Hydrometallurgy at CTH...NaI:s – manual and automated SiLi spectrometers and automated systems and...

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Chalmers University of Technology

Hydrometallurgy at CTH

Hydrometallurgy Seminar March 7th 2015


Sweden

Göteborg

• 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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Short history of Nuclear Chemistry & Industrial Materials Recycling

• 1947 • 1989– Nuclear Chemistry founded

as “Atomkommitténskärnkemilaboratorium”. Headed by Karl Erik Zimenand later Roland Lindner

• 1963– Department of Nuclear

Chemistry formed, Jan Rydberg first full professor

– Jan-Olov Liljenzin new professor

• 2001– Lembit Sihver new professor

• 2007– Industrial Materials

Recycling formed, Christian Ekb fi t fEkberg first professor

• 2012– Christian Ekberg professor in

Nuclear ChemistryJan Rydberg (1923-2015)

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Nuclear Chemistry/Industrial Materials Recycling -personnel

Seniors: 7

Ph.D. students:

15

E tiiEmeretii: 1

Other: 2


SeniorsChristian Ekberg head of unit ProfessorGunnar Skarnemark (part time, retired) ProfessorBritt-Marie Steenari ProfessorMark Foreman Assoc Prof

PhD studentsLovisa Bauhn Lic.Eng.Isabelle Dubois (with KTH) Lic.Eng.Marino Gergoric M.Sc.Toni Gutknecht M Sc

Personnel

Mark Foreman Assoc. ProfChrister Forsgren (part time, STENA) Adj. ProfessorHenrik Ramebeck (part time, FOI) Adj. ProfessorKastriot Spahiu (part time, SKB) Adj. ProfessorHenrik Glänneskog (part time, Vattenfall) DrStefan Allard radiation protection DrDan Costin (post doc) DrBurcak Ebin (post doc) DrAnna Gustafsson DrStellan Holgersson DrMartina Petranikova Assist. ProfT d R A P f

Toni Gutknecht M.Sc.Jenny Halleröd M.Sc.Marcus Hedberg Lic.Eng.Filip Holmberg M.Sc.Ivan Kajan M.Sc.Mikael Karlsson M.Sc.Sravya Kosaraju Lic.Eng.Henric Lassesson Lic.Eng.Artem Matyskin M.Sc.Aneta Sajdova M.Sc.Jinfeng Tang M.Sc.S b i Ti t Fil LiTeodora Retegan Assoc. Prof

Rickard Ylmen (post doc.) DrJan-Olov Liljenzin Prof Em

Sabrina Tietze Fil.Lic.Sandra Tostar Lic.Eng.Cristian Tunsu Lic.Eng.Michail Tyumntcev M.Sc.Jianxu Yang Lic.Eng.Aneta Sajdova M.Sc.

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Nuclear Chemistry & Industrial Materials Recycling


Competence areas

• Aqueous chemistry, thermodynamicsq y, 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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Equipment overview

Autoradiograph Alpha-t t

HPGe:s – manual and automated

NaI:s – manual and automated SiLiAutoradiograph spectrometers and automated

systemsand automated

systemsSiLi

Liquid scintillation counters

AKUFVE (Ti & PEEK)

Surface tension meter ICP-MS/OES Mixer-settlers

Gas-MS Titrators Potentiostat SEM-EDX XRD

Particle sizer UV/VIS-spectrometers TOC-analyzer BET-analyzer

Ion-Chromatograph (anion-, cation-,

organic-columns)


Mixer-settlers

A modular mixer‐settler‐system wasdeveloped and originally used for hotdeveloped and originally used for hottests of the CTH‐process forpartitioning. The volume of the mixingchamber is approximately 30 mL whilethe settler has a volume ofapproximately 100 mL. The impeller ofthe mixer is made of PVDF while therest of the mixer‐settler can be built ofe.g. PVDF or plexiglass. The level of thephase boundary surface is controlledby electronic level meters based on

conductivity measurements.

The picture shows a newly designed mixersettler

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AKUFVE

Ti-AKUFVE1. Centrifuge2. Mixing vessel3. Flow measurement4. Sampling and mixing pumps5. Heat exchanger6. pH-electrode7. Thermo element


AKUFVE

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3.5 30

0.0

0.5

1.0

1.5

2.0

2.5

3.0

‐6.0 ‐5.0 ‐4.0 ‐3.0 ‐2.0 ‐1.0 0.0

log(D

)

0

5

10

15

20

25

0.0032 0.00325 0.0033 0.00335 0.0034 0.00345 0.0035

1

log logB eta1

logB eta2

logB eta3

log ([IS A ‐]) 1/T (K ‐1)


