5/22/2015
Chalmers University of Technology
Hydrometallurgy at CTH
Hydrometallurgy Seminar March 7th 2015
Chalmers University of Technology
Sweden
Göteborg
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12 campuses in the middle of Gothenburg
8 departments
41 Master’s programs all taught in English
11 800 students
1 200 PhD students
~40 % of Sweden’s graduate engineers/architects educated at
Chalmers
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5/22/2015
Chalmers University of Technology
Chalmers University of Technology
Short history of Nuclear Chemistry &
Industrial Materials Recycling
• 1947
– Nuclear Chemistry founded
as “Atomkommitténs
kärnkemilaboratorium”.
Headed by Karl Erik Zimen
and later Roland Lindner
• 1989
– Jan-Olov Liljenzin new
professor
• 2001
– Lembit Sihver new professor
• 1963
– Department of Nuclear
Chemistry formed, Jan
Rydberg first full professor
• 2007
– Industrial Materials
Recycling formed, Christian
Ekb
f
Ekberg fifirstt professor
• 2012
Jan Rydberg
(1923-2015)
– Christian Ekberg professor in
Nuclear Chemistry
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Chalmers University of Technology
Nuclear Chemistry/Industrial Materials Recycling personnel
Seniors:
7
Ph.D.
students:
15
Emeretii:
E
tii
1
Other: 2
Chalmers University of Technology
Personnel
Seniors
Christian Ekberg
Gunnar Skarnemark
Britt-Marie Steenari
Mark Foreman
Christer Forsgren
Henrik Ramebeck
Kastriot Spahiu
Henrik Glänneskog
Stefan Allard
Dan Costin
Burcak Ebin
Anna Gustafsson
Stellan Holgersson
Martina Petranikova
T
d
R
Teodora
Retegan
Rickard Ylmen
Jan-Olov Liljenzin
head of unit
(part time, retired)
(part time, STENA)
(part time, FOI)
(part time, SKB)
(part time, Vattenfall)
radiation protection
(post doc)
(post doc)
(post doc.)
Professor
Professor
Professor
Assoc Prof
Assoc.
Adj. Professor
Adj. Professor
Adj. Professor
Dr
Dr
Dr
Dr
Dr
Dr
Assist. Prof
A
Assoc. P
Proff
Dr
Prof Em
PhD students
Lovisa Bauhn
Isabelle Dubois (with KTH)
Marino Gergoric
Toni Gutknecht
Jenny Halleröd
Marcus Hedberg
Filip Holmberg
Ivan Kajan
Mikael Karlsson
Sravya Kosaraju
Henric Lassesson
Artem Matyskin
Aneta Sajdova
Jinfeng Tang
S
Sabrina
b i Ti
Tietze
t
Sandra Tostar
Cristian Tunsu
Michail Tyumntcev
Jianxu Yang
Aneta Sajdova
Lic.Eng.
Lic.Eng.
M.Sc.
M Sc
M.Sc.
M.Sc.
Lic.Eng.
M.Sc.
M.Sc.
M.Sc.
Lic.Eng.
Lic.Eng.
M.Sc.
M.Sc.
M.Sc.
Fil
Fil.Lic.
Li
Lic.Eng.
Lic.Eng.
M.Sc.
Lic.Eng.
M.Sc.
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5/22/2015
Chalmers University of Technology
Nuclear Chemistry & Industrial Materials
Recycling
Chalmers University of Technology
Competence areas
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Aqueous
q
chemistry,
y, thermodynamics
y
Radiation protection
Handling of substantial amounts of radiactive material
Specialised in alpha active material
Organic synthesis
Detection of ionising radiation
Radiation chemistry and radiation biology
Separation processes
Design of equipment for separation processes
Statistics and uncertainty analysis
Processes for materials recycling
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Chalmers University of Technology
Equipment overview
Autoradiograph
Alphaspectrometers
t
t
HPGe:s – manual
and automated
systems
NaI:s – manual
and automated
systems
SiLi
Liquid scintillation
counters
AKUFVE (Ti &
PEEK)
Surface tension
meter
ICP-MS/OES
Mixer-settlers
Gas-MS
Titrators
Potentiostat
SEM-EDX
XRD
Particle sizer
UV/VISspectrometers
TOC-analyzer
BET-analyzer
IonChromatograph
(anion-, cation-,
organic-columns)
Chalmers University of Technology
Mixer-settlers
A modular mixer‐settler‐system was
developed and originally used for hot
tests of the CTH‐process for
partitioning. The volume of the mixing
chamber is approximately 30 mL while
the settler has a volume of
approximately 100 mL. The impeller of
the mixer is made of PVDF while the
rest of the mixer‐settler can be built of
e.g. PVDF or plexiglass. The level of the
phase boundary surface is controlled
by electronic level meters based on
conductivity measurements.
