EKB 1013

CHEMICAL PROCESS INDUSTRIES

Paper Machines

Manipal International University

Pulp and Paper

Industry

History of Paper Making

105 A.D. Ts'ai Lun, a Chinese court official,
invented paper
mulberry bark, hemp and rags with water

Paper was first produced in Egypt around 900

A.D.
England early in the 14th Century

To this point all paper and

books were produced by hand

History of Paper Making

Gutenberg Press in 1436
On September 30, 1452 Guttenberg's
Bible was published
The printing press allowed
printed materials to be
produced at a greater rate
thus increasing the demand
for paper

History of Paper Making

First North American paper mill in 1690 near
Philadelphia
America's first writing papers were produced
by collecting, separating, and cleaning old
cloth rags
The paper was made in single sheets

History of Paper Making

1798, Nicholas-Louis Robert of France
invented a paper making machine that
produced paper on an endless wire screen
Further developed in England by Brian Donkin

Not put into service until 1804

History of Paper Making

The Fourdrinier

1st Fourdrinier machine

in the US, 1827

History of Paper Making

Two major advancements in pulping were
developed in the late 1800s
1866
American Benjamin Tilghman
developed the sulfite
pulping process

Dominant pulping process

until the 1930s

1879
German chemist, C. F. Dahl,
developed the
Kraft(Sulphate) pulping
process

1930s dominant pulping

process and still is today

The Modern Paper Making Process

Paper Making Process Overview

Pulp and paper mills

Pulp mills separate the fibres of wood or
from other materials, such as rags,
wastepaper or straw in order to create pulp.
Paper mills primarily are engaged in
manufacturing paper from wood pulp and
other fibre pulp, and may also manufacture
converted paper products.

Production process

The production process can be divided into 7

sub-processes:
raw materials processes;
wood-yard;
fibre line;
chemical recovery;
bleaching;
paper production;
products and recycling.

Simplified flow diagram of

integrated mill

Pulping processes
Pulping aims to separate cellulose fibers from
the wood structure.
Possible types of pulp production are:
Kraft (68%)
mechanical (22%)
semi-chemical (4%)
sulphite (4%)
dissolving (2%).

Kraft Pulping
Sulfate or Kraft pulping was invented in
Germany in 1884 and remains the
dominating technology today.
Advantages:
higher pulp strength
wider variety of wood species may be used
more effective at removing impurities like resins.

Disadvantage:
the pulp yield is low, less than 50%.

Ocala National Forest, Dec. 1998

Pine trees are abundant throughout much of the

United States. The Kraft process allowed the United
States to become a major producer of paper
products. However, the Kraft process has created
environmental problems

The Modern Paper Making Process

Five Methods of pulping

1)
2)
3)
4)

Mechanical Pulping
Chemimechanical
Thermomechanical
Chemimechanical and Thermomechanical
Pulping (CTMP)
5) Chemical Pulping

The Modern Paper Making Process

The chemical method is the most popular because it
produces a higher quality paper than mechanical
pulping

The most popular method of pulp production is the

Kraft process, producing nearly 85% of all pulp in the
United States
This will be the focus of the pulping description

The Modern Paper Making Process

Wood Yard

The Modern Paper Making Process

Pulp Digester

The Modern Paper Making Process

Pulp washers

The Modern Paper Making Process

Bleach Plant

Pulping
The problem

Wood (this is what we have)

Fibers (this is
what we want)
22

Types of Pulping
Two main ways to liberate fibers
Mechanically
Chemically

There are also hybrids of these two methods

Chemimechanical
Semi-chemical

23

Popularity of Pulping Technologies

% US pulp production

Mechanical 20%
Chemical
70%
Hybrids
10%

The rest of the world is pretty similar

24

Mechanical Pulping
Uses mechanical energy with little or no
chemicals
Two main processes
Grinding: logs are forced against a revolving
abrasive stone
Stone groundwood process (SGW)
Refining: wood chips are fed between two metal
discs one of them rotating
Thermomechanical pulp (TMP)
25

Mechanical Pulping Overview

Stone Groundwood: Equipment
Stone Groundwood uses logs.
Not used at all in the Pacific
Northwest because we get almost
all our wood as leftovers from saw
mills as chips.

There are a variety of different

designs of this equipment.
Basically, logs are pressed into a
rotating stone. The fibers are
washed off the stone with water.
This also cools the stone. Running
this system under a slight pressure
improves the process.

