CemNet Training - Course TCM01

Module 3 - Session 1

Cement Manufacturing
Technology
3. Pyroprocessing raw mix to cement clinker.
3.1. Chemical reactions.

Cement Technology Training 2005

Cement Technology

3. Pyroprocessing

3.1 Chemistry

At the end of module 2 of our course the cement raw materials have
now been dried, homogenised and ground down to the fine,
intimately mixed powder which is required for their conversion to
cement clinker in the cement kiln.
In this course we will be
focusing on the
manufacture of cement
clinker in rotary kilns.
This pyroprocessing in
the cement kiln is the
heart of the cement
manufacturing process.
Cement Technology Training 2005

Cement Technology

3. Pyroprocessing

3.1 Chemistry

At the end of module 2 of our course the cement raw materials have
now been dried, homogenised and ground down to the fine,
intimately mixed powder which is required for their conversion to
cement clinker in the cement kiln.
This pyroprocessing in the cement kiln is the heart of the cement
manufacturing process.
In modules 3 and 4 of our course we will focus on this
pyroprocessing and conversion of the mixture of raw materials
to cement clinker in the cement kiln.

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

The kiln feed is a mixture of raw minerals:

180

160

Calcium carbonate, CaCO3.

140

Mass kg/100 kg clinker

C3S

Shale.

120

100

C2S
C3A
C4AF

Silica sand.

80

Free CaO
Limestone
Shale

Iron oxide.

60

40

20

0
1

Silica Sand
Iron Oxide

As 44% of the calcium carbonate will be lost as CO2,

a total of 153 kg of raw materials are required to
produce 100 kg of clinker.
3

Cement Technology Training

3. Pyroprocessing

2005

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

When the kiln feed enters the kiln the heating

process begins and the first reaction which takes
place is evaporation of combined water from the
shale as the temperature exceeds 350C.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF
Free CaO

80

Limestone
Shale
Silica Sand

60

Iron Oxide
40

20

0
1

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

When the kiln feed enters the kiln the heating

process begins and the first reaction which takes
place is evaporation of combined water from the
shale as the temperature exceeds 350C.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

This reduces the mass of the shale.

80

Free CaO
Limestone
Shale
Silica Sand

60

Iron Oxide
40

350C
20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

The heating process then continues until

the temperature is in excess of 850C when
the calcination of the CaCO3 begins:

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S

CaCO3 _ CaO + CO2_.

C3A

100

C4AF

Free CaO

With the CO2 being lost in the kiln exhaust

gases, reducing the total mass of CaCO3
and feed.

>850C

80

Limestone
Shale

Silica Sand

60

Iron Oxide

40

And solid CaO being formed in the feed

material.

20

100C
0
1

Cement Technology Training

3. Pyroprocessing

2005

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

The temperature then remains

virtually constant as the energy
consuming, endothermic calcination
of the CaCO3 continues:

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

CaCO3 _ CaO + CO2_.

Free CaO

>850C

80

Limestone
Shale

Silica Sand

60

All the CO2 from the CaCO3 is

eventually lost in the kiln exhaust
gases, reducing the total mass of
feed.
Iron Oxide

40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

The temperature then remains

virtually constant as the energy
consuming, endothermic calcination
of the CaCO3 continues:

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

CaCO3 _ CaO + CO2_.

Free CaO

>850C

80

Limestone
Shale

Silica Sand

60

All the CaCO3 in the feed is

consumed ..
Iron Oxide

40

20

100C
0
1

Cement Technology Training

2005

.. and replaced by free CaO.

5

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

When the CaCO3 is

consumed the
temperature rises again
as the endothermic
calcination is no longer
absorbing the thermal
energy in the kiln.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

Free CaO

>850C

80

Limestone
Shale

Silica Sand

60

Iron Oxide

40

20

100C
0
1

Cement Technology Training

3. Pyroprocessing

2005

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

Simultaneously the free

CaO reacts with the shale,
silica sand and iron oxide
to form C4AF, C3A and
C2S.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

Free CaO

>850C

80

Limestone

The C4AF and C3A

minerals melt providing in
excess of 20% liquid
phase, or flux, in the feed
material.
Shale

Silica Sand

60

Iron Oxide

40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

The presence of the flux promotes the

solid-solid sintering reactions of the
clinker between CaO and C2S.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF
Free CaO

>850C

80

Limestone
Shale
Silica Sand

60

Iron Oxide
40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

When the temperature exceeds 1400C the C2S and

remaining CaO begin to combine to form C3S.

180

160

140
C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF
Free CaO

>850C

80

Limestone
Shale
Silica Sand

60

Iron Oxide
40

20

100C
0
1

Cement Technology Training

3. Pyroprocessing

2005

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

When the temperature exceeds 1400C the C2S and

remaining CaO begin to combine to form C3S.

180

160

140
C3S

Mass kg/100 kg clinker

120

C4AF

C2S
C3A

100

C4AF
Free CaO

>850C

80

Limestone
Shale
Silica Sand

60

C3A
C2S

Iron Oxide
40

C3S

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

The reaction between free CaO and C2S to form C3S

is an energy releasing or exothermic reaction.

180

160

This makes a
major contribution
to heating and
maintaining the
temperature in the
kiln.

