Outline - Hydromet

21.03.2014
Solvent extraction research at UiO
- a common denominator for research related to hydrometallurgy, nuclear fuel cycle and super-heavy elements
ACS meeting, Dallas, TX
19th March 2014
Jon Petter Omtvedt
and Dag Ø. Eriksen, Grethe Wibetoe, Tor Bjørnstad, Dejene Kifle, Håvard Kristiansen
Outline
● Motivation
○ History
○ Nuclear Chemistry at UiO
○ Request from Norwegian Industry
● Status
○ On‐going research and projects
○ Pending Applications
● Future outlook
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Who are we?
● Dag Ø. Eriksen, private consultant working closely together with us and private companies
● Grethe Wibetoe, professor in Analytical Chemistry
● Tor Bjørnstad (IFE), prof. II in Nuclear Chemistry
● Jon Petter Omtvedt, professor in d
f
Nuclear Chemistry
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 3
What is Norway?
Keywords:
• lots of “nature”
• cold and remote
• extremely rich
i energy
in
resources
(hydro, oil &
gas, thorium).
Small and peaceful country to the far north.
○ Area: 385364 km2 (4.0% of US).
○ Population (2014): 5.1 mill (1.6% of US).
○ Produced 1,606 000 barrels/day crude oil in 2012 (25% of US production).
○ About half of the population lives in the south‐east, around Oslo (capital).
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Hydrometallurgy in Norway ‐ History
Former industry processes:
● MEGON: Produced 30 MEGON: Produced 30
tons/year 6N Y2O3 and 5N Sc2O3by proprietary processes. ● Norsk Hydro Fertilizer (presently Yara) produced group separated REE from the Kola apatite feed solution.
Both processes stopped due to competition from Chinese low prices.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 5
MEGON – UiO ‐ Radiochemistry
● There was a close link between radiochemistry research at the Institute for Atomic Energy (IFA, now IFE), UiO and MEGON.
● Extensive research on REE extraction/separation was carried out in labs hired at UiO.
○ Key personnel: Orvar Braaten (Elkem), Aleco
Pappas (UiO), Jorolf Alstad (UiO), Svein Erik Engdal (MEGON), Dag Ø. Eriksen (MEGON).
Pappas 1915-2010
Prof. Nucl. Chem. at UiO
J. P. Omtvedt, ACS, Dallas, 19th March 2014
MEGON was a technological success but an economical fiasco..
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Good Results – 34 years ago
J. inorg, nucl. Chem. 43, p1881, 1981
Quote from Conclusion: “We obtained a separation of (1.2±0.6)x104
between Lu and La and a mean separation factor of 3.05 between adjacent elements. To our knowledge this is the best performance accomplished by this extracting agent.”
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 7
A Detour from Hydrometallurgy..
As economical importance of REE research declined, research focus in the Nuclear
research focus in the Nuclear Chemistry Section at UiO changed toward fundamental science:
○ Chemical separation and rapid transport of short
rapid transport of short lived nuclei for nuclear spectroscopy studies.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
• 1972-1975 short-lived La, Ce
and Pr nuclei studied in Oslo
(produced with a n-generator).
• In 1975-1980
1975 1980 many successful
experiments (La, and Ce) in
Mainz. Parallel to this
chemical separation systems
for Br, I, As, Tc, Ru and Pd is
developed.
• Experiments on Tc isotopes
are started in 1979.
• 243,244Np experiments at GSI
in 1985.
• 1989-1990: 0.8-s 110Tc and
0.8-s 113Ru studied.
• In 1994 the 0.30 s nuclei
111Tc was observed with
SISAK.
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A Detour from Hydrometallurgy..
In close collaboration with researchers at Chalmers (Sweden) and Univ Mainz
(Sweden) and Univ. Mainz (Germany), a fast and continuous LLX system (“SISAK”) was developed and employed for nuclear‐
structure studies of short‐
lived nuclei.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Inlet/outlets
Separation
p
chamber
Rotating cup
Slide 9
AKUFVE and SISAK
SISAK = Short-lived Isotopes
Studied by the AKUFVEtechnique
AKUFVE is a Swedish
acronym for an apparatus for
continuous investigations of
distribution ratios in liquidli id extraction.
liquid
t ti
Reinhardt & Rydberg, JActaChemScand 23 (1969) p2773.
