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process
Introduction
It is well known that cement is made mainly from limestone and clay. Both contain the
essential oxides: silicon dioxide, calcium oxide, aluminum oxide, and iron oxide needed to
form the clinker 4 major components in the rotary kiln. These four oxides exist in limestone
and clay in different percentages. Limestone and clay have also other minerals that contain
some elements that are not required in the process of forming clinker main components.
Some of these minerals exist in different percentage. If these percentages exceeded certain
limits then it creates trouble for the burning process especially in the preheater lower stages
before and after the precalciner, in the kiln inlet area and sometimes in kiln tube itself.
This obliges the kiln operator to work with less excess air in the kiln, which makes things
worse since the circulation of sulfur highly increases at low oxygen level and the problem
becomes worse in the kiln and the build-up of accretion becomes very quick and its nature
will be stronger and harder i.e. the build-up will be harder to clean. This leads directly to a
decrease in kiln production and eventual shut down of the system.
The second result of working with higher levels of sulfur circulation is the formation of a
very dusty clinker. This leads to deterioration of the heat profile of the kiln and preheater
system because high amount of heat will be lost with the dust transported with the kiln
exhaust gas.
This will shift the heat upward away from burning zone affecting the coating condition in
the kiln-burning zone. The kiln then will have a long zone of unstable coating at the upper
transition zone before the burning zone leading directly to brick in this area, since with
every cycle part of the brick that is approximately 10 mm will be lost.
The only real and final remedy for this phenomena preventing it from troubling the burning
process is to install a by-pass system.
The sole and major job of this installation i.e. by-pass installation is to control these
elements to the degree that permits for smooth operation. Therefore, a universal fact should
be noted that the by-pass system does not eliminate the circulation problem of volatile
matters but just controlling it to the degree that makes the kiln operation smooth and
economical. This section is devoted to study in detail the problem of the volatile matters in
the raw materials and the by-pass system and how to make it work smoothly.
Circulation phenomenon
This term is used to represent the phenomena caused by the presence of the volatiles in the
system i.e. alkali chlorides, Sulphates and other related components in the dry kiln system
with preheater and precalciner.
So they start to circulate in the system between the kiln and preheater stages and will
continue endlessly to evaporate in the burning zone of the kiln then precipitate in the
preheater. They return again to kiln burning zone with the fresh material containing fresh
supply of these elements in addition to what is precipitated on them in the preheater.
However, we have to note here that part of these elements leaves the system with the
clinker, the preheater chimney, preheater electrostatic precipitator dust, the by-pass’s
chimney, and by-pass electrostatic precipitator dust.
These cycles continue as long as the kiln is in operation and the process is
called Circulation Phenomenon.
These cycles increase the concentration of the alkali sulfates and chlorides in the system to a
very high level as the operation of the kiln continue. Such concentration increases to fifty
times its original concentration when the kiln is just started.
1. Internal and External Circulation
Phenomena
The INNER-CIRCULE of volatile matters or INTERNAL CIRCULATION PHENOMENON is
between preheater tower lower stages and the kiln-burning zone.
As for the volatile matters that condensate on the material particles of the kiln feed and
have the chance to leave the kiln system with the kiln gas leaving the upper most cyclones,
they precipitate in the preheater electrostatic filter and eventually returning back to the kiln
with the fresh feed but they just enrich the feed with these volatile matters to some degree.
Their cycle from preheater to electrostatic precipitator to kiln feed and back again to the kiln
system is called the EXTERNAL CIRCULE of volatile matters or EXTERNAL CIRCULATION
PHENOMENON.
At a certain concentration, the system atmosphere becomes saturated to the degree that
permits for the precipitation of the volatile matters in the melted phase condition that will
lead to the formation of build-ups and rings in the lower part of the preheater system and
the kiln inlet and in calcining zone in the kiln.
If the concentration of the volatile matters becomes dangerously high either because of
high input of volatile matters to the system or due to high volatility of these matters, then
the installation of a by-pass system is a must.
The by-pass percentage of the kiln gas can be calculated in the following way.
Example
The raw materials contain chlorine [raw meal basis] =0.23 %. What is the bypass %?
Starting from lower most cyclones the temperature starts reaching 800ºC in the kiln system.
From this temperature, part of these elements is volatilized i.e. dissociated and becomes
part of the kiln atmosphere.
As the temperature starts to rise more and more the rate of volatilization increases.
In the kiln atmosphere the fuel will add to the kiln atmosphere additional sulfur after
combustion. When the material reaches burning zone, all the chlorine will be evaporated
with part from sulfate, sodium, and potassium [the harder the kiln feed to burn the higher
will be the evaporation rate of the volatiles and this takes place also in case of a very strong
flame in the main burner] and transported along with the kiln gas back to the areas of lower
temperature. Because of this cyclic mechanism, the circulating elements increase in
progression.
