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How to satisfy the Rare Earths demand
Rhodia Rare Earth Systems initiatives
Alain ROLLAT
Rhodia Rare Earth Systems
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Content
1
What are Rare Earths and what are they using for?
2
World wide Rare Earths resources:
Supply and demand challenges
3
Rhodia RES initiatives to address market challenges
a
Recycling
b
Optimization of the RE usage in Phosphors
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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What are Rare Earths?
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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CHEMICAL & PHYSICAL PROPERTIES
OF RARE EARTHS
Common external orbitals
5d1 6s2 valence electrons
Chemical
properties
Internal orbital
Physical
progressival fillings 4f  0-14
properties
Nucleus
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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RE have very specific properties and cannot be replaced
Rare Earths
Properties
Application
Main LRE needs
Main HRE needs
Magnets
Cars – ElectronicsWind turbine
Nd, Pr
Dy, Tb
NiMH Batteries
Electronics – cars
La, Ce, Pr, Nd
Auto Catalysis
Cars
Ce, La, Nd
Fluid Cracking
Catalysis
Petrochemical
industry
La, Ce, Pr, Nd
Phosphors
Lighting – TV
La, Ce
Polishing Powders
Glass – Flat
screens – eChips
Ce, La, Pr
Capacitors
eCards
Nd
NMR shift
MRI
Gd
Neutron absorption
Nuclear power
Gd
Eu, Tb, Y
Gd, Dy, Ho, Y
Light RE represent main volumes, but some key applications need heavy RE
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Rencontres de l’Usine Nouvelle – Alain Rollat - Rhodia 11 Octobre 2011
Content
1
What are Rare Earths and what are they using for?
2
World wide Rare Earths resources:
Supply and demand challenges
3
Rhodia RES initiatives to address market challenges
a
Recycling
b
Optimization of the RE usage in Phosphors
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Supply/production balance (2014 forescat)
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Indeed, there are quite large and well distributed
reserves, …
Greenland
Canada
5 to 35M tons
CIS
5M tons
19to 38M tons
China
55M tons
USA
13M tons
Vietnam
India
Africa (South
Brazil
>1M tons
Africa, Malawi,
Gabon...)
#5M tons
Reserves are at least 110 M t REO when the ww
consumption is expected to be 150 kT REO in 2016
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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3M
tons
2 to 3M tons
Australia
4M tons
… but WW production has been progressively concentrated
in China.
CIS
1 to 2%
China
>95%
India
1 to 2%
No problem of ressources, but a real problem of supply
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Rare Earths mines in China
Bastnasite
BayanObo
In.Mongolia
BEIJING
BaoTou
Yingkou
Qingdao
Wuxi
LiYang
Bastnasite
Mianing
Sichuan
SHANGHAI
XiChang
GuangZhou
Ionic clays
XW,XF,LN
JiangXi, FJ, GD,
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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13th 2011
Rare Earths – Needs ressources and processing – Alain Rollat - Rhodia June
This situation aroused a lot of mining projects outside of
China
Strange Lake
Tanbreez
Misery Lake
Nechalacho
Kipawa
Kvanefjeld
Hoidas Lake
Lovozero
Norra Karr
Bokan Mountain
Aktau
Bear Lodge
Kutessay
Mountain Pass
Orissa
Mabounie
Pitinga
DongPao
Nam Xe
Kagankunde
Lofdal
Tantalus
Nolans
Zandkopsdrift
Steenkampskraal
Some of the more than 300 RE mining projects…
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Dubbo
Mount Weld
3 new mines will be in production in 2012
Mountain Pass
Step 1: 20000t
Step 2: 40000t
Orissa
#5000t
Mount Weld
Step1: 11000t
Step2: 22000t
In 2012: 35000t REO available outside of China
In 2013: #70000t REO available outside of China
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But all the mining projects are not equivalent from a
composition and mineralogy point of view
• Light RE (La, Ce, Pr, Nd) and heavy RE (Sm -> Lu +Y) are included in
different minerals and deposits
• LRE deposits are based on well known and already processed at
industrial scale minerals (Monazite, Bastnasite)
• New HRE deposits are mainly based on minerals which have never been
processed (Pyrochlore, Eudialyte, Catapleite, Fergusonite…)
Formulae of major minerals containing rare earths
Rare earth
Bastnaesite
Formula
CeFCO3
Type
Fluorocarbonate
Monazite
(Ce,Y)PO4
Phosphate
