Pulp Bleaching

What it Bleaching?

• The treatment of wood pulps with chemical agents to increase

their brightness
• Bleaching of chemical pulps is achieved by lignin removal,
which leads to greater fiber-fiber bonding strength in paper
• but the strong chemical used in bleaching chemical pulps
decreases the length of cellulose molecules, resulting in
weaker fibers.
• Bleaching mechanical pulps is achieved by chemically altering
the portions of the lignin molecule that absorb light (i.e., have
color)
• Called ‘lignin-preserving’ bleaching or ‘brightening’

Why Bleach?

• Improve brightness.
• Improve brightness stability.
• Clean up pulp (impurities).
» Wood based (bark, resins, sand, shives).
» Process based (carbon specs, rust, rubber).
» External sources based (plastics, grease, ash).
• Increase capacity of paper to accept printing.

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 The purpose of bleaching

Bleach plant

Brightness

Light shinning on a sheet of paper is either transmitted,

adsorbed, or reflected.
•Light is scattered by
Light Reflected fibers at air/fiber
interfaces
Absorbed •Light is adsorbed by
certain chemicals in
the fibers (lignin)
Transmitted

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 Brightness Cont’d

• Brightness is measurement of how much light is reflected from a

sheet of paper.
• Whiteness does not mean brightness.
» Whiteness is a physical phenomena related to how the eye
views the paper.
» A very white looking piece of paper may not have high
brightness.
» Example: blue dye added to a yellow tinged sheet of paper
will give a white sheet of paper with low brightness.

Brightness Cont’d

• Brightness determination method:

» Light reflectance measured and compared to light reflectance from
MgO.
» MgO assumed to reflect 100% light.
» Brightness is reported as % of MgO reflectance (85 brightness is
equivalent to 85% of MgO).
• Variables:
» Angle of light: Light is applied to sheet at 45° angle.
» Wavelength: 457 nm (blue light most sensitive).

Two Approaches to Bleaching

• Two types of bleaching:

» Lignin removing: chemical pulps.
» Lignin retaining: mechanical pulps.
• Bleaching is used because at a certain point in the
pulping process, carbohydrate degradation
becoming greater than lignin removal.
» Bleaching chemicals are more selective for lignin.
» Bleaching chemicals much more expensive than pulping
chemicals so they are not used in pulping.

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 General Principles: Chemistry

• Pulping
» Pulping typically involves cleavage of ether linkages and some
substitution (sulfonation).
• Bleaching
» Bleaching involves attacks on aromatic rings, olefinic structures,
and carbonyl groups.
» Substitution reactions play a big role.
» Multiple stages of bleaching required to achieve target brightness
• Pulping vs Bleaching(Discuss in class)

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 ClO2 NaOH ClO2
O2 O2

Unbleached
Pulp EO D EO D Bleached
Pulp

Washing

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4
 General Principles: Defining a Bleaching stage

• Discuss in class

General Principles: Chemicals

Chemical Formula Stage Manufacture Form Applied

Chlorine Cl2 C By electrolysis of Pressurized

NaCl Gas
Hypochlorite NaOCl H By reaction of Cl2 Solution:
with NaOH (on site) ~40g/l as Cl2
Chlorine ClO2 D On-site by reduction Solution:
dioxide of chlorate (ClO3) ~10g/l
Oxygen O2 O Separation from air. Pressurized
Shipped or generated Gas
on site

General Principles: Chemicals

Chemical Formula Stage Manufacture Form Applied

Hydrogen H2O2 P By reduction of Solution 2-5%
peroxide oxygen: shipped as
50% solution
Ozone O3 Z On site by silent Pressurized
electric discharge in Gas (12% O3
O2 in O2)
Hydrosulfite Na2S2O4 Y Reduction of bisulfite Solution

Enzymes - X Fermentation Solution

Sodium NaOH E By electrolysis of Solution

Hydroxide NaCl; 50% solution ~10%

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General Principles: Chemicals

Chemical Function Advantages Disadvantages

Cl2 Oxidize and Effective, Banned in USA
chlorinate lignin economical, good because of
particle removal environmental
problems
NaOCl Oxidize, decolorize, Easy to make and Can cause strength
solubilize lignin use, low cost loss, CHCl3 formation
Banned in USA
ClO2 1. Oxidize, Achieves high Made on site, some
decolorize, brightness chlorinated organics,
solubilize lignin without strength highly corrosive
loss. Good
2. Can protect
particle bleaching
cellulose

General Principles: Chemicals

Chemical Function A dvantages Disadvantages

O2 Oxidize and Low chemical Large amount of
solubilize lignin cost, Cl free equipment, some
effluent strength loss
H 2O 2 Oxidize and Easy to use, low High chemical cost,
decolorize lignin capital cost Poor particle bleaching
Strength losses
O3 Oxidize, decolorize, Effective, Must make on site,
solubilize lignin chlorine free Poor particle bleaching
effluent Strength losses

