On presente une nouvelle methode pour tenir compte de I’oxydation de la magnetite lors de l’induration de pastilles
de minerai de fer dans un four rotatif. La technique s’appuie sur la description mathematique de Saeman (1 95 1) d’un lit
en cascade gami de pastilles dans un four rotatif. A des fins d’illustration, on a applique cette methode a un modele uni
dimensionnel simple de transfert de chaleur et de matiere dans un four rotatif alimente au gaz naturel. Le modele predit
une fraction de l’oxydation magnetique a moins de 5%, ce qui est en accord avec les observations en usine.
Keywords: taconite pellet induration, magnetite oxidation, rotary kiln, mathematical model.
mpart
Aperatures
s of the taconite iron ore pellet induration process,
agnetite in the pellet is oxidized to hematite at tem
high
with oxygen from air. The gratekiln system is com
Proh.ator/Grnta Rotary Kiln
n
monly used for this purpose (Ball et al., 1973; Potts, 1991).
The gratekiln taconite pellet induration system involves sev v
eral stages of heat and oxygen transfer to a traveling bed of To Dryer Cooler
spherical taconite pellets, as shown in Figure 1. At the heart of
the process is the rotary kiln where pellets are heated to tem Secondary air to 1st stage I
peratures in excess of 1600 K with a high temperature flame. Figure 1 Gratekiln system. Arrows indicate the countercurrent
The remaining steps in the process were designed to effi flow of process gasses and pellet bed.
ciently recover thermal energy from the pellet bed. The pellets
exiting the kiln are cooled by an updraft of ambient air through
the pellet bed traveling along a grate in a revolving two stage
cooler. Hot air from the first stage of the cooler is passed to A simple, novel approach to simulating magnetite oxida
the kiln as secondary air where it flows above the pellet bed tion in the kiln is presented here. For the purpose of demon
counter current to the flow of pellets through the kiln. The stration, the magnetite oxidation model was incorporated
gases from the kiln, including secondary air and combustion into a modified form of the onedimensional rotary kiln heat
products, are used to preheat and oxidize the pellet bed on a transfer model of Thornton and Batterham (1982). Concise
traveling grate before the pellets are fed to the kiln. literature reviews of the shrinking core model applied to
Magnetite oxidation is exothermic, and occurs primarily magnetite oxidation and the heat and mass transfer models
along the grate in the preheat h a c e where hot air is drawn of a rotary kiln precedes the theoretical development of the
down through the porous bed of spherical pellets (Potts, magnetite oxidation model for a rotary kiln. This simple
1991). Plant experience indicates that only a small fraction rotary kiln magnetite oxidation model was found to provide
of oxidation occurs in the kiln due to the relatively poor satisfactory results, while avoiding the complicated model
mixing of the pellet bed with the freeboard gases. In addi ing of the gas to solids mixing in the kiln pellet bed (Young
tion, the gas to solids mixing in the rotary kiln is difficult to et al., 1979).
