Gilligan and Nikoloski 2016 Brannerite and gangue interaction - AusIMM U Conference Adelaide 2016
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Transcript of Gilligan and Nikoloski 2016 Brannerite and gangue interaction - AusIMM U Conference Adelaide 2016
The leaching of brannerite:influence of reactive gangue minerals
Rorie Gilligan and Aleks NikoloskiAusIMM International Uranium Conference, Adelaide June 7-8 2016
Introduction
• Brannerite, UTi2O6 is the most common refractory uranium mineral
• Most important uranium mineral after uraninite and coffinite
• Brannerite leaching chemistry studied in detail• Presented at previous AusIMM Uranium
conference (June 2015)
Brannerite - background
• Has a general formula of (U,Th,REE,Ca)(Ti,Fe3+)2O6
• Thorium and light rare earth elements substitute uranium
• Associated with titanium minerals• Complicated by the presence of reactive gangue• Calcite, chlorite, apatite, fluorite
Processing of brannerite and ores• Requires leaching under more aggressive conditions
compared to other U minerals• >75°C, >25 g/L H2SO4
• Brannerite-rich U ores in Ontario, Canada leached~75°C60-75 g/L H2SO4
36-48 h leaching time• Pressure leaching trialled in South Africa in the 1970s-80s
Brannerite in Australia• Minor U mineral at
Olympic Dam (SA) and Ranger (NT)
• Major U mineral in Valhalla, Skal and others, Mount Isa, QLD
• Major U mineral at Curnamona province, Crocker Well, Mount Victoria, SA
Image from: http://www.australianminesatlas.gov.au/aimr/commodity/uranium.html
Mount Isa(Valhalla, Skal)
Olympic Dam
Curnamona Province(Crocker Well and others)
Ranger
Gangue effects• Acid consumers like calcite react rapidly with acid• Others like chlorite react slowly• Phosphate minerals have a more complicated
effect• Scarce information specific to brannerite• Apatite identified with brannerite in Mount Isa
(QLD), Curnamona province (SA), Central Ukrainian Uranium Province
Gangue chemistry• Insoluble uranium(VI) phosphates can form > pH 1.5-2 • Not likely an issue at >25 g/L H2SO4 needed to dissolve brannerite• Phosphate ions hinder the reaction between ferric (Fe3+ or FeSO4
+) and U4+ by forming complexes such as FeHPO4
+
• Fluorite, CaF2 will improve the leaching through formation of HF• Can attack other gangue, improving liberation• Also known to form gelatinous silica however, inhibiting solid-liquid
separation, SX and IX
Leaching experiments• Brannerite leached in ferric sulphate and sulphuric acid• 2.8 g/L Fe3+
• 10-200 g/L H2SO4
• 25-96°C (four intermediate values)• Selected experiments repeated with gangue additives• 10 g/L fluorapatite or fluorite• Uranium and titanium dissolution monitored• Solids characterised by XRD, SEM and EDX
Leaching kinetics – brannerite
0 1 2 3 4 50%
10%20%30%40%50%60%70%80%90%
100%96°C52°C25°C
Time (h)
Ura
nium
ext
racti
on
0 1 2 3 4 50%
10%20%30%40%50%60%70%80%90%
100% 100 g/L H₂SO₄50 g/L H₂SO₄25 g/L H₂SO₄
Time (h)U
rani
um e
xtra
ction
Varied temperature, 25 g/L H2SO4 Varied acid concentration, 52°C
Leaching kinetics – effect of apatite
0 1 2 3 4 50%
10%20%30%40%50%60%70%80%90%
100%96°C96°C + fluorapatite52°C52°C + fluorapatite25°C25°C + fluorapatite
Time (h)
Ura
nium
ext
racti
on
0 1 2 3 4 50%
10%20%30%40%50%60%70%80%90%
100%100 g/L H₂SO₄50 g/L H₂SO₄25 g/L H₂SO₄100 g/L H₂SO₄ + fluorapatite50 g/L H₂SO₄ + fluorapatite25 g/L H₂SO₄ + fluorapatite
Time (h)U
rani
um e
xtra
ction
Varied temperature, 25 g/L H2SO4 Varied acid concentration, 52°C
Final extractions vs. acid concentration (52°C)
0 50 100 150 2000%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
U - ferric sulphateU - ferric sulphate, apatiteU - ferric sulphate, apatite, corrected acid conc.Ti - ferric sulphateTi - ferric sulphate, apatiteTi - ferric sulphate, apatite, corrected acid conc.
[H₂SO₄] (g/L)
Ura
nium
, tita
nium
ext
racti
on
Acid concentration adjusted according to P dissolutionEffect of apatite greater than what can be attributed to a drop in acid concentration
Leaching kinetics – effect of fluorite
0 1 2 3 4 50%
10%20%30%40%50%60%70%80%90%
100%
25 g/L H₂SO₄, 96°C + fluorite100 g/L H₂SO₄, 52°C + fluorite25 g/L H₂SO₄, 52°C + fluorite25 g/L H₂SO₄, 96°C100 g/L H₂SO₄, 52°C25 g/L H₂SO₄, 52°C
Time (h)
Ura
nium
ext
racti
on
Post-leach mineralogy
Varied temperature, 25 g/L H2SO4, apatite
• Residual apatite associated with gypsum
• No uranium phosphates were detected
• A phosphorus enriched titanium oxide rim was identified on leached brannerite
• This suggests that the effects of phosphate on brannerite leaching are more complex than general uranium leaching
Post-leach mineralogy
• Varied acid concentrations, 52°C, apatite
• Some pitting seen at 50-100 g/L H2SO4.
• Higher acid concentrations counteracted the effects of phosphate
P U Ti P S Ca
25 g/L H2SO4
100 g/L H2SO4
50 g/L H2SO4
Post-leach mineralogy
• Varied acidity, 52°C, fluorite
• Brannerite leached alongside fluorite was heavily corroded
• Fluorite did not dissolve completely
• No brannerite identified in 96°C, 25 g/L H2SO4 leach residue
Ca U Ti
25 g/L H2SO4
100 g/L H2SO4
Conclusions• Phosphate minerals inhibit uranium dissolution• Not just due to acid consumption• Also contribute to brannerite passivation• Less of a problem at higher acidities• Acid and sulphate counteract the effects of phosphate• Fluorite significantly increases rate of uranium dissolution
Further reading• Gilligan, R., Nikoloski, A.N. 2015. The extraction of uranium from
brannerite – A literature review. Minerals Engineering 71, 34-48• Gilligan, R., Nikoloski, A.N. 2015. Leaching of brannerite in the
ferric sulphate system. Part 1: Kinetics and reaction mechanism. Hydrometallurgy 156, 71-80
• Gilligan, R., Deditius, A., Nikoloski, A. N. 2016. Leaching of brannerite in the ferric sulphate system. Part 2: Mineralogical transformations during leaching. Hydrometallurgy 159, 95-106
• Gilligan, R., Nikoloski, A.N., 2016. Leaching of brannerite in the ferric sulphate system. Part 3: The influence of reactive gangue minerals. Hydrometallurgy (under review)
Questions?Contact us
[email protected]@murdoch.edu.au