Charge calculations in pyrometallurgical processes

Charge calculations are carried out prior to operating a metallurgical process to determine
the quantity of each type of raw material fed to the furnace in order to obtain the desired
quantity of products

It is similar to stoichiometric problems but the engineer has to have a detailed knowledge on
the internal working of the process in order to write the relevant reactions

Material balance by careful and detailed tracking of all elements in the input and output is
the prerequisite of heat balance and complete definition of the system

Multiple reactions in metallurgical process makes it hard to keep track of all the chemical
species in the reactants and products

Complex charge calculation problems can be solved easily by simplifying assumptions

e.g. It is safe to assume in iron blast furnace that all CaO, MgO and Al2O3 of the charge end
up in the slag
Also molten pig iron can be considered to contain all Fe coming from the ore
All CO2 in the flue gases can be thought to originate from the reactions and air is simply O2
and N2
Charge calculation problems

Hints for effective material balance problem solving:

1 – Read the question to understand the process, materials and unknowns
2 – Draw a diagram
3 – Define a base
4 – Write down the independent equations and relations
5 – Perform degree of freedom analysis
6 – Do stoichiometric and materials balance calculations
7 – Check your calculations
Example – Combustion of coal in furnace
Ultimate Analysis wt%
Material C H N S O
Coal 85 5 1 2 7

Base: 1000 kg coal

C = 0.85*1000= 850 kg T, P Flue gases
H = 0.05*1000= 5 kg CO2
N = 0.01*1000= 10 kg Reacting Gaseous Mixture SO2
S = 0.02*1000= 20 kg H2O
O = 0.07*1000= 70 kg N2
C + O2 = CO2
Air = O2, N2 Chemical reactions H2 + 1/2O2 = H2O
S + O2 = SO2
Degree of freedom analysis
Base: 1000 kg coal
C = 0.85*1000= 850 kg T, P VG Flue gases
H = 0.05*1000= 5 kg XCO2 CO2
N = 0.01*1000= 10 kg Reacting Gaseous Mixture XSO2 SO2
S = 0.02*1000= 20 kg XH2O H2O
O = 0.07*1000= 70 kg XN2 N2
C + O2 = CO2
VA Air Chemical reactions H2 + 1/2O2 = H2O
21% O2, 79% N2 S + O2 = SO2
Material balance type – Initial input + generation = Final output + consumption

6 unknown labeled variables (VA,VG, XCO2, XH2O, XSO2, XN2)

- 4 independent atomic species balances that are involved in the reactions (C, H, S, O)
- 1 molecular balances on independent nonreactive species (N2)
- 1 other equation relating unknown variables (XCO2 + XH2O + XSO2 + XN2 =1)
= 0 degrees of freedom
 Base: 1000 kg coal
C = 0.85*1000= 850 kg STP VG Flue gases
H = 0.05*1000= 5 kg XCO2 CO2
N = 0.01*1000= 10 kg Reacting Gaseous Mixture XSO2 SO2
S = 0.02*1000= 20 kg XH2O H2O
O = 0.07*1000= 70 kg XN2 N2
C + O2 = CO2
VA Air Chemical reactions H2 + 1/2O2 = H2O
21% O2, 79% N2 S + O2 = SO2
Calculate the volume of air necessary for complete combustion

Stoichiometry calculation
nC = 850/12 = 70.83 kg-atom C + O2 = CO2 O2 consumption = 70.83 kg-mole
nH2 = 50/2 = 25 kg-mole H2 + 1/2O2 = H2O O2 consumption = 12.5 kg-mole
nS = 20/32 = 0.625 kg-atom S + O2 = SO2 O2 consumption = 0.625 kg-mole
nO = 70/16 = 4.375 kg-atom nO2 = 2.1875 kg-mole O2 input from coal= 2.1875 kg-mole
O2 input from air= 81.7675 kg-mole
O2 balance – Input + generation (0) = output (0) + consumption

81.7675∗22.4
Volume of air = = 8721 𝑚3 per 1000 kg coal
0.21
Excess reactants

5000 m3 of regenerator gas of following composition is used to heat an open hearth furnace
at 300 C per hour:
Rational Analysis wt%
Material CO CO2 H2 CH4 H2 O N2
Gaseous fuel 22 6 10 3 3 56

Air at 800 C is consumed 20% in excess of the theoretical requirement

300 C, 1 atm V𝐺 Flue gases
XCO2 CO2
Gaseous fuel 5000 m3/hr XH2O H2O
56% N2, 22% CO, 10% H2,
6% CO2, 3% CH4, 3% H2O XN2 N2
XO2 O2

V𝐴 Air 800 C
79% N2, 21% O2

Combustion reactions
CO + 1/2 O2 = CO2
H2 + ½ O2 = H2O
CH4 + 2O2 = CO2 + 2H2O
Degree of freedom analysis
300 C, 1 atm V𝐺 Flue gases
XCO2 CO2
Gaseous fuel 5000 m3/hr XH2O H2O
56% N2, 22% CO, 10% H2,
6% CO2, 3% CH4, 3% H2O XN2 N2
XO2 O2

V𝐴 Air 800 C
79% N2, 21% O2

Combustion reactions Material balance type – input + generation = output + consumption

CO + 1/2 O2 = CO2
H2 + ½ O2 = H2O
CH4 + 2O2 = CO2 + 2H2O

6 unknown labeled variables (V𝐴 , V𝐺 , XCO2, XH2O, XO2, XN2)

+ 3 independent chemical reactions
- 7 independent molecular species balances (CO, H2O, H2, CO2, CH4, O2, N2)
1
- 2 other equation relating unknown variables (XCO2 + XH2O + XO2 + XN2 =1, ∗ 0.21 ∗ V𝐴 = V𝐺 ∗
6
𝑋𝑂2 )
= 0 degrees of freedom
Air at 800 C is consumed 20% in excess of the theoretical requirement

300 C, 1 atm Flue gases

CO2
Gaseous fuel 5000 m3/hr H2 O
56% N2, 22% CO, 10% H2,
6% CO2, 3% CH4, 3% H2O N2
O2

Air 800 C
79% N2, 21% O2
Calculate the volume of air required to burn 1 m3 of regenerator gas per hour, then scale up

Basis: 1 m3/hr of regenerator gas

Gas composition @ 300 C Gas composition @ 0 C
𝑃1 𝑉1 𝑃2 𝑉2
0.22 m3 CO = CO = 0.22*(273/573) = 0.105 m3
0.10 m3 H2 𝑇1 𝑇2 H2 = 0.10*(273/573) = 0.048 m3
0.03 m3 CH4 𝑃1 = 𝑃2 = 1 𝑎𝑡𝑚 CH4 = 0.03*(273/573) = 0.014 m3
0.06 m3 CO2 CO2 = 0.06*(273/573) = 0.028 m3
0.03 m3 H2O 𝑇1 H2O = 0.03*(273/573) = 0.014 m3
0.56 m3 N2 𝑉1 = 𝑉2 N2 = 0.56*(273/573) = 0.267 m3
𝑇2
O2 requirements from combustion reactions Volume of O2 at STP = 0.1045 m3
CO + 1/2 O2 = CO2 O2 = 0.0525 m3 Volume of O2 at 800 C = 0.412 m3
H2 + ½ O2 = H2O O2 = 0.024 m3 Theoretical air volume = 0.421/0.21
CH4 + 2O2 = CO2 + 2H2O O2 = 0.028 m3 = 1.96 m3
Total O2 = 0.1045 m3 Real air volume = 1.96*1.2 = 2.35 m3
Air at 800 C is consumed 20% in excess of the theoretical requirement

300 C, 1 atm 4985 m3/hr

Gaseous fuel 5000 m3/hr Flue gases
56% N2, 22% CO, 10% H2, CO2 14.8%
6% CO2, 3% CH4, 3% H2O H2O 9.1%
N2 74.0%
11750 m3/hr Air 800 C O2 2.1%
79% N2, 21% O2
Calculate the composition of flue gases

