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P A LONGMAN
CHEMISTRY IN THE KILN
CONTENTS
1. INTRODUCTION
2. MINOR COMPONENTS
3. CLINKER NODULISATION
6. STACK EMISSIONS
7. CEMENT QUALITY
8. CONCLUSIONS
REFERENCES
1. INTRODUCTION
As discussed in the Chemistry of Portland Cement(l) an important objective of the cement maker
is to produce a cement of consistent quality which meets customer requirements. However,
another important objective is to minimise production costs. The latter will dictate the use of
impure raw materials (limestone or chalk shale or clay and sometimes sand) and a relatively cheap
fuel such as coal. Many Works are now also using cheaper by-product raw materials (such as
spent alumina, iron oxide, blast furnace slag and power station fly ash) and cheaper waste by-
product fiels (petroleum coke, tyres, saw dust, waste oils and solvents).
In addition to the cost of the raw materials and iiel, to minimise production costs the cement
manufacturer will also want to:-
These features and the two important objectives of maximizing cement quality and minimizing
production costs are not mutually exclusive but they do force the cement maker to pay attention
to kiln control and in particular the nature of the chemical reactions that take place in the kiln and
preheater systems.
In general terms, raw feed preparation costs will depend upon the cost of quarrying, or
purchasing, the individual raw materials and grinding the raw feed. The latter will be i~uenced
by the grindability of the mix and how fine the feed has to be ground in order to combine it in the
kiln. The combinability in turn will depend upon the target clinker chemistry and the raw feed
mineralogy.
Similarly, while the kiln fiel consumption will largely be determined by the type of process, the
combinability of the feed, and kiln running times will be influencing factors.
Provided the kiln is correctly aligned and the refractories correctly installed refractory life will
largely depend upon achieving a good stable clinker coating. This in turn will be influenced by
the amount of liquid that forms in the burning zone, the burning zone conditions, the variability
of the kiln feed chemistry and running times.
Kiln throughput and running times will also be influenced by the formation of rings and back end
build ups. Ring formation is usually due to excessive liquid at burning zone temperatures and/or
excessive dust formation while back end build ups are influenced by the amount and composition
of the recirculating volatiles.
Dust disposal is usually dictated by the need to control clinker alkali levels. One way of avoiding
this is to replace some of the raw materials containing high levels of alkalis (usually clay or shale)
with alternative low alkali materials such as bauxite, waste alumina, spent catalysts or pfa.
Finally, to produce a clinker which is both easy to handle and grind it is necessary to burn the
clinker to an adequate free lime, but not to overburn it and to have an optimum level of liquid
present in the burning zone to achieve adequate nodulisation without forming either excessive
dust or large lumps.
The chemical reactions between the main components in the primary and secondary raw
materials resulting in the formation of the main clinker phases C$3, CJ, C~A and CdAl? have
already been described(l). In most Works clinkers these main phases will account for some
94-97% of the clinker composition. However the remaining 3-6% which can be made up of
around 20 minor components, can significantly influence both production costs and cement
quality.
2
2. MINOR COMPONENTS
Two important properties in these minor components are their volatility and condensation
characteristics. The greater the volatility of a particular component the more will be driven off
as the feed passes through the kiln. This volatilised portion will be carried back in the kiln gases
to the cooler back end where it can condense from the gas stream. The condensation
characteristics of the component (or the compounds it may have formed) and the temperature
profile of the process will influence whether it:-
In general, in the more thermally efficient processes (precalciner, suspension preheater) most of
the volatiles will condense in the preheater; only a small fraction will condense on the precipitator
dust; and virtually none will escape up the stack. In contrast, in the less thermally efficient
processes (wet, long dry) a higher proportion of the volatiles will pass through the kiln system and
condense on the precipitator dust or escape up the stack.
