ISSN 0967-0912, Steel in Translation, 2008, Vol. 38, No. 6, pp. 421423. Allerton Press, Inc., 2008.

Original Russian Text V.M. Abzalov, V.I. Klein, B.P. Yurev, 2008, published in Izvestiya VUZ. Chernaya Metallurgiya, 2008, No. 6, pp. 79.

Oxygen Diffusion in Pores of Iron-Ore Pellets

V. M. Abzalov, V. I. Klein, and B. P. Yurev
Pervouralsk Branch, Ural State Technical UniversityUral Polytechnic Institute
DOI: 10.3103/S0967091208060016

The oxidation of magnetite in pellets is a complex

heterogeneous phenomenon, consisting of numerous
parallel processes. Almost all of these are activational
processes. As a rule, they cannot be isolated or
observed experimentally. Therefore, despite extensive
research, it is still difficult to describe the basic laws of
magnetite oxidation in pellet roasting. Nevertheless,
most researchers describe this process as a sequence of
stages: 1) external mass transfer of oxygen from the gas
flux to the pellet surface; 2) diffusional transfer of oxygen molecules through the pellet pores to the surface of
the magnetite grains; 3) reaction at the phase boundary;
4) diffusion of reagent ions in the lattice due to the
chemical potential gradient.
Since these stages occur in sequence, the rate of the
whole process is determined by the rate of the slowest
stage.
In practice and in laboratory simulations, pellet
roasting is characterized by a turbulent gas flow, in
which the mass transfer is determined by convective
diffusion, including molecular and molar transfer.
Therefore, the external diffusional drag is small in comparison with the internal drag, and may be neglected.
Thus, magnetite oxidation is limited either by internal diffusion (diffusional conditions) or by the reaction
kinetics (kinetic diffusion). Formal description of the
reaction kinetics, corresponding to the Arrhenius law, is
not very difficult. It is considerably more difficult to
describe the diffusional behavior. We consider this
problem in the present work.
For the subsequent analysis, we make two assumptions: the raw pellets are characterized by open pores
throughout their volume; and the magnetite particles
(grains) are in point contact. Thus, the surface of all the
particles is open, and there is an adequate pore surface.
The ratio of the pore-channel diameter (dpc) to the mean
particle diameter (dp) is determined by the pellet porosity
d pc
2
------ = --- ----------- .
31
dp
Internal diffusion consists of a series of parallel processes: I) molecular (free) diffusion in pores whose
radius is large in comparison with the mean free path
length of the gas molecules; II) Knudsen (capillary) dif-

fusion in pores whose diameter is less than the mean

free path length of the molecules; III) activated (surface) diffusion by adsorbed molecules along the pore
walls; IV) diffusion in the solid state through the layer
of reaction products (hematite) that forms. Since these
diffusion processes occur in parallel, the one that makes
the greatest contribution to the total process will be
dominant.
Activated diffusion may be neglected on account of
its slowness and small contribution to the overall diffusion process. Diffusion in the solid state may also be
neglected. That leaves molecular diffusion and Knudsen diffusion, whose contribution depends on the range
of pore sizes.
Division of pores into macrocapillaries (radius rpc >
107 m) and microcapillaries (rpc < 107 m) was suggested in [1]. This distinction was linked to different
mechanisms of gas transfer in these capillaries. In practice, there is no such sharp transition from one type of
diffusion to another. Rather, there is an intermediate
range of pores in which a distinctive transfer mechanism operates.
Pores were divided into three categories as a function of their radius in [2]: macropores, for which rpc >
2 106 m; intermediate pores (mesopores), for which
2 106 > rpc > 1.5 107 m; and micropores, for which
rpc < 1.5 109 m. This classification applies to sorbents
and catalysts characterized by a specific pore surface of
103105 m2/kg and porosity 0.40.5.
Note that any classification is somewhat arbitrary
and depends on the chosen model of the porous body.
The selection of a classification system depends on
methods of investigating the pore structure [3]. It is
more helpful to base the classification on the possibility
of describing gas transport in the pore space. From this
perspective, the diffusion mechanisms in the pores of
pellets with a specific surface of 130200 m2/kg may be
better described by the following categories:
macropores, for which rpc > 105 m; mesopores, for
which 105 rpc 107 m; and micropores, for which
rpc < 107 m. This classification corresponds to values
of the Knudsen number characterizing different diffusion mechanisms in the pore grain [4]. We employ the
Knudsen number = dpc/ (where dpc is the pore diameter and is the free path length of the molecules) for

421

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ABZALOV et al.

