1316

Ind. Eng. Chem. Res. 1999, 38, 1316-1322

Kinetics of the Reaction of Ca(OH)2 with CO2 at Low Temperature

Shin-Min Shih,* Chun-Sung Ho, Yuen-Sheng Song, and Jyh-Ping Lin
Department of Chemical Engineering, National Taiwan University, Taipei, Taiwan 106, Republic of China

The kinetics of the reaction of Ca(OH)2 with CO2 in humid N2 has been studied at 60-90 C by
using a differential reactor. Ca(OH)2 reacted with CO2 to form CaCO3 only when the relative
humidity exceeded 0.08. The reaction ceased before 1 h, and Ca(OH)2 was incompletely converted.
The reaction rate and final conversion of Ca(OH)2 were significantly affected by relative humidity,
were slightly dependent on temperature, and were zeroth order with respect to gas phase CO2
concentration. The carbonation of Ca(OH)2 was well described by the asymptotic equation which
is obtained by assuming chemical reaction control and considering the surface coverage by
product. The rate-controlling step might be the dissolution of Ca(OH)2 at the water-adsorbed
surface. The reaction behavior of Ca(OH)2 with CO2 was similar to that with SO2. The model
derived for the reaction with CO2 may be applied to that with SO2 with proper modifications.
The results of this study are useful to the design and efficient operation of the processes using
hydrated lime to remove SO2 from the flue gas, in which both SO2 and CO2 are present.
Introduction
Hydrated lime has been vastly used in dry and spraydrying flue gas desulfurization (FGD) processes for
absorbing SO2. Due to the abundance of CO2 (about 12
vol %)1 in the flue gas, the reaction between CO2 and
hydrated lime may affect the SO2 removal efficiencies
of these processes. There are some reports about the
reaction between SO2 and Ca(OH)2 in the presence of
CO2 in humid N2,2-4 however, the role of CO2 in the
said FGD processes has not been studied. Recently Ho5
and Ho et al.6 found that the presence of CO2 enhanced
the reactivity of hydrated lime towards SO2.
Hydrated lime has long been known as a good sorbent
for absorbing atmospheric CO2 to form calcium carbonate.7 Most of the research on the reaction between CO2
and Ca(OH)2 has been done for the case that CO2 reacts
with a slurry of Ca(OH)2 to form small size CaCO3.8,9,10
Few papers on the carbonation of dry Ca(OH)2 have
been reported.11,12
Since the basic data about the reaction between CO2
and Ca(OH)2 under conditions similar to a commonly
used dry or spray-drying FGD process are so scarce,
there is a need to undertake such a study.
In the present work, the kinetics of the reaction of
Ca(OH)2 powder with CO2 in humid N2 at temperatures
of 60-90 C was studied by using a differential reactor,
and the kinetic model was derived.
Experimental Section
The hydrated lime used was reagent grade Ca(OH)2
powder (Hayashi Pure Chemical Industries). Its specific
surface area measured by nitrogen adsorption using
BET method was 10.0 m2/g. The true density measured
by volume displacement using helium was 2.21 g/cm3.
The porosity measured by mercury intrusion was about
49%. The particle size distribution measured by laser
diffraction was in the range <100 m with a volume
mean diameter of 19 m. Observation by scanning
electron microscopy (SEM) showed the Ca(OH)2 par* To whom correspondence should be addressed. E-mail:
smshih@ccms.ntu.edu.tw. Fax: 886-2-23623040.

