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Pulp Bleaching

Article · June 2019

DOI: 10.1002/0471238961.1621121613030415.a01.pub3

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PULP BLEACHING
1. Introduction

The principal objective of any type of pulp bleaching is to increase the pulp bright-
ness, which is defined as reflectance measured at a wavelength of 457 nm (1).
Typically, chemical pulp bleaching is performed in multistage bleach plants where
the initial stages focus is upon the removal of residual lignin contained in the
fiber (delignification) while the later stages focus on increasing the pulp bright-
ness. Mechanical pulp bleaching is often referred to as brightening and is often
performed in only one or two stages. In mechanical pulp bleaching, the residual
lignin is not removed. Rather, chromophores within the pulp fibers are modified so
they reflect light rather than absorb light. Unfortunately, upon exposure to heat
or sunlight, these modifications tend to reverse resulting in significant brightness
reversion and yellowing in mechanical pulps. Because lignin is removed in chemi-
cal pulp bleaching, the brightness of chemical pulps tends to be much more stable
than mechanical pulps. Brightening is also done for recycled fibers. Often perox-
ide is combined with deinking to remove ink particles and brighten the recycled
fiber. Oxidative treatments may be used to destroy optical brightening agents in
recycled fiber for inclusion in direct food contact materials. Some recycled pulps,
typically from mixed office waste, are bleached to high quality and high bright-
ness to be used as a partial replacement for short fiber chemical pulp in grades
that require recycled content to meet customer demand.
1.1. Chlorine-Based, Elemental Chlorine Free, and Totally Chlorine
Free Bleaching. There are three main categories of bleaching sequences
employed in the world. Up until the early 1990s, the predominant bleaching
sequence was chlorine based. Typically, chlorine was employed as the first stage
of bleaching to delignify pulp and start the brightening process. Often a small
amount of chlorine dioxide was added as a partial substitution for chlorine in
the first bleaching stage to act as a free radical scavenger and protect the pulp
strength. Chlorine-based bleaching was performed at very low pH and also
tended to remove nonprocess elements from the pulp which reduced or prevented
bleach plant scale formation.
The second type of bleaching sequence, elemental chlorine free (ECF) bleach-
ing is the predominant category of bleaching in the world today. Instead of using
chlorine in the sequence, chlorine dioxide, peroxide, and oxygen are used as the
main oxidative chemicals. No chlorine is added in an ECF sequence but chlorine
atoms are still employed in the form of chlorine dioxide. As a result, the amount of
chlorinated organics formed in the pulp and effluent are significantly lower than is
found in chlorine-based bleaching. Operating conditions for ECF bleaching, unlike
for chlorine-based bleaching, results in nondetectable levels of chlorinated dioxins
and furans in the waste effluents.
The final category of bleaching is totally chlorine free (TCF) bleaching. TCF
bleaching was developed in response to concerns over chlorinated organic species
still being found in pulp and bleach plant effluents associated with ECF bleach-
ing. TCF bleaching uses no chlorine atoms in any form. Rather, the bleaching
is done with oxygen, ozone, peroxide, and peracetic or Caro’s acid for oxidative
chemicals and dithionite as a reducing chemical. As the majority of the oxidative
1

Kirk-Othmer Encyclopedia of Chemical Technology. Copyright © 2019 John Wiley & Sons, Inc. All rights reserved.
DOI: 10.1002/0471238961.1621121613030415.a01.pub3
2 PULP BLEACHING

chemicals are oxygen based, it was initially thought that TCF bleaching would
be highly beneficial from an environmental standpoint. Unfortunately, numerous
studies have suggested that a similar level of environmental concern, albeit some
of different types, exist for TCF bleaching as exist for ECF bleaching (2,3). TCF
bleaching also produces weaker pulps at high brightness as over application of
oxidative chemistries tend to react with the cellulose as well as the chromophores
and damages the pulp.
It should be noted that TCF bleaching does not eliminate chlorinated organ-
ics in the bleaching effluent. There is a background level of chlorinated organics,
albeit much less than what is in ECF effluents, still present in TCF bleach efflu-
ent. In addition to background levels, TCF bleaching also generates low levels of
chlorinated organics. Chloride anions in the recycled water loops typically found
in TCF bleaching systems can be oxidized to Cl2 /HOCl by strong oxidants, such
as ozone, peracetic acid, and Caro’s acid (4,5).
1.2. Modern Bleach Plant Configuration. Chemical pulp bleaching is
typically performed in a multistage process using different chemicals and reac-
tions conditions for each stage. Each stage consists of mixers, pumps, piping,
retention towers or tubes, and washing devices. Figure 1 shows a schematic of
a typical modern bleach plant.
1.3. Tonnage of Elemental Chlorine Free and Totally Chlorine
Free Bleached Pulp Produced. More than 124 million air-dried metric tons
(ADMT) of chemical pulp are bleached each year with operations in 358 different
mills which span the entire world (6). Table 1 lists the areas and number of
mills making bleached pulp. Table 1 breaks out the number of mills by wood and
nonwood-based bleached pulp and by region. Chemical pulps are predominately
produced from wood pulps. A small subset (about 2%) of the chemical pulp
originates from nonwood sources. The bleaching of chemical pulps, from both
wood and nonwood sources, may be broken down into two main types of processes:
ECF and TCF. Of the two, ECF pulp bleaching is by far the dominant bleaching
process with approximately 112 million ADMT of fiber as compared to only 5.9
million ADMT of TCF bleached fiber (6). About 6.2 million ADMT of fiber are still
bleached with elemental chlorine in at least one bleaching stage.
Elemental Chlorine Free and Totally Chlorine Free Bleached Pulp Pro-
duced by Pulp Type. Eucalyptus species are by far the most prevalent form of
bleached pulp produced in the world. Eucalyptus accounts for 31.5% of the ECF
pulp and 20% of the TCF made in the world. The next closest ECF pulp is northern
softwood which accounts for 19% of the ECF pulp followed by southern softwood
and tropical hardwood accounting for 14.8% and 12.4% of the ECF pulp respec-
tively. Northern hardwood and southern hardwood are about tied at 11.1% and
10.9% of the ECF pulp produced respectively. The largest TCF species is northern
softwood accounting for 47% of the total TCF pulp production followed by northern
hardwood representing 24% of the total production (6).

2. Chemical Pulp Preparation for Bleaching

Chemical pulp is produced by cooking the wood or nonwood fibrous raw materials
in an aqueous solution of chemicals (either alkaline or acidic) that breaks down
 Discharge TRPE-1572 TRPE-1548 TRPE-1548 MC
tank
O2 O2
I II
GT Water
Screen tank
room
FT FT
FT

TRPE-1540 MC
TRPE-1548 TRPE-1540 TRPE-1540 TRPE-1540
DO D1 O2
EO

FT FT FT FT FT Hot water
tank

Fig. 1. Schematic of a modern softwood bleach plant provided by Valmet: four-stage bleach sequence with oxygen delignification and
inter-stage press washers. Source: Reproduced with permission of Valmet.
4 PULP BLEACHING

Table 1. Chemical Pulp Mills with Bleaching Capacity Worldwide by Region

Number of Region Number of Region
mills mills
Wood pulp for paper and board Total number of mills (wood and nonwood)
89 North America 101 North America
67 Eastern Europe, Western Europe, 92 Eastern Europe, Western Europe,
or Nordic or Nordic
41 East Asia 89 East Asia
28 Central Asia, South Asia, or 50 Central Asia, South Asia, or
Southeast Asia Southeast Asia
27 South America 32 South America
3 Australasia 4 Africa or Middle East
1 Africa or Middle East 3 Australasia
1 Central America 1 Central America
Wood pulp, dissolving Nonwood pulp
15 East Asia 44 East Asia
11 North America 28 Central Asia, South Asia, or
Southeast Asia
10 Eastern Europe, Western Europe, 17 Eastern Europe, Western Europe,
or Nordic or Nordic
4 Central Asia, South Asia, or 5 North America
Southeast Asia
2 South America 3 South America
2 Africa or Middle East 1 Africa or Middle East
Source: Data from Ref. 6.

and dissolves lignin until the fiber liberation point is reached. When enough lignin
is removed, most of the fibers are able to separate from the starting chips to form
pulp. There are two main types of chemical pulping processes: sulfite and kraft
(also known as sulfate). The sulfite process is an acid process, which produces a
straw yellow relatively weak fiber that is easy to bleach. Kraft (also known as the
sulfate process) is by far the most predominant pulping process. It uses caustic
and sodium sulfide to fragment the lignin and liberate strong, dark brown colored
fibers which are rather difficult to bleach. Because a significantly larger share of
the pulp produced is wood-based kraft pulp, the majority of this discussion will
focus upon kraft pulps derived from wood.
The objective of kraft pulping is to remove as much lignin as possible while
maintaining the integrity of the cellulose and hemicellulose (carbohydrates) poly-
mers contained in the wood. Pulping progress is typically measured by following
the kappa number of the resulting pulp. Kappa number is a standardized test
performed by oxidizing wood pulp with potassium permanganate under standard-
ized conditions (7,8). The kappa number is proportional to the amount of residual
lignin left in the fiber after the pulping process. Typically, for softwood pulps, the
fiber liberation point is reached at about a 28–32 kappa number. For hardwood
pulps, the fiber liberation point is often around 18–20 kappa number. Under con-
ditions of extremely good, extended impregnation, the fiber liberation point will
move toward higher kappa numbers for both soft- and hardwood pulps (9). These
conditions are relatively uncommon in current industrial practice. Pulping is typ-
ically stopped shortly after the fiber liberation point to preserve pulp strength and
 PULP BLEACHING 5

yield. Unfortunately, the kraft process is not highly selective. It tends to attack
the carbohydrates in the wood as well as the lignin resulting in reduced yield and
strength. Frequently, pulp yield will rapidly decrease due to chemical attack of
the carbohydrates if pulping is allowed to continue more than 4–6 kappa points
beyond the fiber liberation point.
Once the pulp is discharged from the digester, the knots are removed in
deknotting devices and it is washed in a countercurrent multistage washing pro-
cess that separates dissolved organic chemicals and spent inorganic cooking chem-
icals from the brown pulp (10). The washed pulp is then screened to remove any
fiber bundles and sand contained in the pulp stream, thickened up and sent to a
storage tank used to feed the bleaching process.

