Paper Making: A Three-Step Process

Identify Source of Cellulose Fibre:

wood
recovered paper
non-wood plants

Produce Usable Cellulose Fibres:
Pulping
Bleaching (where required)

Make Paper:
Sheet - Formation
very dilute water solution of pulp is sprayed on a fast-moving wire
Pressing and Drying
water is removed with pressure and heat to form paper

Roll of paper

Diagrammatic representation of the production of pulp and paper using bleach processes.
(Taken from "Towards Zero-Effluent Pulp and Paper Production", Johnston, P. et al, Greenpeace
International, 1996)
Components Of Wood

Cellulose consists of long, straight chains of glucose molecules. It forms the skeleton of the plant
wall and has the most desired properties for making paper. These fibres are long, strong and
translucent.

Hemicelluloses are short, branched chains of glucose and other sugar molecules. They fill in
space in the plant wall. Hemicelluloses are more soluble in water and are thus often removed
during the pulping process.

Lignin is a three dimensional phenolic polymer network. This "glue from hell" holds the cellulose
fibres together and makes them rigid. Chemical pulping and bleaching processes selectively
remove the lignin without significantly degrading the cellulose fibres.

Extractives account for 3(+/-2)% of softwoods. These materials include plant hormones, resin
and fatty acids along with other substances that help the tree grow and resist disease and pests.
These substances are highly toxic to aquatic life and account for much of the acute toxicity of
pulp mill effluent.

Average composition of softwoods (Smook)
Wood is a natural composite material consisting of hollow, flexible tubes of cellulos bonded together and
rigidified by a glue called lignin (NC State, 1993).
Wood Types
Characteristics of softwood and hardwood fibres
Softwood Hardwood
Cellulose content 42% +/- 2% 45% +/- 2%
Lignin content 28% +/- 3% 20% +/- 4%
Extractives content 3% +/- 2% 5% +/- 3%
Fibre length 2-6 mm 0.6-1.5 mm
Coarseness 15-35 mg/100 mm 5-10 mg/100m
Trees can be divided into two general classes - softwoods and hardwoods. Softwood trees are conifers -
e.g., southern pine, Douglas fir, spruce. Hardwood trees lose their leaves every year. Examples include
birch, aspen, red gum.
Softwood fibres with their length and coarseness are generally used to provide strength to a sheet of
paper. Hardwood fibres, being finer and more conformable, give a sheet of paper its smooth printing
surface and opacity. Hardwood fibres are also easier to bleach to high brightness because they have less
lignin.
Paper generally consists of a blend of hardwood and softwood pulps to meet the strength and printing
surface demands of the customer.
Pulping
Chemical Recovery
Oxygen and Extended Delignification
Kappa Number
In a chemical pulping process, heat and chemicals are added to wood chips in a pressure cooker called
the digester. In the kraft process, an aqueous solution of sodium hydroxide and sodium sulfide, known as
white liquor, selectively dissolve the lignin and make it soluble in the cooking liquid. After 2 to 4 hours, the
mixture of pulp, spent pulping chemicals and wood waste is discharged from the digester. The pulp is
washed to separate it from the black liquor - the pulping chemicals and wood waste. Kraft pulping is a low
yield process - only 45% of the wood used becomes pulp. The pulp, called brownstock at this point in the
process, is ready to be bleached. Softwood pulp from a conventional cooking process contains about
4.5% lignin. This lignin will be removed and the pulp will be brightened during the bleaching process.
Efficient pulp washing is very important because it ensures the maximum recovery of the pulping
chemicals and it minimizes the amount of organic waste carried over with the pulp into the bleaching
process. Poorly washed pulps require higher bleaching chemical doses, thus increasing the cost and the
amount of organic waste discharged in the bleach plant effluent.

Chemical Recovery
The chemical recovery process has four steps:
1. The water from the washer goes to the evaporator, where the black liquor is concentrated to 65%
to 75% solids prior to its entry to the recovery boiler.
2. In the recovery boiler, a specially-designed furnace, the used pulping chemicals are separated
from the wood waste. The pulping chemicals form a lava-like smelt at the base of the recovery
boiler; the wood waste is burned at the top of the recovery boiler. This heat is used to generate
high pressure steam, that can be used to meet the mill 's steam and electricity requirements.
3. The smelt is poured into a large tank of water to form green liquor, a mixture of sodium sulfide
and sodium carbonate.
4. In the next step, lime (calcium oxide) is added to the green liquor to convert the sodium carbonate
into sodium hydroxide, and thus remake the white liquor.
The resulting calcium carbonate is converted back to lime in a lime kiln.
Improved Pulping: Oxygen and Extended Delignification