The picture shows a newly designed mixer
settler
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5/22/2015
Chalmers University of Technology
AKUFVE
Ti-AKUFVE
1. Centrifuge
2. Mixing vessel
3. Flow measurement
4. Sampling and mixing pumps
5. Heat exchanger
6. pH-electrode
7. Thermo element
Chalmers University of Technology
AKUFVE
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Chalmers University of Technology
3.5
30
3.0
25
2.5
lo g 
lo g (D )
20
2.0
1.5
logB eta1
logB eta2
logB eta3
15
10
1.0
5
0.5
0.0
‐6.0
‐5.0
‐4.0
‐3.0
‐2.0
‐1.0
0.0
0
0.0032
log ([IS A ‐ ])
0.00325
0.0033
0.00335
0.0034
0.00345
0.0035
1/T (K ‐11 )
Chalmers University of Technology
SISAK
• The H-centrifuge has a very short hold-up time and it is
therefore also used to study short-lived nuclides and the
transactinide elements. This technique is called SISAK.
• The original H-33 centrifuge (120 mL volume/phase, 30
mL/s,phase) diminished to H-10 (12 mL/plase, 25 mL/s,phase)
to H-0.3 (0.3 mL/phase, 3 mL/s,phase)
• Selective extraction systems developed for 27 elements (from
fifission
i product
d t or h
i reaction
ti product
d t mixtures)
i t
)
heavy-ion
• Detection techniques for very short-lived nuclides
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5/22/2015
Chalmers University of Technology
SISAK
Chalmers University of Technology
SISAK
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Most short-lived studied so far: 114Ru (T½ = 0.47 s)
First identification of about 20 previously unknown nuclides
Nuclear studies of about 80 short-lived nuclides
Chemical studies of Rf, Db and Sg
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Chalmers University of Technology
Use of solvent extraction at CTH
Nuclear
Chemistry
Industrial
Materials
Research
Fundamental
research
Nuclear
Chemistry
Industrial
Materials
Recycling
Applied Research
As part of
other
courses
As dedicated
course
Education
Chalmers University of Technology
Education
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KBT192 – Nuclear Chemistryy I
KBT168 – Nuclear Chemistry II
KBT200 – Radiopharmaceutical Chemistry
KBT215 – Radioecology and Radioanalytical Chemistry
KBT171 – Chemistry of Lanthanides, Actinides and Superheavy Elements
• KBT195 – Solvent extraction
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Chalmers University of Technology
Solvent extraction course
• Lectures
• Calculation Exercises
• Laboratory project (separation of Co, Cu and Zn)
– Batch extraction
– AKUFVE extraction
– Mixer-settler
• Course divided in two tracks:
– NE
– POWRES
– About 80% of the course is identical (thermodynamics, extraction
systems, equipment, multistage extraction etc.)
Chalmers University of Technology
Solvent extraction course
• NE-track
– Uranium production
– Reprocessing of
nuclear fuel
– Partitioning and
transmutation
– Other processes of
interest in nuclear
engineering
• POWRES-track
– Leaching of metal
scrap and ashes
– Methods for
production and
recycling of e.g. Cu,
Co
Co, Ni
Ni, Zn
Zn, Pt
Pt, Rh
Rh,
lanthanides, …
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Chalmers University of Technology
The connection SX – Nuclear Chemistry
• Whyy have almost all SX chemists started as ((or still are)) nuclear
chemists?
Chalmers University of Technology
The connection SX – Nuclear Chemistry
• Whyy have almost all SX chemists started as ((or still are)) nuclear
chemists?
• The first large scale application of inorganic SX was in the field
of nuclear technology (U production, reprocessing). SX
chemistry studies are also rather easy if using radioactive
tracers.
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Chalmers University of Technology
The connection SX – Nuclear Chemistry
• Whyy have almost all SX chemists started as ((or still are)) nuclear
chemists?
• The first large scale application of inorganic SX was in the field
of nuclear technology (U production, reprocessing). SX
chemistry studies are also rather easy if using radioactive
tracers.
