Slaking of lime

Johan B. Holmberg
Department of Chemical Engineering II, Lund Institute of Technology,
P. O. Box 124, S-221 00 Lund, Sweden

Quicklime is produced when limestone is heated above 900 °C, a temperature at which
limestone decomposes to carbon dioxid and quicklime (CaO). Quicklime exists in many
different qualities. Limes of different quality have been characterised, wet slaked and dry
slaked. The characterisation in combination with the wet slaking suggested that the
relationship between the surface concentration of calcium and carbon was the best measure
for the lime reactivity in the slaking process. The higher value for the relationship the more
reactive was the lime. The wet slaking tests showed that the differences in reactivity
decreases when temperature is raised or calcium chloride is added to the water. The dry
slaking tests showed upon very small differences considering the slaking degrees for
different conditions and different qualities of lime. However the tests showed on a
relationship between water content in the reactor and the specific surface for the product,
the higher quote the higher specific surface.

Introduction the porosity of the lime, the amount of

impurities and the particle size distribution.
Quicklime is produced by heating Only three different limes were fully tested
limestone above 900 °C, a temperature at and characterised. Six additional Chinese
which limestone decomposes to carbon limes were tested for impurities, the lime
dioxid and quicklime (CaO). The product content and reactivity. The three limes that
quality is among other things dependent on were fully tested were they from Poland,
this calcining process. Prolonged heating Sweden, a lime from Partek Nordsjökalk,
or heating at too high temperatures and one from China
generate a less reactive lime. Another The tests for available lime showed on a
problem is how the calcining process is distinct difference between the limes.
performed, what sort of furnace that is Table 1 Content available lime
used. Besides how the calcining process is
done, is the product quality governed by Type of lime Available content (%)
the amount of impurities in the lime. Swedish 91
Quicklime is often used in many Chinese 78
processes involving slaking, it is therefor Polish 66
of utmost importance knowing whether the
quicklime will be slaked or not in the To test the porosity a whole varity of
slaking process. To test this quicklimes of variables were tested since it was not
different qualities were investigated. The possible to measure the porosity directly.
limes tested were a couple of Chinese The measurement made were the specific
limes, a Swedish lime and a lime from surface, the pore size distribution, the pore
Poland. volumes and the density.
Table 2 Specific surface (BET)
Characterisation of quicklime
Type of lime BET-surface (m 2 /g)
The normal measurements when Swedish 1.15
quicklime is characterised are the amount Chinese 2.67
of free lime and total lime in the product, Polish 1.10

1
Table 3 Average pore size (BJH) The particle size distribution only show on
one thing that there was close to no
Type of lime Pore diameter (Å)
difference between the Swedish and Polish
Swedish 144 lime considering particle size. The particle
Chinese 200 size distribution also showed that the
Polish 182 Chinese lime consists of particles of a
larger size than the two other limes. This
Table 4 Pore volumes (BJH) might partially explain why the Chinese
lime has a higher density than the Swedish
Type of lime Pore volume (cm 3 /g) lime.
Swedish 0.0035 Examination of the surfaces performed
Chinese 0.0118 with XPS gave no clues whether there
Polish 0.0044 were any impurities on the surfaces. XPS
only showed the existents of only three
Table 5 Density components on the surfaces carbon,
calcium and oxygen.
Type of lime Density (kg/m 3 )
Swedish 1210
Table 7 Surface concentration (atomic
Chinese 1250
fraction)
Polish 1300
Calcium Carbon Oxygen
Since quicklime belongs to the bulk Swedish 0.152 0.177 0.671
chemicals it is difficult to measure the Chinese 0.177 0.146 0.677
density. The density is therefor given as Sample A 0.157 0.175 0.667
the figure for the weight per volume when Sample B 0.155 0.211 0.634
the lime no longer could be compressed Sample C 0.141 0.183 0.677
through shaking. Sample D 0.118 0.377 0.505
The figures listed gave no real answers Sample E 0.137 0.288 0.575
to how reactive each lime would be Sample F 0.124 0.235 0.641
compared to the others. The density
implies that the Swedish lime should be Samples A through F are the six Chinese
much more reactive than both the polish as lime types. The surface concentrations
well as the Chinese lime. The measured gave no real new light to how reactive each
specific surface and the measured pore lime is supposed to be. Apart from the fact
volumes indicate that the Chinese lime that limes with more calcium on the
should be much more reactive than both surface perhaps will be more reactive, it is
the Swedish and the Polish lime, which still hard to say anything about the lime
should show almost the same reactivity. reactivity. Since the surface is only a little
The average pore size for the different lime part of the lime and it is probably not
gave no new light to which lime that is the representative for the rest of the lime.
most reactive. What was noticed during the
Table 6 Particle size distribution characterisation was that there was very
little difference between the Swedish and
Swedish Chinese Polish the Polish limes.
<2.83 mm 1 1 1
<1 mm 0.81 0.61 0.82 Wet slaking
<500 µm 0.72 0.43 0.71
<250 µm 0.61 0.34 0.61 The wet slaking was carried out in an
<125 µm 0.47 0.24 0.50 insulated beaker containing 400 ml water
<63 µm 0.42 0.21 0.40 to which 100 g lime was added. The

