Hydrometallurgy of the rare earth elements VIIth ...

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Oct 14, 2015 - IME Metallurgische Prozesstechnik und Metallrecycling, RWTH Aachen. Prof. Dr.-Ing. Dr. h.c. Bernd Friedrich. Hydrometallurgy of the rare earth ...
VIIth International Metallurgical Congress, Ohrid 2016

Hydrometallurgy of the rare earth elements Srecko Stopic, Bernd Friedrich

IME Metallurgische Prozesstechnik und Metallrecycling, RWTH Aachen Prof. Dr.-Ing. Dr. h.c. Bernd Friedrich

Previous work with my colleagues in the Balkan countries

BUM (1999-2001)

INTREAT (2004-2007) ENEXAL (2011-2013)

New metallurgial cooperation in the Balkan countries?

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Metallurgie

Exchange of new ideas and proposals is required! Recycling

Research fellowship/Awards 2002: Alexander von Humboldt Research Fellowship (award for academic excellence) 2005: Award by “Deutsches Kupfer-Institut in Düsseldorf” for the research in nanotechnology of copper 2011: Research Award by GDMB at 66th Meeting of the GDMB Lead Experts Committee, Pribram, Czech Republic

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Metallurgie

1989, 1990: "Panta Tutundzic" award for academic excellence at the Faculty of Technology and Metallurgy in Belgrade

Recycling

2014: Associate professor RWTH Aachen University Habilitation book in Nanotechnology

2012: Kaiserpfalzpreis, Goslar

My current activities at the RWTH Aachen University Teaching (Master Course) Unit Operations in Nonferrous Metallurgy (English) Metallurgy of rare earth elements (German language) Experimental Design, Analysis of experimental errors Hydrometallurgy of nickel (Seminar)

Research activities EURARE Projekt (2013-2017)-Rare Earths

LUFO Project (2014-2016)-Recycling of Yttrium oxide EU RED MUD Project (2015-2017)- Titanium oxide Nanotechnology (with Prof. Rudolf, Maribor)- Gold

Industrial cooperation RHI, Leoben MEAB Chemie Technik, Aachen Prizma, Kragujevac

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Metallurgie

Johnson Controls, USA Cronimet, Carlsruhe Recycling

Aachen, North Rhine Westphalia, Germany

Population: 240.000

Founded in 7th Century

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Metallurgie

Home of Charlemagne

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Located in EUREGIO Region

Carolus Therme

RWTH Aachen University founded Oct. 1870 approx. 45.000 students 10 faculties, 465 professors 118 study courses, 10 in english 54% engineering courses >12% external students 30% female students

No.1 in Germany for raised funds

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Metallurgie

No.1 in Germany for mechanical engineering, metallurgy and metals processing Recycling

Process Metallurgy and Metal Recycling Staff

Management • Prof. Dr.-Ing. Dr. h.c. B. Friedrich • Chief Engineer Dr.-Ing. R. Fuchs

Scientific staff • 5 post-docs

• 29 scientific engineers (aiming for Dr.-degree) • 28 student workers

Administrative and technical staff

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• 33 employees in accounting, secretary, library, analytical lab and mechanical/electrical/metallurgical workshops Recycling

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Metallurgie

Financing our work in 2014

Recycling

R&D strategy Recycling-Metallurgy Recycling processes and residue utilization Electric arc furnace metallurgy Emission control in metallurgy Hydrometallurgy/chemical process technology

Process Technology of Metals Vacuum- and Inertgas-Metallurgy Production of complex alloys Pyrometallurgical refining Experimental simulation of processes

Special Areas Aqueous and molten salt electrolysis

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Metallurgie

Powder Synthesis (Ultrasonic Spray Pyrolysis/Precipitation) Thermochemical modelling and process simulation

Recycling

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Metallurgie

Rare earth elements

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Motivation  Rare earth elements (REE) self sufficiency within Europe

 Eudialyte concentrate from Greenland/Sweden  Colloidal slurry formation problem in this kind of silicate ore

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Metallurgie

Polinares project, Fact sheet: rare earth oxides, released in 2012 Recycling

Leaching&precipitation Bastnaesite

Xenotime

Eudialyte

Solvent extraction&Ion exchange

Rare earth chloride or carbide

Pyrometallurgy

Monazite

Molten salt electrolysis Rare earth oxide    

Phosphor https://en.wikipedia.org/wiki/ Rare_earth_element Glass Catalysts Functional materials

