ISIJ International, Vol. 37 (1997), No. 5, pp.

477-483

Hydration Kinetics of Recarbonized Lime

A. H. RODRIGUEZ-HERNANDEZ,1)
MACIEL-CAMACHO. A. W. D. HILLS2) and R. D. MORALES3)
Graduate Center, Instituto Tecn016gico de Morelia, Av, Tecn016gico, Morelia Mich.. Mexico.
1) Instituto Polit6cnico Nacional-ESlalE. Department of Metallurgy. Apdo. Postal 75-874. M6xico D. F.. 07300, Mexico.
Instituto Polit6cnico Nacional-ESlalE, Department of Chemical Engineering. Apdo. Postal 75-874, M6xico D. F., 07300
Mexico. 2) Hills Metaliurgical Consultants. Sheffield, UK. 3) Instituto Polit6cnico Nacional-ESlalE, Department
of Metal]urgy, Apdo. Postal 75-874, M6xico D, F., 07300. Mexico,

(Received on September20. 1996.• accepted in final form on January 14. 1997)

The hydration rate of partially recarbonized lime pellets has been studied by employing a single pellet
into a stream of air/vapor water mixtures using a computer aided thermo-gravimettic technique. The hydration
reaction takes piace on a sharp, well defined interface between the product layer and the unreacted core.
It'has been found that the hydration mechanismconsists in two steps. The first observes very slow
hydration rates and the second higher ones. During the first step the water molecules diffuse through a
close porous carbonate structure and the second one begins when these molecules reach the calcium
oxide-calcium carbonate interface to continue through the lime core. A theoretical model was derived to
explain the results of this study. The experimental results were acceptably well predicted with calculations
performed using this model.
Onthe other hand, it wasfound also that the higher is the lime calcination temperature the thinner is the
recarbonized layer formed even under high C02 partial pressures. However, these thin layers are more
effective to increase the hydration resistance of lime pellets than thicker ones. This is an important experimental
finding since it indicates that low recarbonization extents are good enough to increase the hydration
resistance of steelmaking lime without impairing its quality.

KEYWORDS:
Iiquid steel; hydrogen; Iime; kinetics; recarbonization; hydration rate; diffusion coefficient;
layer thickness.

1. Introduction The formation of a recarbonized thin shell on the

There is a great concern amongsteelmakers about the
hydration of lime since this raw material is one of the
main sources for hydrogen pick up in liquid steel. A
usual approach in calcination plants to makelime a lesser
absorbing media of water is to increase the calcination
temperature up to levels of 1473-1 573K.1,2) In this
regard it has been experimentally proved that high cal-
cination temperatures close the pore structure of lime
difficulting the diffusion of water vapor toward a lime
lump core.3) However, this also produces what is called
the industrial world as a "hard lime" which does not
m
accomplish with the requirernents for lime reactivity
established in the test ASTM
C-1 l0-58. Low reactivity
values of lime meanslow dissolution rates in complex
steelmaking slags which is an important operating
parameter in fast steelmaking processes such as BOF
converter.4)
On line with the above mentioned, there is a great
interest to produce lime that can stand up the absorption
of water particularly during its cooling down after the
calcination process, improving also its hydration resis-
tance during its transportation and storing at the facil-
ities of a steelmaking shop and keeping, at the same
time, high reactivity levels.
surface of a lime lump would be very helpful to increase
its hydration resistance based
on a hypothesis that the
porous structure of calcium carbonate formed in situ has
a closer porous structure than calcium oxide. If this is
possible, thus the calcination temperatures will not be
necessarily high, producing a lime with a high reactivity
core, ready to offer greater resistance to water absorp-
tion.
The objectives of this work are to study the effects of
main parameters such as water vapor partial pressure,
calcination and hydration temperatures and the re-
carbonized layer thickness on the hydration kinetics of
partially recarbonized lime. This study should be useful
also to makean assessment on the feasibility of a calci-
nation process involving a final partial recarbonization
of lime.
2. Experimental Apparatus and Procedure
The experiments were carried out using a computer
aided thermo-gravimetric technique employing a vertical
tube furnace for the reaction of lime pellets under mix-
tures of airIC02 and air/H20. The details of the gas
train and reaction furnace have been already reported in
a precedent paper by the authors.3)