This enrichment continues until the total quantity of circulating elements brought into the
kiln system corresponds to the total quantity carried out of it.
The dissociated components become then capable of reacting with other compounds in the
kiln-gas, kiln-dust and burning material.
As an example of how the concentration of a certain volatile element changes through the
process:
If we introduced 1 kg of potassium each hour with the feed and when the reactions achieve
a state of equilibrium of volatiles in the system, then we will have the following condition:
The first, 0.189 kg will remain from one kg, this will start making accumulation and
continue on for hours with addition of new supply from the fresh material. When the
concentration in the kiln atmosphere reaches the concentration of 2.573 kg/h then what is
coming out from the by-pass system dust will be 0.221 kg and with E.P dust 0.042 kg/h
The second, the volatility of potassium permits for the remaining of 0.811 kg/h in the
clinker coming out from the kiln while only 0.189 kg remained in the system but eventually
it will return back to the system with the kiln feed enriching the system with potassium to
reach higher concentration of that element and eventually will reach saturation level if the
by pass system is not applied.
Third, the by-pass system permits only for controlling the volatile elements but not
eliminating them from the system, since the concentration of the potassium coming out
with kiln by-pass dust is only 0.042 kg /hour for each one kg added to the system through
the fresh feed, while nearly 0.800 kg is going out with the clinker.
That indicates the less the volatility of the element in the raw mix in the kiln, the better will
be the condition regarding the circulation phenomena.
Example: 1
The concentration of the sulfate in the clinker in one sample is 1.05 %, SO 3 concentration in
cyclone 4 materials which is collected from the material pipe of cyclone 4 to the kiln inlet is
2 % and the loss on ignition of this same sample is 3.5%
What is the evaporation factor of sulfate [SO3] in this system?
Solution
% SO3 at the kiln inlet loss on ignition free basis=
= = 2.0725
Example 2
The loss on ignition of the sample for chlorine is 3.8 %. Its concentration in the clinker is
0.03 % and its concentration in the hot meal [kiln feed] from cyclone 4 to the kiln inlet is
0.65 %. What is the evaporation factor of chlorine in this system?
Solution
% Chlorine at the kiln inlet loss on ignition free=
Solution:
The % of potassium at the kiln inlet loss on ignition free =
When E = 1 indicate that all volatile elements evaporate and none leave with the
clinker
This is clearly indicated in the case of Example 2 of chlorine where the solution proved in a
very unmistakable way this fact. [E in the example is nearly one].
When E = 0 indicate that none of the volatile elements evaporate and all leave with
the Clinker.
This is clearly indicated in the case of Example 3 of potassium where the solution proved in
a very unmistakable way this fact. [E in the example is very small].
Evaporation factor E
K2O free from chlorine 0.1-0.4
Na2O 0.1-0.25
Alkali SO3 0.2-0.9 [have a relatively high melting point of 1074ºC, boiling at
1689ºC]
Excess SO3 0.75
Cl 0.990-0.996
KCl 0.990-0.996 [have low melting point of 768ºC, boil at 1411ºC]
The volatile matters escape through the preheater dust [preheater valve].
K2O free from chlorine 0.15
Na2O 0.05-0.20
Alkali SO3 0.05-0.25
Excess SO3 ———
Cl 0.05
KCl 0.05
The volatile matters escape through the preheater chimney [preheater filter valve]
K2O free from chlorine 0-0.10
Na2O 0-0.15
Alkali SO3 0-0.20
Excess SO3 ———
Cl 0-0.10
KCl 0-0.10
If the alkalis are in the right proportion with the sulfur in the system, both will combine
together and become built in salts in the clinker minerals. But in the absence of alkalis i.e. if
there is excess sulfur in the system, the more volatile calcium sulfate will be formed in the
kiln system, and it has a higher evaporation factor.
The following equation is used for the estimation of optimum molecular ratio
between sulfur and alkalis in the system:
Example
A kiln feed sample contain the following concentration
In certain stage of build-up a new material starts to exist and causes more trouble in the
system. The formation of spurrite [2 C2S . CaCO3] and sulfo spurrite [2 C2S . CaSO4] in case of
the excess sulfur will exist in abundance. The formation of these compounds is promoted
and made possible only by the presence of the alkalis, chlorine, and sulfur in the raw
material of the kiln feed. The last mentioned build-up will not be due to the present melt
but due to kiln mating together of the needle shaped spurrite crystals.
Cyclone gas-duct i.e. riser-ducts and the cones of lowest cyclones. Coating in these areas
can contain from 8 to 60%circulation elements compounds.
The diameters of the gas ducts decrease by the coating formation. In the area of the
cyclones cones the build-up will end in closing the material pipes at the bottom of the cone
and the eventual result will be the filling of the cyclone by materials and hours will be lost in
clearing the material from the cyclone.
