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ChemistryoftheIronmakingbyBlastFurnace
Process
PostedbySatyendraonNov22,2013inTechnical|0comments

ChemistryoftheIronmakingbyBlastFurnaceProcess
Liquidiron(hotmetal)isproducedinablastfurnacefromtheburdenmaterialsthroughaseriesofchemical
reactionswhicharetakingplaceatvariouslevelsinablastfurnace.Whentheburdenmaterialsdescendfrom
thetopthroughtheblastfurnacestack,theyarepreheatedbytheascendinghotgases.Duetothispreheat,the
cokeburnswithgreatintensitywhenitreachesthelevelofthetuyeresandcomesincontactwiththehotblast
air.Howeverduetotheveryhightemperature(1650degC)andthelargequantityofcarbon(coke),thecarbon
dioxideformedisnotstableandreactswithadditionalcarbontocarbonmonoxide.Hencethecombustionof
carbonintheblastfurnacecanberepresentedbythefollowingequation:
2C+O2=2CO
Thisreactionisthemainsourceofheatforthesmeltingoperationandalsoproducesthereducinggas(CO)that
ascendsintothefurnacestackwhereitpreheatsandreducesmostoftheironoxideintheburdenasitdescend
tothehearth.
Anymoisturepresentinthehotairblastalsoreactswiththecarbonofthecoke.Thisreactionconsumesheat
andproducesmorereducinggaswhichisamixtureofCOandH2.Hencewherehighblasttemperaturesare
available(1000degCto1200degC),itisadvantageoustokeepthemoisturecontentofthehotairblast
uniformlyatahighlevelbythesteamadditionsinordertoincreasetheamountofreducinggasesascendingthe
furnacestack.
C+H2O=CO+H2
Theadvantageofabovereactionisthatthereistheintroductionofhydrogengasinthefurnacereducinggases
whichdecreasesofthedensityoftheascendinggases.Thisresultsinanincreaseintheequivalentvolumeof
reducinggasthusprovidinglessresistancetoburdendescent.
Theascendinggasesstarttoreducetheironoxideoftheburdenintheupperportionoftheblastfurnacewhere
thetemperatureisbelow925degC.Atthistemperature,chemicalequilibriumpreventsalltheCOandH2fro
beingusedforreduction(theequilibriumCO/CO2ratioisaround2.3forthereductionofFeO,iftheratiofalls
below2.3thanironisreoxidized).HencethemolecularratioofCOorH2toironoxidemustbearoundthree
timestheamountshowninthefollowingstoichiometricreactions.
Fe2O3+3CO=2Fe+3CO2
Fe3O4+4CO=3Fe+4CO2
FexO+CO=xFe+CO2
Fe2O3+3H2=2FE+3H2O
Fe3O4+4H2=3Fe+4H2O
FexO+H2=xFe+H2O
Thepartofironoxidewhichisnotreducedintheupperpartofthefurnacewherethetemperaturesare
relativelylow,istobereducedinthelowerpartofthefurnacewherethetemperatureishigh.Inthispart,CO2
andH2Oarenotstableatthisteperatureinthepresenceoflargequantityofcokeandtheyreactwithcarbonas
rapidlyastheyareformed.Inviewofthis,thereductionsinthispartofthefurnacethereductiontakesplaceas
perthefollowingreactions.
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FexO+CO=xFe+CO2
CO2+C=2C01
FexO+H2=xFe+H2O
H2O+C=H2+CO2
InboththecaseswhetherreactantisCOorH2,theoverallreductionreactioninthispartofthefurnaceis
representedbythefollowingequation.
FexO+C=xFe+CO
Gaseousreductionofironoxides
Thecarbonmonoxideiscapableofreducinghematite(Fe2O3)toiron,withmagnetite(Fe3O4)andw?stite
(FexO)appearingasintermediateproductsattemperaturesabove570degC.Ineachcase,thereactionis
reversibleandequilibriumisestablishedwhenthegasattainsacompositionthat,atconstantpressure,is
dependentonlyontemperature.SuchanequilibriumrelationshipisshowninFig.1,togetherwiththoseforthe
lowtemperaturereductionofmagnetitetoiron.