477 @1997 ISIJ

 ISIJ International. Vol. 37 (1997), No. 5
The calcium carbonate were prepared by using
pellets weight of the sample, Wi, and the initial weight, Wo'
gel-flex molds previous]y fabricated
by casting this
material in liquid state in a steel die. "Analar" grade
W
These A measurementswere converted into fractional
reaction, X, using the following relationship;
calcium carbonate powder of about 5-8 pmparticle size
was placed in these molds and the systern was subjected AW
to a pressure of 250 MNw/m2 to conform spheric calcium ~AWt """
carbonate pellets.3)
where AWt denotes the change of weight corresponding
2.1. Experimental Procedure to complete reaction. The expression of AWt for the
recarbonization reaction comesfrom the stoichiometry
The experimental procedure, which wascarried out in
of the chemical reaction:
four main steps, is as follows:
(1) Sintering ofcalcium carbonate Ca0+C02
=CaC03 (2)
..... ..........
(2) Calcination of calcium carbonate
(3) Recarbonization of calcium oxide and is given by:

(4) Hydration experiments AWt= [(44)/(56)] Wo """• (3)

••••••••••
Steps (1), (2) and (4) have been already explained in the
mentioned reference and here only the recarbonization The corresponding expressions for the calcination and
hydration reactions have been already established in Ref.
procedure for calcium oxide pellets will be explained.
3)*
2.2. Recarbonization of Calcium Oxide
3.1. Recarbonization Results
Recarbonization was performed to obtain a layer of
calcium carbonate around the pellet of calcium oxide in Theeffect of temperature on recarbonization rates and
fractional recarbonization is shownin Fig. 2. In all cases,
order to reduce the lime hydration rate. After calcination,
the recarbonization rate is fast during the initial stage,
following the procedure explained in Ref. 3), the sample
but it slows down as the reaction progresses. The re-
was cooled in dry air downto the recarbonization tern- carbonization rate of lime increases as temperature in-
perature. The flow of dry air was then changed to the
desired airIC02 mixture, and the sample weight was creases, reaching its maximum rate at around 773 K. On
further increasing the temperature to 973 K, however,
continuously monitored by the computerised system. The
the recarbonization rate falls. The extent of recarboniza-
composition of the airIC02 mixture wascontrolled using
tion also depends on the recarbonization temperature,
two, previously calibrated, Gallenkamp orifice meters
size No. 3, the flow rate being maintained at I Nl/min. as can be seen in the samefigure; at temperatures less
than 973 K all the curves showa similar pattern and the
Recarbonization was carried out under different con-
ditions of temperature and C02 partial pressure. maximum fractional recarbonization is reached at 773
K
and the minimumat 673 K. The curve obtained from the
2.3. Disclosure of Reaction Interface results of the experiment carried out at
I 123 shows K
the reaction interface was madevisible
The position of the slowest reaction rate and the highest recarbonization
by sectioning and polishing partially reacted samples level. Although the time required to reach the plateau

using SiC papers and cleaning them with alcohol. The part of the curve was around nine minutes in most of
sectioned samples were attacked with phenolphthalein the cases, at the higher temperature of I 123K it
was
which turns pink in the presence of alkali. The pink around 45 min.
calcium oxide core contrasted strongly with the white The effect of C02 partial pressure and calcination
calcium carbonate or calcium hydroxide layers (see Fig.
l).
1

3. Results and Discussion

The weight loss or gain, AW, at any time, t, was z

o
08
determined from the difference of the instantaneous F
~
z
o
Go 06
a:

o
UJ
a:
J 0.4 H~ 773 K
z
O
F ~ g23 K
o ~ 673 K
~
LL 0.2 ~ I 023 K
~ 112e K

o
o 1o 20 30 40 50 60
TIME (min)

Fig. 2. Effect ofthe temperature on recarbonization rate and

Fig. l. Hydration reaction interface in
a recarbonized pellet. rractional recarbonization.

