Colorado School of Mines Work on Rare Earths And

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Oct 5, 2012 - Golden, Colorado. • 21 majors ... Center for Welding, Joining & Coating Research .... rare earths, and the potential shortage in supply, focus in ...
Fluorescent Lighting

Permanent Magnets

Colorado School of Mines Work on Rare Earths And Rare Earth Recycling: Challenges and Opportunities Caelen D. Anderson, MCSM PhD Student Dr. Corby G. Anderson Harrison Western Professor Kroll Institute For Extractive Metallurgy George S. Ansell Department of Metallurgical and Materials Engineering KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

PRESENTATION OUTLINE • CSM & Rare Earths Education & Research • Rare Earth Importance • Rare Earth Recycling Efforts • Rare Earth Magnet Recycling • Rare Earth Fluorescent Light Recycling • Rare Earth Battery Recycling • Rare Earth Red Mud Recycling • Rare Earth Alloy Recycling • Rare Earth Catalyst Recycling • Summary KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Colorado School of Mines • • • • • •

Est. 1874 Golden, Colorado 21 majors 193 Faculty 4300 students “…have a unique mission in energy, mineral, and materials science and engineering…” KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Department of Metallurgical & Materials Engineering - MME • 20 full time faculty members • 5 Centers and Institutes: – Kroll Institute for Extractive Metallurgy – – – –

Colorado Center for Advanced Ceramics Advanced Steel Processing & Products Res. Ctr. Center for Welding, Joining & Coating Research Advanced Coatings & Surface Engineering Res. Ctr.

• Degrees:

– PhD, MS, ME & BS in Metallurgical & Materials Engineering – PhD & MS in Materials Science – PhD & MS in Nuclear Engineering

• Students:

– Graduate level: 120 – Undergraduate level: 50 per year KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

KIEM - Kroll Institute for Extractive Metallurgy & CR 3 - Center for Resource Recovery & Recycling

Patrick R. Taylor

Gerard P. Martins

Brajendra Mishra

Corby G. Anderson

Director, KIEM G.S. Ansell Distinguished Professor of Chemical Metallurgy

Professor of Metallurgical and Materials Engineering

Director, CR3 Associate Director KIEM, Professor of Metallurgical and Materials Engineering

Harrison Western Professor of Metallurgical and Materials Engineering

Paul B. Queneau

Research Professor of Metallurgical and Materials Engineering

Research Professor of Metallurgical and Materials Engineering

EXPERTISE EXPERTISE

EXPERTISE

EXPERTISE

Process and extraction metallurgy Engineered ceramic and metal powders Electrochemical systems Corrosion Transport phenomena Reactor Design

Pyrometallurgy Electrochemistry Materials synthesis Waste Processing Recycling Molten Salt Processing Oxidation

EXPERTISE Mineral Processing Extractive Metallurgy Recycling Waste Treatment & Minimization Thermal Plasma Processing of Materials Thermal Plasma Processing of Wastes

D. Erik Spiller

Extractive Metallurgy  Engineering Design Transport Phenomena Economics Reactor Design Kinetics Mineral Processing Recycling  Waste Treatment & Minimization

EXPERTISE Mineral Processing Comminution Physical separation KineticsFlotation Leaching Liquid-solid separation Project management

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Extractive and process metallurgy Pyrometallurgy Recycling Waste treatment and minimization

MTGN 598/498 Rare Metals Extraction and Refining A Senior and Graduate Level Course Covering Mineral Processing and Extractive Metallurgy of TREO’s and Critical Metals Offered Again In Spring 2013 Colorado School of Mines Golden, Colorado

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

2.5 DAY SHORT COURSE Introduction to Rare Earth Geology, Mineralogy, Mining, Mineral Processing, Extractive Metallurgy & Economics Colorado School of Mines Golden, Colorado July 24-26, 2012

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Bastnasite

Monazite and other ores

Tailings

Phosphoric Acid

Concentrates Purified intermediates: fluorides, oxalates, carbonates, etc.

Oxides Metals & Alloys Magnets

Catalysts Electrodes Etc.

