Doc.

No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 1 -

Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
BLEACHING................................................................................................................................ 2
TERMINOLOGY.......................................................................................................................... 3
Kappa Number .............................................................................................................................................................................3
Kappa Factor ................................................................................................................................................................................3
BLEACHING CHEMICALS ......................................................................................................... 4
BLEACHING STAGES................................................................................................................ 5
Single-Stage Bleaching .................................................................................................................................................................5
Multi-Stage Bleaching..................................................................................................................................................................5
Common Bleaching Stages...........................................................................................................................................................6
BLEACHING SEQUENCES........................................................................................................ 7
BLEACHING EQUIPMENT ......................................................................................................... 8
Pumps ............................................................................................................................................................................................8
Mixers............................................................................................................................................................................................8
Reactors/Towers ...........................................................................................................................................................................9
Washers .......................................................................................................................................................................................11
CHLORINE DIOXIDE STAGE................................................................................................... 12
EXTRACTION STAGE .............................................................................................................. 13
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 2 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 257-02
D
O
2
O
2
HC
Z
LC
e
Debarking Chipping Cooking Deknotting, screening, washing Oxygen delignification
Bleaching Former/Press Bleached Stock
Screening
Dryer Cutter Baling
Bleaching
The goal of bleaching is to produce pulp with a high brightness while maintaining good
strength properties in order to manufacture paper products that have the required brightness
for their end-use. In addition to brightening the pulp, bleaching also removes impurities from
the pulp and improves the printability of the paper products that are produced with the pulp.
The bleaching process completes the delignification (removal of lignin from the fibers) and
modification of the lignin that is present in the pulp. The delignification is initiated in the
cooking process and continued in the oxygen delignification stage (if present).
Lignin is primarily found in between the fibers, it is a glue like substance that binds the fibers
together, however some lignin is also present within the cross-section of the fiber. The pulp
becomes cleaner and brighter as the lignin is removed. When the pulp reaches the bleaching
area it consists primarily of cellulose. However, it also contains a small amount of lignin and
other colored substances, which must be removed very carefully to avoid damaging the
cellulose.
The chemicals used for bleaching are designed to react with the lignin in the pulp. However,
they can also react with the cellulose. When the bleaching reactions are allowed to continue
outside the designed operating limits, the reactions will tend toward cellulose degradation,
affecting the viscosity, strength, and brightness of the pulp. Careful control of the bleaching
conditions will ensure maximum brightness development with minimal damage to the
cellulose while removing as much of the lignin as possible.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 3 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
Terminology
Kappa Number
The pulp kappa number is a measure of the lignin content in the pulp (the kappa number of a
pulp decreases as the lignin content decreases). It is used to measure how much work
(delignification) has been done in a stage and how much work needs to be done in the
following stage(s). The higher the kappa number is the more work that needs to be done.
It is advantageous if as much as possible of the delignifying work, without negatively
impacting the fiber strength or yield, is done during the cooking process and in the oxygen
delignification stage (if present).
Kappa Factor
Kappa factor defines how much bleaching work needs to be performed in a stage using active
chlorine. The kappa factor is expressed as the chemical charge per unit of kappa number. The
kappa factor is used to control the bleaching result and the bleaching economy. The factor that
is chosen for a given stage depends on the kappa number and/or the target brightness. The
higher the final brightness is, the higher the kappa factor must be.
kappa factor x kappa number = chemical charge
where chemical charge is given as kg active chemical per ton of pulp
Example: If the kappa factor in a chlorine dioxide stage is 1.5, and the pulp entering the
stage has kappa number 10, then the chemical charge will be:
1.5 x 10 = 15 kg active chlorine per ton of pulp
In some cases the kappa factor is expressed in per cent of pulp, i.e. in the above example the
kappa factor would be 0.15.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 4 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
Bleaching Chemicals
The chemicals, which are listed below, can be used to bleach the pulp or to enhance the
bleaching process in chemical and semi-chemical pulp mills that use sulfate in the cooking
stage:
STAGE CHEMICAL NAME FORMULA
C Chlorine Cl
2
H Hypochlorite NaOCl, Ca(OCl)
2
E Extraction NaOH
D Chlorine Dioxide ClO
2
P Hydrogen peroxide H
2
O
2
O Oxygen O
2
Z Ozone O
3
Q Chelant EDTA, DTPA
Each of these bleaching chemicals is associated with a bleaching stage. However, several
different bleaching chemicals can be used in a single bleaching stage, e.g. in an (EOP)-stage,
NaOH, O
2
,

