CemNet Training - Course CKPC01

Module 3.3 CO Sources

Cement Kiln
Process Chemistry
Module 3. Emissions from cement kilns.
3.3 CO and volatile organic carbon
compounds (VOCs).

Cement Kiln Chemistry

3.3 CO & VOCs

In session 2.8 we saw that mixing of the combustion air and fuel in a
cement kiln flame relies on jet entrainment of the secondary
combustion air into the flame.
With a recirculating flame oxidising burning conditions can be guaranteed
with a small excess of air above that required for combustion. .as
little as 1~2% oxygen at the
kiln inlet.
Without recirculation the
mixing of secondary air and
fuel is inadequate and
reducing burning conditions
and CO can be present at
4~5% oxygen at the kiln
inlet.

Cement Kiln Chemistry

3.3 CO & VOCs

Combustion of hydrocarbon fuels in a cement kiln flame takes

place by a series of free radical reactions in the gas phase.
At the temperatures in the flame the
bonds in the hydrocarbon
molecules in the fuel are broken to
yield free radicals with unpaired
electrons.
These free radicals then react very
quickly in a series of chain
reactions.

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CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

Combustion of hydrocarbon fuels in a cement kiln flame takes

place by a series of free radical reactions in the gas phase.
The following reactions take place
in the cement kiln flame:
OH + O

1.

H + O2

2.

CnHm + O Cn-1Hm + CO

3.

CO + OH CO2 + H

4.

2CO + O2 + M 2CO2 + M

5.

H2O + O

6.

2C + O2

Cement Kiln Chemistry

2OH

2CO

3.3 CO & VOCs

OH + O

Reaction 1 is critical:

1.

H + O2

As it produces the OH
radicals that react with
CO formed in reactions
2 and 6.

2.

CnHm + O Cn-1Hm + CO

3.

CO +OH CO2 + H

6.

2C + O2

Sufficient oxygen must

be available in the
flame for reaction 1.

2CO

If not then CO and reducing conditions will be present.

Cement Kiln Chemistry

3.3 CO & VOCs

OH + O

Reaction 1 is critical:

1.

H + O2

As it produces the OH
radicals that react with
CO formed in reactions
2 and 6.

2.

CnHm + O Cn-1Hm + CO

3.

CO +OH CO2 + H

4.

2CO + O2 + M 2CO2 + M

6.

2C + O2

Sufficient oxygen must

be available in the
flame for reaction 1.

2CO

Cannot rely on reaction 4 to consume CO as it is 100x slower than

reaction 3 and is not significant in avoiding reduction.

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CemNet Training - Course CKPC01

Cement Kiln Chemistry

3.3 CO & VOCs

OH + O

Reaction 1 is critical:

1.

H + O2

As it produces the OH
radicals that react with
CO formed in reactions
2 and 6.

2.

CnHm + O Cn-1Hm + CO

3.

CO +OH CO2 + H

4.

2CO + O2 + M 2CO2 + M

6.

2C + O2

Sufficient oxygen must

be available in the
flame for reaction 1.

Module 3.3 CO Sources

2CO

With a recirculating flame and some excess oxygen at the kiln

inlet then good mixing can be guaranteed and CO should not be
formed in the main burner flame.. ..provided that there is
consistent delivery of fuel to the burner.

Cement Kiln Chemistry

3.3 CO & VOCs

OH + O

Reaction 1 is critical:

1.

H + O2

As it produces the OH
radicals that react with
CO formed in reactions
2 and 6.

2.

CnHm + O Cn-1Hm + CO

3.

CO +OH CO2 + H

4.

2CO + O2 + M 2CO2 + M

6.

2C + O2

Sufficient oxygen must

be available in the
flame for reaction 1.

2CO

With a recirculating flame and some excess oxygen at the kiln

inlet then good mixing can be guaranteed and CO should not be
formed in the main burner flame.. ..an accurate and
consistent feeder, plus correctly designed storage and
pneumatic delivery lines are critical for solid fuels.

Cement Kiln Chemistry

3.3 CO & VOCs

OH + O

Reaction 1 is critical:

1.

H + O2

As it produces the OH
radicals that react with
CO formed in reactions
2 and 6.