C 1997 ISIJ 478

 ISIJ International, Vol, 37 (1997), No. 5
temperature on recarbonization rates and fractional re- tion. Increasing the calcination temperature allows a very
carbonization are summarised in Figs. and 4 respec- 3 thin and dense product
layer to be produced. The ex-
tively. Even though the experiments carried out at rather perimental results of recarbonization at a partial pres-
similar partial pressures of C02do not follow sure of C02 of 56.65kPa are depicted in Fig. 4. At a
a regular
increase in the recarbonization rate with increases in this lime calcination temperature of 373K the maximum 1
pressure, those performed at quite different pressures extent of reaction achieved was0.06 while in lime calcined
show clearly this trend. This irregular behavior can be initially at 1123 K the reaction extent was O.18.
attributed to the experimental errors involved in these The sample sizeanother important parameter during
is

experiments. However, it can be surely affirmed that the lime recarbonization, the extent of recarbonization will
recarbonization rate follows the following ascending be higher in smaller samples; Figure 5 shows the results
order: 22.3 kPa 101.3 kPa. Both
the reaction rate and the extent of reaction at
of experiments carried out at 773 and 101 kPa partial K
one pressure of C02' Again all cases showa similar behavior;
atmosphere (lOlkPa) partial pressure of C02 Were a fast first stage followed by a plateau.
substantially higher than those at low partial pressures. During the recarbonization process there was an
The lowest fractional recarbonlzation (0.07) was ob- increase in ternperature inside the sample, that fact is
tained at 22.3kPa of C02 partial pressure. Moreover, shown in Fig. 6 where it is observed an initial quick
all
curves show similar behavior at any partial pressure increase followed by a plateau and then decrease. Since
a
of C02reaching the plateau at around the sametime. recarbonization should be an activated process, due to
The initial calcination temperature of the pellet is an its diffusive nature, these high increases in temperature
important parameter during the recarbonization reac-
0.8
0.5
O• Iol,3 kPa
~~405 kPa T=673 K 0.7
> ~50 8 kPa Z
0.4 cs25.3 kPa O 0.6
z F
O
F: ~ 28 4 kPa
~L22 3 kPa
~
:~

N O 0.5
CO
z
O 0.3 a:
oo
:c O
UJ 0.4
C!:

T=773 K
OLU

~
Z 0.3 pco,=101 ,3 kPa
J 0.2 O
z F
O A5,8 mm
O o.a
F
O E [17,3
mm
~o. 1
0.1
09,1 mm

o
o o 5 1o 15 220
O 5 1O 15 220
TIME (min)
TIME (min)
Fig. 5. Effect ofsample size on rate and extent ofrecarboniza-
Fig. 3. Effect ofpco, on recarbonization rate. tion,

o.2 1 ~00
pc02=i02 3 kPa
*,'," ~ 1 1 oo
Z
O +''', ~
H 0.15
N ~? I ooo
Z
O
EO
9: a::)

O
UJ o. 1 H
900
OC
J 0_2uJ

Z
O
F 800
O
~ 0.05
LL

700
pco.=56,65 kPa

o 600o
o 5 Io i5 :20 5 Io i5 20
TIME (min) TIME (min)
Fig. 4. Effect ofthecalcination temperature on rateand extent Fig. 6. Temperature of the sample during recarbonization
of recarbonization .
reaction.

479 C 1997 ISIJ

 ISIJ International, Vol. 37 (1997). No. 5

rate explain the high initial recarbonizing rates shown 1

in Fig. 2. At higher recarbonizing temperatures this
exothermic reaction promotes still higher temperatures PH20=2.8kPa

in the sample, a fact that should surely change the pellet - None
0.8 A0.1 mm
structure difficulting a fast recarbonization. Indeed, this >
o 0.4 mm
is also observed in Fig. 2, at higher temperatures, the zo D 0.5 mm
recarbonization rate is slower, although, the reaction F 0.6 O 0.6 mm
0.8
mm
extent is higher according to the diffusive nature of the o
>
phenomenainvolved. J
The recarbonated layer and the unreacted core showed zo
sharp interface whenviewed macroscopically, see Fig. F
04
a o
1.
The calcium carbonate layer thickness, a, wasobtained a:

using the relationship ~

= ro ~ ri, (see the
list of symbols).
0.2
Here ri = (1 -X)1/3ro; (1 -X) is the unreacted fraction.
On the other hand, we have 413lrr8 = Wolp~, making
explicit ro from this relationship and substituting it in o
the first expression we obtain: o 500 1ooo 1500
TIME (min)