2
temperature rise was measured and this Another way of raising reactivity is by
was correlated to the conversion. The adding calcium chloride.
slaking procedure was carried out
according to the ASTM-standard C110. Table 8 Slaking with addition of CaCl2
Besides that, the initial temperature additive none CaCl2
dependence was tested. Type of lime Time (min) Time (min)
Swedish 6.33 2.67
Chinese 4.67 2
The Swedish lime at different Polish 17 7.67
starttemperatures
50 25 degreas
Tempdiff (°C)

40 30 degreas The figures in the table above are the

30 35 degreas slaking times you get if you add 10 grams
20 of calciumchloride per litres of water. The
40 degreas
10 figures clearly show that the slaking times
50 degreas
0
decreases fairly when you add
0 5 10
Time (min)
calciumchloride.

The Polish lime at different Polish lime with different ammonts of

starttemperatures calciumchloride added
30 25 degreas
Tempdiff (°C)

25 40 0 g/l
Tempdiff (°C)

30 degreas
20 30
15 35 degreas 4 g/l
20
10 40 degreas
5 10 10 g/l

0 50 degreas 0
20 g/l
0 10 20 30 0 10 20 30
Time (min) Time (min)

The Chineese lime at different

Figure 2 The Polish lime wet slaked with calcium
starttemperatures
chloride
40 25 degreas
Tempdiff (°C)

30 30 degreas What’s interesting in the graph above is

20 35 degreas that there is a minimum slaking time when
40 degreas calcium chloride is added and that the less
10
50 degreas reactive the lime is the more effect has
0
increasing the dose of calcium chloride.
0 5 10
Time (min)
Figure 1 Different limes at different starttemperatures
Limes slaked differently
In the figure above we can see big Polish lime

differences in slaking times for the Polish 60

Tempdiff (°C)

lime to the others and we can also notice 40

Polish lime
plus 20 g
that the Chinese lime is a little more CaCl2x2H2O
Swedish lime
reactive than the Swedish lime. We can 20
also notice the slaking time seems to Polish lime
0 50 °C
converge with raised start temperature for
the slaking. Parts of the fact that the Polish 0 20 40
Time (min)
curve increases its reactivity depends on
the fact that the time difference between Figure 3 The Polish lime compared to the Swedish
total slaking time and the slaking time
according to the ASTM-standard levels out
with raised start temperature.