2.

CnHm + O Cn-1Hm + CO

3.

CO +OH CO2 + H

4.

2CO + O2 + M 2CO2 + M

6.

2C + O2

Sufficient oxygen must

be available in the
flame for reaction 1.

2CO

With a recirculating flame and some excess oxygen at the kiln

inlet then good mixing can be guaranteed and CO should not be
formed in the main burner flame.. ..for fuel oils the heating
system to reduce viscosity and the atomisation of the fuel
at the burner tip are critical.

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CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

A consistent flow of fuel, matched to the requirements of the

process is the primary requirement.
Feeding discrete slugs of fuel
into the kiln such as the burning
of whole motor tyres violates
this requirement.
Increased incidence of CO in
the kiln exit gases is inevitable
when whole motor tyres are
being burnt.

Cement Kiln Chemistry

3.3 CO & VOCs

Monitoring and minimising CO in the kiln exhaust gases is

particularly critical when electrostatic precipitators are used for
exhaust gas dedusting.. the presence of CO is used as
an indicator of incomplete combustion of the fuel in the kiln and the
possible presence of volatile organic compounds in the exhaust gas.
If present these volatile organic
compounds can cause an
explosion in the precipitator.
.therefore the high voltage is
switched off the precipitator to
avoid a possible explosion.
Resulting in a period of high dust
emission while the gases are
exhausted without dedusting.

Cement Kiln Chemistry

3.3 CO & VOCs

Monitoring and minimising CO in the kiln exhaust gases is

particularly critical when electrostatic precipitators are used for
exhaust gas dedusting.. the presence of CO is used as
an indicator of incomplete combustion of the fuel in the kiln and the
possible presence of volatile organic compounds in the exhaust gas.
Many of these precipitator trips
are unnecessary..detection
of CO is subject to a time lag of
~20 seconds.
The high voltage has to be switched off
the precipitator at CO concentrations
much lower than strictly necessary as by
the time the CO is detected the gases will
already be in the precipitator.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
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CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

When alternative fuels are burnt on a cement kiln demanding limits

are placed on the CO emissions, again as an indicator of complete
burnout of the fuels in the kiln.
This use of CO as an
indicator of complete
combustion of the fuel is
defeated if the kiln feed
contains any organic
components.
The kiln exhaust gases will
then contain CO..
..irrespective of whether the fuel has been completely
burned in the kiln or not.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
Volatile organic compounds
begin to be liberated from
organics in the feed as soon as
the feed enters the preheater of a
cement kiln, reaching a peak at
350~400C.
Above 350C the volatile organic
compounds are oxidised to
CO.. ..provided that 3% oxygen is present in the
gases (as it would be expected to be).

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
CO formed by this combustion
of organic components in the
feed is not oxidised to CO2 until
the temperature rises to above
680C.
Complete oxidation of carbon to
CO2 below 680C is inhibited by
the formation of hydroperoxyl
radicals rather than hydroxide
radicals.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
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CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
Below 680C hydroperoxyl
radicals are formed.
H + O2 OOH
These peroxyl radicals then react
with further hydrogen radicals to
form hydroxide radicals..
H + OOH OH + OH
..but the hydroxide radicals then react with further
hydroperoxyl radicals
OH + OOH H2O + O2

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
Below 680C hydroperoxyl
radicals are formed.
H + O2 OOH
These peroxyl radicals then react
with further hydrogen radicals to
form hydroxide radicals..
H + OOH OH + OH
All the radicals are consumed and the chain reactions are
terminated.
OH + OOH H2O + O2

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
Below 680C hydroperoxyl
radicals are formed.
H + O2 OOH
These peroxyl radicals then react
with further hydrogen radicals to
form hydroxide radicals..
H + OOH OH + OH
Availability of hydroxide radicals to react with CO is limited
and oxidation of CO to CO2 is suppressed.
CO +OH CO2 + H