Figure 1. Scanning electron micrographs of (a) Ca(OH)2 particles

and (b) sample carbonated at 60 C, 70% RH, and 12.6% CO2 for
1 h.

ticles to have rough surfaces and a layer structure

(Figure 1a). The pore size distribution of the Ca(OH)2
was determined by measuring the nitrogen adsorption
and desorption isotherms at 77 K.
The same experimental apparatus previously described6 was used. The core of the experimental apparatus was a differential fixed bed reactor, where CO2
in the sweep gas reacted with hydrated lime sorbent.
About 20-50 mg of hydrated lime powder was dispersed
into quartz wool; the wool was then set into the quartz
sample pan. The sample pan had dimensions of 10 mm
o.d. and 15 mm height and was perforated at the bottom
to facilitate the passage of the sweep gas. The sweep
gas entered the bottom of the reactor, passed through
the 25 mm i.d. and 365 mm length outer tube, and went
downward through the sample pan and the 10 mm i.d.
and 315 mm length inner tube.
The sweep gas was comprised of CO2, H2O, and N2.
The CO2 and N2 gases were supplied from cylinders. The
concentration of each component in the simulated flue
gas was controlled by adjusting their flowrate. The
relative humidity of the sweep gas was controlled by

10.1021/ie980508z CCC: $18.00 1999 American Chemical Society

Published on Web 03/11/1999

Ind. Eng. Chem. Res., Vol. 38, No. 4, 1999 1317

using a microtube pump to pump deionized water into

an evaporator. The evaporator was heated by a furnace
kept at 200-300 C. The N2 gas from cylinder passed
through the evaporator and was humidified. The reactor
was heated by a furnace which was controlled by a
temperature controller. The temperature of the solid
reactant was measured by a K-type thermocouple
located just below the sample pan.
Prior to each run, the sample bed was humidified for
20 min by humid N2 with a certain relative humidity
at which the experiment was to be performed, which
had been proved to be long enough for the sample to
equilibrate with the gas stream. After humidification,
the reactive gas was admitted into the sweep gas to start
the run. The total flow rate of sweep gas was 4 L/min
(STP).
The amount of water adsorbed on the sample was
obtained from the difference between the weights of the
sample equilibrated with the humid gas and the dry
sample. The conversion of hydrated lime due to the
reaction with CO2 was determined by weight measurement through the following equation:

X)

W/(M2 - M1)
Ws/M1

Figure 2. N2 adsorption and desorption isotherms for Ca(OH)2.

(1)

Here, X is the conversion of Ca(OH)2, W is the weight

increase due to reaction, M1 is the molecular weight of
Ca(OH)2, M2 is the molecular weight of CaCO3, and Ws
is the initial dry sample weight. Sample weights were
measured by a Sartorius electronic balance with an
accuracy of 0.02 mg. The sample together with the
sample pan was transferred as quickly as possible to a
tared weighing bottle equipped with a sealing lid to
minimize the change of the amount of water adsorbed
on the sample due to the change of environment. The
amount of adsorbed water after reaction was found to
be the same as that before reaction. The conversions
determined by weight measurement were checked by
acid/base and Ca2+ EDTA titrations.6 The absolute error
of conversion data was about 0.02.
The differential condition of the reactor with respect
to interparticle CO2 levels at the selected total gas
flowrate and sample weight was confirmed by the
results of experiments using different sample weights.13,14
Varying sample weight from 20 to 100 mg, while
keeping other reaction conditions constant, showed no
effect on the reaction results.
Results
Structure. The nitrogen adsorption and desorption
isotherms for the Ca(OH)2 is shown in Figure 2. The
Ca(OH)2 exhibits a type IV isotherm based upon the
classification of International Union of Pure and Applied
Chemistry (IUPAC).15 The type IV isotherm is characteristic of materials with porosity in the mesopore range
and that typically exhibits a hysteresis loop. The
hysteresis loop for the Ca(OH)2 is of a shape corresponding to a type H3 hysteresis (IUPAC). Type H3
hysteresis is associated with slit-shaped pores or the
space between plate-like particles. Observation by SEM
confirmed this pore and particle shape (Figure 1a).
The pore size distribution of Ca(OH)2 was predicted
by applying the parallel-plate model developed by
Innes16 to the desorption data. As can be seen from

Figure 3. Pore size distribution for Ca(OH)2.

