Criteria, limits and advantages of Rare Earths recycling

Prometia 2014 December 17

RES

Content

RE processing: Advantages and drawbacks of recycling1

The RE market characteristics and the field of recycling2

Recycling of RE from End of Life productsThe example of low consumption lamps3

2

Mining & concentration

RE finishing

Mining siteOre concentrate

RE mix concentratePure RE solutionsPure RE saltsor oxides

Ore cracking

Natural Raw materials:A long value chain from the ore to the pure RE oxides:

RE Separation

3

Collecting& Sorting

RE finishing

RE mix concentratePure RE solutionsPure RE saltsor oxides

Sorted productcracking

From EOL products to the pure RE oxides: Almost the same long value chain with some specificities

RE Separation

No radioactivity

Waste management is easier than with

natural raw materials

Not all RE are present

RE separation stepis simpler than with

natural raw materials

4

RE separation: A critical step

• All the RE applications are based on pure individual RE (even if for some of them the RE are combined in the final application) RE recycling needs a technology able to separate a mixture of RE

into pure individual RE.

• Solvent Extraction is the only industrial process used nowdays for RE separation

Dissolution RE solution

RE concentrate

SX battery Pure Individual RE

5

In 2012 Solvay decided to restart most of its RE separation lines in La Rochelle (France) for recycling

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• Solvay La Rochelle plant is the only facility outside of China able to separate all RE including HRE.

• The plant has 18 SX « batteries » with a total of more than1100 mixer-settlers.

• In 2000 Rhodia/Solvay decided to move most of its separationlines to China, but kept 4 of them in operation and all the others ready to restart.

• In 2012 Solvay decided to restart most of these SX batteries for RE recycling

• This is the 1st step of restart of all the separation lines for separation of RE from natural raw materials from outside of China

Content

RE processing: Advantages and drawbacks of recycling1

The RE market characteristics and the field of recycling2

Recycling of RE from End of Life productsThe example of low consumption lamps3

7

0

20000

40000

60000

80000

100000

120000

140000

2004 2005 2006 2007 2008 2009 2010 2011

Chinaproductionexportquotasexternaldemand

Since 2005 China has decided to limit itsexports by a quotas policy …

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0.00

50.00

100.00

150.00

200.00

250.00

300.00

350.00

H1-

2009

H2-

2009

H1-

2010

H2-

2010

H1-

2011

H2-

2011

H1-

2012

H2-

2012

Jan-

2013

Feb-

2013

Mar

-201

3A

pr-2

013

May

-201

3Ju

n-20

13

La Oxide 5N

Ce Oxide

Nd Oxide

Y Oxide USD

Prices FOB USD/kg

…in 2010 a -40% cut in the quotas generated

a major crisis impactingdrastically the prices

on the market

Most of the RE recycling projects have been launched during the RE crisis

The RE recycling projects must take into account the key RE

market characteristics

What are they?

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1st characteristic: RE are everywhere

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PRESENTATION TITLE - Entity10

Verres

Céramiques

Catalysepétrolière

Médical

DVD TVOrdinateurs

Eclairage Automobile

Energie

Industrienucléaire

BatteriesPiles à

Combustible

Industries de défense

Composants électroniques

GSM Ipod MP3

Alliages spéciaux

Communications

Joaillerie

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USD/kg La Ce Pr Nd Eu Tb Dy Yoxide 6.7 6.7 113 80 1025 950 541 24

metal 12.5 13.5 116 99 1150 727 63

2nd characteristic: The RE prices are very different from one RE to another

0% 5% 10% 15% 20% 25% 30% 35% 40%

FCC Catalysts

Glass additives

Others

Ceramics

Polishing powders

AutoCat

Metal Alloys

Phosphors

Perm magnets alloys

valeur

volume

China FOB prices – September 2013

-The size of the market is different in value and volume

value

3rd characteristic:In most of the applications RE are used as mixture, but eachof them needs to have a very high purity

