CHEMISTRY IN THE KILN

P A LONGMAN

CHEMISTRY

IN THE KILN

CONTENTS

1.

INTRODUCTION

2.

MINOR

3.

CLINKER

4.

RAW MATERIAL

5.

KILN BACK END BUILD UPS AND DEPOSITS

6.

STACK EMISSIONS

7.

CEMENT

8.

CONCLUSIONS

COMPONENTS
NODULISATION
COMBINABILITY

QUALITY

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 byproduct 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:

limit raw feed preparation costs

minimise kiln fiel consumption
maximise refractory life
maximise kiln output and running times
minimise dust disposal
produce a clinker which is easy to handle and grind

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,
clinker
present
dust or

to produce a clinker which is both easy to handle and grind it is necessary to burn the
to an adequate free lime, but not to overburn it and to have an optimum level of liquid
in the burning zone to achieve adequate nodulisation without forming either excessive
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.

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:

condenses in the kiln or preheater possibly resulting in blockages

condenses on the precipitator dust possibly causing a handling problem
escapes up stack possibly resulting in an environmental problem

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.

FIGURE1

: CHLORIBE

BALANCE

(CLINKER

BASIS\

STACK
0.W63 (o.51% LOSS)

FUEL

1.ss62

0.1 ml

0.004

PRECIPITATE
DUST

tI

PREHEATER

0.01492
(9% Condeneatton)

RAW FEED

VOIATIUSED

1.s007

1.6542
(S9% Volatllls@lon)

(90.6% Condensation)

PREHEAIER

KILN FEED

FEED

1.8709

0.1702

0.021

CUNKER
0.01s7
(l%RetenUon)

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:Tons of Chloride per 100 tonnes of Clinker

Feed

Fuel

Total
In

0.021

0.004

0.025

Recirculating

1.6709

Clinker

Stack

Total
out

0.0167

0.0083

0.025

The main features of thk balance are:

of the total chloride input around 67/0 is retained in the clinker and around 33/0 is lost
up the stack
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:-

FIGURE

2: RECIRCULATING

MODEL

(CLINKER

BASIS]

Stack
D

Pre#tator

Yr

Fuel

I~

1
1
Preheater

Cyclones
Ai

!~

R%wfeed
A

.
pgeater

r
1?CIJnker

Total Input

. A+B

Total Output

% Volatilised (or evaporated)

in Burning Zone

= G/F x 100?4o

% Recirculating
(as a percentage of total input)

C+D

_ F-C

1000/0 = (1 - c/F) x 1000/0

_H

1000/0

1000/0

A +B
_

G+B

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)

0/0Collected in Precipitator Dust

(as a percentage of recirculating)

Yoof input lost to stack

_D
x 1000/0
H

_E
x 1000/0
H

_D=

A +B

% Capture (or Fixation)

_c=
A +B

/l+l?-C

A +B

x 1000/0

A+B-D
x 1000/0
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 36% of the clinker composition can have a marked influence on one or more of the following
parameters:

combinability
clinker nodulisation and clinker ring formation
back end blockages and build ups
precipitator dust composition and properties
stack emissions
cement quality

The levels of minor components typically found in BCC, UK clinkers; and their general volatility
characteristics are shown in Table 1.
TABLE 1
TYPICAL LEVELS OF MINOR COMPONENTS
IN BCC CLINKERS
(LISTED IN ASCENDING ORDER OF VOLATILITY~

Component

Mean

Range
Min.

Max.

Non Volatile
YoMgO
% TiOz
/0Pz05
/0Mn203
BaO (ppm)
70 SrO
N1O (ppm)
C0,03 (ppm)
CUO (ppm
CrzO~ (ppm)

1.48
0.27
0.10
0.06
35
0.09
42
25
48
103

0.73
0.21
0.05
0.02
28
0.03
28
23
20
75

2.60
0.32
0.20
0.15
61
0.20
61
31
97
140

Slightly
olatile (5-15%0)
VzOJppm)
Asz03(ppm)
XO
F

100
57
0.07

27
13
0.03

199
211
0.17

Atmreciablv
olatile (20-99/0)
0/0NazO
ZnO(ppm)
~0 K20
?40so,
PbO(ppm)
CdO(ppm)
Hg(ppm)
TlzO(ppm)
Cl(ppm)

