Review No.

127

Laboratory Simulation of Preheater Emissions

Reprint of article published in World Cement, May 1999

By Ebbe S. Jns, F.L.Smidth & Co. A/S, Denmark and Omar Rabia,
Institute of Chemical Engineering, Technical University of Denmark

LABORATORY SIMULATION
OF PREHEATER EMISSIONS
Ebbe Jns, FLS Laboratory, Denmark, and Omar
Rabia, Institute of Chemical Engineering, Technical
University of Denmark, present the results of a
novel laboratory method, developed to simulate the
preheater expulsion of two characteristic volatile
and combustible constituents form raw meals.
FOR THE SPANISH TRANSLATION PLEASE REFER
TO THE SPECIAL SECTION AT THE BACK OF THE ISSUE

Abstract

It is difficult to simulate in a laboratory the expulsion of volatile and

combustible raw meal constituents
from the preheater due to the complex combination of heating sequence and atmosphere that exists
in actual production. It is obvious
that the rate of heating is important,
since slow reactions at low temperatures may differ qualitatively
from faster reactions at higher temperatures.
Three types of reaction
occur:volatilisation, gas reactions
and solid-gas reactions. An innovative isothermal drop reactor was
used to study high temperature
volatilisation and solid gas reactions while keeping gas reactions
at a low level.
It was found that CO and VOC
emissions were hard to predict
from the raw meal composition,
while the emissions of NO and SO2
were more closely related to the
content of nitrogen and sulfide in
the raw meal. Results form the
analysis of two characteristic raw
meals are described in detail.

Introduction

A growing number of publications

are
dealing
with
the
characterisation and effects of organic compounds in cement raw
materials. The main focus is on
three issues: the influence on stack
emissions 1-3; the influence on process heat requirement4; and the
use of raw materials as cement additives5 . Better understanding of

these issues may

also support the
development of
processes and
equipment that
reduce emission
levels.

Figure 1. Calculated heating rates of raw meal in a typical suspension preheater (SP) and an in line Calciner (ILC) cement
plant

The above mentioned issues

require knowledge of the type and
quantity of the organic carbon, organic hydrogen, nitrogen and sulfides present in the raw meal. It is
important to consider under what
conditions they evaporate and
where and into what they oxidise
when exposed to the conditions
that exist in a cement plant
preheater.
The actual raw meal heating
sequence in a cement kiln
preheater is a complex function of
time, temperature and atmosphere which is difficult to simulate under controlled laboratory
conditions. The characteristic features are the stepped time-temperature curve, the short overall
retention time and the special
composition of the atmosphere. It
is common to simulate such a reactor by heating the raw meal in a

WORLD CEMENT May 1999

boat placed in a furnace flushed with

a carrier gas. Heating rates vary form
10- 200 oC/min, far below the actual
heating rate in the preheater which exceeds 1000 oC/min (Figure1).
An isothermal drop furnace was
used to study the influence of heating
rate on the expulsion of gaseous components from the raw meal. The raw
meal is dropped into a filter bed
placed in furnace that is heated to the
desired temperature for measuring. A
carrier gas carries the expelled gases
to consecutive analysers.

Characterisation
of the raw meals

The reactor has been used to study

raw meals form all parts of the world.
This article examines the results of
testing two raw meals, both relatively
rich in organic hydrocarbons and both
composed of natural geological raw

Figure 2. Measurement of organic hydrogen and carbon by heating in

horizontal tube furnace, flushed with N2 and O2 respectively. (Leco RC
412.)

materials. The relevant chemical

analyses are shown in Table 1.
In RC 412, the raw meals are
heated at the rate of 200 oC/min to
900 oC in nitrogen and oxygen
respectively. Organic carbon in
detected as the difference in emitted CO2 and Organic hydrogen as
the difference in emitted water in
the two atmospheres; both gases
are measured in IR-cells. It is difficult to determine organic hydrogen, since the results appear as
number (Figure 2).

