2.

Physico-Chemical Principles of Steelmaking Processes

2.3 KINETICS OF STEELMAKING PROCESSES

2.3.1 Introduction

Kinetics deals with measurements and interpretation of reaction rates.

• provides information which forms the quantitative basis for theories of chemical reactivity.
• define process variables that will best fulfil the requirements of practical operations.
• essential in the research and development of new processes and process modelling

Metallurgical thermodynamics
• interested only in the initial and final states of a transformation process
• reaction path, mechanism of conversion and the time required being of no importance.
• a reaction, thus, cannot be understood based on thermodynamics alone.
• Time is not one of the thermodynamic variable while it is the most important parameter in kinetics.

Both thermodynamics and kinetics are necessary for proper understanding of metallurgical processes.

Kinetics of steelmaking processes is a particular case of the kinetics of chemical reactions which studies
how reaction proceed in time.
• Steelmaking processes carried out at high temperature where reactions proceed very rapidly.
• process further complicated by simultaneous processes of
o heat transfer,
o mass transfer of reagents to the reaction zone,
o the natural or artificial stirring of reagents,
o the removal of reaction products, etc.

Therefore, chemical equilibria are closely attained in some reactions, while in some other reactions and
processes equilibrium is not attained.
• The principles of kinetics can help in process improvement as well as in better understanding.

Reactions in ironmaking and steelmaking are heterogeneous in nature

• they involve more than one phase, like slag and metal, gas and solid, etc.
• The chemical reactions between such phases occur at the phase boundaries (i.e. at interfaces)
• The rate of reactions, therefore, would be proportional to the interface area.

For these heterogeneous reactions to proceed

• transport reactants to the interface and products of reaction away from the interface is necessary.
• This is achieved by the process of mass transfer, which, divided into two categories:
1. Mass transfer in the bulk phase away from the interface (commonly called mixing)
• sufficiently rapid only in fluids when the flow is turbulent in nature.
2. Mass transfer at or near the interface
• depends on the concentration at the interface, T, total area available, etc.

As a result, all heterogeneous reactions take place through a series of kinetic steps:
1. Transfer of reagents to the reaction site;
2. The act of a chemical reaction at the interface;
3. Mixing in the bath fluid, and
4. The separation of reaction products as a phase and their removal from the reaction site.

Each of these stages can in turn be sub-divided into several minor intermediate stages
• the rate of the whole process depends on the rates of its individual stages:
1
𝜈Σ =
1/𝜈1 + 1/𝜈2 + 1/𝜈3 + ⋯

• each stage may limit the whole process if its rate is smaller than the rates of the other stages.
• If, for instance, the rate 𝜈2 is reduced practically to zero, then the ratio 1/𝜈2 will increase up to
infinitely, and therefore, 𝜈Σ will diminish to zero.

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 Rashid . Ferrous Production Metallurgy

In most steelmaking processes

• a chemical reaction occurs practically instantaneously and cannot limit the whole process
• the rate of the whole process is most often determined by the rate with which the reagents are
supplied to the reaction site or by the conditions of the separation and the removal of reaction
products.

In analysing the problem related to the transfer of reagents to the reaction site, one must consider
• the rates of diffusion of an element in the slag and the metal,
• the passage of a given element through interface, and
• the factor of natural or artificial stirring of the metal.

Metal stirring
• increases the rate of mixing, and therefore, the total rate of the process.
• With more intensive stirring, the role of diffusion becomes less important.
• In the extreme case, the rate mixing may be greater than the rate of interaction on the surface
o In this case, rate of interaction will be a slower stage of the process and will limit the
rate process.

In general, solids are assumed to be pure in steelmaking processes

• solid-state diffusion is extremely slow and can be neglected.
• for a large variety of porous solids (e.g. iron ore, sinter, sponge iron, coke, lime, etc.),
o diffusion of gases and even liquids through these minerals is easy
o reaction occurs fast.

