Lecture14:Pyrometallurgicalextraction(Roasting)

Contents
Introduction
Roasting
Sourcesofenergy
Determinationofcalorificvalueofgaseousfuel
Amountofair
Typesofroasting
Conclusions
References
Keywords:roasting,deadroasting,sulphatizingroasting
Introduction:
InPyrometallurgicalextractionofmetal,thermalenergyisoneoftheimportantinputs.Differentunit
processeslikeroasting,smelting,convertingandrefiningrequirelargeamountofthermalenergy.This
lecturediscussesroasting.
Roasting
Roastingistheoxidationofmetalsulphidestogivemetaloxidesandsulphurdioxide.Typicalexamples
are:
2 ZnS
2 FeS
2 PbS

3O
5.5 O
3O

2 ZnO
Fe O
2 PbO

2 SO
4 SO
2 SO

Inadditionotherreactionsmaytakeplace:formationofSO andmetalsulphatesandformationof
complexoxidessuchasZnO. Fe O .
Typically,sulphideoresofcopper,zincandleadareroastedeitherpartiallyorcompletely.Copper
sulphideoresareroastedpartially;whereasoresofleadandZincareroastedcompletelyintooxidesfor
subsequenttreatment.ThisSO isthenabyproduct.
Roastingisusuallycarriedoutbelowthemeltingpointsofthesulphidesandoxidesinvolved,usually
below900 1000 .Bothreactantsandproductsareinthesolidstate.

Inroastingoreconcentrateismixedwithforoxidation.Normallyexcessairisusedforroasting.Fuelmay
ormaynotbeused.
Sourcesofenergy
Differentsourcesofthermalenergyare
a) Heatofreaction:CombustionofStoSO or SO releases 70940 k calkg moland
93900 k calkg molofthermalenergyrespectively.Severaloxidationreactionslike
Fe Fe O , FeS FeO, ZnS ZnOandsoonreleasesthermalenergy.Theseenergiescanbe
calculatedfromtheheatofformation.Heatofformationofsomecompoundsis

Compound

H ,

CU2S

18950

ZnS

44000

FeS2

35500

FeS

23100

CO2

94450

CO

26840

Cu2O

42500

CuO

38500

ZnO

83500

PbO

52500

(kcal/kgmol)

Forexample
Cu S c

2O g

2 CuO c

SO g

(c)iscondensedand(g)isgaseousphase
Thisreactionproducesheatat298K
HR

C O

SO


136990 k cal

HR
ZnS
HR

1.5 O

Z O

HR
PbS

ZnO

SO

SO

Z S

110440 k cal
2O

HR

PbSO

197000 kcal

b) Combustionoffuel
Intheoreconcentratesolidfuelismixedforroasting.Solidfuelcontainscarbonandhydrogenbesides
otherelements.Fuelischaracterizedbycalorificvalue.Grosscalorificvalueofasolidfuelcanbe
calculatedby
Grosscalorificvalue kcalkg
GCV

81%C

341 % H

GCV
%O

22% S.

IfthecoalanalysesC 74%, H 6%, N1%, O9%, S 0.8%moisture2.2%andash8%,GCVofcoalis

32060 kJ/kg.
Determinationofcalorificvalueofgaseousfuel
Indeterminationofgaseousfuel,combustiblecomponentsare:CO, H ,hydrocarbons,NH etc.,
whereasO , CO , N arediluents.
Heatsofformationofsomeoxidesare):
Oxides

H (1atm,298K)kcal/kgmol

CO

29.6x103(CAmorphous)

CO

26.4x103

CO2

97.2x103(CAmorphous)

CO2

94.05x103

H2O(I)

68.32x103

H2O(v)

57.80x103

SO2(g)

70.96x103

SO3(g)

94.45x103

Heatsofformationofsomehydrocarbonsare:
H (1atm,298K)kcal/kgmol
17.89x103
54.19x103
12.5x103
20.24x103
24.82x103

