Professional Documents
Culture Documents
239
by Con G. Manias*
Once raw materials have been selected and blended, and ground and homogenized into a fine and
uniform kiln feed, they must then be subjected to enough heat to allow the clinkering reactions to
proceed. This is the pyroprocessing stage of cement manufacture, beginning with the kiln feed
material extracted from storage and weighed and transported to the kiln, and finishing with the
clinker from the cooler going to clinker storage. A schematic diagram on different stages of cement
manufacturing is shown in Figure 3.1.1
Control
system
Pre-heater
+ Calciner
Fuel
Kiln rotation
Kiln
Fuel
To clinker storage
Cooler
*Managing Director, FCT Group of Companies, 20 Stirling Street,Thebarton, South Australia 5031
ph + 61 8 8352 9999, http://www.fctinternational.com
240
The main chemical reactions to produce the calcium silicates that later give cement its bonding
strength occur in the kiln system. There is a combination of endothermic and exothermic reactions
occurring in an extremely complicated chemical reaction sequence. The raw material composition,
mineralogical composition and the time and temperature profile of these materials in the kiln
determine the ultimate composition and mineralogy of the clinker, which in turn determines the
performance of the cement produced.
The pyroprocessing stage is generally regarded as the heart of the cement-making process. It is the
stage in which most of the operating costs of cement manufacture appear, and is also therefore the
stage where most of the opportunities for process improvement exist.
There are many different kiln system designs and enhancements, but they are all in essence
performing the following material transformation, in order from the feed end:
1. Evaporating free water, at temperatures up to
100C
100C - 300C
450C - 900C
700C - 850C
800C - 1250C
>1250C
7. Formation of C3S
1330C - 1450C
1300C - 1240C
<1200C
1250C - 100C
Figure 3.1.2 shows the transformation reactions taking place at different stages of raw material
pyroprocessing.
On the gas flow side, the sequence from the firing end is as follows:
1. Ambient air preheated by hot clinker from kiln
2000C to 2400C
5. Further heat recovery from gases for drying of raw materials or coal
All kiln systems aspire to optimize heat exchange between the gas streams and material streams at
various stages to minimize waste heat and maximize thermal efficiency.
241
CaCO3
Alite
Clinker
Free lime
Raw meal
Portions by weight
CO2
Belite
Low-quartz
High-quartz
H 2O
Fe2O3
200
Liquid
Cr
C12A7
Clay minerals
400
600
C2(A,F)
800
C 3A
Liquid
C4AF
1000
1200
1400
Temperature, C
KILN SYSTEMS
Early kiln systems for cement clinker manufacture were based on shaft kiln systems. However, as
these are of little relevance to the world at large, this chapter will deal with rotary kilns only.
The first rotary kiln was introduced to the cement industry by Frederik Ransome (1885) when he
took out a patent in England titled Improvements in Manufacture of Cement. The first of these
rotary kilns were up to 2.0 m in diameter and 25 m long, with an enormous production of 30 to
50 ton/day. Today, some kilns are producing as much in a day (>10,000 tpd) as these kilns
produced in a year.
242
The main problem with long wet kilns is their poor fuel efficiency, because of the water to be evaporated from the slurry. This became a severe problem only when the cost of fuel escalated during
the 1970s, and only a few wet kilns have been built since that time. However, there are some rare
situations where raw material moistures, cheap (waste) fuels, low technology workforce, or other
factors may still favor wet process production.
Another disadvantage of a wet process kiln is that it is limited in production rate because of
mechanical limitations on kiln size. A 1500 tpd wet kiln is a large kiln, with 2000 tpd being an
upper economic limit without encountering severe maintenance problems. Apart from the sheer weight and stresses on mechanical drives
and supports, shell deflection makes it increasingly difficult to achieve
acceptable refractory life. Figure 3.1.3 depicts a typical long wet process
kiln.
243
244
Material residence time in the preheater is in the order of 30 seconds and in the kiln about 30
minutes. Kiln speeds are typically 2 rpm. Preheater pressure drops range from 300 mm to 600 mm
water, with gas duct velocities typically 20 m/s in the preheater and cyclones.