3Wo(1-X) 1/3
(4)
Fig. 7. Effect of the layer thickness on hydration rate.
rl
47cps

0.2
Thepresence of a sharp interface reinforced the argument
for adopting this relationship. a[mm]
O1123 K O,35
3.2. The Hydration Rate ofPartially Recarbonized Lime A1273 K O.5
>
The effects of layer thickness, ~, and calcination tem- z
1373
cl
K0,2

O PH20=2.8 kPa
perature of the initial pellet on hydration rates are pre- H
sented in Figs. 7 and 8 respectively. Figure 7 shows the :c
o
results of six experiments carried out using samples >-
r 0.1
with different layer thicknesses. clear from this figure
It is J
that the hydration rate decreases as calcium carbonate zO
F:
layer thickness increases. There is a steady fractional o
hydration which is followed by a marked change in ~
slope, the hydration rate, however, being lower than
the unrecarbonated sample. The samples with greater
carbonate layer thickness showa very low hydration rate
for about 200 min which is then followed by a steady o
increase. o 500 1ooo i 500 2000
TIME (min)
Onthe other hand, the hydration rate tends to decrease
as the initial calcination temperature of the pellet is Fig. 8. Effect ofthe calcination temperature on hydration rate
for recarbonized samples.
increased a result that coincides with the hydration
behavior of unrecarbonated samples.3) This effect is
of unrecarbonized lime pellets3) assuming that the gas
shownin Fig. 8, where a comparison is madebetween
samples calcined at different temperatures. It is evident
film, shell diffusion and act together as
rate kinetics
resistances connected in series opposing to the diffusion
that the sample calcinated at the higher temperature has
of water vapor which is being driven by the difference
the greater hydration resistance.
between the C02partial pressure in the bulk phase and
Visual examination of these pellets revealed extensive
that in equilibrium on the pellet interface. In the present
cracking. The time to achieve the critical extent of
reaction before the calcium carbonate layer started to case a fourth resistance to the mass transfer of water
vapor is added following the same procedure3) under
crack depends on the layer thickness and calcination
steady state conditions. The final kinetic expression is
temperature.
given as:
3.3. Discussion
3.3.1. Overall Kinetic Model (PA,b-PA,.)
nA= -
As it is seen by the klnetic curves shownin Fig. there 7 1 ~ r r, 1
are very slow initial hydration rates followed by higher + 47~r + 471:r + 47zrfk
4ler2k
o g or * DA,.fl , ri DA,*ff
ones after an incubation period which is longer the thicker .(5)
is the recarbonized layer. To explain these results it is
necessary to develop a kinetic model for the hydration The terms of the denominator of this equation maybe
process of partially recarbonized lime pellets. identified respectively as the gas film, calcium carbonate
layer, calcium hydroxide shell and interface resistances.
Amodel based on the unreacted core shrinking model,
UCSM,was developed to study the hydration kinetics The relative importance of the gas film and interface

C 1997 ISIJ 480

 ISIJ International. Vol. 37 (1997), No. 5
resistances depend on the porosity of the calcium
0.5
carbonate and calcium hydroxide layers, at very low
porosities they can be neglected. Now, considering the
equation of continuity expressed by: 0.4 A
-47rp~ri2(dri/dt) A
nA=-p (dV/dt)= ...............
(6)
A C!

