KINETIC INVESTIGATION OF THE REDUCTION BEHAVIOR OF

IRON OXIDE CONTAINING RAW MATERIALS

1. PURPOSE OF THE EXPERIMENT

In this experiment, it was aimed to investigate the kinetics of reduction behavior of iron oxide
containing raw materials with a solid state reduction using solid reducing agents (direct
reduction).

2. THEORETICAL INFORMATION
Iron is found mostly in the oxide form of hematite (Fe2O3) and magnetite (Fe3O4) in earth.
Transformation of oxides to their sub-oxides and/or to metallic state by the removal of oxygen
from their structure with reducing agents having high oxygen affinity such as CO, H2 and C is
called reduction.

Reduction of iron oxides is technologically made with two different methods. In the first
method, coke is used as a reducing agent in blast furnaces where crude steel production is
realized in integrated iron and steel works as the first step of the steel production. In the blast
furnace, iron oxides are reduced with CO gas which is formed by the reaction of CO2 gas
(CO2 occurs with the combustion of carbon with the hot air blast) and existing carbon in the
system according to the Bouduard reaction (Indirect Reduction). Some of the reduction takes
place at the bottom part of the furnace directly with solid carbon (Direct Reduction). Around
the hot air blast region the temperature reaches up to 2000 °C and the final product is crude
steel. In a modern blast furnace daily crude steel production amount is over 10,000 tons.

World crude steel production reached 1.527 billion tons (Mt) for the year of 2011. 1.068
billion tons of this production was realized in integrated iron and steel plants. 2.688 billion
tons of iron ores were used to realize this production [1,2]. Turkey has 3 integrated iron and
steel plants namely Kardemir, Erdemir and İsdemir according to their foundation year. Total
capacity of these 3 integrated steel plants is 9.35 million tons constituting 25.9% of total steel
production of Turkey which was 34.1 million tons for the year of 2011. 74.1% of total steel
production is realized with electrical arc furnaces in 23 mini steel plants [2].

In the second method, reduction of iron oxides to metallic state is realized in the solid state
with solid or gas reducing agents below the melting point of the iron. This method is known
as direct reduction of iron (DRI) and the final product is “Sponge Iron” with a high
metallization degree. Sponge iron is an alternative raw material to high quality steel scrap for
the production of value added products in electric arc furnaces due to its low amount of trace
elements and compositional stability. Although this method is not as widespread as blast
furnaces it still has a commercial importance in iron and steel making. The total DRI
production in 2011 was 73.3 million tons. Today, gas based methods like MIDREX and
HYL-III are the most common DRI production methods constituting the 76.4% of annual
sponge iron production. SL/RN is a widely used coal-based DRI-making process which uses a
rotary kiln.

Thermodynamic Investigation of the Reduction Reaction

Reduction of iron oxides to metallic iron is realized by changing the iron-oxygen-carbon (or
hydrogen) thermodynamic equilibrium towards the reduction condition and removing the
oxygen of the raw materials with reducing agents. In this case, iron oxides are reduced to
metallic iron through a series of reactions.

In the blast furnace the reduction of iron oxide containing raw materials is mostly realized
(see Ellingham Diagram) with the reducing CO gas which is formed by the reaction of CO2
gas (occurs with the combustion of carbon) that is unstable at elevated ambient temperatures
and carbon present in the existing ambient.

C (s) + O2 (g) = CO2 (g) (1)

CO2 (g) + C (s) = 2CO (g) (Boudouard Reaction) (2)

Reduction of hematite to iron with the CO/CO2 gas mixture is realized in three steps. These
reactions and the empirical formulas related to their standard free energy changes (∆GoT)
versus temperature are given in equations ( 3 ), ( 4 ) and ( 5 ).

3Fe2O3 + CO = 2Fe3O4 + CO2 ∆GoT = 4,376,000 + 1454.91 T (3)

Fe3O4 + CO = 3FeO + CO2 ∆GoT = 1,610,900 – 27.54 T (4)

FeO + CO = Fe + CO2 ∆GoT = -18,700 + 22.46 T (5)

In order to determine the reduction condition of iron oxides, equilibrium conditions need to be
determined by using the equations given below.

