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TECHNICAL FORUM

What affect do fuels have on product quality?

conomics are the driving force for

a cement company to burn alternative fuels and therefore these are
the first consideration. Will the
gate fees be high enough? What will be
the costs of handling, storing and delivering the material to the kiln? What equipment will be needed? How profitable will it
be? How much of the material is available?
How long into the future can the increased
profits be anticipated?
Next ones needs to know how difficult
will it be to obtain a licence to burn the
material? Can opposition be expected from
the people living around the cement factory? Can opposition be expected from the
workforce? How strict will the requirements
be to comply with the licence? What monitoring and reporting will need to be put in
place? What will be the penalties if licensing requirements are not met?
There remain two further considerations. What will be the impact on the
process? And the impact on cement quality? In most cases the economic imperatives mean that work-rounds will have to
cope with process or product quality implications. Process and technicians predict
and anticipate the likely implications and
put in place the equipment and procedures
to deal with them.
Prediction and anticipation of the
impact of alternative fuels rely on two
methods. Experience of other cement
companies when burning the particular
materials, and the use of chemistry,
process engineering and technical first
principles. Usually both are used. Only in
very rare cases has no cement company
burnt the material before. For the multinational cement companies there is probably another group company that has paved
the way. But how does an independent
cement producer learn from the experiences of other cement companies? This is
the role of the Cemtech conference,
International Cement Review magazine, the

Survival
fuels
by Dr Michael Clark
Burning alternative fuels is very much on the agenda for many cement
manufacturers. For many companies operating wet-process kilns it is an
absolute imperative for survival. These kilns are generally of low capacity
and inevitably fuel consumption is high due to the need to evaporate the
water in the slurry feed. However, if the cement company is being paid a
fee to burn alternative fuels, then high fuel consumption is an advantage,
as it increases the quantity of these fuels that can be burnt and therefore
the fees earned.
CemNet Technical Forum, the Global
Cement Network, and the individual consultants within that network.

What size of bypass is

required?
A cement company once contacted
Whitehopleman in 2001 to assist in evaluating the implications of burning spent pot
liners from the aluminium industry in its
kilns. The liners are composed of carbon
and are used to line the electrolytic cells
used in the production of aluminium. The
electrolyte used in these cells is cryolite
and some of this is absorbed into the liners
meaning that they have high sodium and
fluoride content. The carbon liners themselves have a good calorific value and the
anticipated price to burn the liners was
attractive, but what would be the impact
of the sodium and the fluoride on the
process? In particular what steps would be
necessary to continue to meet the low
alkali specification in the final cement? As
the current cement was almost on the limit
of this specification it was clear that a

bypass would need to be installed. How big

would that bypass need to be? Would it be
necessary to add calcium chloride to the
feed to promote the alkali cycle?
Answering these questions requires the
development of a mass and energy balance,
and alkali cycle model of the kiln. The mass
and energy balance is required because the
total energy input to the kiln will have to
be kept constant as the fuel mixture is varied. Will replacement of coal with spent
pot liners or other alternative fuels give a
direct one-for-one replacement in terms of
the energy input to the kiln? Probably not.
Differences in the particle size and volatile
content will affect the heat release characteristics in the kiln. The model has to allow
scenarios with varying energy replacement
factors for different fuels.
The mass balance is required because
different fuels will yield different mixtures
of combustion product gases. Carbon dioxide, CO2, and water vapour, H2O, occupy
different volumes due to their different
molecular weights. The size of the bypass
will depend on the volume of the kiln
exhaust gases at the kiln inlet as well as
the proportion that must be bypassed to
bring the alkali content of the clinker down
to the level required to meet the low alkali
cement specification. Temperature of the
gases at the kiln inlet and the degree of
calcinations of the feed entering the kiln
from the preheater will also affect the volume at the kiln inlet.

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TECHNICAL FORUM
Once the mass and energy balance has
been developed the alkali cycle in the kiln
has to be incorporated. Volatile species in
the kiln feed pass down the preheater and
into the rotary kiln. Some of the volatiles
pass out in the clinker, but some evaporate
in the burning zone and are carried away
with the combustion product gases from
the main burner. Any volatile material in
the fuel joins the volatilised material from
the feed, and together they are carried
back to the preheater in the exhaust gases.
In the preheater these volatile species
condense on the cooler incoming feed and
are carried back into the kiln, where they
area again volatilised. The cycle builds up
until conservation of mass demands that
the amount of material exiting in the
clinker equals the amount of material
entering the feed and the fuel. The concentration of recirculating material in the
kiln exit gases and the hot feed is much
higher than in the feed, fuel or clinker.
Modelling the cycle for a particular kiln
requires knowledge of input levels of
volatile species in the feed and the fuel,
the output level in the clinker, and the
recirculating level in the hot meal. This
allows the volatility of the individual
species in the particular kiln to be estimated. This is the key to predicting the
effects of varying inputs of volatile species
as the fuel mixture is changed.
A bypass works because the concentration of recirculating material in the kiln
exit gases is much higher than in the
incoming feed or the fuel. Bleeding out a
small proportion of the kiln exit gases
takes out the equivalent mass of material
that is entering the feed and the fuel, and
the cycle is broken. As the model is tuned
to the particular kiln the proportion of
material that must be bled out through the
bypass to achieve a given residual level in
the clinker can be predicted. This proportion of volatile material can be translated
into a volume of the gases at the kiln exit
that must be bypassed.
Volatility of different species varies
from kiln to kiln, and also dependent on
the relative proportions of the different
species present. The order of volatility
increases in the order Na2O < K2O = SO3 <
Cl, with the volatility of K2O in particular
depending on the amount of chloride, Cl,
that is present in the kiln. This is why
adding calcium chloride, CaCl2, to the feed
can be useful to boost the alkali cycle and
reduce the size of bypass to achieve a
given level of residual K2O in the clinker.
54