Basis: 1 m3 of regenerator gas

Gas composition @ STP Air composition @ STP
CO = 0.22*(273/573) = 0.105 m3 O2 = 0.1045*1.2 = 0.1255 m3
H2 = 0.10*(273/573) = 0.048 m3 N2 = 0.1255*(79/21) = 0.472 m3
CH4 = 0.03*(273/573) = 0.014 m3
CO2 = 0.06*(273/573) = 0.028 m3
H2O = 0.03*(273/573) = 0.014 m3
N2 = 0.56*(273/573) = 0.267 m3

Flue gas composition

CO2 = CO2(combustion1) + CO2(combustion3) + CO2(gas) = 0.105 + 0.014 + 0.028 = 0.147 m3 / 14.8%
H2O = H2O(combustion2) + H2O(combustion3) + H2O(gas) = 0.048 + 0.028 + 0.014 = 0.090 m3 / 9.1%
N2 = N2(gas) + N2(air) = 0.267 + 0.472 = 0.739 m3 / 74.0%
O2 = O2(air) – O2(combustion1,2,3) = 0.1255 – 0.1045 = 0.021 m3 / 2.1%
Nitriding Gas Treatment

Iron is nitrided by passing a mixture of gaseous ammonia and hydrogen through a furnace
Rational Gas Analysis wt%
3000 ml/hr 500 C, 1 atm Material NH3 H2
Gas input at 500 C Incoming gas 10 90
90% H2, 10% NH3
Outlet gas 7 93
Reactions
NH3 = ½ N2 + 3/2 H2 𝑉𝐺 Gas output
½ N2 = N Fe N 93% H2, 7% NH3

Calculate the amount of nitrogen, in gram/hr, that the iron picks up from the gas flowing in at a
rate of 50 ml/min at 500 C

DOF analysis Material balance type – Input + generation - output - consumption =

accumulation
2 unknown labeled variables (V𝐺 , 𝑚𝑁2 )
+ 2 independent chemical reactions
- 3 independent molecular species balances (NH3, H2, N2)
- 1 other equation relating unknown variables (PV=m/MW*RT)
= 0 degrees of freedom
Nitriding Gas Treatment

Iron is nitrided by passing a mixture of gaseous ammonia and hydrogen through a furnace
Rational Gas Analysis wt%
500 C, 1 atm Material NH3 H2
Gas input
90% H2, 10% NH3
Incoming gas 10 90
Outlet gas 7 93
Reactions
NH3 = ½ N2 + 3/2 H2 Gas output
½ N2 = N Fe N 93% H2, 7% NH3

Calculate the amount of nitrogen, in gram/ hr, that the iron picks up from the gas flowing in at
a rate of 50 ml/min at 500 C

Basis: 3000 ml/hours of gas input

Input Output
NH3 = 300 ml NH3 = (300-x) ml where x is volume of consumed NH3
H2 = 2700 ml H2 = (2700+3/2x) ml where 3/2x is the volume of generated H2
Total = 3000 ml Total = 3000+1/2x
%NH3 = 7/100 = (300-x)/(3000+x/2) volume of consumed NH3, x = 86.96 ml/hr

NH3 = ½ N2 + 3/2 H2 N2 generated per hour = 1/2x = ½*86.96 = 43.48 ml

½ N2 = N N consumed in steel = 14 g/11200 ml N2 = 0.5475 g N / 43.48 ml N2
Calcination
Calcination is a thermal treatment process applied to ores and other solid materials in order
to induce removal of volatile components like CO2 and H2O by thermal decomposition

Inputs – Solid ore, fuel gas, air

Outputs – Solid calcine, off-gas

Calcination temperature is below the melting point of the components of the raw material
Solid ores are treated in the solid state and the product is also solid except the volatile
components

Components of fuel gas are typically CO, hydrogen, oxygen and hydrocarbons which are the
combustible components and CO2, N2 which are the diluents that do not take part in the
combustion
Calcination example
Limestone is not the preferred flux in various steel making processes since its decomposition
is associated with a large amount of absorption of energy
Charging of lime after calcination of limestone is more energy efficient

Rotary kiln is very often used to produce lime by calcination of limestone

Rotary kilns are very long kilns that rotate 2 to 3 degree from the horizontal axis
The feed enters and from other side, the calcine material discharges and they are frequently
heated by an externals source of energy

Other commercial uses of rotary kiln is cement and the removal of water from alumina
Calcination furnace analysis
Magnesium carbonate is decomposed to make MgO and CO2 by heating in a rotary kiln,
using as fuel a natural gas
CO2 formed by decomposition of magnesium carbonate mixes with the products of
combustion to form the flue gas product
Fuel consumption is 250 m3/ton MgO at STP
Rational Gas Analysis wt%
Material CH4 C2H6 C3H8 CO2 N2 O2 H2 O

Natural gas 80 15 5
Flue gas 19.27 64.33 3.98 12.42

Ore MgCO3

Flue gases Rotary Kiln

64.33 % N2 Air
3.98 % O2
19.27 % CO2 Fuel 250 m3/ton MgO
12.42% O2 80% CH4
Reactions 15% C2H6
1000 kg/hr Calcine 5% C3H8
MgCO3 = MgO + CO2 MgO
CH4 + 2O2 = 2H2O + CO2
C2H6 + 7/2O2 = 3H2O + 2CO2
C3H8 + 5O2 = 4H2O + 3CO2
𝑚𝑂 Ore
MgCO3

𝑉𝐺 Flue gases Rotary Kiln

64.33 % N2 𝑉𝐴 Air at STP
3.98 % O2
19.27 % CO2 Fuel 250 m3/ton MgO
12.42% H2O 80% CH4
DOF analysis 15% C2H6
1000 kg/hr 5% C3H8
Reactions Calcine
MgO
MgCO3 = MgO + CO2
CH4 + 2O2 = 2H2O + CO2 Material balance type – Input + generation = Output + consumption
C2H6 + 7/2O2 = 3H2O + 2CO2
C3H8 + 5O2 = 4H2O + 3CO2

3 unknown labeled variables (V𝐴 , V𝐺 , 𝑚𝑂 )

+ 4 independent chemical reactions
- 9 independent molecular species balances (MgCO3, MgO, H2O, C3H8, C2H6, CO2, CH4, O2, N2)
- 1 other equation relating unknown variables (E ∗ 0.21 ∗ V𝐴 = V𝐺 ∗ 0.0398)
= -3 degrees of freedom!
 Basis 1000 kg/hr of MgO
Ore
MgCO3

𝑉𝐺 Flue gases Rotary Kiln

64.33 % N2
Air 3687 m3
3.98 % O2
19.27 % CO2 Fuel 250 m3/ton MgO
12.42% H2O 80% CH4
Calcine 15% C2H6
1000 kg MgO
5% C3H8
Calculate the air consumption in m3 per ton of MgO produced per hour

Reactions CO2 balance

MgCO3 = MgO + CO2 kg-mole MgO = 1000/MWMgO = 25 kg-mole = CO2 from MgCO3
CH4 + 2O2 = 2H2O + CO2 kg-mole CH4 = 250*(80/100) = 200 m3/ton MgO = 8.93 kg-mole CH4
= 8.93 kg-mole CO2
C2H6 + 7/2O2 = 3H2O + 2CO2 kg-mole C2H6 = 250*(15/100) = 37.5 m3/ton MgO = 1.67 kg-mole C2H6
= 2*1.67 kg-mole C2H6 = 3.34 kg-mole CO2
C3H8 + 5O2 = 4H2O + 3CO2 kg-mole C3H8 = 250*(5/100) = 12.5 m3/ton MgO = 0.56 kg-mole C3H8
= 3*0.56 kg-mole C3H8 = 1.68 kg-mole CO2
Total kg-mole CO2 = 25 + 8.93 + 3.34 + 1.68 = 38.95 kg-mole
Total flue gas = 38.95*(100/19.27) = 202.155 kg-mole
Total N2 = 202.155*(64.33/100) = 130.04 kg-mole N2

