Paper: Pulping and Bleaching
of properties. Refiner mechanical pulps (RMP) are
Wood pulping processes are broadly categorized as
mechanical or chemical according to the relative
importance of mechanical treatments compared to
chemical modification, degradation, and\or solution
of wood components.
The properties of wood pulps and papers made
from such pulps are affected by the selection of wood
sfpecies (see Pulp and Paper: Wood Sources) and by
the complex mechanical, chemical, and thermal pro-
cesses occurring during pulping and bleaching. The
physical characteristics of the fibers, their chemical
composition, and the supramolecular properties of
the constituent polymers can all change in these pro-
cesses.
Reductions in air and water emissions from pulping
and bleaching processes are being accomplished by
process selection, increased process closure, effective
recovery of chemicals, and\or end-of-pipe treatments.
1. Mechanical Pulping
Mechanical processes use attrition to separate wood
into fibers and fiber fragments. The resulting pulp
properties are highly dependent upon the applied
energy and the nature of the physical interactions with
the wood. Mechanical pulping processes use large
quantities of electrical energy. Equipment design,
chemical applications, and thermal energy are applied
to reduce this energy requirement (Cannell 1999).
Mechanical pulps are produced at high yields, often
exceeding 90% of wood mass. The fibers tend to be
stiff and produce bulky paper structures. Papers can
also be made with good printing characteristics and
opacity. Mechanical pulps are well suited for pro-
duction of newsprint, publication papers, and some
coated catalog and publication grades. Mechanical
pulps are also used in tissue papers, cartons, and
building boards.
1.1 Mechanical Pulping Processes
In groundwood (GW) mechanical pulping, wood logs
or bolts are pressed against a revolving grinding stone,
and fibers and fiber fragments are separated by
abrasion. Pulp characteristics are influenced by the
stone surface characteristics, stone surface speed,
energy consumption, temperature, and pulp consist-
ency in the grinder. Higher strength, longer-fibered
pulps can be made by operating the grinding process at
elevated temperatures (130 mC) and pressures up
to 0n5 MPa in the pressurized groundwood (PGW)
process.
Production of pulp by abrasion of wood chips or
sawdust in a refiner between rotating steel disks allows
greater flexibility in raw material selection and pro-
vides options for producing pulps with a wider range
produced at atmospheric pressures. In thermo-
mechanical pulping (TMP), the refining process is
steam pressurized to allow temperatures up to 170 mC.
The wood lignin is softened and the wood fracture
location is controlled, by temperature, to inside the
fiber wall at 130 mC or in the lignin-rich middle lamella
region between fibers at higher temperatures. Refiner
mechanical pulping processes can utilize two stages in
series to achieve the desired pulp qualities.
Small amounts of chemicals, such as sodium hy-
droxide, carbonate, sulfite, bisulfite, or combinations
thereof, are sometimes added to produce chemi-
mechanical (CMP) or chemithermomechanical
(CTMP) pulps. Wood components are chemically
modified by the additives to be more hydrophilic and,
in some cases, are partly dissolved. Swelling of the
wood is increased and the response to the mechanical
pulping process is altered dramatically. Chemical
additions affect the location of the fracture in the fiber
structure as well as the nature of the fiber surfaces
formed. Both of these factors influence the capacity of
the fibers to develop strong bonds in the final paper
product. Typical yields in chemimechanical pulping
are in the 80–95% range.
Semichemical pulps are produced at yields between
65% and 80% by adding larger amounts of chemicals
and\or increasing the pretreatment time or tempera-
ture. As larger amounts of chemicals are used, re-
covery of the spent chemicals becomes an economic
and environmental consideration.
