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Lecture13:Calcination

Contents

Principlesofcalcination

Applications

Materialsandheatbalanceincalcination

ProblemiDecompositionofCaCO

Problemiiamountoffuelincalcination

ProblemiiicalcinationofAl OH

Problemivfuelsaving

Conclusions

References

Keywords:calcination,electrolysisofalumina,fuelsaving

Principlesofcalcination:

Calcinationisathermaltreatmentprocessandappliedtooresandothersolidmaterialstobring

a) thermaldecomposition
b) phasetransitionand
c) toremovevolatilefractionssuchasCO , H O

Materialisheatedbelowthemeltingpointinrotarykilnorfluidizedbedreactor.Calcinationisdonein
thesolidstate.

Application:

9 ToproducecementfromCaCO
9 Tocausedecompositionofhydratedmineralsasincalcinationofbauxitetoproducerefractory
gradeAl O .
9 TocausedecompositionofvolatilemattercontainedinpetroleumCoke.
9 Toheattreattoeffectphasetransformationasindevitrificationofglassmaterials.
9 ToproduceanhydrousAl O forelectrolysisofAl O toAl inHallHeroultcell

Materialsandheatbalanceincalcination
Calcinationrequiresthermalenergy.Thisisillustratedbysolvingfewproblems.Forcalculation,weneed
severalthermochemicalvalueslikeheatofformation,specificheat,andheatcontent.Thefollowing
thermochemicalvaluesarcusedtosolvetheproblemsinthislecture:

Thermochemicalvalues:

CaCO3=CaO+CO2 H 42750 Kcal/Kg.mol


MgCO3=MgO+CO2 H 24250 Kcal/Kg.mol
CO+1/2O2=CO2 H 67900 Kcal/Kg.mol
2Al(OH)3=Al2O3+3H2O H 24290 Kcal/Kg.mol
C+O2=CO2 H 94300 Kcal/Kg.mol
H2+1/2O2=H2O H 68370 Kcal/Kg.mol

CpCaO=49.622+4.519x103T6.945x105 kJ/Kg.molK

CpMgO=48.995+3.138x103T11.715x105 kJ/Kg.molK

CpCO2=75.438kJ/Kg.molK

CpH2O(v)=30.+10.711x103T0.335x105 kJ/Kg.molK

Heatcontent

H1200H298|CaO =10800 Kcal/Kg.mol


H500H298|CO2 =1987 Kcal/Kg.mol
H500H298|N2 =1418 Kcal/Kg.mol
H500H298|O2 =1455 Kcal/Kg.mol
H1000H298|Al2O3 =18710 Kcal/Kg.mol
H800H298|CO2 =5458 Kcal/Kg.mol
H800H298|O2 =3786 Kcal/Kg.mol
H800H298|N2 =3598 Kcal/Kg.mol
H800H298|H2O(l) =14824 Kcal/Kg.mol
H900H298|CO2 =6708 Kcal/Kg.mol
H900H298|O2 =4602 Kcal/Kg.mol
H900H298|N2 =4358 Kcal/Kg.mol
H900H298|CO =4400 Kcal/Kg.mol
LatentHeatofvaporizationofwater=10520kJ/kg.mol

Problemi:decompositionof
1) Calculatetheheatenergyrequiredtocalcine1000Kglimestoneofcomposition
84%CaCO , 8%MgCO and8% H Ochargedat298K.Limeisdischargedat1173Kandgases
leaveat473K.

Solution:

CaCO CaO CO (1)

Mg CO MgO CO (2)

Materialbalancegives

Calcinedproductandgases

CaO 8.4 kg mols

MgO 0.952 kg mols

CO 9.352kg mols

H O 4.444 kg mols

Heatofdecompositionofreaction1and2 382186 k cal.