3. Pulp Bleaching Chemicals

There are a few basic bleaching chemicals employed in ECF pulp bleaching. The
workhorse chemicals are chlorine dioxide, caustic or sodium hydroxide, oxygen,
and peroxide. More exotic bleaching chemicals include xylanase enzymes, ozone,
sodium hydrosulfite (dithionate), acid washing/treatment, and chelants. Some
chemicals have been mostly discontinued from use in bleaching due to their
environmental impact and legislative changes. These chemicals include chlorine,
sodium hypochlorite, and hypochlorous acid. Even other chemicals, such as
peracetic acid, are rarely used and when they are, it is typically in specialty TCF
applications.
Each bleaching chemical has been assigned a capital letter for use in defining
various bleaching sequences in a uniform way. Details associated with this short-
hand method are available in TAPPI Technical Information Paper TIP 0606-21
published in July 2008 (11). The letter designation for the above listed chemicals
are as follows:

• A = acid treatment
• C = chlorine
• D = chlorine dioxide
• E = caustic extraction (NaOH)
• H = sodium hypochlorite
• M = hypochlorous acid (Monox-L)
• O = oxygen
• P = hydrogen peroxide
• Pa = peracetic acid
• X = xylanase enzymes
• Y = sodium hydrosulfite (dithionate)
• Z = ozone

Although not an official designation, F is sometimes used to represent for-

mamidine sulfinic acid (FAS; thiourea). Caro’s acid (peroxymonosulfuric acid) is
6 PULP BLEACHING

generally denoted as Px. Similarly, an acid stage that uses mixture of peracetic
and peroxymonosulfuric acid is sometimes denoted as Pxa.
3.1. Pulp Bleaching Chemical Nomenclature. It is common practice
to designate each stage of the multistage bleach plant with a capital letter
defining the main bleaching chemical being applied in that stage. Any of the
recommended letter symbols, if used without the modifications described below,
implicitly denotes a series of four operations: chemical addition, mixing into the
pulp, retention time, and washing. Each of these steps is generic. No particular
equipment or mode of operation is to be inferred. Mixing, for example, could be
accomplished using a washer repulper or by a high-shear mixer; retention could
be by a length of pipe, a retention tower or a pressurized chemical reactor.
A multistage bleaching sequence is designated by an ordered list of letter
symbols. For example, ODED denotes a sequence consisting of oxygen delignifi-
cation, chlorine dioxide, caustic extraction, and chlorine dioxide stages, in that
order. Each stage consists of chemical addition, mixing, retention, and washing.
Letter symbols enclosed in parentheses, ( ), represent stages in all but the
last of which chemical addition and mixing are not followed by significant (more
than 1 min) retention or washing. Most frequently, only two chemicals will be
shown in parentheses, indicating that the first is conducted without the usual
retention and washing steps. For example, (DZ) denotes chlorine dioxide addition
followed by ozone addition after a retention time of less than 1 min and with-
out intermediate washing. The ozone addition is followed by the usual mixing,
retention, and washing steps.
A slash “/ ” occurring between stage symbols enclosed by parentheses explic-
itly denotes significant (more than 1 min) retention in the stage denoted by the
letter symbol preceding the slash. Stages like (D/A) denote a bleaching stage
where chlorine dioxide is added and allowed some time to react, then an acid
stage is performed afterward in the same bleaching tower as the D stage without
washing in between the chlorine dioxide and acid addition. The slash notes there
is more than a minute in the reactions between the two stages, there is no wash-
ing between D and A, and that the two steps are conducted in the same reactor
(or tower). A designation like D/A without the parentheses just denotes the two
stages are conducted in separate towers (reactors) with no washing between the
two steps. Another example (D/E) denotes chlorine dioxide addition, mixing and
retention (eg, in a tower) followed, without washing, by a caustic extraction stage.
Letter symbols enclosed in parentheses and separated by a “+” sign denotes
simultaneous addition of two chemicals with no intermediate retention time, the
symbol for the predominant chemical being shown first. The chemical correspond-
ing to the symbol following the “+” sign is added simultaneously with the one
corresponding to the symbol preceding the “+” sign. For example, (D + C) denotes
the simultaneous addition of chlorine dioxide and chlorine with chlorine dioxide
being the dominant chemical and chlorine being the minor chemical.
It is not uncommon to see bleaching chemicals designated with lower case
letters such as an EOP stage. This is simply an improper designation of an (EOP)
stage according to the TAPPI TIP 0606-21. Other organizations may accept chem-
ical designations as subscripts. Detailed nomenclature descriptions and rules are
available in TAPPI Technical Information Paper TIP 0606-21 (11).
 PULP BLEACHING 7

3.2. Chemical Classes. Most of the bleaching chemicals employed are

oxidative chemicals. Oxygen (O) and chlorine dioxide (D) are employed at the front
end of the bleach plant where the pulp has a reasonably high residual lignin con-
tent of about 3.5–4.5 wt % on pulp for many softwood species and 2.2–3.0 wt % on
pulp for several of the hardwood species. The relatively high amount of lignin in
the fiber provides significant electron-rich sites for oxidative chemicals to break
bonds and reduce the molecular weight of the lignin contained in the fiber.
Once the residual lignin contained in the fiber is broken into fragments, the
oxidized fiber is subjected to a caustic extraction stage (E). The lignin fragments
are solubilized in alkaline solutions. Therefore, the lignin fragments produced in
a previous oxidation stage can be removed in the subsequent E stage. The lignin
becomes soluble in the alkali and simply diffuses out of the fiber. In addition to
making lignin fragments soluble, some amount of neutralization of organic acids
also occurs in the E stage.
Often, a small amount of peroxide and/or oxygen is added to the E stage
to enhance lignin oxidation and fragmentation. By reinforcing the E stage with
an oxidative chemical, it is often possible to reduce the amount of chlorine diox-
ide used in the first bleaching stage resulting in potential overall cost reduction
associated with the bleaching process.
After the extraction stage, the residual lignin content in the fiber is reduced
to 0.4–0.9 wt % on pulp. As such, limited amounts of delignification occur in
the remaining bleaching stages. Rather, the pulp is typically oxidized with chlo-
rine dioxide to destroy the remaining chromophores, resulting in increased pulp
brightness. Chlorine dioxide is typically the bleaching chemical of choice because
it is very selective and does not readily damage the cellulose portion of the fiber.
In addition to the oxidative chemicals, a reductive chemical, Y, may also be
used as a bleaching agent. The most prevalent use of reductants is in mechanical
and recycled pulp bleaching, but it has been employed in selected chemical pulp
bleaching sequences as well. A historic reductive bleaching chemical, sulfur diox-
ide, has been used to whiten fiber since the beginning of pulp bleaching. It is not
in typical use as a bleaching agent. Occasionally, sulfur dioxide will be used at
the end of an oxidative stage such as the last D stage to counteract any residual
oxidative chemicals which remain in the final bleached pulp.

4. Bleaching Stages

Each bleaching chemical has its specific advantages and disadvantages. Each
chemical also has its own set of optimal operating conditions which may change
depending upon the location of the specific stage within the bleaching sequence.
For kraft pulping, multiple stages must be strung together in certain ways to
obtain the desired pulp brightness and quality targets. There is no one specific set
of bleaching stages (sequence) required to obtain a specific set of pulp brightness
and strength conditions. Rather, several different sequences can be employed to
reach the same target values. Frequently these different pathways have a diverse
set of operating costs and produce differing pulp strength properties. As such,
it is important to understand the optimal conditions and stated goals of each of
8 PULP BLEACHING

the main bleaching stages in order to best understand how to create an overall
bleaching sequence which will meet a specific set of goals.
4.1. Oxygen Delignification (O Stage). Oxygen delignification is com-
monly employed in European mills and in South American market pulp mills. It is
less commonly employed in North America. Oxygen delignification was first intro-
duced in the 1960s in South Africa with common adoptions starting in the 1970s
in Europe. Oxygen delignification is a yield protecting method for extending the
delignification which occurs in the digester in a more selective manner than is
possible with kraft cooking. It is performed in a caustic (or oxidized white liquor)
environment so the resulting spent cooking chemicals and dissolved organic mate-
rials can be recovered in the brownstock washing process and sent to the recovery
boiler. By recovering all of the dissolved organic material, the load to the waste
treatment plant is reduced and the total oxidative chemical demand associated
with the bleach plant will be reduced.
Oxygen delignification is a three-phase mass transfer process with lignin
dispersed within a solid fiber matrix, a bulk alkaline liquor phase, and gaseous
oxygen. In order to maximize the O stage performance, it is typically performed
at elevated temperatures of around 80–100 C and elevated pressures of around
0.3–0.7 MPa oxygen pressure. Typical alkali and oxygen charges range from about
1.5% to 3.5% NaOH and 2.0–2.4% O2 on pulp. Reaction time is typically about
1 h. Increasing the temperature, the pressure, or the caustic soda concentra-
tion increases the rate of oxidation. Oxygen stages are mostly performed under
medium consistency bleaching conditions of 10–12% consistency. A few mills with
older oxygen stages performed oxygen delignification at a high consistency of
25–30%. No high consistency application has been installed since about 1985.
Two distinct reactions occur during oxygen delignification. These are delig-
nification through oxidation of the residual lignin contained within the fiber and
carbohydrate degradation which damages both pulp strength and yield. In some
instances, the use of magnesium salts in the reaction mixture has been found
to reduce carbohydrate attack. Because of an undesirable carbohydrate degra-
dation reaction, the use of the O stage is typically limited to 50% delignifica-
tion for softwood pulps and to about 35–40% delignification for hardwood pulps.
Newer oxygen delignification systems employ two pressurized reactors and split
the chemical charges in order to optimize rapid and slow delignification reaction
phases to enhance the overall amount of delignification. These efforts have pro-
duced some amount of success.
Although the degree of delignification is limited, treatment with oxygen
decreases the demand for other bleaching chemicals by 40–50%.
4.2. Xylanase Enzyme Stage (X Stage). Xylanase enzymes produced
from both fungi, typically Tricaderma species, and from bacteria, typically Bacil-
lus strains, are used as a pretreatment to bleaching in selective mills. Enzymes
gained a degree of commercial application in North America in the late 1990s.
Mills typically added an X stage as a cost reduction method. A few mills used
enzymes to increase production if they were chlorine dioxide limited and even
fewer used an X stage as a method of raising the brightness ceiling of their pulp
for specialty, high brightness runs of market pulp (12).
Early applications using xylanase from fungal sources were relatively
limited to a narrow pH range of near neutral to slightly acidic to be effective.
 PULP BLEACHING 9