26

Refiner Pulping
This process uses wood chips
as its raw material
Two main processes:
Thermo-mechanical Pulping
(TMP) chips are presteamed
Chemi-thermomechanical
Pulping (CTMP) chips are
given light chemical treatment

28

Refiner Plates
The refiners contain
opposing plates that shred
the chips. These plate are
separated into different
sections
1st section (inlet) rips
chips into wood slivers.
Each subsequent step
reduces the size of the
bundles.
Water carries the fibers
through the disk

29

Products from mechanical pulps

Newsprint
Tissue
Coated publication

30

TMP Economics
Economics for 1 ton of medium brightness TMP pulp
Accuracy of analysis approximately 20%
Capital Cost for 500 ton/day mill = $300,000,000

Production Costs

$/Ton pulp

Chips

100

Electricity

100

Bleaching

50

Labor, Maintenance, etc.

137

Total Cost

387

Selling Price

625

Profits

238

Annual profit $238/ton*500 tons/day*350days/year =

~$41 million/year for a mill that costs $300 million

31

Liquors?
White liquor is a strongly alkaline solution
mainly of sodium hydroxide and sodium
sulfide.
Black liquor is the spent cooking liquor from
the kraft process when
digesting pulpwood into paper
pulp removing lignin, hemicelluloses and
other extractives from the wood to free
the cellulose fibers

Chemical Pulping
Uses chemicals and heat to dissolve lignin
Leave cellulose and some hemicellulose
Major processes
Kraft
Soda
Sulfite

33

Chemical Pulping
Kraft process - caustic
NaOH and Na2S

Soda Process - caustic

NaOH

Sulfite - acid
SO2 and Base: e.g. Mg(OH)2, Ca(OH)2, NH4(OH)

34

Kraft Pulping
These are present in
following proportions in
wood

Cellulose: 38- 42 %
Glucomannan: 2-20 %
Xylan: 7-30 %
Other hydrocarbons < 5 %
Lignin 20-30 %
Resins 2- 6 %

The chemical composition

of the pulp final product
is
Cellulose: 72-73 %
Glucomannan: 2-10 %
Xylan: 10-30 %
Other hydrocarbons. <1 %
Lignin 2-5 %
Resins: <1 %

Products from Kraft Pulp

Linerboard
Xerographic
Food Boards
Source of strong fiber

36

Chemical Reactions
The main chemical reactions in the cooking
process can be described as:
NaOH + NaS2 + Wood -> Na-org. + S-org. + NaHS
Wood represents many different organic
compounds such as: Lignin, Cellulose, Hemicellulose, and Resins. Hemi-cellulose can
bedivided into three major organic group:
Glucomannan, Xylan and other hydrocarbon
groups

Chemical Reactions (cont.)

The solution of Sodium sulphite and Sodium
hydroxide in water is generating a equilibrium as
follows:
S2- + H2O<==>SH- + OHSH- + H2O<==>S2H+OH
Alkali in the cooking liquor is basically consumed
in three different reactions:

With lignin,
Neutralisation of organic acids,
With resins in the wood.

REACTION WITH LIGNIN

As the carbon to carbon bond are stable in
alkaline conditions, the cleavage of oxygen carbon bonds are the most significant reaction
in the cooking process. This reaction will take
place and is producing phenolic hydroxyl groups
from the cleavage of the aryl-alkyl-ether
bounds. One of the main products being the
phenylcoumaran. The phenolic carbons are in
the following reaction mainly converted to
stilbene.(From 20-30% to 2-5%)

NEUTRALISATION OF ORGANIC ACIDS

Most of the alkaline is consumed in the cooking
process by the saccharine acids formed in the
degradation of hemicelluloses.
Hemicellulose is a polysacchrridic substance
which includes galactoglucomannan,
arabinoglucoronxylan, arabinos,
arabinogalactane, and etc.
The saccharinic acids formed by the degradation
contains ; isosaccharidic acids, milk acid, formic
acid and acetic acid.

REACTIONS WITH RESINS OF WOOD

In the cooking reaction many of the resins
forms sodium salts of fatty and harts resins
this are occurring a soap. And are usually
skimmed of from the black liquor in the
evaporation area.
They are also processed to produce tall oil. (An
oil derived from wood pulp and used in
making soaps or lubricants.)

SULPHIDITY IN KRAFT PULPING

The function of sulphide in the kraft process is
two-fold; it promotes and accelerates the
cleavage of the ether links in phenolic units
and is reduces the extent of undesirable
condensation.
Sulphidity is defined as : 100 [ Na2S]/
([NaOH]+[Na2S]) where the concentrations
are expressed as equivalents of Na2O or
NaOH, respectively.