Substituting the values of Mi and i into Eq. (1), we

find that

Diffusion rate, m2/s

2.5

D = 4.269 10 T /P m /s.
4

2.1

0.9

Dm 10
4

0.5
673

0
1

1
f

De

873

1073

1273
1473
Temperature, K

Fig. 1. Influence of temperature on the diffusion coefficient

of oxygen in the pellet (at atmospheric pressure): D 104 is
the free-diffusion coefficient; Def 105 is the effective diffusion coefficient; Dm 106 is the molecular flow coefficient.

(2)

D ef = D,

(3)

where = 1/kt is the labyrinth factor, depending on the

twist of the pore channels; kt is the twist coefficient.
For the pellets, on average, when = 0.3 and = 1/4,
the effective diffusion coefficient is

the diffusion of oxygen in pores over a temperature

range 400900C, with a free path length of around 2
107 m. Then, for macropores, the free-diffusion coefficient may be used when > 100; for mesopores, the
effective diffusion coefficient may be used when 100
1; and for micropores, the diffusion mechanism
changes to molecular flow, with < 1.
In the initial pellet, the mean pore diameter is less
than the macropore diameter but greater than the mesopore diameter: it is (914) 106 m. The Knudsen number = 4570 also indicates that an intermediate diffusion mechanism operates in these pores.
For most of the pores in roasted pellets, the radius is
between 5 106 and 1 107 m. In other words, mesopores predominate in the roasted pellet, with only small
quantities of macropores and micropores. The mean
pore diameter in the roasted pellets is around 1.5
106 m. Thus, on transition from the initial pellet to the
roasted pellet, the mean pore size declines by a factor
of 510.
The rate of free diffusion depends on the mutualdiffusion coefficient D of oxygen and nitrogen [5]. At
constant pressure, D depends on the temperature as
follows [6]
1.5

MN + MO 2
T
- m /s;
D = 853.195 --------------------------- --------------------( N + O )P M N M O

The mechanism of diffusional transfer in mesopores

of a capillary-porous body such as the pellet has certain
distinctive features. The skeleton of the porous body (in
particular, its structure) has a considerable influence on
the mass transfer. The diffusion coefficient declines
with increase in the number and size of the particles
that lie in the path of the diffusional flux [4]. Diffusion
is also subject to the retarding influence of the capillary
walls. For the capillaries of the raw pore, whose diameter is 4570 times the free path length of the oxygen
molecules, the walls have little influence on the gas diffusion. The porosity and twist of the capillaries will
influence the effective diffusion coefficient (Def).
In the transition region, the effective diffusion coefficient may be used [3]

1.7
1.3

1.5

(1)

here T is the temperature, K; N and O are the diameters of the nitrogen and oxygen molecules, 0.1 nm; P is
the total pressure, Pa; MN and MO are the molecular
masses of nitrogen and oxygen.

(4)

D ef = 0.075D.

In steady conditions, the diffusional flux (diffusion

rate) v is as follows, according to Ficks first law
dC
v = FD ------dx
C0 Cr
P
2
- --- mole/s;
= 0.03r pe D ----------------------------------3
T
22.41 10 r pe

(5)

here F is the cross-sectional area of the pellet, m2; rpe is

the pellet radius, m; C0 and Cr are the oxygen concentrations in the heat-carrier gas and at the reaction surface, mole/m3.
For a pellet in isothermal conditions, at constant
pressure, the diffusional flux is
C0 Cr
= 0.03r pe D ----------------------------mole/s.
3
22.41 10

(6)