• Knowledge and experience from the nuclear chemistry research
group is implemented in the industrial materials research group
– this gives added value
Chalmers University of Technology
Research
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Chalmers University of Technology
Selected projects
RECYVAL
NANO
SOE
MAXIMA
SEARCH
g
• lead-claddingfuel interactions
• lead fuel
interaction
SKIN
CINCH-II
LISSEN
COLABATS
• Ra/Ba solubilities
• EU teaching in
NC
• Li-ionbattery
recycling
• cobalt recycling
from Li-ion
SKB
TALISMAN
EREAN
SACSESS
• Simfuel surfaces
• Int’l infrastructure
access
• lanthanide
recycling
• recycling of
nuclear waste
SKB
ASGARD
Pilot plant
REE recovery
• Sorption
modelling
• nuclear fuel
• NiMH batteries
• Fluorescent lamp
waste
• recycling of In and
REE
• recycling of Li-ion
batteries
b tt i
Chalmers University of Technology
Selected projects
RECYVAL
NANO
SOE
MAXIMA
SEARCH
• lead-claddingg
fuel interactions
• lead fuel
interaction
SKIN
CINCH-II
LISSEN
COLABATS
• Ra/Ba solubilities
• EU teaching in
NC
• Li-ionbattery
recycling
• cobalt recycling
from Li-ion
SKB
TALISMAN
EREAN
SACSESS
• Simfuel surfaces
• Int’l infrastructure
access
• lanthanide
recycling
• recycling of
nuclear waste
SKB
ASGARD
Pilot plant
REE recovery
• Sorption
modelling
• nuclear fuel
• NiMH batteries
• Fluorescent lamp
waste
• recycling of In and
REE
• recycling of Li-ion
b tt i
batteries
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Chalmers University of Technology
SOE (styrkeområde energi)
- recycling HEV Li-ion Batteries
(Sravya Kosaraju, Christian Ekberg, Britt-Marie Steenari, Stefan Allard)
Chalmers University of Technology
Process steps
Li‐ion ba ery
Blackmass
Al‐ substrate
Leaching black mass
Mixer se ler
Akufve
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5/22/2015
Chalmers University of Technology
Leaching – HCl
120
Recovery in leachate (%)
100
Al-FB
80
Al-SC
Li-FB
60
Li-SC
Fe-FB
40
Fe-SC
P-FB
20
P-SC
0
0
1
2
3
c (M)
4
5
6
Chalmers University of Technology
Solvent extraction
Aq:
q Li, Mn, Ni HCl in chloride media
Org: Cyanex 272 (5%vol)/Solvent 70
120
Cyanex 272
100
80
%E
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%E, Li
60
%E, Mn
%E, Ni
40
20
0
0
1
2
3
4
5
6
7
pH
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5/22/2015
Chalmers University of Technology
LiFePO4
Batteries
Un-damaged
Electrolyte
Removal
Discharge
Sort basis
State of charge &/damage
Dismantle in Dismantle
in
fume hood
Separate
p
Anodes & cathodes
Anode
Ultra‐sonication
Medium:H2O
Time1h, S/L 1:50
Electrochemically active
material:
active material: carbon
Heat in O2 free atm
carbon 200C
Cu
substrate
Filter
Anode
Shortcircuited/
damaged
Cathode
Remnant H2O after ultra‐
sonication and filtration
Acidify with HCl
Dismantle in Ar‐atmosphere
Removal of
Electrolyte & built-up gas
vaporizes
Cathode
Ultra‐sonication
Medium:H2O
Time1h
S/L 1:50
Filter
Al
substrate
Electrochemically active material: LiFePO4
SX, solvent70 (1M) Cyanex 272
Strip Organic phase
PvDf free carbon powder
Li separation
Chalmers University of Technology
• Colabats EU project on battery recycling (NiMH and
Li ion)
– Solvent Extraction from ionic liquids and related solvents
– Solvent extraction from mixtures with very high ionic strengths
– Both deep eutectics based on choline chloride (below) and true
ionic liquids are being used
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Chalmers University of Technology
((Marino Gergoric,
g
, Mikhail Tyumentsev)
y
)
• Recycling of rare earths
– RE permanent magnets
– e.g. Sm, Co, Nd
– Solvent extraction used; separation difficult due to similarities of
chemical properties
Chalmers University of Technology
EREAN
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Chalmers University of Technology
Recovery of rare earth elements from fluorescent lamp waste phosphor fractions
(Cristian Tunsu, Teodora Retegan)
Chalmers University of Technology
Lamp phosphors based on REEs
Tb
Y
Eu
La
Gd
Phosphor
Ph
h type
t
Red phosphor
Possible
P
ibl compounds
d
Y2O3∶Eu3+
Blue phosphors
BaMgAl10O17∶Eu2+
(Sr,Ca,Ba)5(PO4)3Cl:Eu2+
Green phosphors
CeMgAl10O17∶Tb3+
LaPO4:Ce3+,Tb3+
(Ce,Tb)MgAl11O19
(Ce
Gd Tb)MgB5O10
(Ce,Gd,Tb)MgB
Ce
Standard lamp: 4-6 g phosphors powder (2% of the lamp’s mass).