Chemical Pulping Overview

Equipment: Batch Digester
Large pressure reactors
2500 to 12,500 ft3

Typical mill will have banks

of 6-8 digesters
Heating of system is either
through direct heat (steam)
or though indirect heating
of the cooking liquor with
forced circulation

43

Chemical Recovery
For each ton of pulp produced, 3000-5000
gallons of black liquor produced
Black liquor contains
Organics dissolved wood components
Inorganics cooking chemicals, now spent
(inactive) form

44

Chemical Recovery
For economic and environmental reason, the
black liquor MUST be recovered hence the
Chemical Recovery System
Goals
Burn organics to generate heat
Convert inactive cooking chemicals back into
active form.
98% of pulping chemicals are regenerated

45

IN BLACK LIQUOR BURNING

The main reactions are

Na2O+ CO2 -----Na2CO3 ( 1)

Na + + H+ S2- ......>NaHS ( 2)
Na+ OH -.......> NaOH (3)
Na2O+ SO2 + O2 .........>Na2SO4 (4)
Na2S + 2O2.......> Na2SO4 ( 5)
Na2SO4 + Na2S + O2 .......> 2 Na2S2O3
( 6)
and other reactions:
Na2SO4 + 2 C> Na2S + CO2 ( 7)
Na2SO4 + 4CO ..> Na2S + 4 CO2 (8)

Fly ash :

Fly ash is mainly consisting of:

Na2O + SO3.> Na2SO4
Na2O + CO2 > Na2CO3

In the smelt there is equilibrium reactions:

Na2S(l) + 2 H2O ....> H2S (g) + 2NaOH
and
Na2S(l)+H2O+CO2>H2S(g) + Na2CO3
These reactions are not wanted.

Cooking liquor production

The green liquor produced in the recovery boiler smelter
is then further reduced by the caustizising reaction:
Na2CO3 + Ca(OH)2.....>2 NaOH + CaCO3

After separation of the solid CaCO3( lime mud), from the

white liquor containing NaOH, the solid is burnt in a lime
klin.
CaCO3 .> CaO + CO2
There is usually also some sodium present in the lime
mud, which reacts with any sulphur introduced in the
lime kiln:
2Na + S + 2O2 .....> Na2SO4
And the burnt lime is then reacted with water toproduce:
CaO + H2O ..........> Ca( OH)2

Chemical Recovery process

Black liquor is washed out of the pulp in a
brownstock washer
This weak black liquor is thickened by
removing water in the evaporators
The resulting strong black liquor is then
sprayed into the Recovery Boiler

49

Simplified Flow Diagram of the Kraft

Process
Chips

Lime
Kiln

Pulping
Causticization

Wash
Water

Pulp

Recovery
Boiler
Evaporators
50

New ideas for pulping

Crystallize lignin to make it fragile
Re-engineer the tree; weak or
remove lignin
Engineer enzymes to destroy lignin
and protect carbohydrates
Color the fiber and then use tool
(high tech cutting machine or laser
beam) to remove fiber
Use a different material than wood
to make pulp.
51

Bleaching

52

What is Bleaching?
Bleaching is the chemical process applied to
cellulosic materials to increase their brightness
Cellulose and hemicellulose are white and do
not contribute to color
Lignin, dirt, fiber bundles (shives) do
contribute to color

53

Measurement of Brightness
Reflected
Light

Incident
Light

Paper Sheet

Brightness is measured by shining light on a

sheet of paper and measuring how much is
reflected. Units: %

54

Brightness of Paper
Type of Paper
Copy/Printing paper
Newsprint
Grocery Bag

Brightness, %ISO
80 90
60 70
20 - 30

55

How Does Bleaching Occur?

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

56

Bleaching Chemicals
Oxygen
Chlorine Dioxide
Hydrogen Peroxide
Ozone
Extraction

O
D
P
Z
E

O2
ClO2
H2O2
O3
NaOH

57

Group one reactions and reaction

products:
The main reaction by chlorine and ozone is a electrophilic
substitution on aromatic rings, other reactions are cleavage of aryl
ether linkage i.e.demethoxylation and depolymerization ( 6) .
These reactions take place onany phenolic group (5). The reaction
products are mainly polychlorinatedaromatic rings( with chlorine)
or carboxylates ( with ozone ). Alsoformation of Muconic acid
derivatives has been proposed in reactionsbetween ozone and
phenolic groups.

Group two reactions and reaction

products:

These two agents have in common the fact that they are radicals.
This again indicates that they primarily react with phenolic rings
with free OHgroups ( of all residual lignin this is about 30 % ) (
7,8).The reaction products in this case is carboxylic andcarboxylate
groups .These are soluble in alkaline medium

Group three reactions and

reaction products
The active species are here anions -OOH and ClO- . These anions
reacts almost only with carbonyl groups ( 9,10)

General Principles: Process

Bleaching uses a combination of chemicals in series.
One chemical alone will not remove residual lignin.
Each step reacts with material modified in previous step.