Rare EarthsProperties

ApplicationsMarkets Needs

MagneticsMagnets >Cars

>Electronics>Wind turbine

Nd, Pr Sm, Dy, Tb

ElectricH2 storage

NiMH Batteries>Electronics, cars La, Ce, Pr, Nd

Catalysis Cars depollution Ce, La, Nd

Catalysis Petrochemicalindustry La, Ce, Pr, Nd

Luminescencephosphors

LightingTV –Display La, Ce Eu, Tb, Y

PolishingPowders

Glass – Flat screens – eChips Ce, La, Pr

Dielectric Electronic(Capacitors) Nd Gd, Dy, Y

NMR shift MRI GdNeutron absorption Nuclear energy Gd

Heavy RE

Sm Eu Gd Tb Dy

Ho Er Tm Yb Lu YLa Ce Pr Nd

Light RE

12

The key criteria for a RE recycling project fromEOL products

• The recycling of End of Life products containing RE should be focused:• on existing recycling loops,• on the most valuable applications

• The recycling of RE needs a RE separation unit. Solvay has such a separation unit in La Rochelle

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Based on these criteria, Solvay decided in 2012 to recycle RE from 3 types of EOL products:

- Low energy consumption lamps (La, Ce,Tb, Eu, Gd & Y).- Magnets (Pr, Nd, Dy)- NiMH batteries (La, Ce, Pr, Nd) in cooperation with Umicorewho recycles the nickel.

Content

RE processing: Advantages and drawbacks of recycling1

The RE market characteristics and the field of recycling2

Recycling of RE from End of Life productsThe example of low consumption lamps3

14

Recycling of Low Energy Lamps (fluorescent tubes or compact lamps) – But where are the RE?

UV excitation of Phosphors:-Old generation: White phosphor = Halophosphate-New generation: Red, Blue and Green phosphors

white light emission

Electrode

Phosphor

Hg V

Glass

Triband phosphors are all RE basedLAP : (La,Ce,Tb)PO4CAT : (Ce,Tb)MgAl11019BAM : BaMgAl10O17:Eu2+

YOX : Y2O3 :Eu3+

15

Solvay recycling process

RE recycling from end of life lamps.. to close the loop

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Several thousands Tonsof powders

are landfilled each year Rare Earth recoverySeveral hundreds tons/y

Recycling companies

Rare EarthConcentration

Rare EarthSeparation

Rare EarthFinishing

New Green and red

phopshors

Valorization- glass- metals- plastics- mercury

Used lamps

Collectors

The target of this step is:• To liberate the RE from their minerals• To eliminate as much as possible the non RE elements and mainly

halophosphates1. Halophosphates removal(Sr,Ca)10(PO4)6(Cl,F)2:Sb3+,Mn2+ has a structiure equivalent to apatite and though issoluble in acids and in particular in HCl.

2. RE minerals cracking• YOX :Y2O3 :Eu3+ is also soluble in acids. We must play on pH to separate

halophosphates from YOx• LAP : (La,Ce,Tb)PO4 has a structure equivalent to monazite and though the NaOH

cracking is applicable • CAT : (Ce,Tb)MgAl11019 and BAM :BaMgAl10O17:Eu2+ are both aluminates and very

difficult to attack. Only 2 processes can be applicable:• H2SO4 roasting : calcination at high temperature (>500°C) of the mixture of aluminate with

concentrate H2SO4• or alcaline fusion: calcination at high temperature (>700°C) of the mixture of aluminate with

NaOH, KOH or Na2CO3

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RE recycling from end of life lamps: A complex process

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

YOxYOxLAPLAPConcentrated 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

HCl

NaOH, Na2CO3, HNO3

P2O5Al2O3

18

Phosphors productionPhosphors production

RE recycling from end of life lamps: A process at 2 Solvay sites

RE separation and finishing in La Rochelle

Phosphorattack in Lyon

RE concentate

Phosphor powders

19

Thank you for your attention