Conventional pulping processes remove about 95% of the lignin from the pulp. In the past, the remaining
lignin was removed during the bleaching process. Oxygen has been used to remove lignin from pulp on a
mill scale since the late 1970s. Scandinavian mills first installed oxygen delignification in response to
concerns about the amount of organic waste in the effluent. Union Camp installed the first oxygen
delignification system in the US in 1980 at Franklin, VA.
The pulp is washed after it leaves the tower where it has reacted with oxygen. The waste water or filtrate
can either be used in the brownstock washers or it can be routed directly to the evaporator where it will be
combined with the black liquor. The degraded lignin products will be burned for energy in the recovery
boiler, so less organic waste will be discharged in the waste water from the bleach plant. Today, a well
run oxygen system can remove 55% of the lignin from the unbleached pulp.
Digesters can be modified to remove more lignin from the pulp without damaging the cellulose by using
the same amount of white liquor, but adding it at several points during the cooking process. This
additional wood waste is also sent to the recovery system.
Extended delignification and oxygen delignification are proven technologies that can remove as much as
70% of the lignin before the bleaching process removes the remaining lignin and coloured substances. To
produce high quality totally chlorine-free pulp (TCF), mills will have to install oxygen delignification,
extended delignification or both in order to minimize the use of chemicals in the bleach plant. More
organic waste is burned in the recovery boiler and smaller quantities of bleaching chemicals are required.
These technologies make environmental and economic sense.
Kappa Number
Kappa number measures the amount of lignin present in a kraft pulp
Kappa Number x 0.15% = % lignin in pulp
Examples:

Conventional kraft cooking removes 92-96% of the lignin from softwoods. Softwood is generally
cooked to a kappa number of 32 which corresponds to a lignin content of 4.8%

The kappa number of a conventionally cooked pulp after oxygen delignification is 15. This kappa
number corresponds to a lignin content of 2.25%, a 53% reduction in lignin content.
Bleaching
Bleaching is performed in stages.
The early stages remove remaining lignin; final stages brighten the pulp
Pulp is usually washed between stages to remove any soluble organic material

Classes of bleaching chemicals

o
Strong oxidizing agents
o
Alkali
o
Metal removal agents
Strong Oxidizing Agents
Oxidizing chemicals can either degrade the lignin or remove colour from the pulp depending on operating
conditions.
C
Elemental Chlorine
D
Chlorine Dioxide
H
Sodium Hypochlorite
Z
Ozone
O
Oxygen
P
Hydrogen Peroxide
Elemental chlorine (Cl 2) is an effective delignifying agent. As it breaks lignin bonds, it adds chlorine
atoms to the lignin degradation products, thus producing significant amounts of chlorinated organic
material.
Ozone (O 3) is also an effective delignifying agent. It also brightens the pulp as well. Ozone has not been
used in the past because mills have not been able to improve its selectivity - ozone attacks the cellulose
fibre as well as the lignin. Recent technological developments, however, have solved this problem and
have allowed mills to take advantage of this cost-effective bleaching agent.
Chlorine dioxide (ClO 2) is a highly selective chemical that can both delignify and brighten pulp. It
oxidizes lignin, but does not add chlorine atoms onto lignin fragments; however, small amounts of
elemental chlorine and other chlorine compounds formed during the chlorine dioxide bleaching process
react with degraded lignin to form chlorinated organic compounds.
Oxygen (O 2) is an inexpensive, highly effective delignifying agent that is usually used at the beginning of
the bleaching process. It has intermediate selectivity.
Sodium hypochlorite (NaOCl) is an inexpensive delignifying agent formed by mixing elemental chlorine
with alkali at the mill. Mills are phasing out the use of hypochlorite because it generates large quantities of
chloroform when it is used to bleach pulp.
Hydrogen peroxide (H 2O 2) is mainly used to brighten pulps in the final bleaching stages. Peroxide is
often used at the end of a conventional bleaching sequence to prevent the pulp from losing brightness
over time. Researchers have found operating conditions under which peroxide will delignify pulp, and are
working on technologies that will consume less.
Chlorine and chlorine dioxide are often added together in the first bleaching stage
C/D
C D
C 30 D 70
Chlorine is added first; chlorine dioxide substitution is generally less than 50%
CD Chlorine and chlorine dioxide added together
D/C
D C
D 70 C 30
Chlorine dioxide added first; chlorine dioxide substitution is usually greater than 50%
Bleaching
Strong oxidixing agents
Alkali Extraction
Chlorine Chemistry
Metals Removal
Alkali Extraction
Caustic soda (sodium hydroxide) solubilizes degraded lignin products.
Oxygen, hydrogen peroxide or both are often added to the caustic solution to enhance the removal of
organic waste.
E alkali extraction
E O Alkali extraction reinforced with oxygen
E P Alkali extraction reinforced with hydrogen peroxide
E OP Alkali extraction reinforced with oxygen and hydrogen peroxide
Chlorine, chlorine dioxide and ozone work best when they are run in acidic conditions at pHs that range
from 1.5 to 4. Once the bleaching reactions are finished, the pulp is washed to remove the degraded
lignin or other organic waste that has been dissolved in the waste water. Much of the organic waste,
however, consists of organic acids and alcohols. These compounds are not soluble in acidic water so
they remain with the pulp during washing.
Alkali Extraction Process
R-COOH + NaOH => R-COO-Na + H 2O
organic acid
insoluble in water