andH
2
O
2
are used.
Traditionally, chlorine (C) has been used to bleach pulp, as it is a very effective bleaching
agent. However, the reactions which take place with chlorine form organic chlorine
compounds that are toxic to the environment, and as a result of this chlorine is slowly being
phased out.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 5 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 259-02
Brightness
Chemical charge Chemical charge
Pulp strength
Brightness
Pulp strength
Chemical charge
Chemical charge
Stage 1
Stage 2
Single Stage Bleaching
Multi Stage Bleaching
Stage 3
Bleaching Stages
Single-Stage Bleaching
The pulp brightness that can be achieved in a single bleaching stage is limited, and therefore
ineffective, as shown in figure A above.
Multi-Stage Bleaching
Bleaching pulp in several subsequent stages, using a variety of chemicals, ensures a bright,
strong pulp with minimal cellulose damage, as shown in figure B above. The reason for this is
that the chemicals, which are used in the different bleaching stages, can be controlled to react
with the pulp in different ways. The advantage of a bleaching area that includes several stages
is that the reactions can be carried out under milder conditions (with a lower chemical charge
and at lower temperatures) and the pulp can be washed in between each stage. A portion of
the compounds which are formed by the chemical/pulp reactions, e.g. chloro-lignin
compounds, are removed by the washers that are placed after each stage.
B
A
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 6 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
Common Bleaching Stages
The bleaching stages listed below are commonly used in modern bleach plants:
D-stage D0, D1, D2
E-stage (EO), (EP), (EOP)
P-stage (PO), (OP)
Q-stage
Z-stage
D-stage. Chlorine dioxide (ClO
2
), which is used in the D-stage, oxidizes and degrades the
lignin, and makes it soluble. ClO
2
, has replaced chlorine (Cl
2
), in many bleaching sequences,
because it forms less toxic waste byproducts than Cl
2
does. In such cases where a mill has two
or three chlorine dioxide stages, the first stage is often referred to as the D0-stage, the second
as the D1-stage, and the third as the D2-stage.
E-stage. Sodium hydroxide (NaOH) is the chemical that is common to all of the extraction
stages, i.e. NaOH is the active chemical that does the job. The extraction stage can be
considered as a part of the preceding stage. In the E-stage the substances (lignin compounds)
that are made alkali soluble in the preceding stage, e.g. the D-stage, are dissolved out of the
pulp. The extraction stage is almost always reinforced with at least one oxidizing agent, for
example oxygen in the (EO)-stage and oxygen and peroxide in the (EOP)-stage. The presence
of oxygen makes it possible to operate the stage at higher temperatures and to reach a
somewhat lower kappa number without loosing pulp viscosity. The presence of peroxide
increases the brightness of the pulp, reducing the demand for ClO
2
in the D-stages.
P-stage. Hydrogen Peroxide (H
2
O
2
) delignifies and modifies the lignin so that the pulp is
brightened.
Q-stage. The chelating agents EDTA and DTPA are used to reduce the content of transition
metals in the pulp. This stage is normally placed prior to a stage that uses hydrogen peroxide,
e.g. a (PO)-stage.
Z-stage. Ozone (O
3
) is an effective bleaching agent. The Z-stage is most often placed directly
after the oxygen delignification stage.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 7 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
Bleaching Sequence Lignin-Removing
Stages
Brightening
Stages
ECF D(EOP)DD D(EOP) DD
Z(EO)DD Z(EO) DD
Q(PO)DD Q(PO) DD
TCF OQ(PO)Q(PO) OQ(PO) Q(PO)
(Zq)(PO) (Zq) (PO)
Bleaching Sequences
A few examples of bleaching sequences which can be found in modern bleach plants are
given in the table above. A bleaching sequence describes the order of the bleaching stages that
are included in the bleaching area. There are a large number different bleaching sequences
used today that can produce white/bright pulp. The best sequence for a given application
depends on the specific requirements that are to be met (these normally include fiber strength,
pulp brightness, effluent impact, and chemical costs). Most often the choice of bleaching
sequence is based on a compromise of these requirements.
The first two stages in a bleaching sequence are often referred to as the lignin-removing
stages whereas the final stages are referred to as brightening stages. In general, pulp kappa
number is used to control the lignin-removing stages and brightness is used to control the
brightening stages. The colored material that is present in the pulp after the lignin-removing
stages is the target of the brightening stages. This material consists of lignin and chromophore
compounds (which are relatively dark and present in small amounts).
The brightening stages of the bleach plant finish the job of purifying and brightening the pulp.
Although the brightness increases for each step after the cooking process, the most dramatic
increase occurs at this point. The choice of brightening stages depends primarily on the
desired brightness, on the chemical costs, and on environmental considerations. When the
brightness goal is increased, the amount of work required to achieve this goal is increased.
Mills that produce high brightness market pulp use two or three brightening stages. These
stages raise the maximum brightness and protect the strength of the pulp. It is in general not
possible to produce high brightness market pulp using only one brightening stage. Mills that
try to increase the final brightness in a 'short' bleach plant find that pulp strength is decreased
and the chemical consumption is very high.
Today, most modern mills use an ECF, or in some cases a TCF, bleaching sequence, where
ECF stands for elemental chlorine free, i.e. pulp which is bleached without chlorine, Cl
2
, and
TCF stands for totally chlorine free, i.e. pulp which is bleached without chlorine containing
compounds.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 8 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 263-02
ClO
2

