CemNet Training - Course CKPC01

Module 3.4 - Dioxins

Cement Kiln
Process Chemistry
Module 3. Emissions from cement kilns.
3.4 Dioxins and furans.

Cement Kiln Chemistry

3.4 Dioxins

At the outset of this session we should reiterate that the likelihood of

dioxin emissions from cement kilns is remote... ...a minimum
of three preconditions must be met for their formation.
The issue of dioxin and furan emissions has arisen from the
trend to burning alternative fuels in cement kilns.
Municipal waste incinerators have been identified as point
sources of dioxin and furan emissions .cement kilns
burning such alternative fuels are in direct competition with
these incinerators for the fees to burn such fuels.
The operators of waste incinerators therefore argue that cement
kilns should be subject to the same scrutiny and emissions limits
as incinerators .despite cement kilns having multiple
advantages over incinerators for the disposal of such wastes.

Cement Kiln Chemistry

3.4 Dioxins

At the outset of this session we should reiterate that the likelihood of

dioxin emissions from cement kilns is remote... ...a minimum
of three preconditions must be met for their formation.
However, based on the UK Environment Agency data for 1999
five UK cement sites were in the top 30 sources of dioxin
emissions.
The highest dioxin emission from a cement site was 1.5 grams
per year.
.from cement factories producing
~500,000 tonnes of clinker per year.
Despite these low levels of emission, dioxins are one the dirty
dozen chemicals targeted for global phase-out or severe
reduction under the persistent organic pollutants (POPs)
international treaty.

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 3.4 - Dioxins

3.4 Dioxins

At the outset of this session we should reiterate that the likelihood of

dioxin emissions from cement kilns is remote... ...a minimum
of three preconditions must be met for their formation.
However, based on the UK Environment Agency data for 1999
five UK cement sites were in the top 30 sources of dioxin
emissions.
The highest dioxin emission from a cement site was 1.5 grams
per year.
.from cement factories producing
~500,000 tonnes of clinker per year.
Under the treaty comprehensive abatement measures have to be
taken to eliminate these dioxin emissions.

Cement Kiln Chemistry

3.4 Dioxins

The reason dioxins and furans have been targeted under the POPs
treaty is that they are carcinogenic, mutagenic and teratogenic.
.they may be cancer forming, may cause generic mutations, or
may cause modification of foetal tissue.
Once emitted into the environment they are also persistent..
.they are poorly soluble in water. .not very volatile...
..and adsorb strongly to particles and surfaces.
They are stable in the environment and accumulate in the fatty
tissues of animals and humans.

Cement Kiln Chemistry

3.4 Dioxins

The reason dioxins and furans have been targeted under the POPs
treaty is that they are carcinogenic, mutagenic and teratogenic.
.they may be cancer forming, may cause generic mutations, or
may cause modification of foetal tissue.
There are 75 dioxins .compounds similar to
dichlorobenzo dioxin (CDD) .and 135 furans,
compounds similar to dichlorobenzofuran.
They are polychlorinated dibenzodioxins (PCDDs) and
polychlorinated dibenzofurans (PCDFs).

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 3.4 - Dioxins

3.4 Dioxins

The reason dioxins and furans have been targeted under the POPs
treaty is that they are carcinogenic, mutagenic and teratogenic.
.they may be cancer forming, may cause generic mutations, or
may cause modification of foetal tissue.
There are 75 dioxins .compounds similar to
dichlorobenzo dioxin (CDD) .and 135 furans,
compounds similar to dichlorobenzofuran.
The best known examples are tetrachlorodibenzodioxin (TCDD)
. and tetrachlorodibenzofuran (TCDF).
Cl

Cl Cl

Cl

Cl Cl

Cement Kiln Chemistry

Cl
O

Cl

3.4 Dioxins

There are two mechanisms for the formation of dioxins and furans in
thermal processes.
Homogenous gas phase pyrolytic reactions of chlorinated
organic compounds in the temperature range 200~800C.
Combustion of fuels in both the main burner and precalciner of a
cement kiln is at temperatures above this range ..however,
in precalciners or secondary burners in the preheater only just
above this temperature range.
Halogenated hydrocarbons might not be fully decomposed when
fired in precalciners or secondary burners, therefore such fuels
should only be fired in the main burner of a cement kiln where
dioxin formation by this mechanism cannot take place.