2.3.2 Interfacial Chemical Reaction Rate

In ironmaking and steelmaking processes,

• heterogeneous reactions occur involving an interface between two reacting phases, e.g. solid-gas,
solid-liquid, liquid-gas and two immiscible liquids (slag-liquid metal).
• Kinetic theories proposed for homogeneous reactions can also be applied to these interfacial
chemical reactions with some modifications and additions.

Some important characteristic features of a rate process:

1. a thermodynamic driving force is necessary for any transformation to occur
o the change must imply a lowering of the free energy of the system.
2. transformation to a more stable state will occur only if sufficiently energy is supplied to overcome
a definite energy barrier.
o a negative free energy change by itself does not guarantee onset of transformation.
3. There must be a reaction mechanism which governs the transformation.
o this mechanism may change with time and extend of transformation.

Reaction rate is the rate at which a chemical reaction proceeds.

• can be expressed either in terms of
o the rate of generation of any of the products, or
o that of consumption of any of the reactants.

To measure a reaction rate,

• we need to monitor the concentration of one of the reactants or products as a function of time.
• The rate therefore has units of concentration per unit time, mol/dm3.s.

The kinetics of chemical reactions is based on the law of mass action

• which states that, for the interfacial reaction, the reaction rate is proportional to the product of
concentrations of the constituting substances
• the rate with which B can enter the reaction can be expressed as

bB + dD = mM + nN
𝑑𝐶𝐵
− = 𝑘 𝐶𝐵𝑏 𝐶𝐷𝑑
𝑑𝑡

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 2. Physico-Chemical Principles of Steelmaking Processes

k = constant, known as the velocity constant or rate constant,

CB and CD = concentrations of the reacting substances B and D at time t.
The minus sign indicates that the concentration of substance B decreases in time.

The sum of the exponents b and d are called the order of the reaction, n.
• first-order reaction (n = 1) may be written as A = B + C,
• the reaction rate is proportional to a single concentration term.
• a second-order reaction (n = 2) may be written as A + B = C + D
• sum of the exponents of the concentration terms is two.
• reactions of higher orders can be written in a similar manner.

For a reaction that is far from equilibrium,

• the free energy difference between the reactants and products is large and negative,
• the rate of reaction depends on the concentration of the reactants.
• the backward reaction is unimportant.

But for a reaction close to equilibrium

the overall rate of reaction depends on the rates of both forward and backward reactions.
for chemical reaction B+D = M+N, the overall rate at which B is consumed can be expressed as
𝑑𝐶𝐵 𝐶𝑀 𝐶𝑁
− = 𝑉𝑓 − 𝑉𝑏 = 𝐴(𝑘𝑓 𝐶𝐵 𝐶𝐷 − 𝑘𝑏 𝐶𝑀 𝐶𝑁 ) = 𝐴𝑘𝑓 (𝐶𝐵 𝐶𝐷 − )
𝑑𝑡 𝐾
K = equilibrium constant
A = interfacial area
𝑉𝑓 and 𝑉𝑏 = velocities
𝑘𝑓 and 𝑘𝑏 = rate constants of forward and backward reactions

In ironmaking and steelmaking, first-order reversible reactions, such as B = M, are involved.

• In this situation, the rate of reaction can be modified to
𝐶𝑀
𝑟 = 𝐴𝑘𝑓 (𝐶𝐵 − )
𝐾

The rate constant 𝑘𝑓 increases with temperature following the Arrhenius equation
𝐸
𝑘𝑓 = A exp (− )
𝑅𝑇
E = activation energy, A = pre-exponential factor.

Practical reaction rates in steelmaking processes differ substantially from those determined by the mass
action law due to the following reasons:
1. one must deal with solutions of some or other components in the slag or metal and consider the
effect of the solvent (i.e. non-ideal solution) and
2. real reactions occur, as a rule, in heterogeneous, rather than homogeneous, media.