D
Bleaching Equipment
An example of a chlorine dioxide (D) bleaching stage is shown in the figure above.
The equipment used in a typical bleaching stage includes:
1. Two pumps, one, which feeds the pulp into the reactor/tower and one, which feeds the
washer.
2. One or two mixers, which mix the chemicals and the pulp.
3. One or two reactors/towers, which provide the retention time necessary for the
chemicals to react with the pulp.
4. One washer, which removes the reacted lignin and the unused chemicals from the pulp.
Pumps
In general, MC pumps are used in modern bleaching stages. The consistency of the pulp
depends on the type of stage that is being fed; the desired consistency is normally between 10
to 15% into a reactor/tower, and around 7% up to a washer.
The reactor/tower feed pump is also used to control the system pressure. In some cases, the
pulp is fed directly from the screw conveyor of the preceding stage to the bleaching stage
reactor/tower.
Mixers
A mixer is normally placed between the feed equipment and the reactor to ensure that the pulp
and the chemicals are mixed homogeneously. The means used to achieve homogeneous
mixing will vary, depending on whether the objective is to mix the pulp with a rapid
chemical or a slow chemical, and depending on whether the chemical is in a gas or a liquid
phase.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 9 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 263-02
ClO
2

D
Reactors/Towers
The different types of reactors/towers that are typically used to carry out the reactions in a
bleaching stage include upflow, downflow, and upflow-downflow reactors/towers. A special
type of reactor is used in an ozone (Z) stage.
In general, the term reactor is used if the reaction takes place under pressure or vacuum, and
the term tower is used if the reaction takes place at atmospheric pressure.
The bleaching reactors/towers are dimensioned to give sufficient residence time for the
reactions to go to completion. These can be either pressurized or atmospheric. The
construction material used to build a reactor/tower depends on the process conditions under
which the reactions are carried out and the types of chemicals that are used.
Upflow Reactor /Tower
In upflow reactors/towers, shown in the figure above, the pulp enters through the bottom and
is discharged through the top of the reactor/tower. The pulp is fed to the bottom of the
reactor/tower by a pump. An upflow is designed to provide the necessary hydrostatic pressure
required for the bleaching reaction.
A distributor is placed at the bottom of the upflow reactor/tower and used to evenly distribute
the pulp in the reactor/tower by flinging it outwards. The outward movement of the pulp that
enters the reactor/tower minimizes channeling and plugging, and promotes an even plug flow
upward through the reactor/tower.
For high-consistency bleaching applications a reactor/tower scraper is placed at the top of the
upflow reactor/tower and used to evenly discharge the pulp into the outlet dropleg. The
discharged pulp is then diluted in the outlet dropleg with filtrate, which normally comes from
a subsequent stage. For low-consistency bleaching applications the top of the upflow
reactor/tower will have a conical shape which does not require a scraper.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 10 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 266-02
ClO
2

