Published on March 5, 2014
Processing Murray Basin Mineral Sands David Freeman Warren Bruckard, Mark Pownceby Leanne Smith, Graham Sparrow PROCESS SCIENCE AND ENGINEERING 5 March 2014
IntroducHon • Murray Basin deposit a major heavy mineral sands resource • The in ground wealth is not being fully u@lised • The Victorian Department of State Development, Business and Innova@on commissioned CSIRO to conduct a Review and Assessment of Technology Issues Related to Processing of Murray Basin Mineral Sands • This presenta@on is a summary of the results 2 | Presenta@on @tle | Presenter name
Mineral Sands Provinces in Australia N N 0 1000 10 o Kilometres 20 EASTERN AUSTRALIAN HM PROVINCE o Historical produc@on (1870s) 1934 -‐ Current produc@on 1956 -‐ MURRAY BASIN 30 o Current produc@on 2001 -‐ WESTERN AUSTRALIAN HM PROVINCE o 110 40 o EUCLA BASIN o 130 3 | Processing Murray Basin Mineral Sands | Dave Freeman Current produc@on 2009 -‐ o 150
World ProducHon of Titanates 2011 17.2% 33.3% Australia South Africa 15.4% China India United States Others 3.0% 7.7% 4 | Presenta@on @tle | Dave Freeman 11.7%
World ProducHon of Zircon 2011 10.6% 5.7% 2.1% 43.7% Australia South Africa 12.3% China India United States Others 25.6% 5 | Presenta@on @tle | Dave Freeman
70.0% Ilmenite resources by region 61.1% 60.0% Percentage 50.0% 45.0% 40.0% 35.7% 31.7% EDR (%) 30.0% Inferred (%) 19.3% 20.0% 7.2% 10.0% 0.0% WA Qld Region 6 | Presenta@on @tle | Dave Freeman Murray Basin
RuHle resources by region 100.0% 89.5% 90.0% 80.0% Percentage 70.0% 61.8% 60.0% 50.0% EDR (%) 40.0% Inferred (%) 30.0% 20.0% 20.0% 17.6% 10.0% 5.8% 4.6% 0.0% WA Qld Region 7 | Presenta@on @tle | Dave Freeman Murray Basin
90.0% Zircon resources by region 80.1% 80.0% 70.0% Percentage 60.0% 50.0% 40.9% 40.0% 30.0% EDR (%) 29.3% Inferred (%) 20.0% 16.2% 10.7% 10.0% 4.4% 0.0% WA Qld Region 8 | Presenta@on @tle | Dave Freeman Murray Basin
Murray Basin mineral sand deposits Boundary of Murray Basin Extent of Loxton-Parilla Sands Unit a) Coarse-grained beach placer “strandline” deposit Fine-grained “sheetlike” deposit b) Broken Hill Mildura Mindarie 2 N 9 | Presenta@on @tle | Dave Freeman 1 4 MELBOURNE 160 Kilometres Birthday Gift Karra Castaw C ylinde ay r e rr ibe e Earl K Wemen Woornack Kulwin ck R o wn a Swan Hill Donald Drun g S th Echo Bondi N 0 3 Snapper Ginkgo DE AD ELA I AD ELA ID E Broken Hill 0 160 Kilometres MELBOURNE
Murray Basin Mineral Sand Deposits Strandline Deposits 90-‐300 μm similar to conven@onal deposits Wemen 2001-‐2004 MBTi Iluka (Bondi, Echo) Cristal (Ginkgo, Snapper) Murray Zircon Iluka Iluka Douglas 2004-‐2012 Pooncarie 2005 -‐ Mindarie 2007 -‐ Kulwin 2009-‐2012 Woornack,Rownack & Pirro 2012 -‐ WIM-‐type deposits 40-‐80 μm much ﬁner than conven@onal deposits WIM 50 Iluka WIM 100 Iluka WIM 150 Australian Zircon / Murray Zircon WIM 200 Jackson ASTRON WIM 250 Donald ASTRON 10 | Processing Murray Basin Mineral Sands | Dave Freeman
Murray Basin Ilmenite Concentrates a) b) CP 1 mm 1 mm Coarse grain 11 | Presenta@on @tle | Dave Freeman Fine grain
