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

42750

Kcal/Kg.mol

MgCO3=MgO+CO2

24250

Kcal/Kg.mol

CO+1/2O2=CO2

67900

Kcal/Kg.mol

2Al(OH)3=Al2O3+3H2O

24290

Kcal/Kg.mol

C+O2=CO2

94300

Kcal/Kg.mol

H2+1/2O2=H2O

68370

Kcal/Kg.mol

CpCaO=49.622+4.519x103T6.945x105
CpMgO=48.995+3.138x103T11.715x105

kJ/Kg.molK
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
H500H298|N2
H500H298|O2
H1000H298|Al2O3

=1987
=1418
=1455
=18710

Kcal/Kg.mol
Kcal/Kg.mol
Kcal/Kg.mol
Kcal/Kg.mol

H800H298|CO2

=5458

Kcal/Kg.mol

H800H298|O2
H800H298|N2
H800H298|H2O(l)
H900H298|CO2
H900H298|O2
H900H298|N2

=3786
=3598
=14824
=6708
=4602
=4358

Kcal/Kg.mol
Kcal/Kg.mol
Kcal/Kg.mol
Kcal/Kg.mol
Kcal/Kg.mol
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
Mg CO

CaO
MgO

CO (1)
CO (2)

Materialbalancegives
Calcinedproductandgases
CaO

8.4 kg mols

MgO

0.952 kg mols

CO

9.352kg mols

H O

4.444 kg mols

382186 k cal.

Heatofdecompositionofreaction1and2

UsingCpvaluesonecancalculatesensibleheatincalcinedproductsandgases.Referencestateis298K
Sensibleheatinproducts
SensibleheatinCO

8.4

9.352

Cp CaO dT

0.952

Cp MgO dT

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
10

CO
N

0.238 Y

0.74 Y
O

0.302 Y

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
2H
Materialbalancegivesvolumeoffluegases

CO

O
0.5O

H O

Ondrybasis(%)

11.9
3.7
84.4

100%

Fluegasanalysis:onWetbasis(%)

CO27.8
O22.5
N255.4
H2O34.3

100%
Heatbalancegivesthefollowingresult:
Heatinput(kcal)

Combustionoffuel+2414120*

Heatofdecomposition2381370

Heatavailable:2175983

Heatoutput(kcal)

Fluegases1362135
SensibleheatinAl2O3183431
Heatlosses217598

Total1763164kcal

+indicatedheatinputduetoexothermicandindicatesheatabsorption.

Heatbalanceindicatesthatthereis412819kcalheatissurplus.Thissurplusheatmaybeutilized.If
notthenamountoffuelmaybereducedasillustratedinproblem4

Problem4:Fuelsaving
Calculatetheminimumamountoffuel1000KgAl O .Usethedatagiveninproblem3.
Letxkgfuelisrequired.
C

0.84 xandH

0.16 x

Wehavetocalculatefluegas.Thecalculationgiveskgmols
CO
H O

0.07 x
0.08x

45.45

0.022 x

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