0.16
120
0.73
0.80
16
0.5
0.02
0.3
90

0.07
35
0.55
0.51
0.5
<0.1
0.01
0.04
20

0.25
246
1.09
1.58
95
1.1
0.03
0.5
200

A list of raw materials and fbels commonly used and the minor components
contain are given in Table 2.

they commonly

TABLE 2
MINOR

COMPONENTS

COMMONLY PRESENT
FUELS

IN RAW MATERIALS

AND

Material

Typical Minor Components

Limestone or chalk

MgO, SOS, KZO, NazO

Shale, clay & coals

MgO, SOS, KZO, N~O, Cl, PzO~, TiOz, MnzO~, PbO, F, CdO

Iron oxide

SO,, T1,O

Bauxite

Ti02, CrzOJ

Blast fl.nmace slags

MgO, SOS, TiOz, MnzO~, K20 Na20, Cl, SrO, PzO~

Petroleum coke

so,, V205

Tyres

ZnO, FezO~

Waste solvents

Cl, CdO, Hg, ZnO, PbO, B, Ni

3.

CLINKER

NODULISATION

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:

% liquid at 1338C

=
=

6.lF when A/F>l.38

8.2A - 5.22F when A/F <1.38

% liquid at 1400C

2.95A + 2.2F

0/0liquid at 1450C

3.OA + 2.25F

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
VARIATION

IN VOLIOUID PHASE AT 1338C

WITH CHANGTNG

S/(A+F) AND AF AT 100% LSF

2.5

1.5

40%
>

0.5
1

1.5

2.5

Silica Ratio S/(A+F)

11

TABLE 3: INFLUENCE

Minor Component

OF MINOR

COMPONENTS

ON LIQUID

PROPERTIES

Influence on Liquid Formation

Mgo

Can increase the liquid phase present at burning zone

temperatures by around 1.5A

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.

Mn203

Behaves similarly to FezO~ in increasing the level of

flux and reducing its viscosity.

Cl, F

Lowers the liquid viscosity

Trace Metals

Can either increase or decrease both liquid viscosity

and surface tension depending upon the electronegativity of the ions and the alumina ratio. This
aspect is discussed in more detail in a recent
paper(2)

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
This range in liquid content at 1400C corresponds
coatings to form on the refractories.
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
For example substitutes for CaO will
proportions of the main clinker compounds.
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
These
stabilizing C~S at lower temperatures, thereby encouraging its formation.
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
Typical proportions of these volatiles in the raw
the burning temperature and atmosphere.
materials that are volatilised (in both normal and reducing conditions) as the feed passes through
the kiln system are:

Normal Burning Atmosphere

Chloride
so,
K20
N~O

96-99%
60-90?40
30-7070
20-40?40

Reducimz Burning Atmosphere

97-10070
90- 100?40
30- 7070
20- 40?0

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
EFFECT

OF TEMPERATURE

ON THE VAPOUR PRESSURE

COMPOUNDS

OF ALKALI

b
780

- ----

----

-----

---

700

600 z
:

500

~
a
%400
g
%
&

300

9
200

100

i
700

800

900

1000

1100

Temperature,

12D0 1300

la

15W

15

TABLE 4
TYPICAL

PROPORTIONS
OF RECIRCULATING
VOLATILE
EVAPORATED
IN THE BURNING ZONE

40404060209796-

K, SO,
Na#Oq
2CaSOJ.K$Oa
KZO in solid solution
N~O in solid solution
KC1
NaCl

COMPOUNDS

60V0
60%
100VO
90?40
40V0
99%
99%0
d

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
TYPICAL VOLATILE RECIRCULATING
LOADS IN SUSPENSION PREHEATER
AND PRECALCINER
KILNS (EXPRESSED AS A VOOF TOTAL INPUT)

Chloride
KZO
NazO

so.

16

3000-7000
200- 650
150- 200
200- 800

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
MELTING

& BOILING

POINT DATA

Melting Point
c

Boiling Point

800
884

1440-1465

850-854

Dissociation
c

Sodium:
Chloride
Sulfate
Carbonate
Hydroxide

319-328

dissociates
1390

Potassium:
Chloride
Sulfate
Carbonate
Hydroxide

700-768
1075
894-897
320

1407-1411
1689
dissociates
1320

Calcium Sulfate

over 1200

over 1200

1297

1350

A useful guide is the FLS Incrustation Index:R.