Persson et al. RCA48, (1989) p177.
Commercialized by Swedish company MEAB AB.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Studies of Super‐heavy Element Rf
A enhanced and even faster version of this syste
system was later used as ate used
to study rutherfordium (Z=104), now in collaboration with researchers at Lawrence Berkeley National Lab (LBNL).
Omtvedt et al., J. Alloys & Comp. 271–273 (1998) p303.
Omtvedt et al., J. Nucl. RadioSci. 3 (2002) p121.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 11
Hydrometallurgy in Norway Today
Present processes:
● Elkem’s Silgrain process: FeCl3 in HCl leaches Fe from Si(Fe) Produces 95 99% Si
Si(Fe). Produces 95‐99% Si.
● Glencore Nikkelverk (formerly Xstrata and Falconbridge): Ni, Co, PGM from nickel matte produced by LLX from HCl media.
● KA Rasmussen: Recycling of Ag, Au & PGM from scrap.
● Yara: Producing fertilizer by the HNO3‐route
● Boliden Odda: Producing Zn from matte and sulfuric acid media.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Reestablishing Hydrometallurgy
Norwegian industry have asked the universities to help reestablish hydrometallurgy in Norway.
● Meetings with University of Oslo (UiO) and Norwegian University of Science and Technology
(NTNU) in 2012 and 2013. ● Two large research institutions also included: ○ Institute for Energy Technology (IFE) and
○ SINTEF.
● Dag Ø. Eriksen key person and liaison between industry and universities. J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 13
Competence Building Application
Energy- and environmentally friendly hydrometallurgical technology for exploitation and
refining of complex and poor mineral resources
Motivation:
● Some types of minerals are scarce and the exploitation of less rich deposits or deposits with high content of impurities is to be expected in the future.
● This means that even less than world class deposits in Norway Thi
th t
l
th
ld l
d
it i N
may be considered as resources, and possibly exploited. It is however required, that the processes must be adjusted so that the gangue materials and impurities are removed, and here hydrometallurgy will offer solutions.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Slide courtesy of Tom R. Jørgensen, Yara
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 15
Hydrometallurgy and chemistry
Environ‐
mental
Geo‐
chemistry
Re‐
cycling
Analytical
Mineralogy
Benefici‐
ation methods
NMR
FTIR
…
Radio‐
chemistry
Nano‐
tech.
Organic/
Metalorg
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Hydro‐
metal‐
lurgy
Chroma‐
tography
Simulation
Modeling
Process chemistry
Kinetics
Chemo‐
metry
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Reestablishing Hydrometallurgy
Joint “competence building” application submitted to the Norwegian Research Council
● National
National consortium established, including all consortium established including all
relevant major universities and research institutions.
● Industry partners (20% financing required):
○ Yara
○ Boliden Odda
○ Glencore Nikkelverk
● “Moral” support:
○ Elkem Technology, Nordic Mining ASA, ● Verdict expected end March 2014. J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 17
The Best Way to Earn Money (on Minerals)?
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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The Best Way to Earn Money (on Minerals)?
Norwegian challenge (and not only a technological one..)
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 19
Thorium (and Nuclear Energy)
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Slide courtesy of Øystein Asphjell, CEO Thor Energy
Thor Energy AS is a nuclear fuel technology company
• Advanced, Thorium-based oxide fuel for use in today’s and
tomorrow’s Light Water Reactors
• Near-term benefits to nuclear utilities
• Long-term benefits for the good of society
• Established in 2005 in Oslo, Norway
• Established the «International Thorium Consortium», Dec 2011.
• Loaded Thorium-oxide into the Halden Reactor on April 25 2013
Thorium fuel loaded into the Halden Reactor
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Example of on‐going work (I)
● Develop procedure for removing Cd from current fertilizer process. ○ Will use Cd‐tracers to follow Cd
Will use Cd tracers to follow Cd in the process. in the process
○ Simulate process plant in lab.
● MSc student Håvard Kristiansen.