Murray Basin Strandline Mineral Sand Deposits Project Area Measured resource* Size Grade THM (Mt) (% THM) (Mt) Wemen 21.3 3.3 0.7 Douglas 40.2 9.5 Pooncarie 133 Mindarie Heavy mineral assemblage § Ilmenite Leucoxene Rutile Zircon (%) (%) (%) (%) Wemen 51 n.r. 28 11 3.8 Bondi Main 35.2 7.4 10.3 8.1 3.9 5.2 Ginkgo 69.9 n.r. 12.7 10.4 39.5 3.6 1.4 Mindarie C 65.2 6.6 4.9 19.1 Ouyen 21.0 24.0 5.1 Woornack/ Rownack/Pirro 30.1 n.r 17.9 9.2 Euston 35.4 14.2 5.0 n.r. 42 21 12 10 Balranald n.r. n.r. 14.5 Balranald West n.r. n.r. 10-15 n.r. Twelve Mile n.r. n.r. n.r. Birthday Gift 49.0 8.0 19.0 11.0 * Measured data for the project area. § Total heavy mineral content. n.r. = not reported. 12 | Presenta@on @tle | Dave Freeman Deposit
Murray Basin Heavy Minerals values Global Weighted Average Prices 2011 • Ilmenite US $220/t • Ru@le US $870/t • Zircon US $2500/t Based on possible resources the value of the heavy million in the Murray Basin deposits is around US $200 Billion 13 | Presenta@on @tle | Dave Freeman
SucHon Dredge Mining Mineral Sands Sand pumped to gravity separa@on to produce the HMC concentrate 14 | Processing Murray Basin Mineral Sands | Dave Freeman
Recovery and SeparaHon of Mineral Sands Heavy Mineral Concentrate (HMC) Gravity separa@on using Spirals SeparaHon of Heavy Minerals Magne@c separa@on Ilmenite magne@c Ru@le and Zircon non magne@c Electrosta@c separa@on Ru@le/leucoxene conductor Zircon non conductor (monazite) Flota@on Zircon from ru@le (Byron Bay 1930’s) Monazite (Eneabba 1970’s) 15 | Processing Murray Basin Mineral Sands | Dave Freeman
CharacterisaHon of Ilmenite Ideal composi@on FeTiO3 52.7% TiO2 47.3% FeO (52.6% Fe2O3) Subs@tu@on Mg, Mn, for Fe(II) in the lajce Weathering Oxida@on of Fe(II), Removal of iron, increased TiO2 content Primary Ilmenite 48-‐53% TiO2 Ti/[Ti+Fe] ~ 0.5 Weathered Ilmenite 55-‐62% TiO2 Ti/[Ti+Fe] = 0.5 – 0.6 Pseudoru@le 60-‐70% TiO2 Ti/[Ti+Fe] = 0.6 – 0.7 Hydroxilian Pseudoru@le ~70% TiO2 Ti/[Ti+Fe] = 0.85 – 0.9 Leucoxene >70% TiO2 Ti/[Ti+Fe] = 0.7 – 0.9 Ru@le, Anatase 95% TiO2 16 | Processing Murray Basin Mineral Sands | Dave Freeman
Titania Pigment Processes Sulphate Route Diges@on in conc H2SO4 at 150-‐180°C, dissolu@on of resul@ng porous cake, removal of Fe(SO4).7H2O, hydrolysis and precipita@on of TiO2 Feedstock requirements Primary ilmenite or slag, high Fe(II)/Fe(III) for reac@vity Deleterious Impuri4es Cr, V, Cu, Ni, Mn, Nb (colour pigment) 0.1% Cr2O3 limit Chloride Route Chlorina@on in FB reactor with reductant at 900-‐1000°C, frac@onate metal chlorides to remove impuri@es, oxidise pure TiCl4 at high temperature to TiO2 Feedstock requirements High TiO2 content: synthe@c ru@le, slag, leucoxene, ru@le Size (>100μm) and Density Deleterious Impuri4es Ca, Mg, Mn (bed) Cr, V, Mn (colour) U, Th (disposal) 0.2% Cr2O3 limit 17 | Processing Murray Basin Mineral Sands |Dave Freeman
Current Processing West Coast Ilmenites Primary ilmenite → sulphate process → TiO2 pigment <55% TiO2 99% TiO2 Weathered ilmenite → Becher process → chloride process → TiO2 pigment >58% TiO2 92% TiO2 SR 99% TiO2 18 | Processing Murray Basin Mineral Sands | Dave Freeman
