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Pulp and paper mills involve 4 general steps in the manufacture of pulp and paper.
These steps include:

1) Raw material preparation (e.g., debarking and chipping);

2) Mechanical and/or chemical separation of the wood fibers [i.e., grinding, refining,
or digestion (cooking)] to dissolve the lignin and extractives;
3) Removal of coloring agents (primarily residual lignin) by bleaching; and
4) Paper formation and manufacture.

Raw Material Preparation

Wood received at a pulp mill may be in several different forms, depending on the
pulping process and the origin of the raw material. It may be received as bolts (short
logs) of roundwood with the bark still attached, as chips about the size of a half-dollar
that may have been produced from sawmill or veneer mill waste or pre-chipped from
debarked roundwood elsewhere, or as waste sawdust in the case of some pulping

If roundwood is used, it is first debarked, usually by tumbling in large steel drums where
wash water may be applied. The debarked wood bolts are then chipped in a chipper if
the pulping process calls for chemical digestion or are fed into a grinder in the case of
some mechanical pulps. Chips are screened for size, cleaned, and temporarily stored
for further processing.

Pulping (Fiber Separation)

The objective of pulping is to separate the wood into individual fibers. The fiber
separation stage is the point at which the several pulping technologies diverge.

Three broad classifications of pulping methods:

Mechanical (groundwood)


Combination (chemi-mechanical)
Energy consumption 1000 KW/tonne of pulp
Yield (from wood material) 95%

Fibre length Fibre fragments of different sizes Mainly longer fibres

Paper strength Low High

Pulp production 32% 66%

Dark but bleachable Bright but hard to bleach
Optical Poor light scattering high Good light

Production cost Lower Higher than in case of

mechanical pulp
The pulp forms a highly opaque Offers higher strength
Pulp quality paper with good printing properties and the fibers
properties, but the paper is are more easily breached.
relatively weak and discolors Using chemical pulp to
easily with exposure to light. The produce paper is more
smaller, thinner fibers from expensive than using
hardwoods are more severely mechanical pulp or
damaged by the mechanical recovered paper, but it
action, hence yield a weaker has better strength and
paper. brightness properties
Mechanical pulps are primarily These pulps fulfill the
Uses used in newsprint, as well as demand for chlorine-
papers used in telephone free' products in the
directories, catalogs, "pulp" hygiene paper sector and
magazines, and paper towels and also in printing and
tissues. writing papers.

Mechanical Pulping Processes:

There are six basic mechanical pulping processes:

1) Stone groundwood,
2) Refiner,

3) Thermomechanical pulping,

4) Chemical mechanical,

5) Defibrated or exploded pulping, and

6) Recycled paper.

Mechanical pulping is generally used with softwoods be-cause of the added strength
imparted by the long fiber length of softwood species. Some hardwoods require
chemical pretreatment (chemical mechanical pulping) to produce a suitable groundwood
pulp. Fibers separated mechanically are substantially damaged in the process and
therefore make weaker paper or paperboard. However, since both lignin and cellulose
fibers remain intact, the yield of paper per unit volume of wood is still greater than that
produced by chemical pulping. Pulp yields from all of the mechanical pulping processes
typically are near 90 to 95 percent recovery, which is a much higher yield per unit of
wood than with the chemical pulping methods because of the retention of lignin.
However, paper made from mechanical pulp discolors and becomes brittle with age
because of its lignin content, which results in a shorter useful life than paper made from
chemical pulp.

Stone Groundwood (SGW) wood logs

In the stone groundwood process, debarked short logs (roundwood) are fed whole
against wet stone grinders by hydraulic rams. Counter-revolving steel disks are
sometimes used in place of abrasive stone in the grinding process. The abrasion of the
grinding wheel against the wood physically separates the wood fibers. The grinding
process usually is automatic and continuous. The groundwood pulp is then screened,
bleached or brightened, treated, and prepared for the paper machine.