For these reasons, reaction rates are often determined experimentally for each case.

The rate of a reaction is usually expressed as

• change in concentration of a substance, per cent of the mass of metal (or slag), per unit time (hour
or minute).
• For instance, the rate of carbon oxidation may be 0.5% C/h, etc.

2.3.3 Role of Diffusion

Steelmaking bath contains large interfaces (for instance, during bath blowing), which facilitates appreciably
the nucleation of phases.
• the rate of the whole process is then limited by the mass transfer rate.

In a quiet or poorly stirred bath,

• the decisive role is taken by the diffusion intensity of the reagents.

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 Rashid . Ferrous Production Metallurgy

Diffusion (i.e. molecular diffusion) is governed by the Fick’s first law of diffusion:
𝑑𝑛𝑘⁄
Molar flux = 𝑑𝑡 = −𝐷 (𝑑𝐶𝑘 )
𝑘
𝐴 𝑑𝑥
𝑑𝑚𝑘⁄ ∗
Mass flux = 𝑑𝑡 = −𝐷 (𝑑𝐶𝑘 )
𝑘
𝐴 𝑑𝑥
𝐶𝑘 = concentration of k in mole/volume
𝐶𝑘∗ = concentration of k in mass/volume,
𝐷𝑘 = the diffusion coefficient (i.e. diffusivity) of k having the unit of cm2/s or m2/s.

Values of D (in m2/s) at steelmaking temperatures

• 10–2 to 10–3 for gases
• 5*10–8 to 5*10–9 for liquid steel, and
• 5*10–10 to 5*10–11 for liquid slag.

Steelmaking is concerned with molecular diffusion only through the pores of a porous solids
• diffusion of gases or liquids through pores can be treated by the usual diffusion equations.
• special consideration needed for estimation of D.
• for this, the following equation can be used
𝜀
𝐷𝑘 (in pores) = 𝐷𝑘 (in bulk gas/liquid) ( )
𝜏
𝜀 = volume fraction of pores in the solid
𝜏 = tortuosity factor.
(In the fluid mechanics of porous media, tortuosity is defined as the ratio of the length of a
streamline—a flow line or path—between two points to the straight-line distance between
those points.)

• the tortuosity factor may be taken 2 (this creates a source of uncertainty).

• further source of uncertainty arises due to wettability of the solid.
o If the liquid does not wet the solid, it cannot penetrate the pores properly, and the role
of wettability is thus obvious.

2.3.4 Turbulence and Mixing in Fluids

Turbulence and mixing of fluids (both liquid and gas) is involved in liquid steel and sometimes in liquid
slag during steelmaking process.
• The general equation for mass transfer during mixing for species k in the x-direction is
𝑑𝑛𝑘⁄
𝐽𝑘𝑥 = 𝑑𝑡 = −𝐷 (𝑑𝐶𝑘 ) + 𝐶 𝑣 − 𝐸 (𝑑𝐶𝑘 )
𝑘 𝑘 𝑘 𝐷
𝐴 𝑑𝑥 𝑑𝑥
𝐽𝑘𝑥 = flux of k along x-direction,
𝑣𝑘 = convective velocity of the fluid in x-direction, and
𝐸𝐷 = eddy diffusivity (only in turbulent flow).

Since 𝐸𝐷 ≫ 𝐷𝑘 , for turbulent flow, molecular diffusion can be ignored.

• Therefore, mixing in the bulk fluid occurs by convection and eddy diffusion.

Whenever any addition is made to a liquid, it takes a long time for complete mixing.
• Therefore, for all practical purposes, the mixing time (𝑡𝑚𝑖𝑥 ) is defined as the time required for a
degree of mixing of 95%, i.e. 95% of perfect mixing.

Creation of turbulence and motion requires agitation of the fluid by stirring.