Kiln capacities up to 3500 tpd exist, with specific fuel consumption usually around 750 to 800
kcal/kg (3.2 to 3.5 MJ/kg). The larger capacity kilns are built with two preheater tower systems to
keep cyclone sizes to economic proportions and required efficiency.
Precalciner Kilns
In precalciner kilns, the combustion air for burning fuel in the preheater no longer passes through
the kiln, but is taken from the cooler region by a special tertiary air duct to a specially designed combustion vessel in the preheater tower. Typically, 60% of the total fuel is burnt in the calciner, and the
raw meal is over 90% calcined before it reaches the rotary kiln section. Since the calciner operates at
temperatures around the calcination temperature of raw meal (800C to 900C), there may not be a
flame as such. The calciner efficiency is dependent on uniform air flow and uniform dispersion of
fuel and raw meal in the air. Typically, average residence times calculated on gas flow for early units
were about 1 to 2 seconds for coal and oil, and 2 to 3 seconds for natural gas. In recent years, though,
there has been a trend toward larger calciner vessels to reduce some of the combustion problems of
the earlier designs and provide greater flexibility for using lower grade fuels.
Precalciner kilns can have very large outputs in excess of 10,000 tpd, with specific fuel consumption below 3 MJ/kg (700 kcal/kg). There are many different configurations, with one, two, or three
preheater towers operating with one or two calciner vessels in either an in-line configuration or
separate line configuration. Some (mostly recent) designs include a separate precombustion
245
246
chamber. An in-line calciner has kiln exhaust gases and tertiary air
making up the combustion air (reduced oxygen levels) for the calciner as
shown in Figure 3.1.7, while the separate line system has tertiary air only
with 21% oxygen forming the combustion air as is shown in Figure 3.1.8.
A separate line system therefore has a better combustion environment
and may be preferred for difficult fuels. It has a further advantage when
converting preheater kilns to precalciners in that there is minimal interference with the operating preheater kiln during the construction phase
for the new separate line preheater tower and tertiary air duct.
Figure 3.1.8. Separate line calciner system with two preheater towers.
Other Systems
The rotary kiln has been the standard clinkering unit for cement production over the past century.
During that time, there have been various attempts to produce clinker in other reactors including a
flash calcining/clinkering and fluid bed calcining/clinkering vessels
247
The motivation has been to reduce capital and operating costs or to allow smaller economic clinkering plants to be built in remote locations.
The author was involved with one such project during the 1980s, where clinker was produced in a
fluid bed fed with raw meal. Although this did not proceed to commercialization, it was noted that
the clinker produced from this pilot plant was much more reactive than any conventionally
produced clinker, and gave cement strengths 20% higher than those produced from good quality
rotary kiln clinker. This was thought to be due to the absence of overburning in the fluid bed clinker
because of the more uniform temperature that can be achieved. The mineral structure certainly
showed much finer alite and belite crystals in the 10 to 20 m range. This gives some indication of
the potential quality improvement possible through better control of rotary kiln temperature.
Critical data on the kiln systems discussed above are summarized in Table 3.1.1. The data reflects
mechanical, operational, thermal, fuel, production, and efficiency parameters of each kiln system.
Table 3.1.1. Summary of Critical Data Information on Different Kiln Systems
Kiln
systems
rpm
tpd/m3
L/D
Long wet
0.450.8
3035
Long Dry
0.50.8
3035
Lepol
1.5
1.52.2
1215
Cyclone
preheater
2.0
1.52.2
1416
Precalciner
3.6
3.55.0
1014
SFC
kcal/kg
1300
1650
1100
1300
950
1200
750
900
720
850
Kiln
system
Residence exit
kWh/t time, min T, C
150
230
380
400
100
120
1725
180240
2030
180240
2025
30
25
3040
350
25
2030
300
360
P,
mm
H2O
150
180
150
200
250
400
500
700
500
700
Exit gas,
Nm3/kg
clinker
3.4
1.8
2.0
1.5
1.4
(1)
248
Where
t = residence time, min
L = kiln length, m
p = kiln slope, degrees
D = kiln diameter, m
n = kiln speed, rpm
= angle of repose of material, (40 degrees)
F = constriction factor (usually1 if no dams, lifters etc.)
