How to satisfy the Rare Earths demand Rhodia Rare Earth...
Transcript of How to satisfy the Rare Earths demand Rhodia Rare Earth...
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand1
How to satisfy the Rare Earths demand
Rhodia Rare Earth Systems initiatives
Alain ROLLATRhodia Rare Earth Systems
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand2
Content
World wide Rare Earths resources: Supply and demand challenges2
Rhodia RES initiatives to address market challenges3
Recyclinga
Optimization of the RE usage in Phosphorsb
What are Rare Earths and what are they using for?1
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand3
What are Rare Earths?
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand4
CHEMICAL & PHYSICAL PROPERTIES OF RARE EARTHS
Internal orbital Physicalprogressival fillings 4f 0-14 properties
Common external orbitals Chemical5d1 6s2 valence electrons properties
Nucleus
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand5 5 - Rencontres de l’Usine Nouvelle – Alain Rollat - Rhodia 11 Octobre 2011
RE have very specific properties and cannot be replacedRare Earths Properties Application Main LRE needs Main HRE needs
MagnetsCars – Electronics-
Wind turbine Nd, Pr Dy, Tb
NiMH Batteries Electronics – cars La, Ce, Pr, Nd
Auto Catalysis Cars Ce, La, NdFluid Cracking
CatalysisPetrochemical
industry La, Ce, Pr, Nd
Phosphors Lighting – TV La, Ce Eu, Tb, Y
Polishing PowdersGlass – Flat
screens – eChips Ce, La, Pr
Capacitors eCards Nd Gd, Dy, Ho, Y
NMR shift MRI Gd
Neutron absorption Nuclear power Gd
Light RE represent main volumes, but some key applications need heavy RE
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Content
World wide Rare Earths resources: Supply and demand challenges2
Rhodia RES initiatives to address market challenges3
Recyclinga
Optimization of the RE usage in Phosphorsb
What are Rare Earths and what are they using for?1
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand7
Supply/production balance (2014 forescat)
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand8
Indeed, there are quite large and well distributed reserves, …
Reserves are at least 110 M t REO when the ww consumption is expected to be 150 kT REO in 2016
CIS19to 38M tons
USA13M tons
Canada5M tons
Australia4M tons
India3M tons
China55M tons
Vietnam2 to 3M tons
Africa (South Africa, Malawi, Gabon...)
#5M tons
Brazil >1M tons
Greenland5 to 35M tons
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand9
… but WW production has been progressively concentrated in China.
CIS1 to 2%
India1 to 2%
China>95%
No problem of ressources, but a real problem of supply
Alain Rollat – SEII 2012/09/28 – How to satisfy the Rare Earths demand1010 - Rare Earths – Needs ressources and processing – Alain Rollat - Rhodia June
13th 2011
Rare Earths mines in China
BEIJING
Wuxi
BaoTou
Qingdao
LiYang SHANGHAI
Yingkou
BastnasiteBayanOboIn.Mongolia
BastnasiteMianingSichuan
Ionic claysXW,XF,LN
JiangXi, FJ, GD,
GuangZhou
XiChang
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This situation aroused a lot of mining projects outside of China
Nolans
Mount WeldDubboSteenkampskraal
Kagankunde
Mountain Pass
Orissa DongPao
KutessayAktau
Pitinga
KvanefjeldTanbreez
KipawaNechalachoHoidas Lake
Strange LakeMisery LakeLovozero
Zandkopsdrift
Norra Karr
Bear Lodge
Bokan Mountain
Nam Xe
Some of the more than 300 RE mining projects…
Mabounie
TantalusLofdal
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3 new mines will be in production in 2012
Mount WeldStep1: 11000tStep2: 22000t
Mountain PassStep 1: 20000tStep 2: 40000t Orissa
#5000t
In 2012: 35000t REO available outside of ChinaIn 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…)
Rare earth Formula Type REO max (%)Bastnaesite CeFCO3 Fluorocarbonate 75Monazite (Ce,Y)PO4 Phosphate 65Apatite (Ca,Ce)5{(P,Si)O4}3 (O,F) Phosphate 12Loparite (Na,Ca,Y,Ce)(Nb,Ta,Ti)2O6 Oxide 32Ionic Clays, Laterite (Al,Si)Ox,RE Alumino Silicate 0.2Pyrochlore (Na,Ca,Ce)2Nb2O6F Oxide 6Fergusonite (Y,Er,U,Th)(Nb,Ta,Ti)O4 Oxide 46Samarskite (Y,Ce,U,Ca)(Nb,Ta,Ti)2O6 Oxide 22Euxenite (Y,Ca,Ce,U)(Nb,Ta,Ti)2O6 Oxide 30Churchite YPO4,2H2O Phosphate 44Eudialyte Na15Ca6(Fe,Mn)3Zr3(Si,Nb)Si25O73(OH,Cl,H2O)5 Silicate 10Xenotime YPO4 Phosphate 62Catapleiite (Na2,Ca)ZrSi3O9,2H2O Silicate
Formulae of major minerals containing rare earths
Currently used RE raw
materials
New type of RE raw
materials which must be used in the future
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The 3 very advanced projects are all based on LRE minerals
0.00
10.00
20.00
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100.00
Mount Weld Mountain Pass Orissa
HRE + YLRE
Monazite Bastnasite Monazite
These 3 projects will not deliver significant quantity of HRE
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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
World wide Rare Earths resources: Supply and demand challenges1
Rhodia RES initiatives to address market challenges2
Recyclinga
Optimization of the RE usage in Phosphorsb
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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