• The greater the extent of stirring, the faster is the mixing, and the lower is 𝑡𝑚𝑖𝑥 .
• In case of processing of molten steel in gas-stirred ladles and converters, it has been established
that, in general,
𝑡𝑚𝑖𝑥 = 𝐵 𝑃 −𝑚 𝑓(geometry, size of vessel)
P = specific stirring power input,
B and m = empirical constants.

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 2. Physico-Chemical Principles of Steelmaking Processes

2.3.5 Convective Mass Transfer at Interface

Mass transfer at fluid-solid interface

At fluid-solid interfaces, the fluid can be assumed to be

stagnant. 𝐶𝑘𝑆
• the convection and eddy diffusion can be ignored Fluid
• This causes a significant concentration gradient Solid
• This is called concentration boundary layer for
the species
Ck
Concentration profile
Since only molecular diffusion is involved, the equation
for mass transfer of species k in the x-direction becomes
𝑑𝑛𝑘⁄ 𝐶𝑘0
𝑑𝑡 ) 𝑑𝐶𝑘
( = −𝐷𝑘 ( ) 𝑑𝐶, eff
𝐴 𝑑𝑥 𝑥=0
𝑠𝑢𝑟𝑓𝑎𝑐𝑒
𝐶𝑘𝑆 − 𝐶𝑘0 x =0
x
= −𝐷𝑘 ( ) = 𝑘𝑚,𝑘 (𝐶𝑘𝑆 − 𝐶𝑘0 )
𝑑𝐶, eff Figure 2.6: Concentration boundary layer in fluid
adjacent to a solid surface during mass transfer.

𝑑𝐶, eff = effective concentration boundary layer thickness,

𝑘𝑚,𝑘 = mass transfer coefficient for k = (𝐷𝑘 /𝑑𝐶, eff ).

For more intense stirring (agitation),

• 𝑑𝐶, eff is lower and 𝑘𝑚,𝑘 is higher
• Thus, mass transfer increases with increasing fluid convection and agitation.

Mass transfer at fluid-fluid interface

The fluid-fluid interface differs from the fluid-solid interface in that

1. the fluid layer is not stagnant
• possibility of flow and consequent renewal of interfacial layers is to be considered
2. there may be turbulence at the fluid-fluid interface.

Many surface renewal theories (or models), of mass transfer at fluid-fluid interface have been proposed.
• Out of these theories, two theories are generally employed – Higbie’s surface renewal theory and
Danckwert’s surface renewal theory.

Higbie’s theory
• applicable for laminar flow at the interface and no velocity gradient normal to the interface.
• For example, in slag-metal interactions, the liquid slag is much more viscous than the liquid metal.
Therefore, in a laminar flow situation, the velocity gradient in the slag layer normal to the interface
would be negligible, i.e. the slag layer would behave like a rigid solid.
• In this situation Higbie’s theory may be applied to mass transfer on the slag side (not the metal
side) of the interface.
• For a gas-liquid interface under laminar flow, it is applicable to the liquid phase.
• Higbie’s theory predict that
𝐷𝑘 1/2
𝑘𝑚,𝑘 = 2 ( )
𝜋 𝑡𝑒
𝑡𝑒 = time of exposure of fluid element at the surface.

Danckwert’s theory
• applicable when the flow is turbulent at the interface.
• It predicts
𝑘𝑚,𝑘 = (𝐷𝑘 𝑆)1/2
S = surface renewal factor (for very mild turbulence, S =20/section; for strong turbulence, S =300/section)
• Sometimes, can be estimated theoretically, but in most cases, S must be determined experimentally
or by making an educated guess.

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 Rashid . Ferrous Production Metallurgy

2.3.6 Enhancement of Process Rates

The reaction rates between solids, liquids, and gases can be increased by:
1. Increasing the surface area of the solid by grinding it to a fine powder, and creating drops, bubbles,
and emulsions. These methods are very effective, and the rates can be enhanced by several orders
of magnitude.
2. Ensuring that the solids should have sufficient porosity.
3. Enhanced mixing and mass transfer by increasing fluidity of the liquid and the extent of agitation.