NaOH
O2
Unbleached
Pulp

ClO2

D
Remove lignin

NaOH
O2

EO

ClO2

Bleached
Pulp

Brighten pulp
61

Environmental Impact of Bleaching

Pulping

Wash
Water

Wash
Water

Washing

Chlorine
Based
Bleaching

To Recovery
Boiler

Effluent
Treatment
62

The Modern Paper Making Process

Paper Machine

Paper Machines

Wet End

Dry End
64

Wet End
The "wet end" of a paper machine is a general term for
parts of the system that involve a slurry of fibers, fillers,
and other additives.
When looking at a paper machine it is easy to identify
the "dry end" where a roll of paper is being formed.
The rough dividing line between the wet end and the
dry end is often drawn at the wet-press section, the last
place in which water is pulled from the wet web of
paper.

65

Wet end to Dry end

One exception to this rule is the size press; because
size press treatments can be closely related to what
happens in the wet end, it is common that both
subjects be considered in the same book or course.
The beginning of the wet end is even harder to
define. As a practical matter it may make sense to
draw the line at the main refiner system, since most
papermaking chemicals are added after that point.

66

Wet end Operations

67

The Modern Paper Making Process

Water Treatment

Environmental problems (1)

Regulated wastes and emissions from the pulp
and paper industry include liquid and solid
wastes, air emissions, and wastewater.
Air emissions related with this process are:
sulphur dioxide, nitrous oxides, particulate
matter, methanol, polycyclic organic matter,
hydrogen chloride, formaldehyde, chloroform,
phenol and chlorinated phenolics, dioxins,
furans and other chlorinated compounds.

Environmental problems (2)

Wastewater releases include chlorinated
phenolics, dioxins, furans and other
chlorinated compounds, phosphates and
suspended sediments.
Paper mills also produce non-hazardous solid
waste such as sludge derived from their
pulping and bleaching operations.

By-Products
Lime Kiln
A lime kiln is used to produce quicklime through
the calcination of limestone. The chemical
equation for this reaction is This reaction takes
place at 900C, but a temperature around
1000C is usually used to make the reaction
proceed quickly.

By-Products
Turpentine
Turpentine is a fluid obtained by
the distillation of resin obtained from live trees,
mainly pines.
Widely used as thinning oil-based paints.

By-Products
Methanol
CH3OH
Methanol is the simplest alcohol, and is a light, volatile,
colourless, flammable liquid with a distinctive odour very
similar to, but slightly sweeter than, that
of ethanol (drinking alcohol).
At room temperature, it is a polar liquid, and is used as
an antifreeze, solvent, fuel, and as a denaturant for
ethanol.
It is also used for
producing biodiesel via transesterification reaction.

Pollutants in effluents
The most common organic pollutants are
suspended solids (SS):
lost cellulose fibre,
dissolved organic compounds such as dissolved lignin
compounds, carbohydrates, starch and hemi-cellulose

Acidic compounds are predominantly natural

resin acids.
Chlorinated organics (AOX) are found if
elemental chlorine is used in the process.

Solid wastes
Dirty wood chips or fibers as well as bark.
The broken, low-quality fibres are separated
out to become waste sludge.
All the inks, dyes, coatings, pigments, staples
and "stickies" (tape, plastic films, etc.)
washed off the recycled fibres.

Recycling
In Europe an average of 56% of used paper
is recovered. The recycling process includes
following stages:
Sorting
Dissolving
De inking
Mixing
Papermaking process

Future of Paper
The digital revolution has been beneficial to the
paper industry on the whole. With every new
technological advance, the amount of information
has multiplied, and the volume of paper has risen as
well.
These trends include opportunities as well as threats,
and total demand for printing and writing papers
continues to rise.

Further Uses of Paper

All available recovered fibre was utilized in products
such as paperboard, tissue, and newsprint. The main
contribution of some paper-based products, like
magazines, in a recycled fibre shortage is that they
are a good source of reusable fibre.
Increasing the recovery of paper-based products like
old magazines returns high-grade fibre to the
manufacturing stream. Paper recovery is an
important source of fibre, and an effective way to
take pressure off forests and landfills.

List the trees that are the major sources of papermaking fibers.
Discuss what other uses are made of the trees and of the
forestland owned by the pulp and paper industry.

Describe two ways of getting fibers from wood, and explain

the major differences between them.
Describe how paper is made. Discuss how paper is recycled.

Find out about three career opportunities in the

papermaking industry that interest you. Pick one and find out
the education
.