

RE
Hydroxides

Globally, 68 kilo tons of Nd-Fe-B permanent magnetic materials annuallyand

50 kilo tons in China. Total REMs recovery >90%.
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Recovery of REMs - Hydrogen Storage Materials

Dissemble

Leaching

Leaching Cake

Leaching liquor

Solvent
Extraction

Solvent
Extraction II

Zn, Mn, Fe

CoSO4

Ni(OH)2

Alkalization

Acidification

RECl3

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Recovery of REMs - Catalysts

Filtrate of
Molecular Sieves

Flocculants

Flocculation and
Sedimentation

S/L

HCl

Liquor

Acidification

Extraction

Striping

Strip Liquor with

Concentrated REMs

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Recovery of REMs - Luminescent Materials

Recovery of REMs from fluorescent lamp

Schematic diagram of the fluorescent lamp and

photograph of the luminescent material

Schematic diagram of SFE experimental system

Supercritical fluid extraction of rare earth elements from luminescent material in waste fluorescent lampsJ.
of Supercritical fluid, 332005

235-241

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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
Why to recycle them?
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.
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.

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Recovery of E-wastes: Existing Condition

How to recycle them?

Collect

Dissemble

Heavy Pollution !!!

Recycle

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Recovery of Precious Metal from PCB: Example

Composition and valuable elements of PCBs

/kg
6500

Value from
PCBs
/kg
1.63

Value from
PCBs
%
59.4

0.010

8000

0.8

29.2

Ag

0.1

70

0.07

Cu

16

0.8

0.13

Sn

0.01

Pb

0.3

Ni

0.05

Al

0.9

0.05

Fe

0.1

Zn

0.8

Weight Percent

Value

Au

%
0.025

Pd

Element

Total

2.74

90% of the value of the PCBs is from Au and Pd

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Recovery of Precious Metal from PCB- Methods

Thermal technologies
Pyrometallurgical method
Serious environmental pollution,
thus it was abandoned
gradually
thermolysis method
Low recovery of metals

Biological technologies
Low cost
Clean process
Low leaching rate

Mechanical methods
Simple
Little secondary pollution
Complete liberation of
metals could not be
achieves

Hydrometallurgical technologies
High recovery of metals
Large consumption of
chemical solvents
Eroding the equipment
Bright future of commercial
scale application
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Recovery of Precious Metal from PCB-Physical Separation

A

CrashingMagnetic SeparationElectrostatic Separation

Daimler Benz Ulm Research Centre (Germany) process

Crashing

Magnetic
separation

Nitrogen
freezing

Precious metal
extraction

Crashing

calcinaition

Electrostatic
separation

Metals

Plastics and
precious metal
mixture

B CrashingFluidized Bed Separation Ray Chapman (USA) process

PCBs

Course
Crashing

Fine
Crashing

Fluidized
Bed
Separation

Metal
Concentrate

Plastics

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Recovery of Precious Metal from PCB - Physical Separation

C. CrashingShaking
bedFlotation
separation process

PCBs

Course
Crashing
Fine
Crashing
Coarse
Particles

Shaking Bed
Separation

Sieving

Fine
Particles

Precious
Metal
Concentrate

Flotation
Separation
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Recovery of Precious Metal from PCB - Chemical Separation

A. Acid Leaching

Strong
acid

B. Dissolution

Recover Cu
C. Electrolysis

PCBs

precious metal
containing slag

Further
treatment

precious
metal

PCBs
Dissolution
with acid

Cl containing
solution
dissovling

liquid

Electrolysis

PCBs

Oxidant

Precious
Selective Precious
metal
precipitate Reduction Metals

various
metals

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Recovery of Precious Metal from PCB - New Technologies

Advanced dissemble technology is the key for the efficient
recycling of PCBs
Manual dissembleUtilization of pneumatic and electric tools

Automatic dissemble
SAT( Australia) Automatic scanning, double laser desoldering, and separation under vacuum. 400 kilotons of PCBs
are expected to be dissembled in Europe.
NEC (Japan)utilize infrared to heat and chop PCBs,
advanced thermo shock equipments, and automatic polishing

to remove residue solders.

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Recovery of Precious Metal from PCB - New Technologies

Waste PCBs
Medium Cycle

Separation of metals and nonmetals

by intensified chemical
swelling under extra-fields
Poly-metallic

Wastewater
Treatment

Polymer based plates

Selective metals digestion under

chemical catalysis

Base plates modification

produced flame-retardant
Polyurethane

Cu Recovery by SX

Separation of
Precious Metals

Ag Au

Pd

Cu

SnPb

Flame-retardant
Polyurethane
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Recovery of E-wastes: Comparison

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

Environmental pollutions

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

Pollution Transfer
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Recovery of E-wastes: Comparison

Resource of E-waste
No collection system

China

No stable collection source

Large trading expense
High transportation expense
Stable collection source

Advanced
countries

Low raw material costs

No trading expense
Low transportation expense

In China, less than 10% of the E-wastes are collected through

formal channels (with government licenses)

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Recovery of Precious Metal from E-waste: Solutions

Encouraging secondary resource utilization

Deposit and reimbursement

Policy
Maker

Production
Sale

Taxinformation, education
Encourage utilize green and
durable products
Establishment formal collection system

Tax exemption, loan discount, regulations,

fines, scientific enterprise management

Consumption
Collect

Recycling
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Final Exam
Write a 20 page review about all the metallurgical
treatment 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.

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