Also the crusts that may occur in the cyclones riser ducts may fell down closing the material
pipe at the bottom of the cyclone.
It should be noted that the 4, 5, or 6 cyclone stages preheater with precalciner are very
susceptible to the build-up caused by volatile materials. This can be attributed to the
presence of secondary firing system in the precalciner and due to the temperature profile in
such type of system which induce such type of build –up and the high circulation of dust in
the lower part of the preheater.
1. Practically all of the amount of the volatile elements enter the system is trapped and
caught within the kiln and preheater system which leads to considerable build-up of
concentration of these elements in the system.
2. The maximum concentration of these elements will be found in the area of kiln inlet
and at the areas of lowest –cyclones. This phenomenon takes place because the
temperature profile and the optimal condition for condensation in the area of the
lower most cyclones.
14.3 Decreasing the silica ratio of the kiln feed and thus making the kiln feed easier to
burn.
14.4 Finer grounding of coarser particles especially the free silicates if present in the kiln
feed therefore easier to burn kiln feed. The result will be lower sintering temperature in the
burning zone decreasing the volatility .
14.5 Accepting higher free-lime in the clinker. This requires less fuel in the burning zone,
and there will be no overheating of the burning zone.
14.6 Controlling volatile content in the raw material used for grinding and used as kiln
feed. That means observing the optimum molecular of sulfur to alkali and ensuring that the
excess sulfur is minimized.
14.7 Controlling Oxidation condition in kiln atmosphere. When we have the oxygen
level in the kiln in the higher side, the condition in the kiln will be oxidation condition. The
dissociation of sulfate compounds achieves balance in the favor of forming alkali sulfate in
the oxidation condition in the kiln. If we have reduction condition the alkali sulfate tends to
dissociate to alkali oxide and oxygen. Therefore, the oxygen level in the kiln atmosphere
should be maintained at approximately 2%, but increasing oxygen level beyond 2% will have
limited effect on the volatility of the sulfate.
14.8 Controlling the reduction condition in the kiln atmosphere
Reducing condition in the kiln atmosphere due to incomplete combustion of the fuel [either
due to lower fuel temperature or bad atomization of the fuel] either in the kiln or in the
precalciner increases the calcium sulfate and alkali sulfate in the presence of free carbon.
The reactions will be as follows:
Therefore it is of prime importance to maintain carbon mono-oxide % not more than 0.1%
at the kiln inlet and oxygen level >1.5%. The incomplete combustion of the fuel should be
prohibited in all conditions. This is very important since the high concentration of sulfur in
the system leads to a very dusty clinker from the kiln in spite of the fuel in the kiln burner or
increasing the kiln burning zone temperature. This ends in a very bad heat profile in the kiln
itself and cyclic kiln operation.
In such case the by pass system will be used mainly to control the chlorine and the removal
of it from the kiln system. But the problem of chlorine in the system can’t be blamed alone
as the cause of the problems caused by volatile matters in the suspension preheater kilns,
since in this kiln the volatiles have no escape route in the kiln system.
This leads in the absence of by-system to formation of low-melting phases belonging to the
CaSO4-Na SO4-Kcl system or the excessive entrapment of alkali/sulfur in the clinker.
This is partially overcome by the diverting part of the kiln exit gases with a bypass duct.
A modern by pass system consists of an air quench chamber, a shut-off valve, a water
quench chamber and a dust collector. The air quench chamber is used to mix ambient air
with the kiln gasses to quickly cool the harmful volatile compounds. The water quench
chamber is used to cool the gases quickly to lower temperature for dust collection.
The by-pass systems installation will eventually lead to higher power and heat consumption
in the kiln system. Also one of the major losses with this installation is the dust loss, since
the dust-laden gas streams are thrown out of the system. At 30% bypass the fuel
consumption increases by about 8-10% and material loss by about 3-6%.
1. The chimney
2. The draft-fan
3. The electrostatic-precipitator
4. Dust handling from the electrostatic-precipitator collecting screw-conveyor to the
collecting-pin and consists of: The bucket-elevator, the dust pin, and the granulator
to change the dust into dust balls and the belt conveyor for the dust balls to the
truck.
5. Condition-tower for the hot gas from the quench chamber to decrease temperature
of the gas from 450ºC to 150ºC by water spray system.
6. The quenching chamber for mixing the hot gas with ambient air, laden with the
volatile matters from the kiln riser-duct and decrease gas temperature from 1000ºC
to 450ºC in a matter of seconds to freeze the volatile components in its solid state
and prevent it from existing in the melting phase in the by-pass ducts system. This
mixing chamber is always located in the duct taking the hot gas from the kiln riser
duct and nearly 800mm away from the connecting point to the riser duct.