Kinetics of reduction of iron oxide &

oxidation of carbon
 Fe-O-C system

• 3Fe2 O3 + CO = 2Fe3 O4 + CO2 +10330 cal (Exo)

• Fe3O4 + CO = 3FeO + CO2 – 8750 cal (Endo)

• FeO + CO = Fe + CO2 + 3990 cal (Exo)

• Below 570C, Fe3O4 + 4CO = 3Fe + 4CO2 + 3220 cal

(Exo)

For the overall reaction, Fe2O3 + 3CO = 2Fe + CO2

 • Fe-O-H system

• 3Fe2O3 + H2 = 2Fe3O4 + H2O + 650 cal (Exo)

• 3Fe3O4 + H2 = 3FeO + H2O - 18430 cal (Endo)
• FeO + H2 = Fe + H2O - 5690 cal (Endo)
• Fe3O4 + 4H2 = 3Fe + 4H2O - 35500 cal (Endo)

Overall reaction,
• Fe2O3 + 3H2 = 2Fe+ 3H2O H(1000 K) =
17.42 kcal (Endo)
 Reactions with iron

• In contact with iron,

» 4Fe2O3 + Fe = 3Fe3O4
» Fe3O4 + Fe = 4 FeO
Kinetics of Iron Oxide Reduction
Kinetics of Iron Oxide Reduction
 The rate Laws in reduction
I. Transport of gaseous reactant from the bulk gas phase to
the particle surface through a boundary gas film.
II. Molecular diffusion of the gaseous reductant through the
product layer to the reaction interface
III. Adsorption of the gaseous reductant at the interface
IV. Reaction at the interface (reaction between adsorbed
reductant and the oxygen of the lattice)
V. Desorption of gaseous product from the interface
VI. Mass transport of iron and oxygen ions and transformations
in the solid phase; formation and growth of the reaction
products, viz, magnetite, wustite and iron.
VII. Molecular diffusion of gaseous products through the product
layer to the particle surface.
VIII. Transport of the gaseous product from the particle surface
through the boundary gas film to the bulk gas phase.
 • In case of CO or H2 has free access to the
reaction interface, the interface reaction
rate of oxygen removal from various oxide
of iron can be written as,
d (O)
v  K  p  p   K C C 
0 * ' 0 *

A.dt

Where, v= velocity of reaction per unit area of reacting surface per unit time
K, k = rate constants, depending upon the temperature and nature of the reductant,
CO or H2.
p, C= partial pressure or concentration of CO or H2 at the reaction interface
p*, C*= equilibrium partial pressure or concentration of CO or H2 at the given
temperature.
d (O)

A.dt = rate of oxygen removal
 • The transport of reacting species is given
by,
dc
J  D
dx
Where, D= coefficient of diffusion or diffusivity, cm2/s

dc
 = concentration gradient, the minus sign signifying the
dx decrease in concentration along distance in the direction of
flow.
A = Surface area normal to the flux.

  c
c 0
D
J D
l

l.RT
 p 0
 p

c, c= concentration of CO or H2 at the particle surface and the reaction interface

respectively.
p, p= corresponding partial pressure of CO or H2
l = thickness of the product layer or pore length.
Porous or effective diffusion coefficient (DP)

DP  D. .

 =Open porosity of the layer, volume of open pores relative to

the whole volume of the lump.
 =Labyrinth factor, value 0.1-0.3, to be determined
experimentally.
 Factors influencing diffusivity

• Temperature ( D  T , 1.75<n<2 )
n

1
• Total pressure (D  )
p 1
• Density of gas or molecular weight (D  M
)
• Effective collision diameter of gas
molecules
 Knudsen Diffusion Phenomena
• If the pore radius is smaller, the collisions of the gas
molecules with the pore walls will be more frequent than
those between the molecules, resulting in an overall
decrease in the value of diffusivity. This phenomena is
described by the Knudsen diffusion coefficient, DK:

d  8 RT 
DK   
6  M 

d=mean diameter of the pore

M =molecular weight of the reductant gas
 Nucleation and growth

rate of iron ion diffusion

dn 
rate of oxygen removal

dn is high product layer is porous

 C-O system
• C+1/2O2 = CO H (298k) = -26.42kcal
• C+O2 = CO2 H (298k) = -94.05kcal
• Co+1/2O2 = CO2 H (298k) = -67.84kcal

• About 30-40 percent of the coke carbon is oxidized

to CO2 and the rest into CO.

• Carbon dioxide, in absence of carbon, is stable at

higher temperatures (2000C).

• At high temperatures (1000C),

» C+CO2=2CO H (298k) = +41.21kcal
Boudouard Reaction or carbon gasification reaction
Reverse reaction is exothermic and is called carbon deposition reaction
Boudouard C-CO-CO2 Equilibrium Diagram
The rate laws in Boudouard reaction
I. Transport of gaseous reactant (O2 or CO2) from the bulk gas
phase to the particle surface through a boundary gas film.
II. Molecular diffusion of the gaseous reactant through the
coke particle (pore diffusion) to the reaction interface
III. Adsorption of the gaseous reactant at the interface
IV. Chemical reaction at the interface (reaction between
adsorbed reactant and carbon)
V. Desorption of gaseous product (CO) from the interface
VI. Molecular diffusion of gaseous products through the coke
particle i.e, pore diffusion.
VII. Transport of the gaseous product from the particle surface
through the boundary gas film to the bulk gas phase.
 • Bodouard reaction can be written as,

vc  keff ( n 0
CO2 n *
CO2 )
Where, vc = moles of carbon reacted /cm3.s
Keff = effective velocity constants, 1/s
0
nCO 2 = concentration of CO in gas phase, mole /cm
3
* 2
nCO2
= concentration of CO2 in gas phase in equilibrium with C and CO, mole /cm3