General Principles: Chemicals

C h em ical F un ctio n A dv an tag es D isadv an tag es

N a 2S 2O 4 R edu ce and E asy to use, lo w D eco m p oses rap id ly ,
d eco lo rize h ig h capital co sts low brig htn ess gain
y ield p u lps
E nzym es C ataly ze x ylan E asy to use, lo w L im ited effectiven ess,
(X y lan a se)
rem o val, aid in capital co sts h ig h co st
lig n in rem o v al
N aO H H yd ro lyze E ffectiv e an d D ark ens p ulp
ch lo ro lignin an d econ om ical
so lub ilize lign in

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 Groups of bleaching chemicals

• Bleaching chemicals can be divided into three groups

according to their function:
• 1 Group
» The chlorine (Cl2), ozone (O3) reacts with all aromatic
lignin units (phenolic groups and their =bonds)
• 2 Group
» The chlorine dioxide(ClO2) and oxygen (O2) reacts in
general with lignin structures that have free phenolic
hydroxyl groups
• 3 Group
» The hypochlorite (H) and hydrogen peroxide (H2O2)
reacts only with certain functional groups, for example
carbonyl groups

Bleaching Chemistry

• Bleaching chemicals are used primarily as oxidants,

to break down residual lignin and to increase its
solubility.
• Bleaching reactions can be divided into anionic,
cationic, and radical reactions
• Mode of operation:
» Electrophiles (oxidative reactions, low pH, involve cations)
» Nucelophiles (reductive reactions, high pH, anions)
» Radicals

Bleaching Generalities

• It is important to note that when bleaching with a

specific reagent, it will be converted into a
number of different reactive species which will
react with lignin and carbohydrates differently.
A simple example is when chlorine gas is added
to water; both hypochlorous acid and/or
hypochorite is formed depending on the pH.

Cl2 + H2O H+ + Cl - + HOCl pk = 3.4

HOCl H + ClO - pk = 7.5
+

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 Bleaching Mechanisms

Cationic Radical Anionic

Acidic Acidic or Basic Basic

+.
Cl , O3, OH+ . . . - -
ClO2 , O2 , Cl , ClO2 , HO2
.
HO , HO2.
Electrophiles Nucleophiles

Aromatic and Olefinic Carbonyl and

Conjugated
Carbonyl

Cationic Reactions

• Cationic reactions occur under acidic conditions.

• Reactive species:
» Chlorine: Cl+
» Peroxy acids: OH+
» Ozone: O3
• How can these species be cations?
» Electrophilic substitution reaction:

C  - -
Cl Cl + Cl
C C Cl

Cationic Reactions: Generalities

The most important reaction is +

+ Cl +
Cl
electophillic substitution
OCH3
OCH3
onto the aromatic ring. O
O
R
» There can be multiple R

substitutions.
» Substitution at #1 ring Cl
Cl
position can later cause side Cl
Cl

chain elimination. OCH3

OCH3 O
» Substitution at #3 or #4 Cl O
O O
Cl R
position can lead to the R

formation of an ortho
quinone.
» There is no ring cleavage.

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Radical Reactions

• Nobody adds free radicals to a bleaching reaction;

they are formed from other additives.
• Examples:
» Chlorine: Cl• (chlorine radical)
» Oxygen: -O2• (superoxide radical)
HO• (hydroxyl radical)
• Many free radicals react very rapidly with lignin so
they are good except that they degrade
carbohydrates very rapidly so they are also bad.

Radical Reactions Cont’d

• Pathways are pH dependent.

• Free radicals couple with aromatic rings.
» This and further mechanisms affected by free versus etherified phenolic
hydroxyls.
» Results in generation of free radical structures.
• These structures can undergo additional substitutions
and oxidation reactions.
» Generation of ortho quinones.
» Ring opening reactions.
» Ring substitution by bleaching agent.
» Some side chain cleavage.
• Carbohydrates will react and are degraded.

Radical Reactions: Generalities

Ring Cleavage Ortho Quinones

CO2H
CO2H O
O
R=Aryl

.
( )
R=H
O
OCH3
O

OCH3
OCH3
O
O
R

Side Chain Cleavage

Ring Substitution

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 Anionic Reactions

• These are alkaline bleaching reactions.