Figure 3, most pores are wider than 30 with the peak

pore volume at pore width of about 300 . The volume
of micropores (pore width less than 20 ) is negligible.
SEM observation of the reacted samples showed that
the basic shape of the particles is only slightly affected
by the carbonation, but the surfaces of the particles
become rougher and the edges smoother for sample with
higher conversion. The rhombohedral crystals of CaCO3
were present in the sample reacted at 70% RH and 60
C for 1 h (X ) 0.28) (Figure 1b) but were not observed
in the sample reacted at 30% RH for 1 h (X ) 0.09).
This result indicates that the form of the CaCO3
crystallites and the structure of the CaCO3 layer were
markedly affected by the reaction conditions.
Effects of Particle Size and BET Surface Area.
Since the Ca(OH)2 contained particles of various sizes,
the possible effect of particle size was studied. Two size
fractions, 70-100 m (dp ) 89 m) and <45 m (dp ) 9
m), were prepared by sieving the Ca(OH)2 powder. The
conversions of the unsieved Ca(OH)2 and the two sieved
fractions at three reaction times are compared in Table
1. As indicated from this table, the <45 m fraction was
the least reacted, whereas the 70-100 m fraction the
most reacted. However, comparing the BET surface
areas of the three materials, the conversion levels are
seen to be in accordance with the magnitude of the BET
surface area. The 70-100 m fraction possessed the

1318 Ind. Eng. Chem. Res., Vol. 38, No. 4, 1999

Table 1. Effects of Particle Size and BET Surface Area on the Carbonation of Ca(OH)2 (Reaction Conditions: 60 C, 70%
RH, 12.6% CO2)
X/Sg (10-3 g/m2)

X
material
unsieved (dp ) 19 m)
70-100 m (dp ) 89 m)
<45 m (dp ) 9 m)
slurried

Sg

(m2/g)

1 min

6 min

20 min

1 min

6 min

20 min

10.0
12.7
9.6
21.8

0.051
0.085
0.046
0.103

0.213
0.297
0.194
0.430

0.277
0.331
0.271
0.533

5.1
6.7
4.8
4.7

21.3
23.4
20.2
19.7

27.7
26.1
28.2
24.4

largest BET surface area, and the <45 m fraction had

the least surface area. Furthermore, the conversions per
unit surface area at the same reaction time for the three
materials are about the same, their differences being
within the range of experimental error. The effect of
particle size is consequently a result of the different
reaction surface areas of particles and does not result
from the intraparticle mass transfer resistance, which
is a function of particle size. This fact indicates that the
particles of the Ca(OH)2 used in this study are small
enough for the reaction to be free from the intraparticle
mass transfer effect.
The linear relation between conversion and BET
surface area was further checked by using a Ca(OH)2
of 21.8 m2/g surface area. This Ca(OH)2 was prepared
by slurrying the Ca(OH)2 powder and quartz sand with
water and then subjecting the slurry to vacuum drying.
As can be seen from Table 1, the conversion of this
slurried Ca(OH)2 at each reaction time is about twice
of that of the unsieved Ca(OH)2, which has a surface
area of 10.0 m2/g, indicating that the linear relation
between conversion and BET surface area holds at least
up to a surface area of 21.8 m2/g. This kind of effect of
BET surface area on the reaction is attributed to the
layer structure of the Ca(OH)2.
Effects of Relative Humidity and Temperature.
The reaction of Ca(OH)2 with CO2 had been studied at
temperatures of 60, 70, and 90 C and relative humidities (RH) of zero to 70%. Some experimental results are
shown in Figure 4 in terms of conversion X vs time t.
As can be seen from these plots, the conversion of Ca(OH)2 is incomplete for a reaction time as long as 1 h,
and the time to reach the final conversion, i.e., the
maximum conversion for the run, is about 10-20 min
from the beginning of reaction for all of the runs.
Figure 5 illustrates the effect of relative humidity and
temperature on the final conversion of Ca(OH)2. It can
be seen that there is a critical relative humidity at about
8%, below which the carbonation of Ca(OH)2 does not
proceed and above which the final conversion of Ca(OH)2
increases with relative humidity and temperature,
reaching a value of 34.8% at 90 C and 70% RH.
From Figures 4 and 5, one can see that the reaction
rate and final conversion of Ca(OH)2 increase with
increasing temperature and relative humidity. However,
temperature affects this reaction mildly, and relative
humidity affects this reaction significantly.
Effect of Gas Phase CO2 Concentration. The
effect of gas phase CO2 concentration on the carbonation
of Ca(OH)2 can also be seen from Figure 4. The conversions of Ca(OH)2 are of no difference for 3.15, 6.30, and
12.60% CO2. Thus this reaction is zeroth order with
respect to CO2 in the concentration range of this study.

