Cellulose

Major

component of woody plants

Constantly replaceable
Its conversion to paper products
is the function of the pulp and
paper industries

Pulp and Paper

Industry
Consumers

of large
quantities of
chemicals
Largest energy
users in the
country, for this is
energy-intensive
business

 2500
o

and 2000 B.C.

Writing paper first

appeared made from a
tall reed called
PAPYRUS which grows
along the Nile River in
Egypt
The sheet was superior
to calf and goatskin
parchments, clay,
bricks, waxed boards,
and other writing
materials

A.D.

105
oChinese invented good processes for paper
manufactured from bamboo and cotton
14th century
o Southern Europe learned of the process
and began to manufacture rag paper

 17th

century

English manufacturers
became established
1690
o Paper mill was
established in the United
States
o All European paper was
made from cotton and
linen rags
o Book printing began with
Gutenbergs bible and
greatly increased the
demand for paper
o

 1750

the beater was developed

and adopted in Holland,
hence it became Hollander
1799
o Robert (Frenchman)
invented the process for
forming sheet paper on a
moving wire screen
(Fourdrinier machine)
1809
o Dickinson invented the
cylinder machine
o

 1830

The Fourdriniers
superiority for making
fine papers was
established
1826
o Steam cylinders were
first used for drying
1827
o the first Fourdrinier was
received in the US
o

 Keller

of Saxony
o Developed a mechanical process for
making pulp from wood, but the
quality of the paper produced was
low
Watt and Burgess
o Developed in 1851 the soda process
for making pulp from wood
Tilghman
o An American chemist who was
granted in 1857 the basic patent for
the sulfite process, which produced
good, readily bleachable pulp

 Dahl

in Danzig (1884)
o Conducted basic eperiments which results
to the kraft process (from the German word
kraft = strong)
o Commonly referred to as the sulfate process
because sodium sulfate is used as a makeup chemical for the cooking liquor. The
dissolving agent is not Na2SO4.
1909
o The sulfate process was introduced into the
US. At that time, pulp production was
divided into 48% mechanical, 40% sulfite,
and 12% soda.

Sulfate Process
o has come to dominate the industry and in 1981
the distribution had become 10.5% mechanical
and thermochemical. 3.5% sulfite, 78.2% sulfate,
and 7.7% semi chemical
Rayon, cellulose esters and ethers, and cellulose
nitrate for both plastic and explosive use have
become commercially important and consume
much high quality wood pulp. The control and
utilization of the industrys by-products have
required much attention. The creation of useful
products from lignin and waste liquors represent
increased income for the industry and a solution
to the steam pollution problems.

USES AND ECONOMICS

In

1980, the production of paper and

paperboard in the US was about
59.7x10^6t. The consumption of
newsprint alone was estimated at
10.1x10^6t and 61000t of wood pulp
were produce. The US consumes about
half of the worlds paper production.

Pulp

lignocellulosic fibrous
material prepared by
chemically or mechanically
separatingcellulose
fibresfromwood,fibre
cropsorwaste paper.The
wood fiber sources required
for pulping are, 55% sawmill
residue, 21% logs and chips,
and 34% recycled paper
(Canada, 2014).[
one of the most abundant
raw materials world wide.

Cellulose fibers must be freed from the

matrix of lignin which cements them together
They may be separated by mechanical
procedures or by solution of the lignin by
various chemicals
The pulp thus formed has its fibers cemented
together to form paper when suitable
additives are used
Pulp made by mechanical or thermochemical
means is inferior in quality to that produced
chemically
Kraft process dominates the field with
semichemical means a poor second

RAW MATERIALS
Cottons and linen rags once the major
sources of fibers for paper
Both hard and soft wood are used to
make pulp, but soft wood is preferred
because fibers are longer
Bark cannot be used because it is not
fibrous and is difficult to bleach. It is
rather removed at the pulp mill by one of
two debarking methods (hydraulic
debarking)

PULPING PROCESSES
Goal:

to release the fibrous cellulose

from its surrounding lignin while keeping
the hemicelluloses and celluloses intact,
thereby increasing the yield of useful
fibers
Goal: to obtain good color without
degradation and loss of yield

MAJOR PROCESSES
Sulfate

or kraft process
Groundwood and thermochemical
process
Semichemical process
Sulfite process

Casey differentiates:
5

mechanical processes
7 chemimechanical and thermochemical
processes
5 semichemical processes
3 high yield chemical processes
12 full chemical processes
2 process suitable for dissolving (high or
chemical) pulp

Alkaline process by which most pulp is presently

made
An outgrowth of the obsolete soda process which
cooked with a strong (12%) solution of NaOH and
Na2CO3.
Soda process gave low yields and worked well only
with short-fibered hardwoods
Material added to the cooking liquor for the kraft
process is Na2SO4
Cooking is done with a solution containing Na2s,
NaOH, and Na2CO3
It is very important that the chemicals used can be
recycled and regenerated, reducing or even
eliminating stream pollution
Odoriferous materials released during cooking are
strong air polluters and difficult to control
Use coniferous woods, and the process deals
readily with the large amounts of oil and resins in
these woods

Kraft Pulp
Made

from coniferous woods

Has the longest fibers of all the pulps
Chemicals used are not so harsh
Makes possible the production of very strong
papers

Recovery of the Black

Liquor
Essential

factor in the kraft process

Contains 95-98% of the total chemicals
charged to the digester
Sodium carbonate is present, as are also
small amounts of sodium sulfate, salt,
silica, and traces of lime, iron oxide,
alumina, and potash
Total solids average about 20%
Concentrated, burned, and limed

NaSO4 + 2C
2CO2
Thomlimson

Na2S +

Kraft Recovery

Furnace
Unit presently most widely used for
burning concentrated black liquor
Black liquor is concentrated to about
35% solids

 Brought

about by a procedure similar to

that used for sulfate pulp, except that
the dissolving agent is NaOH/Na2CO3
and the make-up chemical is Na2CO3
instead of Na2CO4.
Its importance is too small to warrant
additional details here.