○ Supervised by Dag Ø. Eriksen, Grethe Wibetoe and J.P. Omtvedt.
● In close collaboration with Yara.
In close collaboration with Yara
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 23
Example of on‐going work (II)
Separation of REE
Several liquid chromatographic (analytical scale) methods has been developed/optimized for separation of REEs (see below). Work is on‐going to improve the resolution and capacity for potential preparative use.
Determination of purity of individual REE
Method development is going on to determine the purity of individual REEs.
There is challenges to document purity of e.g. > 99.999%.
System A: Increased retention with decreasing atomic number (Lu –La)
System B: Increased retention with increasing atomic number (La – Lu)
Work by PhD Dejene Kifle, Prof. Grethe Wibeto and co-workers
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Example of on‐going work (III)
● Build a lab‐scale mixer‐settler battery for development work and competence training. ● Develop computer models to quickly seek out Develop computer models to quickly seek out
favorable systems, e.g. for counter‐current setups:
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Possible LLX Research at UiO
Hydrometallurgy Technology and
Methods Development
LLX
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Nuclear Energy, Safety and (Re‐)Processing of spent fuel
Super‐heavy Element Research (using LLX and LSC) ‐ SISAK
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Possible LLX Research at UiO
Hydrometallurgy Technology and
Methods Development
LLX
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Nuclear Energy, Safety and (Re‐)Processing of spent fuel
Super‐heavy Element Research (using LLX and LSC) ‐ SISAK
Slide 27
Conclusions and Questions
● Poorer and more contaminated mineral sources provide economical and technological challenges.
● Hydrometallurgy has a close link to Nuclear Hydrometallurgy has a close link to Nuclear
Chemistry (at UiO and elsewhere).
○ Nuclear methods (tracers) useful for development of new processes. ● Hydrometallurgy provide a good opportunity for cross‐disiplinary
cross
disiplinary collaboration both inside and collaboration both inside and
outside the university.
● Actual financial support from industry not fantastic.
● Is it fundable?
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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End
The future is nuclear..
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 29
Solutions are needed for:
●
●
●
●
●
●
●
●
Nordic Mining is developing a process for recovery of rutile from the Naustdal deposit. With approximately 5% rutile, TiO2, the remaining 95% of the ore material must be removed and deposited.
Yara is establishing a pilot plant for enabling tests of new raw materials, and also to recover valuable elements and to remove unwanted constituents.
Norsk Separation Technology in co‐operation with UiO is testing new technology for purification of lanthanides by chromatographic means.
Glencore Nikkelverk has for the last decade been toll refining nickel matte from various sources. The nickel market is, however, in a state of change and the traditional nickel sulphide resources are depleted and oxidic ores (laterites) are taking over. To produce high purity nickel from laterites require new hydrometallurgical methods as these ores also contain a variety of metallic and non‐metallic impurities.
Boliden Odda wants to implement new technology for removal of halogenides. This will open up the market for use of secondary Zn resources and waste as raw material.
up the market for use of secondary Zn resources and waste as raw material.
With improved knowledge in hydrometallurgy and liquid‐liquid extraction in particular, Boliden Odda will be able to extract Pb and Ag from the present waste streams.
The mineral and refining industry expect tougher demands regarding removal of As for the waste water in the coming years. Since the present technology is inadequate there is a need for new research and development.
New copper‐ and gold mines are under development in Northern Norway. Sulphide containing gangue material deposits may represent a serious threat to environment due to effluents.
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Application Work Packages:
1. Recovery of halogenides in minute concentrations from aqueous solutions
2. Extraction of high value metals from dilute aqueous solutions, e.g. Pd, Pt, Ag, Au, Cu
3. Extraction of components from high flow systems, i.e. systems with low concentrations and high flows. E.g. purification of effluents from mine tailings.
p
g
4. Extraction of toxic elements, e.g. As, Ni, Cd, Ra, Th, and U from aqueous solutions
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 31
MEGON
● Metal Extractor Group Of Norway established in 1969.
● Based on work by a REE group established by the Research Council aiming to explore REE fields in
Research Council aiming to explore REE fields in Norway (Iveland, Glamsland og Fen).