Isothermal drop furnace

The isothermal drop furnace

was based on a reactor developed
in co-operation with the CHEC
Research Center at the Technical
University of Denmark6,7. It consists
of a vertical quartz glass tube
placed in a tube furnace. The raw
meal sample can be dropped in the
reactor form a small bin placed on
the top. The raw meal falls into a
bed and is rapidly heated to the
furnace temperature. The reactor
outlet is directly connected to a
heart traced silicone tube.
The rate of heating the raw

Figure 3. Plot of crude data from measurment using

0.2 g of raw meal 1 at 850 oC (Carrier gas : 5% O2
27% CO2 in N2)

meal to the furnace temperature was

estimated by placing a naked thermocouple directly in the bed. A temperature drop of 6 and 14 oC, respectively, was observed after adding 0.2 and 0.5 g of raw meal.
The gas volume form bed to furnace exit is approximately 20 cm3.
This corresponds to a gas retention
time form bed outlet to furnace outlet
of 0.5 seconds with 1 l/min carrier gas
at 600 oC. This means that most of
the gas phase reactions that might occur in an actual preheater are unaccounted for in the test set-up.

Analyser set-up

The analyser set-up used for

these measurements was of a provisional nature, consisting of portable instrument designed for field
work. The specifications are shown
in Table 2.
The gas is taken to the VOC
analyser through heat traced tube
(170 oC). After the VOC analyser, the
gas is cooled to condense water before it is taken to the IR cells. The
logging frequency is 1 Hz. Most experiments were made with 1.0 l/min
carrier gas of the following composition: 5%O 2,27%CO 2 in N 2 .

Treatment of crude
measurement data

The results of a typical experiment

are shown in Figure 3. The signals
form the various detectors arrive in
consecutive order: the VOC signal
first, followed by simultaneous CO
and SO2 signals the NO signal, and
finally the O 2 signal which is
further delayed due to the slow
response of the electrochemical
cell.
The crude data is treated as follows: adjustment for difference in
time lags in made based on injected pure gases. The adjusted
signals are integrated over different
time periods and presented as a
function of time and temperature.
All data is stated relative to the total content in the sample: VOC and
CO are stated as a percentage of
the total organic carbon content.
No is related to the nitrogen content and SO2 to the sulfide content.
The trend curves in the figures are
indicative only and based on third
degree polynomial fit. Most measurements are averages of duplicates.

VOC results

After several experiments,

brown coatings were observed on
the internal reactor walls at the
furnace exit. CH2CL2 extracts form
the coatings showed an unspecified content of carbon. It was concluded that the coatings were
caused by condensation of
volatilised fragments of the organic
carbon in the raw meal. This implies
that not all volatilised hydrocarbons
WORLD CEMENT May 1999

Figure 5. This shows the accumulated expulsion after 20 seconds and

the total expulsion at infinite time.
Raw meal 1 shows much faster expulsion at much lower temperature
than raw meal 2. The difference decreases at higher temperatures.

NO results

Figure 4. Released VOC as a function of the temperature of raw meals 1 and 2 in 5% O2 27% CO2 in N2

Figure 5. Accumulated CO release after 20 seconds and after end of test. Carrier gas 5%
O2 and 27% CO2 in N2

were detected by the VOC analyser

although the piping was carefully
heated to 170 oC from furnace exit
to analyser entrance. It has not
been possible to quantity the
amount of condensed carbon, and
it appears likely that measurement
in real preheaters will suffer the
same difficulty.
The time response of the VOC
signal at higher temperatures had
the same shape as the response
from injected sample of CH4. This
indicates that the VOC signal is primarily related to instantaneous
volatilisation. The VOC results for
the two raw meals are shown in figure 4, presented as described in
the previous section. The similarities and differences between the
two groups of curves are striking.
The curves are bell shaped with a
peak temperature at approximately

600 - 700 oC but the size of the signal

varies considerably, from a maximum
of 5% of raw meal TOC (total organic
carbon) to only 0.8% as maximum.
The comparison is somewhat improved if the VOC expulsions are regarded as relative to the content of
organic hydrogen, but there is still a
significant difference. It is obvious that
the organic hydrocarbons in the raw
meals are quite different.

CO results

The time response of the CO signal is

much slower than that of the VOC signal. This indicates a solid gas reaction where the kinetics are related to
the character of the solid carbon. The
CO signal as a function of time may
differ considerably from raw meal to
raw meal, which is also the case for
raw meals 1 and 2 as shown in
WORLD CEMENT May 1999

The NO emissions are related to

the content of nitrogen in the raw
meals. The response for the two raw
meals is identical within the uncertainty margin of the experiments: The
NO release starts at approximately
600 oC at which point the VOC signal begins to decrease. It remains
at the same level form 750 oC to the
maximum temperature reached during the experiments. The results with
raw meals 1 and 2 shown in Figure 6.
The raw meal NOx reaches approximately 50% of the total nitrogen
content of the raw meal at high temperatures. This would correspond to
a preheater emission of 150 - 200
ppm NO if the maximum expulsion
measured in the test set-up were
found as preheater emission in practice. This, however, is far from
proved, and preliminary experiments
with NO containing carrier gas show
that a complicated combination of
NO reduction and emission is to be
expected in practice.