K a component is partially volatilised in the burning zone and then partially recombines into the
feed at the back end then it is possible for a large amount of the component to continuously
recycle around in the kiln system. This is known as an internal cycle. If some of the component
is also collected in the precipitator dust which is then returned to the kiln (or if some is trapped
in the raw feed if the ex kiln gases are passed through the raw mill) then this forms an external
cycle. The combined effect of both cycles can be that the amount of the component in the
material entering the burning zone can be many times higher than the amount of the component
the raw materials and fiel.
This effect is illustrated in Figure 1 for the level of chloride in a suspension preheater system.
3
FIGURE1 : CHLORIBE BALANCE (CLINKER BASIS\
STACK
0.1 ml 1.ss62
FUEL
0.004
PRECIPITATE
DUST
tI
I 0.01492
(9% Condeneatton)
PREHEATER
1.s007
(90.6% Condensation)
VOIATIUSED
1.6542
(S9% Volatllls@lon)
At this Works, the combined chloride content of the raw materials is 0.013 5Yo.Thus to produce
100 tonne of clinker 0.021 tonne of chloride will enter the system in the raw materials. In the
burning zone 1% of this chloride will be retained in the clinker and 99% will be volatilised. The
fiel used at this Works contains 0.04% chloride and the fbel consumption is 10%. Thus for eve~
100 tonnes of clinker produced 0.004 tonnes of chloride enter the kiln with the fiel. This is all
volatilised as the fuel burns and is carried back in the kiln gases along with that volatilised from
the feed. At the back end 90.5% of the chloride in the gases condenses on the material passing
through the preheater, 9A will condense on fine material trapped by the precipitators and O.5A
will escape up the stack as very fine dust, alkali chloride fime or as HCL gas. The chloride in the
precipitator dust and the chloride trapped in the feed passing through the preheater will then be
carried back to the burning zone where again 1/0will be retained in the clinker and 99/0 will be
volatilised. With each cycle the quantity of chloride recirculating will gradually increase until that
retained in the clinker and escaping up the stack equals that in the raw materials and fiel. Thk
is the balance shown in Figure 1, It can also be expressed as follows:-
of the total chloride input around 67/0 is retained in the clinker and around 33/0 is lost
up the stack
6 the level of chloride in the material entering the burning zone is around 66 times higher
than the total input.
The above is a simplified example of the behaviour of chloride in a suspension preheater system.
For any component in any process it is possible to define mathematically the behaviour of the
recirculating cycle. For example in the illustration in Figure 2:-
Stack
D Fuel
H
Pre#tator I~
Yr 1
E 1 3
Preheater Cyclones
Ai G
!~
F
. r
R%wfeed pgeater
1?CIJnker
A
Total Input . A+B
_ F-C
x 1000/0 = (1 - c/F) x 1000/0
F
% Recirculating
_H
(as a percentage of total input) x 1000/0
A +B
_ G+B
x 1000/0
A +B
?40
Condensed in Preheater
(as a percentage of recirculating) . J+K+L+M~ loo%
H
% Lost to stack
(as a percentage of recirculating) _D
x 1000/0
H
_c= A+B-D
% Capture (or Fixation) x 1000/0
A +B A +B
In terms of the amount of volatile captured in the system or the amount of volatile that is
discharged to atmosphere up the stack it is more common to express these as a percentage of the
total input.
However, in terms of understanding what is going on in the kiln system, such as what levels of
volatiles are being trapped in the cyclones, or how effective a kiln bypass would be at reducing
the levels of volatiles in the system it is common to express the amount of volatiles at each point
as a percentage of that recirculating. For example if a 10/0bypass were installed in Figure 2 it
would potentially bleed out 10/0of the recirculating volatiles h~ 10/0 of the total input.
At the other extreme, the non-volatile components are more likely to influence combinability and
the quantity and nature of the liquid phase which forms in the burning zone, and hence the
nodulisation of the clinker and/or the propensity for clinker rings to form, and the clinker quality.