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Matt Esquibel is a MS student. His research is on the recycling of indium and rare earths from plasma display panels (flat-panel displays) with Dr. Taylor.

Caelen Anderson is a PhD student. His research involves the Surface Chemistry of Rare Earth Minerals with Dr. Taylor.

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Ben Kronholm, MS student working on TREO ion exchange with Dr. Anderson.

Daniel Haughey, MS student working on rare earth recovery from thermal spray wastes with Dr. Taylor.

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

James Wright MS student working on Rare Earth Recovery from magnets lights with Dr. Taylor.

Patrick Eduafo MS student working on Rare Earth Recovery from Fluorescent lights with Dr. Mishra. KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Hill Hall, home of KIEM Please come see what we’re up to. The Kroll Institute for Extractive Metallurgy Department of Metallurgical and Materials Engineering Colorado School of Mines www.kiem.mines.edu

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Why Are REEs Important to the U.S.? Usage of REEs by Application (%) Category

Applications

La

Permanent Magnets

Precision Guidance, RADAR, Traveling Wave Tubes, Electric Motors

Recharge-able Batteries

Electric /Hybrid Cars

50

Metal Alloys

Ferrous/ Nonferrous

Catalysts

Ce

Pr

Nd

23.4

69.4

33.4

3.3

10

26

52

5.5

16.5

Auto Emissions

5

90

2

3

Catalysts

Petroleum Refining

90

10

LEDs, Flat Panel Displays

Defense, Commercial

8.5

11

Sm

Eu

Gd

Tb

Dy

2

0.2

5

1.8

4.6

Y

3.3

4.9

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

69.2

REE USES As of 2009, the USGS reports the distribution of rare earths by end use, in decreasing order, was: - chemical catalysts 22% - metallurgical applications and alloys 21% - petroleum refining catalysts 14% - automotive catalytic converters 13% - glass polishing and ceramics 9% - rare earth phosphors for computer monitors, lighting, televisions 8% - permanent magnets 7% - electronics 3% - others 3 %

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

CURRENT REE RECYCLING • The amount of REE recycling is quite small and – consists primarily of rare earth magnet scrap – although with the sharp increase in the price of rare earths, and the potential shortage in supply, focus in this area is continually growing

• Thus, the opportunities, whether realistic or not, are extremely vast in the recycling of rare earth containing materials KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

REE MAGNET RECYCLE

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

RECYCLING OF RARE EARTH PERMANENT MAGNETS • Currently, investigations occurring in the area of recycling both: – production scrap – end-of-life materials

• The following techniques illustrate potential methods for the recovery of rare earths from secondary REE magnet sources KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

RECYCLING OF REE MAGNET SLUDGE BY SELECTIVE CHLORINATION • During the production of neodymium magnets a “magnetic sludge” byproduct is produced – Contains high amounts of Nd

• The process involves:

– placing the magnetic sludge, iron chloride, and activated carbon in graphite crucibles – heating the samples to 10731273K in an inert argon atmosphere – Collecting the condensate products at the top of the furnace in “collectors”

2 Nd(in sludge) + 3 FeCl2 ↔ 3Fe ° + 2NdCl3 ½ Nd2O3 + 1.5FeCl2 + 1.5C ↔ 1.5Fe ° + NdCl3 + 1.5CO(g)

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

RECYCLING OF REE MAGNET SLUDGE BY SELECTIVE CHLORINATION • Experimental results show that – 96% of the neodymium – 94% of the dysprosium present in the magnet sludge were extracted into the chloride phase

• This process produced a 99.2% pure mixture of neodymium and dysprosium tri-chlorides.

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Neodymium Magnets Using Molten Magnesium • A process for the direct extraction and recovery of neodymium from REE magnetic scraps using liquid magnesium as the extraction medium was investigated • Magnesium has been selected as an ideal extracting agent for this process due to – – – – –

its strong affinity for Nd ability to form a low viscosity liquid alloy low interaction with iron high vapor pressure above 800°C melting point of 649° C

• In the process, Nd magnet scraps were pulverized to sizes of a few mm and placed in an iron crucible

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Neodymium Magnets Using Molten Magnesium •

The crucible was suspended over a tantalum crucible containing Mg



The reaction vessel was then sealed shut by TIG welding Heated in an electric furnace to a temperature range of 1073-1273K



– High vapor pressure of Mg (0.59 atm at 1300K) – Low vapor pressure of Nd (10-6 at 1300K) •

The Mg in the bottom crucible evaporates and condenses in the top vessel



The Nd present in the scrap is transferred to the liquid magnesium Nd drains to the bottom vessel via slots in the bottom of the crucible.



KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Neodymium Magnets Using Molten Magnesium • Results show that metallic Nd of 98% purity was directly recovered using this process. • Additionally, the extracting agent, Mg, is able to be reused for further extraction of Nd from magnetic scrap

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Nd-Fe-B Scrap Using Acidic Dissolution and Precipitation • A process for the utilization of sulfuric acid leaching and recovery of neodymium from Nd-Fe-B magnet scrap was investigated • Results showed that extraction of Nd reached almost 100% – without the aid of heating or agitation – using a acid to scrap ratio of 2 at a molarity of 2 KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Nd-Fe-B Scrap using Acidic Dissolution and Precipitation • After dissolution, the aqueous Nd was precipitated as either – a Nd double salt prior to fluorination – or directly fluorinated using hydrofluoric acid.

• Results showed that recoveries exceeding 99% were possible using this method. – Additionally, aqueous iron present was removed via the precipitation of jarosite (KFe3+3(OH)6(SO4)2) KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Nd-Fe-B Scrap using Acidic Dissolution and Precipitation

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Nd-Fe-B/Sm-Co Alloy Magnets via Roast/Leach/Solvent Extraction • The process involves

– Oxidative roasting, – Hydrochloric acid leaching – Solvent extraction

• In this process, the Nd-Fe-B compound and SmCo alloy were ground to 100% passing 200 US mesh • Each sample was then roasted at 700°C for 8 hours prior to lixiviation KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Nd-Fe-B/Sm-Co Alloy Magnets By Way Of Roast/Leach/Solvent Extraction • Leaching results showed

– Nd and Sm dissolution increased with increasing HCl concentration and residence time – Extraction rates of 97% (Nd) and 94% (Sm) were achieved

• The pregnant solution was then sent to solvent extraction – Sm was extracted using EHPNA/TOPO extractant – Nd was extracted using EHPNA – At a pH of 2, extraction rates exceeded 95% KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Nd-Fe-B/Sm-Co Alloy Magnets by Way of Roast/Leach/Solvent Extraction

Pyro/Hydro Flowsheet for Recycle Magnet Nd/Sm Extraction KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials • A method (US patent application # 0162267) has been proposed for the recovery of rare earth elements from fluorescent lamps – terbium, europium, and yttrium

• There is approximately 10% by weight, calculated as oxide, of these elements in this material • This process involves:

– dismantling the lamps by a proprietary mechanical method – dissolution of the contained rare earth elements – precipitation of compounds suitable for further processing

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials

Method for the Recovery of REE from Fluorescent Lamps 3 KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE )PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials • Powder coating on the inner surface of fluorescent glass tubes containing: – – – – –

1.62% europium oxide 1.65% yttrium oxide 34.48% calcium sulfate 61.52% calcium orthophosphate 0.65% other impurity metals

• Are subjected to a pressure leaching/solvent extraction process for the recovery of Eu and Y • After breaking the tubes in 30% aqueous acetone, to avoid Hg emissions, the contained powder was collected KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials • This material pressure leached – – – –

8 hours temperature 125°C, 4 molar sulfuric/nitric mixture operating pressure of 5MPa

• 96.4% Y and 92.85% Eu dissolution • After leaching, the sulfate solution is converted to a thio-cyanate and is sent for solvent extraction using a tremethylbenzyl-ammonium chloride extractant KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials • The extraction step yielded 99% Y and 97% Eu extraction, at solvent:organic ratios of 2 • The loaded phase was stripped using N-tributylphosphate in 1 M nitric acid – producing nitrate salts of Eu and Y

• The europium nitrate is separated from the yttrium nitrate by dissolution in ethyl alcohol • After separation of the nitrates, both are ready for thermal hydrogen reduction and production of both europium and yttrium metal KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials

Flowsheet for the Recovery of Metallic Eu and Y. KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials • An integrated process for the recovery of mercury and Y contained within fluorescent lamp phosphor powder has been investigated • Full factorial experimental design was implemented to determine the factors which significantly influence the extraction and yttrium • Three different lixiviants – nitric – hydrochloric – sulfuric acid

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials • Due to the formation of “NOx” during the use of nitric acid, its use was discontinued. • Yttrium extraction were – 90% with hydrochloric – 85% with sulfuric acid

• In addition, sulfuric acid showed advantageous due to the reduction of soluble Ca, Pb, and Ba • Precipitation experiments performed on synthetic solutions using oxalic acid to produce yttrium oxalate, showed that a 99% pure yttrium oxalate product is possible KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of Luminescent Lighting Materials

Recovery of Y from Fluorescent Lights

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of NiMH Batteries

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Hydrometallurgical Recovery of REE From NiMH Batteries With A Sulfuric Acid Leach • A process for the hydrometallurgical recovery of rare earths from spent nickel hydride batteries has been investigated • In this process, the battery type AB5 and AB2 were cut in half longitudinally – positive and negative electrodes were mechanically crushed prior to leaching – A 2M sulfuric acid solution – S:L ratio of 1:10 – temperature of 20°C

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Hydrometallurgical Recovery of REE From NiMH Batteries With A Sulfuric Acid Leach • After lixiviation, caustic soda was added to raise the pH – Selectively precipitation the rare earth elements as “double sulfates” i.e. Nd2(SO4)3:Na2SO4

• Experimental results show that from 1 tonne of spent battery material about 37.5 kg of rare earths (as metal) can be recovered at a grade of approximately 80%

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Hydrometallurgical Recovery of REE From NiMH Batteries With A Sulfuric Acid Leach • Research performed by Rodrigues and Mansur has shown that leaching in 2M sulfuric acid is an efficient method for the dissolution of rare earth elements – independent of temperature and the addition of hydrogen peroxide as an oxidizing agent

• Experimental results show that it is possible to separate aqueous Cd, Co, and Ni from the leach liquor using solvent extraction techniques KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recovery of Ni, Co, and Rare Earths From NiMH Batteries • A process utilizing the use of sulfuric acid lixiviation and selective precipitation using sodium sulfate as the precipitant was performed • Experimental leaching results show that leaching conditions – – – –

residence time of 3.4 hours L:S ratio = 1.5 1.8M initial H2SO4 concentration leaching temperature or 80°C

• Precipitation results show that a solution pH = 2 and precipitation temperature of 60°C allow for 96.7% of the rare earth elements present to be recovered KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recovery of Rare Earths and Yttrium From Red Mud By Selective Leaching

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

ALUMINUM – A RARE METAL IN 1887

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

BAYER ALUMINA 1887 PROCESS

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

REE RECOVERY FROM RED MUD Al2O3

Composition of Bauxite and Products Bauxite, % Red Mud, % Calcined Al2O3, % 57.8 14.0 99.55

SiO2

3.5

7.6

0.05

Fe2O3

24.3

57.6

0.04

TiO2

2.5

5.7

Nil

Example Concentrations of REE in Bayer Process Red Mud, ppm. Ce Er Eu Gd Ho La Lu Nd Pr Sc Sm Tb Tm Y Yb 404.5 19.0 6.7 74.0 9.3 149.2 8.7 133.4 106.7 89.1 29.3 4.3 9.2 90.1 16.6 •

About 1 dry tonne and 5 wet tonnes of Red Mud are produced per tonne of Alumina produced



Annually 120 M tonnes of Red Mud are produced

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

REE RECOVERY FROM RED MUD • A method for the recovery of REEs and yttrium from red mud, a byproduct of the aluminum industry, has been investigated • Leaching conditions for this work were T=25°C, t =24hours, and the liquid:solid ratio =1.5 • Experimental results show that dilute (0.5M) nitric acid allowed for the highest selective recoveries of the lanthanides, especially yttrium KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