Becher Processing CondiHons Weathered ilmenite → Kiln reduc@on → Aera@on → Synthe@c ru@le >58% TiO2 with coal NH4Cl 92-‐95% TiO2 1150°C Modiﬁed Becher CondiHons remove Mn S in kiln and acid leach awer aera@on SyntheHc RuHle Enhancement Process (SREP) remove U and Th Borate ﬂux in kiln and acid leach awer aera@on 19 | Processing Murray Basin Mineral Sands | Dave Freeman
Commercial Ilmenite Upgrading Processes Acid Leaching with HCl Wah Chang Process ReducHon and Acid Leaching Benelite Process reduc@on to Fe(II) with C at 700-‐900°C HCl leach Ishihara Process reduc@on to Fe(II) with C at 900°C H2SO4 leach Becher Process reduc@on to Fem with C at 1150°C aerate NH4Cl SmelHng OperaHons South Africa AC submerged arc, DC arc plasma furnaces with C at 1700°C UGS Canada (upgraded slag) oxidn at 1025°C, redn CO/H2 at 850°C , HCl leach 20 | Processing Murray Basin Mineral Sands | Dave Freeman
CharacterisaHon of Murray Basin Ilmenites Electron microprob e mapping 21 | Processing Murray Basin Mineral Sands | Dave Freeman
CharacterisaHon of Murray Basin Ilmenites Iden@ﬁca@on of @tanate phases present 22 | Processing Murray Basin Mineral Sands | Dave Freeman Increasing altera@on
Results for Murray Basin Ilmenite Concentrates Removal of chrome spinels MagneHc fracHonaHon Scalp very magne@c chrome spinels Obtain a primary and a weathered product feed 0.94% Cr2O3 primary ilmenite 0.43% Cr2O3 and weathered ilmenite 1.45% Cr2O3 FlotaHon feed 1.23% Cr2O3 product 0.56% Cr2O3 Roast and MagneHc SeparaHon Aim to increase magne@c proper@es of the ilmenite but not of the chrome spinels ilmenite-‐hema@te solid solu@on or form magne@te on grains Use oxidising or reducing condi@ons controlled by the degree of weathering of the ilmenite 23 | Processing Murray Basin Mineral Sands | Dave Freeman
Results for Murray Basin Ilmenite Concentrates Removal of chrome spinels by roasHng CSIRO Roast and MagneHc SeparaHon Roast at 575-‐650°C feed 0.74 % Cr2O3 product 0.09% Cr2O3 Trical Roast and MagneHc SeparaHon Roast at 450-‐600°C feed 1% Cr2O3 products <0.2% Cr2O3 ERMS Roast and MagneHc SeparaHon Roast at 750-‐850°C feed 1.25% Cr2O3 products 0.15% Cr2O3 CSIRO Sulphidising Roast Roast with sulphur addi@on and use ﬂota@on to remove the chrome spinels (preliminary results obtained) 24 | Processing Murray Basin Mineral Sands | Dave Freeman
Results for Murray Basin Ilmenite Concentrates Upgrading Ilmenite Fluidised Bed Processes Oxida@on/Reduc@on/Leaching processes All tested at the pilot plant stage Murso oxidn 900°C, redn 800-‐850°C to Fe(II), HCl leach 95% TiO2 0.2% Cr2O3 NewGenSR oxidn 925-‐975°C, redn 850°C to 85% Fem, aera@on, leach 95% TiO2 ERMS oxidn 950°C, redn 850°C to Fe(II), HCl leach 97% TiO2 25 | Processing Murray Basin Mineral Sands | Dave Freeman
Results for Murray Basin Ilmenite Concentrates Upgrading Ilmenite Kiln Processes Hybrid redn 950°C to 85% Fem, remove Fem and leach 95% TiO2 Forma@on of an acid soluble M2O3 impurity bearing phase good impurity removal Becher redn 1150°C to 100% Fem, aerate, leach 92.5% TiO2 Forma@on of insoluble M3O5 phase Mg not removed Acid Soluble SyntheHc RuHle Addi@on of Mg salts to make a sulphuric acid soluble phase Other High Temperature Processing Smel@ng, CRA Ru@le Process, SREP, TiRON 26 | Processing Murray Basin Mineral Sands | Dave Freeman
