CemNet Training - Course CKPC01

Module 3.7 SO2 Abatement

Cement Kiln
Process Chemistry
3. Cement kiln emissions
3.7 SO2 emissions and their abatement.

Cement Kiln Chemistry

3.7 SO2 Emissions

In session 3.5 we saw that formation of acid rain is one the primary
..this
reasons to reduce NOx emissions from cement kilns..
is also the main driver behind tightening regulations on SO2
emissions from cement kilns.
Cement companies operating in the
European Union and North
America are gradually applying
expensive technologies to reduce
SO2 emissions.
Sulphur enters cement kilns in either the raw materials or the
fuels used to fire the kilns.. ..however, the principal
cause of SO2 emissions from cement kilns is the presence
of sulphides in the raw materials, rather than sulphur
compounds in the fuels.

Cement Kiln Chemistry

3.7 SO2 Emissions

Sulphur compounds contained in the fuels used to fire cement kilns

do not usually result in SO2 emissions in the kiln exhaust.
Feed
Sulphur compounds in the fuels are
oxidised to SO2 by the combustion
reactions in the kiln or precalciner.
S + O2 SO2
In precalciners the acidic SO2 immediately
encounters alkaline CaO and forms
calcium sulphite and sulphate..

Fuel

SO2 + CaO CaSO3 + O2 CaSO4

..which is then carried back into the kiln with the feed
building up into a sulphate cycle in the kiln.

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CemNet Training - Course CKPC01

Module 3.7 SO2 Abatement

3.7 SO2 Emissions

Cement Kiln Chemistry

Sulphur compounds contained in the fuels used to fire cement kilns

do not usually result in SO2 emissions in the kiln exhaust.
Feed
Sulphur compounds in the fuels are
oxidised to SO2 by the combustion
reactions in the kiln or precalciner.
S + O2 SO2
SO2 from the main burner comes into
intimate contact with alkaline CaO in the
lower stages of preheaters and again forms
calcium sulphite and sulphate.

Fuel

SO2 + CaO CaSO3 + O2 CaSO4

SO2 from fuels is therefore completely
retained in the process.

Cement Kiln Chemistry

SO2

3.7 SO2 Emissions

Sulphur compounds contained in the fuels used to fire cement kilns

do not usually result in SO2 emissions in the kiln exhaust.
Sulphur compounds in the fuels are
oxidised to SO2 by the combustion
reactions in the kiln or precalciner.
S + O2 SO2
In long kilns there is not the same degree
of intimate contact between SO2 and
alkaline CaO as in preheaters and
therefore fuel sulphur compounds can
result in SO2 emissions.
SO2

Cement Kiln Chemistry

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2

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 3.7 SO2 Abatement

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2
Some will be absorbed by
CaCO3 in the raw mill to
form calcium sulphite..
SO2 + CaCO3
CaSO3 + CO2
This calcium sulphite, CaSO3, is readily oxidised to calcium
sulphate, CaSO4.
CaSO3 + O2 CaSO4

Cement Kiln Chemistry

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2
Some will be absorbed by
CaCO3 in the raw mill to
form calcium sulphite
..and is returned to
the kiln in the kiln feed.
Forming an external
cycle between the
preheater and the raw
mill.

Cement Kiln Chemistry

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2
Some will be absorbed by
CaCO3 in the raw mill to
form calcium sulphite
..and is returned to
the kiln in the kiln feed.
However, adsorption of SO2 in the raw mill is 80% at
best... ..adsorption rate falls off if the moisture content of
the material in the mill is below 15%.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2
Some will be absorbed by
CaCO3 in the raw mill to
form calcium sulphite
..and is returned to
the kiln in the kiln feed.
When the raw mill is stopped and the kiln exhaust gases pass
directly to the dedusting equipment the adsorption of SO2 is
drastically reduced... ..and emissions rise dramatically.

Cement Kiln Chemistry

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2
Some will be absorbed by
CaCO3 in the raw mill to
form calcium sulphite
..and is returned to
the kiln in the kiln feed.
These are the circumstances that demand deployment of
expensive SO2 emission abatement technologies. many
cement factories do not have sulphides in their raw
materials and do not face these SO2 emission problems.