UsingCpvaluesonecancalculatesensibleheatincalcinedproductsandgases.Referencestateis298K

Sensibleheatinproducts 8.4 Cp CaO dT 0.952 Cp MgO dT

SensibleheatinCO 9.352 Cp CO dT

SensibleheatinH O l canbeevaluatedas

H O , H O ,

H O , H O ,

H O 4.44 Cp H O dT

. Answer

Problem2:amountoffuelincalcination

Itisdesiredtoproduce10kg.mollimefromcalcinationsofCaCO (pure)inarotarykiln.Producergasof
compositionCO 7.2%, O 1.6%, CO 16.6%andN 74.6%iscombustedwith20%excessairtoobtain
thedesiredtemperatureinthekiln.Thelimestoneandairaresuppliedat298K,whereasproducergasis
heatedto900K.Limeisdischargedat1200Kandat500K.
Calculatetheamountofproducergas(1atm.and273K).

LetYkgmolistheproducergas

Materialbalancegives

CO 10 0.238 Y

N 0.74 Y 0.302 Y

O 0.0134 Y

Calorificvalueofproducergas=11271Ykcal.

Performingheatbalance:Heatinput=Heatoutput.

Sensibleheatinproducergas+calorificvalueofproducergasHeatofdecompositionofCaCO =
sensibleheatinCaO sensibleheatinfluegases CO , N and O

Wecalculateallthevaluesandget . Answer

Problem3Calcinationof

Intheelectrolysis,anhydrousaluminaisrequired.Forthispurpose Al OH iscalcinedat1700Kin
rotarykiln.AkilnreceivesadampfiltercakeofAl OH analyzing55% Al O and45%totalH O(free
andcombined)andproduce,pureAl O assolidproduct.Thefuelconsumptionisestimatedtobe0.2Kg
offueloilofcomposition84% Cand16% HperKgofalumina.Airforcombustionis20%excessthan
theoreticalrequired.Assumecompletecombustionandheatlosses10%ofheatinput.Find

a) Thevolumeofgases(At1atm,273K)leavingthekilnper1000KgofAl O produced.
b) Wetanddrycompositionoffluegases.
c) Performtheheatbalanceandcommentontheresults.Assumereactantsenterat298Kand
productsnamelyAl O at1000Kandfluegasesat800K.

Solution:Basisofcalculation1000KgcalcineAl O

Calcinationreaction:

2Al OH Al O 3H O

Combustionreactions

C O CO

2H 0.5O H O

Materialbalancegivesvolumeoffluegases
Fluegasanalysis:onWetbasis(%) Ondrybasis(%)

CO27.8 11.9
O22.5 3.7
N255.4 84.4
H2O34.3

100% 100%

Heatbalancegivesthefollowingresult:

Heatinput(kcal) Heatoutput(kcal)

Combustionoffuel+2414120* Fluegases1362135
SensibleheatinAl2O3183431
Heatofdecomposition2381370 Heatlosses217598

Heatavailable:2175983 Total1763164kcal

* +indicatedheatinputduetoexothermicandindicatesheatabsorption.

Heatbalanceindicatesthatthereis412819kcalheatissurplus.Thissurplusheatmaybeutilized.If
notthenamountoffuelmaybereducedasillustratedinproblem4

Problem4:Fuelsaving

Calculatetheminimumamountoffuel1000KgAl O .Usethedatagiveninproblem3.

Letxkgfuelisrequired.

C 0.84 xandH 0.16 x

Wehavetocalculatefluegas.Thecalculationgiveskgmols

CO 0.07 x

H O 0.08x 45.45

O 0.022 x

N 0.496 x

Heatbalance:

Heat of combustion Heat taken by flue gas Heat taken by Al O heat losses
Performingheatbalancecalculation,wecanget

x 141kgfuelisrequiredtoproduce1000Kgalumina.

Wesave /

Conclusion:

Thislecturediscussesthebasicsofcalcinationbysolvingproblems.Theimportanceofheatbalance
calculationsisshowninproblem4whichshowsthatfuelsavingcanbeachieved.

References:

1)Rao,Y.K:StoichiometryandThermodynamicsofMetallurgicalprocess,CambridgeUniversityPress,
1985

2)Butts,Allison:MetallurgicalProblems,McGrawHillBookCompany,1943

3)Fine,H.AlanandG.H.Geiger:HandbookonMaterialsandEnergyBalanceCalculationsin
MetallurgicalProcesses

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