Pressurized Groundwood Pulping pressurized groundwood pulping; debarked logs

are fed to the grinding wheel through a heated, pressurized chamber. The heat and
pressure help separate the fiber, thus breaking fewer fibers in the grinding process and
improving pulp quality. Paper produced from pressurized groundwood pulp is more tear
resistant than paper made from stone-ground pulp, but is slightly inferior to that of
thermomechanical pulp. Pressurized groundwood pulping may have the potential for
displacing some high-quality chemical pulps in the manufacture of newsprint and other
printing papers.
Refiner mechanical pulping (RMP) uses chips in lieu of roundwood and produces
paper with higher strength than conventional groundwood because of less damage to
the fibers in the pulping process. The chips are passed through a refiner that has fixed
and rotating disks operating under a stream of water. A wider range of species, including
hardwoods, can be processed by the refiner pulping process, Sawdust and other saw
mill wastes can also be used.

Thermomechanical process (TMP) was developed as a modification of the refiner

mechanical pulping process. In TMP, the wood chips are steamed for several minutes
under pressure and subsequently refined in one or two stages. The lignin is softened by
heating the wood chips with pressurized steam before they are refined (i.e., blended by
passing the fiber through rapidly rotating disks). The refined wood pulp, although still
weaker than chemical pulp, makes a stronger paper than groundwood or refiner pulp
with only a small sacrifice in yield but with large energy requirements. Some newsprint
is now produced wholly from thermomechanical pulp, thus eliminating the need for the
addition of chemical pulp often needed for strengthening paper made from mechanical

Chemical Thermomechanical Pulping Chemical thermomechanical pulping

involves treating softwood chips with mild sulfite solutions to modify the lignin and
partially delignify the wood prior to grinding in a refiner. This sulfonation treatment
results in paper with higher tear resistance than thermomechanical, refiner, or stone-
ground pulps. Pulp yields decrease slightly to between 85 and 90 percent with chemical
thermomechanical pulping, but these yields are still higher than chemical pulping (40 to
56 percent).


Chemical pulping involves treating wood chips with chemicals to remove the lignin and
hemicellulose, thus separating and cleaning the fibers. Delignification gives the fibers
greater flexibility, resulting in a substantially stronger paper (because of greater contact
between the fibers in the finished sheet) than can be manufactured from high-lignin
fibers produced by mechanical pulping. Paper strength and durability is gained at the
expense of fiber yield. Chemical processes may yield only half the fiber that can be
recovered by the use of mechanical pulping techniques.

For chemical pulp, logs are first chopped into wood chips which are then cooked with
chemicals under high pressure.

Cooking removes lignin and separates the wood into cellulose fibres. The resulting
slurry contains loose but intact fibres which maintain their strength.
During the process, approximately half of the wood dissolves into what is called black
liquor. The cooked pulp is then washed and screened to achieve a more uniform quality.
The black liquor is separated out from the pulp before the bleaching process.

Two major chemical pulping processes are currently in commercial use:

1) Kraft (sulfate) pulping, and

2) Sulfite pulping. Which is further divided into 4 different processes, Acid sulfite,
alkaline sulfite, neutral sulfite and bisulfite.

The kraft process dominates the pulp and paper industry, accounting for 76 percent of
the pulp produced for paper and paperboard.

The Kraft process was developed in Germany in 1879 and was first applied to a
Swedish mill in1885. The resulting paper was much stronger than any paper previously
made, and therefore the process was named Kraft, (German and Swedish for
strength). Kraft pulping creates dark brown paper which is used for boxes, paper bags,
and wrapping paper. Kraft pulp can also be used for writing paper and paperboard when
bleached, and for diapers when fluffed.

Kraft pulping involves treating wood chips and sawdust with a sodium sulfide and
sodium hydroxide solution.
Kraft pulping is the most popularly used process. This is an alkaline process. Na2SO4 is
added to the cooking liquor. So its common name is sulfate process. The presence of
sodium sulfide makes bleaching of pulp easier and the paper produced has better
Process Description

The three main steps involved in Kraft pulping are:

1. Digestion: wood chips are cooked

2. Washing: black liquor is separated from the pulp

3. Chemical recovery: chemicals are recovered from the black liquor for reuse

Turpentine and tall oil may also be recovered for use or resale.

The Making of Pulp

Description of Process

1. Digestion
The first step in pulping wood is to cook the wood chips. A digester, heated by steam,
cooks the wood chips in white liquor (a mix of sodium hydroxide (NaOH) and sodium
sulfide (Na2S) until done. The cooking process dissolves most of the lignin
hemicellulose and only some of the, leaving mostly cellulose to hold the fibers together.
The digester system may be a batch or a continuous process.