• ClO -, HOO – added reagents
. .
» Other species generated: O2-, O-, etc.
» These chemicals are involved in nucleophilic attacks.
• Target of attacks: carbonyls and
conjugated carbonyls.
• Products of reactions:
» Ring opening: Dicarboxylic acids
» Side chain cleavage

Anionic Reactions:

HC O -
HC O HC O HC O
CH CH CH
O XO CH
CH XO CH CH - CHO
O CH

OCH3 OCH3 OCH3 OCH3 OCH3

O O O O O

X = OH, Cl

(-)
+ OX (-)
O (-)
O CO2
O X
CO2H
O O

X = OH, Cl, ClO

Bleaching Sequences

• Bleaching sequences are described by capital letters which describe the

chemicals used.
» C = chlorine, H = hypochlorite, D = chlorine dioxide, O = oxygen (with
NaOH), P = peroxide, Z = ozone, Y = hydrosulfite, X = enzymes, E =
NaOH, Q = chelants, Paa = peracetic acid
• Letter represents each chemical followed by a washing step.
» CED = Cl2/wash/NaOH extraction/wash/ ClO2/wash
• If washing is omitted, a parenthesis is added around the steps.
» C(EO)D = Cl2 /wash/NaOH/Oxygen/wash/ClO2/wash
• If chemicals are added simultaneously, the letters are placed in parenthesis
separated by a + sign. C(E+O)D = Cl2
/wash/NaOH+Oxygen/wash/ClO2/wash
» People will also list this as CE/OD
• Sometimes small amounts of chemicals are added to fortify a step. The
additives are typically listed as subscripts: EO or EP or EOP
• Subscripts are also used to designate differences in conditions (ie temp,
pH, etc): D0, D1, D2

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Differences in Chlorine Dioxide Stages

Condition D0 D1 D2

Final pH 1.5-2.5 3.5-5 3.5 - 5

Temp °C 40°C - 60°C 55°C - 75°C 60°C - 85°C

Consistency 10-15% 10-15% 10-15%

Time 30-80min 2-4 hours 2-4 hours

Charge 1-2 times 4-6 times 4-6 times

kappa # kappa # kappa #

Typical Bleaching Sequence

Stage Chemicals Charge Temp. Time

(kg/ton pulp) ( C) (min)
O O2 + NaOH 15 + 20 100 60
D+C ClO2 + Cl2 12 + 18 70 45
EO NaOH + O2 15 + 5 70 120
D ClO2 17 70 180
EP NaOH + H2O2 8+3 70 90
D ClO2 5 70 180

Traditional Sequences
Sequence Comments
CEH Classical sequence for semi-bleached
pulp
(C+D)EODED Market pulp sequence of 1980’s
DEODED ECF for kraft pulp
OZEOD First sequence using ozone in North
America
YP Two stage for mechanical pulp

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 Some Current Sequences

Sequence Comments
OD0EOPD1E(p)D2 Don't know why (p)????
OD0EOPD1D2
OD0EOPD1P
Oq(OP)(ZE)DD Z-ECF Bleaching
(Z(EO))DnD Dn designates the addition of
NaOH to bring up the pH
Oq(OP)(ZQ)(PO) TCF Bleaching

Elemental Chlorine Free

• ECF pulping signifies that there is no

elemental chlorine (Cl2) used in the bleaching
sequence.
» Most often oxygen or ClO2 is used for lignin
removal.
» Brightening is most often accomplished by using
DED.
» Peroxide is used mainly to reinforce oxygen or in the
extraction stages.

Total Chlorine Free

• TCF means that there is no chlorine of any kind used

in the bleaching process.
• There has been significant effort made in this
direction for the following reasons:
» There is no possibility of the generation of AOX (AOX =
Absorbable Organically Bound Halogens).
» Chlorine free bleach plant effluent can be burned thus
allowing a pulp mill to have basically no effluent.
• The problem to date with TCF is that it has not been
possible to obtain desired brightness without
significant strength loss.

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 Bleaching Sequence exercise

• Name the Sequence exercises:

• O2/wash/ClO2 /Cl2 /wash/NaOH then O2/wash/ClO2
/wash/NaOH then H2O2/wash/ClO2

Water Dilution calculations

• Consistency: amount of pulp in pulp slurry

• Bleaching occurs at consistency of 3-10%
• Higher consistencies of 10-20 % are used with chemicals such as oxygen,
peroxide, and hypochlorite, which react with the lignin slowly
• Dilution water is solved using the equation:
• The water per ton of pulp ratio (V) is solved from the consistency (c) as V =
(100-c)/c.
• Example. After the brown stock washers, the consistency of unbleached pulp is
11.2%. Calculate the volume of water (in m^/t ovendry pulp) required to dilute
the slurry to 3% consistency for chlorination.
• Solution: SOLUTION. At 11% consistency there are 89 t water/(11t pulp) = 8.09
t water/t pulp. At 3% consistency there are 97 t water/(3 t pulp) = 32.33 t/t.
Therefore 32.33 - 8.09 =24.24 t water/t pulp to be added. Since 1 t = 1000 kg = 1
m3 of water, this is 24.24 m^3 of water per metric ton of pulp.

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