Fig.1:Equilibriuminthepresenceofsolidcarbon
Intheblastfurnacestack,reductioniscomplicatedbythepresenceofcokethatcausestheCOconcentrationto
beinfluencedbytheBoudouardreactionwhichisnamedafterOctaveLeopoldBoudouard.Itis
theredoxreactionofachemicalequilibriummixtureofcarbonmonoxideandcarbondioxideatagiven
temperature.Itisthedisproportionationofcarbonmonoxideintocarbondioxideandgraphiteoritsreverse.
2CO?CO2+C
DuetoBoudouardreaction,thechangesareexperiencedbyanelementofgasasitenterstheblastfurnacestack
ataninitialtemperatureofabout1000degCandrisestothethroatreducingandheatingtheburdenonitsway.
FromFig.1inwhichtheBoudouardlineissuperimposedontheoxidereductionequilibriums,itcanbeseen
thatagasconsistingof100%COiscapableofreducingtheoxidetometalliciron.Ifthetemperaturefallsto
900degC,equilibriumwithFexOisestablishedat70%CO+30%CO2.
Theelementofgasmaythenbesupposedtocomeintocontactwithcokeand,ifthetemperaturefallsagain,
thistimeto800degC,COwouldberegeneratedanditsconcentrationisraisedto90%,sothatitisagain
possibletoreduceFexOtometalliciron.Oscillationbetweenthegascompositionsindicatedbythetwolines
couldcontinueuntilthetemperaturehadfallento700degC,whentheinfluenceoftheBoudouardreactionwill
besuchthatnoreductionofFexOcantakeplace,althoughattemperaturesbetween700degCand650degC,
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reductionofFe2O3toFexOviaFe3O4,willstillbepossible.Attemperaturesbelow650degC,Fe2O3canbe
reducedtoFe3O4,butthereactionrateisexpectedtobeslow.
Thegaseousreductionissometimesknownas`indirectreduction,becausethereducingagent,i.e.CO,is
derivedfromthecombustionofcarbon.Gaseousreductionisneverthelessthetermthatispreferredhere,since
itencompassesreductionbyhydrogen.
Reductionbysolidcarbon
Burdenenteringtheboshispreheatedandpartiallyreduced.Theremainingoxygenisremovedbyreduction
withsolidcarbonasperthefollowingequation.
FeO+C=Fe+CO
Carbonreductionishighlyendothermicandrequiresthecombustionofcoketomakegoodtheheatit
consumes.Theuseofcarbonasareductantisdirectreduction,calledcarbonreduction.
Comparisonofgaseousandcarbonreduction
Atthefaceofit,theendothermicnatureofcarbonreductionappearstobeunattractiveincomparisonto
gaseousreduction,whichisexothermic.Howeverinactualthesituationisslightlymorecomplex.
Firstly,theCOcomesfromcoke,andtheequilibriumlimitationspreventcompletecombustiontoCO.
Secondly,gaseousreductionyieldsalargethermalsurplus,andbywayofcontrast,thoughcarbonreductionis
associatedwithathermaldeficit,itusesonlyonethirdoftheamountofcarbontoproduceeachmoleofiron.
Hereliestheattractionofacombinationofthetworeductionmechanisms,sincesomeoftheheatgeneratedby
gaseousreduction(ormoreaccuratelybythecombustionofcoketoCO)canbeusedtocompensatefortheheat
requirementsoffuelsavingcarbonreduction.Bothtypesofreactionsarethereforeencounteredintheblast
furnace,withsome60%to65%oftheoxygenoriginallypresentintheburdenbeingremovedbygaseous
meansandtheremainderbycarbonreduction.
ReductionofManganese
Atthetemperatureintheupperpartoftheblastfurnacestack,thehigheroxidesofmanganesearereducedby
COasperthefollowingreactions.
MnO2+CO=MnO+CO2
Mn3O4+CO=3MnO+CO2
Howevertheloweroxidesofmanganese(MnO)arenotreducedbyCOorH2atanyofthetemperaturesthat
areexperiencedinthestack.Thefinalreductionofmanganeseisduetothefollowingreactionthattakesplace
attemperaturesabove1500degC.
MnO+C=Mn+CO
Thisreactionabsorbslargequantitiesofheat.Athighertemperaturesthepercentageofmanganesethatcanbe
reducedincreases,butinmostbasicpracticesmanganesereductionisaround65%to75%oftheamountof
themanganesecharged.Themanganesethatisreduceddissolvesinthehotmetalwhiletheunreducedportion
remainsasthepartoftheslag.Duetoit,manganesepartitioningisanindicatorofthethermalstateofthe
hearth.
