CemNet Training - Course CKPC01

Module 3.9 Metals Hg & T

Cement Kiln
Process Chemistry
3. Cement kiln emissions
3.9 Heavy metals mercury and thallium.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
With regard to emissions two
heavy metals, mercury, Hg, and
thallium, Tl, attract the greatest
as a
attention..
consequence of their volatility
and their toxicity.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Mercury is the only metal that
is a liquid at room
temperature.. ..meaning
that the metal and the salts of
the metal have high vapour
pressures and volatility.
All mercury compounds in the
feed to a cement kiln will
evaporate in the preheater. ..and be drawn through
the induced draft fan as gases.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Mercury metal vapours are
extremely toxic ..meaning
that emission limits are
restricted to fractions of a
milligram per cubic metre of
cement kiln exhaust.
Mercury is only present as
minute traces in cement raw
..normally the extremely low emission
materials.
limits are not approached, let alone exceeded, in cement
kiln exhausts.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Mercury metal vapours are
extremely toxic ..meaning
that emission limits are
restricted to fractions of a
milligram per cubic metre of
cement kiln exhaust.
Mercury is only present as
minute traces in cement raw
..the emission levels are so low as to be
materials.
at the limits of detection.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Mercury metal vapours are
extremely toxic ..meaning
that emission limits are
restricted to fractions of a
milligram per cubic metre of
cement kiln exhaust.
Alternative fuel burning raises
the possibility of higher
mercury emissions. ..particularly refuse derived fuels
and sewage sludge.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
As mercury exits the preheater
as vapour the temperature
regime along the gas flow path
behind the induced draft fan is
critical for retention of mercury
within the process
.the
critical factor is the temperature
of the gases entering the final
filter ..when operating in combination with drying
raw materials in the raw mill the temperature can be as
low as 90C, just above the dew point of ~77C.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
As mercury exits the preheater
as vapour the temperature
regime along the gas flow path
behind the induced draft fan is
critical for retention of mercury
within the process
.the
critical factor is the temperature
of the gases entering the final
filter ..these low temperatures and the intimate contact
with the raw mill product and dust mean that mercury
compounds condense on the mill product.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
As mercury exits the preheater
as vapour the temperature
regime along the gas flow path
behind the induced draft fan is
critical for retention of mercury
within the process
.the
critical factor is the temperature
of the gases entering the final
filter ..these condensed mercury compounds then
build up into an external cycle between the preheater and
the raw mill.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
As mercury exits the preheater
as vapour the temperature
regime along the gas flow path
behind the induced draft fan is
critical for retention of mercury
within the process
.the
critical factor is the temperature
of the gases entering the final
filter ..when the raw mill is stopped the temperature
entering the final filter rises and the intimate contact with
material in the raw mill is lost.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
As mercury exits the preheater
as vapour the temperature
regime along the gas flow path
behind the induced draft fan is
critical for retention of mercury
within the process
.the
critical factor is the temperature
of the gases entering the final
filter ..mercury emissions to atmosphere therefore rise
when the raw mill is stopped.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
As mercury exits the preheater
as vapour the temperature
regime along the gas flow path
behind the induced draft fan is
critical for retention of mercury
within the process
.the
critical factor is the temperature
of the gases entering the final
filter ..these mercury emissions when the raw mill is
stopped are an effective bleed on the external cycle.
..but can also exceed emission limits.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
The solution to these mercury
emissions when the raw mill is
stopped is an intermittent dust
purge when the raw mill is
running .the level of
recirculating mercury in the
external cycle needs to be
allowed to build up to greater
than the input levels in the feed
and fuels ..then the dust is purged from the system for
a period to bleed mercury out of the external cycle.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
The solution to these mercury
emissions when the raw mill is
stopped is an intermittent dust
purge when the raw mill is
running . ..in that way
the level of mercury circulating
in the external cycle is
controlled and at a sufficiently
low level when the raw mill
stops
..the emissions when the raw mill stops are lower
than the emission limits.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
The solution to these mercury
emissions when the raw mill is
stopped is an intermittent dust
purge when the raw mill is
running . ..intermittent
dust purges are also the means
to control the cycles of
thallium
..along with selection of raw materials that
do not contain this toxic metal.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Thallium is almost as volatile as
mercury .all the thallium
inputs to a cement kiln will
again evaporate in the
preheater. ...measurements in
each stage of preheaters have
shown the greatest concentration
of thallium chloride in the top
..in common with mercury the
stage cyclone..
volatility of thallium is such that none will exit in the
clinker and cycles must be broken in other ways.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Thallium is almost as volatile as
mercury .all the thallium
inputs to a cement kiln will
again evaporate in the
preheater. ...measurements in
each stage of preheaters have
shown the greatest
concentration of thallium in the
top stage cyclone.. ..significant quantities exit the
preheater in the dust and build up into an external
cycle between the dust filter and preheater.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Thallium is also extremely
.gastro-entiritus is
toxic
followed by hair loss and attack
on the central nervous system
and death.
Vegetation loss and balding of
rabbits was the first indication
of the thallium emissions from
the well documented case of the
Lengerlich cement factory in
Germany.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
The most common source of
thallium inputs to cement
manufacturing are iron
additives .at Lengerlich
residues of pyrite roasting were
used as an iron additive.
The dust filters were highly
efficient at collecting cement kiln
..but the thallium was found to be bound to
dust..
particles in the 0.2~0.8 micron size range.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
The most common source of
thallium inputs to cement
manufacturing are iron
additives .at Lengerlich
residues of pyrite roasting were
used as an iron additive.
The dust filters were highly
efficient at collecting cement kiln
.. the dust filter only achieved 50% efficiency
dust..
in collection of these thallium rich particles.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
The most common source of
thallium inputs to cement
manufacturing are iron
additives .at Lengerlich
residues of pyrite roasting were
used as an iron additive.
The dust filters were highly
efficient at collecting cement kiln
..between 140~200 grams of thallium
dust..
per hour were emitted.

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 3.9 Metals Hg & T

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
Elimination of the pyrite
roasting residues from the raw
mix reduced these thallium
emissions by more than 99%.
An intermittent dust purge is the
solution if traces of thallium are
present in the main limestone or
clay raw materials of a cement
factory ..again intermittent to allow the level of
recirculating thallium in the external cycle to build up
to the levels entering the kiln in the feed and fuels.

Cement Kiln Chemistry

3.9 Metals, Hg & Tl

As a further consequence of burning alternative fuels in cement

kilns.. ...and the generally tightening regulatory environment
...heavy metal
within which cement factories operate.
emissions have inevitably come under scrutiny.
This brings us to the close of
our exploration of the emissions
and
from cement kilns..
indeed, almost to the end of the
entire kiln chemistry course.
In the next and final session of
the course we will review the
information presented over the
..and venture some suggestions
last six weeks..
regarding the optimum ways to operate a cement kiln
from a chemistry perspective.

Cement Kiln
Process Chemistry
3. Cement kiln emissions
3.9 Heavy metals mercury and thallium.

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