Kiln Slope
Rotary kilns slope from the feed end to the discharge end for material to travel in that direction
utilizing gravitational force. The slope is typically 2% to 4%, or 1 to 2, and is decided in conjunction with the kiln rotational speed. A lesser slope with a higher rotational speed may improve heat
transfer because of the greater tumbling of kiln charge.
Kiln Capacity
When designing a kiln for a certain capacity, or when evaluating an existing kiln for potential
output, there are a number of key parameters that must be evaluated. These include:
Burning zone heat loading
Secondary air velocity
Burning zone gas velocity
Kiln exit gas velocity
Kiln exit gas temperature
Preheater tower gas velocities
Preheater tower pressure drops
Preheater tower exit gas temperature
Volatile concentrations
Material residence time
Cooler grate loading
CLINKER COOLERS
Cooling of clinker takes place at two locations: 1) in the kiln after the material passes the burning
zone region, and 2) in the specially designed clinker coolers after the material falls out of the kiln.
The rate of cooling can be critical to the clinker quality and performance of cement. The rate of
cooling in the kiln is determined by the flame and resulting heat flux, flame temperature, and
speed of material flow through the kiln. As the clinker temperature exiting the kiln is normally
1200C to 1250C, the clinker characteristics have been already largely established before the
clinker enters the cooler. A long flame gives slow heat-up and slow cooling of the kiln charge
before it falls from the kiln. This will tend to produce clinker with large alite and belite crystals,
resulting in a coarse-grained clinker matrix with poor reactivity and poor grindability. Slow cooling can also result in reversion of C2S from the ' phase to the less reactive form, or in extreme
cases even to the unreactive form, and can even allow C3S to revert to C2S and CaO. All of these
have a negative impact on cement strength.
A further quality problem can arise if there are high levels of MgO in the clinker, because slow
cooling allows large periclase crystals to form such that when these hydrate slowly in concrete, the
expansion can cause the concrete to rupture.
There are two main types of coolers used in cement clinker production. These are the satellite (or
planetary) type and the oscillating grate type. The 1990s saw tremendous advances in clinker cooler
technology that greatly improved heat efficiency and potential output from a given kiln system.
Clinker coolers perform the function of:
Transporting clinker from the kiln to the clinker delivery system
Cooling the clinker to a safe temperature for subsequent transport
Finalizing the clinker mineralogy through rapid cooling
Preheating combustion air by heat exchange with hot clinker
Coolers are treated in more detail elsewhere in this publication and will not be elaborated on
further here.
249
250
KILN BURNERS
Combustion and the Cement Process
Pyro-processing is the heart of the cement-making process. It is usually the major cost element and
kiln performance dictates the efficiency, plant output, emissions, product quality, and plant run
factors. Combustion will be the major factor in determining kiln performance, and seemingly
small improvements here can have a major impact on the economics of running the whole plant.
An additional 5% to 10% production in a year will impact spectacularly on the profit line given the
large proportion of fixed costs at a cement plant.
The cement kiln requires a particular heat transfer regime for best fuel economy, optimum product quality and maximum production. Generally, a short hot burning zone at the front of the kiln
is optimal. This gives rapid heat up and cool down of clinker to give the best reactivity, reduced
back end temperature for minimizing heat losses in the exit gases and from shell radiation, best use
of I.D. fan capacity, and reduced NOx formation. This needs to be balanced against refractory heat
load and kiln operating stability. The flame must not impact on the kiln charge or refractories and
complete combustion must occur in the kiln to reduce potential for build up and ring formation.
When deciding on a burner, it can be false economy to simply select on the basis of initial purchase
price alone, and suffer long-term poor performance for the plant or extended commissioning
times. The capital investment in a cement plant is substantial and it is high risk to entrust the
performance of this investment to a relatively low-cost component (the burner system) without
taking all reasonable steps to mitigate this risk.