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

Free CaO

>850C

80

Limestone
Shale

Silica Sand

60

Iron Oxide
40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

Because of this exothermic reaction, a cement kiln is

partially self-fuelling..provided that the
temperature is kept
above 1400C,
which is the
>850C
threshold
temperature for C3S
formation.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

Free CaO

80

Limestone
Shale

Silica Sand

60

Iron Oxide

40

20

100C
0
1

Cement Technology Training

3. Pyroprocessing

2005

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

If the temperature falls below 1400C the C3S

formation stops, the exothermic contribution is lost
and the kiln very quickly cools down and blacks out.

180

160

140

C3S

Mass kg/100 kg clinker

120

C2S

This is one of the

main reasons why
stable feed
composition and
control are vital for
cement kilns.
C3A

100

C4AF

Free CaO

>850C

80

Limestone
Shale

Silica Sand

60

Iron Oxide

40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

In this session 1 of module 3 we will focus on the chemical reactions

which take place, as the mixture of raw materials is converted into
cement clinker.
Reaction Sequence

180

160

140

Every time a cement kiln stops the energy investment to raise

the temperature above 1400C, to re-establish the C3S
formation, must be repeated.
Long uninterrupted
campaigns of
>850C
operation are vital
for cement kilns to
minimise the times
this energy
investment must be
made.
C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

Free CaO

80

Limestone
Shale

Silica Sand

60

Iron Oxide

40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

These thermodynamic factors are critical to the operation of cement

kilns.
The evaporation of any residual water, dehydration of clay
minerals, CaCO3 calcination and clinker flux formation are all
endothermic and consume large amounts of energy.
The final combination of the
C3S significantly reduces the
overall energy required for
cement clinker formation.

3000
2000
1000

C3S
formation

Clinker flux
formation

Deydration of
clay minerals

Calcination of
limestone

Evaporation
of Water

0
-1000

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

This diagram is useful for explaining the chemical reactions and

mineral composition changes in a cement kiln.
We must remember that the minerals are not discrete.
.we rely on them being intimately mixed
for the reactions to take place.
Reaction Sequence

180

160

140
C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF
Free CaO

>850C

80

Limestone
Shale
Silica Sand

60

Iron Oxide
40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

Cement Technology

3.1 Chemistry

This diagram is useful for explaining the chemical reactions and

mineral composition changes in a cement kiln.
The Portland cement clinker produced is a partially fused, or
sintered, agglomeration of these minerals.
Reaction Sequence

180

160

140
C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF
Free CaO

>850C

80

Limestone
Shale
Silica Sand

60

Iron Oxide
40

20

100C
0
1

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

This diagram is useful for explaining the chemical reactions and

mineral composition changes in a cement kiln.
After complete combination of all the free CaO in the clinker it
must be quench cooled to freeze the minerals in their high
temperature crystalline state.
Reaction Sequence

180

160

140

This quench cooling takes place in the outlet section of the rotary
kiln, before the clinker falls into the cooler.
C3S

Mass kg/100 kg clinker

120

C2S
C3A

100

C4AF

Cooler operation will be discussed in a later session of the

course.
In this session 3.1 we are focusing on the material and it is
Free CaO

>950C

80

Limestone
Shale

Silica Sand

60

Iron Oxide

40

20

0
1

important to understand that the secondary air rising out of the

cooler quench cools the clinker, freezing the clinker in its high
temperature crystalline state..
2

Cement Technology Training

2005

Cement Technology

3. Pyroprocessing

3.1 Chemistry

This diagram is useful for explaining the chemical reactions and

mineral composition changes in a cement kiln.
The C4AF and C3A are frozen
into a glass rather than
crystallising out of the melt.
This glass is the interstitial
material seen in a thin section of
the clinker under a microscope.
Quench cooling prevents the C3S from growing into large
crystals due to prolonged contact with the melt at a high
temperature.
Cement Technology Training 2005

Cement Technology

3. Pyroprocessing

3.1 Chemistry

This diagram is useful for explaining the chemical reactions and

mineral composition changes in a cement kiln.
Quench cooling prevents the
C3S from growing into large
crystals due to prolonged contact
with the melt at a high
temperature.
Quench cooling produces small,
more hydraulically reactive
crystals of the C3S in the
clinker.

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com

CemNet Training - Course TCM01

Cement Technology

Module 3 - Session 1

3.1 Chemistry

After this quench cooling in the outlet zone of the rotary kiln the
clinker falls over the nose ring of the kiln into the cooler.
Conversion
The
raw materials
of the raw
have been
fully converted
materials
into cement
into cement
clinker
clinker at this
consumes
largestage.
amounts of
thermal energy.
We need to discuss some of the
otherisprocesses
place in
This
providedtaking
by burning
the
cement
the
fossil
fuels kiln,
in thealongside
cement kiln.
chemical reactions which
In
the next
convert
the session
raw mixoftomodule
clinker3
we
willgoing
consider
thecooler
combustion
before
on to
process
which takes place in the
operations.
cement kiln.
Cement Technology Training 2005

3. Pyroprocessing

Cement Manufacturing
Technology
3. Pyroprocessing raw mix to cement clinker.
3.1. Chemical reactions.

Cement Technology Training 2005

3. Pyroprocessing

This document is for the sole use of students enrolled on course TCM01 and cannot be reprinted, reproduced or distributed without prior written consent from Tradeship Publications Ltd 2005
http://training.CemNet.com