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TECHNICAL FORUM

TXI Midlothian kiln line #5

he start point for the debate was

Leas table of thermodynamic heats
of reaction for the formation of
cement clinker, as shown in column
two of Table 1.
The argument was that Leas table
could be used to assess the energy required
to convert 1kg of slag added to the kiln
inlet into cement clinker. This energy was
expected to be less than for kiln feed and
the proposition was that the energy saved
could be used to convert more kiln feed
into clinker. Consideration of the reactions
and processes that slag kiln feed will and
will not have to go through to become
cement clinker are represented in column
three of Table 1.
On the heat absorbed side, slag will
have to be heated up to 1400C and will
absorb energy to be melted in the kiln, but
there is no clay to dehydrate or calcium
carbonate to dissociate. On the heat
evolved side the resulting clinker will need
to be cooled to 20C, but there will be no
CO2 or water vapour to be cooled, there is
no clay to exothermically dissociate and
there will be no exothermic formation of
clinker minerals as the slag already
comprises clinker minerals. (The latter
point is arguable but if there is exothermic
formation of clinker minerals from slag
then the thermodynamics become more
beneficial).
The net heat of formation of 1kg of
clinker from 1kg of slag is therefore
155kcal/kg. That is a saving of 265 (420155) kcal/kg of clinker. This energy saving
can be used to convert kiln feed into an
additional 0.63 (265/420) kilograms of
clinker for each kilogram of slag added to
the kiln inlet. In total, each 1kg of slag
therefore provides 1.63kg of clinker.
This seems a very happy result, but a
little further chemistry needs to be taken
into consideration. Slags are deficient in
lime and this has to be made up by
increasing the CaO content of the kiln

First
principles
by Dr Michael Clark
The IEEE/IAS-PCA conference was held in Dallas in May with one of the
plant visits being to the TXI Midlothian cement factory. This is the site
where the patented Cemstar process for adding slag to the inlet of the kiln
was developed. In the months leading up to the conference a debate was
raging concerning whether the increases in kiln output that Cemstar
provides can be explained by thermodynamic first principles. This seems a
timely topic for this months Technical Forum.
feed. This is done by adding more highgrade limestone and is one of the limiting
factors in using the Cemstar process. If
high-grade limestone is not available then
the deficiency in lime of the slag cannot be
corrected and Cemstar will not work.
The amount of extra CaO derived from
limestone that will be needed can be calculated from the difference between the
CaO contents of the clinker and the slag.
CaO from limestone = (CaO in clinker
CaO in slag)/CaO in clinker

With a slag of 40 per cent CaO each

kilogram of slag added to the kiln inlet will
require an additional 0.385kg of CaO
derived from limestone to correct the deficiency in lime of the slag. The energy
required to convert limestone into 0.385kg
of clinker can be calculated by multiplying
the energies in column four of Table 1 by
0.385kg. The net heat of formation of
0.385kg of clinker from limestone is therefore 148kcal/kg.
The addition of 1kg of 40 per cent CaO

Table 1: thermodynamics of cement clinker formation from various raw materials (after Lea)

Heat absorbed

kcal/kg

Raw Materials

Slag

Heating materials 20 - 450C

Dehydration of clay at 450C
Heating materials 450 - 900C
Dissociation of calcium carbonate at 900C
Heating decarbonated material from 900 - 1400C
Net heat of melting
Total

Kiln
feed
170
40
195
475
125
25
1030

Limestone

170
0
195
0
125
25
515

170
0
195
475
125
0
965

Heat evolved
Exothermic reaction of dehydrated clay
Exothermic heat of formation of cement compounds
Cooling clinker from 1400 - 20C
Cooling carbon dioxide from 1400 - 20C
Cooling steam 450 - 20C including condensation
Total

10
100
360
120
20
610

0
0
360
0
0
360

0
100
360
120
0
580

Net theoretical heat to form 1kg clinker

420

155

385

INTERNATIONAL CEMENT REVIEW / JULY 2003

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TECHNICAL FORUM
can be used to convert kiln
feed into an additional 0.28
(117/420) kg of clinker for
each kilogram of slag added
to the kiln inlet. In total,
each kilogram of slag therefore provides 1.66kg of
clinker.
An equally happy result
and the correction of the
lime deficiency of the slag
has been taken into consideration! How real is this
result? Well the proposition
rests on the capacity for
thermal conversion of material being the limiting facTXI Chaparral Midlothian Electric Arc Furnace steel making
operation
tor of the kiln. For
marginal clinker production
this is often not the case. Many kilns are
slag to the inlet of a cement kiln will
fan or draft limited. Also Leas table only
therefore yield 1.385kg of clinker when the
takes into consideration the thermodynamlime deficiency of the slag has been corics of clinker formation. An industrial kiln
rected and there will be a saving of 117
also suffers energy losses in the preheater
(420 155 148) kcal. This energy saving

40

INTERNATIONAL CEMENT REVIEW / JULY 2003

and cooler exhaust gases and through radiation from the shell. The most efficient
kilns consume 690kcal/kg clinker rather
than 420kcal/kg.
Predicting the impact of slag addition
on an industrial kiln would require the
development of a mass and energy balance
model for the particular kiln and the
testing of various slag addition scenarios
on that model. However, the arguments
summarised above made for an interesting
debate and the prediction from consideration of Leas table actually under-estimates
the additional clinker production that has
been achieved in practice.
Why is Cemstar even more successful
than can be predicted from thermodynamics? Well that would make for another
interesting debate and Technical Forum
article in the future. The reasons are
undoubtedly connected with fluxing and
mineralisation of the kiln which in turn
changes all the values in Leas table!
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