1.2 Bleaching Mechanical Pulps
Production of high brightness mechanical pulps
requires consideration of the entire process including:
selection of the wood source, in-process storage of the
wood, the pulping process, and pulp bleaching, as well
as the intended use of the product. Light-colored
woods without fungal discoloration or dark-colored
resins are preferred. Wood lignin and resins are
modified and partially removed in the preparation of
mechanical or semichemical pulps. Remaining lignin,
resins, extractives, and other minor components of the
wood contribute to the color of these pulps. Chemicals
applied in pulping can reduce loss of brightness in the
process and, in some cases, improve the color of the
pulp. Mechanical pulp bleaching processes are
designed to remove chromophoric structures and
brighten the pulp with minimum losses of mass.
Lignin-preserving bleaching is accomplished commer-
cially primarily with hydrogen peroxide and\or so-
dium dithionate. Sequential bleaching stages with
these chemicals are used to achieve high brightness.
Chelating or complexing agents can be applied to
control trace amounts of metal ions which can form
colored complexes or adversely impact the bleaching
process by decomposing hydrogen peroxide.
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Paper: Pulping and Bleaching
While reasonably high brightness can be developed
with mechanical and chemimechanical pulps, it is
difficult to prevent reversion or brightness loss over
time. Exposure to heat and light accelerates brightness
reversion. Brightness reversion often limits mechanical
pulps to products with relatively short life cycles.
1.3 EnŠironmental Emissions from Mechanical
Pulping
Water-soluble wood components, pulping and bleach-
ing chemicals, and wood substances dissolved in the
mechanical pulping processes contribute biological
oxygen demand (BOD), chemical oxygen demand
(COD), and color to the aqueous effluent. Emissions
of volatile organic compounds can occur in pulping
and bleaching. Aqueous effluents are treated with
primary and secondary treatment processes before
discharge. ‘‘Zero effluent’’ production of bleached
CTMP has been commercialized in Canada to avoid
aqueous emissions ( Meadows 1996).
2. Chemical Pulping Technology
Chemical pulping processes produce low brightness
pulps in yields ranging from 40% to 65% by dissolving
lignin, hemicellulose and cellulose carbohydrates, and
extractives from the wood. At the lower yields, intact,
individual fibers are readily separated from the wood
structure. Chemical pulps made at the higher yield
levels and containing larger amounts of the wood
lignin require appreciable mechanical energy input
from disk refining equipment to complement the
chemical pulping process.
2.1 Alkaline Pulping
In the commercially dominant kraft (sulfate) process,
sulfide and hydroxide ions are used to depolymerize
and dissolve the wood extractives, lignin, and some
hemicelluloses. The pulping reactions require one to
three hours at temperatures up to 170 mC. Both batch
and continuous pressurized digesters are used. Kraft
pulping has been improved by the use of additives,
selective control of chemical concentrations, and opti-
mization of temperature profiles. Modified kraft pulp-
ing processes apply four principles to improve the
selectivity of lignin removal: leveled-out hydroxide
concentration, high initial hydrosulfide concentration,
low sodium ion and dissolved lignin concentrations in
the final part of the cook, and avoidance of high
temperature. These principles have been employed in
various ways to achieve improved pulping and the
ability to pulp to lower lignin contents (Teder et al.
1997).
Anthraquinone (AQ) addition to kraft pulping
increases the rate of the delignification reaction and
2
the yield of carbohydrates. Although AQ is used at
very low levels, less than 0n1% on wood, it is a
relatively expensive chemical and is often used on an
as-needed basis to provide incremental production
capability.
Polysulfide (PS) ions in kraft pulping stabilize the
carbohydrates against the alkaline degradation re-
action known as ‘‘peeling.’’ With PS addition, the
yield of kraft pulp can be increased by 1–3%. To
maintain the sulfur balance in the pulping-recovery
cycle, it is necessary to regenerate PS from the
recovered pulping chemicals. Polysulfide and anthra-
quinone can be applied together in the PS-AQ process
to get synergistic pulp yield benefits.
Soda pulping using sodium hydroxide avoids the
odorous sulfur-containing gases associated with kraft
pulping. However, pulp strength properties are ad-
versely impacted by the high concentrations of hy-
droxide ion needed to achieve practical pulping rates.
