7.

PULP AND PAPER

7.1. INTRODUCTION

Writing paper was first used in Egypt, made from the papyrus reed.

Papyrus Making 2.Peeling

1.Harvesting

 only the inner part of the reed is used to

make the writing material.
 3.Cutting

 Once the outer layer is removed, the inner part of the reed is cut into strips.

4.Soaking
Soaking the papyrus strips is important
for softening the papyrus and activating
the plant's natural juices, which act as a
glue to hold the strips together.
 5.Rolling

After they have soaked for a few days in water, a wooden rolling pin is used to drive out
the water and flatten the papyrus strips.
6.Pressing, Drying

When the strips have all been laid out, they are covered with a sheet of linen & felt, & then
sandwiched between two boards in a press. The sheet will remain in the press for a few days
until it is dry.
7.Final Product

Initially, the surface of the papyrus is somewhat rough. It may be burnished

slightly with a stone, and then it is ready to receive writing.
History of Papermaking

Paper manufacture began in China about AD 105 from plant (mulberry) fibers.
 Developed by Chinese Emperor by Ts'ai Lun
In 1690 the first American paper mill began its operation.

America's first writing papers were produced by collecting, separating, and

cleaning old cloth rags. The paper was made in single sheets
1796: First continuous paper machine developed near Paris by Nicholas-Louis
Robert. Fiber source - rags (cotton)

1840: Ground wood pulping developed in Germany

1854: Soda pulping process developed in England
Two major advancements in pulping were
developed in the late 1800s

1866 1879
American Benjamin German chemist, C. F.
Tilghman developed Dahl, developed the
the sulfite (acid) Kraft (sulfate)
pulping process pulping process
Dominant pulping 1930s dominant
process until the pulping process
1930s and still is today
 7.2 THE CHEMISTRY OF WOOD
 Woody plants are made of strong, relatively thick-walled long cells that make
good fibers. The cell wall in these types of plants is a complex mixture of
polymers that varies in composition. But it can be roughly divided into 70%
polysaccharides & 28% lignin.

 The polysaccharides in wood are called holocellulose or total cellulose

carbohydrates. They can be subdivided into
(i) Cellulose (40%), a high molecular weight linear polymer composed of
glucose units with high chemical resistance, &

(ii) Hemicellulose (30%), other polysaccharides besides cellulose that are of

lower molecular weight & have lower chemical resistance to acids & alkalies.
Xylose Arabinose
 Lignin has been described as "the adhesive material of wood" because it
cements the fibers together for strength.

 It is a complex cross-linked polymer of condensed phenyl

propane units joined together by various ether & carbon linkages.

 A representative structure of the phenylpropane units in lignin is

given in following figure.
The three common monolignols : coniferyl alcohol (1), sinapyl alcohol (2) & p-
coumaryl alcohol (3)
The structure of lignin

Lignin is the main wood component that must be effectively removed from
the pulp.
 Lignin can be
 considered to be a polymer of coniferyl alcohol. About 50% of the linkages
are p-aryl ethers.
 degraded with strong alkali, with an acid sulfite solution, & with various
oxidizing agents. It is therefore removed from the wood to leave cellulose
fibers, commonly called pulp.
 Besides the holocellulose & lignin of the cell wall, wood contains about 2%
extractives. These can be separated by steam distillation or solvent extraction.
 The average composition of most woods is summarized as follows:
(i) holocellulose, 70% (including 40% cellulose and 30% hemicellulose),
(ii) lignin, 28% , and (iii) extractives, 2%.
7.3. PULP MANUFACTURE
Raw Materials
Paper industry consumes a wide variety of raw materials
Cellulosic Raw Material
Cellulosic : derived from forest, agricultural residues and waste papers.
Major Cellulosic raw materials used by paper industry is bamboo, wood (hard wood
& soft wood, Logs (chipped directly from logs for pulp production) & Chips (residuals
from saw mill operations)), bagasse, waste paper and agricultural residue like wheat
straw, rice straw, grasses, etc.
Non-cellulosic: Coal, chlorine, lime, sodium hydroxide, sodium sulphide, fuel oil, etc.