∆GT = 0 (Equilibrium Condition) (6)

o
∆G T = -RTlnKp (7)

For the reaction ( 7 );

a 2 Fe3O4 .PCO2
Kp= (8)
a 3 Fe2O3 .PCO

When Fe3O4 and Fe2O3 are regarded as pure their activities equal to “1”. In this case;

PCO2 PCO
∆GoT = -RTln = RTln (9)
PCO PCO2

 P 
By using this,  CO  value can be calculated at temperature T1 for the reduction
 PCO 
 2  Equilibrium
reactions. The main thermodynamic condition for the reduction of iron oxides is as shown
below for each reaction.

∆GT < 0 ( 10 )
 P   P 
 CO  >  CO  ( 11 )
 PCO   PCO 
 2  Ambient  2  Equilibrium
Bauer-Glaessner diagram and Boudouard curves plotted using equations ( 2 ) and ( 9 ) are
shown in Figure 1.

Figure 1. Bauer-Glaessner diagram and Boudouard curves

According to Figure 1, for Pco + Pco2 = 1 atm total pressure the reduction of iron oxides to
metallic iron is possible above 705 oC, while below 705 oC hematite is transformed to
magnetite and magnetite to wustite. It can be seen from Figure 1 that between 650 and 750 °C
magnetite to wustite and below 650 °C hematite to magnetite transformations take place. It
can be said that with increasing PCO + PCO2 total pressure the reduction temperature of iron
oxides increases and reduction becomes more difficult.

Kinetic Investigation of the Reduction Reaction

Rate of a reaction can be determined from the change of the amount of that matter according
to time. Taking this into account, the reaction rate can be defined as ;
dC
r ( 12 )
dt

Reaction rate can be calculated from the slope of concentration change vs. time. Temperature
and concentration are the most important parameters affecting the rate of a homogenous
reaction.

k = reaction rate constant (temperature dependent)

dC
r  kC n C = concentration ( 13 )
dt
n = degree of reaction
One of the most important parameters affecting the rate of chemical reactions is temperature.
In homogeneous reactions, Arrhenius equation gives the relation between temperature and
rate constant.
k=A.e- EA/ RT ( 14 )

In this equation EA is the activation energy, A is the pre-exponential factor or simply

the prefactor, R is the universal gas constant (R= 8.314 J/mol K), k is the rate constant and T
is the temperature. In order to calculate the activation energy, rate constants (k) should be
determined at least for two different temperatures. As seen from Arrhenius equation, reaction
rate is exponentially dependent on temperature. Therefore, a small change in the temperature
increases the rate constant dramatically. By taking the logarithm of both sides in the
Arrhenius equation, the equation given below is obtained.

EA
ln k  ln A  ( 15 )
RT

When the ln k – 1/T change is plotted to calculate the activation energy, slope of the obtained
curve is equal to (-EA / R) value.

Figure 2. Plot of the change of reaction rate vs. temperature

According to the plot;

a) The higher is the slope of the straight line the higher is the activation energy.
b) Comparing with reactions which have low activation energies, reactions with high
activation energies are more dependent on temperature. This means that they are more
affected by the temperature changes.
c) Reactions realized at lower temperatures are more dependent on temperature than the
reactions realized at higher temperatures.
d) Pre-exponential factor (prefactor) is not affected by the temperature dependence of the
reaction so it is not dependent on temperature.
Reactions can be either homogeneous or heterogeneous according to the reactants being in the
same phase or in two or more phases. Homogeneous reactions are chemical reactions in
which the reactants are in the same phase, while heterogeneous reactions have reactants in
two or more phases. Heterogeneous reactions are characterized with the presence of an
interface between reactants. Reduction of iron oxide containing raw materials is a
heterogeneous reaction. For example, in a solid-gas reaction the interface is the outer surface
of the solid in contact with gas. In this case, all heterogeneous reactions can be categorized
into five groups according to their interface. Solid-Gas, Solid-Liquid, Solid-Solid, Gas-
Liquid, Liquid-Liquid.

