omtvedt acs hydrometallurgy talk v05 18mar2014 · with improved knowledge in hydrometallurgy and...

21.03.2014

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Solvent extraction research at UiO- a common denominator for research related to hydro-

metallurgy, nuclear fuel cycle and super-heavy elements

Jon Petter Omtvedtand Dag Ø. Eriksen, Grethe Wibetoe, Tor Bjørnstad, Dejene Kifle, Håvard Kristiansen

ACS meeting, Dallas, TX19th March 2014

Outline

● Motivation

○ History

○ Nuclear Chemistry at UiO

○ Request from Norwegian Industry

● Status

○ On‐going research and projects

J. P. Omtvedt, ACS, Dallas, 19th March 2014 Slide 2

○ Pending Applications

● Future outlook

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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

d f


● Jon Petter Omtvedt, professor in Nuclear Chemistry

What is Norway?Keywords: • lots of “nature”• cold and remote• extremely rich

i

Small and peaceful country to the far north.○Area: 385364 km2 (4.0% of US).

○Population (2014): 5.1 mill (1.6% of US).

in energy resources (hydro, oil & gas, thorium).


○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).

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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)


Both processes stopped due to competition from Chinese low prices.

produced group separated REE from the Kola apatite feed solution.

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), AlecoPappas (UiO), Jorolf Alstad (UiO), Svein Erik Engdal (MEGON), Dag Ø. Eriksen (MEGON).


Pappas 1915-2010Prof. Nucl. Chem. at UiO

MEGON was a technological success but an economical

fiasco..

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Good Results – 34 years agoJ. 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.”

A Detour from Hydrometallurgy..

As economical importance of REE research declined, research focus in the Nuclear

• 1972-1975 short-lived La, Ceand Pr nuclei studied in Oslo (produced with a n-generator).

• In 1975-1980 many successfulresearch focus in the Nuclear Chemistry Section at UiO changed toward fundamental science:

○ Chemical separation and rapid transport of short

In 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


rapid transport of short lived nuclei for nuclear spectroscopy studies.

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 Separation

Inlet/outlets

(Sweden) and Univ. Mainz (Germany), a fast and continuous LLX system (“SISAK”) was developed and employed for nuclear‐structure studies of short‐

pchamber

Rotating cup


lived nuclei.

AKUFVE and SISAK

SISAK = Short-lived Isotopes Studied by the AKUFVE-techniquetechnique

AKUFVE is a Swedish acronym for an apparatus for continuous investigations of distribution ratios in liquid-li id t ti


liquid extraction.

Reinhardt & Rydberg, JActaChemScand 23 (1969) p2773.Persson et al. RCA48, (1989) p177.Commercialized by Swedish company MEAB AB.

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Studies of Super‐heavy Element Rf

A enhanced and even faster version of this system was later used syste as ate usedto 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.

Hydrometallurgy in Norway Today

Present processes:

● Elkem’s Silgrain process: FeCl3 in HCl leaches Fe from Si(Fe) Produces 95 99% SiSi(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.

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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.

Competence Building Application

Energy- and environmentally friendly hydro-metallurgical 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.

● Thi th t l th ld l d it i N

refining of complex and poor mineral resources


● This means that even less than world class deposits in Norway 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.

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J. P. Omtvedt, ACS, Dallas, 19th March 2014 Slide 15Slide courtesy of Tom R. Jørgensen, Yara

Hydrometallurgy and chemistry

AnalyticalGeo‐

Environ‐mental

Re‐cycling

Hydro‐metal‐lurgy

Analytical

Chroma‐tography

SimulationModeling

Mineralogy

chemistry

Radio‐chemistry

NMRFTIR

Benefici‐ation

methods


KineticsProcess chemistry

Organic/Metalorg

Nano‐tech.

Chemo‐metry

FTIR…

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Reestablishing HydrometallurgyJoint “competence building” application submitted to the Norwegian Research Council

● National consortium established including all● National 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.

The Best Way to Earn Money (on Minerals)?


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The Best Way to Earn Money (on Minerals)?

Norwegian challenge (and not only a

technological one..)


Thorium (and Nuclear Energy)


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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

Slide courtesy of Øystein Asphjell, CEO Thor Energy

• 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


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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 in the process○ Will use Cd‐tracers to follow Cd 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.

Example of on‐going work (II)Separation of REESeveral 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 REEMethod 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

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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:


Possible LLX Research at UiO

Hydrometallurgy Technology andMethods Development

LLXNuclear 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 andMethods Development

LLXNuclear Energy, Safety and (Re‐)Processing of spent fuel


Super‐heavy Element Research (using LLX and LSC) ‐ SISAK

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 collaboration both inside and


cross disiplinary collaboration both inside and outside the university.

● Actual financial support from industry not fantastic.

● Is it fundable?

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End


The future is nuclear..

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.

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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.


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4. Extraction of toxic elements, e.g. As, Ni, Cd, Ra, Th, and U from aqueous solutions

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 inResearch 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), DetNorske 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.

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J. P. Omtvedt, ACS, Dallas, 19th March 2014 Slide 34Slide courtesy of Tom R. Jørgensen, Yara

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Education:Virtual institute of separation science,collaboration with UiO, NTNU, Sintef, IFECovering:

Laboratory test work• R&D at lab scale

• High quality research• Experimental validation of

d l d i l t

Competence Building Application

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, emissions,..

models and simulators• Creation of data bases for

use in science and industry

A jewel of knowledge


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External income possibility:Provide technical and chemical expertise at all levels of R&D and at all scales

International collaborations:• Chalmers Technical University, SE• Lappeenranta University of

Technology, SF• Technische Universität Aachen,

DE• …

Critical Raw Materials for the EU ‐ July 2010

Rare Earths

Su

pp

ly R

isk


Economic Importance

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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

Various processes


● Group separation of REEs

● Separation of individual REEs

● Analysis of raw materials and final products (purity?)

Purity?

MEGONs 99.999% Y2O3 og Sc2O3


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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 i i l f h h lpreparative use. Special focus on the rare earth elements

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)

Recent publications:● Kifle, Dejene; Wibetoe, Grethe; Frøseth, Morten; Bigelius,

Jonas (2013): “Impregnation and Characterization of High Performance Extraction Columns for Separation of Metal

” SO O O G lIons”, SOLVENT EXTRACTION AND ION EXCHANGE Volume: 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

omtvedt acs hydrometallurgy talk v05 18mar2014 · with improved knowledge in hydrometallurgy and...

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