AQ can be added for improved pulping rates.
Alkaline sulfite pulping processes have shown pro-
mise for increased pulp yield and good pulp quality.
AQ and\or methanol are additives in some alter-
natives. Commercial application has been limited by
the lack of a cost-effective recovery option.
2.2 Sulfite and SolŠent Pulping Processes
In sulfite pulping, usually conducted under acid or
neutral conditions, sulfur dioxide and\or bisulfite ions
react with lignin to produce water-soluble sulfonated
lignins that are degraded by acid hydrolysis reactions.
Sulfite pulping can be controlled to produce pulps
over a wide range of lignin contents and pulp yields.
The residual lignin in sulfite pulps is sulfonated and is
relatively easy to remove in pulp bleaching processes.
The conditions of sulfite pulping lead to extensive
hydrolysis of the carbohydrates, and sulfite pulps
typically have less strength potential than kraft pulps
in papermaking applications. The recovery and re-
generation of chemicals in the waste liquors from
sulfite pulping are more difficult than for kraft liquors.
Solvent pulping processes have been extensively
evaluated in laboratory and pilot tests, but have found
only limited commercial application. Many organic
solvents have been used including alcohols, acids,
ketones, esters, and others. Often an inorganic acid is
added to promote hydrolytic cleavage of lignin bonds.
Solvent pulping offers possibilities for alternative
chemical recovery processes with lower capital costs
and by-product recovery. Very high solvent recovery
must be achieved for economic and environmental
reasons.
2.3 RecoŠery of Chemicals for Pulping
Efficient recovery and regeneration of pulping chemi-
cals are essential for chemical pulping processes. Wood
components dissolved in the pulping process are

converted to useful by-products, such as tall oil soap
and lignin, or to energy by combustion. The avail-
ability of a cost-effective chemical and energy recovery
cycle for kraft pulping contributes to the dominance of
this process. Kraft pulping operations are often energy
self-sufficient.
In the kraft pulping\recovery cycle, pulp from the
digester system is washed with water to separate a
solution of spent pulping chemicals and dissolved
wood components known as black liquor. This black
liquor is concentrated by multiple effect evaporation
to a high solids concentration (
50%) and then
burned in a heat recovery boiler. The inorganic
compounds are removed from the furnace as a molten
smelt and are dissolved in water to form green liquor.
The active pulping liquor, a solution of sodium
hydroxide and sodium sulfide called white liquor, is
regenerated by causticizing the green liquor with lime.
The lime is also regenerated in a separate cycle using a
kiln to convert calcium carbonate to calcium oxide.
The recovery cycle operations for kraft pulping are
capital intensive, and many alternatives have been
evaluated. Gasification processes under development
for burning the concentrated black liquor offer prom-
ise for improved energy recovery by application of
combined cycle power generation.
2.4 Bleaching Chemical Pulps
Chemical pulps contain 2–5% lignin after the pulping
process and are dark brown in color. For white
products, these chromophoric residues are removed in
multistage processes with oxidative chemicals such as
oxygen, chlorine, hypochlorites, chlorine dioxide, and
hydrogen peroxide. Alkaline extraction facilitates
removal by solubilization of the oxidatively degraded
materials.
An oxygen stage is often used as a transition between
pulping and bleaching. Oxygen delignification re-
moves 30–60% of the residual lignin. Oxygen stages
operate at either medium (" 13%) or high (" 30%)
consistency with 1–4% sodium hydroxide addition.
Temperatures range from 80 to 120 mC with oxygen
pressures up to 10 atmospheres. Two oxygen stages in
series are sometimes used. Oxygen stages are inte-
grated with the washing of the unbleached pulp so that
wood components dissolved in this stage can be
processed in the chemical recovery cycle. This closure
of the process is a major advantage of oxygen
compared to many other bleaching chemicals where
the effluent is not recovered and must be treated before
discharge to the environment.