Unfortunately, unbleached kraft mill pulps are typically alkaline with a pH of at

least 10 or higher. To reach an acceptable pH for xylanase application, mills had
to either add acid or carbon dioxide to the pulp resulting in increased application
cost and complexity, safety concerns, and often metallurgical issues. Initial
xylanase applications also had temperature limitations which were sometimes
difficult to obtain in typical kraft mill operations. Even with the operating limi-
tations, mills did successfully use enzymes to reduce chlorine dioxide demand in
the bleach plant. Unfortunately, the amount of reduction was rarely over 10–15%
thus, the results often resided within the statistical noise of the process and were
difficult to see on a continual basis. New processing methods of bacterial enzymes
obtained from Family 11 xylanases have now been reported to operate at pH
and temperature conditions which more closely resemble typically operating
conditions. The net reduction of chlorine dioxide has also been increased from
about 10% to closer to 15–20% when the process is operating smoothly. Even with
this level of reduction, it is difficult to justify an enzyme stage for cost reduction.
The X stage does not typically lower the kappa number (residual lignin
content) of the pulp by more than 1 or 2 points if at all. Rather, it appears to
remove reprecipitated xylan from the surface of the fibers rendering enhanced
access of lignin oxidation sites for chlorine dioxide or other oxidative reactions
which, in turn, allows for a reduction in oxidative chemicals (typically chlorine
dioxide) in the first stage of bleaching. Thus, not only are the results close to
the statistical noise associated with the process, it is often difficult to monitor
successful operation until after the fact, making the X stage a relatively niche
application in pulp bleaching.
Enzyme bleaching results have suffered because no known mill has built a
dedicated enzyme bleaching stage. Rather, the X stage has been retrofitted into
most bleaching sequences by adding pH control and xylanase into the pulp going
to a high-density storage chest. Mixing is typically less than ideal, pH and tem-
perature control is at best variable, and the towers often channel badly creating a
variable and short retention time. All these factors contribute to less than optimal
enzyme performance. An ideal X stage would have excellent pH and temperature
control, good mixing, and a controlled residence time. The X stages in current use
have limited to none of these controls.
4.3. Hot Acid Hydrolysis (A-Stage). Hot acid or A stages have become
common pretreatment methods for bleaching eucalyptus kraft pulps and for some
hardwood pulps such as birch. The A-stage is used to remove hexenuronic acids
(HexA) formed during the pulping process. Hexenuronic acids may be loosely
defined as a product of alkaline cooking, and their degree of prevalence in the
pulp depends on the amount of 4-O-methyl-𝛼-D-glucuronic acid originally present
in the raw material and how alkaline cooking is conducted. Figure 2 shows the
formation of HexA during pulping.
The double bond between the C-4 and C-5 carbon atoms in the HexA struc-
ture is readily oxidized by powerful oxidants, such as HOCl/Cl2 , O3 , and reacts
with KMnO4 used in the kappa number test. Therefore, kappa number cannot be
used as a true measure of residual lignin in pulps containing significant amounts
of HexA. HexA does not react with oxygen so pulps with high HexA content do not
respond particularly well toward oxygen delignification.
10 PULP BLEACHING

O HO O HO
O HO O O HO O
HO O HO O
O O O O
HO Kraft or soda HO
HO pulping HO
H3CO O O
HOOC 4-O-Methyl − CH3OH Hexenuronic
glucuronic acid COOH acid
(MeGlcA) (HexA)
group group
Fig. 2. Conversion of 4-O-methyl-𝛼-D-glucuronic acid groups (MeGlcA) attached to xylan
chains into hexenuronic acid groups (HexA) during alkaline pulping. Source: Reproduced
with permission of Brian N. Brogdon.

Several methods for quantifying the amount of HexA in pulp have been
developed with results usually expressed in mmoles of HexA per kg of pulp. This
unit can be converted into kappa number by conversion factors that vary in the
range of 9.6–11.9 mmol HexA/kg pulp per kappa unit, depending on the method
used for HexA quantification.
Industrial conditions for the A-stage are dependent on pulp type but, in gen-
eral, pH values of 3–3.5, temperatures of 85–100∘ C, and reaction times of 2–4 h are
typically used. Approximately 80% of hardwood pulp HexA is removed using 95∘ C,
pH 3, and 2 h retention time. The removal of hexenuronic acids in the A-stage
results in significant chlorine dioxide savings in ECF bleaching. One mill which
converted an ODED bleaching sequence for birch into an OADED by adding an
A-stage which removed about 90% of the pulp’s HexA resulted in a 6.8 kg ClO2 /air
dried metric ton of pulp savings (13). For a pine kraft pulp, the saving was only
about 3 kg ClO2 /admt pulp when converting an ODEDED sequence into OAD-
EDED thus highlighting that A-stages have a bigger impact on hardwood pulps
than on softwood pulps.
A-stages are generally only effective at saving ClO2 if the kraft pulp contains
>30 mmol HexA/kg pulp. Most softwood pulps contain <30 mmol HexA/kg pulp, so
an A-stage is generally not used due to poor economics/benefits. Hardwood pulps,
such as eucalypt and birch, contain high levels of HexA (40–70 mmol HexA/kg
pulp) and hot A-stages are economically feasible.
Significant loss in both pulp yield and pulp strength result when an
A-stage is pushed too hard. An A-stage run at 120∘ C, pH 5, and 2 h retention
time decreased the kappa number of an oxygen-delignified eucalypt kraft pulp
from 9.1 to 5.8, with consequent viscosity and yield losses of 3.1 mPa s and
8% respectively. The high yield loss renders these conditions undesirable for
commercial application. When the same treatment was run at 70∘ C for 5 h, no
impact on kappa number or yield was observed. It has been determined that a
temperature of >85∘ C is required for the HexA acid hydrolysis reaction to occur.
If the temperature is <85∘ C, no HexA removal happens thus proving temperature
is essential to achieve the goal of removing HexA from the pulp.
In addition to reduced chlorine dioxide or ozone demand, pulps treated with
an A-stage contain lower residual HexA and are less prone to brightness rever-
sion than pulps not treated with an A-stage. Another significant benefit of A-stage
implementation is reduced scaling in the mill. Industrial experience in Brazilian
and Scandinavian pulp mills have shown a greater than 50% decrease in calcium
 PULP BLEACHING 11

oxalate scaling after A-stage implementation. The effect is attributable to the

effective removal of calcium along with HexA under the A-stage conditions.
Very high carryover (24–26 kg COD/adt pulp) can render the A-stage ineffec-
tive in terms of chemical savings (14). Carryback from the A-stage to the brown-
stock washer showers contributes variable amounts of acid-soluble lignin and
furan compounds, which also affect A-stage performance. “A” stages in bleach-
ing are usually only found in Scandinavia where large amounts of birch are being
processed or in South American where eucalyptus is the predominant species.
Hot Chlorine Dioxide Stage (DHT Stage) Modification of the A-Stage.
To reduce complexity and limit capital costs, the hot acid stage has been com-
bined with the first chlorine dioxide stage, D0 , without the use of a washer in
both an A/D and D/A configuration. Mills have created an A/D stage by convert-
ing the high-density storage/bleach plant feed tank into a modified A-stage simply
by raising the temperature and lowering the pH of the stock being sent to the
tank. After some retention time in the tower, unwashed stock can be mixed with
chlorine dioxide and sent to the D0 stage.
Early laboratory studies on the A-stage found the key reaction product of
the A-stage was 2-furoic acid, which reacts only slowly with chlorine dioxide, so
it will only slightly interfere with D0 stage reactions. Because of this feature, the
A-stage can be connected to a D0 stage without intermediate washing. A very
small increase in chlorine dioxide consumption may result from this combina-
tion. Retrofit applications, where a storage tower is used as the reaction vessel,
can have problems in controlling retention time because the high-density storage
towers are not usually designed for uniform retention.
In new bleach plants built with an A-stage, the A/D technology is usually
installed as an upflow tower and designed for approximately 2 h retention time.
With these types of designs, a hot D0 stage is performed in a short reactor directly
after the A-stage. Upflow bleaching towers are used for the A-stage to guaran-
tee a constant retention time at full production rate. Uniform kappa reduction
can be achieved by adjusting the temperature and pH as needed. The improved
retention-time control and optimized process conditions enable 3–4 unit kappa
reduction on eucalyptus pulp and make it possible to produce high brightness
market eucalyptus pulps with only 9.5–11.5 kg ClO2 /admt and 3–5 kg H2 O2 /admt
pulp using three bleaching towers and three washers.
When a (D/A) stage is employed, chlorine dioxide performs a dual function
in a single reactor, namely, lignin removal followed by HexA removal. The idea
behind the (D/A) stage is that the reaction rate of chlorine dioxide with lignin is
2.2 times faster than the apparent reaction rate of chlorine dioxide with HexA
(15). Therefore, if a mill can be disciplined to only add the amount of chlorine
dioxide required to react with the true lignin in the fiber, it will react with the
lignin and only a minor amount will react with the HexA. Only chlorine dioxide
will be consumed in the first minutes of the reaction by reacting with lignin, and
in the remaining 2–3 h retention time, the HexA groups will be degraded under
the hot acid conditions of the stage. The pulp does tend to darken within the reac-
tor but the brightness loss is recovered in the subsequent bleaching stages. The
D/A technology results in more efficient overall bleaching than a conventional D0
stage when significant amounts of HexA are present. This technology is extremely
12 PULP BLEACHING