Pulping

 The process of pulping, degrading the lignin to a more soluble form so the
cellulose fibers can be separated from it, involves some interesting chemistry.

i.e., Pulping aims to separate cellulose fibers from the wood structure.
 Possible types/methods of pulp production are:
1. Mechanically: “Grind up” raw material (most of the lignin retained).
Mechanical pulping uses mechanical abrasion to separate cellulose fibers
which are held together by lignin.
2. Chemically: Dissolve away the lignin
• Kraft (sulfate) pulping: NaOH/NaSH (dominant process) the most popular b/c
it produces a higher
• Sulfite pulping : (Sulfur Dioxide/bisulfite/sulfite) quality paper than
mechanical pulping
 Soda Chemical Pulping
Chemical pulping achieves fiber separation by dissolving the lignin.
3. Semi-chemical

.
Semi-chemical pulps are essentially mechanical pulps that have been pre-treated
with a sulfite or sodium hydroxide liquor to improve breakdown and reduce
energy requirements during processing.
 Soda Pulping:
 It is the original chemical pulp & is produced by cooking chips of
deciduous woods in a solution of caustic soda under pressure.

Kraft(Sulfate) Pulping:

 An aqueous solution of NaOH & Na2S, known as white liquor,

selectively dissolve the lignin and make it soluble in the cooking liquid.

Sulfite Chemical Pulping:

uses sulfurous acid & an alkali to produce pulps of lower physical

strength & bulk, but exhibits better sheet formation properties.
 The kraft or alkaline sulfate process dominates the pulping industry.
Approximately
 78% of all pulp is made by the kraft process
 3% by the acid sulfite process
 7% by the neutral sulfite semichemical (NSSC) process
 10% by a nonchemical, mechanical method called ground
wood, &
 2% by other methods.

 The strongest pulp fibers can be made by Kraft Process .

7.3.1 The Kraft Process/pulping (Alkaline sulfate treatment)
 Invented in Germany in 1884 & remain the dominating technology today.
 Any pulping process
 lowers the molecular weight of the hemicellulose,
 depolymerizes the lignin, and
 gives a much larger percentage of cellulose fibers.
 The important chemistry in the kraft method is divided into
(i) Inorganic and (ii) Organic parts.
 The inorganic loop is a closed system with the exception of sodium sulfate
being added periodically. Only wood enters the loop and only pulp leaves.
 Although the digester is shown as containing NaSH and NaOH, the typical
entering white liquor is analyzed at about 59% NaOH, 27% Na2S, and 13%
Na2CO3—Na2SO4—Na2SO3.

 Digestion of the wood-white liquor mixture occurs at 170-175oC and 100-135

psi for 2-5 hr. A typical digester is 40 ft high with a diameter of 20 ft and can
hold up to 35 tons of wood chips at a 1:4 wood: white liquor weight ratio.
 The resulting pulp is separated from the black liquor (colored with
organics), which is then oxidized to Na2S2O3 (S-2 to S+2) and further
oxidized in the furnace to Na2SO4 (S+2 to S+6).

 The organic material from the digestion process may be simplified as

 Carbon, is oxidized in the furnace to CO2 (C0 to C+4)

 Whereas the Na2SO4 is reduced back to Na2S (S+6 to S-2), the original
oxidation state of sulfur in the process in the recovery part.
 The CO2 is absorbed by NaOH to form Na2CO3.
 Water is added to the material from the furnace, forming a green liquor containing
NaSH and NaOH.
 The Na2CO3 is reacted with CaO and water to give more NaOH (causticizing) and
CaCO3, which is usually filtered & transformed on site back into CaO by a lime kiln.
Chemical Recovery Plant:
 The pulping process generates a high amount of black liquor.
 Chemical recovery is necessary because it minimizes the environmental impacts
of waste, recovers NaOH and Na2S.
Chemical recovery involves the following steps:
a. Evaporator: Black Liquor from the washer is concentrated to the point that it can
be burned in a recovery boiler.
b. Recovery Boiler: Concentrated black liquor is burnt in the absence of oxygen to
form Na2S, which is dissolved further to create green liquor.
c.Causticizing: Green liquor reacts with lime to produce NaOH, whereas Na2S
remains unchanged in this stage. The green liquor is sent back to the digester for
pulping.
d. Lime Mud Recovery: The precipitate CaCO3 is heated in a lime kiln to release
CaO to reuse later.
‍
 Finishing Kraft pulp
 After the crude pulp is obtained from the alkaline sulfate process, it must be
bleached in stages with elemental chlorine, extracted with sodium hydroxide, and
oxidized with Ca(OCl)2 (Calcium hypochlorite), ClO2, and H2O2.
This lightens it from a brown to a light brown or even white (difficult) color.
 Typical end-uses of kraft pulp are brown bags, paper boxes, and milk cartons.
 The strong odor is caused by methyl mercaptan & dimethyl sulfide, both of
which are formed by bisulfide cleavage of methoxy groups in lignin.

Important side products of the kraft process

(i)DMSO

 Much of the methyl mercaptan & dimethyl sulfide can be oxidized to

dimethylsulfoxide (DMSO), it is a common polar, aprotic solvent in the
chemical industry.