Total input molar S

Total input molar KZO + !/ztotal input molar N~O

where R >1

hard SOS based incrustations can occur

R = 0.7- 0.9

incrustations are relatively soft

hard carbonate based incrustations can occur

< 0.5

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

Process
Works
Total Volatiles
@t (Clinkerbasis)
0/0
Total S as SO,
K20
Na20
cl

VOLATILE

RECIRCULATING

BCI KILNS

SuspensionPreheater

Precalciner
Cauldon

LOADS IN SELECTED

Dunbar

Aberthaw

Harleyville

Lichtenburg

Plyrnstock

1.38
0.85
0.10
0.015

2.57
0,54
0.07
0.028

I.09
0.71
0.16
0.03

0.90
0.23
0.10
0.015

0.40
0.18
0.09
0.006

0.91
1.32
0.2
0.023

1.8

4.9

1.5

3.5

1.9

0.7

1.72
2.33
0.13
0,43

2.08
0.75
0.07
0.27

2.86
3.21
0.24
1.69

4.50
2.68
0.13
1.95

4,13
0.95
0.12
0.32

2.06
4.09
0.43
0.96

so,
K20
Na,O
cl

1.10
0.80
0.09
0.011

1.40
0.48
0.06
0.01

0.95
0.64
0.15
0.05

0.80
0,16
0,06
0.003

0.27
0,15
0.09
0.001

0.91
1.30
0.20
0.01

Volatileslost UPthe
-k
0/0
S03
K20
Na,O
cl

0.28
0.05
0.01
0.004

1.17
0.06
0.01
0.018

0.14
0.07
0.01
0.015

0.10
0.07
0.04
0.012

0.13
0.03

0.02

0.005

0.013

FLS Incrustation
Index
Recirculating
Volatiles
0/0
so,
K20
Na,O
cl
Volatilesin the
clinker
0/0

6.

STACK EMISSIONS

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

Particulate

Mainly influenced by the quantity of recirculating

volatiles and the effect these may have on precipitator
efficiency.

Sox

Enhanced by the presence of sulfides in the raw

materials which oxidise to form SOZ at low
temperatures. (In the precalciner and suspension
preheater processes this can occur in the upper stages
of the preheater before the calcium carbonate has
decomposed.
In the absence of any reactive CaO to
react with much of the S02 can escape up the stack.)

NO,

Can be lowered by using mineralisers to lower the

burning zone temperature.

co,

COZ can only be marginally reduced by lowering the

burning zone temperature or the clinker LSF. Higher
reductions on a cement basis can be achieved by using
additionsifillers such as pfa, slag or limestone. These
can be maximised by producing a reactive clinker.

Highly toxic elements

(e.g. Cd, Hg and Tl)

Relative volatilities suggests greater risk with Hg and

T1 (95-99% volatility) than Cd (60-90% volatility).
However due to the condensation characteristics the
loss to stack is typically less than 5?40of the total
input.

Moderately toxic elements

(e.g. As, Co, Nl)

Less risk due to their lower relative volatilities. The

loss to stack is typically less than 0.5% of the total
input (7) (8).

Toxic elements

Relative volatilhies suggests greatest risk is with lead

(60-80% volatility)

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.
These will include:

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
increasing
increasing
increasing
increasing
increasing

the surface area will improve workability and strengths at all ages
the 45 micron residue will decrease workability and strengths
the C3S content will increase strengths, particularly early strengths
CqA content will increase early strengths; and decrease the workability
the LOI will decrease strengths
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

Alkalies

4s alkali sulfate can enhance early strengths and

:oncrete slump but depress late strengths.
%salkali in solid solution can enhance the reactivity of
]elite and C~A.
~an also lead to durability problems due to alkali
iilica reaction and may need to be restricted to below
).6% Equivalent N~O.

S03

3xcess SOS over alkalis will form 2CaSOJ.KJO~ and

iee CaSOJ. Can result in larger less reactive alite
;rystals.
Will also limit gypsum addition and produce a more
iifllcult cement grindability.
[n reducing conditions, dissociation of SOS
~ompounds can result in a raised free lime content or
nore alkalis entering into the C~A phase thereby
ncreasing the reactivity. If free alkali oxide forms this
-eacts with moisture from the atmosphere and can
~dversely affect the cement flowability.