65
Apatite
(Ca,Ce)5{(P,Si)O4}3 (O,F)
Phosphate
12
Loparite
(Na,Ca,Y,Ce)(Nb,Ta,Ti)2O6
Oxide
32
Ionic Clays, Laterite
(Al,Si)Ox,RE
Alumino Silicate
0.2
Pyrochlore
(Na,Ca,Ce)2Nb2O6F
Oxide
6
Fergusonite
(Y,Er,U,Th)(Nb,Ta,Ti)O4
Oxide
46
Samarskite
(Y,Ce,U,Ca)(Nb,Ta,Ti)2O6
Oxide
22
Euxenite
(Y,Ca,Ce,U)(Nb,Ta,Ti)2O6
Oxide
30
Churchite
YPO4,2H2O
Phosphate
44
Eudialyte
Na15Ca6(Fe,Mn)3Zr3(Si,Nb)Si25O73(OH,Cl,H2O)5 Silicate
10
Xenotime
YPO4
Phosphate
62
Catapleiite
(Na2,Ca)ZrSi3O9,2H2O
Silicate
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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REO max (%)
75
Currently
used RE raw
materials
New type of
RE raw
materials
which must
be used in
the future
The 3 very advanced projects are all based on LRE
minerals
Monazite
Bastnasite
Monazite
100.00
90.00
80.00
70.00
60.00
HRE + Y
50.00
LRE
40.00
30.00
20.00
10.00
0.00
Mount Weld
Mountain Pass
Orissa
These 3 projects will not deliver significant quantity of HRE
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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All the HRE projects will take more time to start up
• Current HRE deposits in China are very specific:
• REE are ion adsorbed on clays : Treatment is an easy process (ion exchange by heap
lixiviation)
• Main of the new HRE deposits are more difficult to work than ionic clays currently
worked in China
• Polymetallic deposits requiring to valorize several elements (RE / Nb, Ta / Zr / U)
• Minerals requiring development of new processes (ex: Eudialyte, Noujaite…)
• Beneficiation seems very difficult to acheive (more complex mineralization). Main of the
new HRE projects are based on concentrates containing less than 5% REO
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Content
1
World wide Rare Earths resources:
Supply and demand challenges
2
Rhodia RES initiatives to address market challenges
a
Recycling
b
Optimization of the RE usage in Phosphors
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Rhodia has more than 50 years experience in RE processing and
refining and more than 30 years experience in Heavy RE refining
La Rochelle (France)
plant in 1948
HISTORY
1919: Georges Urbain founds the « SOCIETE DE PRODUITS CHIMIQUES DES TERRES RARES » in
Normandy, France
• More than 50-years in Rare Earths Processing and refining
• More than 25 years experience in customer oriented product improvement and development
• Established chemical and process expertise and proprietary know-how
In 2012, one plant in France, two plants in China, one in Japan, and one in North America
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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From ore to separated Rare Earths
Deposit
REO = 0.2% to 15%
Physical treatment
Ore Mining
crushing & grinding
Rhodia doesn’t have
wide expertise, but can
orientate the mining
companies to get the
best concentrate for the
downstream part
RE mineral beneficiation
(flotation, magnetic separation)
REO = 20 to 70%
Concentrated ore
Chemical treatment
Ore attack
RE concentate (SX, IEx, Chemical)
Rhodia core
competency
RE concentrate
Solvent extraction
La
Ce
Pr
Nd Sm
Eu
Gd
Tb
Dy
Ho
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Er
Tm
Yb
Lu
Y
The Rhodia way to secure HRE supply:
Diversification of raw materials sourcing including recycling
There will not be any significant Heavy rare Earth project starting before
2015
Rhodia is starting the recycling of phosphors from End of Life lamps
Heavy Rare Earths are more difficult to separate than Light Rare Earths
Rhodia decided to restart its La Rochelle HRE separation unit
•
•
•
Rhodia La Rochelle plant is the only existing facility outside of China able to separate
all RE including HRE
From 2000 and up to end of 2011, only 4 separation units (SX batteries) were running
over 18 existing units
We are restarting all these units according to new raw materials availibility
• Short term: Recycling
−
−
•
EOL lamps
RE from Magnet
restarting of 4 SX batteries (Eu, Gd, Tb & Y)
restarting of 3 SX batteries (Pr, Nd, Dy)
Medium/long term: New HRE mines outside of China
−
Progressive restarting of all the 18th SX batteries
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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May 2012
September 2012
January 2013
ColeopTerre Project
REE recycling from
End Of Life lamps
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Low Energy Lamps – How it works?