Hydrocarbons
CH4
C2H2
C2H4
C2H6
C3H8

Tonote

1 kgmol
1 kgmol

22.4 m 1 atm, 0
24.45 m 1 atm, 25

Consideranexampleofgaseousfuelofthefollowingcomposition:
CH

4%

C H

3%

C H
N and CO

0.5%
Rest

LetuscalculateCVofthisfuel
In1kgmoleofgaseousfuel:
Kgmoles

0.94
0.03
0.005

CH4=
C2H6=
C3H8=

HeatofcombustionofMethane
CH4(g)+2

(g)=

Heat of combustion

Heat of formation of products

Heat of formation of reactants

Bysubstitutingthevaluesofheatofformationoneobtainsheatofcombustionofmethaneequals
194.91 10 k calkg mol.
Similarly,combustionequationsforC H andC H canbewrittenandheatofcombustionvaluecanbe
calculated.

HeatofcombustionofC H
350.56 10 k calkg molandofC H is
498.18 10 k calkg molwhenreferencestateofPOCisvapour.Thusnetcalorificvalue(NCV)of
naturalgasis
|NCV|

0.94

194.91

10

0.03

350.56

10

0.005

498.18

10

10 k calkg molofnaturalgas

196.22

10 k calm (1atmand273K)

8.76

Amountofair
Inroasting,airisusedforoxidationofsulphidesaswellasforcombustionofcoal.Calculationofamount
ofairisimportant.
Stoichiometricamountofair(Alsotermedtheoreticalairorairforcompleteconversionofsulphideinto
oxideorforcompletecombustion)canbecalculatedbyconsideringtheproductsofcombustion.
Considerthereaction
C

CO 1)

ZnS

1.5 O

PbO

SO 3)

PbS

1.5 O

PbO

SO 4)

H O2)

Theequations1to4arechemicallybalancedequations.Inequation1,werequire1moleofoxygento
produce1moleof CO andinequation3or4werequire1.5molofSO .Itisknownthat1moleof
oxygenisobtainedfrom4.76molesofair.
Letuscalculatestoichiometricamountofairforcombustionofsolidfuelofcomposition
84%C, 5%H, 5%moistureand6%ash,perKgofcoal.Followingthestoichiometryofcombustion,the
amountofairwouldbe
0.84
12

0.05
2

4.76

0.452

moles
coal
kg

10.12m 1 atm, 273K /kg coal

Note1 kg mole

22.4 m 1 atm, 273 K

Excess air

Actual amount of air theoretical air

theoretical air

actual amount of O
theoretical O
theoretical air O

100

100

Intheaboveexampleifactualamountofairis0.5molsthen
Excess air

0.5 0.452
0.452

100

10.62%

Wecanalsocallthat110.62%theoreticalairisusedforcombustion.
Similarlystoichiometricamountofaircanbecalculatedforreaction3and4.Ifreactions3and4occur
simultaneouslythenstoichiometricamountofoxygenis3molsandstoichiometricairis14.28mols.
Typesofroasting
Indeadroastingallsulphidesareconvertedintooxide.ThisisdonetoextractZnfromitssulphideore.
Insulphatisingroasting,sulphideisconvertedintosulphateassulphatecanbedissolvedeasilyintoan
aqueoussolution.Typicallyusedforhydrometallurgicalextractionofleadsulphideores.
Conclusions
Thislecturediscussesroasting.Roastingismainlyusedinproductionofcopper,lead,zincetc.Inroasting
sometimefuelisused.Thecalculationprocedureforcalorificvalueofsolidfuelandgaseousfuelis
illustratedthroughanexample.Typeofroastingpresentedhereisinbrief.Detailscanbeseeninthe
referencesgivenbelow.

Reference:
1) Resenquist:principlesofextractivemetallurgy
2) HSRay,RSridharandK.PAbraham:extractionofnonferrousmetals.