Unit 2: Pulp and Paper

Industries
 WHAT IS PULP?

• Pulp is a cellulose fiber material, produced by chemical

or mechanical means, from which paper and paperboard
are manufactured.
• Sources of cellulose fiber include wood, cotton,
bagasse, bamboo, etc.
• Cellulose is the most abundant organic substance and is
the major component of wood.
• Industries convert the cellulose in the wood to useful
pulp and paper products.
 •Before paper can be made from wood, the cellulose
fibers must be freed from the matrix of lignin which
cements them together.
Cellulose
• Cellulose makes up nearly
50% of woody plant.
• Cellulose is made up the
starches, proteins, and
sugars.
• It is the most abundant
organic material on Earth.
SEM image of Bleached
Cellulosic Fibers
Lignin
• Lignin is a polymer that holds together the cellulose and
hemicellulose components of woody biomass.

• Lignin constitutes about 15 to 25% of the weight of

woody biomass.

• Lignin has not yet been used as a raw material for

industrial purposes in large quantities. This reflects the
chemical complexity of lignin.

• All processes used for pulping have the same goal-to

release the fibrous cellulose from its surrounding lignin
while keeping the hemicelluloses and celluloses intact,
thereby increasing the yield of useful fibers.
• The fibers thus obtained are naturally colored and must
be bleached before they can be used for paper.

• Here again, the goal is to obtain good color without

degradation and loss of cellulose fibers.

• There are many processes and variations of basic

processes which can be used for making pulp from
wood

• Chemical pulping is the most common pulping

process..
Mechanical Pulping
•Mechanical pulping utilizes steam, pressure, and high
temperatures instead of chemicals to tear the fibers.

•The fiber quality is greatly reduced because mechanical

pulping creates short, weak fibers that still contain the
lignin that bonds the fibers together.

•The presence of the lignin limits the amount that the pulp
may be bleached because the lignin binds with the
bleaching chemicals.

•Newspaper and paperboards are typical products of the

mechanical pulping
Semi-Chemical Pulping
Semi-chemical pulping techniques use weak chemical
solutions composed of sodium sulfite (Na 2SO3) and
sodium carbonate (Na2CO3) to help digest the lignin in the
pulp. In addition to the chemical solutions, mechanical
refining is used to separate the fibers.
In the recycle (i.e., secondary fiber) pulping process, pulp
fiber from previously manufactured products (e.g.,
cardboard, office paper) are recovered by hydration and
agitation.
Secondary fibers include any fibrous material that has
undergone a manufacturing process and is being recycled
as the raw material for another manufactured product.
Secondary fibers have less strength and bonding
potential than virgin fibers.
•Dissolving kraft and sulfite pulping processes are used
to produce highly bleached and purified wood pulp
suitable for conversion into products such as rayon,
viscose, acetate, and cellophane.

•Non-wood pulping is the production of pulp from fiber

sources other than trees.

•Non-wood fibers used for papermaking include straws

and grasses (e.g., flax, rice), bagasse (sugar cane), hemp,
linen, ramie, kenaf, cotton, and leaf fibers.
•
•Pulping of these fibers may be performed by mechanical
means at high temperatures or using a modified kraft or
soda process.
• KRAFT PULPING:- Kraft, or sulfate, pulping is an
alkaline process by which most pulp is presently made.
• Kraft pulping is by far the most common pulping
process. In the process it involves three types of liquors
White liquor.
Fresh pulping liquor for the kraft process containing
NaOH, Na2S.
Black liquor.
The waste liquor from the kraft pulping process.
Contains most of the original inorganic components
(most in different forms) and a high concentration of
dissolved organics. But can be recovered.
Green liquor.
Partially recovered kraft liquor (intermediate liquor in
recovery sequence)
Typical White Liquor Composition
Chemical Amount Class* Source of unwanteds:
(as Na2O) (Recovery System)
NaOH 81 - 120 g/l Active NA
Na2S 30 - 40 g/l Active NA
Na2CO3 11 - 44 g/l Inactive Incomplete Caustizing
Na2SO3 2 - 6.9 Inactive Incomplete Reduction
Na2SO4 4.4 - 18 g/l Inactive Incomplete Reduction
Na2S2O3 4 - 8.9 g/l Inactive Oxidation of Sulfide
 Simplified Liquor Scheme

White Liquor Lime

Kilm

Digester Green Liquor

Recovery
Black Liquor Furnace

PSE 476: Lecture 6 13

•The production of pulp by the kraft process can be divided into three
areas, namely, (1) the making of pulp, (2) the recovery of cooking
chemicals, and (3) the bleaching of pulp.

•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.
•
•The material added to the cooking liquor for the kraft process is
Na2SO4, hence the common name of the sulfate process.

•The cooking, however, is done with a solution containing Na2S,

NaOH, and

•Na2CO3 formed from the sulfate during preparation and recovery of

the cooking liquor.
• Although all sorts of woods can be cooked by the kraft
process and the fibers obtained are bleachable and
strong, it is very important that the chemicals used can
be recycled and regenerated, in order to reduce
pollution issues.