ReductionofSilicon
Therearetwodifferentreactionsgoverningsilicontransfertothehotmetal.Amongthewayssiliconmonoxide
gascanformiswhencokeburnsinfrontofthetuyeresandsilicaintheashisreducedandvolatized.The
siliconmonoxidereactswithmoltenironasperthefollowingreactionandsiliconcontentoftheironincreases.
SiO(g)+Fe=Si+FeO

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TheFeOissubsequentlyreducedbytheeverpresentCO.ThereductionofSiO2alsotakesplaceatveryhigh
temperaturesasperthefollowingchemicalreaction.
SiO2+2C=Si+2CO
Therateofthisreactionisrelativelyslowbutaccelerateswithanincreaseinthetemperature.Foraparticular
burdenandslagcompositionthesiliconcontentofthehotmetalisproportionaltothehotmetaltemperature.
Thepercentageofsiliconinthehotmetalcanbeincreas3dbyincreasingthesiliconcontentofthechargeand
thecokerate.
ReductionofSulphur
SulphurenterstheblastfurnacemainlyincokeandisreleasedintotheblastfurnacegasstreameitherasH2Sor
agaseouscompoundofcarbonmonoxideandsulphur(COS)whenthecokeisburned.Asthegasascends
throughthestacksomeofthesulphurcombineswiththelimeinthefluxandsomecombineswiththeiron.The
exactmechanismofthereactionbywhichsulphurcombineswithironisnotknown.However,itisgenerally
believedtobeasfollows:
FeO+COS=FeS+CO2
Thesulphurthatcombineswiththeironisremovedattheveryhightemperaturesthatexistinthehearth.This
isdonebyreductionofironsulphideinthepresenceofabasicfluxsuchaslime(CaO)asperthefollowing
equation.
FeS+CaO+C=Fe+CaS+CO2
Theamountofsulphurremoveddependsonthetemperatureofthehearth,theslagbasicity
(CaO+MgO/SiO2+Al2O3,andtheslagvolume.
Reductionofphosphorus
Thereductionofphosphorusintheblastfurnacetakesplaceasperthefollowingreaction.
P2O5+5C=2P+5CO
Thefinalreductionofphosphorusalsotakesplaceonlyatveryhightemperatures.However,unlikemanganese
andsiliconthephosphorusisessentiallycompletelyreduced.Forthisreason,virtuallyallofthephosphorusin
theburdenmaterialswilldissolveinthehotmetal.
Slagformation
Ganguematerialsintheoressuchassilicaandaluminaandashinthecokearethebasisoftheslagthatcollects
inthehearthofthefurnace.Theformationoffusibleslagisfacilitatedbytheinclusionoffluxesintheburden
materialssuchaslime(CaO)andmagnesia(MgO).Theseelementsareusedtoproduceaslagofthedesired
composition.Thefactorsdeterminingtheoptimumcompositionarephysical,chemicalandcommercialandthe
finalchoiceisusuallythatofacompromisebetweenthethree.Slagmustbefluidtorunfreelyfromtheblast
furnaceandalsoitshouldhavethecapacitytoabsorbsulphur.Thesiliconandmanganeselevelsinthehot
metalandtherecirculationofalkalisarealsoinfluencedbyslagcomposition.
ThemajorconstituentsofblastfurnaceslagsarethefouroxidesCaO,MgO,SiO2anAl2O3andthesumof
theirconcentrationsusuallyexceeds95%.OtherelementsintheslagareMnO,S,K2O,FeOandNa2Oetc.
Meltingtemperaturesvarybetween1200degCto1400degC.Chemicalcharacteristicsoftheslagis
determinedbyitscompositionandaccordinglyitcanbeeitheracidicorbasic.SlagshavinghigherCaOcontent
arebasicwhileslagswithhighSiO2contentareacidic.Theslagbasicityisaratiowhichisdefinedeitheras
CaO/SiO2oras(CaO+MgO)/(SiO2+Al2O3).Theslagbasicityinfluencesthedistributionofelements
betweenslagandhotmetalandhenceaffectsthehotmetalcomposition.

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