Sadly though, it is often the case that evaluation and choice of burners either for new kilns or
replacement systems is based on capacity and purchase price only, without much indication of
how they will perform with the specific kiln under consideration.
The combustion system should be considered as an integral part of the pyro-processing system,
including kiln, cooler, tertiary air ducts, calciner etc., and be designed with due consideration of
this total system.
Kiln Aerodynamics
It is surprising how small differences in cooler throat, cooler bull nose, kiln hood, tertiary air offtakes, secondary air temperature and velocity, and air leakage points to name a few can have an
enormous effect on the air flow patterns in the combustion environment of the rotary kiln.
Tertiary air inlet design and location, and tertiary air temperature and velocity will likewise determine the airflow patterns in a flash calciner.
251
The fuel introduced by the burner will clearly be influenced by the secondary and tertiary air flow
patterns, given that 85% to 100% of the combustion air comes from this source and the momentum of these large airflows dominates the combustion region. Typical aerodynamic patterns in two
different kiln combustion zones are shown in Figure 3.1.9-a,b.
Hood
Flame
(a)
Flame
(b)
Figure 3.1.9-a,b. Some typical kiln aerodynamic patterns encountered during kiln studies.
252
Geometric design of cooler, cooler bull nose, cooler throat, kiln, off-take ducts, burner position, burner angle, burner channels (types, numbers and sizes), calciner size and shape, and
tertiary air inlet
Process design, such as fuel rate, type, properties; primary air mass and velocity; secondary air
and tertiary air temperature, mass and velocity; production rates; heat transfer (convection,
conduction, radiation); and heat flux profiles developed
As no single modeling technique can provide all the answers, a combination of physical and mathematical modeling provides the best information for arriving at an optimized burner design.
Observation from a fuel/air mixing model using acid-alkali techniques is shown in Figure 3.1.10.
The overriding consideration when implementing results of modeling work is understanding the
limitations and the conclusions that can be drawn from each technique, as well as ensuring that
the techniques used have been adequately validated.
253
In a rotary kiln, the secondary air to be entrained into the fuel jet is limited to that coming from
the cooler, and the expansion of the fuel jet is constrained by the diameter of the kiln. If the burner
jet momentum (fuel and primary air) is less than that required for complete entrainment, then
fuel/air mixing will be inadequate for good combustion, and a long, lazy flame with high CO is the
likely result.
If the burner momentum is greater than that required for complete secondary air entrainment,
then the excess momentum of the fuel jet is dissipated in pulling back exhaust gases from further
down the kiln into the flame. This so-called recirculation has a positive effect in stabilizing the
flame (making it less susceptible to minor process fluctuations) and in protecting refractory
surfaces from burning fuel particles. Note though, that too much recirculation can be detrimental
to fuel efficiency and produce an overly aggressive combustion environment. An ideal flame from
use of secondary air entrainment and recirculation is shown in Figure 3.1.11.
Secondary
air
Primary air
and fuel
Secondary
air
Recirculated
combustion gases
Figure 3.1.11. Idealized flame in rotary kiln showing secondary air entrainment and recirculation of combustion gases indicating adequate burner momentum for satisfactory fuel/air
mixing.
Good burner design therefore requires optimizing fuel jet momentum and primary
air mass and velocity to create a recirculatory flame while interacting with that
particular kiln systems aerodynamics. The secondary air temperature, mass,
velocity, and directional flows must all be considered in the design process
as these affect the burner system design. The variables to optimize include primary air mass and velocity, axial and radial
flow splits, fuel jet momentum, and burner insertion
length and direction. A typical multi-fuel burner
used in a rotary kiln is shown in Figure 3.1.12.
254
Flame Stability
Unstable flames adversely affect kiln operation as well as being unsafe to plant and personnel. An
unstable flame is one that has a varying ignition point and a variable stand off distance from the
burner tip as shown in Figure 3.1.14. There is a high risk of flame out, and substantial amount of
unburnt fuel between the burner tip and the ignition point that is a potential explosion risk. Gas
burners are more prone to instability because of the high ignition temperature, slow flame propagation speed, and narrow flammability limits for this fuel.