Heterogeneous reactions in which the reactants are in more than one phase is realized as given
below [4, 5]:

1. Transportation of the reducing gas to the reaction interface (diffusion).

2. Interface reactions.
a) Adsorption of the reducing gas to the reaction interface.
b) Chemical reaction in the interface.
c) Desorption of the reaction products.
3. Transportation of the reaction products from the interface (diffusion).

Generally, rate constant of one of the steps given above is so much lower than the others’ rate
constants. In this case, this step controls rate of the reaction and also rate of this step
determines rate of the total reaction. According to the slowest step, heterogeneous reactions
can be:

- Diffusion Controlled
- Chemical Reaction Controlled

or in the case of the rate constants of these steps are equal to each other;

- Mixed Controlled

Due to the difference on the temperature dependence of diffusion constant and chemical
reaction rate constant, diffusion controlled processes are less dependent on temperature than
the chemical reaction controlled processes. Diffusion constant is dependent on temperature
linearly, while in chemical reactions the rate constant is exponentially dependent on
temperature. In other words, with increasing the temperature twice, D increases about twice,
while k increases almost 100 times. Only in solid-solid reactions diffusion constant is
dependent on temperature exponentially and these types of reactions are known to have high
activation energy.

The mechanism of a process may change from chemical reaction controlled at lower
temperatures to diffusion controlled at elevated temperatures and this behavior can be
observed from the lnk - 1/T change (see Figure 3).

According to Figure 3, two straight lines are obtained with different slopes with a high
activation energy at lower temperatures (Region I) and a low activation energy at higher
temperatures (Region II). At low temperatures rate of the chemical reactions is lower than the
rate of diffusion so it is expected that the reaction is chemical reaction controlled. Increasing
the temperature increases the rate of the chemical reaction dramatically, therefore at high
temperatures the reaction becomes diffusion controlled.

Since the amount of substance transported from one phase to another is dependent on the
surface area of the interface, in heterogeneous reactions surface area of the interface has a
crucial importance. In solid state reactions, solids with small grain size have higher surface
area; therefore they have a higher reaction rate comparing to solids with larger grain size [4,
5, 6, 7].

Figure 3. Effect of temperature on rate of reaction in heterogeneous reactions

Geometric shape of a solid which is in reaction with a liquid or gas has an important role on
determining the rate of the corresponding reactions. If the solid has a disk-like or plate-like
geometry, it is assumed that the surface area of the solid remains constant during the reaction
since in disk-like or plate-like shape solids the reaction proceeds from surface to the inside of
the material by preserving its surface area. However, if the solid is spherical or is like a pellet
then the reaction proceeds from outer surface of the sphere to inside. In this case, since the
diameter of the reaction surface decreases, surface area changes continuously and therefore
the reaction rate decreases. In general, solid reactants are regarded as a sphere so in
heterogeneous reactions the relation between reaction rate and degree of reaction is given as
below:

1  (1  R)1 / 3  kt ( 16 ) R = Degree of Reaction (can also be shown with

n, x, F, L)
Wo = Initial weight
W  Wo W = Final weight
R ( 17 )
Wo k = Reaction rate constant
t = Time
In reactions realized with spherical solid materials, surface area of the reaction interface is
very distinctive. With the proceeding of the reaction, interface moves from outer surface of
the material to center and an absolute boundary between reacted and unreacted parts appears.
This type of reaction model is called topochemical model or shrinking core.

If the reaction products dissolve in ambient phase the surface area decreases with respect to
time. Combustion of carbon with air or dissociation of a solid in liquid can be given as typical
examples for this case. In this reaction model, reaction rate determining step is again either
chemical reaction or diffusion.

Figure 4. Schematic illustration of the reduction of hematite particle and shrinking core
behavior in reduction reaction [5, 6, 8].

If reaction products, as observed in oxidation of metals and metal sulfides or reduction of

oxides with gas, forms a layer between the original solid material and gases then the
molecules need to be transported through this layer with diffusion for the continuation of the
reaction. In solid state reactions depending on the porous or nonporous structure of the
reaction products, the reaction kinetics will be different. Depending on the type of the product
layer, diffusion takes place in the crystal lattice with solid diffusion or with diffusion of gas
from the pores of the reaction product.

