Reactivity Laboratory Industrial Limes
Reactivity Laboratory Industrial Limes
Reactivity Laboratory Industrial Limes
Abstract: Quicklimes produced in an industrial kiln have a very low hydration activity compared
to those produced in the laboratory. In this study, we seek to explain these differences in reactiv-
ities by providing quantitative data on the kinetics of the two mechanisms involved in the
production of quicklime: the calcination of limestone to produce quicklime, and the undesirable
sintering of quicklime. The first mechanism increases the specific surface area of the product
from a few m2 g21 to more than 80 m2 g21, making the quicklime highly reactive: the time to
react with water is less than 10 s. The second mechanism reduces the specific surface area
down to a few m2 g21—which is typical for an industrial quicklime—and severely reduces its
reactivity: the time to react with water is around 15 min. The impact of the local temperature
and of the local partial pressure of CO2 is quantified for both mechanisms, by experimenting
the two extreme cases of pure N2 atmosphere and pure CO2 atmosphere using specially
designed laboratory apparatus. Some correlation between the quicklime reactivity and the
specific surface area is found. The work demonstrates that industrial furnace calcining large
limestone pellets, leads to low reactivity quicklimes both because the calcination temperature
is too high and the CO2 pressure is too elevated.
Keywords: lime; reactivity; sintering; calcination; CO2.
Characterization of Quicklime
The calcination degree of all the quicklimes produced was
determined by measuring the residual loss on ignition. A
mass mi was deposited into a quartz crucible as a thin
layer (less than 2 mm), and introduced in a muffle furnace
at 9758C for 30 min. The final mass mf was then measured.
The calcination progress, t, was expressed by
mi $ mf
Figure 1. Crossed fixed bed. (1) Quartz tube; (2) electrical heater; (3) t¼ (1)
0:44 mi
particles bed; (4) filtering sheet; (5) exhaust gases; (6) lime particles;
(7) ruby balls; (8) water column manometer; M—mass flow meter/
controller; N2—nitrogen; CO2—carbon dioxide. where the term 0.44 mi is the theoretical maximal mass loss
by CO2 release after complete calcination of initial limestone
(0.44 is the ratio of molar mass of CO2 and of CaCO3).
The specific surface area and the density of the quicklimes
of the reactor. The calcination reactions are stopped rapidly produced were measured by N2 adsorption (BET) and He
as the sample is quenched by connecting the exit of the pycnometry respectively.
internal tube to a pump and sucking fresh air through the The hydration reaction of quicklime is an exothermic
sample. reaction and can be expressed by
Table 1. Experiments realised in crossed fixed-bed reactor; calcina- Quicklime reactivity is typically measured using the water
tion temperature, duration of experiment, gas used as atmosphere extinction test following the European standard procedure
in reactor, and calcination conversion after reaction.
(NF EN 549-2, 2002); a mass of 150 g of lime is introduced
Calcination Calcination Specific into 600 g of water in an adiabatic receiver (Dewar), shaken
temperature Duration conversion surface by a magnetic stirrer. A thermometer placed in the suspen-
Atmosphere (8C) (s) (%) (m2 g21 lime) sion measures the temperature of water, which increases
N2 600 3600 10.11 due to the heat released during hydration of CaO and then
N2 600 5400 24.28 79.28 stabilizes to a final value. Different characteristics can be
N2 700 1860 50.09 derived from this test:
N2 700 1920 53.81
N2 700 2520 73.04 46.66 . a static property: the maximal temperature reached after
N2 750 1860 95.06 32.81 complete quicklime hydration;
CO2 90 2700 36.1 15.64 . a dynamic property: the time to reach this maximal temp-
CO2 910 1920 59.7 10.08
CO2 920 1200 71.8 11.26 erature, which characterizes the activity of the quicklime
(Maciel-Camacho et al., 1997; French norm, 2002).
Table 2. Specific surface area, density and chemical analysis of limestone.