important for eucalyptus pulps and Scandinavian birch pulps, but not as impor-
tant for North American hardwoods.
When using the (D/A) methodology, pH of the stage is automatically lowered
because of chlorine dioxide reactions with lignin. The HexA reacts mainly with
hypochlorous acid formed during chlorine dioxide bleaching reactions but, this
reaction is considerably slower than the reaction of hypochlorous acid with lignin
(15). Therefore, HexA destruction occurs only after the lignin reacts with chlorine
dioxide. Industrial operation of the (D/A) stage takes discipline because operators
tend to want to over-apply chlorine dioxide to react with the HexA immediately
rather than wait for the lower pH and hypochlorous acid to destroy the unwanted
material.
4.4. Chlorine Dioxide Delignification Stage (D0 Stage). The first
stages of bleaching continue the process of removing residual lignin in a more
selective manner than either the pulping or oxygen delignification processes.
Historically, chlorine was used as a first bleaching stage often with a small
amount of chlorine dioxide added to the stage as a strength (viscosity) protector
for the pulp. When it was discovered that measurable amounts of dioxins,
furans, and various adsorbable organic halogens (AOX) were formed in the first
chlorination stage, the industry moved to mainly ECF bleaching by substituting
100% of the chlorine in the first bleaching stage with chlorine dioxide.
Chlorine dioxide has an unpaired electron; therefore, it is a free radical
with only limited stability. It is produced as a gas under standard conditions and
explodes spontaneously at partial pressures above 40 kPa. For this reason, pure
chlorine dioxide cannot be transported and stored. It is generated on site and
normally handled as a dilute aqueous solution. Chlorine dioxide decomposes into
chlorine and oxygen. Often, chlorine dioxide generators experience decomposition
reactions called “puffs.” Generators are fitted with explosion hatches which vent
to safe areas to accommodate these events. If heated or exposed to light, it can
explode even at lower concentrations, but with less violence.
Chlorine dioxide generators are typically operated under vacuum with the
reaction media being an acidic mixture of sodium chlorate and either methanol or
hydrogen peroxide serving as the reducing agent. Sulfuric acid is typically used
to maintain the acidic environment. These processes generate very pure chlo-
rine dioxide in a gaseous stage, highly diluted with air or water vapor to avoid
explosions. The chlorine dioxide is absorbed in cold water to produce an aqueous
solution with a concentration of 6–12 g/L.
Chlorine dioxide is a strong oxidizing chemical. It reacts with free phenolic
groups and aliphatic double bonds, resulting in demethylation and ring cleav-
age in the lignin structure. Chlorine dioxide is relatively unreactive toward fully
etherified phenolic units in lignin and is nearly inert toward cellulose and other
carbohydrates in pulp.
The D0 stage is typically performed at standard mill operating temperatures
of between 50 and 75∘ C. Some hardwood stages will be operated closer to 95∘ C in
order to remove HexA as discussed above. Some northern mills have to add steam
to the pulp during extreme winter months to get their process temperatures up
to 50∘ C but this is also rare. When employed in the first bleaching stage, chlorine
dioxide will have a terminal pH of about 3.0–3.8 if no acid or caustic is added to
 PULP BLEACHING 13

the stage. Chlorine dioxide does not affect the degree of polymerization of cellulose
within an operating pH range of about 2–5 (16).
Typically, an optimal pH of about 3.0 would be chosen from a delignification
standpoint. Unfortunately, the pulp entering the D0 stage contains a significant
amount of nonprocess elements (NPEs) such as calcium. These NPEs are typically
removed in the first acid stage encountered in the pulping and bleaching process
(D0 Stage) via washing of the acidic pulp. One of the major forms of scale formed
by these NPEs is calcium oxalate. It has been determined and modeled that cal-
cium oxalate scale will rapidly form when the pH is 3 or higher (17). To avoid
undesirable scale formation on the processing equipment, the pH of the D0 stage
is typically operated between 2.5 and 2.8 to avoid the optimal range for oxalate
scale formation. A more detailed discussion of NPEs will be presented later in this
document.
4.5. Ozone (Z Stage). The application of ozone in pulp bleaching was
patented in 1889 (18). Process conditions for ozone bleaching of chemical pulps
were identified in 1949. Commercial application was delayed because methods of
rapidly mixing ozone gas into medium and high consistency pulp had to be opti-
mized to ensure good reaction performance without loss of strength. Interest in
ozone for pulp bleaching accelerated in the 1990s as the development of ECF and
TCF bleaching accelerated due to the advent of more stringent environmental reg-
ulations regarding waste effluents (commonly known as the cluster rules) which
eliminated chlorine bleaching as the first delignification stage in pulp bleaching.
Since then, ozone bleaching has evolved from pilot plant operations to commer-
cial installations. By 1995, there were 13 bleach plants employing ozone. Ozone
usage has progressed into the 2000s, but the use of chlorine dioxide has become
the preferred method to replace chlorine in most bleach plants. Ozone continues to
represent both an environmentally attractive alternative to chlorine dioxide with
the number of mills with active ozone installations increasing to 23 worldwide as
of 2010. This number has increased to 30 fiberlines today which produce about 10
million ADMT of ozone bleached pulp per year.
Ozone is a powerful oxidizing agent which tends to react with pulp rapidly
and indiscriminately. Therefore, its application must be carefully controlled to
prevent strength loss. As with chlorine dioxide, ozone must be produced on-site.
Ozone is typically produced from pure oxygen via a corona electrical discharge.
The pure oxygen atmosphere allows a high ozone concentration of up to 12 wt %
to be formed in a gaseous phase. The high ozone concentration facilitates gas/fiber
mixing in the Z stage. Ozone rapidly reacts with lignin, cellulose, and hemicellu-
loses. In order to minimize the cellulose reactions, a pH less than 4 and a reaction
temperature less than 50∘ C are required. When the temperature becomes ele-
vated, brightness stability suffers and the pulp tends to yellow. Commercial ozone
delignification technology is performed either at medium consistency (8–12% pulp
consistency) or high consistency (25–35% pulp consistency), at pH range of 2–3
and 40–70∘ C. The ozone charge is usually limited to a maximum of 1% on pulp
with typical applications being less than 0.5% as higher ozone charge has a pro-
nounced negative effect on pulp strength.
Ozone can be substituted for a portion of the chlorine dioxide in the D0 stage.
If chlorine dioxide is added followed by ozone the stage is designated as a (DZ)
stage. If ozone is mixed into the pulp just prior to chlorine dioxide addition, the
14 PULP BLEACHING

stage is referred to as a (ZD) stage. The combination of chlorine dioxide and ozone
has been reported to effectively reduce both the chemical cost and AOX formation
in an ECF kraft pulp bleaching sequence.
4.6. Caustic Extraction Stage (E Stage). Extraction was developed
almost a century ago to lower the chemical demand and increase the final
pulp brightness. The development of the E stage led to multistage bleaching
sequences, which resulted in significantly higher brightness pulps. The D0
stage is almost always followed by an E stage. E stages are also often employed
after ozone-containing stages. The purpose of the alkaline extraction stage is to
solubilize and ionize reacted lignin fragments, diffuse these fragments from the
fiber into the bulk liquor phase and to neutralize any organic acids (typically
carboxylic acids) formed during the previous oxidation stages.
Typical E stage operating conditions are 1–2 h at 60–90∘ C and 10–12%
consistency. Recent softwood studies have suggested that the optimum sodium
hydroxide charge reported as percent on pulp should be roughly 0.085–0.11
times the kappa number of the pulp entering into the D0 -stage. Hardwood pulps
generally require less caustic so the optimal hardwood pulp charge tends to be
about 0.075 times the kappa number of the pulp entering the D0 stage. The
terminal pH of the E Stage should be 10.5 or greater when measured at 25∘ C.
It should be noted that the pH value of extraction filtrates can be 1–1.5 pH
units higher at room temperature than at the extraction process temperature.
Correction factors supplied by Reid and Morissette (19) or Spriggs (20) can be used
to correct for temperature variations due to samples being measured at process
conditions rather than being allowed to cool to room temperature prior to being
measured. Extraction efficiency, as determined by post-extraction kappa number,
can be negatively affected if the end pH becomes too low (ie, <9) to ionize and
disperse the oxidized lignin into the filtrate.
Cold caustic extraction plays a critical role in the purification of dissolving
pulps. It removes resins, extractives, and hemicelluloses, in addition to residual
lignin, from sulfite and prehydrolyzed kraft pulps. High dosages of caustic soda,
5–15% on pulp, are used in this extraction process in order to produce purified
alpha-cellulose with a specific molecular weight distribution required for dissolv-
ing pulps.
Oxygen and/or Peroxide Reinforced Caustic Extraction ((EO), (EP),
(EOP) Stage). In modern ECF bleach plants, adding some form of oxidative
reinforcement to the first extraction stage is almost always standard operating
practice. Oxygen, charged at 0.3–0.6% on pulp, is frequently added to softwood
pulp E stages to convert the stage into an oxygen-reinforced extraction (EO)
stage. Higher oxygen dosages do not further enhance delignification. Rather,
higher oxygen charges can result in tower channeling, as well as a stock that is
more difficult to wash due to gas entrainment. The reactions of oxygen with the
pulp in the (EO) stage are very rapid, normally on the order of one to five minutes
as long as the oxygen gas is efficiently dispersed into the medium consistency
pulp. Oxygen mixing is done with either a high-intensity mixer or with a gas
sparger, just ahead of the (EO)-stage. A hydrostatic head pressure of 0.2–0.3 MPa
at the bottom of the pre-retention tube or upflow (EO) tower is sufficient to ensure
the oxygen gas can dissolve in the liquid to react with the pulp. Operations of the
(EO) stage at higher pressures, 0.4–0.7 MPa, with a pressurized upflow tube are
 PULP BLEACHING 15

not uncommon. The kappa number reduction of an (EO) versus a nonreinforced

E-stage is generally not due to more lignin removal but reflective of a more highly
oxidized residual lignin in the (EO) pulp.
Often, hydrogen peroxide is added either along with or instead of oxygen
to transform the E stage into an (EOP) stage or an (EP) stage. Peroxide dosages
are in the range of 0.2–0.7% on pulp. Higher peroxide dosages can be used as
long as higher extraction temperatures of 80–95∘ C are used. It is possible to use
longer retention times of greater than 1.5 h possibly in conjunction with the higher
temperatures to ensure complete peroxide consumption although 1 h is typical.
It is undesirable to have a peroxide residual after an (EP) or (EOP) stage since
residual oxidant can carry over into the D1 -stage and consume additional chlo-
rine dioxide. The addition of either oxidant or their combinations in extraction
generally increases brightness and decreases post-extraction kappa number for a
chlorine dioxide delignified pulp at a given kappa factor. Extraction reinforcement
oxidizes susceptible residual lignin that would otherwise consume additional chlo-
rine dioxide in subsequent brightening stages. The amount of ClO2 displaced by
an (EOP) stage can vary from 0.6 to 2.5 kg per kg H2 O2 used depending on process
conditions and wood species.
The extraction stage is reinforced with an oxidant to enhance lignin removal
and to decrease downstream bleaching chemical costs. In order to make the rein-
forced stage more effective, it is often desirable to decrease the amount of oxidizing
chemical employed in the D0 stage as the efficacy of oxidant-reinforced extraction
is dependent upon amount of oxidant (chlorine dioxide typically) used in the previ-
ous D0 stage. Figure 3 shows the impact of varying the amount of chlorine dioxide
in the D0 stage upon the post-extraction kappa number for both a D0 stage and
an (EP) stage. Note the changes in the amount of lignin removed in the extraction