Diffusion of gas from the pores of the reaction product takes place when volume of the
reaction products is less than volume of the original reactant. In this case, a porous reaction
product layer forms. However in oxidation of most metal oxides, metal oxide covers a higher
volume than the original reactant. In this case, a nonporous and dense product layer forms and
the diffusion takes place in crystal lattice. As understood from the above explanations reaction
rate controlling mechanism can change depending on the temperature and type of the product
layer formed. In this case, writing the rate equations according to the reaction control
mechanism [4, 5]:

1) In a reaction product having a limited thickness of porous layer, generally chemical

reaction determines the rate of reaction under certain temperatures. In this case, relation
between R-t is given with the equation below;
1
1 (1  R ) 3  kt ( 18 )

In case of the reaction is chemical reaction controlled, [1-(1-R)1/3] - t is linear and rate
constant is determined from the slope.

2) In the case of a dense reaction product layer formation, the diffusion is slow and interface
reaction is in equilibrium. Therefore, it is expected that the reaction rate is controlled by
diffusion. In this case, relation between R-t is given with the equations below;

a) Jander’s equation:
2
1 (1  R ) 1/3  kt ( 19 )

b) Crank and Ginstling – Braunshtein’s equation:

2
1  23 R (1  R ) 3  kt ( 20 )

In diffusion controlled reaction, plot of the left side of the equations given above versus time
is linear and the slope gives the rate constant.

3. MATERIALS AND EQUIPMENTS

1) Iron oxide pellets and powders of coke/lignite coal
2) Tube furnace (max temperature of 1200 oC)
3) Digital Balance with a sensitivity of 10 -2 g
4) Stainless steel boat crucible and rod

4. EXPERIMENTAL PROCEDURE
1) 5 or 6 pellets produced from iron oxide concentrates are chosen in order to observe
the reduction behavior.
2) When the tube furnace reaches the working temperature, the iron oxide pellets
which were weighed before the experiment are put in the stainless steel boat
crucible together with the powders of coke or lignite coal and placed in the tube
furnace by pushing with the stainless steel rod.
3) Take out a pellet from the furnace every 10 minutes and weigh to calculate its
weight after reduction. Kinetic investigation is realized according to the weight
change observed in these pellets.

5. ASSIGNMENTS
1) Plot the degree of reduction vs. time.
2) Calculate the instantaneous rate of reaction (dR/dt) at the 15th and 25th minutes.
 3) Calculate the activation energy of the reduction reaction by using the reaction rate
constant values that will be given.
4) Under what circumstances, kinetics of the reduction of iron oxide containing raw
materials is controlled by chemical reaction mechanism, diffusion mechanism or
mixed-controlled mechanism? How do you observe this difference in a partially
reduced iron oxide pellet? Plot schematically.
5) By using the equations given in ( 4 ) and ( 5 ) plot the CO% vs. temperature
change and name the stable phases on the graph for a total of 1 atm CO + CO2
containing ambient at 700-800-900 and 1000 oC temperatures.

6. REFERENCES
1) www.worldsteel.org, International Iron and Steel Institute (IISI), official website,
Internet.
2) www.dcud.org.tr, Turkish Iron and Steel Producers Association, official website,
Internet.
3) www.midrex.com, Midrex Technologies, Inc., official website, Internet.
4) Aydın, S., Metalurji Kinetiği Ders Notu, 1994.
5) Habashi, F., Kinetics of Metallurgical Processes, Métallurgie Extractive Québec,
Sainte-Foy, Québec, 1999.
6) Şeşen, K., Metalurjik Süreçlerin Kinetiği, ITU Kimya-Metalurji Fak. Ofset
Atölyesi, Istanbul 1998.
7) Ray, H.S., Kinetics of Metallurgical Reactions, Oxford, New Delhi, 1993.
8) Biswas, A.K., Princles of Blast Furnace Ironmaking, Cootha Publish House,
Brisbane, Australia, 1981.