Results for Murray Basin Ilmenite Concentrates Processing step Technology/Unit Process Issues when applied to Coarse-‐grained strandline deposits Fine-‐grained WIM-‐type deposits Gravity concentra@on Magne@c separa@ons Electrosta@c separa@on Flota@on Improve equipment to increase recovery, separaHon eﬃciency and throughput Flota@on not usually applied Austpac ERMS process demonstrated at pilot plant scale, others at a laboratory scale only Require a demonstraHon plant in the basin Weathered ilmenite to a chloride pigment feedstock (Upgrade ilmenite to >92% TiO2 and lower Mg, Mn and Cr levels) Magne@sing roast at ~600°C in a ﬂuidised bed reactor Austpac condi@ons CSIRO condi@ons Trical condi@ons WIM condi@ons Fluidised bed processes Murso process Austpac ERMS process NewGenSR process ModiﬁcaHons to exisHng equipment are required to handle the ﬁner minerals Dust is an issue Flota@on can handle ﬁne minerals Use to separate rather than concentrate the ﬁne minerals Economic reagent schemes required to be demonstrated Blow over of ﬁnes from a ﬂuidised bed reactor is an issue Require design and tesHng of a circulaHng ﬂuidised bed reactor to prevent blow over InvesHgaHon of the aﬀects of agglomeraHon on retenHon of ﬁnes also required Kiln-‐based processes (Modiﬁed Becher) Hybrid process Acid soluble synthe@c ru@le RUTILE Technology Mineral concentra@on and separa@on (Produce a heavy mineral concentrate and separate mineral concentrates) Primary ilmenite to a sulphate pigment feedstock (Lower Cr levels) 27 | Processing Murray Basin Mineral Sands | Dave Freeman Austpac ERMS process demonstrated at pilot plant scale Require a demonstraHon plant in the basin Require demonstraHon of the possible technologies at a larger scale Blowover of ﬁnes from a ﬂuidised bed reactor is an issue Require design and tesHng of a circulaHng ﬂuidised bed reactor to prevent blow over of the ﬁne minerals InvesHgaHon of the aﬀects of agglomeraHon on retenHon of ﬁnes also required Reten@on of ﬁnes in a kiln is an issue due the high exhaust gas ﬂows from a kiln InvesHgaHon of the aﬀects of agglomeraHon and ﬂux addiHons on losses of ﬁnes from kiln is required
ProperHes of Murray Basin Zircons RadioacHvity Levels in Zircon can be an issue Commercially required to keep U + Th < 500 ppm industry keen to show there is not a problem Zircons from ﬁne grained deposits have high levels of U+Th at over 1000 ppm CharacterisaHon of MB zircons 28 | Processing Murray Basin Mineral Sands | Dave Freeman Y Yb U Th
Processes for TreaHng of Murray Basin Zircons Heat and Leach Process NaOH Fusion Zircon → fusion with NaOH → water leach → calcine → zirconia ZrSiO4 600°C 700°C ZrO2 Pure Zircon Process Zircon → heat with borate → leach with HCl → zircon 1000 ppm U + Th 1100-‐1400°C 29 | Processing Murray Basin Mineral Sands | Dave Freeman 450 ppm U + Th