In the kraft process, wood chips are cooked at an elevated temperature (160-180C)
and pressure 800 kPa (120 psi) in an aqueous solution of sodium hydroxide and sodium
sulfide (also called white liquor). The sodium sulfide in the cooking liquor serves to
buffer and sustain the cooking reaction, while the sodium hydroxide is consumed by
reaction with the lignin and carbohydrates in the wood.
Relief gases are vented continuously from the digester, which helps remove air and
other non-condensable gases and reduce the pressure at blow, when the pulp is
discharged to the blow tank. After the cooking process, the pulp and black liquor (the
chemical mix left after the cooking process) are discharged to a blow tank.

Chemical reactions involved

(i) Digestion (hydrolysis and solubilization of lignin)


R-R + Na2S Mercaptans

(ii) Chemical recovery from black liquor

(a) Smelting

2NaR + air Na2CO3 + CO2

Na2SO4 + 2C Na2S + 2CO2
(from R) (white liquor)

(b) Causticizing
Na2CO3 (aq) + Ca(OH)2 (s) 2NaOH (aq) + CaCO3 (s)
(green liquor) (white liquor)

CaCO3CaO + CO2

CaO +Lime Ca(OH)2



Slaked lime Burnt lime

Recovery Furnace
White liquor (NaOH + Na2S ) Green liquor
Na2CO3+ NaOH+ NaSH

Black liquor thick black liquor smelt (Na2CO3 +

Na2S )

Make up Na2SO4

There are 2 types of digester systems, batch and continuous. Most kraft pulping is done
in batch digesters, although the more recent installations are of continuous digesters. In
a batch digester, when cooking is complete, the contents of the digester are transferred
to an atmospheric tank usually referred to as a blow tank. The entire contents of the
blow tank are sent to pulp washers, where the spent cooking liquor is separated from
the pulp. The pulp then proceeds through various stages of washing, and possibly
bleaching, after which it is pressed and dried into the finished product. The "blow" of the
digester does not apply to continuous digester systems.

In the case of batch digesters, air trapped with the chips and gases formed during
digestion are relieved intermittently during cooking. In softwood pulping, the relief gases
are condensed for turpentine recovery before venting.
The cooking period ranges from two to six hours. At the end of the cook, the digester
contents are transferred to an atmospheric tank, called the blow tank. Gases leaving the
blow tanks pass through a condenser to remove moisture, and the uncondensed gases
are incinerated in a combustion device.

Sequence of events in batch digester

1. The digester is first opened and filled with chips, white liquor, and black liquor.
2. After initial circulation of the liquor additional chips are added as the contents settle.
3. The digester is then sealed and heating with steam begins. The temperature rises for
about 90 minutes until the cooking temperature is achieved.
4. The cooking WL and temperature is
Chips In
maintained for about 20-45
minutes for the kraft process.
Impregnation Zone
During the heating Extraction time, air and other
non condensable Liquor Out gases from the
digester are heating/washing vented.
5. When the cook (start of bulk is completed, as
determined by the delignification) kappa of pulp from
the digester, the contents of the
digester are Delignification
discharged to the
blow tank. Wash
6. The digester is Water opened and the
sequence is Counter-current
delignification) White

Wash Water
Pulp Out

Continuous Digester

A continuous digester is a tube-shaped digester where chips are moved through a

course that may contain elements of presteaming, liquor impregnation, heating,
cooking, and washing.
In continuous digesters, which are extremely tall (25 30m) and large cooking vessels an
uninterrupted flow of wood chips and cooking liquor enters from the top. Pulp is
withdrawn continuously from the bottom into a blow tank, while the spent liquor is drawn
off and transferred to a flash tank. Chips are preheated with volatilizing turpentine and
non-condensable gases. Non condensible gases (NCGs) are vented, and in the case of
softwoods, turpentine is decanted from the condensate

Continuous digesters tend to be more space efficient, easier to control giving increased
yields and reduced chemical demand, labor-saving, and more energy efficient than
batch digesters. Special feeder is needed e.g., Screw feeder, Rotary valve.
For controlling digestion temperature, cooking liquor is withdrawn as side streams and
circulated through heat exchanger. Cooking time is about one and a half hours at
170C. Temperature is maintained at 140-180C and pressure at about 10 atm. Bottom
temperature is maintained at 65C

By-products can be recovered from the digestion process. For example, turpentine
distills with water out of the blow tank and the evaporators and is separated to be used.
The resin acids and fatty acids dissolved from the wood form sodium soaps which are
skimmed off the black liquor from storage tanks, evaporators, and black liquor oxidation
tanks, and then acidified with sulfuric acid to form tall oil.

