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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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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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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Johnson Controls, USA Cronimet, Carlsruhe Recycling
Aachen, North Rhine Westphalia, Germany
Population: 240.000
Founded in 7th Century
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Home of Charlemagne
Recycling
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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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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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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Powder Synthesis (Ultrasonic Spray Pyrolysis/Precipitation) Thermochemical modelling and process simulation
Recycling
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Rare earth elements
Recycling
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
Recycling
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
Recycling
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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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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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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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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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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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
Recycling
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
Recycling
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
Recycling
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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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”