The chemistry of pulp bleaching has changed
dramatically since the mid-1980s, when trace amounts
of dioxin were found in bleached chemical pulps and
effluents from bleaching processes using chlorine in
the first oxidative bleaching stage at low pH. Dioxin
formation was avoided by changing chlorination stage
conditions or by bleaching without chlorine (elemental
Paper: Pulping and Bleaching
chlorine free, ECF). Bleaching technologies also were
developed that avoid all chlorine bleaching chemicals
(totally chlorine free, TCF) (Nelson 1998). ECF
bleaching processes provide several pulp quality
advantages relative to TCF. Comparative evaluations
demonstrated that treated effluents from the two
approaches are comparable. ECF bleaching sequences
have been preferred by the industry for kraft pulp
bleaching.
Hypochlorite bleaching uses chlorine at alkaline pH
conditions with either sodium or calcium as the base.
Hypochlorite reactions with lignin produce chloro-
form as a by-product. As a result, hypochlorite
bleaching has been largely replaced by hydrogen
peroxide or by increased use of chlorine dioxide.
Chlorine dioxide is a very effective pulp bleaching
chemical. Initially, because of its high cost, chlorine
dioxide was used mostly in the later stages of bleaching
to remove the last traces of residual color in the pulp.
In ECF bleaching, chlorine dioxide is used in the first
stage as a delignifying chemical to replace chlorine.
Chlorine dioxide is a very selective chemical that
removes lignin residues with very little chemical attack
on the carbohydrates in the fiber. The first dioxide
stage of a bleaching sequence is usually followed by an
alkaline extraction stage where oxidized fragments of
lignin are solubilized and removed from the pulp.
Alkaline extraction stages are sometimes used between
two dioxide stages in the last stages of bleaching.
Recycling of ECF bleaching effluents to recovery
requires additional processing to remove sodium
chloride that can accumulate in the pulping–recovery
cycle liquors and cause corrosion problems.
Hydrogen peroxide has become more important
in both ECF and TCF pulp bleaching processes.
Hydrogen peroxide is most effectively used as a pulp
brightening chemical. It is often used as an additive to
alkaline extraction stages.
TCF bleaching applies combinations of oxygen,
ozone, and peroxide bleaching stages. Trace metal
ions present in the unbleached pulp can adversely
affect the stability of peroxide resulting in wasteful loss
of the chemical as well as radical species that can
attack the pulp carbohydrates. The effects of trace
metals can be reduced by removal of the metals with
an acid or chelant treatment.
Ozone was developed as a commercial bleaching
chemical in the late 1980s in response to the need for
more effective chlorine-free bleaching chemicals.
Ozone stages can be operated at medium or high
consistency. Ozone is a very reactive chemical, and
undesired reactions with the pulp carbohydrates must
be controlled. Efficient mixing of the ozone gas with
the pulp is a major challenge. Developments in the
technology for generation of ozone have resulted in
ozone becoming a cost-competitive option for the
industry. Effluents from ozone stages early in the
process can be recycled back to the chemical recovery
cycle.
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Paper: Pulping and Bleaching
Achieving very high brightness levels has been a
challenge with TCF bleaching processes. To facilitate
these processes, it is common to extend delignification
of unbleached pulp to lower lignin contents and to
operate the oxygen stage at higher delignification
levels. These steps, as well as the alkaline conditions
and high temperatures used in TCF peroxide stages,
raise concerns about the loss of additional carbo-
hydrates and thus pulp yield.
The most significant effects of bleaching on the
properties of chemical pulps are related to the extent
of oxidative chemical attack by the bleaching chemi-
cals on the cellulose and hemicellulose polymers. Some
hemicelluloses can be dissolved during bleaching; if
significant amounts are intentionally removed, as in
the production of high-purity α-cellulose pulps, the
properties of the pulp can be strongly affected.