SISAK

• The H-centrifuge has a very short hold-up time and it istherefore also used to study short-lived nuclides and thetransactinide 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 fi i d t h i ti d t i t )fission product or heavy-ion reaction product mixtures)

• Detection techniques for very short-lived nuclides

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SISAK


SISAK

• 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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Use of solvent extraction at CTH

Nuclear Chemistry

Industrial Materials Recycling

Nuclear Chemistry

Industrial Materials Research

As part of other

courses

As dedicated course

Applied Research EducationFundamental research


Education

• KBT192 – Nuclear Chemistry Iy

• KBT168 – Nuclear Chemistry II

• KBT200 – Radiopharmaceutical Chemistry

• KBT215 – Radioecology and Radioanalytical Chemistry

• KBT171 – Chemistry of Lanthanides, Actinides and Super-heavy Elements

• KBT195 – Solvent extraction

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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– NE

– POWRES

– About 80% of the course is identical (thermodynamics, extractionsystems, equipment, multistage extraction etc.)


Solvent extraction course

• NE-track • POWRES-track• NE-track– Uranium production

– Reprocessing of nuclear fuel

– Partitioning and transmutation

• POWRES-track– Leaching of metal

scrap and ashes

– Methods for production and recycling of e.g. Cu, Co Ni Zn Pt Rh– Other processes of

interest in nuclear engineering

Co, Ni, Zn, Pt, Rh, lanthanides, …

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The connection SX – Nuclear Chemistry

• Why have almost all SX chemists started as (or still are) nucleary ( )chemists?




• The first large scale application of inorganic SX was in the fieldof nuclear technology (U production, reprocessing). SX chemistry studies are also rather easy if using radioactivetracers.

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• The first large scale application of inorganic SX was in the fieldof nuclear technology (U production, reprocessing). SX chemistry studies are also rather easy if using radioactivetracers.

• Knowledge and experience from the nuclear chemistry research group is implemented in the industrial materials research group– this gives added value


Research

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Selected projects

RECYVAL NANO

SOE• recycling of Li-ion

b tt i

MAXIMA • lead-cladding-

SEARCH • lead fuel

• recycling of In and REE

batteries

LISSEN • Li-ionbattery

recycling

COLABATS • cobalt recycling

from Li-ion

EREAN • lanthanide

recycling

SACSESS • recycling of

nuclear waste

gfuel interactions interaction

SKIN • Ra/Ba solubilities

CINCH-II• EU teaching in

NC

SKB• Simfuel surfaces

TALISMAN• Int’l infrastructure

access

Pilot plant• NiMH batteries

REE recovery• Fluorescent lamp

waste

SKB• Sorption

modelling

ASGARD• nuclear fuel


Selected projects

MAXIMA • lead-cladding-

SEARCH • lead fuel

RECYVAL NANO

SOE• recycling of Li-ion

b tt ig

fuel interactions interaction

SKIN • Ra/Ba solubilities

CINCH-II• EU teaching in

NC

SKB• Simfuel surfaces

TALISMAN• Int’l infrastructure

access

• recycling of In and REE

batteries

LISSEN • Li-ionbattery

recycling

COLABATS • cobalt recycling

from Li-ion

EREAN • lanthanide

recycling

SACSESS • recycling of

nuclear waste

SKB• Sorption

modelling

ASGARD• nuclear fuel

Pilot plant• NiMH batteries

REE recovery• Fluorescent lamp

waste

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SOE (styrkeområde energi) - recycling HEV Li-ion Batteries

(Sravya Kosaraju, Christian Ekberg, Britt-Marie Steenari, Stefan Allard)


Process steps

Blackmass

Al‐ substrate

Li‐ion ba ery

Leaching black mass

Akufve Mixer se ler

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Leaching – HCl

120

20

40

60

80

100R

eco

ver

y in

lea

chat

e (%

)

Al-FB

Al-SC

Li-FB

Li-SC

Fe-FB

Fe-SC

P-FB

P-SC

00 1 2 3 4 5 6

c (M)


Solvent extraction

• Aq: Li, Mn, Ni HCl in chloride mediaq

• Org: Cyanex 272 (5%vol)/Solvent 70

Cyanex 272

60

80

100

120

%E %E, Li

%E, Mn

0

20

40

0 1 2 3 4 5 6 7

pH

%E, Ni

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Short-circuited/damaged

Sort basisState of charge

&/damage

Dismantle in Ar‐atmosphereDischarge

Dismantle in

LiFePO4

Batteries

Un-damaged

Electrolyte

Removal of Electrolyte & built-up gas

vaporizes

SeparateDismantle in fume hood

ElectrolyteRemoval

AnodeUltra‐sonicationMedium:H2O

Time1h, S/L 1:50

CathodeUltra‐sonicationMedium:H2O

Time1hS/L 1:50

Filter FilterCusubstrate

Alsubstrate

pAnodes & cathodes

Anode Cathode

Electrochemically active material:

Remnant H2O after ultra‐sonication and filtration

PvDf free carbon powder

Acidify with HCl

active material: carbon

Heat in O2 free atmcarbon 200C

Electrochemically active material: LiFePO4

SX, solvent70 (1M) Cyanex 272

Strip Organic phase

Li separation


• Colabats EU project on battery recycling (NiMH andColabats 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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(Marino Gergoric, Mikhail Tyumentsev)( g , y )

• Recycling of rare earths– RE permanent magnets

– e.g. Sm, Co, Nd

– Solvent extraction used; separation difficult due to similarities of chemical properties


EREAN

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Recovery of rare earth elements from fluorescent lamp waste

phosphor fractions

(Cristian Tunsu, Teodora Retegan)


Lamp phosphors based on REEs

Ph h t P ibl dPhosphor type Possible compounds

Red phosphor 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)MgB O

CeCe

EuEu

YY

LaLa

TbTbGdGd

(Ce,Gd,Tb)MgB5O10

Cuif et al., 2005; Ronda et al., 1998; US Department of Energy, 2009; Raposo et al., 2003

Standard lamp: 4-6 g phosphors powder (2% of the lamp’s mass).

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• Efficient leaching of Eu and Y (>95%) with

Hydrometallurgical approach: leaching + solvent extraction

• Efficient leaching of Eu and Y (>95%) with diluted mineral acids, at room temperature;

• The other four REEs (Ce, La, Tb and Gd) areharder to leach and require concentratedacids/temperature/ultrasound;

• Because of this, selective leaching is possible;possible;

• Leaching is carried out using nitric acidsolutions.


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 (slowerkinetics 15‐20 min.); selective stripping possible;

• Separation of light elements (Ce, La) from heavier ones (Tb) possible;

• Diluents tested : TetraPropyleneHydrogenated > kerosene >Diluents tested : TetraPropyleneHydrogenated > kerosene > Tertbutyl benzene > 1‐octanol;

• Scale up: mixer settlers.

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SACSESS

Grouped Actinide Extraction Process Research at Chalmers

(Emma Aneheim, Christian Ekberg, Jenny Halleröd, Elin Löfström-Engdahl)


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Transmutation


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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The research has two branches:1. Process development2. Basic Science

An example of process optimization: exchange of the diluentcyclohexanone to the diluent phenyl trifluoromethyl sulfonecyclohexanone to the diluent phenyl trifluoromethyl sulfone

An example of basic research: investigating the influence of extractantAn example of basic research: investigating the influence of extractantconcentration on the rate of americium extraction. This feature is importantfor process development as well as separation of elements.


Pilot plant – NiMH batteries

Hydrometallurgical technology for recovery of metalsHydrometallurgical 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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Current state of HEVs technology

• Road transport is responsible for 17-18% of global CO2 emissions from fossil fuel comb stioncombustion.

• NiMH battery technology is most used in HEVs technology.

• Lifetime of the battery = lifetime of the vehicle (250 000 – 320 000km).


Current state of NiMH recycling

Mechanical pre-treatment

Pyrometallurgical treatment

Hydrometallurgical treatment

REEs

slag

Umicore Rhodia

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Hydrometallurgical process developed at Chalmers

1. Dismantling of batteries

2. Leaching of electrode material with HCl

3. Solvent extraction using Cyanex 923





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NiMH battery dismantling

1.4%

0.5%

1.7%

19.8%

0.6%

1.4% Toyota Prius Battery – before dismantling Battery modules (38)

74.6%

cables and copper aluminium

modules plastic

steel printed circiut boards

other

Other components

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Equipment

L hi

- glass reactor with double wall

(with heating/cooling system)

- volume: 2 or 5L

- titration devices

Leaching

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• Extractant: Cyanex 923:

mixture of trialkyl-phosphine oxides:

R P(O) R R'P(O) RR' P(O) R' P(0)R3P(O), R2R'P(O), RR'2P(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- PVDF mixer-settlers (volume: 120,

500 ml)

- electromagnetic pumps

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organic flow

ion

Principle of counter-current flow

extraction scrubbing stripping

rege

nera

t

regeneration

Raffinate Scrubbing

liquorStripping

liquor


Thank you for your attention!

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Hydrometallurgy at CTH...NaI:s – manual and automated SiLi spectrometers and automated systems and...

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