Figure 4. Plot of conversion versus time for the carbonation of

Ca(OH)2: (a) 60 C; (b) 70 C; (c) 90 C.

Kinetic Analysis
Kinetic Model. If one assumes that the carbonation
of hydrated lime is controlled by surface reaction and

that the surface reaction only takes place on the reactive

surface which is not covered by product, then the
reaction rate of solid per unit total surface area, rs, can

Ind. Eng. Chem. Res., Vol. 38, No. 4, 1999 1319

Figure 5. Final conversion for the carbonation of Ca(OH)2. The

curves represent the results calculated by using eqs 8a and 16.

Figure 6. Arrhenius plot for k1.

From eqs 3, 5, and 8, the rate of conversion can be

expressed as a function of conversion:

be expressed as

rs ) ks

(2)

where ks is a function of temperature, concentrations

of reacting species, and relative humidity; is the
fraction of surface area which is not covered by product.
For a solid reactant composed of platelike pores or
grains or if the conversion of the solid is low, the rate
of conversion of the solid is

dX/dt ) SgMrs ) SgMks

(3)

where Sg is the initial specific surface area of the solid

and M is its molecular weight.
How changes with reaction time depends on the
reaction rate and the way by which the product deposits
on the surface; thus, one may assume that

-d/dt ) kprsn-1 ) kpksn

(4)

where n-1 is a function representing the way of product

deposition and kp is a proportional constant, which is a
function of temperature, concentrations of reacting
species, and relative humidity.
Equation 4 can be integrated to get as a function of
time:

) exp(-k1k2t) for n ) 1

(5a)

) [1 - (1 - n)k1k2t]1/(1-n) for n * 1

(5b)

k1 ) ksSgM

(6)

k2 ) kp/(SgM)

(7)

where

By substitution of eq 5 into eq 3, one can integrate

eq 3 to obtain the relation between conversion and time:

X ) [1 - exp(-k1k2t)]/k2 for n ) 1

(8a)

X ) [ln(1 + k1k2t)]/k2 for n ) 2

(8b)

X ) {1 - [1 - (1 - n)k1k2t](2-n)/(1-n)}/[(2 - n)k2]
for n * 1, 2 (8c)

dX/dt ) k1(1 - k2X) for n ) 1

(9a)

dX/dt ) k1 exp(-k2X) for n ) 2

(9b)

dX/dt ) k1[1 - (2 - n)k2X][1/(2-n)] for n * 1, 2 (9c)

Equations similar to parts a and b of eq 8, named as
asymptotic and direct logarithmic equations, respectively, have been used to describe the film growth for
the oxidation of metals at low temperature.17,18 Krammer et al.19 have used an equation similar to eq 9b to
simulate the reaction of hydrated lime with SO2 at low
temperature.
As can be seen from Figure 4, our experimental data
are well correlated by both parts a and b of eq 8. Fitting
parts a and b of eq 8 to all the experimental data gave
average standard deviations in conversion of 0.015 and
0.013, respectively. We also fitted eq 8c to the data; the
best value of n obtained is 1.7 with an average standard
deviation of 0.012. These values of standard deviation
are within the range of experimental error; thus, it is
difficult to determine which rate expression is the most
appropriate for the carbonation of hydrated lime. Since
eq 8a is the simplest to use and it predicts the final
conversion directly by the reciprocal of k2, the following
kinetic parameter analysis is based on eq 8a.
Kinetic Parameter Analysis. According to the
definitions of k1 and k2, they are functions of solid
specific surface area, temperature, concentration of CO2,
and relative humidity. These functions can be derived
by analyzing the data of k1 and k2 which were obtained
by fitting eq 8a to each set of experimental data.
Since the gas phase CO2 concentration has no effect
on the reaction in the concentration range of this study,
k1 and k2 are independent of gas phase CO2 concentration.
Values of k1 and k2 are plotted according to the
Arrhenius relationship:

ki ) Ai exp(-Ei/RT) i ) 1, 2

(10)

in Figures 6 and 7. The values corresponding to the

same relative humidity can be represented by a straight
line. These plots show that k1 increases with increasing
temperature and relative humidity and that k2 decreases with increasing relative humidity and is almost
independent of temperature. Values of E1 and E2 were

1320 Ind. Eng. Chem. Res., Vol. 38, No. 4, 1999

Figure 9. Plot of ln A2 vs 1/RH.

Figure 7. Arrhenius plot for k2.

Figure 8. Plot of ln A1 vs ln(-ln RH).

obtained from the slopes of the straight lines fitted to

the data in Figure 6 and 7, respectively. The slopes of
the straight lines appear to vary with relative humidity.
However, the differences between the slopes are within
the range of variation estimated from the error of the
data. Thus E1 and E2 were considered to be independent
of relative humidity. The average values of E1 and E2
obtained are +17.4 and -2.9 kJ/mol, respectively. The
value of E1 indicates that the effect of temperature on
the reaction rate is weak. The value of E2 implies that
k2 and the final conversion of hydrated lime, which is
the reciprocal of k2, are nearly independent of temperature. The insensitivity of final conversions to temperature is in agreement with the experimental observations as shown in Figure 5.
By using the values of E1 and E2, values of A1 and A2
in eq 10 were calculated. Values of A1 and A2 thus
obtained for samples of the same specific surface area
are functions of relative humidity only. The equations
which best correlate them with relative humidity were
searched. The results are shown in Figures 8 and 9. In
Figure 8, values of A1 are plotted logarithmically against
-ln RH. The least-squares straight line fitted to the
data gives

A1 ) 11.1(-ln RH)-0.96

(11)

Values of A2 are plotted in terms of ln A2 vs 1/RH in

Figure 9. The linear least-squares fitting of the data

Figure 10. Comparison of the calculated and the experimental

conversion values.

gives

A2 ) 0.531 exp(0.603/RH)

(12)

According to eqs 6, 7, and 10, A1 and A2 contain the

specific surface area of the sample. The values of the
constants in eqs 11 and 12 are for hydrated lime of 10.0
m2/g specific surface area. Equations for A1 and A2 thus
can be rewritten as

A1 ) 1.11Sg(-ln RH)-0.96

(13)

A2 ) 5.31Sg-1 exp(0.603/RH)

(14)

Substituting E1, E2, eq 13, and eq 14 into eq 10 yields

k1 ) 1.11Sg(-ln RH)-0.96 exp(-17400/RT) (min-1)

(15)
k2 ) 5.31Sg-1 exp(0.603/RH) exp(2900/RT)

(16)

Equation 8a together with eqs 15 and 16 constitutes

the kinetic model for the carbonation of hydrated lime.
Conversions calculated by the kinetic model are compared with the experimental results in Figure 10, which
shows that the calculated results are in good agreement