26
D0 Stage
23
EP Stage
Kappa number after D0

20
or EP stage

17

14

11

5
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2 0.22 0.24

Kappa factor in the D0 Stage

Fig. 3. Kappa number exiting the D0 and D0 (EP) stages as a function of D0 kappa factor for
a softwood kraft pulp with starting kappa number of 25.1. The (EP) stage was performed
at 70∘ C with 3 kg hydrogen peroxide per ton of pulp for 1 h. Kappa factor is a ratio of
the wt % applied oxidant reported as active chlorine divided by the kappa number of the
entering brownstock pulp. For a chlorine dioxide, D0 stage kappa factor is (% applied ClO2
* 2.63)/kappa number.
16 PULP BLEACHING

stage (delta between the two lines) as the applied chlorine dioxide charge in the
D0 stage increases.
The post-extracted kappa number for softwood kraft pulp exhibits a non-
linear relationship with the D0 kappa factor. The kappa number asymptotically
approaches a “floor-level” level at high chlorine dioxide charges beyond which the
application of more of the same type of oxidant will not lower the kappa number.
Generally, combinations of oxygen and peroxide are advantageous since the oxi-
dants react with different lignin functional groups and complement one another
resulting in enhanced delignification.
Hardwood pulps, which have lower brownstock and oxygen-delignified kappa
numbers than softwoods, differ in how they respond to alkaline extraction. The
post-extracted kappa number of hardwoods is slightly lower but runs almost par-
allel to the post-D0 kappa number as the kappa factor charge is increased. It
has been proposed that post-extracted brightness is a better control parameter
to gauge future bleach consumption than post-extracted kappa number for hard-
woods and low-lignin pulps.
Hardwood pulps are frequently treated with (EP) stages. Oxygen reinforce-
ment alone is often found to be ineffective for several types of hardwood pulps
while adding oxygen to an (EP) stage often results in similar post extracted kappa
numbers as with peroxide alone and increases operating costs.
4.7. Chlorine Dioxide Brightening Stages (D1 and D2 Stages). The
application of chlorine dioxide for delignification is a fairly recent development
which began in the 1980s with full ECF implementation in the 1990’s. In contrast,
the use of chlorine dioxide in brightening stages came about much earlier. Chlo-
rine dioxide brightening was made possible by the invention of commercial scale
chlorine dioxide generators in 1946. By 1957, there were 43 mills using chlorine
dioxide in brightening stages in North America alone.
Pulp leaving the E stage tends to be quite dark. There is some small amount
of residual lignin present (typically between 0.44 and 1.18 wt % on fiber), which
will be mostly removed during the brightening phases of bleaching. There is also
a significant amount of chromophores present in the pulp. Chromophores are
chemical structures contained within the pulp fibers which absorb light. Poten-
tial chromophores in wood and pulp include catechol metal complexes, quinones,
and carbonyl groups (21). Several of these structures result from lignin and its
degradation products. These chromophores, especially the ones resulting from
delignification degradation are the components responsible for the majority of the
light absorption in the visible region (21). The purpose of the brightening stages
is to modify the lignin and other chromophores so that these compounds do not
absorb light.
When caustic extracted pulp is mixed with chlorine dioxide at reaction stage
temperatures, the brightness response displays a rapid rate that slows as an
asymptotic limit is approached. The asymptotic limit represents the brightness
ceiling. Every brightening stage has a brightness ceiling and the bleaching
sequence as a whole has a brightness ceiling. The ceiling is determined by pulp
type and the various reaction conditions to which the pulp was exposed prior to
the current brightening stage. For example, in a D1 stage a high extraction stage
kappa number of say 6–8 units leads to a low brightness ceiling. In a D2 stage a
low initial brightness coming from the D1 stage leads to a low brightness ceiling.
 PULP BLEACHING 17

Experienced operators know that if the initial D0 chlorine dioxide delignification

phase fails to sufficiently react with the pulp, it is usually difficult to obtain
target brightness, regardless of how much chemical is added. For this reason,
many operators will over apply chlorine dioxide in the front end of the bleach
plant at the expense of total bleaching cost. The stage brightness ceiling is due to
a limit on how much chemical modification can take place in that specific stage
while the sequence brightness ceiling is a combination of the cumulative stage
limits and the specific limitations associated with the specific wood species being
bleached.
A typical D stage used for brightening consists of an upflow tube with a
retention time of approximately 20–30 min followed by a downflow tower with
approximately 3–4 h retention time. Retention times can vary by as much as 50%
from these values as mill production rates are frequently pushed well past their
design capacities. Older mills or mills with diffusion washers may simply have an
upflow tower with only 1.5–3 h retention time. Frequently, the D2 stage will have
a longer retention time than the D1 stage.
To achieve maximum retention times, consistencies should be as high as pos-
sible and dilution zones controlled to specified levels within the tower. D stage
brightening towers are designed to operate at about 12% consistency. Studies
on chlorine dioxide brightening stages have generally shown that there is lit-
tle change in chemical efficiency when operating within the consistency range
of 9–16%. Tower channeling becomes significant when pulp consistency is below
9%. If a tower channels, the actual retention time could be reduced from a few
hours to only a few minutes. The potential for channeling still exists at 10–15%
consistency but is greatly reduced.
Brightening stages are typically performed at elevated temperatures. The
D1 stage in a bleaching sequence with more than one brightening stage is often
performed at lower temperatures than the terminal brightening stage. Also, if one
of the goals of the first D stage is to reduce/eliminate shives, it is run at a lower
temperature as well. Typical rule-of-thumb operating temperatures are 65–70∘ C
for the D1 stage attempting to remove shives or 70–75∘ C for a D1 stage simply
focusing on brightness development. The D2 stage is typically operated between
75 and 85∘ C depending on the terminal brightness target and the stage retention
time. Operating at a higher temperature has also been shown to decrease bright-
ness reversion by as much as 50%. However, for reduction of dirt and shives, a slow
reaction rate resulting from lower temperature operation is desirable as the slow
reaction allows diffusion of chlorine dioxide into the shives resulting in enhanced
shive delignification/destruction before the chlorine dioxide is depleted in various
brightening reactions.
As discussed above, both time and temperature are critical for D brighten-
ing stages. These two operating parameters can and should be considered together
as crucial elements in determining the efficiency of the D stage. Remember, the
reaction between chlorine dioxide and pulp proceeds through a rapid initial phase
followed by a slower phase as the brightness ceiling is approached. As the reaction
time proceeds, chlorine dioxide available for the reaction will be depleted. Increas-
ing the temperature of the reaction will increase the rate of both the brighten-
ing reactions and of chlorine dioxide consumption. As with the D0 stage, a 10∘ C
increase in temperature approximately doubles the reaction rate.
18 PULP BLEACHING

Temperature and time can have an effect on brightness, brightness

reversion, and shive reduction, but the most critical effect for all mills to consider
is the impact of retention time at temperature upon chlorine dioxide residual. If
the conditions are right, the brightening reactions will proceed until the chlorine
dioxide is just short of being fully consumed resulting in a slight residual being
left at the end of the tower. Several researchers have determined that maintaining
a residual of 0.01–0.02 g/l is a good operating target. They have also determined
that the relationship between chemical dosage and temperature required for low
residual is nearly linear for a given retention time. Maintaining a slight residual
is desirable to prevent brightness reversion within the tower. Higher residuals in
the tower have been documented to enhance dirt and shive reduction in both D1
and D2 stages. The impact of chlorine dioxide concentration on shive reduction
is especially important in the D1 tower. A good operating target residual of
0.01–0.02 g/l is typically recommended under most operating scenarios.
If high chlorine dioxide residuals remain after the brightening stage and
the stage is near its brightness ceiling, reducing the chlorine dioxide dosage may
decrease the residual with little to no effect on the pulp brightness obtained from
that stage. The only impact will be lower total bleach chemical costs for the bleach-
ing sequence. However, if the brightening stage is not near its brightness ceiling
and more chlorine dioxide must be consumed to reach higher brightness targets.
In order to consume more chemical, the operator must either increase the tem-
perature or increase the retention time in the tower. As the volume of the tower
is fixed and an operator cannot typically reduce the production rate, the most
logical alternative is to increase the temperature. As long as oxidative chemical
remains, either increasing the reaction time or raising temperature will produce
higher brightness if the stage is operating below the brightness ceiling.
The one exception to this concept is if significant retention time remains in
the tower once the chlorine dioxide residual reaches either trace or zero level,
the brightness will decrease from its maximum. Despite this brightness loss, sub-
sequent chlorine dioxide treatment will recover this loss with no net additional
chemical requirement. Therefore, the in-tower brightness loss is only considered
to be a critical issue for final D stage after which there will be no opportunity to
regain the brightness. If a mill is using a brightness based control strategy for
chlorine dioxide in addition to the terminal brightening stage, loss of brightness
in an internal brightening stage due to loss of residual can result in overdosing
the terminal brightening stage. Therefore, it is still desirable to operate a middle
D stage (D1 in a four or five stage sequence) at conditions giving a slight residual
for energy and control purposes. If the mill is running zero residual there is an
opportunity to save steam by lowering the temperature until the residual returns.
Also, if a mill is running a D1 stage to zero residual and experiencing brightness
loss in the tower, any brightness measurement after the D1 stage tower might be
a false indication of the actual bleaching demand of the subsequent D2 stage.
In addition to time, temperature, and chlorine dioxide residual, the ter-
minal pH of each of the brightening stages is critical for optimal brightness
development. Understanding the effect of pH on the D stages is critical to
optimizing performance (16). Chlorine dioxide reacts with extracted residual
lignin through multiple reaction pathways depending upon the localized pH.
Some of these pathways are more beneficial and efficient than others. In addition,
 PULP BLEACHING 19