Limestone 315 –400 mm 1.6 2.69 45.36 0.63 1.0 11.81 0.0 0.0 0.0
The quicklime produced in the laboratory experiments was and calcining limestone at 7508C for 2 h 50 min. The surface
available in quantities of a few grams only, and a specific area of this quicklime was 15.18 m2 g21
CaO.
device had to be developed. Shi et al. (2002) determined Sintering experiments were carried out under N2 and under
the hydration activity by conductive microcalorimetry. This CO2 atmospheres, between 1100 and 13008C. A mass of 4 g
device allows the heat flux released during hydration to be of quicklime was put inside a 6 cm diameter cylinder with a
measured, but the values obtained are far from results bed height of less than 5 mm; this crucible was then placed
found in standard devices. We used a 10 ml flask in which in the furnace. The sample was heated at 108C min21 until
1.5 g of quicklime was introduced together with a magnetic the selected sintering temperature was reached. Then, the
bar (see Figure 2). Three thermocouples, which crossed temperature was maintained constant for 2 h. Finally, the
the cap of the flask, were placed in the flask. The flask was sample was cooled at 108C min21.
then put on a 15 mm thick insulating material and laid in a
drum (Figure 2) in order to protect the flask from eventual
forced convection with air in the room. RESULTS AND DISCUSSION
Water was then rapidly fed into the flask and the tempera-
Calcination Kinetics
ture variation of the mixture was recorded.
Because of the small size of the experiment, heat losses The kinetics of limestone calcination under N2 and CO2
from the water and quicklime mixture into the environment atmosphere was studied using data from experiments carried
cannot be neglected; even insulating the flask did not prevent out in the crossed fixed bed reactor. It is clear from these results
heat losses. A thermal model was therefore developed to that calcining limestone under CO2 atmosphere requires a
take account of heat losses. Preliminary experiments were much higher temperature (900 –9208C) than under the N2
carried out (without quicklime) in which we measured the atmosphere (600 –7008C).
temperature decrease of hot water placed in the flask. It A plot using the Arrhenius representation should help in
was found that the expression of the heat losses following interpreting these values. Given the small size of the particles
equation: and the high degree of control of the nature of the atmos-
phere around each grain, a simple first order kinetic model
F ¼ 4:72 % S % (T sample $ T amb )0:25 (2) can be adopted, and will be validated further. The reaction
kinetics can be expressed by
provides a very good description. By applying this model, the
temperature curve versus time is identical in this test to that dmCaCO3
¼ $kmCaCO3 (3)
measured for an industrial lime with the standard test. This dt
technique enabled extinction durations as short as 10 s to
be measured using a sample mass of 1.5 g only. which is equivalent to
d(1 $ t)
¼ k(1 $ t) (4)
dt
Sintering Set-Up and Procedure
with
The sintering mechanism was studied in a specific AUBRY
furnace which allows samples to be heated up to 16008C. A mCaCO3 ¼ mf $ 0:56 mi (5)
quicklime with a high surface area was first prepared. This
quicklime was then used to study sintering reaction. The we obtain
high reactivity quicklime was prepared using a muffle furnace
ln (1 $ t)
k¼$ (6)
tr
where tr is the residence time (s), and k is the kinetic rate (s21)
of the calcination reaction. The kinetic rate under N2 and CO2
atmosphere are plotted simultaneously in Figure 3. For a
given atmosphere, the experimental results follow a straight
line in the Arrhenius representation, which indicates that the
adopted kinetic model correctly describes the reaction.
The calcination kinetic rate under CO2 atmosphere is much
smaller than that found under N2 atmosphere. At a given
temperature, i.e., on a vertical line, several decades separate
the two kinetic rates. The activation energies—determined
from the slopes of the curves—are 180 and 1077 kJ mol21
Figure 2. Lime activity measurement device. for calcination under N2 and under CO2 atmospheres
Figure 3. Calcination kinetics and specific surface area during lime-
stone calcination under N2 and CO2 atmosphere. Surface: specific
surface area of samples (m2 g21CaO). Figure 4. Specific surface after sintering at different temperature
under N2 and under CO2 atmosphere (initial lime for all sintering
experiments: surface area of 15.18 m2 g21).