Ind. Eng. Chem. Res., Vol. 38, No. 4, 1999 1321

with the experimental data with an error in the range

of (0.04 in conversion. The curve corresponding to the
equation of k2-1 is plotted in Figure 5. One can observe
that the curve satisfactorily simulates the experimental
final conversions and predicts the critical relative
humidity to be about 0.08.
Discussion
For gas adsorption on a porous solid, the thickness of
the adsorbed layer of the gas on the pore surface has
been expressed as being proportional to [-ln(P/P0)]-1/n
(Wheelers form), and the pore size below which the
capillary condensation of the gas takes place is proportional to [-ln(P/P0)]-1 (Kelvin equation), where P is the
partial pressure of the gas and P0 is its vapor pressure
at the system temperature.20 For the present case, P/P0
is the relative humidity. At the lowest temperature (60
C) and the highest relative humidity (70%) of this
study, the largest pore width for the condensation of
water vapor to take place was estimated to be about 30
by the Kelvin equation. Since the volume of pores
smaller than 30 for the Ca(OH)2 used in this study is
very small (Figure 3), the capillary condensation of
water vapor may not be important to the reaction. Thus
eq 13 may indicate that k1 is a function of the amount
of adsorbed water per unit surface area or the thickness
of water layer.
The thickness of water layer on the sample used in
the present work has been reported by Ho and Shih.14
The thickness is about 1.50 monolayer thick at 30% RH,
and increases to about 2.33 at 70% RH, nearly independent of temperature in the range 60-90 C.
The form of eq 12 which represents the decrease of
k2 with increasing relative humidity has been used by
Irabien et al.4 for the surface heterogeneity parameter
in their model for the low temperature reaction of Ca(OH)2 with SO2. The effect of relative humidity on k2
may indicate that at low humidity the reaction product
covers the Ca(OH)2 surface more uniformly, whereas at
higher humidity the product builds up more clusterlike
and covers less surface. Thus the reaction of hydrated
lime will reach a higher final conversion at higher
relative humidity. A similar argument has been set forth
by Krammer et al.19 to explain the effect of relative
humidity on the reaction rate of Ca(OH)2 with SO2.
The carbonation of hydrated lime requires the presence of adsorbed water. The following reactions may
take place at the water-adsorbed surface:

Ca(OH)2 f Ca2+ + 2OH-

(17)

CO2 + H2O f CO2H2O

(18)

CO2H2O + 2OH- f CO32- + 2H2O

(19)

Ca2+ + CO32- f CaCO3

(20)

The above reactions are very fast in bulk aqueous

solution,21,22 but for an adsorbed water film less than
three molecular layers thick, their rates may be reduced.
The migration or diffusion rates of the reacting species
through such thin layer would be very fast; the rate
estimated by using the typical value of ion diffusivity
in solution,23 10-9 m2/s, is greater than the actual
carbonation rate by several orders of magnitude.

Equation 18 represents the adsorption and subsequent hydration of CO2. These two processes can occur
at the surface of the water layer which covers both Ca(OH)2 and CaCO3; therefore, they will not be greatly
affected by the extent of carbonation. If eq 19 is the
slowest step, the reaction will also take place at a water
layer covering both Ca(OH)2 and CaCO3. The observed
carbonation rate, however, is independent of gas phase
CO2 concentration and decreases markedly with conversion. It is therefore concluded that the adsorption and
the hydration of CO2 and the formation of CO32- should
be fast, and the dissolution of Ca(OH)2 (eq 17) may be
the slowest step, except at the very beginning of the
reaction, since the sample was humidified prior to
reaction with CO2 and the Ca2+ and OH- ions should
be already present at that time.
The dissolution of Ca(OH)2 occurs only at the watercovered surface of Ca(OH)2 which is not occupied by
CaCO3 particles, and its rate increases with increasing
water amount. The formation of CO32- (eq 19) and
CaCO3 (eq 20) thus also occurs at the surface of the Ca(OH)2. The product CaCO3 molecules, nuclei, or particles
may deposit directly on the surface of Ca(OH)2 (thin
water layer) or may also deposit on the formerly formed
product particles (thick water layer), depending on the
thickness of the water layer. The thicker water layer
provides the wider range for the species to move, and
less product particles deposit directly on the surface of
Ca(OH)2, as compared to the case of thinner water layer
at the same conversion level of Ca(OH)2. Thus at higher
humidity the uncovered surface area of Ca(OH)2 decreases slower with conversion, and the overall reaction
rate diminishes at higher conversion.
As the carbonation proceeds, the product particles
occupy more of the surface of Ca(OH)2 and also build
up a thicker product layer, which increases the resistance of the diffusion of the reacting species through
the pores within the product layer. Thus the diffusion
of reacting species may become important at the final
stage of carbonation. The carbonation of Ca(OH)2 was
observed to stop before 1 h. However, carbonation may
continue by product layer diffusion, the rate of which
is too slow to be detected in the range of carbonation
time used in this study.
The present model is valid for a Ca(OH)2 of initial
BET surface area up to 21.8 m2/g. For larger surface
area, the use of the initial BET surface area in the model
may not be valid, if a significant fraction of the surface
area is contributed by small pores (e.g., micropores);
since the small pores would be blocked rapidly by the
product and the surfaces there would be no longer
available for the reaction to take place. In such case,
however, an effective specific surface area may be used
for the model.
The reaction behavior of hydrated lime with SO2,
which has been studied by Ho and Shih14 under the
same temperature and relative humidity ranges of this
study, is similar to that with CO2 except that the
reaction with SO2 was affected by SO2 concentration.
Thus the mechanism and kinetic model proposed here
for the reaction with CO2 may be applied to the reaction
with SO2 with modifications to take into account the
effect of SO2 concentration. Since flue gas contains both
SO2 and CO2, accurate models for the reactions of SO2
and CO2 with hydrated lime are important to the design
and efficient operation of the dry or semidry flue gas
desulfurization processes using hydrated lime.