Although it acts as mineraliser, it also adversely

~ffects the hydraulic properties leading to extended
setting times and lower early strengths. However, if
limited to around 0.2% and used with alkalis and SOS
strengths can be maximised.

Cr

Can increase activity of belite but soluble chrome can

lead to dermatitis. Some countries limit soluble
;hromium to less than 2ppm.

TiOz, MnzOq

Slightly depress early strength.

ZnO, CUO, V20,, PbO

Above O.5% retard hydration and depress strength

development.

cl

Can accelerate strengths but can also cause corrosion

of steel reinforcing. Many cement standards limit the
level of chloride in the cement to O.1?40.For
reinforced concrete the specified maximum chloride
(cement basis) is also O.1?40. To accommodate
chloride in the water and aggregates it is normal to
limit the chloride content of the cement to below
0.0570.

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

CONCLUSIONS

8.

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
SUMMARY

OF FACTORS NEEDED
SETTING CLINKER
Parameter

TO BE TAKEN INTO ACCOUNT

CHEMISTRY TARGETS

WHEN

Factors

1.

LSF

Cement strengths, workability combinability

2.

SIA+F

Cement strengths, workability,

combinability, flux content (clinker
nodulisation - kiln output and dusty
conditions; and refractory coating refractory life)

3.

A/F

Cement early strengths and workability;

cement colour, mobility of flux (similar to
flux content)

4.

Minor non-volatile components

(P,O,, Ti02, Mn20,, MgO)

Cement setting times; cement soundness;

cement colour; flux content and viscosity

5.

Minor volatile components

(S0,, Alkalis, Cl)

Cement quality; durability (ASR); back end

kiln deposits - restriction on output; dust
disposal and/or kiln bypass; stack emissions

6.

Trace components

Cement quality; stack emissions, back end

deposits; refractory life

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
SUMMARY

Element

Antimony (Sb)
Arsenic (As)
Beryllium (Be)
Cadmium (Cd)
Chromium (Cr)
Fluorine (F)
Cobalt (Co)
Mercury (Hg)
Lead (Pb)
Nickel @i)
Selenium (Se)
Tellurium (Te)
Thallium (Tl)
Vanadium (V)
Zinc (ZnO)
Strontium (SrO)
Barium (BaO)
Phosphorus
(P2 05)
Titanium (TiOJ
Copper (Cu)
Sulphur (SOJ
Chloride (Cl)
Alkalis
(eq Na,O)
BzO~

OF MINOR

Max.
recommended
input kghonne
clinker

COMPONENT

0/0
on clinker

3
0.2
0.09
0.01
0.1
2
0.1
0,002
0.3
0.1
0.05
0.4
0.005
0.6
10
5
5

0.3
0.02
0.009
0.001
0.01
0.2
0.01
0.0002
0.030
0.01
0.005
0.04
0.0005
0.06
1.0
0.5
0.5

10
10
1
15
0.3

1.0
1.0
0.1
1.5
0.03

10
5

1.0
0.5

LIMITS

Limitation
E = Environment
H = Health at work
P = Manuf process
Q = Clinker quality
E
ELI
E
E
HIQ

Q
H
E
E
E
E
E
E
E/P

Q
Q
Q
Q
Q
Q
P
PIQ
P/Q

25

9,

REFERENCES

1.

GKMoirTC95021
Technology course.

2,

G K Moir and F P Glasser Mineralisers, Modifiers and Activators

Process - paper presented at Itl ICCC Delhi 1992.

3.

GB Patent 1498057 (US Patent 4042408).

4.

GB Patent 2055786.

5.

International Patent WO 93/21 122.

6.

TC 94049 C P Kerton CETIC Sub-Commission

Kilns Final Progress Report May 1994.

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.

9.

G K Moir Hydration
Course.

10.

G K Moir Quality aspects of cement milling paper presented at Cement Technology

Course.

11.

A R Rogers Cement Performance

26

Chemistry of Portland Cement Clinker paper presented at Cement

in the Clinkers

Behaviour of Volatile Materials in

of Portland Cement paper presented at Cement Technolo~

paper presented at Cement Technology Course.