Building the ability to make these predictions into the model of the kiln requires
that variation in the volatility of the K2O
be taken into consideration.

Mineralisation
Predicting the effects of the fluoride addition in the spent pot liners is a bigger
challenge. The volatility of fluoride itself is
fairly low and it does not build up into a
significant recirculating load. However,
increased stickiness of the feed in the
lower sections of the preheater is reported.
This is associated with low temperature
eutectics and melts with mixtures of halide
and sulphate salts in the feed in the hotter
parts of the preheater.
Within the kiln itself the fluoride has a
mineralising effect reducing the temperature and therefore the energy required for
clinker formation. Energy savings of
between 20 and 50kJ/kg clinker have been
achieved for each 0.1 per cent of fluoride
addition. This energy saving can then be
converted into additional output from the
kiln by consideration of the reduced combustion product exhaust gas volume. But
will the fluoride have this desirable effect
when added in conjunction with increased
sodium in the spent pot liners?

Clinker mineralogy
A number of cement companies are adding
calcium fluoride to produce mineralised
clinker on their kilns, but the driving force
is generally not reducing the fuel consumption or increasing the output from their
kilns. Fluoride has two beneficial effects of
the mineralogy of the clinker. The primary
phase field of the alite, C3S, mineral is
expanded, and the rhombohedral polymorph of the alite is stabilised. The first
effect means the clinker can contain more
C3S and therefore the lime saturation can
be lifted. The second effect means the
reactivity and strength development properties of the C3S are improved. Cement
companies want to add more supplementary cementitious materials to blended
cements and a more reactivity C3S mineral
allows this without lowering quality.
Modelling and predicting these effects
is a real challenge. For certain the Bogue
calculation of clinker mineralogy becomes
more irrelevant. This is why the techniques
of Dr Chromy become increasingly important. These can be combined with
Whitehopleman raw mix proportioning
software to provide a method for real
clinker mineralogy control. Dr Chromy is a

INTERNATIONAL CEMENT REVIEW / OCTOBER 2003

specialist in clinker microscopy and has

developed a unique approach to clinker
mineralogy control. His approach is based
on microscopic examination of the clinker,
however the it would be equally valid with
X-ray diffraction and Rietveld analysis.
Samples of clinker from the kiln are
analysed under the microscope and the
quantities of alite, belite and interstitial
material are estimated. Significant deviation from the targets for these mineral
components triggers adjustment of the targets for kiln feed lime saturation and silica
modulus in the Whitehopleman raw mill
feed proportioning software.
The estimate of the real clinker phase
composition, the oxide analysis determined
by X-ray fluorescence and the free lime
content are also entered into the
Whitehopleman software. Multiple regression between the true mineral composition
and the oxide analysis is carried out providing coefficients for the multiple relationship between these dependent and
independent variables. This relationship
can then be used to predict the real mineral composition of clinker samples that
have not been examined microscopically.
Dr Chromy is an advocate of the visual
inspection of clinker samples under the
microscope, but skilled persons cannot be
provided on every shift and inevitably the
quality of analysis can vary. Whitehopleman
advocates the use of Kvant pattern recognition software to automatically estimate
the clinker mineral composition.

Techniques and other fuels

These techniques can be applied to predict, anticipate and monitor the impact of
any change in the cement kiln process. If
you are thinking of burning meat and
bonemeal you will be concerned about the
impact of P2O5 on clinker mineralogy. If
you are converting to petcoke you need to
check the effect on ring formation in the
kiln, possible formation of large balls of
clinker, dusting of the clinker in the burning zone, recirculation of dust from the
cooler, high free lime in clinker due to
decomposition of C3S into C2S and CaO.
Every new fuel or raw material is likely
to have some impact on the process or
clinker mineralogy. The way to predict and
anticipate these is from experience gained
elsewhere and chemistry, process engineering and technical first principles. When
implemented the only way to monitor and
correct for the effects is by controlling the
real mineralogy of the clinker. ________