Cement Kiln Chemistry

3.7 SO2 Emissions

As we saw in session 1.7 sulphides in the kiln feed will oxidise in

..and are lost as
the upper stages of the preheater..
gases (SO2) in the
preheater exhaust gas.
S2- + O2 SO2
Some will be absorbed by
CaCO3 in the raw mill to
form calcium sulphite
..and is returned to
the kiln in the kiln feed.
For those cement factories that do have sulphides in their raw
materials the best solution is to feed these materials directly
the same solution as for raw
to the precalciner.
materials containing organic carbon compounds.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

SO2 abatement technologies for cement kilns fall into two broad
categories... ..in process or ex-process solutions.
Ex-process solutions are also referred to as end-of pipe
..the SO2 content of the exhaust gases is
solutions...
reduced at the end of the process.
In-process solutions are generally less expensive to install or
operate than ex-process solutions... ..but are only
applicable in certain situations and for limited levels of SO2
emission.

Cement Kiln Chemistry

3.7 SO2 Emissions

Slaked lime, (Ca(OH)2, adsorbent addition is the most commonly

applied in-process solution.
The slaked lime can be added to
Ca(OH)2
kiln feed.. ..or injected into
the preheater.
Slaked lime does not have a high reactivity
therefore a molar ratio of 3~6 for
Ca(OH)2/SO2 is required to achieve
60~80% SO2 emission reduction.

Ca(OH)2

If SO2 emissions are above 1200 mg/m3 the

amounts of slaked lime required and the
attendant costs are likely to be prohibitive.
SO2

Cement Kiln Chemistry

3.7 SO2 Emissions

Slaked lime, (Ca(OH)2, adsorbent addition is the most commonly

applied in-process solution.
The slaked lime can be added to
Ca(OH)2
kiln feed.. ..or injected into
the preheater.
Slaked lime does not have a high reactivity
therefore a molar ratio of 3~6 for
Ca(OH)2/SO2 is required to achieve
60~80% SO2 emission reduction.
However, the addition of slaked lime can
be applied intermittently to reduce peak
SO2 emissions... ...such as when the
raw mill is stopped.

Ca(OH)2

SO2

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CemNet Training - Course CKPC01

