Lime Kiln Imps PDF
Lime Kiln Imps PDF
Lime Kiln Imps PDF
ABSTRACT
A lime kiln is used to convert lime mud into lime for reuse
in the causticizing plant of the kraft recovery process. Many
of the problems encountered in lime kiln operations can be
related to kiln chemistry, including TRS and SO2 emissions,
dusting, ringing and refractory brick thinning.
Understanding the composition and thermal behaviour of
lime mud and the major chemical reactions involved is
critically important in developing preventive measures for
the problems.
INTRODUCTION
In the causticizing plant of a kraft pulp mill, calcium oxide
(CaO) is used to causticize sodium carbonate (Na2CO3) in
the green liquor to produce sodium hydroxide (NaOH).
CaO(s) + H2O(l) Ca(OH)2(s,aq)
... Reaction 1*
Na2CO3(aq) + Ca(OH)2(s,aq) =
2 NaOH(aq) + CaCO3(s)
... Reaction 2
Impurities
... Reaction 3
2.3-1
Weight Percent
80
CaO
CaCO3
Reaction 7
Thus, as the mud moves further inside the kiln, watersoluble sodium becomes a mixture of Na2CO3 and Na2SO4,
which, in the presence of other impurities in the mud, melts
at about 800oC (1470oF). This melting temperature is
approximately the same as the calcination temperature of
the lime mud in the kiln.
100
60
..
40
20
decreased mud solids content;
inadequate mud washing;
increased dust recycling load
Impurities
0
Lime Mud
Reburned Lime
Water-insoluble Sodium
SODIUM COMPOUNDS
Reaction 4
...
Reaction 5
..
Reaction 6
(Ca1-xNa2x)CO3
x < 0.01
2.3-2
Burner
Na
Lime
Na Total = Na Acid-soluble
= [Na Water-soluble + Na Water-insoluble + Na Guarded]
While acid-soluble sodium is somewhat more difficult to
analyze for than water-soluble sodium, the value is more
suitable for use in kiln control since it represents all types of
sodium in the mud.
1.2
Wt% as Na
1.0
Waterinsoluble
0.6
Guarded
Na
Mud
Total Sodium
0.8
Chains
Dust
0.4
Watersoluble
0.2
0.0
A B C D E F G H I J K L M N O P R Q S T
Mud Identification
2.3-3
50 mm
RING FORMATION
Ring formation is the most troublesome problem in lime
kiln operation. In severe cases, ringing results in
unscheduled kiln shutdowns for ring removal (Figure 8).
Shell Core
24 mm
2.3-4
160
140
120
100
80
20
0
0
10 20 30 40 50 60 70 80 90 100
CaCO3 Content (wt %)
CaCO3
CO2
... Reaction 9
CaO
Pure CaO
40
Lime
60
CaO
CaO
CaO
< 800oC
(1500oF)
Figure 11. Hardening of ring deposits via recarbonation of
lime
Figure 12 shows how temperature fluctuations may cause
rings to grow. The refractory surface is initially coated with
a thin, soft layer of CaO particles. This soft layer will turn
into a hard CaCO3 layer by recarbonation if its temperature
drops slightly below 800oC. The resulting CaCO3 layer then
becomes a new surface on which a thin, soft layer of CaO
particles will form. The new soft layer will insulate the old,
hard layer from the flame, keeping the temperature of the
old layer low, thereby maintaining its strength even after the
gas temperature has returned to normal. The new soft layer
will harden at the next drop in gas temperature and become
a new surface for the next deposition. The hardening cycle
is repeated as the gas temperature fluctuation repeats,
making rings grow thicker with time.
60
50
40
30
20
10
0
0
200
400
600
800
1000
Temperature (oC)
2.3-5
Normal
Kiln Wall
Low
Temperature
CaO (soft)
CaCO3 (hard)
CaCO3 (hard)
CaO (soft)
Normal
Low
Temperature
CaCO3 (hard)
Normal
DUSTING
Normal
High Soda
Kiln Wall
CaO (soft)
CaO (soft)
Normal
CaCO3 (hard)
CaO (soft)
High Soda
CaCO3 (hard)
CaO (soft)
Normal
CaCO3 (hard)
CaO (soft)
Lime mud is usually fed into the kiln in the form of large,
moist lumps, which are dried and broken into small pieces
by chains and/or by the sliding and tumbling motion of the
mud. The lower the moisture content in the mud, the easier
it is for the mud to dry, become powdery and be entrained
in the kiln gas.
2.3-6
1000
600
1%
400
5%
200
8%
0
0
Temperature (oC)
Figure 14. Effects of Temperature and O2 concentration on
H2S oxidation (Gases were well mixed, reaction
time = 0.8 second)
TRS EMISSIONS
The main component of malodorous TRS (total reduced
sulphur) gases emitted from a lime kiln is hydrogen
sulphide (H2S), which is derived from two different sources:
i) fuel at the front end and ii) lime mud at the feed end.
For kilns that burn only natural gas, TRS emissions can
only result from high residual white liquor in the lime
mud, since natural gas contains no sulphur.
At the front end of kilns that burn high sulphur content oil,
petroleum cokes and/or concentrated non-condensible gases
(CNCG), H2S is formed as a result of reactions between
sulphur (S) and hydrocarbon in the fuel under local
reducing conditions caused by poor burner performance. In
kilns that burn CNCG, H2S is one of the main components
of the gases. At the feed end, H2S is formed as a result of
the reaction between sulphides in the residual white liquor
in the mud and CO2 and H2O in the kiln gas (Reaction 6).
0% O2
800
Reaction 11
Reaction 13
Reaction 14
While CaO is used widely to control SO2 emissions in coaland oil-fired boilers, its ability to capture SO2 in lime kilns
2.3-7
12
70%
alumina
brick
10
8
6
60% alumina brick
4
2
0
0
10
15
20
25
30
2.3-8
7.
8.
9.
SUMMARY
Many of the problems encountered in lime kiln operations
can be related to kiln chemistry including: ringing, dusting,
TRS and SO2 emissions and refractory brick thinning.
Understanding the compositions of solids and gases at
different locations in the kiln and the major chemical
reactions involved helps develop preventive measures for
the problems.
REFERENCES
1.
2.
3.
14. Tran, H.N., Mao, X., Villarroel, R., and Gazoni, T.A.,
Effects of CNCG Burning on Lime Composition and
SO2 Emissions from a Lime Kiln, Tappi Journal,
Vol.3: No7, p.26-30 (2004)
4.
5.
6.
2.3-9