Although temperature does have a strong influence on reaction rates, in most cases, it is not possible to
increase it to any significant extent owing to various other technological reasons (refractory attack, vapour
formation, etc.)

Example 2.5
A bubble of nitrogen gas of diameter 0.5 mm, at a pressure of 1.5 atm, is rising through a stagnant
melt of steel of composition 0.5% C, 0.5% Mn and temperature 1600 °C. Assuming mass transfer in
the melt to be rate controlling, and Higbie’s theory to be applicable, calculate the rate of transfer of
nitrogen from gas to melt.
Given data: For the reaction 1/2(N2) = [N], log 𝐾𝑁 = −581/𝑇 + 2.937.
Solution:
Rate of nitrogen (atomic) transfer through the bubble surface area A
𝑟𝑁 = 𝐴 𝑘𝑚,𝑁 (𝐶𝑁𝑆 − 𝐶𝑁0 ) = (𝜋𝑑2 )𝑘𝑚,𝑁 (𝐶𝑁𝑆 − 𝐶𝑁0 )

𝑘𝑚,𝑁 is given by Higbie’s equation

𝐷𝑁 1/2
𝑘𝑚,𝑁 = 2 ( )
𝜋 𝑡𝑒
Diffusivity of N in liquid steel at 1600 °C is 3.8*10 –9 m2/s. The exposure time, 𝑡𝑒 = 𝑑/𝑣𝑡 , where 𝑣𝑡 is
the rising velocity of the bubble of size d (according to Stokes’ law).
𝑔 𝑑2 (𝜌𝑙 − 𝜌𝑔 )
𝑣𝑡 =
18 𝜂

Using g = 9.81 m/s2, 𝜌𝑙 = 6.73*103 kg/m3, 𝜌𝑔  0, and 𝜂 = 5*10–3 Pa.s, we get from Stokes’ law,
𝑣𝑡 = 0.1834 m/s, which gives 𝑡𝑒 = 2.73*10–3 s and 𝑘𝑚,𝑁 = 13.32*10–4 m/s.
Assume the bulk concentration of N (i.e. 𝐶𝑁0 ) = 0 and the surface concentration 𝐶𝑁𝑆 is at equilibrium
with the N2 gas. Then at 1.5 atm nitrogen pressure, using 1/2(N2) = [N], the weight per cent of N at
equilibrium is
1/2
[ℎ𝑁 ]𝑝𝑝𝑚 = 𝐾𝑁 𝑝𝑁2

581
At 1600 °C, log 𝐾𝑁 = − (1873) + 2.937 = 2.6268 𝑜𝑟, 𝐾𝑁 = 423.45. Then

[ℎ𝑁 ]𝑝𝑝𝑚 = (423) (1.5)1/2 = 518.62

Again, from the relation

[ℎ𝑁 ]𝑝𝑝𝑚 = 𝑓𝑁 (104 𝑤𝑡%𝑁)𝑝𝑝𝑚

log[ℎ𝑁 ]𝑝𝑝𝑚 = 4 + log 𝑓𝑁 + log 𝑤𝑡%𝑁

log[ℎ𝑁 ]𝑝𝑝𝑚 = 4 + 𝑒𝑁𝑁 (𝑤𝑡. % 𝑁) + 𝑒𝑁𝐶 (𝑤𝑡. % 𝐶) + 𝑒𝑁𝑀𝑛 (𝑤𝑡. %𝑀𝑛) + log(𝑤𝑡%𝑁)

Substituting values of interaction coefficients from Table 2.2,

log(518.62) = 4 + 0 + 0.13(0.5) + (−0.02)(0.5) + log(𝑤𝑡%𝑁)
𝑤𝑡%𝑁 = 0.0457%

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 2. Physico-Chemical Principles of Steelmaking Processes