 Caution must be used when handling DMSO b/c of its extremely high rate of
skin penetration.
(ii) Sulfate turpentine

The turpentine (C10H16) is obtained from the gases formed in the digestion
process. From 2-10 gal of turpentine can be obtained per ton of pulp.

Raw sulphate turpentine is mainly used in the production of perfumes and

flavors.
(iii) Tall oil

 Tall oil soap is a black viscous liquid of rosin & fatty acids that can be
separated from the black liquor by centrifuging. Acidification gives tall
oil.

 The composition of crude tall oil varies a great deal, depending on the
type of wood used.

 Used as a bonding agent in printing ink and road marking paint; as emulsifiers
in rubber production; and as a paper treatment agent.
7. 3.2 Other Pulp Processes

 The acid sulfite process is used to obtain a higher quality paper. It is also more
water polluting. Digestion occurs in a mixture of sulfur dioxide and calcium or
magnesium bisulfite. The magnesium bisulfite process is better for pollution but
still not so good as the kraft process.

 Sulfite pulp is used for bond paper and high-grade book paper.

 In the neutral sulfite semichemical process sodium sulfite is buffered with

sodium carbonate, bicarbonate, and hydroxide to maintain a slightly alkaline pH
during the cook.
7.4. BLEACHING
 Raw pulp contains an appreciable amount of lignin and other discoloration, it
must be bleached to produce light colored or white papers preferred for many
products.

There have been many changes in the bleaching process for pulp during the 1990s.

Chlorine bleaching has been challenged by environmental concerns and dioxin

emission guidelines since studies done in the 1980s showed chlorinated dioxins and
other chlorinated organic compounds in the effluent of pulp and paper mills.

Discharges of dioxins in wastewater could be slashed by up to 95% by switching

from chlorine to chlorine dioxide. Furans could be reduced by 99%.

Replacements for chlorine include sodium chlorate, hydrogen peroxide, and

oxygen.

These three chemicals are more powerful bleaching agents than chlorine.
 Another way of cutting the need for bleaching is by recycling of final paper
products.

The majority of the recycled paper (about 75%) is used with no attempt to remove

inks, dyes, or pigments from the paper.

 This pulp is poor in color and quality but can be used in paperboard.

 Deinked grades require special equipment to remove inks, coatings, adhesives,

solvents, and surfactants.
Pulp Making Process
Wood Trunks Debarking Chips Digester

Pulp Bales Pulp Machine Bleaching Tower

7.5. PAPER MANUFACTURE

Less chemistry is involved in the manufacture of paper once the pulp has been
made, but it is a complex process that can be summarized in the following steps:

Stock Preparation

 Pulp mixed with water, fillers, coloring agents in

a hydrapulper. Here the pulp is softened by

beating and refining through rotating blades.

 Different additives are mixed with refined pulp

to bring it to desired properties for papermaking.

 Paper additives include pigments and dyes, wet-

strength resins, sizes, biocides, etc.

 1. Beating and refining the pulp to make the fibers stronger, more uniform, denser,
more opaque, and less porous.

 Paper made from unbeaten stock is low in strength, fluffy, porous, and unfit for
most use, whereas paper made from beaten stock is strong, dense, and hard in
texture.

2. Adding Coagulants: to neutralize the surface charge of suspended materials

and remove electrostatic barriers, preventing them from colliding with each other
and sticking together.
 Among inorganic coagulants, the most widely used is aluminum sulfate, or
„papermakers‟ alum.‟
Alum derives its coagulating ability from the trivalent character of aluminum,
plus a tendency to form oligomeric species.
3. Adding Fillers: to occupy the spaces between the fibers. These fillers are usually
inorganic clays (Kaolin, Al4Si4O10(OH)8), CaCO3, or TiO2. Improve surface and optical
properties of the paper.

4. Adding Sizing agent (Rosin): to impart resistance to penetration by liquids.

Sizing makes paper hydrophobic and prevents the spreading of ink or color.

 This process is achieved either before sheet formation or after finishing by

surface coating (size press).
 Internal Sizing agents included:
1- Rosin (C15H20O6) & Alum (eg. KAl(SO₄)₂·12H₂O)
2- Alkyl ketene Dimer (AKD)
3- Alkenyl Succinic Anhydride (ASA)
5. Adding Wet strength resins: to increase the strength of the paper when wet.

It used for wetted paper sheets to protect the natural hydrogen bonds from attack
by moisture.

Wet-strength agents included: Polyethylene imines (PEI), polyamides, Urea-

formaldehyde resins , Polyamidoamine-epichlorohydrine (PAAE).