The minor components in the raw materials and fiel, therefore, while only totalling to around 3-
6% of the clinker composition can have a marked influence on one or more of the following
parameters:-
combinability
s clinker nodulisation and clinker ring formation
back end blockages and build ups
precipitator dust composition and properties
stack emissions
cement quality
7
The levels of minor components typically found in BCC, UK clinkers; and their general volatility
characteristics are shown in Table 1.
TABLE 1
Min. Max.
Non Volatile
YoMgO 1.48 0.73 2.60
% TiOz 0.27 0.21 0.32
/0Pz05 0.10 0.05 0.20
/0Mn203 0.06 0.02 0.15
BaO (ppm) 35 28 61
70 SrO 0.09 0.03 0.20
N1O (ppm) 42 28 61
C0,03 (ppm) 25 23 31
CUO (ppm 48 20 97
CrzO~ (ppm) 103 75 140
Slightly
olatile (5-15%0)
VzOJppm) 100 27 199
Asz03(ppm) 57 13 211
XOF 0.07 0.03 0.17
Atmreciablv
olatile (20-99/0)
0/0NazO 0.16 0.07 0.25
ZnO(ppm) 120 35 246
~0 K20 0.73 0.55 1.09
?40so, 0.80 0.51 1.58
PbO(ppm) 16 0.5 95
CdO(ppm) 0.5 <0.1 1.1
Hg(ppm) 0.02 0.01 0.03
TlzO(ppm) 0.3 0.04 0.5
Cl(ppm) 90 20 200
A list of raw materials and fbels commonly used and the minor components they commonly
contain are given in Table 2.
TABLE 2
Shale, clay & coals MgO, SOS, KZO, N~O, Cl, PzO~, TiOz, MnzO~, PbO, F, CdO
Blast fl.nmace slags MgO, SOS, TiOz, MnzO~, K20 Na20, Cl, SrO, PzO~
In the pure C-A-F-S system liquid will begin to form at 1338C and will increase with increasing
temperature. This liquid (often referred to as flux) is essentially molten C~A and C& with a
small quantity of dissolved silica. The amount of liquid that forms will decrease with increasing
silica ratio and can be estimated by the following formulae:
The alumina ratio influences the quantity of liquid that forms initially (maximum at an alumina
ratio of around 1.4- see Figure 3) but has only a small influence on the quantity of liquid that
forms at higher temperatures. However, as the alumina ratio increases, the viscosity of the liquid
formed also increases.
The above comments apply to normal burning conditions. If a kdn is operated under reducing
conditions such that some, or all, of the FezO~ is reduced to FeO then this would result in both
a lower quantity of liquid forming than would be predicted by the above formulae and a higher
liquid viscosity. Some of the FeO may substitute as CaO in the other phases thereby increasing
the basicity of the mix. As a consequence, reducing conditions in the kiln tends to restrict
nodulisation and produce a dusty clinker.
Several of the minor components commonly present in cliiers can also influence the liquid phase,
in particular the temperature that liquid formation occurs, the quantity at burning zone
temperatures and the viscosity and surface tension of the liquid which in turn will influence the
nodulising properties. A summary of the main effects are shown in Table 3,
10
FIGURE 3
.
2.5
1.5 40%
>
.
0.5
1 1.5 2 2.5 3
11
TABLE 3: INFLUENCE OF MINOR COMPONENTS ON LIQUID PROPERTIES
KZO,Na,O and SO, Forms a separate liquid to the main oxide flux at
around 1250C. At higher temperatures it is partiaiiy
miscible and results in both a higher viscosity and
higher surface tension.
Overall effect is to accelerate the formation of
nodules at a lower temperature but restrict their
growth resulting in a dustier clinker.
Whether account is taken of the minor components will depend upon their levels present but in
general the cement manufacturer prefers to keep the amount of liquid that is formed at 1400C
within the range 20-24/0. Below this the feed will become increasingly more difficult to nodulise
in the burning zone. Above 24/0 liquid there will be an increasing tendency for heavy clinker
coatings to form on the refractories. This range in liquid content at 1400C corresponds
approximately to a range in silica ratio of 2.2-2.8. Whhin this range, however, it is also important
to minimise fluctuations as varying amounts of liquid due to a variable kiln feed chemistry and/or
variable burning conditions can result in the refractory coating being stripped and/or clinker rings
forming.
