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Investigations performed to predict the SO2 and HCl emissions of rotary kilns have shown that
Investigation performed to predict the SO2 and HCI emissions of rotary kilns have shown that the chemical
reactions needed to assess these emissions also enable quantification of the generation rate of build-ups
in the preheating zone of these kilns. As anticipated by the theory and confirmed by industrial tests,
sulphur and chlorine loops were found. The chlorine loop is closely interconnected to the sulphur loop
that is itself influenced by the process conditions prevailing in the kilns. The quantification of the thus
resulting emissions and generation of build-ups requires a precise assessment of all reactions involving
sulphur and chlorine. However the first results of the modelling showed only a fair agreement between
calculations and monitoring results. Further investigations were therefore carried out. Accordingly it was
found that potassium plays a key role in the chemical reactions occurring in rotary lime kilns.
The inclusion of this element in the modelling enabled a significant increase in the accuracy of the prediction.
This paper presents the chemical reactions used in the model.
TEXT Dr.-Ing. Thomas Schlegel, Dipl.-Ing. (ENSCCF) Guilhem Padox, EESAC SAS Duingt/France
All authors
EESAC SAS
CO = 10x%
the chemical and physical conditions (temperature) CO = 9x%
60%
prevailing in the different areas of the kiln, sulphur CO = 8x%
CO = 7x%
can be potentially chemically converted and gener- 50%
CO = 6x%
ate SO2 emissions. 40%
CO = 5x%
2.1.3).
10%
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PROCESS
(9) 30%
20%
10%
(10) 0%
0°C 200°C 400°C 600°C 800°C 1000°C 1200°C 1400°C 1600°C
Temperature
Without SO2 With SO2 (molar raƟo SO2 / CaCl2 = 1)
The yield of the thermal decomposition of calcium
chloride according to (10) is presented as an ex- 3 Decomposition yield of CaCl2 at different temperatures and SO2 levels
ample shown in Figure 3.
Figure 3 emphasizes that, in the presence of
100%
small amounts of SO2, calcium chloride can be al-
ready totally decomposed below 500° C and thus 90%
60%
2.2.3 Behaviour of MgCl2 50%
0%
(11) 0°C 200°C 400°C 600°C 800°C 1000°C 1200°C 1400°C 1600°C
Temperature
Without SO2 With SO2 (molar raƟo SO2 / MgCl2 = 1)
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Generation
CaSO3, CaSO4, of SO2 & HCl
(mineral Cl) in LKD
Transport of CaSO3, Decomposition of
CaSO4 & CaCl2 CaSO3, CaSO4 & CaCl2
Release of SO2 & HCl
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PROCESS
9 Vapour pressures of different salts found in lime kilns as a function 10 KCl formation yield from K2SO4
of the temperature
140 100%
90%
120
80%
100 70%
Vapour pressure [kPa]
60%
80
50%
60
40%
40 30%
20%
20
10%
0 0%
900°C 1000°C 1100°C 1200°C 1300°C 1400°C 0°C 200°C 400°C 600°C 800°C 1000°C 1200°C 1400°C
Temperature Temperature
KCl NaCl K2SO4 Na2SO4 OdžLJĚĂƟve condŝƟons Reducing condŝƟons
3.2.2 Behaviour of potassium feldspar Under oxidising conditions and a residence time 11 Potassium chloride
These clays are in general chemically and thermally of 2 hours at 1000° C, the conversion rate of loop in a lime rotary
kiln with shaft preheater
very stable but they are subject to ion exchange re- K2SO4 into K2O is about 15 % only, whereas un-
actions in solid solutions, especially in the presence der reducing conditions the reaction rate is much
of sulphate and chloride salts [13] as described in faster and the conversion yield in the order of
the following equations: magnitude of 70 %.
The potassium oxide generated in the previous
reactions is very reactive with HCl, thus leading
(17) to the formation of KCl as described hereafter:
(22)
(18)
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12 Typical relationship
2,5
between chloride and
potassium contents in
the LKD of different
types of rotary kilns
2,0
1,5
1,0
0,5
0,0
0 0,5 1 1,5 2
K2O content [%]
According to Figure 11, potassium chloride is col- » Since the sorbed sulphur and chorine species
lected in the Lime Kiln Dust (LKD) together with are fed back to the kiln, they can be decom-
other chloride compounds (as shown in Figure 7). posed again leading to the formation of sulphur
This result is based on the following facts: and chlorine loops
» X-ray diffraction (XRD) analyses confirm the
presence of KCl in LKD According to the preliminary modelling results, it
» Chemical analyses of LKD show quite often that was found, and frequently confirmed by in-situ
there is a good correlation (r 2 > 0,8) between measurements, that reducing conditions favour SO2
the chloride and the potassium contents for a emissions and often HCl emissions. However these
given fuel mix and stone quality (see Figure 12), chemical reactions that considered mainly calcium
thus suggesting that that chlorine is essentially salts were neither able to predict sufficiently well
linked with potassium the magnitude of SO2 and the HCl emissions of ro-
tary lime kilns, nor the clogging of the preheat-
Remark: since sodium chloride is the salt with the ing zone. Further investigations were consequently
highest chloride input into the kiln, it can be ex- performed to increase the accuracy of the model.
pected that there would be large amounts of NaCl These highlighted the major influence of potas-
in the LKD and thus that the chloride and sodium sium on the HCl emissions and the formation of
contents would in fact correlate. Since this corre- built-ups in rotary lime kilns. Actually the potas-
lation is clearly not found, the modelling of the sium is introduced into the kiln through the stone
chemical reactions that predicts that the chlorine feed or the fuels. Following different chemical
loop is essentially due to a recirculation of potas- reactions that were clearly identified and quanti-
sium chloride is further confirmed. fied, a substantial amount of this potassium can be
transformed into potassium oxide. This substance
4 Conclusion can then easily react with HCl in the kiln, thus re-
Based on the inventory of the chemical reactions ducing accordingly the HCl emissions but increas-
involving sulphur and chlorine in rotary kilns, de- ing the amount of KCl. As potassium chloride is
tailed thermo-chemical calculations could be car- a volatile salt, it can leave the kiln with the flue
ried out. In the next step, these enabled a more gas and then partially condensate in the preheat-
precise assessment of the fate of both elements in ing zone. Part of the potassium chloride goes back
the kilns and in particular: to the kiln together with the pebbles thus creating
» Sulphur and chlorine inputs can lead to the re- a potassium loop. The part that is captured in the
lease of SO2 and HCl in the preheating and the preheater favours the accumulation of dust which
kiln areas. Both gases can be chemisorbed on leads finally to build-ups that clog the preheater.
the external layer of the limestone / lime peb- Since the chemical reactions occurring in rotary
bles in the preheating zone lime kilns are now identified and quantified, the
REFERENCES
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