Rare earth metals or alloys  Magnet  NiMH battery

http://www.elementsales.com /set-re-1.htm

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Green energy technology

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REE in a Puris CVMR News, 14th October, 2015

Hydrometallurgy

Rare earth industry

Simple Metallurgy for processing of ores Steenstrupine is a Unique and Friendly Mineral for Rare Earths

Can be concentrated 10 times

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Non Refractory Concentrate = Atmospheric Leaching

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Development of sustainable exploation sheme for REE www.eurare.eu

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Grant agreement 309373: 01.01.2013-31.12.2017 Recycling

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Metallurgie

IME/MEAB- hydrometallurgical processing of Eudialyte

Recycling

Norra Kärr concentrate Compound

SiO2

Al2O3

Fe2O3

CaO

MgO

Na2O

K2O

Cr2O3

TiO2

MnO

Zr

REE total

wt.%

53,2

8,78

15,2

2,17

0,31

12

1,47

0,02

0,21

0,68

2,91

1,36

*Analysis provided by IME laboratory

REE distribution

Grain size distribution

La 9,37%

30,0 Y 30,87%

25,0

Ce 25,04%

%

20,0 15,0 Lu 0,35%

10,0 Yb 2,74%

5,0

Tm 0,40%

Er 2,87%

Nd 12,29%

Dy 4,47%

Ho 0,93%

0,0 200-125

125-90

125-90

90-63

Grain size, µm

63-45

45-32

< 32

Pr 2,84%

Gd 3,68% Sm 3,05%

Tb 0,74% Eu 0,35%

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Metallurgie

Eudialyte Na15Ca6(Fe,Mn)3Zr3SiO(O,OH,H2O)3(Si3O9)2(Si9O27)2(OH,Cl)2 Recycling

Two strategies for the leaching of eudialyte concentrate Second Strategy

First Strategy Eudialyte concentrate

H2SO4 HCl

Pretreatment (Predissolution of eudialyte)

Filtration

Leaching

Solution enriched with REE

Solid

mixed slurry L

Residue

S

solution enriched with REE

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Metallurgie

to REE separation Recycling

NaF

Leaching

treated concentrate

HCl (H2O)

Concentrate

concentrate filtrate

Two stages HCl-strategy: Total Recovery of REE

Recovery, %

100,00

98

98 95

80,00

57 58

60,00

55

65

63

64 18

40,00

14

20,00 13

0,00 2M HCl 1:5 V25

1M HCl 1:5

V26

2M HCl 1M HCl H2O

2M HCl 1:2 V27

Types of the leaching solution

1M HCl 1:2 V28

Solutions and solid-liquid ratios

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Metallurgie

 The right acid addition method provides good filterability in the next step  No difference between light and heavy rare earths recovery  Second step (leaching process) took 1 hour Recycling

Strategy 2

One stage leaching with H2SO4 and NaF addition

Two stages treatment with HCl

Total Recovery of REE

48%

97-99%

Recovery of LRE

8%

97-99%

Recovery of HRE

70%

91%

Stages

1 stage

1st stage

2nd stage

Leaching agent

H2SO4

HCl

H2O

Additives

NaF - toxic

no

no

Temperature

70°C

100°C

30°C

Solid-liquid ratio

1:10

1:5

1:10

Reuse of acid

no

possible

Equipment

simple

complicated

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Strategy 1

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Metallurgie

Comparison of two leaching strategies

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Building of new demonstration plant for a treatment of ores leaching cascade containing four stirred glas reactors (3x10l, 1x8,5l)

Main Aim: Production of rare earth carbonate required for the solvent extraction

filter press

stirred collecting container

(250l)

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preparation units (2x100l)

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Some important points regarding to scale up (MEAB/IME) Very strict roules for the work at our demonstration plant!

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1. Safety issues (evaporation during work with 30% HCl at 50-70°C) 2. Corrosion resistance of an exhaust system 3. New reactors for the fuming process (especially mechanically anchor stirrers) 4. Transport of an eudialyte concentrate from fuming reactor to the leaching reactors 5. Neutralisation of waste water formed during the process after the filtration 6. High safety transport and an injection of hydrochloric acid to the fuming reactors

Recycling

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Our pre-testing experiment (sand, water, no heating)

Recycling

Pre-testing experiment Aimed: -Testing of mixing of 2 x 10 kg sand in fuming reactors -Flowing of suspension during cascade -Filtration in the filter press

Realized:

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-Maximal 7.5 kg sand is mixed in a fuming reactor -transport of suspension through cascade line -Filtration in the filter press