respectively. The slope of the curve is clearly higher for the
experiments under CO2 than for the experiments under N2
atmospheres. If one extrapolates the two curves to higher specific surfaces still decrease when temperature is increased
temperatures, they cross at a temperature close to 9608C to 13008C. At this temperature, the surface area falls to
(1/T ¼ 8.1.1024 K21). This means that at this temperature, 0.68 m2 g21 under N2, and at 0.6 m2 g21 under CO2.
a CO2 atmosphere should not slow down the reaction kinetics
any more. This result is in agreement with literature (Tashimo
et al., 1999; Zhong and Bjerle, 1993). Quicklime Reactivity
We have also plotted in Figure 3 the specific surface area
of the quicklimes obtained versus the calcination tempera- In this section, the reactivity of quicklime is determined
ture. Since the calcination of limestone is not complete, we from the water hydration test, and interpretations are pro-
have expressed the specific surfaces in m2 g21 of CaO and posed on the basis of previous observations. The hydration
not in m2 g21 of total mass (CaO þ CaCO3). Figure 3 of quicklime was first realized for all quicklimes obtained
shows that very high specific surfaces can be developed if after simple calcination. The temperature increase of the
calcination is achieved at a low temperature: the quicklime quicklime þ water mixtures during the hydration tests were
obtained at 6008C has a specific surface area as high as recorded versus time. They were converted into degrees Cel-
80 m2 g21. When the calcination temperature is increased, sius per gram of CaO and not per gram of CaO þ CaCO3.
the specific surface area decreases to 30 m2 g21 for a calci- The motivation for this was to highlight the hydration activity
nation at 7508C. The same decrease in the specific surface of the reactive fraction of the partially calcined products,
area for increased temperatures is observed in the case of excluding the non-reactive limestone fraction left. The results
experiments under CO2 atmosphere. Moreover, all the quick- are plotted in Figure 5 for quicklime calcined under N2, and in
limes obtained under CO2 atmosphere—and at a higher Figure 6 for quicklime calcined under CO2. As a result of the
temperature than under N2 atmosphere—exhibit smaller expression of the results in m2 g21 CaO, the final temperature
specific surfaces than quicklimes obtained under N2 atmos- increase observed for all experiments is similar: 55– 608C;
phere. This result is in agreement with the literature (Rubiera it corresponds to the heat release of the quicklime hydration
et al., 1991), and can probably be attributed to CaO sintering. reaction and is thereabout the same with the data provided
Indeed, Glasson (1958) showed that the specific surface area by Kantiranis (2003). One can note that once the maximum
increases during calcium carbonate decomposition until it is temperature has been reached, the temperature calculated
complete; then the surface decreases by CaO sintering. In using the thermal model describing heat losses remains con-
order to gain understanding of the contribution of sintering, stant, which validates the thermal model.
specific experiments were devoted to the study of this The hydration reaction of quicklimes produced under N2 in
phenomenon and are described below. our study is extremely fast: the maximum temperature is
reached within less than 10 s. The time to extinguish an
industrial quicklime is typically 15–20 min: there is a drastic
difference in reactivity between industrial limes and limes
Sintering
obtained in the laboratory.
In a second step, the kinetics of quicklime sintering, when In the case of calcination under CO2 atmosphere, the time
submitted to high temperature, was studied. Results of sur- to reach the maximum temperature is much longer than after
faces obtained after sintering are plotted versus temperature calcination under N2: 50–500 s. Nevertheless, it is still much
in Figure 4. It can be observed that the specific surfaces are shorter than for an industrial quicklime.
very small after sintering as compared with the surface of The work realized by Shi et al. (2002) has shown that
the initial quicklime. At 11008C, they are 1.65 m2 g21 and hydration activity of CaO is a macroscopic reflection of its
1.15 m2 g21 under N2 and CO2 respectively. The sintering pro- microstructure. Industrial quicklime, less reactive than our
cess has already taken place to a significant extent. The quicklime, has a specific surface area of 4.2 m2 g21 CaO
Figure 7. Hydration activity of lime sintered under N2 and CO2;
hydration activity and industrial lime produced in packed-bed.