Uranium Recovery from Copper

Concentrate

By : Grenvil Dunn1
Peter Bartsch2
Yong Teo1
1 Orway Mineral Consultants
2 Alchemides Pty Ltd

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 Overview

 Copper Deposits Containing Uranium

 Mineralogy
 Atmospheric Leach Process
 Pressure Leach Processes
 Ausenco Copper Process
 OMC Process
 Testwork and Plant Equipment

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 Copper Deposits Containing Uranium

Sotkamo

Bingham
Canyon

Jadugoda
Salobo
Lumwana
Alemao
Olympic Dam
Palabora Hillside

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 MINERALOGY

Bornite Chalcopyrite

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 Copper Concentrate Mineralogy

Distribution
Mineral Compound (%w/w)
Pyrite FeS2 8- 15
Chalcocite/digenite Cu2S 1 – 30
Covellite CuS 0- 4.4
Chalcopyrite CuFeS2 10 – 70
Bornite Cu5FeS4 10- 30
Hematite Fe2O3.xH2O 8-13
Quartz/Sericite/Silicates 2-6

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 Concentrate Elemental Assay

Element Units Value

Cu % 30-50
Fe % 17-29
S(tot) % 23-31
U ppm 80-1100

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 Uranium Mineralogy

 Uraninite / Pitchblende (UO2)

 Coffinite (U(SiO4)1-x(OH)4x
 Brannerite (U4+,Ca)(Ti,Fe3+)2O6

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 Uranium Liberation
Examples of Uranium Minerals in Copper Concentrate

Chalcocite
Uraninite/Coffinite
Uraninite/Coffinite

Uraninite/Coffinite Uraninite/Coffinite
Fe Oxides/Hydroxides Chalcopyrite

Uraninite/Coffinite
Uraninite/Coffinite
Chalcocite Sulfides

Uraninite/Coffinite Pyrite
Pyrite Uraninite/Coffinite
Fe Oxides/Hydroxides

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 ATMOSPHERIC LEACH

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 Atmospheric Leach
Copper Chemistry
ANSTO Patent (WO 2004/106561 A1)
Leach process consists of 2 steps :
1. Oxidation of bornite to produce the ionic copper

Cu5FeS4(s) + 2H2SO4(l) + O2 (g) → 4CuS(s) + CuSO4(aq) + FeSO4(aq) + 2H2O(l)

2. Upgrade of copper concentrate involving the reduction of bornite and reaction with
copper ions

Cu5FeS4(s) + 2SO2(g) + 3CuSO4(aq) + 4H2O(l) → 4Cu2S(s) + FeSO4(aq) + 4H2SO4(aq)

With addition of a reductant

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 Metathesis

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 Atmospheric Leach
Uranium Chemistry

UO2(s) + 2CuSO4(aq) + 2H2SO4(aq) →H4(UO2)(SO4)3(aq) + Cu2SO4(aq)

CuSO4 and Fe2(SO4)3 Soluble species

oxidises U (4+) to U(6+)

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 Atmospheric Leach
Flowsheet
Reductant

Copper Stage 1 Stage 2 L S Upgraded

L S
Conc. Leach Leach Cu Conc.

Float
Tails Leach
Tails

L S
Tails

Copper
SX/EW
Copper
Raffinate Cathode

Uranium SX/
Raffinate Precipitation
Uranium
Product
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 Atmospheric Leach
Chemistry
Stage 1 Leach
Conditions Value
Temperature >80˚C
Acidity 100g/L H2SO4 for 8-12h
Duration 12-24h
Slurry Density >50%w/w solids
ORP <380mV

Stage 2 Leach
Conditions Value
Temperature >70˚C
Acidity 20g/L H2SO4
Duration 5h
Slurry Density >50%w/w solids
ORP <300 mV
Reductant Sodium sulfite
Copper Concentration <100 g/L Cu
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 Atmospheric Leach – Benefits

U Concentration (ppm)
Flotation Cons 80-1100ppm U in solid
Leached Flotation Cons 60-80%

Benefits of Atmospheric Leach Process

 Upgrading of chalcopyrite by removing Fe to produce an
upgraded concentrate suitable for smelting
 60-80% reduction of uranium in copper concentrate

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 PRESSURE LEACH

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 Pressure Leach
1. Ausenco Copper Process
2. OMC Process

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 Metathesis

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 Ausenco Copper Process
Process Steps

Ausenco Process (Patent 20080173132)

Leach process consists of 2 main steps:

1. Pressure Leach Process with Flash Thickener Recycle
(FTR) circuit

2. Mild Oxidising Leach

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 Ausenco Copper Process
Chemistry

1. POX Leaching of lower grade concentrate (15-25% Cu) to produce copper

ions, ferric ions and heat.