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
La Rochelle (France) plant in 1948
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From ore to separated Rare EarthsDeposit
REO = 0.2% to 15%
Physical treatment
Chemical treatment
RE mineral beneficiation(flotation, magnetic separation)
REO = 20 to 70%
Ore attack
RE concentrate
Solvent extraction
La
Ore Miningcrushing & grinding
Concentrated ore
Ce Pr Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Y
RE concentate (SX, IEx, Chemical)
Rhodia doesn’t have wide expertise, but can
orientate the mining companies to get the
best concentrate for the downstream part
Rhodia core competency
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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 2015Rhodia is starting the recycling of phosphors from End of Life lamps
Heavy Rare Earths are more difficult to separate than Light Rare EarthsRhodia 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 restarting of 4 SX batteries (Eu, Gd, Tb & Y) May 2012− RE from Magnet restarting of 3 SX batteries (Pr, Nd, Dy) September 2012
• Medium/long term: New HRE mines outside of China− Progressive restarting of all the 18th SX batteries January 2013
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ColeopTerre Project
REE recycling from End Of Life lamps
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Electrode
Phosphor
Hg V
GlassLow Energy Lamps – How it works?
UV excitation of Phosphors:-Old generation: White phosphor = Halophosphate -New generation: Red, Blue and Green phosphors
white light emissionTriband phosphors are all RE basedLAP : (La,Ce,Tb)PO4CAT : (Ce,Tb)MgAl11019BAM : BaMgAl10O17:Eu2+
YOX : Y2O3 :Eu3+
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Several thousands of Tons of powders
are landfilled each year
Several hundreds oftons/y of HRE
80 000 tons ofLamps ww
15~20% of used lamps
phosphate to be recycle
< 200 tons of final Solid waste
RE recycling from end of life lamps to close the loop
Lampcollection
ConsumersProfessionals
Lamptreatment
De-mercurising
Lamp users
Collectors
Recycling Companies
Rhodia recycling project
Valorisation -glass-metals-plastics-mercury
Sorting
Rare EarthConcentration Rare Earth
Separation
Rare EarthFinishing
Rhodia projectRare Earthvalorization
Eco-organisms
LAP & YOx
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RE recycling from end of life lamps: A complex process
Lamp Manufacturers
Powders from EOL lamps
Glass & mercury / Phosphors separationGlass & mercury / Phosphors separation
LaLa EuEuTbTb YY
Physical treatment
Chemical attack and RE separationsYOxYOxLAPLAP
Concentrated PhosphorsConcentrated Phosphors
Halophosphates removalHalophosphates removal
RE phosphors concentrateRE phosphors concentrate
Solvent extractionSolvent extraction
CeCe
Glass, Hg
P2O5
RE phosphors crackingA multi steps process
( oxides, phosphates, aluminates)
RE phosphors crackingA multi steps process
( oxides, phosphates, aluminates)
RE concentrateRE concentrate
Phosphors production
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RE recycling from end of life lamps: A process at 2 Rhodia sites
RE separation and finishing in La Rochelle
Phosphor attack in Lyon
RE concentatePhosphor powders
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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
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RE Recycling from EOL lamps is starting nowRE separation: Restarting of 4 SX batteries in La Rochelle
plant (France)
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RE Recycling from EOL lamps is starting nowPhosphor precursors : Restarting YOx and securing LAP
production in La Rochelle plant (France)
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Content
World wide Rare Earths resources: Supply and demand challenges1
Rhodia RES initiatives to address market challenges2
Recyclinga
Optimization of the RE usage in Phosphorsb
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Absorption length in a green (LAP) Phosphor grain
Significant part of Cerium and Terbium doping ions are not useful for brightness emission
I0
I/I0
x
1-R
Irefl
Particle
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
4 to 7 µm
LAP : (La,Ce,Tb)PO4
240 290 340 390 440 490 540 590 640 690
(nm)
5D4→7F5 Tb3+
emission
4f-5d Ce3+
absorption
Ce3+→Tb3+
transfer
1
2
3
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New design of LAP phosphor is achievable with same quality of morphology and particle size
Low Tb
High Tb
High Tb
Particle size distribution (Laser, Linear)
0
1
2
3
4
5
6
7
8
9
0 2 4 6 8 10 12 14 16 18 20
Particle size (µm)
Cou
nts
(a.u
.)
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High Terbium saving can be achieved with the new design of phosphors
Light output on powder under 254 nm excitation for LAP phosphors, versus Tb content
8486889092949698
100102104106
50 60 70 80 90 100 110 120 130 140 150
Tb4O7 (g / kg phosphor)
LO o
n po
wde
r vs
com
mer
cial
LA
P
Standard LAP
New design
Optimizing the use of rare earths: # 30% of Terbium can be saved
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Thank you for your attention