12
4. RAW MATERIAL COMBINABILITY
Although the combinability of a kiln feed is primarily determined by its main chemical parameters
(LSF, silica ratio and alumina ratio), its mineralogy and its fineness, the combinability can also be
markedly affected by the minor components present in the feed entering the burning zone.
In general terms, the minor components can influence the combinability in one or more of the
following ways:-
They can modi~ the liquid phase as discussed above resulting in an easier combinability
(more liquid, less viscous, lower surface tension) or a harder combinability (more viscous,
higher sufiace tension).
They can enter into solid solution in the main clinker phases and alter the relative
proportions of the main clinker compounds. For example substitutes for CaO will
effectively raise the LSF of the clinker making the combinability more diticult.
Some components, such as PzO~, BzO~ alkalis (if in excess over SOJ or SOS (if in excess
over alkalis) can enter into solid solution in the CJ phase and stabilise this phase above
1250C thereby impeding the formation of C$. This forces the cement manufacturer to
burn harder to achieve the same free lime. In the case of alkalis and SOS if there is an
imbalance it can counter the beneficial effect of early liquid formation.
Some components, of which fluorine is the most effective, have the opposite effect of
stabilizing C~S at lower temperatures, thereby encouraging its formation. These
components are often referred to as mineralisers. By using a combination of mineralisers,
in particular F, SOS and alkalis, it is possible to significantly reduce the combinability
temperature such that compositions of htgh LSF and silica ratio can be easily combined.
The production of cements in this way with high strengths has been patented by both Blue
Circle (3) (4) and Aalborg (5). A number of trial productions have been made in UK,
Denmark Finland, South Africa and USA and Aalborg have now switched all their OPC
clinker production to this type of clinker.
Some of the calcium compounds which form as a result of recirculating volatiles, notably
calcium sulfate, will decompose in the burning zone and result in globules of free lime
being encapsulated in the main clinker phases so that firther combination is made difftcult.
This forces the cement manufacturer to burn harder or accept higher free limes.
13
5. KILN BACK END BUILD UPS AND DEPOSITS
In addition to how easy a feed combines and nodulises in the kiln system, a fiu-ther factor which
will affect production rates, kiln stops and fiel consumption and hence costs will be the propensity
for blockages and build ups to format the back end.
The formation of build ups is largely determined by the quantities of SOS, alkalis and chloride that,
are recirculating in the kiln system and how they condense at the back end. The quantities
recirculating are in turn influenced by the relative amounts in the fuel and raw materials and what
proportions are volatilised in the kiln system. In general, all the volatiles present in a fuel will be
volatilised as the fiel burns. In contrast, dtierent proportions of the volatiles, in the raw materials
will be volatilised depending upon their composition, mineralogy, vapour pressure and
temperature - time profile, the intimacy of contact between gas and solid and the degree of
saturation of the gas which in turn will be dictated by the solid/gas ratio in the kiln system, and
the burning temperature and atmosphere. Typical proportions of these volatiles in the raw
materials that are volatilised (in both normal and reducing conditions) as the feed passes through
the kiln system are:
As can be seen the main effect of a ~educing atmosphere in the kiln is to enhance the volatisation
of the SOS primarily due to dissociation of SOS compounds and the formation of S02.
When volatiles condense on to the raw feed and are carried back towards the burning zone they
form, depending upon the overall chemistry and burning conditions, a range of volatile
compounds which themselves partially evaporate and are partially retained in the clinker - either
as discrete compounds or in solid solution in the clinker phases.
