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Valorisation ofMiningand

MetallurgicalWastes
theExampleofBauxiteResidues
Prof.Ioannis Paspaliaris

National Technical University of Athens


TheBayerProcessforAluminaProduction

Seeding

Filtration

Alumina
Calcination

Precipitation

Bauxite
Lime+CausticSoda

BauxiteResidue
Milling Digestion Thickening
(RedMud)
Washing
TheBayerProcessforAluminaProduction

Seeding

Filtration

Alumina
600kg Calcination
Precipitation

Bauxite(wt%)
Lime+CausticSoda
Al2O3 56 Bauxite
Fe2O3 25
SiO2 2
1000kg
TiO2 3 RedMud(wt%)
Al2O3 16
CaO 1 RedMud Fe2O3 48
Na2O
LOI 12
400kg SiO2 6
Milling Digestion Thickening TiO2 6
CaO 11
Washing Na2O 2
LOI 11
GlobalBauxiteResiduesProduction

Producedasaslurry
100120Mt/year
Usualhandlingpractice:
Disposedinsealedor
unsealedartificial
impoundments
BauxiteResiduesDamFailure

Hungary2010
AluminumandAluminaProductioninGreece

AluminiumofGreece(ALSA),aluminarefineryand
aluminiumproductionplant
Producing800,000tonsofalumina and165,000tonsof
aluminiumannually
Theonlyverticallyintegratedbauxite,aluminaandaluminium
productionplantinEurope.

ALSA:650,000tonsofbauxiteresidues(redmud) 6
BauxiteResidues:ThecaseofAluminium ofGreece

DewateringBRinFilter
Presses
Thefiltercakehasamoisture
contentto25%,whichmakes
iteasiertohandle
AoG wasoneofthefirst
WesternEuropeanplantsto
applythistechnology
AoG Produces650,000tBR
peryear

CanthisBRcakebeapotentialresource?
BriefHistoryinBRExploitation
Since1999AoG,NTUAareactivelyparticipatinginRTDprojectsforBRtreatment
Road Construction Mine Remediation Landfill BR clay

AoG BRusedin
BR Soil BR clay
CementIndustry(ironsourcein
clinker)
Brick/TileIndustry(substitution
ofclay)
Geopolymer bricks
SoilRemediation/Vegetation
cover
RoadBaseConstruction
BR Soil BR Geopolymers
Landfillbarrier/cover
BackfillingofAbandonedMines
NewApproachesinBauxiteResidueValorisation

Al2O3 CaO SiO2 TiO2 Fe2O3 Na2O LOI

Bauxite(wt%) 56 1 2 3 25 12

RedMud(wt%) 16 11 6 6 48 2 11

RedMudcontainsabout48%ironoxide.
IronisapotentialelementthatcouldberecoveredfromRedMud.
Is itfeasible??
ReductiveSmeltingofBauxiteResidue

FineRedMud PigIron
48%Fe2O3 95%Fe

CokeFines Slag
Reductive
Smelting
+

Fluxes Off Gases

Innovative Electric Arc Furnace with a novel feeding system, capable to directly
treat finely sized material, without significant material loss in the offgases. The
material is directly fed to the EAF and prior agglomeration is not necessary.
ReductiveSmeltingofBauxiteResidue

RedMud

PigIron
ReductiveSmeltingofBauxiteResidue

Twotestcampaignshavebeencarriedout
ThefirstonewithNTUAa750kVA pilotElectricArcFurnace
ofa600kgbatchcapacity

Pilotplantinstallation PigIronProduction

ThesecondatAluminium ofGreecewith1MVAElectricArcFurnace
ofa1000kgbatchcapacity
CaseStudywithBauxiteResidues

Totalcharge:550kg
77kg 350kg 53kg 70kg Fluxes:351kg/tnRM

MolarratioC:Fe=2.43 [StoicheometircreductionratioC:Fe=1.5]

(%wtCaO+%wtMgO)/(%wtSiO2)=0.94 [NeutralSlag=1.0]

Experimental conditions
Preheatslag:200kg OpticalPyrometry
AroundElectrodes17002400C
FeedingRate:3kg/min
MeltsurfaceT=14001600C
Smeltingtime:3.5h CrustsurfaceT=9001100C

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CaseStudywithBauxiteResidues