Before the washing process, the pulp is usually sent to deknotters, screens used to
remove knots (large pieces of fiber not completely broken down in the digester).

2. Brown stock Washing

From the blow tank, the pulp and spent cooking liquor are diluted and pumped to a
series of brown-stock washers, where the spent liquor is separated from the pulp,
usually by countercurrent washing. Brown-stock washers are typically of the rotary-drum
vacuum filter type although the newer diffusion-type washers are becoming increasingly
common, especially with continuous digesters. The washed pulp, still brown in color,
may then be subjected to a bleaching sequence.

The balance of the kraft process is designed to recover the cooking chemicals and heat.
Spent cooking liquor and the pulp wash water are combined to form a weak black liquor
which is concentrated in a multiple-effect evaporator system to about 55 percent solids.
The black liquor is then further concentrated to 65 percent solids in a direct-contact
evaporator, by bringing the liquor into contact with the flue gases from the recovery
furnace, or in an indirect-contact concentrator. Concentrated black liquor is sprayed into
the furnace and the organics in the black liquor, which are derived from pulping the
wood, are combusted. This generates sufficient energy to produce steam and, more
important, to reduce the sodium sulfate in the liquor to sodium sulfide. The bulk of the
inorganic molten smelt that forms and collects in the furnace bottom consists of sodium
carbonate and sodium sulfide in about a 3: 1 weight ratio. The smelt is continuously
withdrawn through smelt spouts into a smelt dissolving tank.

In the smelt-dissolving tank, jets of water are used to quench the molten smelt to form
green liquor, which consists of an aqueous solution of Na 2C03 and Na2S. The quenching
of molten smelt results in large quantities of steam leaving the tank, carrying with it
small amounts of particulate matter, containing mainly Na 2C03 and Na2S. The green
liquor is then transferred to a causticizing tank where quicklime (calcium oxide) is added
to convert the Na2C03 to NaOH. This results in a white liquor solution containing NaOH,
Na2S, and lime mud precipitate (mainly CaC0 3). The white liquor is then recycled to the
digesters and the entire process repeated.

Valuable extractives (e.g., turpentine, tall oil, and resin) are separated for sale as
commodity chemicals. Process chemicals are recovered with only a relatively small loss
in volume, and after replenishment with sodium salts, they are returned to the digester
for reuse.

Sulfite Pulping
Lignin can be dissolved by sulfonation with an aqueous solution of sulfur dioxide and
calcium, sodium, magnesium, or ammonium bisulfite cooked at high temperature and
pressure in a digester .There are four basic sulfite pulping processes currently in
commercial use:
1) Acid sulfite,
2) Bisulfite,
3) Neutral sulfite, and
4) Alkaline sulfite.

Bright, easily bleached pulps
Relatively easily refined pulps,
pulp that forms a less porous sheet that holds more water than kraft pulps (for
use in grease-resistant papers),
Pulps with higher yield than kraft.
Sulfite pulp is a light color and can sometimes be used without bleaching if high
brightness is not required.
Weaker than kraft
Not all species of wood can be pulped easily,
Cooking cycles are long,
Chemical recovery is complicated.

The major differences between the sulfite processes are the levels of acidity and
alkalinity of the sulfite chemical solutions used to break down the wood and remove the
Sulfite pulping processes are suitable only for species with low extractive contents (i.e.,
those low in tannins, polyphenols, pigments, resins, fats, and the like) because of the
interference of these substances with the sulfite pulping process. Although calcium is
the cheapest sulfite base available, it forms insoluble compounds that cannot be
reclaimed economically. Thus, calcium-based pulping is seldom used. Because
magnesium- and sodium based chemicals are recoverable, and ammonium based
chemicals are less expensive and can be burned without harmful environmental effects,
they are the most frequently used.
Process Description -
The production of acid sulfite pulp proceeds similarly to kraft pulping, except that
different chemicals are used in the cooking liquor. In place of the caustic solution used
to dissolve the lignin in the wood, sulfurous acid is employed. To buffer the cooking
solution, a bisulfite of sodium, magnesium, calcium, or ammonium is used.