Types of
Process

Kraft, or Sulfate,
Pulp (Alkaline)

Sulfite Pulp
(Acid)

NSSC (Neutral
Sulfite SemiChemical )

Cellulose raw
material

Almost any kind of

wood

Coniferous; must be
of good color; free
from phenolic
compounds

Hardwood chiefly
used, some
softwood

Principal reaction
in digester

Hydrolysis of lignins to
alcohols and acids;
some mercaptans
formed

RC:CR + Ca(HSO3)2

Lignin sulfonation
and hemicellulose
hydrolysis lead to
formation of
acetate and
formate

Composition of
cooking Liquor

12.5% solution of
NaOH. Na2S, and
Na2CO3. Typical
analysis of solids:
58.6% NaOH, 27.1%
Na2S, 14.3% Na2CO3.
Dissolving action due to
NaOH and Na2S.
Na2CO3 inactive and
represents the
equilibrium residue
between lime and
Na2CO3 in the
formation of NaOH

(RCHCRSO3)2Ca

7% by wt. SO2, of
which 4.5% is
combined as
sulfurous acid and
2.5% as calcium or
Mg(HSO3)2. Cooking
1t of pulp requires
175-220 kg of SO2
and 55-68 kg of MgO.
Recent signification
toward use of
Mg(OH)2, NH4OH as
base to speed lignin
solution

Na2S buffered
with Na2CO3
bicarbonate, or
kraft green liquor.
Concentration of
90-100g/L of
Na2S. Cooking
liquor does not
complete freeing
of fibers, but
mechanical
treatment does.

Types of
Process

Kraft, or Sulfate,
Pulp (Alkaline)

Sulfite Pulp
(Acid)

NSSC (Neutral
Sulfite SemiChemical )

Cooking
Conditions

Time 2-5h; temp. 170176C; pressure 660925 kPa

Time 6-12h; temp.

125-160C or higher,
pressure 620-755 kPa

Time 48-46min;
corrugating-grade
pulped from mixed
hardwoods 12-15
min; temp. 160180C, pressure
660-1100 kPa

Chemical
recovery

Most of process is
devoted to the
recovery of cooking
chemicals, with
incidental recovery of
heat through burning
organic matter
dissolved in liquor
from wood; chemical
losses from system
are replenished with
salt cake, Na2SO4

SO2 relief gas

recovered;
magnesium liquor
recovered and reused
after wood digestion
and pulp washing

Characterized by
high yield 6585%. Pulping losses
35-15% of wood
components.
Special recovery
methods and byproduct utilization

Types of
Process

Kraft, or Sulfate,
Pulp (Alkaline)

Sulfite Pulp
(Acid)

NSSC (Neutral
Sulfite SemiChemical )

Materials of
Construction

Digesters, pipelines,
pumps, and tanks can be
made of mild steel or,
preferably, of stainless

Acid liquor requires

digester lining of
acid-proof brick;
fittings of chromenickel steels, lead,
and bronze

Serious corrosion
problems
encountered in
digesters and
handling
equipment;
stainless steel
protection needed.

Pulp
Characteristics

Brown color; difficult to

bleach; strong fibers;
resistant to mechanical
refining

Dull white color;

easily bleached,
fibers weaker than
kraft.

Stiff, dense paper

of low capacity;
fibers approach
chemical pulps in
strength

Typical paper
products

Strong brown bag and

wrapping, multiwall
bags, gumming paper,
building paper, strong
white paper from
bleached kraft,
paperboards such as
used for cartons,
containers, milk bottles,
and corrugated board,

White grades; book

paper; bread wrap,
fruit tissue, sanitary
tissue

Unbleached: large
percentage for
corrugated board,
also newsprint,
specialty boards
Bleached: writing,
bondpaper, offset,
mimeo, tissue, and
toweling

Toilet Paper was used in China as early as

875 A.D., twenty years prior to the earliest
known Hebrew manuscript of the Old
Testament on paper.
The U.S. consumption of paper and
paperboard in 1999 was approximately 354
kilograms (about 800 pounds) per person.
Each year, the United States uses 85.5
million tons of paper, of which we recycle
22%, or 19 million tons. Of the remaining
paper, we could recycle up to 70% or 46
million tons. And those 46 million tons could
save 782 million trees.

 An

average family of 3 produces about 5

lbs. /week, 20lbs. /mo., or 250 lbs./yr. of
used newspaper. (39, 63)
Every day, Americans buy about 62
million newspapers and throw out
around 44 million of them. If we
recycled just half our newsprint every
year, we would need 3,200 fewer
garbage trucks to collect our trash.
Recycling one stack of newspapers
about 6 feet tall saves the life of one
tree 35 feel tall.