• Odors that are released during cooking are, however,

strong air polluters and difficult to control.
• The cooking process causes chemical reactions
involving the hydrolysis and solubilization of the
lignin, thus freeing the cellulose fibers.

• The hydrolysis frees some of the organic sulfides

which are the source of the foul odor associated with
kraft mills.
• When using a continuous digester, the manufacture of
sulfate pulp involves the following sequences:
• Logs are cut to convenient lengths and debarked, then
conveyed to the chippers, which are large rotating disks
holding four or more heavy knives.
• These reduce the wood to chips of preselected size
• The chips are screened on either rotating or vibrating
screens to separate the oversize chips, the desired
product, and the sawdust.
• The oversize chips are sent to re chippers to reduce
them to the proper size.
• Chips enter the continuous digester and are pre
steamed at approximately 100 kPa, volatilizing the
turpentine oil and non condensable gases.
 They then pass to a higher-pressure impregnation
zone at about 900 kPa, where their temperature is
adjusted and they meet with the cooking liquor.
 Cooking time is about 1 1/2 hours at 170°C.

 A quench flow of cold cooking liquor quickly stops

the cooking reaction.

 Countercurrent displacement washing then reduces the

chemical content of the chips, and the pressure is
then reduced, producing flash steam which is used for
the pre steaming step on the entering chips.

 The chips thus produced, along with their adhering

liquor, are known as brown stock
• The spent cooking liquor, commonly called black
liquor, is now ready to be treated to recover its chemical
content for reuse and its organic content as heat.

• Some method of heat recovery from this material usually

precedes the washing step.

• The washed pulp is passed over screens to remove

knots, unreacted chips, slivers, trash, etc., then sent on to
thickeners and filters.
Recovery of Cooking Chemicals
For economic and environmental reasons, chemical and
semi-chemical pulp mills employ chemical recovery
processes to reclaim spent cooking chemicals from the
pulping process.
The chemical recovery process involves concentrating weak
black liquor, combusting organic compounds, reducing
inorganic compounds, and reconstituting the cooking liquor.
Black liquor concentration. Residual weak black liquor
from the pulping process is a dilute solution of wood
lignins, organic materials, oxidized inorganic compounds
(sodium sulfate [Na2SO4], Na2CO3), and white liquor (Na2S
and NaOH).The weak black liquor is first directed through a
series of multiple-effect evaporators.
Recovery furnace
•The concentrated black liquor is then sprayed into the
recovery furnace, where organic compounds are combusted,
and the Na2SO4 is reduced to Na2S.
• Na2SO4 + 2C Na2S + 2CO2
•The inorganic process chemicals, also know as smelt, flow
through the floor of the recovery boiler to be recausticize.
Smelt is drawn off and dissolved in weak wash water in the
smelt dissolving tank (SDT) to form a solution of carbonate
salts called “green liquor,” which is primarily Na 2S and
Na2CO3.
•Green liquor also contains insoluble unburned carbon and
inorganic impurities, called dregs, which are removed in a
series of clarification tanks.
Causticizing and calcining.
•Decanted green liquor is transferred to the causticizing
area, where the Na2CO3 is converted to NaOH by the
addition of lime (calcium oxide [CaO]) .

•The green liquor is first transferred to a slaker tank,

where CaO from the lime kiln reacts with water to form
calcium hydroxide (Ca(OH)2).

•From the slaker, liquor flows through a series of

agitated tanks, referred to as causticizers, that allow the
causticizing reaction to go to completion (i.e., Ca(OH) 2
reacts with Na2CO3 to form NaOH and calcium
carbonate [CaCO3]).
•The causticizing product is then routed to the white
liquor clarifier, which removes CaCO3 precipitate,
referred to as “lime mud.” The lime mud is washed in the
mud washer to remove the last traces of sodium.
•The mud from the mud washer is then dried and calcined
in a lime kiln to produce “reburned” lime, which is
reintroduced to the slaker.
•The white liquor (NaOH and Na2S) from the clarifier is
recycled to the digesters in the pulping area of the mill.
•The thickened pulp is next bleached.
•Chlorine dioxide is less damaging than Cl 2 or
hypochlorite and is generally used in the first stage of a
multiple-stage bleaching process.
Bleaching
Bleaching involves removing virtually all of the lignin that
still remains after cooking, as the lignin contains the
chromophoric groups which make the pulp dark.
In practice, there are two separate "bleaching" process
steps: oxygen delignification and final bleaching.
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 or NaOH removes hydrogen
ions from the lignin and then the O2 breaks down the
polymer.
The aromatic part of the lignin is partly destroyed and it is
then depolymerised to lower molecular weight compounds.
Then, the pulp is treated with ClO2 then a mixture of
NaOH, O2 and peroxide and finally with ClO2 again to
remove the remaining lignin.
After bleaching, the pulp is washed and rethickend in
preparation for making it into coarse sheets dry enough to
fold into a bundle,store, and shipping purposes.
The pulp may also be used directly for making paper.
1. Na2SO4 + 2 C → Na2S + 2 CO2

2. Na2CO3 + Ca(OH)2 ←→ 2 NaOH + CaCO3

3. CaCO3 → CaO + CO2

4. CaO + H2O → Ca(OH)2