Digestion is carried out under high pressure and high temperature, in either batch mode
or continuous digesters, and in the presence of a sulfurous acid/bisulfite cooking liquid.
When cooking is completed, either the digester is discharged at high pressure into a
blow pit, or its contents are pumped into a dump tank at lower pressure. The spent
sulfite liquor (also called red liquor) then drains through the bottom of the tank and is
treated and discarded, incinerated, or sent to a plant for recovery of heat and chemicals.
The pulp is then washed and processed through screens and centrifuges to remove
knots, bundles of fibers, and other material. It subsequently may be bleached, pressed,
and dried in papermaking operations.

Because of the variety of cooking liquor bases used, numerous schemes have evolved
for heat and/or chemical recovery. In calcium base systems, found mostly in older mills,
chemical recovery is not practical, and the spent liquor is usually discharged or
incinerated. In ammonium base operations, heat can be recovered by combusting the
spent liquor, but the ammonium base is thereby consumed.
In sodium or magnesium base operations, the heat, sulfur, and base all may be feasibly
If recovery is practiced, the spent (weak) red liquor (which contains more than half of
the raw materials as dissolved organic solids) is concentrated in a multiple-effect
evaporator and a direct contact evaporator to 55 to 60 percent solids. This strong liquor
is sprayed into a furnace and burned, producing steam to operate the digesters,
evaporators, etc. and to meet other power requirements.

When magnesium base liquor is burned, a flue gas is produced from which magnesium
oxide is recovered in a multiple cyclone as fine white power. The magnesium oxide is
then water slaked and is used as circulating liquor in a series of venturi scrubbers,
which are designed to absorb sulfur dioxide from the flue gas and to form a bisulfite
solution for use in the cook cycle.

When sodium base liquor is burned, the inorganic compounds are recovered as a
molten smelt containing sodium sulfide and sodium carbonate. This smelt may be
processed further and used to absorb sulfur dioxide from the flue gas and sulfur burner.
In some sodium base mills, however, the smelt may be sold to a nearby kraft mill as raw
material for producing green liquor. If liquor recovery is not practiced, an acid plant is
necessary of sufficient capacity to fulfill the mills total sulfite requirement. Normally,
sulfur is burned in a rotary or spray burner. The gas produced is then cooled by heat
exchangers and a water spray and is then absorbed in a variety of different scrubbers
containing either limestone or a solution of the base chemical.


In kraft (or sulfite) pulping, the process does not permit a complete delignification for
reasons of pulp yield and quality. The remaining small amounts of lignin, usually in the
order of ~25 % (on pulp) depending on wood species and process details, give the
fibers a brownish color and, therefore, the manufacturing of white fiber products require
a further delignification and bleaching of the fibers.
Goals of bleaching are
1. Attack and remove remaining lignin
2. Attack and destroy colour causing molecules
3. Attack and remove/decolorize dirt and fibre bundles
4. Improve pulp brightness and cleanliness

This is accomplished by a series of alternating oxidation and extraction treatments

ultimately leading to an almost lignin-free fiber. In its simplest form, the chemistry can be
written as shown in

Most common bleaching chemicals are very strong oxidizers. In most cases these
oxidizers are strong electrophiles, so they steal electrons from lignin and other
molecules, causing chemical bonds to break.