2CuFeS2(s) + 8O2(g) + H2SO4(l) → 2CuSO4(aq) + Fe2(SO4 )3(s)

4CuFeS2(s) + 17O2(g) + 2H2SO4(l) → 4CuSO4(aq) + 2Fe2(SO4 )3(aq) + 4H2O(l)

CuFeS2(s) + 4O2(g) → CuSO4(aq) + FeSO4(aq)

Fe2(SO4)3(aq) + 2H2O(l) → 2Fe(OH)SO4(s) + H2SO4(aq)

Fe2(SO4)3(aq) + 3H2O(l) → Fe2O3(s) + 3H2SO4(aq)

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 Ausenco Copper Process
Chemistry
2. In the Upgrade Autoclave, the chalcopyrite in the high grade concentrate
(>25% Cu) reacts with ionic copper in a metathesis reaction replacing iron
with copper to form copper sulfides minerals.

3CuFeS2(s) + 6CuSO4(aq) + 4H2O(l) → 5Cu1.8S(s) + 3FeSO4(aq) + 4H2SO4(aq)

UO2(s) + 2CuSO4(aq) + 2H2SO4(aq) → H4(UO2)(SO4)3(aq) + Cu2SO4(aq)

 Metathesis
 Reduced Copper in Leachate

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 Ausenco Copper Process
Metathesis

Fe2+
SO42-
H+
Cu2+
H2O

CuFeS2 Cu2S CuS

(Cp) (Ch) (Cv)

1) CuFeS2 +CuSO4 →CuS+FeSO4

2) 3CuFeS2 +6CuSO4 +H2O→5Cu1.8S + 3FeSO4 + 4H2SO4

6CuS + 3CuSO4 + 4H2O→ 5Cu1.8S + 4H2SO4

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 Ausenco Copper Process
Flowsheet
High Grade Upgrade Upgraded
Repulp L S L S Cu Conc.
Copper Conc. Autoclave

Flash

Low Grade POX

S L
Copper Conc. Autoclave

Iron
Low Grade Leach
Ore or
Float Tails Uranium Tails
CCD
Recovery Leach

Uranium Tails
Product 23
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Source : La Brooy, S.R. and Claflin, J., The Ausenco Copper Process, 2013 Alta Conference (as modified)
 Ausenco Copper Process
Testwork Condition
POX Autoclave
Conditions Value
Copper Extraction 99.3%
Temperature 210-220˚C
Pressure 3.0 MPa(g)
Retention Time 70 minutes

Upgrade Autoclave
Conditions Value
Copper Enrichment 70-75%
Uranium in Upgraded Conc. 20-30 ppm
Iron in Upgraded Conc. 5 - 7%
Sulfur in Upgraded Conc. 23 - 28%
Temperature 160˚C
Pressure 0.5 Mpa
Retention Time 120 minutes
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 Ausenco Copper Process
Example Test Results

Uranium Deportment
Unit POX Upgrade
Autoclave
Feed %U 100 100
Discharge Solids %U 7 10-15
Extraction %U 93 85-90
Copper in Product % Cu - 55-60

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 Ausenco Copper Process
Benefits
 Produces matte-grade feed for converting process
 Maximises copper recovery from ore
 Transfer exothermic heat from POX to upgrade
autoclave
 Reduces impurities in concentrate to the smelter (RNs
remain)
 Treats smelter dusts
 Provides ferric ion as an oxidant for the tailings leach
 Wet process that lower particulate emissions
 Based on proven technology and process equipment

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 OMC Process
Chemistry
 Similar to but more intense than the Ausenco Copper Process
 Same developers

Leach process consists of 2 main steps:

1. Copper Pressure Leach (CPL)
2. NONOX Leach

1. Copper Pressure Leaching with lower intensity pressure oxidation

condition compared to the Ausenco Copper Process to produce copper ions,
ferric ions and heat.