Since N2 in air = N2 in flue gas, Air consumption = 130.04*(100/79) = 164.6 kg-mole air/ ton MgO
= 164.6*22.4 = 3687 m3 (STP) / ton MgO
 Basis 1000 kg of MgO
Ore
MgCO3

Flue gases
Rotary Kiln Air 3687 m3
202.155 kg-mole
64.33 % N2
3.98 % O2 Fuel 250 m3/ton MgO
19.27 % CO2 80% CH4
12.42% H2O
Calcine 15% C2H6
1000 kg MgO
5% C3H8
Calculate the percent excess air

Excess O2 = 202.155*(3.98/100) = 8.055 kg-mole

Excess air = 8.055*(100/21) = 38.36 kg-mole
% Excess air = (38.36/(164.6-38.36))*100 = 30.38

Theoretical air = 164.6-38.36 = 126.24 kg-mole

Roasting

Roasting is a preliminary step of metal extraction from sulphide ores

The process is partial or complete conversion of metal sulphide to oxide, sulphate or chlorides
Oxide can be easily reduced; sulphate and chloride can be easily dissolved

Sulphide ores cannot be used to produce metal by pyrometallurgy

It is very difficult to reduce sulphide directly into the metal

Carbon and hydrogen are not effective reducing agent to
produce metal from sulphide as seen in the Ellingham

Another issue with direct reduction of metal sulphides is

that there exist a mutual solubility between metal and
sulphides which makes it difficult to extract the metal by
pyrometallurgy

So the only route is to convert sulphide to oxide

Inputs – Sulphide ore, air, fuel if necessary

Outputs – Calcine, off-gas
Roasting is carried out below the melting point of the components of the ore
By virtue of this, the roast product is in solid state in addition to the solid ore concentrate

Temperatures involved during roasting is of the order of 900 to 1100 degrees Celsius

Byproducts of roasting are rich in SO2 because sulphide ore has 20-30 % sulphur depending
on the deposit
So a large amount of a SO2, SO3 and nitrogen will be produced as the off-gas
These sulphurious gases are used to produce H2SO4

Oxidation of sulphides is exothermic and can supply all the energy needed for roasting to be
self-sustaining

Heats of formation of some sulphides:

Cu2S = -18950 kilocalories per kg mole Cu2 S + O2 = 2CuO + SO2
ZnS = -44000 kilocalories per kg mole
FeS2 = -35500 kilocalories per kg mole Heat generated by oxidation reaction
CuO = -37100 kilocalories per kg mole -136900 kilocalories per kg mole
SO2 = -70940 kilocalories per kg mole
SO3 = -93900 kilocalories per kg mole
CO2 = -94450 kilocalories per kg mole
CO = -26840 kilocalories per kg mole

If fuel is also used, there is also carbon dioxide and carbon monoxide in the off-gas
Types of roasting

Oxidizing roasting
Sulphide ore is oxidized by passing air and providing an oxidizing atmosphere
The amount of oxidation must be controlled so that the formation of metal sulphate is
avoided if it is not desired
e.g. PbS + O2 = PbSO4 and PbO
High temperature is required to break up the metal sulphate

In dead roasting all sulphur is eliminated

However, if the extraction of metal is to be done through hydrometallurgical means, sulphate
formation is preferred because sulphates dissolve easily in the solvent

Sulphatising roasting
As the name suggests the objective is to convert all sulphide into sulphate in an oxidizing
atmosphere

Chloridizing roasting
The objective of chloridizing roasting is to convert a metal sulphide or oxide into chlorides
e.g. 2NaCl + MS + 2O2 = Na2 SO4 + MCl2 direct chlorination
4NaCl + 2MO + S2 + 3O2 = 2Na2 SO4 + 2MCl2 indirect chlorination
Roasting furnace analysis
Pyrometallurgical extraction of ores rich in CuS, FeS2, ZnS is uneconomical due the difficulties
involved in concentrating the ore
Roasting is needed to remove all of the sulfur and subsequently to leach the ore in dilute
sulfuric acid for the recovery of copper and zinc by hydrometallurgical methods
Rational Analysis wt%
Material Cu Fe Zn SiO2 S CaO, SO2 SO3 O2, N2
Al2O3, etc
Ore 6 25 4 20 33.6 11.4
Roast gases 2.5 0.4 97.1

Copper, iron and zinc of the ore oxidize to CuO, Fe2O3 and ZnO
Basis 1000 kg of copper ore
Ore Flue gases
4% ZnS 2.5% SO2
6% CuS 0.4% SO3
25% FeS2 O2, N2
20% SiO2
11.4% CaO, Al2O3, etc
33.6% S
Air Calcine
Reactions ZnO
CuS + 3/2O2 = CuO + SO2 CuO Leaching
Fe2O3
2FeS2 + 11/2O2 = Fe2O3 + 4SO2 SiO2
ZnS + 3/2O2 = ZnO + SO2 CaO, Al2O3
SO2 + 1/2O2 = SO3
1000 kg Ore
4% Zn
6% Cu VG Flue gases
25% Fe 2.5% SO2
20% SiO2 0.4% SO3
11.4% CaO, Al2O3, etc XO2 O2
33.6% S XN2 N2

VA Air at STP mc Calcine

XZnO ZnO
XCuO CuO Leaching
Reactions XFe2O3 Fe2O3
CuS + 3/2O2 = CuO + SO2 XSiO2 SiO2
2FeS2 + 11/2O2 = Fe2O3 + 4SO2 XCaO, Al2O3,etc CaO, Al2O3, etc
ZnS + 3/2O2 = ZnO + SO2
SO2 + 1/2O2 = SO3 Material balance type – Input + generation = output + consumption

DOF analysis
10 unknown labeled variables (VA,VG, mc, XZnO, XCuO, XFe2O3, XSiO2, XCaO, Al2O3,etc, XO2, XN2)
- 5 independent atomic species balances that are involved in the reactions (Zn, Cu, Fe, S, O)
- 3 molecular balances on independent nonreactive species (N2, CaO, SiO2)
- 2 other equations relating unknown variables (XO2+ XN2=0.971, XZnO + XCuO + XFe2O3 + XSiO2 + XCaO
= 1)
= 0 degrees of freedom
 Basis 1000 kg of copper ore
Ore Flue gases
4% Zn as ZnS 2.5% SO2
6% Cu as CuS 0.4% SO3
25% Fe as FeS2 O2, N2
20% SiO2
11.4% CaO, Al2O3, etc Calcine
33.6% S ZnO SiO2 Leaching
Air CuO CaO, Al2O3
Fe2O3
Calculate the weight and approximate analysis of the calcine resulting from roasting 1 ton ore
Base: 1000 kg ore
Input 1000 kg Output
Cu 60 kg CuO 60*(80/64) = 75 kg
Fe 250 kg Fe2O3 250*(160/112) = 357 kg
Zn 40 kg ZnO 40*(81/65) = 50 kg
SiO2 200 kg SiO2 200 kg
CaO, Al2O3, etc 114 kg CaO, Al2O3, etc 114 kg
S 336 kg
Total 1000kg Total solids 796 kg