Cement Kiln Chemistry

3.4 Dioxins

There are two mechanisms for the formation of dioxins and furans in
thermal processes.
A greater potential concern is the chlorination of non-chlorinated
organic compounds by inorganic chloride compounds (HCl or
NaCl) via a suitable transition metal catalyst.
So-called de Novo synthesis of dioxins.. this can
take place in the temperature range 200~450C by
heterogeneous reaction between combustion gases and particle
surfaces.

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 3.4 - Dioxins

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
Firstly the presence of unburnt hydrocarbons in the exhaust
..which in themselves need to be avoided because
gas.
of their potential for smog formation. ..as discussed in the
previous session this is best avoided by eliminating any raw
materials containing organic compounds from the kiln feed...
.such materials should be delivered directly to precalciners
or the kiln inlet at the base of the preheater.
Secondly there must be inorganic chloride compounds (HCl or
..we have already
NaCl) in the kiln exhaust gases.
seen in sessions 1.7 and 1.8 that chlorides do build up in an
external cycle between the preheater and the exhaust gas
cleaning equipment....this cannot be avoided.

Cement Kiln Chemistry

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
Firstly the presence of unburnt hydrocarbons in the exhaust
..which in themselves need to be avoided because
gas.
of their potential for smog formation. ..as discussed in the
previous session this is best avoided by eliminating any raw
materials containing organic compounds from the kiln feed...
.such materials should be delivered directly to precalciners
or the kiln inlet at the base of the preheater.
Thirdly there must be the presence of a suitable transition metal
..a
catalyst. ..usually copper as CuCl or CuCl2..
metal that might well be present in some of the process
equipment.

Cement Kiln Chemistry

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
Avoiding the presence of unburnt hydrocarbons in the exhaust
..is therefore the best defense against dioxin
gas.
..backed up by
formation by de Novo synthesis.
ensuring that the exhaust gases are rapidly cooled through the
temperature window of 450~200C in which de Novo
synthesis of dioxins can take place.
This requirement for rapid cooling of the exhaust gases through
this temperature window is worth thinking about ...concerns
regarding de Novo synthesis of dioxins are a relatively new
development... ..the process design of many kilns will not
have taken this into consideration.

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 3.4 - Dioxins

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
Avoiding the presence of unburnt hydrocarbons in the exhaust
..is therefore the best defense against dioxin
gas.
..backed up by
formatio by de Novo synthesis.
ensuring that the exhaust gases are rapidly cooled through the
temperature window 450~200C in which de Novo synthesis
of dioxins can take place.
When electrostatic precipitators are used for exhaust gas dedusting
the gases are usually cooled to below 200C by evaporative
cooling with water in a conditioning tower ..hot dry
electrostatic precipitators, air-to-exhaust gas heat exchangers,
or alkali bypasses might involve the exhaust gases being more
slowly cooled through the critical temperature window.

Cement Kiln Chemistry

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
Avoiding the presence of unburnt hydrocarbons in the exhaust
..is therefore the best defense against dioxin
gas.
..backed up by
formatio by de Novo synthesis.
ensuring that the exhaust gases are rapidly cooled through the
temperature window 450~200C in which de Novo synthesis
of dioxins can take place.
These concerns should not be taken out of context ..dioxin
formation in cement kiln exhaust is an extremely unlikely
..which can be avoided by complete
event.
combustion of organic compounds in fuels and feed within the
process.

Cement Kiln Chemistry

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
If dioxins are present in the exhaust gases from a cement kiln
then very expensive end-of-pipe solutions need to be
applied. ..cleaning the exhaust gases of dioxins prior to
their exhaust from the process.
This can be achieved in an
activated carbon filter
..or by catalytic oxidation on
a vanadium or tungsten oxide
catalyst supported by an
alumina or titania substrate.

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 3.4 - Dioxins

3.4 Dioxins

There are therefore three precursors required for dioxin formation in

cement kiln exhaust gases by de Novo synthesis.
If dioxins are present in the exhaust gases from a cement kiln
then very expensive end-of-pipe solutions need to be
applied. ..cleaning the exhaust gases of dioxins prior to
their exhaust from the process.
This can be achieved in an
activated carbon filter
..the need for the application
of such expensive technologies
can be avoided by process
design.

Cement Kiln
Process Chemistry
Module 3. Emissions from cement kilns.
3.4 Dioxins and furans.

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