Common bleaching chemicals are

Oxygen O O2
Chlorine Dioxide D ClO2
Hydrogen Peroxide P H2O2
Ozone Z O3
Extraction E NaOH

To measure the lignin content in pulp, a number called the "Kappa number" is used. The
Kappa number is directly proportional to the lignin content of the pulp. Pulp from the
digester has a Kappa number of 20-35 for softwood and 15-20 for hardwood (hardwood
contains less lignin and can therefore be cooked to a lower Kappa number). Oxygen
delignification removes about half of the lignin remaining after the cooking process, so
that the Kappa number of the oxygen delignified pulp is typically 12-18 for softwood.
The final bleaching removes all remaining lignin and decreases the Kappa number to

Kappa Number: The kappa number is the number of milliliters of 0.1 KMn0 4 consumed
by one gram of pulp in 0.5 N sulfuric acid after a ten minute reaction time at 25C (77F)
under conditions such that one-half of the permanganate remains unreacted.

Oxygen delignification
In oxygen delignification, washed pulp is treated with a highly alkaline solution of
sodium hydroxide. The high pH ionizes phenolic groups in the lignin, which are then
attacked by molecular oxygen. The aromatic part of the lignin is partly destroyed and it
is then depolymerised to lower molecular weight compounds. These are more soluble in
water and can be removed from the fibres. It is important that the pulp has been at least
partly washed beforehand because the black liquor solids in unwashed pulp consume
oxygen. After the oxygen delignification stage, the pulp has to be washed very well, as
otherwise the organics carry over to the final bleaching process, consuming chemicals
there and also decreasing the environmental benefits.

Final bleaching
The final bleaching is always carried out in several stages to improve the efficiency of
the chemicals used, and to decrease the strength loss of the pulp. There are quite a
number of bleaching chemicals used commercially, and many more have been tried in
the laboratory.
The chemicals used are:
Chlorine dioxide
Sodium hypochlorite
Of these chemicals, the first three contain chlorine atoms, whilst the last three use non
chlorine oxidizing compounds. Elemental chlorine (Cl2) was for many years the work
horse of the bleaching process. It is efficient in bleaching the pulp and (if properly used)
does not degrade the pulp strength. However, it produces a large amount of chlorinated
organic compounds in the effluent, and strenuous efforts have therefore been made to
decrease its usage. For the same reason, the use of sodium hypochlorite (which also
tended to affect the pulp strength) is now virtually eliminated.
Modern bleach plants therefore use no elemental chlorine. They are what is called ECF
plants: elemental chlorine free bleach plants.
Chlorine dioxide, which is used instead (in addition to non-chlorine compounds), is
environmentally much more benign than Cl2. However, while chlorine dioxide is good at
preserving pulp strength, it is not as effective as elemental chlorine in
delignification/bleaching. ECF plants therefore have to have a rather low incoming
Kappa number, and this is normally achieved by using oxygen delignification ahead of
the final bleaching.
Most ECF plants use a three step bleaching process of chlorine dioxide followed by a
mixture of NaOH, O2 and peroxide (the 'extraction' stage) and then finally chlorine
dioxide again.
A sequence of chlorine dioxide then NaOH and O2 followed by more chlorine dioxide is
used. The chlorine dioxide stages normally run at a pH of 3-4.5, and the 'extraction'
stages at a pH of 10-11. The temperature is kept at 70-80 oC to achieve sufficiently fast
rate of reaction.

In old bleaching technology, a treatment of the pulp with aqueous elemental chlorine (C)
followed by alkaline extraction (E) was used as the predominant delignification stage.
The final brightening was done with chlorine dioxide (D) and the complete sequence
being e.g. CEDED.

Paper making
Paper making is the process whereby pulp fibres are mechanically and chemically
treated, formed into a dilute suspension, spread over a mesh surface, the water
removed by suction, and the resulting pad of cellulose fibres pressed and dried to form
The mechanical treatment of the fibre normally takes place by passing it between
moving steel bars which are attached to revolving metal discs - the so-called refiners.
This treatment has two effects: it shortens the fibre (fibre cutting) and it fibrillates the
fibre. The latter action increases the surface area, and as the fibres bond together in the
paper sheet by hydrogen bonding, the increased surface area greatly increases the
bonding and strength of the paper. Paper strength is dependent on the individual fibre
strength and the strength of the bonds between the fibres. It is usually the latter, which
is the limiting factor. Refining increases the interfibre bonding at the expense of the
individual fibre strength, but the net result will be an increase in paper strength.
Pressing and calendering (feeding through rollers) increase density and promote
Various chemicals are added, e.g. to give water resistance, to give increased strength to
produce coloured paper, or to serve as inorganic filters.