model rigorously. Consequently, most models of the grate
kiln iron ore pellet induration process have ignored oxida Magnetite oxidation in the pellet
tion in the kiln by limiting this reaction to the grate in the
preheater and cooler (Thurlby, 1988; Young et al., 1979). The overall reaction of oxygen with magnetite to form
However, ignoring this reaction fails to account for the addi hematite is
tional temperature rise in the kiln due to the heat released by
this exothermic oxidation reaction. According to Potts 4 Fe304 + 0, + 6 Fe203 . . . . . . . . . . . . . . . . . . . . . (1)
(1991), up to 5% of the magnetite is oxidized in the kiln,
which can result in as much as a 10% increase in the kiln The magnetite oxidation reaction may be assumed irre
pellet bed temperature. versible for the kiln conditions in this analysis (Papanastassiou
and Bitsanes, 1973). Taconite pellets are roughly spherical
with magnetite evenly distributed throughout the pellet. The
well known shrinking core model (Levenspiel, 1972)
You may contact the author by Email: rdavis@d.umn.edu applied to taconite pellets, assumes a retreating reaction
1004 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 74, DECEMBER, 1996
interface between an outer ash layer of hematite and an except for a constant flux of entrained gas from the sec
unreacted magnetite core. Experimental evidence suggests ondary air stream to the flame stream. It was recognized that
that the interface between the shrinking core and the ash the flame shape is generally not symmetric about the kiln
layer is sharp, and that the oxidation reaction is controlled centerline, and that some turbulent mixing of these streams
by the diffusion of 0, through the ash once the outside pel occurs. However, this description of the process was chosen
let surface is oxidized (Monson et al., 1994; Pape et al., in order to simplify the mathematics of radiation heat transfer,
1976; Papanastassiou and Bitsanes, 1973). By applying the while providing reasonable results for gas and solids tem
stationarystate approximation to the changing core size rel perature profiles, as described in the literature (Silcox and
ative to the flow rate of 0, to the reacting interface, as out Pershing, 1990; Barr et al., 1989; Gorog et al., 1983;
lined by Levenspiel (1992), the shrinking core model results Thornton and Batterham, 1982, Jenkins and Moles, 1981).
in the following expression for the rate of change in the core The differential energy balances for the gas streams along
radius. the length of the kiln, z, are of the form:
drc
_  doe [0 2 ,3 .................... z4hi
dT
= 41  c dF:
(  p p f ~ , Y i )... . . . . . . . (3)
H ~2
dz
CONSERVATION OF ENERGY where 4 is the solid fill angle and rk is the inside kiln refrac
tory radius, as defined in Figure 2. As the flame stream
For convenience, the gases in the luln are divided entrains the secondary air, the radius grows, increasing the
between a flame stream and secondary air stream. The flame rate of entrainment. In the limit of z + 0, this model reduces
and secondary air streams were assumed to be distinct, per to the semiempiricalexpression for gas entrainment by a jet
fectly mixed, concentric flows, with no inter stream mixing, in a moving fluid derived by Ricou and Spalding ( 1961).
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 74, DECEMBER, 1996 1005
completely combusted with the air entrained by the flame.
A differential material balance for each of the combustion
.....

a
5
! = py,prlVg .............................. (9)
dz
1006 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 74, DECEMBER, 1996
motion behavior, such as slipping or centrifuging, as where Vp  4nrp3/3 is the individual spherical pellet volume.
described by Henein et al. (1983). Equation (17) is rearranged in terms of the differential
Assuming that all of the 0, in the bed is reacted with change in r,:
magnetite between cascades. the total molar flow rate of 0,
entrained by the bed is calculated by integrating the 0, con 2
centration in the bed over the entire free bed volume: drc  1 Pdn, . . . . . . . . . . . . . . . . . . . . . .
d r  a l / h p c [ L c ) dz
Lk
Fo, ,h = C [0 2 1 , &bAbdZ . . . . . . . . . . . . . . . . . . . . . . (12) where a is the pellet surface area per unit bed volume,
0 defined as follows.
where L, is the kiln length, &b is the pellet bed porosity, and
A , is the cross sectional area of the bed, perpendicular to the a= 3(l€b) .............................. (19)
direction of flow. The local concentration of 0, in the bed is ‘P
calculated from an equation of state at the local conditions of
the bed temperature and secondary air partial pressure above The total moles of magnetite oxidized per pellet is
the bed. The justification for the stationarystate approxima
tion in the shrinking core model is also assumed to apply in
the bed; thus allowing the composition of the gas in the free
bed volume to instantaneously match the freeboard gas
composition. Equation (12) was differentiated to give the
local flow rate of 0, per unit length to the bed, required by The change in the unreacted core radius is calculated
Equation (10) to account for magnetite oxidation: from the total moles of magnetite oxidized:
. (13)
rc =[(r:r 21 113
. . . . . . . . . . . . . . . . . . . . . . . . (21)
The heat generation rate per unit length from the mag where rz is the average pellet core radius feeding into the
netite oxidation in Equation (6) is now defined in terms of kiln.