And equatlng this equation with Eq.

followed by a (5)
0.3 []
A
rearrangement of the resultant expression, using the * C!

relative thickness of recarbonized and hydrated layers, o

ll
o
the following overall equation in terms of ,f, defined as
O.2
(1 -ri/r*), is obtained:
Exp. pH20 (kPa)
df '

_ r~( I )2
(pA,b - PA,.)/ R Tr* p*
"(7)
A 13 1,5
dt
-, f +8r.(1 f) +, (f f 2)+ 1 ~ 0.1 * 3 2.4
O o 5 3.6
1'gkg roDA,.fl DA,*rr k Model
Integrating Eq. (7) and using a further rearrangement o -
gives the integrated rate equation for the hydration rate O 500 1OOO 1500
TiME (min)
of recarbonized llme pellets:
Fig. 9.
on hydration rate (comparison between
Effect ofpll,o
r~(~f- ~f2 +,f3) ~r.(3f'- ~f'2 +f3) experiments and theory).
3r~kg + 3,•.DA,*fl
+
/'.(~f'2 ~f'3) ,f' (pA,b -PA,.)
Table 1. Effective diffusivity for CaC03Iayer.
- + .
t (8)
6DA,*rr k RTr,p~ ..........
Exp. No Ca c n. T 5 (mm} Inoculation Porosity Effective diffusivity

(K] Time (min} (.} ofCaC03Iayer

Since, from thermodynamic calculations,5) the partial Im=/s} X 10"

pressure of C02 in equilibrium

with lirne at the lime-
1 1123 o.60 90 0.22 6.70
calcium carbonate is very low then the value of pA,*
2 1123 0.50 90 0.22 4.60
can be neglected in the previous equation. Additionally,
making the approximation that DA,.ff=DA,*fl=D. and 3 1123 0.10 40 0.22 0.42

considering that the gas-film is also negligible compared 4 1123 o 80 190 o 22 5.60
with the resistances to masstransfer offered by the layers 5 1123 o 35 90 0.22 2.30
of calcium carbonate, calcium hydroxide and hydration
s 1123 0.10 40 o 22 o 42
kinetics, this layer being calculated employing the ex-
perimental data already reported (Fig. 7of Ref. 3)), the 7 1123 0.47 90 0.22 4.10