Flame envelope
Unburnt gas
Ensuring early ignition of fuel entering the combustion zone enhances flame stability. In some
applications, this can be by a continuous pilot burner, but in rotary kilns this is best achieved by
ensuring recirculation of hot gases as the ignition source for new fuel. Once a kiln is up to operating temperature, radiation from refractory provides the ignition energy.
255
External circulation from properly designed burners brings hot combustion gases back into the combustion region to help stabilize the ignition point. Internal circulation can be even more effective.
Internal circulation can be induced by the use of a bluff body to create a low pressure region in the
center of the burner nozzle that then draws hot combustion gases back into this region. This can
then act as the ignition source for the new fuel. Bluff bodies, though, can suffer heat damage in this
demanding location (see Figure 3.1.15).
Reverse flow
Primary air
Gas
Primary air
Bluff body
Figure 3.1.15. Stabilization of flame with internal recirculation created by bluff body.
A more durable means of creating internal flame re-circulation is the use of swirl in either the fuel
or primary air jet stream as shown in Figure 3.1.16. However, swirl would broaden the flame that
can adversely affect refractory life due to flame impingement (see Figure 3.1.17). In gas firing, the
most effective design uses limited swirl for both primary air and gas fuel. In oil firing, primary air
swirl is typically used, while for solid fuel firing swirl is often unnecessary for producing a stable
flame. Each case is designed on the merits of the fuel and the combustion environment in which it
will operate.
Burner
Flame envelope
256
20,000
14,000
6000
5000
J
N
CL
Primary jet
2498
2600
Outlet
Dam
cone 2498 ring
Discharge
zone
4290 Dia.
4750 Dia.
27,000
Burning zone
4600
Cam
section
Gyro-Therm Burners
The Gyro-Therm Precessing Jet burner technology has been designed to be mechanically very
simple, but the novel fluid-mechanical flow provides a genuinely new way of mixing fuel and air.
This produces flames with different characteristics (compared to turbulent diffusion jet burners)
that have been proven to give operational and environmental advantages in kiln firing.
This emerging technology has so far been used in gas burning or gas/coal burning applications.
However, a coal-only burner using Gyro-Therm technology is near commercialization.
The precessing jet nozzle used in these burners produces a fuel jet stream exiting the burner nozzle
that exhibits a stirring action into the combustion environment as shown in Figure 3.1.18.
Gas
Jet
precession
Figure 3.1.18. Cross sectional diagram of the precessing jet nozzle and the flow field generated
from it.
257
The flame itself does not precess. The effect is to produce large-scale mixing, via the stirring
action of the jet and a rapidly spreading flame. This is in contrast to the fine scale mixing of turbulent jet diffusion burners. The precessing motion is generated without any moving parts within the
Gyro-Therm nozzle.
The resultant effects of this new technology include:
Sub-stoichiometric combustion within flame envelope with complete combustion at the flame
boundaries in a normal kiln environment
Highly luminous flames enhancing heat transfer to kiln charge
Low axial velocity of fuel jet giving short bulbous flame
Low thermal NOx formation
No primary air needed for gas fuel and a stable flame anchored to the nozzle
Although the flame spreads more than that from a conventional turbulent jet nozzle, the amount
of spread can be controlled. This fact is important in rotary kilns where direct impingement of a
flame on the product could produce instability or reducing conditions which would be detrimental
to product quality or damage the refractory. A simple but extremely effective flame shaping technique is built into the burner. The technique for flame shape adjustment is based on a high
momentum gas jet injected at a critical point into the precessing jet flow field. This jet (termed the
center body jet, CBJ) is expelled through the center body of the precessing jet nozzle, modifying
the pressure fields within the vicinity of the burner in such a way that the fuel gas is directed more
toward the kiln axis. As the proportion of gas is increased through the center body jet, the flame
spread is reduced and the heat flux profile lengthened. An air channel is provided for burner cooling and for flame shaping during the warm-up phase. A schematic of Gyro-Therm burner with gas
channel for flame adjustment and cooling air is shown in Figure 3.1.19.
PJ Gas
Figure 3.1.19. The design of the Gyro-Therm burner includes an additional gas channel for
flame shape adjustment and optional cooling air.