it is important to note that the pH falls as the reaction proceeds. The key to
optimization is to select an end pH which favors the best set of intermediate
reactions throughout the entire retention sequence. The optimal pH is dependent
on the chemical used for pH adjustment, furnish species, and chlorine dioxide
dosage (16). Typical terminal pH values have been determined to be around a
pH of 3.5 for the D1 washer vat and a terminal pH of at least 4.1 for the D2
stage washer vat. Several recent studies have suggested the optimal terminal
brightening stage pH might be as high as near neutral.
There are four basic methods available to control D1 stage chlorine dioxide
charge: (1) feed forward based on extraction kappa, (2) feedback based on an
online brightness measurement, (3) compensated brightness as suggested and
sold by various vendors, and (4) manual dosage control based on an operator
measured brightness. Most control schemes employ a combination of the all of
the above methods, especially manual operator brightness bias to the suggested
control dosage. Regardless of control method, one of the most important target
variables for the optimization of a four or five stage sequence is the D1 stage
brightness. This target sets the balance for the brightening phase of the sequence.
When using the D1 stage brightness for control, it is important to factor the D1
stage residual into account and to account for the actual bleaching sequence
being employed. For instance, a four-stage sequence offers significant advantage
over a three-stage sequence based upon operating chemical cost. For the same
extraction stage kappa, less chemical is required to reach target brightness for
the four-stage sequence.
When operating two brightening stages, it is important for chemical/cost
optimization to distribute the oxidizing chemicals properly. The split between the
D1 and D2 stages varies somewhat depending upon the final brightness target and
the species being bleached. A common method used to determine an optimal split
is to evaluate the total chlorine dioxide requirement to reach a brightness target
against the percentage of total D1 and D2 chlorine dioxide added to the D1 stage.
One study conducted on red oak found that the optimal distribution was wide and
flat for a low brightness target of 86% ISO. This study determined that 30–70% of
the chlorine dioxide could be charged in the D1 stage. When the brightness target
was increased to 91% ISO, the optimal range shifted up to an optimal D1 stage
application of 65–80% of the total D1 + D2 chlorine dioxide being applied in the D1
stage. In several other studies, authors have shown the optimum distribution of
chlorine dioxide to be between 70% and 90% in the D1 stage for softwood furnishes.
Balancing the chlorine dioxide charges across the D0 , D1 , and D2 stages can be a
crucial optimization exercise. The D0 chlorine dioxide will mainly be used to delig-
nify the pulp while the D1 and D2 stage chlorine dioxide will be used to brighten
the pulp. Understanding the concepts of brightness ceiling and bleachability can
be helpful in achieving the right dosages across the sequence.
There may be mill specific reasons to deviate from an optimum distribution.
If one stage is limited by short retention time or low temperature, it may be nec-
essary to shift the bleaching load to the stage with greater flexibility. If a mill is
using the D1 stage as a shive reduction stage, it may benefit from a higher chlorine
dioxide dosage in the D1 stage than would be considered optimal from a purely
brightening perspective. The higher D1 stage charge would ensure a high chemical
20 PULP BLEACHING

residual within the tower which would ensure diffusion of chlorine dioxide into the
shives to facilitate shive destruction.
The goal of the D1 and D2 brightening stages is to increase the brightness
of the pulp by modifying residual lignin fragments and other chromophores
so that these compounds do not absorb light. When discussing brightness, it
is important to understand that brightness has two components, a chemical
component and a physical component. These two components are well repre-
sented in the Kubelka–Munk equation by the absorption coefficient (k) and a
physical component, represented by the scattering coefficient (s). The absorption
coefficient accounts for the chemical component of brightness (chromophores that
lower brightness). The scattering coefficient accounts for physical components
which are largely determined by the fiber wall thickness, amount of fiber collapse,
degree of refining, and sheet formation. Bleaching has minimal impact upon
the scattering coefficient. As such, the brightness ceiling is impacted by each
fiber species because each type of wood has a different morphology. No matter
how much chemical treatment is applied, each species exhibits a specific upper
brightness limit determined somewhat by the scattering coefficient associated
with that specific species. An early study into the brightness ceilings for various
species showed some hardwoods at 90% ISO, southern pine at 88% ISO and
spruce at 86% ISO brightness. It is generally accepted that eucalyptus pulps
have the highest brightness ceiling among the commonly pulped species with
some eucalypt species being reported with a 92% ISO brightness ceiling.
4.8. Peroxide Brightening Stage (P Stage). Alkaline peroxide is occa-
sionally employed as the last or sometimes as the next to last brightening stage.
Peroxide stages that are located in these positions are strongly influenced by the
entering pulp brightness. P-stage brightness development is a function of enter-
ing brightness and peroxide charge. Brightness gains on the order of 1–7 points
may be realized when 0.1–0.6% peroxide on pulp is used. P stages are typically
conducted under alkaline conditions. The alkaline environment assists with the
ionization of hydrogen peroxide, which is weakly acidic in water. Hydrogen perox-
ide has pKa value of 11.0 to 9.5 at temperatures of 50–110∘ C. The resulting perhy-
droxyl anion (HOO− ) is accredited as the primary species for the bleaching action
of peroxide. Perhydroxyl anions are strong nucleophiles which attack carbonyl-
and conjugated carbonyl-containing structures composing residual and heavily
oxidized kraft lignin such as quinones, coniferyl aldehydes, and muconic acids.
Like most bleaching agents, hydrogen peroxide can generate secondary oxi-
dizing species with the predominant intermediates being hydroxyl radicals (HO• ),
superoxide radical anions (O2 •− ), and/or oxygen due to catalytic reactions with
either hydroxide or transition metal cations (like iron and manganese). These
species result from peroxide/perhydroyl anion decomposition. Hydroxyl radicals
are highly reactive intermediates that indiscriminately react with lignin and car-
bohydrates. They do little to no brightening and cause significant carbohydrate
degradation. Oxygen formation during peroxide brightening results in a loss of
bleaching efficiency as oxygen does no pulp brightening for low kappa number
pulps found in the latter bleaching stages. Judicious suppression of secondary
peroxide decomposition ensures that the highest possible concentration of per-
hydroxyl radicals will be available for brightening reactions and is essential to
maximizing the full brightening potential of a P stage. It is difficult for a P-stage
 PULP BLEACHING 21

to brighten to ∼85% ISO when the prebleached kappa number is greater than 5
unless more aggressive conditions of a high peroxide dosage and temperatures of
greater than 90∘ C are employed.
Sodium hydroxide is used in conjunction with hydrogen peroxide to generate
the perhydroxyl anion in situ. The amount used for a conventional, nonpressur-
ized P-stage is roughly 80–120% of the hydrogen peroxide charge on a mass basis.
The pH of the peroxide brightening stage is around 10.2–11. Enough alkalinity
should be present to ensure that 20–40% of the total applied hydrogen perox-
ide is ionized. The reaction temperature influences both the measured pH and
the amount of perhydroxyl anion formed. Increasing the reaction temperature
decreases the pH and the amount of perhydroxyl anions for a given amount of
sodium hydroxide.
As with D stage brightening, P stage brightening proceeds in two distinct
phases: (1) a rapid initial brightening phase and (2) a much slower brightening
phase. The initial phase, which lasts for the first 20–30 min, accounts for most
of the brightening. The subsequent slower phase contributes only 20–30% of the
overall brightness gain. The amount of peroxide that a partially bleached pulp will
readily consume at nominal reaction temperatures of 60–90∘ C is about 0.2–0.7%
on pulp. Higher reaction temperatures of at least 90∘ C or higher are required to
accelerate peroxide consumption of 1% or higher. If the harsher conditions are
not employed, the post P-stage pulp will have an excessive peroxide residual of
at least 30% of the applied peroxide. If lower reaction temperatures are employed
with high peroxide dosages, excessively long retention times of greater than 4 h
will be required to consume the peroxide.
A terminal P-stage in a bleaching sequence tends to stabilize the final pulp
brightness better than a terminal D stage. Several researchers have reported
reduced brightness reversion for terminal P stage pulps as compared to terminal
D stage pulps for various ECF bleaching sequences.

5. Nonprocess Element (NPE) Scale Formation

Water consumption in pulp production has decreased significantly over the last
15 years. Volumes have declined from greater than 50 m3 /t of pulp in the 1990s to
about 15 m3 /t of pulp in modern pulp mills. NPEs in wood limit a further reduction
in water usage as they tend to concentrate and precipitate onto process equipment
resulting in reduced performance and plugged lines. The reuse of process filtrates
and the recovery and reuse of various process chemicals also results in concen-
tration of these elements in the system. Therefore, some level of effluent or solids
discharge is necessary for a well-performing bleach plant.
Most cations enter the process with the wood. Table 2 shows concentration of
several of the common cations associated with various wood species. The common
cations are predominantly metals such as Ca, Mg, Fe, Mn, and Cu. Chloride and
sulfate ions are the main counter ions found in the bleach plant.
Process improvements designed to minimize the impact of NPEs often result
in modifying the form in which the ions precipitate through the manipulation
of the process pH or reducing the concentration of specific ions so they will not
precipitate. A couple applications of these methods are reviewed below.
22 PULP BLEACHING

Table 2. Trace Metals Associated with Various Wood Species (22)

Species Ca, K, Mg, Na, Mn, Fe, Al,
mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg
green Ash 1992 1560 467 238 23 70 25
red Maple 1937 974 290 198 82 75 22
red Oak 908 998 139 149 183 77 34
white Birch 740 270 180 – 34 – 23
aspen 2230 1230 270 – 29 – –
loblolly Pine 889–1155 104–125 250–311 197–256 95–112 56–68 –
red Spruce 820 200 70 – 144 – –
balsam Fir 830 770 270 – 127 – –
eastern Hemlock 750 400 110 – 145 – –
Source: A. W. Rudie, P. W. Hart in P. W. Hart, A.W. Rudie, eds. The Bleaching of Pulp: 5th Edition,
TAPPI Press, Atlanta, p. 179 (2012).