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First experiment in Demoplant with Norra Kärr concentrate 7.5 kg x 2 Eudialyt Concentrate

7.5 L x 2 30% HCl

Fuming

92.5L x 2 Tap Water

Leaching

~5kg Limestone

Neutralization

4L, 0.1% Flocculant

Filtration

~200L REE Containing PLS

29 L Tap Water

Washing and Filtration

29 L Washing solution

18.1kg Wet-residue

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9.15kg Dry-residue

Recycling

8.95kg Water Vapour

Experimental work for production of rare earth carbonate Parameters Fuming Temperature Fuming Time Addition of Eudialyte Conc. Addition of HCl (30% w/w) Leaching Temperature Leaching Time Addition of water in fuming reactor

Values 25-50 °C 60 min 7.5 kg per reactor 7.5 L per reactor 50°C 60 min ~15 L per reactor

Addition of water in leaching reactor 92.5 L per reactor Flocculant 0.1-0.2% w/w (Kemira A- 4 L 137) CaCO3 (for neutralisation) ~5 kg

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Na2CO3

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at pH= 5.7

Fuming process

Go lumpy in fuming reactor!

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Improvement is needed! Using of previously dried Norra Kärr concentrate enables a prevention of the lump formation! Recycling

Leaching after fuming process

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An additional injection of oxygen gas was used for an oxidation. Recycling

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Neutralisation/filtration/drying

Recycling

Leaching efficiency of rare earth elements and impurities pH=1.0

5,05 1,09

42,14

La

83,16

Ce

31,84

Y Nd 89,64

Gd

89,83

Zr Si 68,43

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L/Neut. Efficiency pH-1.20 pH-2.97 pH-4.02 pH-4.08

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La 81,86 82,33 80,41 77,37

Fe 88,81

Rare Earth Metals Ce Y Nd 87,72 90,94 66,51 89,30 89,87 68,84 86,68 86,57 65,23 83,49 85,63 62,49

Al

Gd 96,39 95,74 91,93 90,60

Zr 31,63 0,21 0,34 0,32

Impurities Si Fe 0,76 5,37 0,67 2,53 1,06 2,26 0,44 2,68

Al 41,60 39,13 3,68 5,61

2016

My future work

Eudialyte Concentrates Processing in Aachen 500 kg Norra Karr Mineral Concentrate @ 1.5% REO

06/2016

09/2016

250 kg TANBREEZ Mineral Concentrate 2.1% REO

Eudialyte Leaching Pilot Plant (RWTH, Germany)

Solvent Extraction Pilot Nd & Pr Plant oxides (MEAB, Germany)

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Heavy REE La-Nd & Sm-Tb Chlorides Chlordes Yttrium Chloride

Recycling

Project Meeting

2017 ERES 2014 - First European Rare Earth Resources Conference organized by EURARE 31 - Project Overview 70 papers and presentations and over 150 people attended / Proceedings are available through the EURARE web site

http://eres2017.eresconference.eu/

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ERES 2017 28-31 May 2017 in Santorini, Greece

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T H A N K The EURARE project team

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32 - Project Overview www.eurare.eu Recycling

www.eurare.brgm-rec.fr

Projects based on rare earth treatment in Aachen

Hydrometallurgy of rare earth elements EURARE, 2013-2017 Development of a sustainable exploitation scheme for Europe,s Rare Earth ore deposits

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Unit Operations • Dissolution • Filtration • Precipitation • Solvent-Extraction • Electrolysis • Reduction

Recycling

LuFo Project, 2014-2016 Recovery of Yttrium from ceramic scrap

Demonstration Plant

RED MUD, 2014-2017 Recovery of TiO2 and rare earths from red mud (La, Ce, Y, Sc)

Leaching reactor



Why is Sc important? Sc is an “exotic” REE produced in minor quantities from Uranium, TiO2 and other tailings



Sc can ‘substitute’ Y in many material applications achieving superior results:





Sc drastically improves Aluminium alloy properties increasing strength, corrosion resistance, allowing welding and others



The Al-Sc-Mg alloy powder is used in 3D printing by AIRBUS Pro ze

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 Metallurgie

In SOFC Sc-stabilized Zirconia has lowered operational temperatures leading to commercialization of the technology

Recycling

APWorks, 2 Decemeber 2015

“We did produce 122 out of the 162 parts on our M400 out of SCALMALLOY®. TheSc-SOFC partition weights a massive 45% deployed at less than current Airbus A320 NASA partition building designs”