CARBOTHERMAL REDUCTIVE MELTING
1. AIM OF THE EXPERIMENT
To show the detail of carbothermic reduction with using lead oxide as sample and to
determine the reduction conditions by given values of time, temperature, reductant and other
additives and finally determination of the efficiency of metal recovery.
2. THEORETICAL INFORMATION
Lead exists as a compound in a lot of minerals, since it is very rare to find it in free metal
form. The most important one of these minerals is “galena” which is a mineral of lead sulfide
(PbS).
Production of lead starts with a sintering process which is being done to oxidize the galena
ore. After this step, oxidized lead is charged to shaft furnace with coke (coal) and this is
where the carbothermic reduction takes place. The material that comes out is pure lead.
Although the shaft furnaces are used commonly still, there are more economical and
environmental friendly smelting processes. Imperial Smelting Process (ISP) is used for the
ores that contain both lead and zinc. QSL and Kivcet processes are created by USA-Germany
and Russia, respectively. These two processes also depend on the principle that does not
require the sintering process during the production of lead.
Generally, sintered concentrate with all the additives (fluxes) and mid-products are charged to
shaft furnace together with coke. Figure 2.1 indicates a schematic drawing of a shaft furnace.
The materials that come out from the furnace; liquid metal (specific weight of lead is
approximately 10.5), matte (specific weight, approximately 4.5-5) and slag (specific weight
3.5-3.8). The difference between the specific weights and immiscible properties make the
mechanical separation possible. Additionally, there are two different reservoir types
depending on the way of taking liquid materials from the shaft furnace.
Figure 2.1 Schematic drawing of shaft furnace and flue gas cleaning systems
2.1 Thermodynamics
2.1.1 Sintering Reactions
The goal in the sintering roasting of the ores and concentrates that have high grade is to have
a total oxidation which converts lead, zinc and iron into oxides. However, in the case of the
concentrates that have high copper concentrations, it is crucial to have some sulfur left in the
system so that matte can be formed and in order to do this, the sintering process is done via
partial oxidizing roasting.
Reactions that take place are solid-gas (ore-air) systems and exothermic. Average temperature
range is 973-1173 K (even 1273 K for some cases) therefore, partial smelting within the
material can take place and particles will be sintered since they will stick to each other.
Reactions are;
PbS+3/2 O2 PbO+SO2 G1173 K= -318.373 kJ (1)
ZnS+3/2 O2ZnO+SO2 G1173 K= -355.057 kJ (2)
2FeS+7/2 O2Fe2O3+2SO2 G1173 K= -892.947 kJ (3)
Iron (III) oxide has a catalytic effect and with SO2, the sulfates; PbSO4, FeSO4, Fe2(SO4)3 etc.
are formed.
Using “Outokumpu HSC for Windows 3.0” program (that calculates thermodynamic data),
simulations are made for the Pb-S-O system for the temperatures 1173 K and 1473 K (figure
2.2 and 2.3). As it can be seen when air is used for the 1173 K stable product can be PbSO4
and PbO.PbSO4. At 1473 K PbSO4 is not stable anymore and the products are 2PbO.PbSO4
and PbO.
Figure 2.2 Simulation of Pb-S-O system at 1173 K
Figure 2.3 Simulation of Pb-S-O system at 1473 K
2.2.2 Reactions that take place in reduction
Thermodynamically speaking, selection of the reducing agent has a crucial effect on getting
the metal from metal oxide. For reduction to take place, partial oxygen pressure which created
by reductants presence, should be lower than the pressure needed for reducing the metal
oxide.
Carbon is the first non-metallic element that comes to mind as a reductant. If the excess
amounts of Carbon is present (e.g. at 1273 K) these reactions could occur;
2C+O2(g) = 2CO(g) ∆G1223 K= - 439.265 kj (4)
CO2(g) = C(g) + O2(g) ∆G1223 K= 396.093 kj (5)
C+ CO2(g) = 2CO(g) ∆GT1223 K= - 43.172 kj (6)
This reaction is called the Boduard reaction and using HSC program, simulations are carried
out at 273-1273 K, which given in Figure 2.4. In the presence of excess carbon, amount
changes of C, CO and CO2 in the C-O system is showed. As it can be clearly seen the amount
of CO is at its maximum after 1200 K while CO2 is almost finished.