caustic soda
(sodium hydroxide)
organic sodium salt
soluble in water
water
In the alkali extraction stage, these organic acids and alcohols react with the caustic (sodium hydroxide)
to form organic sodium compounds and water. These organic substances do dissolve in water. In fact,
most of the color and organic waste in mill effluent comes from this first extraction stage. There is much
less organic waste in the second extraction phase, if one is used, because very little lignin is removed in
the later stages of the bleaching process.
Chlorine Chemistry
Chlorine Chemistry with Elemental Chlorine
Lignin + Cl 2 => Chlorinated organic compounds
Chlorine Chemistry with Chlorine Dioxide
Lignin + ClO 2 => Oxidized Lignin + HOCl <=> Cl 2
Elemental chlorine and chlorine dioxide react differently with lignin. Elemental chlorine breaks up the
lignin molecule by adding chlorine to the lignin.
Chlorine dioxide transfers an oxygen to the lignin to break up the rings. Hypochlorous acid is also formed.
It can react directly with the aromatic rings on the lignin or be converted to elemental chlorine.
Thus, the only way to be sure that chlorinated organic compounds including dioxins are not formed in the
bleaching process is to eliminate all chlorine-based bleaching chemicals.
Metals Removal
Transition metals present in wood react with ozone and hydrogen peroxide; thus, they are removed
before these chemicals are applied to the pulp.
A Acid wash
Q Chelating agent
Environmental Impacts Of Bleaching With Chlorine
As soon as pulp is exposed to chlorine or chlorine dioxide during the bleaching process, the concentration
of chloride ions in the waste water makes it too corrosive to be recirculated to the recovery system where
the organic waste is stripped from the water and burned for energy in the recovery boiler. The organic
waste in the effluent must be discharged to the effluent treatment system and ultimately rivers and lakes.


Pollution Prevention Strategies
Low Effluent TCF
Replace chlorine bleaching stages with oxygen based chemicals so that all of the effluent can be
recirculated to the recovery system
Pulp mill effluent contains a large mixture of organic substances. At this point, 415 have been identified -
315 of these contain chlorine. We will continue to see concerns about different substances in the effluent
as scientific research continues. A reasonable long term strategy would be to install technologies that will
eliminate the discharge of any effluent from the mill.

75% of effluent is sent to the recovery system (Q-stage is discharged)
Low Effluent ECF
Mill-Scale Demonstration
Remove chloride ions from bleach plant effluent and burn organic waste in the recovery boiler

Champion International is currently [1996] testing this system at its Canton, NC mill.
Champion claims that they have demonstrated a technology on a laboratory scale that will allow them to
remove the corrosive chloride ions from the effluent. The remaining water and organic waste can then be
sent to the recovery system where the organic waste can be burned.
Champion assumes that they will be able to burn small quantities of chlorinated organics in the recovery
boiler without generating any dioxins. Air emissions from the recovery boiler and recovery boiler ash will
have to be tested for dioxin content.
NOTE: Reach for Unbleached! does not endorse the movement of mills to this system. While it may lead
to reduced effluent, testing still has not been done to show that chlorinated organics do not end up in the
air and ash instead of the water. It also does not address the worker and community safety concerns of
using chlorine dioxide. As shown below, it is also likely to be more expensive. For the cost, mills should
do the right thing and move to Totally Chlorine Free. For further information on our reasons see our
report, Zero Discharge in the Library.
NOTE 2005: This mill has been sold and the testing of this system discontinued.
See also Zero Discharge: Technological Progress Towards Eliminating Kraft Pulp Mill Liquid Effluent,
Minimising Remaining Waste Streams And Advancing Worker Safety

Economic Benefits
Chart Developed in 1996 - US dollars
Technology Option
Capital costs
(Millions
of Dollars)
Annualized
Capital Costs
($/ADMT)
Incremental
Operating
Costs
($/ADMT)
Total Cost
($/ADMT)
Mill 1
(1000 ADMT/D Softwood)

C 60D 50EDED $0 $0.00 $0.00 $0
ECF $28.9 $9.00 $8.70 $17.70
Low Effluent TCF $52.8 $16.40 ($2.20) $14.20
Low Effluent ECF $55.8 $17.40 $3.60 $21.00
Mill 2
(500 ADMT/D softwood)

C 60D 50EDED $0 $0.00 $0.00 $0.00
ECF $18.0 $12.40 $8.70 $21.10
Low Effluent TCF $36.3 $24.90 ($1.50) $23.40
Low Effluent ECF $38.3 $26.30 $4.00 $30.30
Tax rate 34%; Cost of capital of 10%; project life of 15 years.
Annualized Capital Costs include tax savings associated with straight-line depreciation of equipment.