Analysis of calcine
CuO = (75/796)*100 = 9.4% Fe2O3 = (357/796)*100 = 44.9%
ZnO = (50/796)*100 = 6.3% SiO2 = (200/796)*100 = 25.1%
Others (CaO, Al2O3, etc) = (114/796)*100 = 14.3%
 Basis 1000 kg of copper ore
Ore Flue gases
40 kg Zn 2.5% SO2
60 kg Cu 0.4% SO3
250 kg Fe O2, N2
200 kg SiO2
114 kg CaO, Al2O3, etc Calcine
336 kg S ZnO SiO2 Leaching
Air CuO CaO, Al2O3
Fe2O3
Calculate the volume of flue gases per ton of ore
Reactions
96
60∗64
CuS + 3/2O2 = CuO + SO2 VSO2 = 22.4 ∗ 1 ∗ = 21 𝑚3
96
120
250∗112
2FeS2 + 11/2O2 = Fe2O3 + 4SO2 VSO2 = 22.4 ∗ 4 ∗ 120
= 200 𝑚3 235 𝑚3
97
40∗65
ZnS + 3/2O2 = ZnO + SO2 VSO2 = 22.4 ∗ 1 ∗ = 14 𝑚3
97
SO2 + 1/2O2 = SO3 VSO2 = 235 − x 𝑚3 , V SO3 = x 𝑚3
%SO2 = 2.5/100 = (235-x)/Vfluegas
%SO3 = 0.4/100 = (x/Vfluegas)
Vfluegas = 8103.5 𝑚3 , VSO3 = x = 32.4 𝑚3 , VSO2 = 202.6 𝑚3
 Basis 1000 kg of copper ore
Ore Flue gases 8103.5 𝑚3
40 kg Zn SO2 202.6 𝑚3
60 kg Cu SO3 32.4 𝑚3
250 kg Fe O2, N2 7868.5 𝑚3
200 kg SiO2
114 kg CaO, Al2O3, etc Calcine
336 kg S ZnO SiO2 Leaching
Air CuO CaO, Al2O3
Fe2O3
Calculate the volume roasting air, percent excess and the composition of the flue gases
Roasting reactions Volume of O2 consumed
96
3 60∗64
CuS + 3/2O2 = CuO + SO2 VO2 = 22.4 ∗ ∗ = 31.5 𝑚3
2 96
120
11 250∗112
2FeS2 + 11/2O2 = Fe2O3 + 4SO2 VO2 = 22.4 ∗ 2
∗ 120
= 275 𝑚3
97 343.7 𝑚3
3 40∗65
ZnS + 3/2O2 = ZnO + SO2 VO2 = 22.4 ∗ 2 ∗ = 21 𝑚3
97
1
SO2 + 1/2O2 = SO3 VO2 = 32.4 ∗ 2 = 16.2 𝑚3
Theoretical air input Vair-th = (343.7/0.21) = 1636.67 𝑚3
Percentage of excess air has to be calculated from O2+N2 balance in order to obtain actual air V
𝑉𝑂2+𝑁2 = 𝑉𝑎𝑖𝑟−𝑡ℎ + 𝑉𝑒𝑥𝑐𝑒𝑠𝑠 − 𝑉𝑂2𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
7868.5 = 1636.67 + 1636.67 ∗ 𝑦 − 343.7
𝑦 = 4.02, 𝑉 = 1636.67 + 1636.7 ∗ 4.02 = 8216.07 𝑚3
𝑉𝑂2𝑒𝑥𝑐𝑒𝑠𝑠 = 8216.07 ∗ 0.21 − 343.7 = 1381.67 𝑚3 , 𝑉𝑁2 = 8216.07 ∗ 0.79 = 6490.69 𝑚3
Smelting
It is a unit process similar to roasting, to heat a mixture of ore concentrate above the melting
point
The objective is to separate the gangue mineral from liquid metal or matte
The state of the gangue mineral in case of smelting is liquid which is the main difference
between roasting and smelting

Inputs – Ore, flux, fuel, air

Output – Metal or Matte, slag

When metal is separated as sulphide from smelting of ore, it is called Matte smelting
e.g. Cu2S and FeS
When metal is separated as liquid, it is called reduction smelting
e.g. Ironmaking

Density of liquid metal or matte is around 5-5.5 g/cm3

Density of slag is around 2.8-3 g/cm3

The additives and fluxes serve to convert the waste or gangue materials in the charge into a
low melting point slag which also dissolves the coke ash and removes sulphur
Ironmaking
About 1 billion tonnes of iron is produced in the world annually by blast furnaces
Blast furnace economics are such that larger units have lower unit production costs, hence
modern blast furnaces are bigger and produce more than 10000 tonnes per day

The blast furnace is a counter-current reactor in which the descending column of burden
materials reacts with the ascending hot gases
The process is continuous with raw materials being regularly charged to the top of the furnace
and molten iron and slag being tapped from the bottom of the furnace at regular intervals

free moisture is driven off from the burden

materials and hydrates and carbonates
are disassociated indirect reduction of the iron oxides by
carbon monoxide and hydrogen occurs
the burden starts to soften and melt, at 700-1,000 C
direct reduction of the iron and other oxides
and carbonization by the coke occurs
at 1,000-1,600 C
Molten iron and slag start to drip combustion air that is preheated
through to the bottom of the furnace to 900-1,300 C and often enriched with
oxygen is blown into the furnace
in the combustion zone at 1,850-2,200 C, coke
reacts with the oxygen and steam in the blast
to form carbon monoxide and hydrogen
as well as heat iron and slag melt completely
The blast furnace itself is a steel shaft lined with fire resistant, refractory materials
The hottest part of furnace - where the walls reach a temperature >300 °C - are water cooled

Coke is a principle source of thermal energy and as well as chemical energy in ironmaking
Carbon of the coke reduces iron oxide to iron
The combustion of carbon of coke also provides a thermal energy

Hot blast air is introduced through the tuyere so a counter current against the descending
burden is created by the gases travelling upward

In any counter current heat and mass exchange reactor, which consists of gas and solid, the
permeability of the bed and the distribution of the burden are very important issues

For the smooth operation of the blast furnace, the upward rising gases should travel
unhindered
They should also transfer their heat and mass to the descending burden
The burden distribution should be homogeneous so that it constitutes a uniform distribution
of iron and facilitate smooth movement of burden gases
Carbon of coke reacts with O2 at the tuyere level because of availability of oxygen
C + O2 + 3.76N2 = CO2 + 3.76N2
CO2 + 3.76N2 + C = 2CO + 3.76N2

Upward gas rising consists of CO, CO2 and nitrogen

A temperature approximately around 1900-2100 C is created as a result of reaction of carbon

of coke with oxygen at the tuyere level
The exit temperature of the gas is approximately somewhere between 200 to 250 C during
the discharge from the top of the furnace

The following reactions do not require very high percentage of carbon monoxide
So they can occur towards the upper region

3Fe2 O3 + CO = 2Fe3 O4 + CO2

Fe3 O4 + CO = 3FeO + CO2

whereas, the reaction FeO + CO = Fe + CO2 requires high concentration of CO

So it occurs near the middle of the furnace where the concentration of CO is high
At around 900 C, the equilibrium concentration of CO in the CO-CO2 mixture is around 65 to
70 percent for FeO to be able to reduce to iron
Some iron oxide is also reduced directly by carbon
This reduction is endothermic in nature, whereas all other reactions are exothermic
reduction.
Iron blast furnace analysis

Consider an iron blast furnace charged with iron ore, limestone and coke of following analyses:
Rational Analysis wt%
Material Fe2O3 SiO2 MnO Al2O3 H2 O C CaCO3
Ore 80 12 1 3 4
Limestone 4 1 95
Coke 10 90

The ultimate analysis of the pig iron gives 93.8% Fe, 4% C, 1.2% Si, 1% Mn
For every ton of pig iron produced, 1750 kg of iron ore and 500 kg limestone are used and 4200
m3 of flue gas is produced
The rational analysis of flue gases gives 58% N2, 26% CO, 12% CO2, 4% H2O
Basis 1000 kg of pig iron
Blast furnace gas 4200m3
Ore 1750 kg
Limestone 500 kg Slag
Coke