the rate of 0, consumption by the bed and the heat of reac Although Equations (13) and (14) are used in the kiln
tion per mole of 0,, Hrxn: material and energy balances to account for 0, consump
tion, Equation (2 1) is used directly to calculate the effect of
oxidation on the core radius in the kiln. This avoids an iter
dFO, ,b
qox = Hrxn 7 ........................... ative trial and error solution for rc at the pellet discharge end
of the kiln that would be required to match the calculated
initial pellet core radius with the known value for ( at the
The fraction of magnetite oxidized in the kiln bed is cal feed end of the kiln, due to the counter current flow of gas
culated according to the stoichiometry of Equation (1) and and pellets through the kiln.
the rate of consumption of 0,. The total moles of 0, reacted The assumption of complete 0, consumption in the bed
by the magnetite in the bed per solids residence time is: between cascades was evaluated by solving the shrinking
core model for the bed 0, concentration during the time
between cascades, at typical temperature and gas composi
. . . . . (15) tion conditions in the kiln. The differential 0, concentration
balance is proportional to the time gradient in the core radius:
dnM  ( l  ~ ~ ) p ~ 42dr
 zr,
2. v,
................. k=
dz dz Vp .........................
6 ....
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 74, DECEMBER, 1996 1007
TABLE1
Rotary kiln process simulation parameters
pellet feed rate
pellet radius
bed porosity
mb
'P
E~
141 kg/s
0.0062
0.4
m n
magnetite concentration
fuel feed rate
kiln length Lk
% 9 I 00 m0i/m3
100 molh (1 0% stoich. air)
40m
refractory inside radius rk 3m
bed angle of repose 4 0.7 rad
kiln angle of inclination 6' 0.052 rad
bed angle of repose a 0.7 rad
1800
3.75
E 1600 Y t (s)
E 3.70
v
c Figure 4  O2 consumption between cascades.
L"
1400
3.65
1200 gas entrainment flux in Equation (3) was adjusted for rea
sonable model prediction agreement with the measured bed
3.60 1000 and gas temperatures reported by Potts (1991). The gas
entrainment flux was found to be 4mole/m2.s. The result
3.55 .A 800 ing temperature profiles, shown in Figure 3, are in agree
0 5 10 15 20 25 30 35 40 ment with plant data and other models for these operating
(m) conditions (Thurlby, 1988; Thornton and Batterham, 1982;
Figure 3 Temperature and magnetite core radius profiles in the Young et al., 1979).
rotary kiln. The shrinking magnetite core radius profile is plotted
along with the process temperature profiles in Figure 3.
Approximately 3 3% of the oxidation was calculated to
where D, is the difhivity of 0, in the kiln gas at the bed occur in the kiln for the conditions of Table 1. T h s com
conditions, and 6 is the gas film boundary layer thickness pares favorably with the 5% maximum oxidation observed
around a spherical pellet. An estimate of the film thickness in the plants (Potts, 1991). The shnnking core model was
was made from the hydraulic radius for the open, free space used to test the assumption of complete 0, consumption in
between three, adjacent, connecting, spherical pellets in a the pellet bed between cascades. The equations were solved
plane: for the case of an 0, partial pressure of 20 kPa above the
bed, and pellet bed temperatures of 1000, 1200, 1400, and
1600 K. The 0, diffusion coefficient was calculated from
the correlation of Wilke and Lee (Reid et al., 1987). The
effective diffusivity was calculated based on pellet porosity
and pore tortuosity, D,=Do, Ep/t (Shigeno et al., 1990). The
where the angle between the coordinate sphere centers, cp, is average time between cascades of pellets in the rotating kiln
d 3 radians. This estimate of the film thickness is considered was estimated from Equation (23) to be 15 seconds. As
conservative because the expected smaller values of 6 will shown in Figure 4, the shrinking core model predicted that
result in larger mass transfer coefficients that yield higher most of the 0, is consumed in less than half the time
oxidation rates. between cascades.