258
CALCINER BURNERS
Calciner combustion is quite different from kiln combustion. Often, there is no defined flame in
the vessel, with oxidation of the fuel occurring under flameless conditions. As for any combustion environment, satisfactory fuel/air mixing is the first requirement for good combustion.
Calciner aerodynamics are dominated by the tertiary air due to its mass and comparatively high
velocity at the calciner inlet. The airflow patterns can become quite complex with changes in the
calciner cross section producing effects such as strong recirculation zones and streaming as
depicted in Figure 3.1.20.
With such prevailing conditions,
the location and design of calciner burners can become
extremely critical to the performance of the calciner. As for
kiln burners, physical modeling
can reveal the flow patterns
within a calciner, and allow the
location of burners and their
design (injection velocities and
momentum) to be determined
for best performance. FurtherFigure 3.1.20. Typical aerodynamic problems encountered in more, modeling can often determine simple redesign of internal
calciner operation that impair calciner combustion.
refractory profiles to produce
much improved calciner aerodynamics and hence greatly improve calciner combustion.
Due to the short residence time in calciners (2 to 3 seconds), combustion can be sensitive to fuel
properties. Some fuels such as petcoke because of its low volatile content, and natural gas
because of its more stringent combustion prerequisites, require more residence time (larger
calciner) for satisfactory combustion.
Calciner burner designs can vary from a simple pipe through which to introduce fuel, to more
sophisticated designs that are smaller versions of kiln burners. In most cases, a simple pipe will
perform as well as the more complex designs if it is correctly located and designed. This is obviously a cheaper capital and operating cost solution. Only in rare cases will primary air be required
in a calciner burner to overcome any serious aerodynamic problems.
259
OXYGEN INJECTION
The technical benefits available from using oxygen to replace air for combustion in cement kilns
have long been recognized. These benefits arise from increased flame temperature (leading to
improved heat transfer rates), faster reaction rates with some difficult fuels, and reduced combustion gas volume (due to less nitrogen).
In general, this will lead to reduced specific fuel consumption (less waste gas volume and better
heat transfer) and increased production from a particular kiln. The effect on NOx emissions will
be variable, but with small amounts of oxygen substitution NOx will usually increase as a consequence of elevated flame temperature.
However, the cost of oxygen has generally been prohibitive in the past, preventing the wholesale
use of oxygen to enhance cement kiln performance.
The availability of cheaper production methods for oxygen such as the vacuum swing adsorption
process, together with increased demand for cement, have combined in some regions to make the
strategic use of oxygen a viable alternative for increasing production. This is particularly so where
short term peaks in demand are encountered and oxygen injection can be implemented without
significant plant down time for modifications.
Oxygen injection can be carried out either in the kiln or calciner. A process evaluation of the
specific kiln system will reveal the most advantageous point. Generally, this will involve identifying
bottlenecks to increased production and how these can be addressed through the use of oxygen. A
modeling strategy for designing oxygen-injecting system for a calciner is shown in Figure 3.1.21.
Strategic use of oxygen can impart the following processing benefits:
Allow more fuel to be burned in either the
kiln or calciner where fan capacity is
limiting output, and therefore increase
output
Reduce gas velocity in the burning zone,
kiln back end, calciner exit, through the
preheater tower, or through the bag filter
or electrostatic precipitator
Reduce pressure drop through the kiln
system because of reduced gas velocities
Reduce preheater exit temperature
because of higher feed-to-gas ratio
260
However, there are also potential risks of overheating refractories and kiln charge or calciner feed
unless due consideration is given to the design of injection points and oxygen lances.