D
CPDU I 2053 267-02
O
2

H
2
O
2
NaOH
EOP
Downflow Reactor/Tower Upflow-Downflow Reactor/Tower
Downflow Reactor/Tower
In downflow reactors/towers, the pulp enters the reactor/tower through the top and is
discharged through the bottom of the reactor/tower. Downflow reactors/towers are also used
as buffer tanks, to allow for production rate changes, and to control the reaction time (the time
required for the reaction to take place).
The pulp can be fed to the top of the reactor/tower directly by a screw conveyor or by a pump.
The actual residence time in a downflow reactor/tower is not directly proportional to the total
reactor/tower volume, as there is always a section at the top of the reactor/tower that is empty
and a zone at the bottom of the reactor/tower that is used for dilution.
Upflow -Downflow Reactor/Tower
In an upflow-downflow reactor/tower the pulp is fed to the bottom of the upflow
reactor/tower (also referred to as the pre-tube depending on the application) and flows
upwards to the top of the downflow reactor/tower. The pulp then flows downwards and is
discharged at the bottom of the downflow reactor/tower.
An upflow reactor/tower is normally pressurized, this allows the initial reactions to take place
under pressure.
The upflow-downflow reactor/tower can be used for large production rates because it can be
sized so that the required residence time can be achieved, and the majority of the chemicals
can be consumed in the upflow reactor/tower.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 11 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
Washers
The pulp is normally washed after each bleaching stage in the bleaching area in a washer, e.g.
a filter or a press, which is placed after the reactor/tower. The purpose of washing the pulp is
to remove the dissolved material released in the bleaching reaction, and to remove residual
bleaching chemicals. Good pulp washing is an important goal in the bleaching area. Washing
the pulp sufficiently will reduce bleach chemical consumption and minimize the
environmental impact of the bleaching area.
The wash liquor that is used to remove the dissolved material (lignin, chromophore
compounds, unused chemicals etc.) comes from a subsequent stage or from a fresh water
source. The "dirty water" (filtrate/pressate) is collected in a tank which is placed under the
washer. This filtrate is either discharged to the effluent treatment plant/sewer or sent to a
preceding stage in the bleaching area.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 12 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 299-02
D EOP D D
Chlorine Dioxide Stage
Chlorine dioxide (ClO
2
), which is used in the D-stage, oxidizes and degrades the lignin, and makes
it soluble. ClO
2
has replaced chlorine (Cl
2
), in many bleach plants, as it forms less toxic material
than chlorine does. However, chlorine dioxide reacts with lignin much slower than chlorine does
and, consequently, requires a longer residence time. To avoid the need for very large reactors, i.e.
towers, the reaction parameters in a D-stage are controlled.
Bleaching with chlorine dioxide removes a part of the coloured lignin, thereby brightening the
pulp. To some extent the cellulose is also affected which can be noticed by a decrease in
viscosity.
A typical example of a bleach plant sequence is shown in the figure above. The first D-stage
in this sequence (D0-stage) is a lignin-removing stage and is used to pre-bleach the pulp by
reducing the lignin content. The two following D-stages in this sequence (D1 and D2-stage)
are brightening stages and brighten the pulp by removing and/or decolorizing the remaining
lignin.
The D0-stage is normally performed in an upflow tower, whereas the D1 and D2-stages are
carried out in either an upflow or an upflow/downflow tower system. The advantage of an
upflow/downflow stage is that it can better absorb variations in the production rate.
In some plants chlorine (Cl
2
) is added to the D-stage, these stages (depending on their
configuration) are either referred to as either a (DC)-stage or a (CD)-stage.
Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 - 13 -
Metso Paper Proj. No: 100657
Master: CPDU D 2043 747-02 Rev: - 2004-04-28
Bleaching General Technology
CPDU I 2053 299-02
D EOP D D
Extraction Stage
Sodium hydroxide (NaOH) is the chemical that is common to all of the extraction stages.
Alkali (NaOH) is used to leach out the compounds that are made soluble in a previous acid
stage, e.g. a D-stage. Therefore, the extraction stage is often considered to be a part of the
preceding stage.
A modern extraction stage is almost always reinforced with at least one oxidizing agent, e.g.
oxygen, as is the case in an (EO)-stage or a combination of oxygen and peroxide as is the case
in an (EOP)-stage. The presence of oxygen makes it possible to operate at higher temperatures
and to reach a somewhat higher kappa number without loosing pulp viscosity. The presence
of peroxide increases the brightness of the pulp.
The above figure is an example of a bleach plant that includes an (EOP)-stage that is placed
after the D0-stage.
An extraction stage is performed in either an upflow or an upflow/downflow tower, and
carried out under controlled conditions.