1322 Ind. Eng. Chem. Res., Vol. 38, No. 4, 1999

Conclusion

Greek Symbol

The kinetics of the reaction of Ca(OH)2 with CO2 in

humid N2 has been studied at 60 to 90 C by using a
differential packed-bed reactor.
The carbonation rate diminishes rapidly before 1 h,
and the conversion of Ca(OH)2 is incomplete. The
relative humidity is a deterministic factor affecting the
reaction of Ca(OH)2 with CO2. The reaction occurs only
when the relative humidity is higher than a critical
value of 8%, and the reaction rate and final conversion
of Ca(OH)2 increase with increasing relative humidity.
The reaction is slightly dependent on the reaction
temperature and is zeroth order with respect to gas
phase CO2 concentration.
The experimental results have been modeled by
assuming the carbonation rate being controlled by
chemical reaction on Ca(OH)2 surface and taking into
account the surface coverage by product. Model equations have been derived, and the asymptotic equation
correlates the experimental data well. The analysis of
the model parameters indicates that the rate-controlling
step may be the dissolution of Ca(OH)2 at the wateradsorbed surface.
The reaction behavior of Ca(OH)2 with CO2 is similar
to that with SO2. The mechanism and kinetic model for
the reaction with CO2 may be applied to that with SO2
with proper modifications. The results of this study are
useful to the design and efficient operation of the dry
or semidry processes using hydrated lime to remove
SO2 from the flue gas, in which both SO2 and CO2 are
present.

) fraction of surface area which is not covered by product

Acknowledgment
This research was supported by the National Science
Council of Taiwan, Republic of China, under Grant NSC
77-0410-E002-37.
Nomenclature
A1, A2 ) Arrhenius preexponential factor for k1, min-1, and
k2
d ) pore width,
dp ) particle diameter, m
E1, E2 ) activation energy for k1 and k2, J/mol
kp ) constant defined by eq 4, m2/mol
ks ) initial reaction rate of solid, mol/(min m2)
k1 ) ksSgM, min-1
k2 ) kp/(SgM)
M ) molecular weight of solid, g/mol
M1 ) molecular weight of Ca(OH)2, 74 g/mol
M2 ) molecular weight of CaCO3, 100 g/mol
n ) constant defined by eq 4
R ) gas constant, 8.314 J/mol K
RH ) relative humidity
rs ) reaction rate of solid per unit total surface area, mol/
(min m2)
Sg ) initial specific surface area of solid, m2/g
T ) reaction temperature, K
t ) time, min
V ) pore volume, cm3/g
Va ) volume of gaseous nitrogen adsorbed, cm3(STP)/g
W, Ws ) sample weight, initial dry sample weight, g
X, Xf ) conversion, final conversion

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Received for review August 4, 1998

Revised manuscript received January 6, 1999
Accepted January 11, 1999
IE980508Z