3
 What you can see in the last figure is
that when both raising the start temperature
and adding calcium chloride to the slaking
water the difference in slaking times
between the Swedish lime and the Polish
lime decreases dramatically.
As with many positive effects there is
also a downside. Adding calcium chloride
lowers the BET-surface of the slaked
product, see Table 9.
Table 9 BET-surfaces
Additive none
Sort of lime Surface
(m2 /g)
Swedish 26.5
were fully comparable. Besides one of the
samples all samples had a well definable
slaking time according to the ASTM-
standard. However one of the samples
lacked this cause there were no
temperature measurement made in the end
besides the end point. Plotting the slaking
times against the ratio between calcium
and carbon atomic surface concentrations
gave an almost perfect linear function apart
from the outlier discussed earlier.
CaCl2 The slaking time versus the
Surface relationship between calcium and
(m2 /g) carbon on the surface
25

Slaking time
20
Chinese 23.4 9.7

(min)
15
10
Polish 18.2 7.9 5
0
0 0.2 0.4 0.6 0.8 1
The surfaces in the table above are those
Ca/C (atomic concentrations)
for the products slaked at a starting
temperature of 25 °C. Figure 4 The slaking time plotted against surface
The third way of raising the limes concentrations of calcium and carbon
reactivity is grinding. The Polish lime was
ground, the fraction above 125 µm was The slaking seems to be divided into two
ground to under 125 µm, when you parts one initial part that probably involves
compare this reactivity to that one for the bursting of the particles and a second phase
original lime you notice that reactivity has that seems to be a part where the reaction
increased dramatically, as you can see in goes on, on the surface of the cores of the
the figure below particles. The data from the wet slaking
were fitted to the shrinking core model for
a surface reaction.
Polish lime ground

40 Shrinking core reaction control for the

Tempdiff (°C)

Polish lime
30 Swedish lime
20 0,8
25 degreas
Polish lime
10
1-(1-x)^1/3

ground 0,6 30 degreas

0 0,4 35 degreas
0 10 20 30 0,2 40 degreas
Time (min) 0 50 degreas
Figure 3 The Polish lime ground 0 100 200 300
Time (s)

The six additional samples from China
were also slaked. These samples were
slaked with another equipment totally
according to the ASTM-standard. Since
these latter samples were slaked with the
same equipment and at the same time they
Figure 5 Shrinking core reaction control for the Swedish
lime
The model was valid for conversions
between 0.4 and 0.9. The figures were
adjusted for the different temperatures and

4
the temperature dependence was calculated In the figure above you can clearly see
according to the arrenhius equation and how the specific surface of the slaked
gave the activation energies for the slaking product depends on the water content in
processes, 38 kJ/mol for the Swedish lime, reactor. This result was not dependent of
56 kJ/mol for the Polish and 60 kJ/mol for the lime quality.
the Chinese lime. Slaking with addition of Triethanolamin
was tested for the Swdeish lime. The major
Dry slaking difference was that BET-surface doubled
and that the amount of small pores in the
The limes from Sweden and Poland product increased.
were also slaked in a two-step dry slaker.
The slaker could be modelled as a tank Results and disscussion
followed by a tube. What was measured
was the specific-surface and slaking It was showed that the only really good
degrees of the slaked products. The slaking way of measure and characterise lime is by
degrees were measured with a TGA, where measuring the relationship between
the slaking degrees could be calculated calcium and carbon on the surfaces. The
from the weight loss when the lime was correlation between the reactivity and the
heated above 600 °C, a temperature at different surface concentrations may
which lime decomposes into quicklime and depend on some sort of mass transport
water. problem associated with the amount of
It was showed that the slaking degrees carbon on the surfaces or it may somehow
for the Polish lime were close to those for be connected to the fact that there is much
the Swedish lime. The slaking degrees are carbonates in the lime.
It has further been shown that the wet
slaking times for different limes can be
Swedish lime
decreased by raising the temperature or by
BET-surface (m2/g)

40
5.2 kg/h
adding calcium chloride or by doing both.
30 6.7 kg/h
This temperature dependence behaviour
20 7.8 kg/h may explain why there is only small
10 3.7 kg/h differences between slaking degrees in the
0 dry slaking.
0 0,2 0,4 0,6 0,8 It’s also suggested that the differences in
Relationship lime/water
(kg/kg) specific surfaces in the dry slaking
experiments arise from the fact that the
temperature is lowered when extra water is
correlated to the content available lime.
added and that this might have an positive
influence on the specific surface.
Polish lime
30
BET-surface (m2/g)

25 Literature cited
20 5.85 kg/h
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0
0 0,2 0,4 0,6 0,8
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Figure 6 The specific surface plotted against the water
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