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
The liberation of volatile organic
compounds from the feed as soon
as the feed enters the preheater of
a cement kiln introduces the
possibility of further emissions
problems from cement kilns.
Volatile organic compounds are
themselves subject to stringent
.their presence is also one of
emissions limits..
the precursors for the possible formation of dioxins in
cement kiln exhaust gases.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
We will consider the remote
possibilities of dioxin emissions
from cement kilns in the next
session of the course..
..however, the best way to
avoid these is for any raw
materials containing organic
components not to be included in
kiln feed
.any such raw materials should be fed
directly to the precalciner or kiln inlet where the
temperature is above 680C and complete oxidation to
CO2 will take place.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
As we have seen one of the
major trends in cement
manufacture is the use of
alternative fuels.. ..the range
of materials used is widening to
include a whole class of materials
whose properties are intermediate
between raw materials and
fuels .they have some hydrocarbon and calorific
content and also significant ash content composed of the
primary oxides for cement manufacture, SiO2, Al2O3,
Fe2O3 and CaO.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
As we have seen one of the
major trends in cement
manufacture is the use of
alternative fuels.. ..the range
of materials used is widening to
include a whole class of materials
whose properties are intermediate
between raw materials and
fuels .paper sludges, sewage sludges and rice husks
are all examples of these alternative raw materials/fuels.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
As we have seen one of the
major trends in cement
manufacture is the use of
alternative fuels.. ..the range
of materials used is widening to
include a whole class of materials
whose properties are intermediate
between raw materials and
fuels . In the case of sludges they also contain
significant moisture content and therefore have negative
calorific content combined with hydrocarbon content.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
As we have seen one of the
major trends in cement
manufacture is the use of
alternative fuels.. ..the range
of materials used is widening to
include a whole class of materials
whose properties are intermediate
between raw materials and
fuels . All need to be fed to the precalciner or kiln
inlet to avoid the liberation of volatile organic carbon
compounds in the preheater.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
Volatile organic carbon
compounds are themselves
subject to stringent control
limits.. ..because together
with NOx they are one of the
precursors of urban smog
formation.
We will be devoting an entire session to NOx formation
and abatement of their emissions in cement kiln exhaust
gases.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
Volatile organic carbon
compounds are themselves
subject to stringent control
limits.. ..because together
with NOx they are one of the
precursors of urban smog
formation.
However, before closing the subject of volatile organic
carbon compounds we need to briefly talk about their
detection.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
The US EPA considers any
gaseous organic compound that
undergoes photochemical
reactions to form smog to be a
volatile organic compound
(VOC).. ..this link with
photochemical reactivity
eliminates some organic
compounds that have been shown
to have neglible such activity......methane, ethane,
acetone, chlorinated compounds, chlorofluorocarbons,
hydrofluoro- or hydrochlorofluorocarbons.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
The US EPA considers any
gaseous organic compound that
undergoes photochemical
reactions to form smog to be a
volatile organic compound
(VOC) ....this link with
photochemical reactivity
eliminates some organic
compounds that have been shown
to have neglible such activity......however, most
cement plants measure total hydrocarbons (THCs) because
it is difficult to measure VOCs.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
The US EPA considers any
gaseous organic compound that
undergoes photochemical
reactions to form smog to be a
volatile organic compound
(VOC) ....this link with
photochemical reactivity
eliminates some organic
compounds that have been shown
to have neglible such activity......a flame ionisation
detector is used that cannot differentiate between organic
compounds that show photochemical reactivity.

Cement Kiln Chemistry

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
The US EPA considers any
gaseous organic compound that
undergoes photochemical
reactions to form smog to be a
volatile organic compound
(VOC) ....this link with
photochemical reactivity
eliminates some organic
compounds that have been shown
to have neglible such activity......this means that
cement factories that are measuring THCs are
overestimating their VOC emissions.

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com

CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.3 CO Sources

3.3 CO & VOCs

With organic components in the kiln feed the exhaust gases will
contain CO, irrespective of whether the fuel is completely burned in
the kiln.
That concludes this session of
the course where we have been
discussing the sources of and
solutions to CO and volatile
organic carbon emissions from
cement kilns.
In the next session we will discuss the special case of
dioxin and furan emissions from cement kilns.

Cement Kiln
Process Chemistry
Module 3. Emissions from cement kilns.
3.3 CO and volatile organic carbon
compounds (VOCs).

This document is for the sole use of students enrolled on course CKPC01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd
http://Training.CemNet.com