A novel approach to account for magnetite oxidation in a
Results and discussion rotary kiln was presented. The method gives results for the
fraction of magnetite oxidized that are in reasonable agree
The rotary kiln magnetite oxidation model results in a ment with plant experience. This model should be limited
coupled system of firstorder, ordinary, differential equa to bed motion such as slumping, or cascading, where pel
tions describing the heat and mass transfer between the lets are turned over in the bed. It may be considered as an
flame, secondary air, pellet bed, as well as the magnetite upper limit to the extent of oxidation expected in extreme
oxidation. The model equations were solved numerically by bed motion, such as slipping or centrifuging. Further refme
an improved Euler method with two extrapolations, which ments to this modeling approach to magnetite oxidation in
gives global error estimates and fourth order accuracy a rotary kiln should incorporate theory for the volume frac
(Hanna and Sandall, 1995). These simulation results apply tion of cascading pellets exposed to the freeboard gas and
to a rotary kiln at the USS Minntac taconite pelletizing plant the effects of solids mixing between the outer mantle of
(Potts, 1991). The plant operation parameters used in the pellets and the inner bed core (Thornton and Batterham,
model calibration and simulation are listed in Table 1. The 1982).
1008 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 74, DECEMBER, 1996
Acknowledgements References
The author is grateful to Raymond Potts at U.S. Steel Minnesota Ball, D. F., J. Dartnell, J. Davison, A. Grieve and R. Wild,
Ore Operations, and Ronald Visness with the Minnesota “Agglomeration of Iron Ores,” Heinemann, London ( 1973).
Department of Natural Resources for guidance in choosing plant Barr, P. V., J. K. Brimacombe and A. P.Watkinson, “A Heat
operating parameters. This work was sponsored by the Minnesota Transfer Model for the Rotary Kiln: Part 11. Development of the
Iron Ore Research Cooperative Program. Cross Section Model,” Metall. Trans. B 20B, 403419 (1989).
Gorog, J. P., T. N. Adams and J. K. Brimacombe, “Heat Transfer
Nomenclature from Flames in a Rotary Kiln,” Metall. Trans. B 14B, 41 1 4 2 4
(1983).
a = pellet bed surface area per unit bed volume, m’ Hanna, 0. T. and 0. C. Sandall, “Computational Methods in
A = cross sectional area, m2 Chemical Engineering,” PrenticeHall, Engelwood Cliffs, NJ
c = cascade frequency, sI (1995), pp. 281283.
D = 0, gas diffusivity, m2/s Henein, H., J. K. Brimacombe and A. P. Watkinson, “Experimental
F = gas stream molar flow rate, mole/s Study of Transverse Bed Motion in Rotary Kilns,” Metall.
H = enthalpy, J/mol Trans. B 14B, 191205 (1983)
k = mass transfer coefficient, m / s Jenkins, B. G. and F. D. Moles, “Modeling of Heat Transfer From
L = length, m a Large Enclosed Flame in a Rotary Kiln,” Trans. Inst. Chem.
m = mass flow rate, kg/s Eng. 59, 1725 (1981).
n = moles Kohav, T., J. T. Richardson and D. Luss, “Axial Dispersion of
N = molar flux, mole/m2.s Solid Particles in a Continuous Rotary Kiln,’’ AIChE J. 41,
P = perimeter, m 24652475 (1 995).
= heat transfer rate, Wlm Levenspiel, O., “Chemical Reaction Engineering,” 2nd ed., John
q
r = radius, m Wiley & Sons, New York, (1972), p. 365.
T = temperature, K Monson, B. E., S. E. Olsen and L. Kolbeinsen, “Kinetics of
u = velocity, m / s Magnetite Oxidation,” Scand. J. Metallurgy 23, 7480 (1994).