REE RECOVERY FROM RED MUD • In addition to higher yttrium recoveries, the use of nitric acid facilitates the proposed solvent extraction step better than HCl due to larger distribution coefficients obtained • Recoveries obtained were approximately – – – –

90% for Y 70% for (Dy, Er, Yb) 50% for (Nd, Sm, Eu, Gd) 30% for (La, Ce, Pr) KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

REE RECOVERY FROM RED MUD

Recovery of the Red Mud REE by Leaching With 0.5M Nitric, T=25°C, S:L =1.5 KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recovery of Rare Earths From Scrap Metal Alloys

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recovery of Rare Earths From Scrap Metal Alloys • A process for the recovery of rare earths from alloy scrap (likely Nd-Fe-B magnets) containing rare earths has been patented (US #: 5,129,945) • In this process, the rare earth containing material is leached in a sulfuric acid solution (2M) to dissolve the contained REE • After dissolution, a hydroxide such as NaOH, KOH, or NH4OH is added to precipitate – the “double salt” of the REE – alkali element (Nd2(SO4)3.Na2SO4) or an ammonium compound KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recovery of Rare Earths From Scrap Metal Alloys • After precipitation, this salt is converted to a rare earth salt amenable for use in thermite or other metallothermic reduction processes • Hydrofluoric acid may be used as the fluorinating agent to form a rare earth fluoride • Aqueous iron can be precipitated out of solution as jarosite – as well as boron via a zinc borate precipitation KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recovery of Rare Earths From Scrap Metal Alloys

Recovery of REE from REE Alloy Scraps

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts • Although catalysts make up approximately – 49% of rare earth end uses • 22% chemical catalysts • 14% petroleum refining catalysts • 13% automotive catalytic converters

– there is very little data available on the recovery of REE from any of these secondary sources

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts • Fluid Cracking Catalysts (FCC) are used in the refining operation of crude oil and is the major contributor to “value-add” in the refining process • The process enables the transformation of heavy molecules into lighter compounds that make up gasoline and other fuels such as gas, jet fuel and diesel • Rare Earths play a major role in the catalysts used in modern petroleum refineries KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts

FCC Petroleum Process Diagram KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts • Lanthanum and cerium serve to stabilize the structure and chemistry of the high surface area zeolites used as a molecular filter • Praseodymium and neodymium may also be added in smaller quantities • The FCC market is driven by oil consumption and the quality of oil being refined; heavy oils and tars require an increased amount of Rare Earths • As crude from oil sands and shales, such as those from Alberta, Canada are increasingly used, the amount of FCC used per barrel of oil will increase compared to sweet light oils

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts

Automobile Catalytic Converter KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Recycling of REE From Catalysts • Interestingly enough, the USGS reports that all Pt-Re catalysts used in the petroleum industry were recycled in 2010 • UMICORE estimates only 50% of PGM bearing automobile catalysts are recycled but none of the cerium is recovered • Thus, the ability to adequately collect REE containing catalysts exists, although the technology for an economical recovery method may not, yet • With 49% of the market share, the potential areas of research in this area are remarkably high KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

SUMMARY • Rare Earth Element Recycle is in its Infancy • There are Many Major Secondary sources for Rare Earth Recycle And Recovery • Analogous to Primary REE Production – The Application of Mineral Processing and Extractive Metallurgy are the Key Technologies for Recycled Rare Earth Beneficiation, Separation, Precipitation and Reduction KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

Metallurgical Innovation Philosophy

Thank You For This Opportunity to Present ! KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

QUESTIONS ??????????????????????????????? If you want a copy of the presentation or our TREO recycle paper please give me a business card or email me at [email protected]

KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012

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Colorado School of Mines Work on Rare Earths And Rare Earth Recycling: Challenges and Opportunities Caelen D. Anderson, MCSM PhD Student Dr. Corby G. Anderson Harrison Western Professor Kroll Institute For Extractive Metallurgy George S. Ansell Department of Metallurgical and Materials Engineering KNOWLEDGE PLATFORM ON RARE EARTH RECYCLING (RARE3)PROGRAM KICKOFF UMICORE , HOBOKEN, BELGIUM OCTOBER 5, 2012