Pigiron Exp%wt
%Fe 87.09% Slag Exp%wt
%C 4.05% %Na2O 1.89%
%S 0.05% %MgO 4.65%
%P 0.20% %Al2O3 24.23%
%Si 1.70% %SiO2 32.62%
%Ti 0.45% % SO3 1.09%
%V 0.28% %CaO 29.65%
%Cr 4.43% %TiO2 6.79%
TOTAL 99.83% %Cr2O3 0.41%
PigIronPhase 120kg %Fe2O3 1.11%
%C 0.49%
Fe%Recovery 97%
TOTAL 102.43%
HighCrpresencedueto SlagPhase 280kg
initialrefractory Basicity 1.05
dissolution

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Resultsfrom750kVA experiments

Proved the feasibility of producing Pig Iron from Bauxite


Residues

High Cr presence due to initial refractory dissolution need to


change refractory type

Determination of appropriate operation conditions to be used in


the second experimental campaign at the 1 MVA EAF of
Aluminium of Greece

Questionsraised
Whatcanwedowiththeproducedslagfrom
thesmeltingprocess?
NewApproachesinBauxiteResidueValorisation

RedMud

PigIron

MineralWool

Fiberisation
CaseStudywithBauxiteResidues

Slagfiberization

Preliminary slag blowing tests has shown


that the slag produced can be fiberized.
The chemical composition of the slag is
within mineral wool industrys specs.
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PilotTestsinAluminium ofGreece

AoG PilotPlant
1MVAAMRTEAF(AC,3electrode,dust
treating,batchcapacity1t)

MeltFiberizing Line

StaticBedElectricDryer

Duringatwoyearlongexperimental
campaignstreatedmorethan25tofBR
Morethan5tofPigIronproducedand
testedinsecondarysteelproduction
HighQualitymineralwoolproduct
producedfromtheslag 18
TheENEXALBauxiteResidueTreatmentProcess
AoGs 1stPilotPlant

RedMudEAFCarbothemic Smelting
Openbathoperation
Continuousfeeding6.65kg/min
MeltTemperatureapp1600oC
EnergyConsumption:1508kWh/tofBR
Dustinfilters4%wt offeed
Feed Batch
Dry BR (kg) 700
Silica (kg) 126
Lime (kg) 105
Coke (kg) 140
Total Feed (kg) 1071
ENEXALBRTreatment

PigIronProduction
Producedmetalwithinspecificationforusein
secondarysteelindustry,asanupto20%
steelscrapsubstitute
Morethan5tpigironproducedintotal

PigIron Refr1 Refr2


Fe(%wt) 95.47 93.44
C(%wt) 3.36 4.59
S(%wt) 0.26 0.07
P(%wt) 0.08 0.22
Si(%wt) 0.01 1.12
Cr(%wt) 0.82 0.50 WhiteIrongrindingballsproduced
Total 99.99 99.94 fromBRiron(21%wtsubs)
ENEXALBRTreatment

MineralWoolProduction
Slagmeltwithinempiricalindexes
Fibrewithgoodquality:
=0,034W/(mk)[UNIEN12667]
Averagefiberdiameter7micron
Brightcolor(lowMn content)
HighMechanicalresistanceduetohighTiO2

Slag Refr1 Refr2


Fe2O3 5.0 1.1
SiO2 27.6 26.5
CaO 25.3 23.4
Al2O3 20.9 31.1
Cr2O3 3.0 0.1
MgO 8.89 8.3
TiO2 5.6 6.1 Mineralwoolusedinsidetheplant
Na2O 2.4 1.8
ENEXALBRTreatment

BR
Mineral
Wool

Commercial
Mineral
Wool
TheENEXALBauxiteResidueTreatmentProcess
AoGs 2ndPilotPlant

Smeltingenergy14.5%in
excessofthermodynamic
requirement

Overallplantconsumption
2MWh/tBR
BRTreatmentresults

Upscalingwillbringhigherenergy
efficiency,especiallyinBRdrying

Initialstudiesshowtheprocessto
beprofitable

Breakevenpointisachievedwitha
fairlylowmineralwoolprice

but
Pigironrevenuesaccountsonlyfor
25%oftheoperatingcosts

TreatingtheAoG annualBR
productioncanproduce0.5Mtof
MineralWoolproducts
OnGoingResearch