Air Pig iron 1000 kg

Reactions
Fe2O3 + 3CO = 2Fe + 3CO2 SiO2 + 2C = Si + 2CO
CaCO3 = CaO + CO2 MnO + C = Mn + CO
C + 1/2O2 = CO CO2 + C = 2CO
Basis 1000 kg/hr of pig iron
Ore 1750 kg/hr Blast furnace gas 4200m3
80% Fe2O3, 12% SiO2, 1% MnO,
58% N2, 26% CO, 12% CO2, 4% H2O
3% Al2O3, 4% H2O
Limestone 500 kg/hr Slag 𝑚𝑆
95% CaCO3, 1% H2O, 4% SiO2
Fe2O3, SiO2, MnO, Al2O3, CaO
Coke 𝑚𝐶
10% SiO2, 90% C
Air Pig iron 1000 kg
Reactions 93.8% Fe,4% C, 1.2% Si, 1% Mn

Fe2O3 + 3CO = 2Fe + 3CO2 SiO2 + 2C = Si + 2CO

CaCO3 = CaO + CO2 MnO + C = Mn + CO
C + 1/2O2 = CO CO2 + C = 2CO
C + O2 = CO2

DOF analysis

8 unknown labeled variables (V𝐴 , 𝑚𝐶 , 𝑚𝑆 , XFe2O3, XSiO2, XMnO, XAl2O3, XCaO)

+ 7 independent chemical reactions
- 14 independent molecular species balances (Fe2O3, SiO2, MnO, Al2O3, H2O, CaCO3, C, CO, CO2,
O2, N2, Mn, Si, Fe)
- 1 other equation relating unknown variables (XFe2O3+ XSiO2+ XMnO+ XAl2O3+ XCaO =1)
= 0 degrees of freedom
Basis 1000 kg of pig iron
Ore 1750 kg Blast furnace gas 4200m3
80% Fe2O3, 12% SiO2, 1% MnO,
58% N2, 26% CO, 12% CO2, 4% H2O
3% Al2O3, 4% H2O
Limestone 500 kg Slag
95% CaCO3, 1% H2O, 4% SiO2
Coke
10% SiO2, 90% C
Air Pig iron 1000 kg
Reactions 93.8% Fe,4% C, 1.2% Si, 1% Mn

Fe2O3 + 3CO = 2Fe + 3CO2 SiO2 + 2C = Si + 2CO

CaCO3 = CaO + CO2 MnO + C = Mn + CO
C + 1/2O2 = CO CO2 + C = 2CO

Calculate the quantity of coke used per ton of pig iron

Carbon balance:
Ccoke + Climestone = C pig iron + Cflue gas let x be the weight of coke

0.9𝑥 0.95 ∗ 500 ∗ 12/100 0.04 ∗ 1000 4200 ∗ 0.26 4200 ∗ 0.12
+ = + +
12 12 12 22.4 22.4

0.075x + 4.75 = 3.333 + 71.25, x= 69.833/0.075=931 kg coke per ton of pig iron

Calculate the air consumption per ton of pig iron

N2 balance:
N2(air) = N2(flue gas) = 4200*0.58 = 2436 m3, Air consumption = 2436*(100/79) = 3083.5m3
Basis 1000 kg of pig iron
Ore 1750 kg Blast furnace gas 4200m3
80% Fe2O3, 12% SiO2, 1% MnO,
58% N2, 26% CO, 12% CO2, 4% H2O
3% Al2O3, 4% H2O
Limestone 500 kg Slag
95% CaCO3, 1% H2O, 4% SiO2
Fe2O3, SiO2, MnO, Al2O3, CaO
Coke
10% SiO2, 90% C
Air Pig iron 1000 kg
93.8% Fe,4% C, 1.2% Si, 1% Mn

Calculate the composition of the slag

Fe2O3 balance:
Fe2O3(ore) = Fe2O3(pig iron) + Fe2O3(slag)
1750*0.8 = 0.938*1000*(160/112) + Fe2O3(slag), Fe2O3(slag)=1400-1340= 60 kg
SiO2 balance:
SiO2(ore) + SiO2(limestone) + SiO2(coke) = SiO2(pig iron) + SiO2(slag)
1750*0.12 + 500*0.04 + 931*0.1 = 0.012*1000*(60/28) + SiO2(slag), SiO2(slag)=210+20+93.1-25.7
MnO balance: =297.4 kg
MnO(ore) = MnO(pig iron) + MnO(slag)
Total slag composition:
1750*0.01 + 0.01*1000*(71/55) + MnO(slag)
Fe2O3 60 kg 8.82%
MnO(slag) = 17.5 – 12.9 = 4.6 kg
SiO2 297.4 kg 43.70%
Al2O3 balance:
MnO 4.6 kg 0.67%
Al2O3(ore) = Al2O3(slag) = 1750*0.03 = 52.5 kg
Al2O3 52.5 kg 7.71%
CaO balance:
CaO 266 kg 39.10%
CaO(limestone) = CaO(slag) = 500*(56/100)*0.95 = 266 kg
Total 680.5 kg
Smelting
It is a unit process similar to roasting, to heat a mixture of ore concentrate above the melting
point
The objective is to separate the gangue mineral from liquid metal or matte
The state of the gangue mineral in case of smelting is liquid which is the main difference
between roasting and smelting

Inputs – Ore, flux, fuel, air

Output – Metal or Matte, slag, off-gas

When metal is separated as sulphide from smelting of ore, it is called Matte smelting
e.g. Cu2S and FeS
When metal is separated as liquid, it is called reduction smelting
e.g. Ironmaking

Density of liquid metal or matte is around 5-5.5 g/cm3

Density of slag is around 2.8-3 g/cm3

The additives and fluxes serve to convert the waste or gangue materials in the charge into a
low melting point slag which also dissolves the coke ash and removes sulphur
Matte Smelting
Advantages of matte smelting
• Low melting point of matte so that less amount of thermal energy is required by converting
the metal of the ore in the form of sulphide and then extracting the metal
e.g. melting point of Cu2S and FeS is around 1000 degrees Celsius

• Cu2S which is contained in the matte, does not require any reducing agent
It is converted to oxide by blowing oxygen

• Matte smelting is beneficial for extraction of metal from sulphide ore, particularly when
sulphide ore is associated with iron sulphide which forms eutectic point with Cu and Ni

The grade of the matte is defined as the copper grade of matte

A matte of 40 percent means, it has 40% copper, so matte is always given in terms of copper,
because it is used to produce copper not iron

Slag in matte smelting is mixture of oxides

e.g. in smelting of copper ore concentrate the slag may contain SiO2, Al2O3, calcium oxide, FeO,
Fe2O3, Fe3O4
The desirable properties of slag are low viscosity, solubility, low melting point
Typical reactions in Cu matte smelting:
6CuO + 4FeS = 3 Cu2 S + 4FeO + SO2
or if the O2 pressure is high 6CuO + 4FeS = 2CuSO4 + 2FeS
2CuSO4 + 2FeS = Cu2 S + 2FeO + 3SO2
Cu2 O + FeS = Cu2 S + FeO

Oxygen has greater affinity for iron than copper:

10Fe2 O3 + FeS = 7Fe3 O4 + SO2
3Fe3 O4 + FeS = 10FeO + SO2

In the ideal condition matte contains only Cu2S and FeS, plus little amount of Fe3O4 if oxygen is
dissolved

Higher oxides of iron are difficult to remove by the slag

Roasting has to be controlled in order to minimize the formation of Fe2O3 or Fe3O4, which may
enter the matte during smelting

Off-gas consists of SO2, nitrogen, oxygen if excess amount of air is used and sometimes SO3
depending on the reaction
If fuel is used, CO and CO2 may also be present depending upon the state of combustion
Flash Smelting

Conventionally smelting is carried out in reverberatory furnaces, fired with coal or oil
Nowadays reverberatory furnaces are being replaced by flash smelting furnaces that have been
developed in recent years

The advantages of flash smelting is that it combines both converting and smelting, whereas in
the reverberatory furnace the ore has to be smelted first and then it is transferred to
reverberatory furnace for converting purposes
The reason for this combination is the economical processing of large amount of sulphur
dioxide that is created especially in roasting
Collecting the concentrated off-gas from flash smelting and converting to H2SO4 is much more
feasible

Other advantages of flash smelting:

• Very fine particles of ore concentrates are injected, so the reaction is extremely rapid and
very high temperatures are created
• Heat generated is sufficient to carry out the smelting
Examples – In a copper ore, chalcopyrite (CuFeS2) is 34%, pyrite (FeS2) is 30% and SiO2 is 36%
a) Determine the % Cu and % gangue in the ore
b) What % Fe in the ore concentrate is to be removed to make 40% matte? Consider Cu2S
c) If only excess S is eliminated in the ore concentrate, what is the composition of the
resulting matte?
AWCu= 64, AWFe= 56, AWS= 32

a- ore = Cu2S + gangue

% Cu = 34 * (64/184) = 11.83 %
Gangue = 100 – 11.83*(160/128) = 85.21 %, % Cu2S = 14.78 %

40 11.83%
b– 100
= 14.78%+%𝐹𝑒𝑆

0.4(14.78+%FeS) = 11.83, % FeS = 14.795 after removal of FeO, % Fe = 14.795*(56/88) = 9.415

Initial % Fe = 34*(56/184)+30*(56/120) = 24.35 %
% Fe to be removed = 24.35 – 9.415 = 14.935 %

c– CuFeS2 decomposes according to the reaction 2CuFeS2 = Cu2S + 2FeS + S

FeS2 decomposes according to the reaction FeS2 = FeS + S
% FeS = 24.35*(88/56) = 38.26 %
% 𝐶𝑢
Matte grade = % 𝐶𝑢 𝑆+% 𝐹𝑒𝑆 ∗ 100 = 22.2 %
2
Examples – A copper matte may be represented as mCu2S.nFeS with no fixed values of m and n
Calculate m and n for a matte grade of 38 %

𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑢
0.38 =
𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐶𝑢2 𝑆 + 𝐴𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐹𝑒𝑆

160𝑚 ∗ 128/160
=
160𝑚 + 88𝑛

60.8𝑚 + 33.44𝑛 = 128𝑚

𝑚 33.44
= ≈ 0.5
𝑛 67.2

Matte may be represented as Cu2S.2FeS or 2Cu2S.4FeS or 3Cu2S.6FeS

Example – Copper ore is smelted in a reverberatory furnace together with a copper
concentrate. The fluxes are pure CaCO3 and iron ore. (Neglect off-gases for simplicity)
Rational Analysis wt%
Material Cu2S FeS2 SiO2 Fe2O3

Copper ore 17.5 67.5 15

Copper concentrate 35 25 40
Iron ore 20 80
Iron ore

Copper ore Slag

Reverberatory furnace

Copper concentrate Matte

Flux: CaCO3

Reactions: CaCO3 = CaO + CO2

FeS2 + O2 = FeS + SO2 3Fe3 O4 + FeS = 10FeO + SO2
 mo Iron ore (80% Fe2O3, 20% SiO2)

1000 kg Copper ore mS Slag

17.5% Cu2S 35% SiO2
15% SiO2 20% CaO
Reverberatory furnace
67.5% FeS2 45% FeO

mC Copper concentrate mM Matte

35% Cu2S 37.5% Cu2S
40% SiO2 62.5% FeS
25% FeS2
mF Flux: CaCO3
Reaction: CaCO3 = CaO + CO2

DOF analysis
5 unknown labeled variables (mC, mo, mF, mS mS,)
+ 3 independent chemical reactions
- 8 independent molecular species balances (Cu2S, FeS2, SiO2, Fe2O3, CaCO3, CaO, FeO, FeS)
- 0 other equation relating unknown variables
= 0 degrees of freedom
 Iron ore (80% Fe2O3, 20% SiO2)

1000 kg Copper ore Slag

17.5% Cu2S 35% SiO2
15% SiO2 20% CaO
Reverberatory furnace
67.5% FeS2 45% FeO

Copper concentrate Matte

35% Cu2S 37.5% Cu2S
40% SiO2 62.5% FeS
25% FeS2
Flux: CaCO3
Reaction: CaCO3 = CaO + CO2
Calculate the quantities of concentrate, iron ore and flux in order to smelt 1000 kg of
copper ore and obtain a matte grade of 30% Cu and a slag with the composition 35% SiO2 , 20%
CaO, 45% FeO

Let X be the quantity of Cu concentrate

Let Y be the quantity of matte
Let Z by the quantity of iron ore
Let U be the quantity of slag

Four equations are needed to solve for the four variables X, Y, Z, U

 Z kg Iron ore (80% Fe2O3, 20% SiO2)

1000 kg Copper ore U kg Slag

17.5% Cu2S 35% SiO2
15% SiO2 20% CaO
Reverberatory furnace
67.5% FeS2 45% FeO

X kg Copper concentrate Y kg Matte

35% Cu2S 37.5% Cu2S
40% SiO2 62.5% FeS
25% FeS2
Flux: CaCO3
Cu2S balance: SiO2 balance:
Cu2S(in ore) + Cu2S(in Cu conc.) = Cu2S(in matte) SiO2(Cu ore) + SiO2(Cu conc.) + SiO2(iron ore)=
Cu2S(in ore) = 17.5% * 1000 = 175 kg SiO2(slag)
Cu2S(in Cu-conc.) = 0.35 * X 0.15% * 1000 + 0.40X + 0.20Z = 0.35U
Cu2S(in matte) = 37.5% * Y = 0.375 Y Equation 2: 0.40X + 0.20Z – 0.35U = -150
Equation 1: 175+ 0.35X = 0.375Y

Fe Balance:
Fe(Cu ore) + Fe(Cu conc.) + Fe(iron ore) = Fe(matte) + Fe(slag)
Fe(Cu ore) = 67.5% * 1000 * (56/120) = 315 kg Fe(Cu conc.) = 25% * X * (56/120) = 0.117X kg
Fe(iron ore) = 80% * Z * (112/160) = 0.56Z kg Fe(matte) = 62.5% * Y * (65/88) = 0.398Y kg
Fe(slag) = 45% * U * (56/72) = 0.35U kg Equation 3: 315+0.117X+0.56Z=0.398Y+0.35U
 Z kg Iron ore (80% Fe2O3, 20% SiO2)

1000 kg Copper ore U kg Slag

17.5% Cu2S 35% SiO2
15% SiO2 20% CaO
Reverberatory furnace
67.5% FeS2 45% FeO

X kg Copper concentrate Y kg Matte

35% Cu2S 37.5% Cu2S
40% SiO2 62.5% FeS
25% FeS2
Flux: CaCO3
Sulphur balance:
S(Cu ore) + S(Cu conc.) = S(matte), S(flue gas)≈0
S(Cu ore) = (0.175 * (32/160) * 1000) + (0.675 * (64/120) * 1000) = 395 kg
S(Cu conc.) = (0.35 * X * (32/160)) + (0.25 * X * (64/120)) = 0.203X kg
S(matte) = (0.375 * (32/160) * Y) + (0.625 * (32/88) * Y) = 0.3023Y kg
Equation 4: 395+0.203X = 0.3023Y
Equation 1: 175+ 0.35X = 0.375Y Z=589.6 kg Iron ore X=3210.2 kg Cu conc.
Equation 2: 0.40X + 0.20Z – 0.35U = -150 U=7463.4 kg Slag Y=3462.7 kg Matte
Equation 3: 315+0.117X+0.56Z=0.398Y+0.35U

CaO in slag: 20% * 7463.4 = 1492.7 kg CaO, 1492.7 * (100/56) = 2665.5 kg CaCO3
Converting
Liquid metal or matte coming from the smelting furnace with impurities is converted to high
purity metal in oxidizing environments
Either steady air, blown air or blown oxygen are utilized to oxidize the gangue species
Gangue oxide minerals are removed with the initially forming slag

Inputs – Pig iron, cast iron for steel converting, Cu-Fe matte for copper converting, flux, air
Outputs – Slag, steel or blister copper, off-gas

Furnaces used
Hearths
Puddling furnaces
Cementation furnaces
Bessemer furnaces
Open Hearth furnaces
Basic oxygen furnaces
Electric arc furnaces
Converting Pig Iron
Wrought or worked iron was the main malleable iron used in rails and structures until large
scale, commercial production of steel
It contained low amount of carbon (0.04 to 0.08%) and was worked by hand into bars and
various shapes due to its malleability
Slag up to 2% is mixed in its microstructure in the form of fibrous inclusions like wood
Pig iron and cast iron were initially converted to wrought iron in hearths in ancient times then
in puddling furnaces during 18th century
In these processes the charge was heated to melting temperature by burning charcoal and
oxidized by air
Puddling process involves manually stirring the molten pig iron, which decarburizes the iron.
As the iron is stirred, globs of wrought iron are collected into balls by the stirring rod and those
are periodically removed by the puddler

Horizontal (lower) and vertical (upper) cross-sections of a single puddling furnace.