W = width, m Papanastassiou, D. and G. Bitsanes, “Mechanisms and Kinetics
y = mole fraction Underlying the Oxidation of Magnetite in the Induration of Iron
z = kiln axis coordinate. m Ore Pellets,” Metall. Trans. 4, 487496 (1973).
Pape, P. O., R. D. Frans and G. H. Geiger, “Magnetite Oxidation
Greek letters Kinetics and Thermal Profiles in a Magnetite Pellet Plant
Cooler,” Ironmaking Steelmaking 3, 138145 (1 976).
a = bed angle of repose, rad Potts, R. D., “Induration of Taconite Pellets Using a GrateKiln
= f I , indicates the direction of entrainment flux to or from
System,” in Proc. AIMEAJniversity of Minnesota Mining
p Symposium, Duluth, MN, (1991).
a gas stream
6 = film thickness, m Reid, R. C., J. M. Prausnitz and B. E. Poling, “The Properties of
E = porosity Gases and Liquids, 4th ed.,” McGrawHill, New York (1987).
8 = kiln angle of inclination, rad Ricou, F. P. and D. B. Spalding, “Measurements of Entrainment by
;1 = specific heat capacity, J/(mol or kg).K hisymmetrical Turbulent Jets,” J. Fluid Mech. 11,2132 (1961).
= density, (kg or mol)/m3
Saeman, W. C., “Passage of Solids Through Rotary Kilns,’’ Chem.
p Eng. Prog. 47, 508514 (1951).
r = pellet pore tortuosity
u = reaction stoichiometric coefficient, (mol of species i)l Shigeno, Y., T. Sakakibara and Y. Omori, “In Situ Measurement of
Effective Gas Diffisivity through Hematite Pellets during
(mol 0 2 ) Stepwise Reductions,” Metall. Trans. B 21B, 677686 (1990).
4 = solids fill angle, rad
Silcox, G. D. and D. W. Pershing, “The Effects of Rotary Kiln
= bed angle from kiln centerline, rad
Operating Conditions and Design on Burden Heating Rates as
Subscripts Determined by a Mathematical Model of Rotary Kiln Heat
Transfer,” J. Air Waste Manage. 40, 337344 (1 990).
Thomton, G. J. and R. J. Batterham, “The Transfer of Heat in
b = to or in the pellet bed
Kilns,” in Proc. Chemeaca 82, Tenth Australian Chemical
c = pellet core or convection
Engineering Conference, Inst. of Engineers, Sydney, National
CH, = methane
CO, = carbon dioxide
publication no. 82/9, (1 982) pp. 260266.
Thurlby, J. A,, “A Dynamic Mathematical Model of the Complete
e = effective property
Grate/Kiln IronOre Pellet Induration Process,” Metall. Trans. B
f = to or in the flame stream
19B, 1031 12 (1988).
g = from or in secondary air stream
Tscheng, S. H. and A. P. Watkinson, “Convective Heat Transfer in
H 2 0 = water
a Rotary Kiln,” Can. J. Chem. Eng. 57,433443 (1979).
k = kiln
Young, R. W., M. Cross and R. D. Gibson, “Mathematical Model
M = magnetite
of GrateKilnCooler Process Used for Induration of Iron Ore
ox = magnetite oxidation
Pellets,” Ironmaking Steelmaking 1, 113 (1 979).
0, = oxygen
Zahl, R. K., L. A. Haas and J. Engesser, “Formation of NO, in Iron
p = pellet Oxide Pelletizing Furnaces,” US Bureau of Mines, NRRI, St.
r = radiation
Paul, Minnesota DNR final report, September 29 (1 995).
mn = reaction
Superscripts
’ = initial condition Manuscript received May 21, 1996; revised manuscript received
‘
= per unit length, m1 September 23, 1996; accepted for publication October 2, 1996.
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 74, DECEMBER, 1996 1009