In general chloride will preferentially form potassium chloride (KCl) and only when there is excess
chloride over the requirement for chemical combination with available potassium will sodium
chloride @aCl) form in the re-circulating volatiles. Sodium will tend to form both sodium sulfate
(Naz SO,) and sodium oxide with the latter going into solid solution in the clinker phases.
Potassium will preferentially form potassium sulfate (K#OJ and only when there is an excess of
alkalies over sulfate will potassium oxide go into solid solution in the clinker phases. In contrast,
if there is an excess of sulfate over alkalies the so-called calcium langbeinite (2 CaSOJ.K#OJ is
first formed and only when there is excess sulfate over this compound does calcium sulfate form
as a discrete compound in the burning zone. (6)
14
Volatilisation (evaporation) is an endothermic reaction which absorbs heat, while condensation
(recombination) is an exothermic reaction which evolves heat. Thus a high recirculation of
volatiles in a kiln system can lead to a noticeable transfer of heat from the burning zone to the
back end.
The vapour pressure of some of the alkali compounds are shown in Figure 4, while typical
proportions of the volatile compounds that are evaporated in the burning zone (in the absence of
reducing conditions) are shown in Table 4.
FIGURE 4
b
780 - ---- ---- ----- --- -
700
600 -
z
: 500
~
a
%400
g
%
& 300
9
200
100
i i I I I I
700 800 900 1000 1100 12D0 1300 la 15W
Temperature, C
15
TABLE 4
As a result, are-circulating volatile cycle builds up, which only reaches equilibrium when the total
amount leaving the system (via clinker, dust and losses to the stack) equals that entering the
system (via the raw feed and fhel).
In reducing conditions, as discussed above, the SOg compounds in Table 4 will dissociate and SOZ
will be driven off leaving KZO N~O and CaO in the clinker.
In the wet and long dry process it is possible for over half the volatiles to escape up the stack or
be trapped in the precipitator dust. If the latter is not all returned to the kdn then the dust
discarded acts as a bleed and the volatile recirculating load is lowered. For this reason relatively
high concentrations of volatiles can be tolerated in the raw materials and fiel without causing kiln
operational problems in a long dry or wet process.
In the Lepol, semi-wet and semi dry processes less volatiles can escape this way and a
proportionally larger volatile recirculating load occurs in these systems, thereby reducing the
levels that can be tolerated in the raw materials and fiels.
In the suspension preheater and precalciner processes, unless a kiln by pass is installed, virtually
all the volatiles are trapped in the system and this leads to high volatile recirculating loads as
shown in Table 5.
TABLE 5
Chloride 3000-7000
KZO 200- 650
NazO 150- 200
so. 200- 800
16
The effect these re-circulating volatiles have on the formation of back end build-ups is dependent
both on the composition (which dictates the temperature of liquid formation and hence the
location and hardness of the build-up) and the quantity (which dictates the rate of build-up).
The melting points of the main compounds involved are given in Table 6.
Alkali chlorides condense at around 700-800C. Unacceptable levels of chloride based build ups
normally occur when the level of recirculating chloride exceeds around 1.6/0. In a suspension
preheater or precalciner process this level will normally be reached when the total chloride input
on a clinker basis is around 0.025- 0.03/0.
Carbonate and sulfate compounds condense at around 850-900C and 900-1100C respectively
and the nature of the build up will depend upon the relative proportions of the compounds.
TABLE 6
Sodium:
Chloride 800 1440-1465 over 1200
Sulfate 884
Carbonate 850-854 dissociates
Hydroxide 319-328 1390
Potassium:
Chloride 700-768 1407-1411 over 1200
Sulfate 1075 1689
Carbonate 894-897 dissociates
Hydroxide 320 1320
17
As a general guide the typical concentrations of SOS and alkflles that can be tolerated in the lower
stages of a preheater are 2.5-4. 5/0 SOS and 2.5-3. 5/0 equivalent N~O. However, if fluorine
is present this can exacerbate the problem by rnineralising the formation of the build up. Reducing
conditions in the burning zone leading to the dissociation of the sulfate compounds and an
enhancement of S02 volatilisation can also result in higher concentrations of SOg at the back end.