Cu2S(s) + H2SO4(aq) + 2.5 O2(g) → 2CuSO4(aq) + H2O(l)

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 OMC Process
Chemistry
2. In the NONOX Autoclave, the chalcopyrite and bornite reacts with ionic copper in
a metathesis reaction replacing iron with copper to form copper sulfides minerals.

3CuFeS2(s) + 6CuSO4(aq) + 4H2O(l) → 5Cu1.8S(s) + 3FeSO4(aq) + 4H2SO4(aq)

Fe2+
SO42-
H+
Cu2+
H2O

CuFeS2 Cu2S CuS

(Cp) (Ch) (Cv)

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 OMC Process
Flowsheet
Float
Upgraded
Tails
Cu Conc.
Tails
CPL S L
Neutralisation
Copper
Repulp NONOX
Conc.
L S Tails

Loaded Strip
Copper SX
Raffinate

Uranium SX
Raffinate Uranium
Product

Tails
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 Testwork Equipment
Batch Leach Autoclave

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 Testwork Equipment
Pilot - Autoclave

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 OMC Process
Testwork Conditions
CPL Autoclave
Conditions Value
Copper Extraction 90%
Temperature 130-140˚C
Pressure 0.7-0.9 MPa(g)
Retention Time 120-180 minutes

NONOX Autoclave
Conditions Value
Copper Enrichment 90-100%
Uranium in NONOX Conc. 2-3 ppm
Iron in NONOX Conc. 5%
Sulfur in NONOX Conc. 22-23%
Temperature 160-220˚C
Pressure 0.5- 2.5 Mpa
Retention Time 60-120 minutes
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 OMC Process
Example Test Results

Uranium Deportment
Unit CPL NONOX
Autoclave
Feed %U 2 100
Discharge Solids %U <0.5 2
Extraction %U 85-90 98
Copper in Product % Cu - 58-68

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 OMC Process
Benefits
 Produces matte-grade feed for converting process
 Maximises uranium recovery from concentrate
 Wet process that lower particulate emissions
 Based on proven technology and process equipment

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 Comparison of
Ausenco Vs OMC Processes
POX/CPL Autoclave
Conditions Ausenco OMC
(POX) (CPL)
Copper Extraction 99.3% 90%
Temperature 210-220˚C 130-140˚C
Pressure 3.0 MPa(g) 0.7-0.9 MPa(g)
Retention Time 70 minutes 120-180 minutes

Upgrade / NONOX Autoclave

Conditions Ausenco OMC
(Upgrade Autoclave) (NONOX)
Copper Enrichment 70-75% 90-100%
Uranium in Upgraded Conc. 20-30 ppm 2-3 ppm
Temperature 160˚C 160-220˚C
Pressure 0.5 Mpa 0.5- 2.5 Mpa
Retention Time 120 minutes 60-120 minutes
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 Copper Pressure Leach Reactor

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 Plant Equipment
CPL Autoclave Impeller

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 NONOX Autoclave

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 Plant Equipment
NONOX Autoclave Impeller

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 Uranium Solvent Extraction Plant

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 References
 Lawson, B and Dudley, K., Hydrometallurgical Operations at Olympic Dam, Alta 2003 Conference, 2003.
 Patent Publication Number WO 2004/106561 A1, Process of Upgrading a Copper Concentrate, Australian
Nuclear Science and Technology Organisation (Applicant), 2004.
 Patent Publication Number 20080173132, Integrated Hydrometallurgical and Pyrometallurgical Processing of
Base Metal Sulphides, Ausenco Services Pty Ltd, 2008.
 Patent Publication Number WO 2014138808 A1, Hydrometallurgical Method for the Removal of
Radionuclides from Radioactive Copper Concentrates, 2014.
 La Brooy, S.R. and Claflin, J., The Ausenco Copper Process, Alta Conference 2013, 2013.
 Dunn, G.M., Uranium Processing, Presented at IAEA Conference in Algeria, 2012

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 Thank You
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