For a pellet whose radius is 0.65 102 m

= 36.43 10 D ( C 0 C r ) mole/s,
7

(7)

and for atmospheric oxygen

= 7.65 10 D mole/s.
7

(8)

The molecular-flow coefficient Dm may be found

from the approximate Knudsen formula
2
8RT 2
D m = --- r pc.eq ----------- m /s,
3
M O
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OXYGEN DIFFUSION IN PORES OF IRON-ORE PELLETS

initial pellet (Fig. 1). The slope of the curves, which

indicates the influence of the temperature on the diffusion coefficient, declines on passing from free diffusion
to molecular flow. The diffusion rate of oxygen in the
pellet pores also reflects the influence of the temperature (Fig. 2).
Pores at the boundary of macropores and mesopores
predominate in the initial pellet, whereas mesopores
predominate in the roasted pellet. We may then assume
that, in the oxidation of magnetite on pellet heating, the
diffusion rate must be calculated on the basis of the
effective diffusion coefficient, which depends on the
pore structure of the pellet. Note that the macropores
are characterized by free diffusion, which does not
depend on the pore structure, while the micropores are
characterized by molecular diffusion. Since these types
of diffusion have little influence on oxygen transport in
the pellet pores, however, they may be neglected.

Diffusion rate, m2/s

1.8

1.4

1.0
4

0.6

1
f

m 1

06

0.2
673

873

1073

1273
1473
Temperature, K

Fig. 2. Influence of temperature on the diffusion rate of oxygen in the pellet (at atmospheric pressure): v 104 is the
free-diffusion rate; vef 105 is the effective diffusion rate;
vm 106 is the molecular flow rate.

where rpc.eq is the equivalent pore radius, cm; R =

8.314 J/K mole is the gas constant.
Substituting the known values into Eq. (9), we
obtain
1/2

(10)

D m = 0.54r pc.eq T .

Since molecular flow applies to pores whose radius

is less than 107 m, we may write
D m = 0.54 10 T .
7

1/2

(11)

The molecular flow rate vm is [5]

C0 Cr
P
-,
v m = 0.02Fr pc.eq --------------------------- ---------------2M O RT l

(12)

where l is the capillary length, m.

Then, for the pellets
v m = 9.67 10

11

PT

1/2

(13)

and hence the molecular flow rate declines as the temperature rises, on account of the increase in the free
path length.
The mechanisms of free diffusion, effective diffusion in the porous material, and molecular flow appear
in the sequence corresponding to the diffusion coefficients of oxygen calculated for the pore structure of the

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CONCLUSIONS
Pores have been classified in terms of the characteristics of gas transport in the pore space, which is related
to different diffusion mechanisms in the porous pellet.
For the pore structure of the initial pellet, mechanisms
of free diffusion, effective diffusion, and molecular
flow are employed. The results may be used in masstransfer calculations and in studying diffusional processes in porous bodies, with the determination of the
effective diffusion coefficient of oxygen to the reaction
front.
REFERENCES
1. Lykov, A.V., Yavlenie perenosa v kapillyarno-poristykh
telakh (Transport Phenomena in Capillary-Porous Bodies), Moscow: Gostekhizdat, 1954.
2. von Bogdandy, L. and Engel, H.J., The Reduction of Iron
Ores, New York: Springer, 1971.
3. Karnaukhov, A.L., Metody issledovaniya vysokodispersnykh i poristykh tel (Methods of Investigating Highly
Disperse and Porous Bodies), Moscow: Izd. AN SSSR,
1958.
4. Akselrud, G.A. and Altshuler, M.A., Vvedenie v kapillyarno-khimicheskuyu tekhnologiyu (Introduction to
Capillary-Chemical Technology), Moscow: Khimiya,
1983.
5. Statnikov, B.Sh., Bratchikov, S.G., and Yurev, B.P., Izv.
Vyssh. Uchebn. Zaved., Chern. Metall., 1972, no. 6,
pp. 4245; no. 8, pp. 4245.
6. Shkodin, K.K., Sb. nauchnykh trudov LPI (Proceedings
of Leningrad Polytechnic Institute), Leningrad: Metallurgiya, 1964, issue 225, pp. 3453.