Results for Murray Basin Zircon Concentrates Processing step Technology/ Unit Process Issues when applied to Coarse-‐grained Fine-‐grained WIM-‐ strandline deposits type deposits Processing NaOH fusion zircon concentrates Thermal dissocia@on (To remove U+Th and Heat with a ﬂux and radionuclide daughters) leach WIM condi@ons Pure Zircon process 30 | Presenta@on @tle | Presenter name Require scale up of a process (eg Pure Zircon process) Loss of ﬁnes from a ﬂuidised bed or kiln is an issue Radioac@vity levels in waste streams is an issue Require laboratory and pilot scale tesHng of processes
PotenHal Processing OpHons for Murray Basin Heavy Mineral Concentrates Assessment of most likely opHons for Murray Basin ores • Frac@ona@on of primary and weathered ilmenite products • Removal of chrome spinels Uniform roaster condi@ons Chromite as a product • Upgrading ilmenite Synthe@c ru@le product • Pigment plant Chloride process to treat weathered ilmenites Treatment of ﬁne grained ores • Processing of zircon Lower U +Th levels • Recovery of monazite 31 | Processing Murray Basin Mineral Sands | Dave Freeman
PotenHal Processing OpHons for Murray Basin Heavy Mineral Concentrates Ilmenite concentrate MAGNETIC SEPARATIONS Primary ilmenite MAGNETISING ROAST weathered ilmenite OXIDISING ROAST Chloride ilmenite product UPGRADING PROCESS MAGNETIC SEPARATIONS Chrome spinels Waste or re-processing Iron-rich stream 32 | Presenta@on @tle | Dave Freeman Sulphate ilmenite product
PotenHal Processing OpHons for Murray Basin Heavy Mineral Concentrates Non-magnetics from HMC Radionuclides HEAT AND LEACH To disposal or recovery of U and Th Zircon Zircon <500 ppm U+Th <500 ppm U+Th Zircon >1000 ppm U+Th Nonmagnetics MAGNETIC SEPARATIONS Nonconductors ELECTROSTATIC SEPARATIONS Magnetics Monazite product Zircon product 33 | Presenta@on @tle | Dave Freeman Conductors Rutile product
Conclusions • Murray Basin Heavy Mineral Sands deposits is an enormous resource • Diﬃculty in maximising beneﬁt due to generic issues across the Murray Basin • Varia@on in weathering of the ilmenite • Chrome spinels associated with the ilmenite • High U + Th levels • Fine grain deposits • There is a range of commercial processes at various stages of development which may help unlock the in ground wealth • Further research is required • To maximise the beneﬁt of the research eﬀort Government, Mineral Sand Companies, Equipment suppliers and Research and Development providers need to work together 34 | Presenta@on @tle | Presenter name
Thank you Process Science and Engineering David Freeman Project Leader t +61 3 9545 8825 e email@example.com www.csiro.au/cpse ADD BUSINESS UNIT/FLAGSHIP NAME
Process Science and Engineering Mark Pownceby Principal Research Scien@st t + 61 3 9545 8820 e firstname.lastname@example.org w www.csiro.au/cpse Process Science and Engineering Leanne Smith Experimental Scien@st t + 61 3 9545 8667 e email@example.com w www.csiro.au/cpse Process Science and Engineering Warren Bruckard Research Program Leader t + 61 3 9545 8566 e ﬁrstname.firstname.lastname@example.org w www.csiro.au/cpse Victorian Government Anthony Hurst Execu@ve Director Earth Resources Development t e w PROCESS SCIENCE AND ENGINEERING
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