Then
𝐶𝑁𝑆 = mass of 𝑁 per m3 of melt = wt. fraction of 𝑁 in melt x density of liquid iron
= 0.0457*10–2 x 6.73*103 = 3.075 kg N/m3
Therefore, the rate of N transfer
𝑟𝑁 = 𝜋 x (0.5 ∗ 10−3 𝑚2 ) (13.32 ∗ 10−4 𝑚/𝑠)(3.075 − 0 𝑘𝑔/𝑚3 )
𝑟𝑁 = 32.17 ∗ 10−10 𝑘𝑔/𝑠

Example 2.6
Consider the following slag-metal reaction at 1600 °C.
[Si] + 2(MnO) = (SiO2) + 2[Mn]
where Si in the liquid iron and MnO in slag phase. Compare the maximum rates of transfer of Si and
Mn in liquid iron at the slag-metal interface. Assume validity of Danckwert’s surface renewal theory.
Given data: DSi (in liquid iron) = 2.5*10–9 m2/s, DMn (in liquid iron) = 4.0*10–9 m2/s at 1600 °C; the
composition relation in iron, at equilibrium with slag, is [𝑤𝑡. % 𝑆𝑖]⁄[𝑤𝑡. %𝑀𝑛]2 = 0.23; liquid iron
contains 0.3 mol% Si and 0.5 mol% Mn.

Solution
The rate of transfer of Si from the liquid metal to the slag-metal surface is
0
𝑟𝑆𝑖 = 𝐴 𝑘𝑚,𝑆𝑖 [𝐶𝑆𝑖 − 𝐶𝑆𝑖𝑆 ]

And the rate of transfer of Mn from the slag-metal surface to the liquid metal is
𝑆 0 ]
𝑟𝑀𝑛 = 𝐴 𝑘𝑚,𝑀𝑛 [𝐶𝑀𝑛 − 𝐶𝑀𝑛

Since the mass transfer coefficients 𝑘𝑚,𝑆𝑖 and 𝑘𝑚,𝑀𝑛 follow Danckwert’s surface renewal theory, then
𝑘𝑚,𝑆𝑖 (𝐷𝑆𝑖 𝑆)1/2 𝐷𝑆𝑖 1/2
= 1/2
= ( ) = 0.79
𝑘𝑚,𝑀𝑛 (𝐷𝑀𝑛 𝑆) 𝐷𝑀𝑛

At the maximum rate of Si transfer, the concentration of Mn in the liquid iron remains uniform at 0.5
mol %. Then, Si concentration at the slag-metal interface is given by the chemical equilibrium reaction
0.23 x [mol % Mn]2 = 0.23 (0.5)2 = 0.0575
Since, concentration is proportional to the mole fraction, the maximum rate of Si transfer
0
𝑟𝑆𝑖 = 𝐴 𝑘𝑚,𝑆𝑖 [𝐶𝑆𝑖 − 𝐶𝑆𝑖𝑆 ] = 𝐴 𝑘𝑚,𝑆𝑖 [0.3 − 0.0575] = 0.2425 𝐴 𝑘𝑚,𝑆𝑖

In a similar way, the maximum rate of Mn transfer

𝑆 0 ]
𝑟𝑀𝑛 = 𝐴 𝑘𝑚,𝑀𝑛 [𝐶𝑀𝑛 − 𝐶𝑀𝑛 = 𝐴 𝑘𝑚,𝑀𝑛 [(0.3⁄0.23)1/2 − 0.5] = 0.6421 𝐴 𝑘𝑚,𝑀𝑛

Then, the ratio of the rates of Si and Mn transfer

𝑟𝑆𝑖 0.2425 𝐴 𝑘𝑚,𝑆𝑖 0.2425 (0.79 𝑘𝑚,𝑀𝑛 )
= = = 0.298
𝑟𝑀𝑛 0.6421 𝐴 𝑘𝑚,𝑀𝑛 0.6421 𝑘𝑚,𝑀𝑛