● Owned by a range of industry and mining companies (Elkem, Sydvaranger, Årdal og Sunndal verk, S.D. Cappelen, H. Bjørum (Glamsland gruve), Det
Norske Zinkkompani, Dyno Industrier, Norwegian Talc, Sulitjelma Gruber).
● Joint venture (1979) with Mitsubishi to produce 6N Y
(from imported concentrates)
(from imported concentrates). ○ Plant established at Kjeller, at the then Institute for Atomic Energy (IAE) – they had extensive competence in hydrometallurgy in connection with reprocessing of spent fuel. ○ Produced 30 ton Y per year. J. P. Omtvedt, ACS, Dallas, 19th March 2014
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J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide courtesy of Tom R. Jørgensen, Yara
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 33
Slide 34
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Competence Building Application
Education:
Virtual institute of separation science,
collaboration with UiO, NTNU, Sintef,
IFE
Covering:
•
•
•
•
•
•
•
•
Leaching of minerals and waste
Solvent extraction and Ion exchange
Solid-liquid separation
Crystallisation and precipitation
Simulation of processes
Chemometry
Fluid dynamics
Environmental issues:
Recycling,
y g, emissions,..
,
External income possibility:
Provide technical and chemical
expertise at all levels of R&D and
at all scales
Laboratory test work
• R&D at lab scale
• High quality research
• Experimental validation of
models
d l and
d simulators
i l t
• Creation of data bases for
use in science and industry
A jewel of
knowledge
International collaborations:
• Chalmers Technical University, SE
• Lappeenranta University of
Technology, SF
• Technische Universität Aachen,
DE
• …
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 35
Critical Raw Materials for the EU ‐ July 2010
Supply Risk
Rare Earths
Economic Importance
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Methodologies:
● From raw material to final pure products (individual metals, metaloxides etc.)
● Extraction of REEs from various sources (minerals, recycled material etc.)
● Separation of REE from unwanted metals
● Group separation of REEs
● Separation of individual REEs ● Analysis of raw materials and final products (purity?)
Various processes
Purity?
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 37
MEGONs 99.999% Y2O3 og Sc2O3
J. P. Omtvedt, ACS, Dallas, 19th March 2014
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Separation and analysis of metal and metal compounds
Analytical chemistry group, Section for Environmental analysis, Department of Chemistry, University of Oslo
Development of methodologies for analyses and potential preparative use. Special focus on the rare earth elements
i
i lf
h
h l
People
●
Professor Grethe Wibetoe
●
Post doc Dejene Kifle
●
PhD student Muhammad Ramzan
●
Master students
Present external cooperation includes: Norwegian Separation Technology (Leader: Sigve Sporstøl)
Main techniques used:
●
Inductively coupled optical emission spectrometry (ICP‐OES)
●
Inductively coupled mass spectrometry (ICP‐MS)
●
High performance liquid chromatography (HPLC)
●
HPLC‐ICP‐MS and ICP‐OES (ICP‐MS and ICP‐OES are used as specific detectors for HPLC) ●
Solid phase extraction (SPE)
J. P. Omtvedt, ACS, Dallas, 19th March 2014
Slide 39
Recent publications:
● Kifle, Dejene; Wibetoe, Grethe; Frøseth, Morten; Bigelius, Jonas (2013): “Impregnation and Characterization of High Performance Extraction Columns for Separation of Metal Ions”, SOLVENT EXTRACTION AND ION EXCHANGE
” SO
O
O
G Volume: l
31 Issue: 6 Pages: 668‐682 ● Kifle, Dejene; Wibetoe, Grethe (2013): “Selective liquid chromatographic separation of yttrium from heavier rare earth elements using acetic acid as novel eluent”, JOURNAL OF CHROMATOGRAPHY A Volume: 1307 Pages: 86‐90 ● Kifle, Dejene; Wibetoe, Grethe (2013): “Retention and elution of precious metals on cyano‐modified solid phase microparticle sorbent”, MICROCHIMICA ACTA Volume: 180 Issue: 11‐12 Pages: 981‐987 J. P. Omtvedt, ACS, Dallas, 19th March 2014
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