Eq. (8) can be considerably simplified according to: 8 1273 o 47 375 0.00 0.98

9 1373 0.20 325 o oo o 2i

~~~;~ ~_3D[r8 (~f~ ~f2 +,f3) +
3f2-2f3J
~
•t
_
. _o 2
.(9) seen in Figs. 7 and 8.
Thus appears reasonable to conclude that the
it

A plot using the experimental data to calculate the left hydration of the partially
rate recarbonized samples
hand side (LHS) of Eq. (9) against the experimental occurs by the same mechanism of the unrecarbonized
results given by the term in brackets of this equation, ones.3) The only difference is that
an inoculation period
simply defined as e(t), should be a straight line. This is, exists during which water vapor is diffusing through
just the case as is observed in Fig. which shows a plot 9 highly coherent layers of calcium carbonate on the
of the LHSof Eq. (9) against O(t) for the experimental outside of lime.
results shownin Fig. 7. An important feature of this plot From the slopes of the straight lines in Fig. 9 the
is that the extrapolations of these straight lines to zero averaged diffusion coefficients or rather the global
value for O(t) do not coincide with the origin as is the diffusion coefficient. D*, for the steps of steady hydration
case for the hydration of non-recarbonized samples.3) In rates, after the incubation period, shownin Fig. 8, are
fact the interceptions with the LHSaxis correspond to easily derived and presented in Table I Thesecoefficients .

the so called incubation time periods, are four orders of magnitude lower than those deter-
Fromthe above discussion it results evident that the mined for the hydration of unrecarbonized samples3)
water vapor diffuses in a first step through a very low which is a reasonable result if the presence of the re-
porosity layer of calcium carbonate giving as a result a carbonized layer is taken into account.
time period of slow hydration rate called here as an Onthe other hand, giving the very slow hydration rate
incubation period. Once the molecules of water vapor during the incubation period it would be interesting to
are able to reach the calcium oxide~)alcium carbonate know, at least, an estimation of the magnitude of the
interface their diffussion through a more open lime diffusion coefficient of the water vapor in the calcium
structure is facilitated considerably observing, conse- carbonate layer. From the experimental data it is not,
quently, an increase in the hydration rate as is clearly unfortunately, possible to calculate this value. However,

481 C 1997 ISIJ

 ISIJ lnternational, Vol. 37 (1997), No. 5

an indirect way is possible from the theory of diffusion 0_1 5

in solids6)whlch establishes that the time, t*, taken for (a)
a concentration change to penetrate a distance ~, Is
related to the diffusion coefficient, D., through the fol-
i
lowing equation: Q
0_1
~=Jb!~ •••••••
••••••••••(lO)

Thus, employing the values of ~shownin Fig. 7and the

l ~
incubation time calculated by the intercept values on ~>

LHSaxis of Fig. 9 and substituting both values in Eq. o.05

D
;o
(lO) an estimation of the searched diffusion coefficient
~,
of water vapor in the carbonate layer can be carried out. D
These values are also shown in Table I and have an
interesting characteristic: Whenthe thickness of the layer
o ~ - ".~'.

is about 0,1
or O.2
mm, coefficients are of the order
the
o 500 1 OOO 1 500 :2000
of 10 ~ 12 m2s~ 1, whereasthey are an order of magnitude TIME (min)
greater when the layer thickness is about 0.5-0.6mm
0_1 5
regardless of the calcination temperature. Literature
values for the diffusion coefficient of water vapor in pure (b)
PH20=1.2 kPa
calcium carbonate could not be found, but experiments c:~ 1123 K
in zeolites7) have provided values of the order of A 1273 K
1373 K
l0~10m2s~1. Zeolites have an open structure that is o.1 ~ Model
relatively easy for water vapor to diffuse through, so that -
a diffusion coefficient value of l0~12m2s~1 could in- l D
dicate that water is diffusing through the calcium car- CJ

bonate lattice across a less porous and coherent layer. Q

0_05 -
There is some evidence in Table I to support this O

suggestion since the bottom two results, for the low

porosity lime originally calcined at 1273 and 1373K,
showrecarbonized layers of zero porosity, and the lowest
diffusion coefficients.
Thevariation of the estimated diffusion coefficient with
the layer thickness could be explained if the advancing
recarbonization reaction were under compression as the
lime crystallites enlarged as they transformed into the
carbonate. The compressive forces would have two
effects. They would
compress the crystallites together to
form a zero porosity barrier to the diffusing C02 and
they would place layers of the recarbonized layer outside
the reaction front which should be subjected to tension
forces. These layers would then open up, forming low
porosity channels for the water vapor to diffuse rela-
tively easily. As a consequence, the diffusion coefficient,
estimated from the carbonated layer as a whole, would
increase as the total layer thickness increased. This, of
course, is the tendency exhibited by the results in Table
This mechanism, proposed here, could explain the
A
AAA
A
~A
o
o 500 Iooo 1500 2000 a500
Fig. lO. Effect ofrecarbonized film on hydration rate (a) Iayer
thickness (b) calcination temperature,
the structure and allowing the higher diffusion coeffi-
cients, calculated from Fig. 9, to be established.
The hydration rate is lower as increases and its ~
porosity decreases, the layer porosity having a stronger
effect than the layer thickness. This is
a very important
finding because it suggests that the formation of
a very
thin carbonate layer of low porosity would be effective
in inhibiting hydration without impairing the quality of
lime, and would, moreover, minimize losses of CaO.
The experimental results and those obtained using Eq.