Figure 2.4: The change of C-CO-CO2 system with temperature.
Raw lead metal is produced in a shaft furnace through the reduction of lead oxide with fluxes
and coke. Sum of boduard reaction and reduction of PbO with CO (at high levels) at 1123 K;
2PbO+2CO(g)=2Pb(l)+2CO2(g) G1223 K= -155.289 kJ (7)
C+ CO2(g)= 2CO(g) G1223 K= - 43.172 kJ (8)
2PbO+C=2Pb+CO2(g) G1223K= -198.461 kJ (9)
Reactions and events that occur in a shaft furnace resemble the events in an iron blast furnace.
However, the job is to make FeO from iron oxides and never reduce them into the metallic
form.
3. EQUIPMENTS USED IN EXPERIMENTS
Vertical furnace that can operate at 1473 K
90 ml chamotte ladles and iron ladle
+0.001 precision weighing machine
Tools; spatula, hammer
Chemical substances; litharge (PbO), silica (SiO2), coke (%85 C).
4. EXPERIMENTAL PROCEDURE
Known quantities of PbO, SiO2 and carbon as the reducing agent, are weighed and mixed
together before they are placed into the chamotte ladles. Then the ladles are placed into the
Muffle type furnace which is set at 1200-1300 K. The ladles are held in the furnace for 25
minutes before taking them out. The status of the charge can be examined through an
observation hole on the furnace. When the smelting process is complete, ladles are removed
from the furnace and the charge is cast into the mould immediately. The sample is removed
when the solidification is complete. In this step of the experiment, characteristic properties of
the slag (color, structure, etc), the positions of the slag and lead are examined and saved. Then
the sample is broken into pieces by means of light hammer blows. Lead is removed from the
slag and both are weighed.
QUESTIONS
1- Theoretically calculate the amount of lead produced and calculate the efficiency.
2- Find the amount of slag and estimate its compound formula.
3- Check to see if the ladle is worn and think why it is worn or not.
4- Calculate the partial oxygen pressure needed in reduction of PbO at desired
temperature.
5- Calculate the CO/CO2 ratio needed for this oxygen pressure and temperature.
Thermodynamic data for questions 4 and 5
Table 4.1: Thermodynamic data for Pb+0.5O2(g)=PbO
Pb(l)+0.5O2(g)=PbO(l)
T H S G Keq
K kJ J/K kJ
1100 -191.493 -75.854 -108.054 1.35E+05
1150 -190.569 -75.033 -104.282 5.46E+04
1200 -189.642 -74.244 -100.55 2.38E+04
1250 -188.714 -73.486 -96.857 1.12E+04
1300 -187.789 -72.76 -93.201 5.56E+03
1350 -186.865 -72.063 -89.58 2.93E+03
1400 -185.944 -71.393 -85.994 1.62E+03
Table 4.2: Thermodynamic data for CO(g)+0.5O2(g).
CO(g)+0.5O2(g)=CO2(g)
T H S G Keq
K kJ J/K kJ
1100 -282.135 -86.708 -186.757 7.40E+08
1150 -281.928 -86.523 -182.426 1.94E+08
1200 -281.717 -86.343 -178.104 5.67E+07
1250 -281.502 -86.168 -173.792 1.83E+07
1300 -281.283 -85.997 -169.488 6.47E+06
1350 -281.062 -85.829 -165.192 2.47E+06
1400 -280.837 -85.666 -160.905 1.01E+06
Figure 4.1: Phase diagram of PbO-SiO2.
REFERENCES
1- BOR, F. Y., “Ekstraktif Metalurji Prensipleri II”, İTÜ, 1989
2- HAYES, P.C., “Process Selection in Extractive Metallurgy”, Hayes Publishing Co.,
1985.
3- MOORE, J.J., “Chemical Metallurgy”, Butterworth & Co. Ldt, 1981
4- HSC Chemistry for Windows. Ver. 3, by Outokumpu Research
5- HABASHI, F., “Principles of Extractive Metallurgy” Vol 3.1Gordon and Breach
Science Publishers.,1986