Raw meal
Loss free
Coal ash
Clinker
SiO2
14.4
22.3
54.3
22.6
Al2O3
3.2
5.0
26.2
5.2
Fe2O3
1.8
2.8
16.7
2.9
42.4
65.7
0.6
65.0
CaO
MgO
1.30
2.02
0.8
2.0
SO3
0.37
0.57
0.1
0.6
K2O
0.60
0.93
1.2
0.9
Na2O
0.17
0.26
0.1
0.3
TiO2
0.17
0.26
Mn2O3
0.12
0.19
P2O5
0.11
0.17
Cl
0.03
0.05
0
LOI
35.5
SR
2.9
2.9
1.3
2.78
AR
1.8
1.8
1.6
1.77
LSF
91.7
91.7
0.3
91.1
C3S
60.6
60.6
-610.1
53.6
C2S
18.3
18.3
616.0
24.4
C3A
8.4
8.4
41.2
8.8
C4AF
8.5
8.5
50.8
8.9
The hypothetical compounds are calculated using the Bogue equations to determine the percentage of calcium silicates (C3S and C2S), calcium aluminate (C3A) and calcium alumino ferrite
(C4AF) phases, which would be present in the clinker if all reactions proceeded to completion
under equilibrium conditions. In reality, the calculated or hypothetical composition differs from
actual analysis of clinker by X-ray diffraction or microscopic analysis. This is because chemical
equilibrium is reached only occasionally, and the degree to which actual analysis differs from the
calculated analysis is influenced by the heat treatment of the material. In addition, small amounts
of trace elements can have a profound effect on the eventual mineralogical composition of clinker.
In general, it is found that:
Alite content is usually higher than the calculated amount by an average of 13%
Belite is usually lower than the calculated amount by an average of 6%
Aluminate and ferrite phases can be either higher or lower, but on average are 2% lower than
calculated
The critical stages for clinker quality are:
The heat-up rate of the kiln charge after the calcination process
The maximum temperature and residence time at that temperature
The cooling rate to below 1200C
These stages determine the size of alite and belite crystals and their reactivity, the formation of
these crystals (, , ), and the nature of the liquid phase, as well as the position in the structure
where minor elements such as Mg, Na, and K, are found; all are critical to cement quality.
Some aspects of plant operation that help kiln performance are kiln feed size, homogeneity, kiln
time/temperature profile, heat balance, and volatile and dust cycles; these are discussed in the
following sections.
261
262
Time/Temperature Profile
The kiln charge must spend sufficient time at a high enough temperature to reach near complete
reaction to form clinker minerals. There must be no material flushing or underburning, as this
produces poor quality clinker. The material bed must tumble adequately to ensure uniform heating through the mass.
If clinker is underburnt, it will form small crystals of alite surrounded by abundant (solidified)
liquid phase, whereas the belite will exist in discrete clusters. There may also be significant free
lime present together with alite and belite, which has not had the opportunity to completely react.
Overburnt clinker will have large alite and belite crystals, and exhibit poor reactivity.
kJ/kg
170
1990
105
2050
4315
kJ/kg
40
420
105
1400
500
85
2550
kcal/kg
40
475
25
490
1050
kcal/kg
10
100
25
335
120
20
610
1765
420
kJ/kg
Dry
Wet
process
process
20
2100
840
1250
650
360
kcal/kg
Dry
Wet
process
process
5
502
201
299
156
86
Add Inefficiencies
Heat losses related to inefficiencies
during the kiln operation
Evaporation of water
Heat losses, gas, clinker, dust
Radiation, convection loss
Total heat consumption =
(endothermic heat exothermic heat)
+ heat losses due to inefficiencies
3275
5475
782
1307
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The heat of formation (Q) of the clinker minerals is a function of the chemical composition and
the mineralogical composition. It can be expressed as kcal/kg in a general equation as follows:
Q = 2.22% Al2O3 +5.86% hH +6.48% MgO+7.646% CaO 5.116% SiO2 0.59% Fe2O3
(2)
Where hH = % water of crystallization in the clay, g/100g clinker, and all analyses are on clinker.
If alkalies are present, the heat of formation is reduced by about 2 kcal/kg.
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Other less insidious factors are the sensible heat of introduced streams, the secondary air heat
input to the kiln, the calcination reaction, and heats of formation of the various components.
The heat exchange occurring within a kiln is therefore a multi-dimensional phenomenon.
Kiln Volatiles
The kiln volatiles referred to in cement manufacture are those compounds that volatilize in the
burning zone of a rotary kiln and recondense in the cooler parts of the kiln or preheater. They are
usually sodium or potassium sulfates and chlorides, but can also include certain calcium salts.