The oxidative chemicals used in pulp bleaching have
different potentials for affecting pulp properties. These
chemicals can both depolymerize the hemicellulose
and cellulose polymers and introduce new functional
groups into these polymers. Some depolymerization
can occur without strength loss but, beyond a certain
point, strength properties decrease sharply as the
polymer molecular weight decreases. Depolymeriza-
tion is often monitored by empirical measurements of
the solution viscosity of the pulp in selected solvents,
but changes in the chemical composition of the pulp
also affect the results of this test.
By proper selection of bleaching chemicals and
operating conditions, it is possible to minimize changes
in pulp strength properties during bleaching. Usually,
the most active chemicals, such as oxygen and ozone,
are applied in the early stages of bleaching, where the
larger amounts of residual lignin present in the pulp
rapidly consume the chemical and protect the carbo-
hydrates. Hypochlorites, when used, are applied in
intermediate stages of bleaching. The amount of un-
desired chemical attack by hypochlorites is reduced
by controlling the reaction pH and by limiting the
amount of the chemical used. Hydrogen peroxide
bleaching can be a relatively mild process and is often
applied in the final bleaching stages. Chlorine dioxide
has the least effect on pulp strength properties and is
favored for the final stage of bleaching when pulps
having high brightness and high strength are desired.
3. Biotechnology in Pulping and Bleaching
Application of biotechnology in pulping and bleaching
has been evaluated extensively for both chemical and
mechanical pulp processes. A commercial product
uses a fungus to degrade extractives in wood chips
before pulping to prevent later deposition of pitch
on process equipment. Biomechanical pulping uses
lignin-degrading microorganisms, primarily white-rot
fungi, to pretreat wood chips prior to refining. Signifi-
cant reductions in energy requirements and increases
4
in strength properties have been reported, with bio-
mass losses up to 25%. Many fungi strains have been
screened to take advantage of the natural differences
in the lignin- and carbohydrate-degrading ability of
these organisms. Fungal pretreatments have also been
evaluated for improved delignification and bleach-
ability in sulfite and kraft pulping (Messner 1998).
Isolated xylanase enzymes are used to enhance
chemical pulp bleaching. Xylanase treatments before
bleaching result in higher brightness after bleaching or
lower bleaching chemical costs.
4. Process Effects on Pulp Properties
The physical properties of chemical pulps depend
markedly on the pulping yield. The strength of wood
pulp fibers is primarily caused by the high-molecular
weight, highly oriented cellulose polymer in the fiber.
Since the cellulose component is less affected by the
pulping processes, the fraction of cellulose in the pulp
increases as the yield decreases. Also, the number of
fibers per unit weight of pulp increases as more
material is removed by pulping. Pulp strength proper-
ties thus improve as yield decreases, up to a point
where chemical attack on the cellulose becomes
significant.
In addition to the basic fiber strength, hydrogen
bonds formed between the fiber elements in the paper
affect the strength developed from a pulp. The de-
velopment of hydrogen bonds in paper is determined
to a great extent by how the fiber swells in water during
the preparation of the fibers for papermaking. Many
of the effects of pulping and bleaching on pulp
properties can be understood in terms of the relative
amounts of the hydrophobic lignin polymer removed
and the hydrophilic hemicellulose retained in the pulp
fiber. The location in the fiber structure and degree of
crystallinity of hemicellulose can also be affected by
the pulping process.
Mechanical action during processing of pulps, such
as occurs when pulps are discharged by hot blowing
from high-pressure pulping vessels, pumped, mixed,
or conveyed, can decrease fiber strength. Such mech-
anical action may cause undesired ‘‘dislocations’’ or
weak spots in the fiber wall or formation of fiber debris
by mechanically disrupting the basic fiber structure.
5. Conclusions
Many alternatives for production of pulps with wide
ranges of end-use specific properties have been de-
veloped and are applied commercially. Environmental
issues are being addressed with new technologies,
alternative chemicals, and progressive reduction of
process emissions.
See also: Cellulose: Chemistry and Technology; Wood,
Constituents of; Pulp and Paper : Wood Sources

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ISBN: 0-08-0431526
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