How to satisfy the Rare Earths demand Rhodia Rare Earth ...seii.org/.../archives/2012-09-28_A_Rollat_Terres_rares.pdf · How to satisfy the Rare Earths demand Rhodia Rare Earth Systems

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


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


What are Rare Earths?


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


Content



Recyclinga


What are Rare Earths and what are they using for?1


Supply/production balance (2014 forescat)


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


… 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


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


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


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


The 3 very advanced projects are all based on LRE minerals

0.00

10.00

20.00

30.00

40.00

50.00

60.00

70.00

80.00

90.00

100.00

Mount Weld Mountain Pass Orissa

HRE + YLRE

Monazite Bastnasite Monazite

These 3 projects will not deliver significant quantity of HRE


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


Content



Recyclinga



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


8

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


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


ColeopTerre Project

REE recycling from End Of Life lamps


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+


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


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


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


RE Recycling from EOL lamps is starting last now

Lamp phosphors attack: A new unit close to Lyon started last month


RE Recycling from EOL lamps is starting nowRE separation: Restarting of 4 SX batteries in La Rochelle

plant (France)


RE Recycling from EOL lamps is starting nowPhosphor precursors : Restarting YOx and securing LAP

production in La Rochelle plant (France)


Content



Recyclinga



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


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

.)


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


Thank you for your attention

Documents

How to satisfy the Rare Earths demand Rhodia Rare Earth ...seii.org/.../archives/2012-09-28_A_Rollat_Terres_rares.pdf · How to satisfy the Rare Earths demand Rhodia Rare Earth Systems