Typical volatile inputs, volatile recirculating loads and FLS incrustation indices for some of the
Blue Circle suspension preheater and precalciner processes are shown in Table 7.
18
TABLE 7: TYPICAL VOLATILE RECIRCULATING LOADS IN SELECTED BCI KILNS
Both an increasing awareness of the impact on the environment and legislation have forced the
cement manufacturer to examine more closely stack emissions.
In general, the main factors influencing the levels of stack emissions are the efficiency of the
precipitators and the thermal efficiency of the process with less being emitted from the more
thermally efficient processes - partly as a result of their lower fiel consumption and partly
because more volatiles are scrubbed from the kiln gases at the back end and are trapped in the
feed.
Another important parameter is the burning conditions in the ~ with hard burning, and reducing
condhions in particular, leadlng to higher NOXand volatile emissions. These aspects are discussed
in more detail in the presentations on firing systems and stack emissions.
However a summary of how, the chemist~ and mineralogy of the raw materials and fiels and the
chemical reactions that can take place in the kiln system can influence stack emissions is given in
Table 8.
20
TABLE 8: INFLUENCE OF CHEMICAL REACTIONS ON EMISSIONS
21
7. CEMENT OUALITY
The composition of Portland Cement has already been discussed in paper 1 and the effect this and
the fineness of cement have on cement quality will be outlined in subsequent lectures.
In striving to maximise output, minimise the impact on the environment and minimise costs it is
important to remember that the quality of the cement must meet customers expectations and
requirements.
the rate of reaction with water and hence the workability; setting times; heat of
hydration; and strength development
the safety and handling properties of the cement
the colour of the cement
the durability of the finished product
the impact on the environment associated with the possible leaching of minor constituents
from the cement and finished product
In general:-
, increasing the surface area will improve workability and strengths at all ages
increasing the 45 micron residue will decrease workability and strengths
increasing the C3S content will increase strengths, particularly early strengths
increasing CqA content will increase early strengths; and decrease the workability
increasing the LOI will decrease strengths
increasing the CiAF content will darken the cement
However, the minor components will also influence cement quality and a summary of the effects
are given in Table 9.
22
TABLE 9: INFLUENCE OF MINOR COMPONENTS ON CEMENT QUALITY
ZnO, CUO, V20,, PbO Above O.5% retard hydration and depress strength
development.
PZO,, B20~ Above O.5% for PzO~ (0.25% for B20J can extend
setting times and adversely affect early strengths.
Heavy metals
Can leach out fi-om cement and concrete causing an
environmental m-oblem.
23
8. CONCLUSIONS
The interactions between the major and minor components originating from the raw materials and
fiel are complex.
However, to be able to minimise production costs and the impact on the environment, maximise
cliier output, and at the same time produce a cement of the desired quality it is essential these
interactions are understood and are allowed for when designing and operating the kiln system and
selecting the raw materials and fiels.
A summary of the factors which should be taken into account when setting targets for the main
chemical parameters are given in Table 10.
TABLE 10
Parameter Factors
24
The limitations placed on the typical minor and trace components encountered in the raw
materials and fiels used for cement manufacture in a modern dry process are shown in Table 11.
TABLE 11
Max. Limitation
recommended 0/0 E = Environment
Element input kghonne on clinker H = Health at work
clinker P = Manuf process
Q = Clinker quality
25 I
9, REFERENCES
4. GB Patent 2055786.
7. S Sprung and W Rechenberg Level of Heavy Metals in Clinker and Cement Zement
Kalk Glps No. 71994.
8. Adel. F Sarofim et al Emissions of metal and organic compounds from Cement Kilns
using waste derived fbels Hazardous Waste and Hazardous Materials Vol 11 No. 1994
pp 169-192.
10. G K Moir Quality aspects of cement milling paper presented at Cement Technology
Course.
26