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General Technology

Bleaching

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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology
Debarking Chipping Cooking Deknotting, screening, washing

Bleaching
Oxygen delignification

O2

O2

Bleaching

Bleached Stock Former/Press Screening


D HC

Dryer

Cutter

Baling

e
LC

CPDU I 2053 257-02

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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology Terminology


Kappa Number

Bleaching

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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology Bleaching Chemicals

Bleaching

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 C H E D P O Z Q CHEMICAL NAME Chlorine Hypochlorite Extraction Chlorine Dioxide Hydrogen peroxide Oxygen Ozone Chelant FORMULA Cl2 NaOCl, Ca(OCl)2 NaOH ClO2 H2O2 O2 O3 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, O2, and H2O2 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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology
Single Stage Bleaching Brightness

Bleaching

Pulp strength

A
Chemical charge Multi Stage Bleaching Brightness Chemical charge

Pulp strength

Stage 3

Stage 2 Stage 1 Chemical charge CPDU I 2053 259-02 Chemical charge

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.

Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology
Common Bleaching Stages The bleaching stages listed below are commonly used in modern bleach plants: D-stage E-stage P-stage Q-stage Z-stage D0, D1, D2 (EO), (EP), (EOP) (PO), (OP)

Bleaching

D-stage. Chlorine dioxide (ClO2), which is used in the D-stage, oxidizes and degrades the lignin, and makes it soluble. ClO2, has replaced chlorine (Cl2), in many bleaching sequences, because it forms less toxic waste byproducts than Cl2 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 ClO2 in the D-stages. P-stage. Hydrogen Peroxide (H2O2) 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 (O3) 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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology

Bleaching

Bleaching Sequence

Lignin-Removing Stages D(EOP) Z(EO) Q(PO) OQ(PO) (Zq)

Brightening Stages DD DD DD Q(PO) (PO)

ECF

D(EOP)DD Z(EO)DD Q(PO)DD OQ(PO)Q(PO) (Zq)(PO)

TCF

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, Cl2, 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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology

Bleaching

ClO2

CPDU I 2053 263-02

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. 2. 3. 4. 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. Two pumps, one, which feeds the pulp into the reactor/tower and one, which feeds the washer. One or two mixers, which mix the chemicals and the pulp. One or two reactors/towers, which provide the retention time necessary for the chemicals to react with the pulp. One washer, which removes the reacted lignin and the unused chemicals from the pulp.

Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology

Bleaching

ClO2

CPDU I 2053 263-02

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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology

Bleaching

ClO2

NaOH

H2O2 O2

EOP

CPDU I 2053 266-02

CPDU I 2053 267-02

Downflow Reactor/Tower
Downflow Reactor/Tower

Upflow-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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology
Washers

Bleaching

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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology

Bleaching

EOP

CPDU I 2053 299-02

Chlorine Dioxide Stage


Chlorine dioxide (ClO2), which is used in the D-stage, oxidizes and degrades the lignin, and makes it soluble. ClO2 has replaced chlorine (Cl2), 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 (Cl2) 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 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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General Technology

Bleaching

EOP

CPDU I 2053 299-02

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.

Doc.No: CPDU P 2054 578-02 Rev: - 2008-01-28 Metso Paper Proj. No: 100657 Master: CPDU D 2043 747-02 Rev: - 2004-04-28

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