TheAoG BRalsocontainsapproximately
0.1%wtREE
(mainlyasSc,CeandNd)

Whatcouldbeapossibletechnologyfor
theirrecovery?
SelectiveleachingofREEfromRedMud

OngoingRTDeffortfortheselective
leachingofREEfromredmudusing
IonicLiquids
100
90
REEinRedMud~1200ppm 80
600 70

%recovery
500 60
400 50
40
ppm

300
30
200 20
100 10
0 0
Ce La Sc Nd Y Pr Sm Dy Gd Yb Er Dy La Nd Y Ce Sc Si Al Fe Ca Na Ti Cr V

Directleachingofredmudwith
HbetTf2Ninwaterat60Cwith
10%pulpdensity
IonicLiquidNTUAPilotPlant
REEconcentrate IntheframeworkofEURAREaILpilotplantisbeing
/RedMud setupinNTUA
Thepilotwilldemonstratethefullprocessingchain
fromconcentratetoREEmetalusingIL
ILLeachingstage
2X1.0lt reactors
0.1kgbatch
220C ILSeparation
MixerSettlers
Units
S/Lseparation 20 stages
12lt/hour Upto100C ILelectrowinning
95C Flowrate1lt/h
100mlvolume
PrecipitationUnit
REEMetal
2X1.0lt reactors
95C
AlSc Alloy
RedMud Steel
Industry

REEandTh
Removaland
Separation
REE Holistic
industry Approach PigIronProduction

Safe
disposal

SlagValorization

Cement MineralWool Geopolymers


OtherPotentialApplications

ThecaseofLateritesandthe
FerroNickelIndustry
CaseStudywithFeNislag

FeNi Slags in LARCO :


Annual production is approximately
2 million tons of FeNi slag
There are no special processing
issues
Treating the slag insitu, before
cooling would mark significant
energy savings.

30
ProposedSolution

Bothbyproductsarechemicallysimilar
OriginatingfromlateriticweatheringdepositsinGreece
Containinghighamountofironoxides(4050%wt)
Containingatleast30%wtaluminosilicates

RedMud Al2O3 CaO SiO2 TiO2 Fe2O3 Na2O V2O5 LOI

(wt%) 16.22 10.73 6.08 5.93 47.74 2.51 0.21 10.42

FeNislag Al2O3 CaO SiO2 MgO Fe2O3 Cr2O3 NiO LOI

(wt%) 9.69 3.47 38.27 5.13 39.78 2.47 0.10 0.95

EAF
Carbothermic ProduceMineralWool ProducePigIron =ZeroWasteProcess
Smelting
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BauxiteResidueGeopolymeric Tiles/Bricks

BauxiteResidues85% Metakaolin 15%


CompressionStrength:20,5MPa MW
(ModerateWeatheringConditions)

Bendingstrength:600N(goodfortiles)

WaterAbsorption1.28%

Negligiblewaterpermeability

LowresistancetoFreezingThawingCycles

Suitablebuildingmaterialformoderate
climates(e.g.Mediterranean)
CombinedGeopolymers forBricksandTiles

BauxiteResidues50% FeNi Slag50%

ExcellentMechanicalproperties
Comp.Strength:>40MPa
BendingStrength:4MPa
Density:2350kg/m3
Waterabsorption:0.57%
Suitablebuildingmaterial
Waterpermeability:Negligible
foralmostanyclimate
HighresistancetoFreezing
ThawingCycles

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ResearchProjects

20102014AoG /NTUACoordinatedtheFP7
ENEXALProject,demonstratingthecomplete
conversionofBauxiteResiduestopigironand
mineralwoolproducts.

20132017NTUACoordinatestheFP7
EURAREProject,researchingtechnologies
forREEextractionfromBR.

From2015AoG andNTUAwillundertake4PhDstudies
undertherecentlyapprovedMarrie Currieprojecton
EuropeanTrainingNetworkforZeroWasteValorisation
ofBauxiteResidue(RedMud)
TheENEXALBauxiteResidueTreatment
PreliminaryEconomicEvaluation

PigIronrevenues(fixedmarketprice400EUR/t)amountto
38%ofoperationalcosts
Mineralwoolrevenuesdependonmarketprice(dependson
productqualityandmarketdemand)