In the early 1990s when mills first replaced chlorine with chlorine dioxide
as the first bleaching stage, there was a corresponding switch to higher pH in this
stage because the natural pH of chlorine dioxide in a D0 bleaching stage is near
4. This is also around the traditional optimum pH for D1 and D2 stage bleaching.
When operated around pH 4, the D0 stage is not as efficient at dissolving calcium
and barium as compared to the old chlorine stage. The net result of this decreased
efficiency was that many mills began to encounter more serious scale problems.
These scales manifested as both calcium oxalate and barium sulfate in the D0
stage and calcium carbonate in the first extraction stage. When looking at scale
formation fundamentals, the reasons for increased calcium oxalate scale are obvi-
ous. When operating near pH 4, calcium carbonate brought into the bleach plant
with the fiber will be dissolved. Unfortunately, pH 4 is not low enough to pro-
tonate the divalent oxalate ion, resulting in conditions where calcium oxalate is
likely to form. When chlorine was used, the stage pH was often 2 or less resulting
in minimization of the divalent oxalate anion. Therefore, calcium oxalate could
not form in the chlorination stage but can form in the non-pH modified D0 stage.
Calcium oxalate is not only the source of scale in the D0 stage, but it remains the
major problem with bleach plant mineral scale, and precipitated calcium oxalate
trapped in pulp fibers in D0 contributes to formation of lime scale in the subse-
quent E stage.
For calcium scale, either calcium oxalate in D0 and/or calcium carbonate in
extraction, one potential process solution is to control the terminal pH of the D0
stage to a range of 2.5–2.8. The insoluble form of calcium in this stage is calcium
oxalate, and the target pH of 2.5 is near the first pKa for oxalic acid, meaning
the oxalic acid exists in the acid and mono-anion forms, not as the dianion. The
mono-anion form does not tend to precipitate out under D0 bleaching conditions
allowing for its removal through effective D0 stage washing (17). Luckily, the tar-
get pH of 2.5 is still within the optimal pH range for use of chlorine dioxide in a D0
stage. Mills that have adhered to this pH range target have been able to operate
relatively calcium scale free in the D0 and E stages.
Unfortunately, controlling barium sulfate scale deposits is not as simple
as changing the process pH within acceptable operating ranges. The only
process-based control is to reduce the concentration of sulfate ion in the system.
 PULP BLEACHING 23

Operating the D0 stage at a higher pH will help reduce sulfate ion as sulfuric
acid is typically employed to lower the pH. It is important to not simply trade
one type of scale off for another type of scale, so for mills with calcium oxalate
scale problems, it is important to maintain the end-stage pH of the D0 stage
near 2.5. Even with pH modification, there are several changes mills can make
to minimize the sulfate ion concentration in the D0 stage. A summary of various
practical steps (23) includes as follows:

1. Eliminate spent chlorine dioxide generator acid (sodium sesquisulfate) for

pH control of the D0 stage because this adds four times the amount of sulfate
anion to the D0 stage as sulfuric acid.
2. If that does not work, improve brownstock washing.
3. A potential capital fix is to install oxygen delignification as washing and
further lignin reduction ahead of the D0 stage removes much of the residual
carryover sulfate, sulfide, and lignin-bound sulfur from the pulp (23). The
key is to remove as much sulfate as possible while barium is sequestered as
barium carbonate.

6. Multistage Bleaching Sequences

Chemical pulp bleaching started as a one-step batch process applying bleach

power (ie, calcium or sodium hypochlorite) in a Hollander bleacher. Once the
extraction stage was developed, the single bleaching stage was expanded into
a three-stage process utilizing chlorination (C), alkaline extraction (E) and
hypochlorite (H) with inter-stage washing. Multistage bleaching allowed for
increases in production rates along with lower chemical costs, higher brightness
targets, and a minimal strength loss. With the advent of on-site chlorine dioxide
generation in the mid-twentieth century, D stage brightening slowly started to
replace the terminal H stages. Brightness levels of +85% ISO were also achieved
with sequences which expanded to include CEHD or CEHDED. Because chlorine
dioxide was found to be more selective and to have a wider optimal operating
window as compared to hypochlorite, the CEDED sequence became the dominant
bleaching process for several decades. During the 1970’s–mid 1990’s, optimization
efforts gradually improved the operation of the CEDED sequence to minimize its
environmental impact, reduce water usage, decrease energy usage, and decrease
bleaching costs. With the discovery of polychlorinated dioxins and furans in
C stage effluent and the advent of the cluster rules, chlorine and hypochlorite
were replaced with chlorine dioxide, oxygen, and peroxide. The modern ECF
bleach plant now employs bleaching sequences such as OD(EO)DD, D(EOP)DD,
D(EP)DD, D(EP)DP, D(EOP)D or different variation on the same theme for
elemental chlorine-free (ECF) bleaching.
Several studies have been performed to help understand the fundamen-
tal chemistry, reaction kinetics, stage design, process control methodology,
and operation of each individual stage for the modern ECF bleach plant.
Unfortunately, attempts to optimize each stage in isolation often results in
overall sequence sub-optimization. Changes made to one stage in a sequence
24 PULP BLEACHING

inevitably impact the operations of preceding and subsequent stages. Some work
has been done to help optimize the overall ECF sequence from a holistic approach
(24). More work in needed in this area. The costs of ECF commodity chemicals,
such as sodium chlorate, caustic, hydrogen peroxide, and sulfuric acid, as well
as energy costs, have been increasing and quite volatile over the last decade.
As such, some efforts have been made to better understand the impact volatile
chemical and energy prices upon overall bleaching sequence cost optimization
within the constraints of strength and brightness requirements (25). The modern
ECF bleachery must be able to optimize the total bleaching sequence to balance
these costs to remain globally competitive.
6.1. Optimal Chlorine Dioxide Split Between Delignification
and Brightening. When using chlorine dioxide in two or three different stages
within a single bleaching sequence, for example D(EOP)D or D(EP)DD, the split
of chlorine dioxide addition between the stages will be important for obtaining
the lowest cost pathway to a given brightness target. Early studies suggested the
lowest total ClO2 consumption for the three stages occurred when 40–50% of the
ClO2 was applied in the D0 delignification stage. Work reported for a three-stage
D(EOP)D sequence starting with 30 kappa pine pulp suggested approximately
60–65% of the total ClO2 charge is effective in the D0 stage. A similar analysis
performed for a 20 kappa number pine brownstock moves the optimal split to
65–70% of the total ClO2 charge being applied in the D0 delignifying stage.
Unlike softwoods, hardwood pulps tend to be rather insensitive to the split
between the delignifying and brightening stages. The optimal split has been
reported to range between 30% and 80% of the chlorine dioxide addition in the
first stage. General rule of thumb operation suggests that adding about half to
65% of the chlorine dioxide into the front end of the bleach plant (going toward
higher numbers as the kappa number entering the bleach plant decreases) will
give optimal performance for a three-stage bleaching sequence. About 40–50%
of the total chlorine dioxide should be applied to the first stage for a four or five
stage bleach plant.

7. Totally Chlorine Free (TCF) Bleaching of Chemical Pulps

TCF bleaching services a small part of the pulp bleaching industry. It is mainly
used to make niche pulp grades, such as specialty dissolving pulps. In general,
TCF bleaching uses mainly oxygen and hydrogen peroxide for bleaching. Chelants
are often used for transition metals management control to prevent peroxide
decomposition. TCF bleaching is often a series of QP stages strung together to
reach a desired brightness. Ozone or peracetic acid is sometimes used in addition
to these chemicals when high brightness targets are desired. In TCF bleaching
trade-offs between high brightness and high strength pulps are often required
as it is difficult to simultaneously obtain high brightness and high pulp strength
under the same set of bleaching conditions.
Hydrogen peroxide is the primary chemical in any TCF sequences. As with
chemical pulps, applying a terminal P stage after a delignifying stage provides
optimal brightness stability. The main difference from ECF bleaching is the
delignifying stage is typically a Z stage instead of a D stage. Therefore, typical
 PULP BLEACHING 25

TCF market softwood bleaching sequences include OZP, OZEP, OZ(EOP)P, and
O(QZ)Q(PO).
For higher brightness targets, it is often beneficial to include a peroxide acti-
vation step ahead of the P stage. Small amounts of peracetic acid, CH3 COOOH,
(also referred to as a Pa Stage) is occasionally used as an activation step prior to
a P stage to either increase target brightness or to reduce peroxide consumption
for a given target. The Pa stage is conducted under mild acidic conditions which
results in a hydroxylation reaction of the residual lignin. When being employed
as a delignification agent, typical bleaching conditions for a Pa stage are an ini-
tial pH of 6–7, temperature 70–80∘ C, and reaction time 1–1.5 h. Pa stages are
generally conducted at medium consistency. The peracetic acid consumption is
3-kg/delignified kappa unit.
Peracetic acid is produced in an equilibrium reaction by mixing acetic
acid, sulfuric acid, and hydrogen peroxide. Equilibrium peracetic acid cannot
be shipped in quantities required for bleaching and must be generated on-site.
Currently, no known mill is using equilibrium peracetic acid as a bleaching agent.
Distilled peracetic acid is concentrated from the equilibrium reaction to increase
peracetic acid concentration. Vacuum distilled peracetic acid from equilibrium
peracetic acid has been used to produce a 35% solution in water. Distilled per-
acetic acid needs to be stored below 4∘ C to prevent an equilibrium with hydrogen
peroxide and acetic acid from being re-established. The only known supplier of
distilled peracetic acid for bleach plant quantities is Kemira in Oulu, Finland.
The only mills currently using a Paa stage are using distilled peracetic acid.

8. Mechanical Pulp Bleaching

Mechanical pulps are produced through various attrition methods to liberate fiber
from wood without sacrificing pulp yield. Grindstones and refiner plates, in con-
junction with heat have been successfully employed in mechanical pulping meth-
ods. The main mechanical pulp bleaching processes include stone groundwood
pulp (SGW), refiner mechanical pulps (RMP), thermo-mechanical pulp (TMP),
chemi-thermomechanical pulp (CTMP), bleached chemi-thermomechanical pulp
(BCTMP), and alkaline peroxide mechanical pulp (APMP). In contrast, chemical
pulping methods dissolve the lignin holding the fibers together to liberate the
fibers but, in the process, they solubilize lignin and carbohydrates substantially
reducing the pulp yield.
Unlike chemical pulp bleaching where the goal is to delignify pulp and
then brighten it to high target brightness, the objective of brightening high-yield
mechanical pulp is to modify or destroy chromophores in lignin without deligni-
fying and lowering the yield of the pulp. The production method can intensify
the color of the lignin retained in mechanical pulps. SGW typically has the
highest unbleached brightness of all the mechanical pulps, while RMP and
refiner pulps involving thermal pretreatment such as TMP are slightly darker.
Chemical treatment of wood whether prior to pulping, during, or after pulping
may lower or increase unbleached brightness. Alkaline processing usually results
in “alkali pulp darkening”, but practical exceptions to this rule involve the use of
either sodium bisulfite, sodium sulfite, or hydrogen peroxide along with alkali to
26 PULP BLEACHING