A. Fireplace grate; B. Firebricks; C. Cross binders; D. Fireplace; E. Work door;
F. Hearth; G. Cast iron retaining plates; H. Bridge wall
Commercial production of low carbon, low impurity steel was limited to inefficient and
expensive process of adding carbon to carbon-free wrought iron between 17th and 19th
centuries

The manufacturing process, called cementation process, consisted of heating bars of wrought
iron in a furnace in between powdered charcoal layers at about 7000 C for about a week
Carbon slowly diffuses into iron and dissolves in the iron, raising the carbon percentage
Steel obtained from this process is called “blister steel” due to the blister-like marks formed on
the surface due to the evolved gases during the manufacturing process

Up to 3 tons of coke was burnt for each ton of steel produced

The fuel and labor costs resulted in a small scale
production of steel that was about 8 times more expensive

The Bessemer process reduced the time needed to make

steel of this quality to about half an hour while only
requiring coke to melt the pig iron initially
The Bessemer process - Henry Bessemer patented the process in 1855
The process is carried out in a large ovoid steel container lined with clay or dolomite
The capacity of a converter is from 8 to 30 tons of molten iron

The key principle is removal of impurities from the iron by oxidation with air being blown
through the molten iron
The oxidation process removes impurities such as silicon, manganese, and carbon as oxides
These oxides either escape as gas or form a solid slag
The oxidation also raises the temperature of the iron mass and keeps it molten
The refractory lining of the converter also plays a role in the conversion—the clay lining is used
in the acid Bessemer, in which there is low phosphorus in the raw material
Dolomite, limestone or magnesite are used when the phosphorus content is high in the basic
Bessemer
Once the converter is charged with molten pig iron, a strong thrust of
air is blasted across the molten mass through tuyeres provided at the
bottom of the vessel

The conversion process called the "blow" is typically completed in

around twenty minutes

During this period the progress of the oxidation of the impurities is

judged by the appearance of the flame issuing from the mouth of the
converter since there is not enough time to make material analyses

The blow may be interrupted at certain periods to avoid the oxidation

of certain impurities

Required amount of flux is added at the beginning of each period to

produce the slag of desired composition and amount

At the end of the process all traces of the silicon, manganese, carbon,
phosphorus and sulphur are oxidized, leaving the converter with pure
iron

In order to give the steel the desired properties, other impurities can
be added to the molten steel when conversion is complete
Steel converter analysis

A basic pneumatic steel converter is charged with 25 tons of pig iron containing various
impurities
In addition to the removal of all of the C, Si, Mn and P, iron equivalent to 5% of the weight of
charged iron oxidizes at a constant rate throughout the bessemerizing operation
Enough lime is added to obtain a slag containing 35% CaO
2/3 of the carbon in steel oxidizes to CO and 1/3 goes to CO2
Air compressor delivers air at a rate of 500 m3/min for specific periods of time
Flux Flue gas
CaO CO, CO2, N2

Pig iron Bessemer converter Slag

Fe2O3, P2O5, SiO2
Air MnO, CaO

Steel

Ultimate Analysis wt%

Material Fe C Si Mn P
Pig iron 91 3.5 2 1 2.5
 mF Flux 𝑉𝐹 Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter mS Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C 𝑉𝐴 Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn mSt Steel
2.5% P

DOF analysis
12 unknown labeled variables (𝑉𝐴 , 𝑉𝐹 , mF, mS, mSt, XFe2O3, XP2O5, XSiO2, XMnO, XCO, XCO2, XN2)
+ 6 independent chemical reactions
- 14 independent molecular species balances (Fe, C, Si, Mn, P, SiO2, Fe2O3, CaO,, MnO, P2O5, CO,
CO2, N2, O2)
- 4 other equation relating unknown variables (XFe2O3+ XP2O5+ XSiO2+ XMnO = 0.65, XCO+ XCO2+ XN2
5% Fe oxidizes, 1/3 C oxidizes to CO2)
= 0 degrees of freedom
 Flux Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn Steel
2.5% P
Calculate the volume of air required for the operation
Basis 25 tons of pig iron

Oxidation step 1: Si + O2 = SiO2 Oxidation step 3: C + 1/2O2 = CO, C + O2 = CO2

Weight of Si in Pig iron = 0.02 * 25000 = 500 kg Weight of C in iron = 0.035 * 25000 = 878 kg
nSi= 500/28 = 17.857 kg-atom nC = 878/12 = 72.917 kg-atom
nO2= 17.857 kg-mole nC(for CO) = (2/3) * 72.917 = 48.611 kg-atom
nO2 = (½) * 48.611 = 24.306 kg-mole
Oxidation step 2: 2Mn + O2 = 2MnO nC(for CO2) = (1/3) * 72.917 = 24.306 kg-atom
Weight of Mn in Pig iron = 0.01 * 25000 = 250 kg nO2= nC(for CO2) = 24.306 kg-atom
nMn= 250/55 = 4.545 kg-atom
nO2= 4.545/2 = 2.273 kg-mole Oxidation step 4: 4P + 5O2 = 2P2O5
Weight of P in iron = 0.025 * 25000 = 625 kg
nP=625/31 = 20.161 kg-atom
nO2=(5/4) * nP=25.201 kg-mole
 Flux Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn Steel
2.5% P
Calculate the volume of air required for the operation
Basis 25 tons of pig iron

Total O2 used during Si, Mn, C, P oxidation = 93.94 kg-mole

Considering small amount of Fe oxidizing in all steps:

nFe = 1137.5/56 = 20.312 kg-atom
2Fe + 3/2 O2 = Fe2O3
nO2 = (¾)*nFe = (¾)*20.312 = 15.23 kg-mole

Total O2 used = 2.273 + 17.857 + 24.306 + 24.306 + 25.201 + 15.23 = 109.17 kg-mole O2
Volume of air required = (109.17/0.21) * 22.4 = 11644.8 m3/25 ton of Pig iron
Total blowing time = 11644.8/500 = 23.29 minutes
 Flux Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn Steel
2.5% P
Calculate the durations of each blowing period

Total O2 used = 2.273 + 17.857 + 24.306 + 24.306 + 25.201 + 15.23 = 109.17 kg-mole O2

Volume of air required for period 1= (2.273/0.21) * 22.4 = 242.45 m3/500 kg Si

Volume of air required for period 2= (17.857/0.21) * 22.4 = 1904.75 m3/250 kg Mn
Volume of air required for period 3= (48.162/0.21) * 22.4 = 5137.3 m3/878 kg C
Volume of air required for period 4= (25.201/0.21) * 22.4 = 2688.1 m3/625 kg P
Volume of air distributed in all periods= (15.23/0.21) * 22.4 = 1624.5 m3/1138 kg Fe
Total blowing time = 11644.8/500 = 23.29 minutes
FeFe2O3
Period 1 Period 2 Period 3 Period 4
SiSiO2 MnMnO CCO, CO2 PP2O5
0 4.43 4.99 Time (min) 17.04 23.29
 Flux Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn Steel
2.5% P
Calculate the weight of CaO added to the converter