Their melting points and relative volatilities in the kiln burning zone are given in Table 3.1.4.
Table 3.1.4. Melting Points and Relative Volatilities of Different
Compounds in Kiln Burning Zone
Volatile compounds
KCl
K2SO4
NaCl
Na2SO4
CaCl2
CaSO4
Melting point, C
776
1069
801
884
772
1280
Range of volatility, %
60 to 80
40 to 60
50 to 60
35 to 50
60 to 80
These materials are not usually in the pure form, but form a eutectic mixture with an overall melting point below that of the pure salts. In practice, these salts generally will appear in the melt in the
temperature range of 600C to 800C.
The volatile compounds cannot readily escape from the kiln system because they condense (before
they can be removed in the exit gas stream) and re-enter the kiln. Their concentration will therefore
continue to build, sometimes reaching a concentration in the recycle stream significantly greater
than the concentration in the raw materials. As they pass through a sticky condition during the
melting/vaporization and recondensing stages, they can be catalysts for forming coating buildup in
the preheater tower and rings in the back end of the kiln. These can be particularly disruptive to
kiln operation in the cyclone preheater tower, and older preheater kilns can run into severe operational problems because the effect of the volatile cycle was unrecognized in their design.
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As a guide, the acceptable concentration limits of these materials (as % of clinker) in the kiln riser are:
Na2O and K2O
< 3% to 5%
SO3
< 3% to 5%
Cl
(3)
A low oxygen level shifts the equilibrium to the right. The volatility of sodium and potassium is
less affected by oxygen levels than that of sulfur.
Increased water vapor promotes formation of alkali hydroxides that are more volatile than the
sulfates. Potassium volatility is increased at 1200C, while sodium volatility is increased at
1400C.
SO2 (from the fuel) reduces the volatility of potassium, while the sodium volatility is
unaffected.
The mineralogical composition of raw materials producing volatiles is a major determinant of
the alkali volatility, depending on the alkali carriers. Mica > illite > feldspar. Also, an easier
burning material means lower burning zone temperature and hence less volatility.
The fineness of raw meal has an indirect effect if it produces an easier burning mix.
A further factor is the alkali-to-sulfur ratio. Alkalies will preferentially combine with any chloride
present. The best alkali-to-sulfur ratio is when there is just enough sulfur present to combine stoichiometrically with the remaining alkalies. If there is an excess of sulfur, then calcium sulfate will
form from which the sulfur will volatilize completely.
If there is an excess of alkalies, alkali aluminate can form which will cause stiffening problems in
concrete and mortar. There are also likely to be rings and buildup formed in the kiln system from a
variety of other alkali salts produced.
In some cases, where low alkali cement is the target, and there is an alkali bypass installed. Alkali
volatility is an advantage, and CaCl2 can be added to the mix to promote alkali volatility.
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Sinter Rings
Sinter rings form at the beginning of the burning zone, and they also have an appearance and
composition like clinker. These rings establish at the point in the kiln where the liquid phase is
beginning to form, but during the course of a kiln turn, the melt comes into contact with a cooler
surface and resolidifies, binding clinker particles together. This process can repeat until a ring
forms. This type of ring is most likely to develop where there is a long and flat heat flux profile in
the kiln.
CONCLUSIONS
The heat transfer processes occurring inside a kiln are multi-dimensional and extremely complicated. There is no single factor that can be considered in isolation when seeking to optimize kiln
performance and product quality.
The raw materials and kiln feed preparation will have a major impact on kiln performance and will
set the blueprint for fuel economy, kiln stability, clinker quality, refractory life, kiln throughput,
and environmental impact. The kiln operation and the combustion system will determine as to
what extent the potential inherent in the raw materials will be realized.
An optimization approach to a cement manufacturing plant should therefore consider a total
holistic approach from the quarry to the lorry, examining each stage in detail and the impact of
each stage on the total plant operation and economics.
REFERENCES
Ransome, F., Improvement in Manufacture of Cement, English Patent #5442, May 2, 1885.
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