maintain or increase brightness. The APMP process is an excellent example of

peroxide offsetting alkaline darkening during the combined mechanical pulping
and bleaching process. Finally, mechanical pulp brightness will vary depending
on the wood species being bleached and the inherent color of the lignin in the
starting wood.
The main bleaching chemicals employed in mechanical pulp bleaching are
hydrogen peroxide and sodium hydrosulfite. Sometimes, a chelant such as DTPA
(diethylenetriaminepentaacetic acid) or EDTA (ethylenediaminetetraacetic acid)
is used prior to peroxide treatment to remove transition-metal ions from mechan-
ical pulp in a pretreatment stage, called the chelation stage (Q stage). Sodium
hydrosulfite can be purchased in either a solution or powder form. It can also be
produced as a solution on site by the reaction of sodium borohydride and sodium
hydroxide to reduce sulfur dioxide or sodium bisulfite.
Hydrogen peroxide is used to achieve up to 28 points of brightness gain, but
more typically is used to gain 10–25 points of brightness. It destroys chromophores
without attacking the aromatic rings of lignin, so that yield losses are relatively
low. As with chemical pulp bleaching, peroxide requires an alkaline environment.
The more peroxide applied to the pulp to obtain higher brightness targets, the
more alkali is required to activate the peroxide, which lowers the bleached pulp
yield.
The peroxide bleaching is usually blended into a “bleach liquor” consisting
of caustic soda, sodium silicate, water, and sometimes Epsom salts to stabilize the
peroxide. Sodium silicate functions as a peroxide stabilizer by sequestering metal
ions and is a useful buffer in peroxide brightening systems. Brightening response
as well as residual peroxide is seen to have a positive correlation to silicate addi-
tion rate. Bleach liquor is mixed with the fiber then sent to a bleaching tower for
1–5 h, at 50–80∘ C. Residual peroxide is neutralized at the exit of the tower by low-
ering the pH to 4–6.5 with sodium bisulfite or sulfur dioxide dissolved in water
and pressed to a consistency of 25–35%. Pressing allows the removal of much of
the undesired material, such as anionic trash, from the pulp. Peroxide bleach-
ing, especially a second stage of peroxide bleaching, is often performed at high
pulp consistencies to enhance the peroxide kinetics and reduce undesirable side
reactions.
Sodium hydrosulfite or dithionate (Y stage) as it is sometimes called is used
to achieve up to 12 points of brightness gain, but more typically is used to gain
5–9 points of brightness. Unlike the oxidative peroxide chemistry, hydrosulfite
is a reductive treatment. When employing a Y stage it is important to exclude
air/oxygen from the system as much as possible to avoid loss reactive chemical
through oxidation. Hydrosulfite bleaching can be performed in a refiner, a stock
chest, or a specially designed tower. Typical operating conditions are temperature
in the range of 50–70∘ C, about a 4.5–6 pH, and about 1 h of retention time. Much
shorter retention times of as little as 15 min have been reported as brightness
development is extremely rapid.
Occasionally, higher brightness (>80% ISO) mechanical pulps are desired.
These are obtained with a multistage sequence of either PY or PP bleaching. For a
first peroxide stage, increasingly less brightness gain is achieved for the peroxide
applied after 1–2 wt % peroxide has been applied. Following this with a reduc-
ing agent such as sodium hydrosulfite results in a different brightening process
 PULP BLEACHING 27

resulting in an incremental 1–3 points of brightness in a cost-effective manner. A

side benefit of a second-stage hydrosulfite treatment is a decrease in pulp yellow-
ness at equivalent brightness due to a reduction in alkali pulp darkening due to
a reduction in pulp alkalinity.
In a PY sequence, brightened pulp is usually not washed either between
stages or after the hydrosulfite stage. The reduced sulfur compounds formed dur-
ing hydrosulfite brightening go to the paper machine. If white water is recycled
back to dilute unbleached pulp discharged from a grinder or refiner, residual
reduced sulfur compounds can become oxidized by peroxide to sulfates, wasting
peroxide. This effect is minimized if peroxide brightening is done at high consis-
tency with efficient pressing. Ideally, recycled paper machine whitewater would
be used for dilution and souring of pulp after peroxide brightening since this will
destroy peroxide residual that would otherwise destroy hydrosulfite being applied
sequentially. In some mills, sodium bisulfite is used to sour the pulp after a perox-
ide stage. The addition of bisulfite lowers the pH and neutralizes residual peroxide
prior to the Y stage.
Second-stage hydrosulfite response varies by wood species but typically is
ineffective if applying more than 3 wt % peroxide as residual peroxide will con-
sume enough hydrosulfite to destroy the process economics. The residual peroxide
may be neutralized by the addition of sodium bisulfite prior to the Y stage chemical
addition. This practice will also result in poor process economics.
Two-stage PP brightening is used for high brightness pulps such as softwood
BCTMP beyond 80% ISO and hardwood BCTMP beyond 85% ISO. This type of
bleaching sequence is used in market pulp mills in Canada and several other coun-
tries in mills producing hardwood and softwood BCTMP grades for packaging,
printing and writing paper, and sanitary product end uses. Normally, the second
peroxide stage is operated at 30–35% consistency while the first stage operates at
10–12% consistency. Fresh bleach chemicals are added principally to the second
stage, while residual bleach chemicals and press filtrate along with some fresh
chemicals get added at first stage. The benefit of splitting peroxide charge into
two stages is that washing after first stage brightening can help remove species
harmful to peroxide brightening and result in a higher brightness than possible
in a single stage of brightening.
As with chemical pulps, nonprocess element scale formation is also a poten-
tial processing issue with mechanical pulps. Common scaling issues include sili-
cate, calcium carbonate, and calcium oxalate scale formation. Hard silicate scales
can be partially mitigated when Epsom salt (MgSO4 ⋅7H2 O) is used as an additive
in peroxide bleach liquor as it forms a soft Mg-silicate scale that is easier to con-
trol/remove from process equipment as compared to traditional hard silicate scale.

9. Bleaching of Recycled Pulp

With more and more people wanting to be “green” and using environmentally
friendly products, the need for higher quality, high brightness recycled fiber has
increased substantially over the last couple of decades. Historically, bleached recy-
cled fiber has been incorporated mainly into newsprint and tissue grades with
some amount being used in supercalendered (SC grades) and in printing and
28 PULP BLEACHING

writing papers. Today, there is a portion of high brightness recycled pulp that
achieves a quality close to that of short fiber chemical pulp. Often this high bright-
ness, high-quality grade has been bleached to not only increase its brightness but
to destroy optical brightening agents (OBAs) so it can be added to direct food con-
tact paper grades such as cupstock and plate grades.
Mixed paper waste used for high end recycled fiber is sorted to remove
mechanical pulp grades as the bleaching process tends to react with mechanical
pulps resulting in low yields and high effluent CODs. Once the better fiber is
sorted, it is repulped and deinked. The mechanical pulp wastepapers from this
sorting, such as old newsprint (ONP) and old magazine (OMG), can be repulped,
deinked, and bleached as lower pulp grades.
Printing inks generally cannot be bleached, as they consist mainly of
pigments like carbon black and hydrophobic polymers. These pigments must
be removed by mechanical means through either washing or foam floatation.
Caustic and a surfactant are added during the repulping phase. Caustic swells
the fibers and helps loosen the ink pigments into the surfactant generated foam.
Ink particles and other contaminants detach from the fiber and collect on the
surface of the surfactant foam which floats to the surface with dissolved air and
is removed via scrapers.
If untreated, the repulped and deinked fiber will undergo alkaline yellowing
due to the caustic added in the repulping step. To prevent this, hydrogen peroxide,
sometimes in conjunction with sodium silicate, is added to the repulping stage typ-
ically resulting in a small increase in pulp brightness. For deinking by washing,
repulping can be performed under either alkaline or neutral conditions. Surfac-
tants are added to facilitate ink removal. The washing process removes ink, fillers,
and fines simultaneously making it a preferred method for tissue production.
If an additional 5–10 points of pulp brightness is required after the deinking
and cleaning stages, the deinked pulp is often bleached with peroxide in a separate
bleaching tower. This process is often referred to as post-bleaching.
Under some methods such as neutral deinking, no or only a very low dose of
caustic is added to the repulper prior to washing or floatation. In these cases, no
peroxide is added to the repulper.
Higher grade, higher brightness recycled colored papers have to remove
dyes through a combination of oxidative and reductive treatments. Typically,
the oxidative treatment is done with peroxide but can be performed with ozone.
The reductive bleaching is often performed with FAS, CH4 N2 O2 S, which is also
called thiourea dioxide. The optimum process conditions for FAS treatment are
addition of caustic to obtain an initial pH of about 10, reaction temperature of
60–90∘ C for 0.5–1 h. FAS is normally delivered in powder form. It is soluble at
30 g/L at 20∘ C. FAS is relatively stable at room temperature exhibiting a slow
decomposition rate when exposed to moist air. When heated to about 120∘ C it
rapidly decomposes into SO2 gas in an exothermic reaction.
Ozone, an oxidative treatment can also be used to brighten highly colored
papers. Ozone is particularly reactive toward dyes. The mechanical properties
of the furnish, such as tensile and burst, are frequently improved by an ozone
treatment. Ozone should only be used in mechanical pulp free furnishes as ozone
will selectively attack the lignin in mechanical pulp resulting in decreased pulp
yield and increased environmental loading on the effluent treatment plant.
 PULP BLEACHING 29

The common chemicals used to bleach high quality recycled fibers are oxygen
(O), ozone (Z), and hydrogen peroxide (P), for the oxidative chemicals, and sodium
hydrosulfite (Y) and FAS (F) for the reductive chemicals. Chlorine dioxide (D)
is also used in some cases to destroy OBAs while brightening the pulp. When
starting with mixed office waste to make a short chemical fiber pulp replacement,
multiple stages are required. Frequently an OP, OD, ZP, OPY, or OZP sequence
is used to obtain high quality, high brightness recycled pulps. A Z or a D stage is
required for direct food contact grades as these are the two main oxidative chem-
icals which will react with and destroy stilbenes found in OBA’s.

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 30 PULP BLEACHING

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SUGGESTED ADDITIONAL READING

P. W. Hart and A. W. Rudie, eds., The Bleaching of Pulp, 5th ed., TAPPI Press, Atlanta, GA,
2012.
V. J. Gomes and co-workers, TAPPI J. 17(7), 373–381 (2018).
R. B. Santos and co-workers, TAPPI J. 15(9), 581–586 (2016).
P. W. Hart and R. B. Santos, TAPPI J. 12(10), 19–29 (2013).
P. W. Hart, C. Houtman, and K. Hirth, TAPPI J. 12(7), 59–65 (2013).
P. W. Hart and A. W. Rudie, Chem. Eng. Educ. 45(1), 15–20 (2011).
P. W. Hart and A. W. Rudie, Pulp Paper Canada 111(4), T60–T63 (2010).
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PETER W. HART
WestRock – Research and Innovation,
Richmond, VA, USA

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