SO2 results

The SO2 expulsions measured are

similar to those observed in practice8.
The expulsion observed is related to
the sulfide content of the raw meals
in Figure 7. The temperature expulsion curves are bell- shaped with a
maximum expulsion at=600 oC up
to 50% of the sulfide content. The
expulsion is well understood as a
combination of combustion of sulfides (such as pyrite) and partial absorption by the raw meal of the SO2
formed:
FeS2 +O2 = FeS + SO2
CaCo3 + SO2+ O2 = CaSO4 + CO2

Oxygen consumption

The oxygen consumption can be

used to establish a mass balance
for the multiple reactions occurring in the reactor. The mass balance will only tally if combustion
of organic hydrogens in taken into
consideration since the hydrogen

carbon atomic ratio often exceeds

1(Table 1).

Discussion

The aim of future efforts is to relate the results for the test set-up to
actual emission from preheaters in
operation. The ultimate goal is to
directly simulate or at least perform
a model of actual emission. This
may not be an easy especially if absorption effect are also to be modelled.
As previously mentioned the
main drawback of the present test
setup is the low gas retention time
at increased temperature. This can
easily be set right. It is ore difficult
to operate the test setup with the
right high moisture carrier gas including minor constituents like
NOx, SOx and chlorides. Some of
the real constituents have already
shown their influence in preliminary
tests.
The strength of the test setup is
that ut visualises high temperature
reactions which at lower heating
rates are easily asked by low temperature reactions of a qualitatively
different character. The isothermal
drop reactor offers insight into
preheater reactions that probably
cannot be studied in reactors with
slow heating rates.

Figure 6. Total NO expulsion as a function of temperature. Carrier gas 5% O2 and 27%

CO2 in N2

Conclusion

The expulsion of VOCs and CO

is not a simple function of the content of organic carbon in the raw
meal. The content of organic hydrogen is a better marker for the
emission.
The CO formation is slow when
compared to the heating rate in a
preheater. This explains why some
raw meals with a considerable content of organic carbon generate
little CO emission.
Raw meal NOx, parallel with
fuel NOx, and thermal NOx, seems
to be a real factor in preheated NO
emission.
The SO2 expulsion in the test
setup reproduces the results obtained in practice.
The large oxygen consumption
particularly during tests at high temperature can be explained form a
considerable content of hydrogen

Figure 7. Total SO2 expulsion as a function of temperature. Carrier gas 5% O2 and 27%
CO2 in N2

in raw meals, often present at the

atomic ratio 1:1 between organic carbon and hydrogen.

Acknowledgment

The authors wish to acknowledge

the fruitful discussions with Lars
Skaarup Jensen and the useful ideas
received form him.

References
1

SADOWSKY ,U.,
KUHLMANN K. and
SCHNEIDER,
M.,
Entstehung
von
kohlenmonoxid aus den organischen
Bestandteilen des Rohmaterials bei der
Zementherstellung.
ZKG
International,
(50) 5/1997 p.272
SHKOLNIK , E and MACGREGOR MILLER,
F, Differential scanning calorietry for
deternining the volatility and combustibility of cement raw meal, World Cement
Reasearch cnd Development, May 1996.

WORLD CEMENT May 1999

3
4
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6
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SIDHU, S and DELLINGER, B., Contribution

of Cement Kiln Ras Meal Organics to PIC
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JNS, E and HUNDEBOL S Die
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SPRUNG S and SIEBEL E Beurteilunhg der
Eignschaften
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Kalakstein
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(PKZ) ZKG International (44)1/1991.
JENSEN, L.S., NOx from cement production
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Technical University of Denark, 1998.
JOHNSSON, J.E. et al., Decomposition
and reduction of N2O over liestone
under FBC conditions, Proceedings of the
14th international conference on Fluidised
Bed Cobustion, 1997 p, 953-966
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