Glass
Electrode
V
Hg
Phosphor
UV excitation of Phosphors:
-Old generation:
White phosphor = Halophosphate
-New generation:
Red, Blue and Green phosphors
white light emission
Triband phosphors are all RE based
LAP :
(La,Ce,Tb)PO4
CAT :
(Ce,Tb)MgAl11019
BAM :
BaMgAl10O17:Eu2+
YOX :
Y2O3 :Eu3+
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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RE recycling from end of life lamps to close the loop
Rhodia recycling project
Rhodia project
Rare Earth
valorization
Several thousands of
Tons of powders
are landfilled each year
Rare Earth
Concentration
Rare Earth
Separation
< 200 tons of final
Solid waste
phosphate to be recycle
Rare Earth
Finishing
Recycling Companies
Valorisation
-glass
-metals
-plastics
-mercury
Eco-organisms
De-mercurising
LAP & YOx
Lamp
treatment
Consumers
Professionals
Sorting
Lamp
collection
Collectors
80 000 tons of
Lamps ww
15~20% of used lamps
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Lamp users
Several hundreds of
tons/y of HRE
RE recycling from end of life lamps: A complex process
Physical treatment
Powders from EOL lamps
Glass & mercury / Phosphors separation
Phosphors production
Glass, Hg
Concentrated Phosphors
Chemical attack and RE separations
LAP
YOx
Halophosphates removal
P2O5
RE phosphors concentrate
RE phosphors cracking
A multi steps process
( oxides, phosphates, aluminates)
RE concentrate
Lamp
Manufacturers
Solvent extraction
La
Ce
Tb
Eu
Y
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RE recycling from end of life lamps:
A process at 2 Rhodia sites
Phosphor powders
RE concentate
Phosphor
attack in Lyon
RE separation and
finishing in La Rochelle
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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RE Recycling from EOL lamps is starting last now
Lamp phosphors attack: A new unit close to Lyon started
last month
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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RE Recycling from EOL lamps is starting now
RE separation: Restarting of 4 SX batteries in La Rochelle
plant (France)
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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RE Recycling from EOL lamps is starting now
Phosphor precursors : Restarting YOx and securing LAP
production in La Rochelle plant (France)
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Content
1
World wide Rare Earths resources:
Supply and demand challenges
2
Rhodia RES initiatives to address market challenges
a
Recycling
b
Optimization of the RE usage in Phosphors
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Absorption length in a green (LAP) Phosphor grain
LAP :
(La,Ce,Tb)PO4
I/I0
1-R
1
4f-5d Ce3+
absorption
5D →7F
4
5
Tb3+
emission
3
I0
x
Ce3+→Tb3+ 2
transfer
240
290
340
390
440
Particle
Irefl
490
540
590
640
690
 (nm)
4 to 7 µm
 The green light output is a result of Cerium absorption, Cerium to Terbium transfer, and Terbium emission.
 More than 95% of incident light is absorbed in a 1 µm layer
 Significant part of Cerium and Terbium doping ions are not useful for brightness
emission
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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New design of LAP phosphor is achievable with same
quality of morphology and particle size
High Tb
Low Tb
High Tb
Particle size distribution (Laser, Linear)
9
8
Counts (a.u.)
7
6
5
4
3
2
1
0
0
2
4
6
8
10
12
Particle size (µm)
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14
16
18
20
High Terbium saving can be achieved with the new
design of phosphors
LO on powder vs commercial LAP
Light output on powder under 254 nm excitation for LAP
phosphors, versus Tb content
New
106
design
104
102
100
98
96
Standard LAP
94
92
90
88
86
84
50
60
70
80
90
100 110 120 130 140 150
Tb4O7 (g / kg phosphor)
Optimizing the use of rare earths: # 30% of Terbium can be saved
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand
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Thank you for your attention
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