Cement Kiln Chemistry

Module 3.7 SO2 Abatement

3.7 SO2 Emissions

Envirocare have patented a method of reducing SO2 emissions that

involves injection of micro-fine lime into the conditioning tower
water.
Conditioning tower water injection
rates rise when raw mills are
stopped and SO2 emissions are
likely to rise therefore this solution
matches the SO2 emission
reduction requirements of the
process.
However, high wear rates on the conditioning tower water
more
injection nozzles have been reported
information on this technique is required.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
The Untervaz factory of Holcim in
Switzerland has installed a dry
scrubber supplied by Lurgi.
A venturi reactor column produces as
fluidised bed of slaked lime and kiln
feed, resulting in intimate contact
between SO2 and adsorbent at close to
the dew point temperature with long
residence time. ..resulting in up to 90% reduction of
SO2 emissions.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
The Untervaz factory of Holcim in
Switzerland has installed a dry
scrubber supplied by Lurgi.
The gases exiting the venturi are
cleaned of adsorbent in an electrostatic
precipitator. ...with the collected
adsorbent partially returned to the
column and partially directed to the kiln
inlet. ..where all sulphur compounds will be
retained in the process and discharged in the clinker.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Wet scrubbers are more commonly
applied for reducing SO2 emissions in
power station and cement factory
exhausts (although this is not yet
common in cement manufacturing).
SO2 is absorbed in a liquid slurry
containing finely ground limestone,
CaCO3, that is sprayed in countercurrent to the gas flow.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Wet scrubbers are more commonly
applied for reducing SO2 emissions in
power station and cement factory
exhausts (although this is not yet
common in cement manufacturing).
Calcium sulphite, CaSO3, is formed and
the slurry is collected in a recycle tank
at the bottom of the scrubber, where the
sulphite is oxidised to gypsum,
CaSO4.2H2O.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Wet scrubbers are more commonly
applied for reducing SO2 emissions in
power station and cement factory
exhausts (although this is not yet
common in cement manufacturing).
After separation the gypsum is used in
cement milling and the water is
recycled to the spray tower.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Wet scrubbers are more commonly
applied for reducing SO2 emissions in
power station and cement factory
exhausts (although this is not yet
common in cement manufacturing).
SO2 emissions are reduced by up to
90% to less than 200 mg/m3, from peak
values in excess of 2000 mg/m3 at the
inlet.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Wet scrubbers are more commonly
applied for reducing SO2 emissions in
power station and cement factory
exhausts (although this is not yet
common in cement manufacturing).
The cleaned gases have to be reheated
to above their dew point before
...this
exhausting to atmosphere
can achieved by mixing with cooler
exhaust air.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
An alternative to wet or dry scrubbers
are activated carbon filters such as
installed at the Siggenthal factory of
Holcim, Switzerland.
Deactivated coke is extracted from the
bottom of the filter and activated coke
is charged from the top ...the deactivated coke is then burnt
as an alternative fuel on the kiln.
At Siggenthal SO2 emissions are reduced by 90% to less
than 50 mg/m3 from maximum at the inlet of 600 mg/m3.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
An alternative to wet or dry scrubbers
are activated carbon filters such as
installed at the Siggenthal factory of
Holcim, Switzerland.
Activated carbon filters will not only
clean SO2 from the exhaust gases
...volatile organic compounds (VOCs), dioxins, metals,
ammonia and ammonium compounds, HCl and HF will
also be removed in addition to any residual dust.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
An alternative to wet or dry scrubbers
are activated carbon filters such as
installed at the Siggenthal factory of
Holcim, Switzerland.
Activated carbon filters will not only
clean SO2 from the exhaust gases
...this is in fact a general advantage of these end-of-pipe
emission reduction technologies... ...a wet scrubber will
also significantly reduce HCl, metal, ammonia and
residual dust emissions.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
An alternative to wet or dry scrubbers
are activated carbon filters such as
installed at the Siggenthal factory of
Holcim, Switzerland.
Activated carbon filters will not only
clean SO2 from the exhaust gases
...dedusting of the gases prior to these filters is a requirement
...however there are
to prevent blinding of the filters...
end-of-pipe technologies available that combine
dedusting with SO2 removal.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Filsorption systems combine absorbent
injection with bag filters.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Filsorption systems combine absorbent
injection with bag filters.
An absorbent mixer/humidifier can be
installed beneath a bag filter or
electrostatic precipitator.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Filsorption systems combine absorbent
injection with bag filters.
An absorbent mixer/humidifier can be
installed beneath a bag filter or
electrostatic precipitator.
These end-of-pipe emission abatement technologies seem
certain to find wider application in cement manufacturing as
...and
emissions regulations continue to tighten
pressure to apply best available technology, BAT,
increases.

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 3.7 SO2 Abatement

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Filsorption systems combine absorbent
injection with bag filters.
An absorbent mixer/humidifier can be
installed beneath a bag filter or
electrostatic precipitator.
These end-of-pipe emission abatement technologies seem
certain to find wider application in cement manufacturing as
...the growing
emissions regulations continue to tighten
trend of burning alternative fuels invites this pressure.

Cement Kiln Chemistry

3.7 SO2 Emissions

If SO2 emissions are above 1500 mg/m3 then an end-of-pipe solution

these
becomes the most economic solution
involve some type of scrubber to clean the exhaust gases of SO2
before discharging to atmosphere.
Filsorption systems combine absorbent
injection with bag filters.
An absorbent mixer/humidifier can be
installed beneath a bag filter or
electrostatic precipitator.
The advantage of these end-of-pipe technologies in solving
multiple potential trace emission problems from cement kiln
exhausts is particularly relevant to the emissions we will
discuss in the final sessions of the module 3 ...plumes,
blue hazes and heavy metals.

Cement Kiln
Process Chemistry
3. Cement kiln emissions
3.7 SO2 emissions and their abatement.

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