6. Adding Coloring Agents (Dyes and Pigments): Impart desired color.

Pigments used for paper dying are

 Inorganic (iron oxide, cadmium, chromium oxide);
 Organic (azo and polycyclic); and metal complex
 Specialty Additives

Fire-resistant papers: produced by the addition of flame-retardants to the pulp or

to the coating.
Examples include calcium chloride, magnesium chloride, diammonium ethyl
phosphate and mixtures of zinc borates, antimony oxides and organic halides salts,
as well as inorganic bromides and oxybromides.

Anticorrosion paper is impregnated or coated with chemicals that inhibit

corrosion, e.g. sodium nitrite or sodium benzoate.
Paper Machine:

a. Headbox: This is a stock distribution zone, where prepared stock (slurry) is

pushed onto the wire to form a fragile sheet. The pulp is 99.5 % water to 0.5 %
pulp.

b. Wire: This is a mesh conveyor belt used to handle feed from the headbox. At
the wire, primary sheet formation occurs. Gravity, suction, and a mechanized
vibration of the screen quickly begin to remove 20% of the water.

c. Press: Water is squeezed out from the paper sheet. The purpose of the Press is to
provide maximum dryness in a paper sheet for input to dryers. (With the water still
at 60%)

d. Dryers: Hot paper drying cylinders (The Largest part of a paper machine) are
used to evaporate the remaining water in the paper sheet. The paper passes through
steam heated dryers that leave the product with a moisture content of 2-6%.
e. Size Press: Apply sizing solutions to the surface of the paper sheets. These could
be starch solutions or coating colors. At this point, a starch solution is applied to both
sides of the sheet.

The starch solution enhances its ability to resist water and ink penetration during the
offset printing process. This step of the paper making process also gives the paper
the ability to receive toners and liquid inks used in various types of digital printing.

f. Calendar: For the perfect surface finish of a paper sheet, the paper passes through
different big, heavy rollers/cylinders with different surfaces, from tough steel to soft
rubber (according to the paper type), with each applying pressure and temperature.

g. Winder: the paper is wound on a large reel called the winder. The winder offers
the ability to customize sheeter roll sizes to maximize the efficiency and limit waste.
PAPER MACHINE

Headbox Wire Press

Winder Post Dryers

(Reel) (calendar)
Size Press Pre Dryers
7.6. GENERAL USES OF PAPER PRODUCTS

 Paper (50%)

 Newsprint, books, tissue, corrugated boxes, bags, cigarette paper, food containers,
plates, wallpaper, disposable clothing

 Paperboard (50%)

 Fiberboard (fibers with added phenolics):

 panelling, furniture, insulation Particleboard (waste wood chips or dust plus a resin)

 panelling, subflooring, general plywood and lumber replacement Paper-base laminates

(plies of wood plus a phenolic, urea, or melamine resin)

 structural and machine parts

 Recycling
The recycling process includes following stages:
• Sorting
• Dissolving
• De – inking
• Mixing
• Papermaking process
 ENVIRONMENT IMPACT OF PULP AND PAPER
MANUFACTURING PROCESS

Pulping often releases a range of pollutants, including

organic products which cause eutrophication in water,
aluminum salts and sometimes also generation of sulphur
dioxide.

When bleaching is carried out with chlorine or

hypochlorite, it may generate dioxin. These pollutants
have direct impacts on freshwater and marine ecosystems
near pulp mills.

2,3,7,8-tetrachlorodibenzo-p-dioxin or TCDD
Air Emissions
Air pollution mainly occurs from digesters blow tanks,
steam boilers, chemical recovery boilers.

Air emissions related with this process are: sulphur dioxide, nitrous oxides,
particulate matter, methanol, polycyclic organic matter, formaldehyde,
chloroform, phenol and chlorinated phenolics, dioxins, furans and other
chlorinated compounds.
Solid waste

 Solid waste is generated in the form of sludge, ash, wood waste,

screening, centricleaner rejects and sand.
 The major concerns with these wastes is their disposal.

Paper mills also produce non-hazardous solid waste such as

sludge derived from their pulping and bleaching operations.
Pollutants in effluents
Wastewater releases include:

lost cellulose fibre,

dissolved organic compounds (such as dissolved lignin

compounds, carbohydrates, starch and hemi-cellulose),

chlorinated phenolics, dioxins, furans and other chlorinated

compounds if elemental chlorine is used in the process, and

suspended sediments.
 Reduction of Wastewater
Reduce the demand for the high quality bright-white paper
For “lower quality” papers use a combination of other chemicals
in the bleach process (Eg.O2,O3,H2O2)

Raw water use

• Pulp mills are big water users.
• Consumption of fresh water can seriously harm habitats near mills,
reduce water levels necessary for fish, and change water
temperature, a critical environmental factor for fish.
Conclusion