Si + O2 = SiO2 4P + 5O2 = 2P2O5

Weight of Si in Pig iron = 0.02 * 25000 = 500 kg Weight of P in iron = 0.025 * 25000 = 625 kg
nSi= 500/28 = 17.857 kg-atom nP=625/31 = 20.161 kg-atom
nSiO2= 17.857 kg-mole nP2O5= 20.161/2 = 10.081 kg-mole
Weight of SiO2 in slag = 17.857*60 = 1071.4 kg Weight of P2O5 in slag = 17.081*142 =
1431.5 kg
2Mn + O2 = 2MnO
Weight of Mn in Pig iron = 0.01 * 25000 = 250 kg 2Fe + 3/2 O2 = Fe2O3
nMn= 250/55 = 4.545 kg-atom nFe = 1137.5/56 = 20.312 kg-atom
nMnO= 4.545 kg-mole nFe2O3 = 20.312/2 = 10.156 kg-mole
Weight of MnO in slag = 4.545*71 = 322.7 kg Weight of Fe2O3 in slag = 10.156*160 =
1625kg
MnO + SiO2 + P2O5 + Fe2O3 = 4450.6 kg, 35% CaO= (4450.6/0.65)*0.35 = 2396.5 kg CaO in slag
 Flux Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn Steel
2.5% P

Calculate the weight and composition of the slag

Component Weight (kg) Weight %

SiO2 1071.4 15.64%
MnO 322.7 4.71 %
P2O5 1431.5 20.90%
Fe2O3 1625 23.75%
CaO 2396.5 35.00%
Total 6848 100.00%
 Flux Flue gas
CaO CO, CO2, N2
25 tons
Pig iron Bessemer converter Slag
91% Fe Fe2O3, P2O5, SiO2
3.5% C Air MnO, 35% CaO
2% Si 500 m3/min
1% Mn Steel
2.5% P
Calculate the weight of CaO added to the converter in each blowing period

Total CaO added as flux = 2396.5 kg CaO

FeFe2O3
Period 1 Period 2 Period 3 Period 4
SiSiO2 MnMnO CCO, CO2 PP2O5
0 4.43 4.99 Time (min) 17.04 23.29

CaO consumed each minute = 2396.5/23.29 = 102.9 kg

CaO consumed in period 1 = 102.9 * 4.43 = 455.8 kg
CaO consumed in period 2 = 102.9 * 0.56 = 58.02 kg
CaO consumed in period 3 = 102.9 * 11.95 = 1229.4 kg
CaO consumed in period 4 = 102.9 * 6.25 = 643.3 kg
Copper converting
Liquid matte from the smelting process is oxidized in a bessemer or basic oxygen furnace by
blowing air or oxygen
The difference between steel converting and copper converting is that the value mineral Cu2S
is oxidized as well in the latter process

Cu2 S + O2 = Cu l + SO2

FeS2 in the matte is oxidized initially due to its higher oxidation free energy
Excess S in the matte may also oxidize preferentially prior to reduction of copper

Blowing, fluxing and slagging may be done periodically due to convenience

Flux is commonly added in batches due to the high amount of charge material and the limited
space of furnaces
The amount of flux batches and blowing rate affects the time taken to produce slag in periods

SO2 on the surface of the copper evaporate and form blisters on the solidifying copper
Blister copper purity is around 99% and electrolysis treatment is needed to obtain pure copper
Converted blister copper is considered as 100% pure for convenience in material balance
Copper converter analysis

40 tons of matte carrying 34% Cu is charged in a bessemer converter

The flux is added in batches of 3000 kg, the converter is blown after each addition to obtain
slag of the given composition
Blister copper is produced after the removal of slags formed using partially added fluxes
Air is blown at a rate of 100 m3/minute

Flux Slag

Matte Bessemer converter Blister copper

Air V Off-gas
XSO2
XN2
Rational Analysis wt%
Material FeO CaO SiO2 Al2O3 Cu2S FeS2

Slag 59 8 32 1
Flux ? 75 ? 2 5
Air is blown at a rate of 100 m3/minute
3000 kg Flux
75% SiO2
2% Cu2S
ms Slag 59% FeO, 8%
5% FeS2 CaO, 32% SiO2, 1%
XCaO Al2O3
XAl2O3 Bessemer converter mbc Blister copper
40 tons Matte
34% Cu
Xfe Air
100 m3/min V Off-gas
XS XSO2
DOF analysis XN2

9 unknown labeled variables (ms , mbc ,V , XFe, XS, XCaO, XAl2O3, XSO2, XN2)
- 4 independent atomic species balances that are involved in the reactions (Cu, Fe, S, O)
- 4 molecular balances on independent nonreactive species (N2, CaO, SiO2, Al2O3)
- 3 other equation relating unknown variables (XFe + XS =0.66, XCaO+ XAl2O3=0.18, XSO2+ XN2=1)
= -2 degrees of freedom!
 Air is blown at a rate of 100 m3/minute
3000 kg Flux
75% SiO2 Slag 59% FeO, 8 CaO
2% Cu2S 32% SiO2, 1% Al2O3
5% FeS2
Bessemer converter Blister copper
40 tons Matte
34% Cu
Air
100 m3/min V Off-gas
Calculate the time of each partial blow XSO2
XN2
Cu2S in matte = 40000 * 0.34 * (160/128) = 17000 kg, FeS=23000 kg

Let X be the weight of slag Let Y be the weight of FeS oxidized in one blow
SiO2 balance: Fe balance:
75% * 3000 = 0.32 X (56/88) * Y + 5% * 3000 * (56/120) = 59% * 7031 * (56/72)
X = 7031 kg Y = 4963 kg = 56.4 kg-moles

Oxygen required for 1 blow:

FeS + 3/2O2 = FeO + SO2 FeS2 + 5/2O2 = FeO + 2SO2
O2 required = 56.4 * (3/2) = 84.6 kg-moles O2 required = 1.25 * (5/2) = 3.125 kg-moles
Total O2 required = 87.725 kg-moles
87.725 22.4
Time for 1 blow = ∗ = 93.57 minutes
0.21 100
 Air is blown at a rate of 100 m3/minute
3000 kg Flux
75% SiO2 7031 kg Slag 59%
2% Cu2S FeO, 8 CaO
5% FeS2 32% SiO2, 1% Al2O3
40 tons Matte Bessemer converter Blister copper
17 tons Cu2S
23 tons FeS
Air V Off-gas
100 m3/min XSO2
XN2
Calculate the number of partial blows and the weight of flux to be added for the last partial
blow to completely remove FeO in the slag

87.725 22.4
Time for 1 blow = 0.21 ∗ 100 = 93.57 minutes
The weight of FeS oxidized in one blow = 4963 kg = 56.4 kg-moles
Number of partial blows = 23000/4963 = 4.63 ≈ 5

FeS oxidized in the 5th blow = 23000 – (4*4963) = 3148 kg

Let Z be the amount of flux batch added in the last period
O2 balance:
(3148/88) *(3/2) + (0.05Z /120) *(5/2) = 87.725 * 3148/4963
Z= 1903 kg
 Air is blown at a rate of 100 m3/minute
3000 kg Flux
75% SiO2 7031 kg Slag 59%
2% Cu2S FeO, 8 CaO
5% FeS2 32% SiO2, 1% Al2O3
40 tons Matte Bessemer converter Blister copper
17 tons Cu2S
23 tons FeS
Air V Off-gas
100 m3/min XSO2
XN2
Calculate the total time for blowing the charge to convert to blister copper

Blow Period (min)

1 93.57
2 93.57
3 93.57
4 93.57
5 3148/4963 * 93.57 = 59.40 minutes
Total time to remove Fe in the matte and flux completely = 431.68 minutes

Cu2 S + O2 = Cu l + SO2
Total Cu2S = 17000/160 = 108 kg-moles, Total O2 required = 108 kg-moles
Total air required = (108/0.21) * 22.4 = 11520 m3, Time required to convert Cu = 115.2 minutes
Total time of operation = 546.88 minutes