Cuif et al., 2005; Ronda et al., 1998; US Department of Energy, 2009; Raposo et al., 2003
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Chalmers University of Technology
Hydrometallurgical approach: leaching + solvent extraction
• Efficient
Efficient leaching of Eu
leaching of Eu and Y (>95%) with and Y (>95%) with
diluted mineral acids, at room temperature;
• The other four REEs (Ce, La, Tb and Gd) are
harder to leach and require concentrated
acids/temperature/ultrasound;
• Because of this, selective leaching is possible;
• Leaching is carried out using nitric acid
solutions.
Chalmers University of Technology
Solvent extraction – Cyanex 923
• Mix of trialkyl phosphine oxides; readily available, commercial extractant;
• Solvating extractant → no pH adjustment step → possibility of re‐
using the raffinate for subsequent leaching.
• Fast extraction of REEs (< 1 min.); co‐extraction of Fe; Hg (slower
kinetics 15‐20 min.); selective stripping possible;
• Separation of light elements (Ce, La) from heavier ones (Tb) possible;
• Diluents tested : TetraPropyleneHydrogenated
Diluents tested : TetraPropyleneHydrogenated > kerosene > > kerosene >
Tertbutyl benzene > 1‐octanol;
• Scale up: mixer settlers.
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Chalmers University of Technology
SACSESS
Grouped Actinide Extraction Process
Research at Chalmers
(Emma Aneheim, Christian Ekberg, Jenny Halleröd, Elin
Löfström-Engdahl)
Chalmers University of Technology
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Chalmers University of Technology
Transmutation
Chalmers University of Technology
Transmutation requires separation from fission, corrosion and
activation products  solvent extraction
At Chalmers we are working with a so called Grouped actinide extraction
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Chalmers University of Technology
The research has two branches:
1. Process development
2. Basic Science
An example of process optimization: exchange of the diluent
cyclohexanone to the diluent phenyl trifluoromethyl sulfone
An example of basic research: investigating the influence of extractant
concentration on the rate of americium extraction. This feature is important
for process development as well as separation of elements.
Chalmers University of Technology
Pilot plant – NiMH batteries
Hydrometallurgical technology for recovery of metals
from spent car NiMH batteries
(Martina Petranikova, Irena Herdzik-Koniecko, Kristian Larsson, Britt-Marie
Steenari, Christian Ekberg)
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Chalmers University of Technology
Current state of HEVs technology
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Road transport is responsible for 17-18% of global CO2 emissions from fossil fuel
comb stion
combustion.
NiMH battery technology is most used in HEVs technology.
Lifetime of the battery = lifetime of the vehicle (250 000 – 320 000km).
Chalmers University of Technology
Current state of NiMH recycling
Mechanical pre-treatment
Pyrometallurgical
treatment
Hydrometallurgical
treatment
REEs
Umicore
Rhodia
slag
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Chalmers University of Technology
Hydrometallurgical process developed at Chalmers
1. Dismantling of batteries
2. Leaching of electrode
material with HCl
3. Solvent extraction
using Cyanex 923
Chalmers University of Technology
1. Dismantling of batteries
2. Leaching of electrode
material with HCl
3. Solvent extraction
using Cyanex 923
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Chalmers University of Technology
Chalmers University of Technology
NiMH battery dismantling
Toyota Prius Battery – before dismantling
Battery modules
(38)
1.4%
1.4%
0.6%
0.5%
19.8%
1.7%
74.6%
Other components
cables and copper
aluminium
modules
plastic
steel
printed circiut boards
other
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Chalmers University of Technology
1. Dismantling of batteries
2. Leaching of electrode
material with HCl
3. Solvent extraction
using Cyanex 923
Chalmers University of Technology
Equipment
L
Leaching
hi
-
glass reactor with double wall
(with heating/cooling system)
-
volume: 2 or 5L
-
titration devices
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Chalmers University of Technology
1. Dismantling of batteries
2. Leaching of electrode
material with HCl
3. Solvent extraction
using Cyanex 923
Chalmers University of Technology
•
Extractant: Cyanex 923:
mixture of trialkyl-phosphine oxides:
R3P(O),
P(O) R2R'P(O),
R'P(O) RR'2P(O),
P(O) R'3P(0)
R = [CH3(CH2)7] - normal octyl,
R'= [CH3(CH2)7] - normal hexyl
•
Solvent: kerosene (Solvent 70)
•
Equipment:
-
PVDF mixer-settlers (volume: 120
120,
-
electromagnetic pumps
500 ml)
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Chalmers University of Technology
Principle of counter-current flow
extraction
Raffinate
scrubbing
Scrubbing
liquor
stripping
regeneration
organic flow
regeneration
Stripping
liquor
Chalmers University of Technology
Thank you for your attention!
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