(9) together with the experimental values of D*
were
I .
compared. Suchcomparisons are madein Figs. 10(a) and
10(b). The relative product layer thickness curves pre-

enormous difference between the fractional hydration dicted by the model match fairly well with the experi-
rates for a non-recarbonized sample and that recar- mental results until the calcium carbonate layer cracks
bonized forming a very thin carbonate layer of 0.1 due to the swelling of the calcium hydroxide shell.
thickness as can be seen in Fig. 7. The effective diffu-
mm The critical extent of hydration required to carbonate
sion coefficient for the first case is of the order of layer beginning to crack depends on its thickness, and
8 x 10~6m2 s~ I while in the second one it is of the order the time required to reach such extent of hydration also
of l0~12m2s~ 1. depends on its thickness and porosity. After the layer
The same type of mechanismcould explain the ac- has been broken the sample losses its hydration im-
celeration in the hydration rate, once the inoculation permeabilisation. Figure 7 shows that a O.1 layer
period is completed. This acceleration occurs once the thickness required an extent of reaction of O.2 for
mm
water vapor has penetrated the recarbonized layer and cracking. So, for a 18 at 1373K
is starting to react with lime. The compressive forces
mmpellet calcinated exposed
and a recarbonized layer thickness of 0.2 in
mm
created in the zone of this reaction would, again, place an I .2kPa partial pressure of water vapor atmosphere
the outer layers of the sample under tension, opening up will require more than 150 h to reach such level of hy-

@1997 ISIJ 482

 ISIJ lnternational, Vol. 37 (1997), No. 5
dration while a sample without a carbonated layer will carbonizations extents of lime lumps will be required
be completely hydrated in around 24 h. The lime used to obtain high hydration resistances without irnpairing
in steelmaking is calcined in the temperature range of the lime quality.
1 K
273-1 473 and the average of the atmospheric mois-
Acknowledgments
ture is 1.2 kPa.
Whenlime is calcined in a battery of shaft furnaces The authors give the thanks to CoNaCyT,Instituto
Polit~cnico Nacional and Instituto Tecn016gico de
a partial recarbonization can be performed by the
employmentof a circuit for gas fiow handling similar to Morelia for their strong support to carry out this work.
that employed in the original HyL process for direct Thanks are also given to the institutions SNl and
reduction of iron ore.8) During the time that a batch of COFAA for their permanent assistance to the Process
limestone is being calcined in a furnace the exhaust C02 Metallurgy Group at IPN.
produced by the reaction is compressed and sent to Nomenclature
another furnace containing calcinated lime for cooling DA,*ff effective diffusion coefficient of water vapor in
:
and recarbonizing purposes. The process proceeds by the calcium hydroxide layer (m2 s~ 1)
cooling-recarbonizing-calcination cycles in a very similar
DA,*f] : effective diffusion coefficient of water vapor in
fashion to that employed for direct reduction of iron the calcium carbonate layer (m2 s~ 1)
ores in the process mentioned above. As the reaction is D* : effective global diffusion coefficient of water
fast and the thickness of the recarbonised pellet is rather
vapor in the calcium carbonate-calcium hy-
small the reaction times should be short. It is expected
droxide layers (m2 s~ l)
that the present results will be useful as an initial proposal
D. : effective diffusion coefficient of water vapor in
for the design of such lime calcination process to produce
calcium carbonate structure (m2 s~ 1)
a 1lme with better hydration resistance. ,f
: fractional reacted layer thickness (-)

4. Conclusions
k: reaction rate constant (m s~ 1)
kg : masstransfer coefficient in the gas film (m s~ l)
The hydration of partial recarbonized lime
kinetics nA : overall molar flow rate of water vapor to the
pellets as well as the carbonization rates of lime pellets pellet (kmol s~ l)
under streams of air/water vapor and airIC02 gaseous PA,b : Partial pressure of water in the bulk gas (Pa)
mixture respectively were studied using a computer-aided PA,. : Partial pressure of water in equilibrium with
thermogravimetric technique and the following conclu- lime (Pa)
sions have been established: r: radial coordinate (m)
(1) The recarbonization rate oflime is fast during an 1'o : Pellet radius (m)
initial stage, but it slows downas the reaction progresses. :
ri radius of the unreacted core (m)
The recarbonization rate also increases as temperature :
r* unrecarbonized core radius (m)
increases reaching a maximum rate at around 773 K. On R: universal gas constant (kJ mol~I K~l)
further increasing the temperature the carbonization rate t: time (s)
falls. Wo: initial weight of sample (kg)
(2) The higher the partial pressure of C02the higher W: weight of sarnple (kg)
the carbonization rate of lime. X: fraction hydration of lime (-)
(3) The higher temperature the lower
the calcination Greek symbols
the carbonization rate. With high calcination tempera- ~: difference between pellet radius and radius of
tures only a thin layer of calcium carbonate is formed the interface (m)
even at high partial pressures of C02' O: right hand side of Eq. (9)
(4) The masstransfer of water vapor takes place in p~ : molar density of solid (kmol m~3)
two stages; the first is a kind of incubation period where
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The first
stage is
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the porous structure of calcium carbonate. This is of 8) The Making, Shaping and Treating of Steel USSteel, Pitt. Pa..
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enormous practical importance because only small re-

483 C 1997 ISIJ