Bleaching operation

Lecture VII
 What is Bleaching?
• Bleaching is the treatment of wood
(and other lignocellulosic) pulps with
chemical agents to increase their
brightness.
Bleaching is the process of removing
color from pulp.

The color of pulp is due to presence of

lignin and extractive such as fats,
resins etc.

For this reason lignin and extractive

are called chromophores.

Prior to bleaching, the color of wood

pulp ranges from cream to dark
brown.

Bleaching agents are used for

removing color.
• Bleaching of chemical pulps
– involves a much different strategy than
bleaching mechanical pulps.
– Bleaching of chemical pulps is achieved
by lignin removal.
– Lignin removal in chemical pulps 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).
– bleaching mechanical pulps is referred
to as lignin-preserving.
– Sometimes bleaching mechanical pulps
is called "brightening" to distinguish it
from bleaching of chemical pulps.
 Brightness

• Brightness is a term used to

describe the whiteness of pulp or
paper, on a scale from 0% (absolute
black) to 100% (relative to a MgO
standard, which has an absolute
brightness of about 96%) by the
reflectance of blue light (457 nm)
from the paper.
• The approximate brightness levels of
some pulps are as follows:
 Color Reversion
• Color reversion is the yellowing of
pulps on exposure to air, light, heat,
certain metallic ions. and fungi due
to modification of residual lignin
forming chromophores.
• Mechanical pulps are particularly
susceptible to color reversion.
• Chemical pulps may experience this
when exposed to high temperatures.
 Consistency
• Bleaching stages are carried out at
consistencies from 3-20 %.
• Higher consistencies of 10-20 % are
used with chemicals such as oxygen,
peroxide, and hypochlorite, which
react with the lignin slowly.
• By using high consistencies, higher
concentrations of the bleaching
agent are realized for a given
chemical loading, which increases
the reaction rate.
 Bleaching Agents
• Reductive bleaching agents:
– Sodium hypochlorite, Zinc Hypochlorite
• Oxidative bleaching agents:
– Elemental chlorine, Chlorine dioxide,
Hydrogen peroxide, Hypochloric acid.
 Mechanical Pulp bleaching
• Mechanical pulps are bleached with chemicals
designed to alter many of the chromophores.
• Chromophores are most often conjugated double
bond systems arising in the lignin of pulps.
• Other chromophores such as sap-stain induced by
microorganisms, dirt, metal ions such as ferric
that complex with lignin, and water impurities
may impart color to paper.
• Bleaching of mechanical pulps involves masking
the lignin that is present, instead of removing the
lignin as is the case for bleaching chemical pulps.
• To emphasize this distinction, bleaching
mechanical pulps is often referred to as
brightening.
• Brightening mechanical pulps is accomplished with
reducing agents, such as dithionite, or oxidants, such
as hydrogen peroxide, often in a single stage
process.
• Fairly limited brightness improvements are realized
(6-12% typically) with a maximum brightness of 60-
70% in a single stage, or up to 75% in a two-stage
process.
• The pulp brightness also depends on the wood
species from which the pulp was derived.
• Brightened mechanical pulps are subject to color
reversion. Since the lignin is largely decolored, but
not removed, there is only a small loss of yield.
• If two stages are used, the oxidative stage is used
before the reductive stage or else the oxidant will
undo what the reductive compound accomplished.
 Dithionite, hydrosulfite bleaching
• Hydrosulfite (the common name in the industry, but
dithionite is the preferred name) bleaching is carried out
with 0.5-1.0% dithionite on wood.
• Previously, zinc dithionite was used because it is very
stable.
• As Zinc is toxic to fish, so, the sodium form has replaced
the zinc form.
• Zinc dithionite was prepared in the pulp mill from zinc and
sulfur dioxide as follows:
Zn+2SO2=ZnS2O4
• Bleaching is carried out at pH 5-6 with chelating agents
such as ethylene di-amine tetra acetic acid (EDTA) or
sodium tri-poly-phosphate (0.1- 0.2% on pulp) to prevent
metal ions such as iron(III) from coloring the pulp.
• Bleaching is often carried out in the refiners.
• The reaction time is on the order of 10-30 minutes.
• The brightness gain is only 5-8%.
• Dithionite reacts with oxygen, so
bleaching with it is carried out at 4%
consistency; (consistency below this is
unnecessarily dilute, so reaction with
dissolved oxygen consumes dithionite.)
• Consistency above 4% leads to
entrained air that consumes
dithionite.
• [The solubility of oxygen in the
atmosphere is only a few milliliters of gas
per liter of water at 25°C (77°F), and
decreases with increasing temperature;
thus, entrained oxygen is more significant
than dissolved oxygen at high
• Using temperatures as high as 70°C
(158°F) reduces the oxygen
solubility in water.
• Dithionite ion reduces lignin and is
itself oxidized to sulfite ion.
• If hydrogen peroxide and dithionite
are used in a two-stage process,
• The dithionite must be the second stage
or hydrogen peroxide will reoxidize
those reduced by the dithionite.
• The reaction of dithionite is shown below.
 Peroxide bleaching
• Some metal ions, such as Fe 3+, Mn2+, and
Cu2+, catalytically decompose hydrogen
peroxide, so peroxide bleaching is carried out with
agents that deactivate these metal ions.

• Chelating agents, such as ethylene-di-amine-

tetra acetic acid (EDTA), have the added gain
of preventing pulp discoloration by binding
with ferric ion that would otherwise form a
colored complex with the phenolic lignin
structure.
• Sodium silicate (5% on wood) is also used
(usually after the addition of magnesium ion).
• The mechanism for inactivating the
ions by sodium silicate is not clear;
– it may precipitate the ions, but, strictly
speaking, it is not a chelating agent.
– Buffering action is required to keep the
pH high even as organic acids are
produced as a result of some
carbohydrate degradation.
– Sodium silicate acts as a buffering
agent.
• Bleaching conditions are 0.5-3%
peroxide and 0.05% magnesium ion
(to mitigate carbohydrate
degradation by oxygen under
alkaline conditions) on pulp,
• Temperature of 40-60°C (104-
140°F) (about 20°C lower than with
chemical pulps since lignin removal
is not the goal),
• pH of 10.5-11, consistency of 10-
20%, 1-3 hour retention time, with a
brightness gain of 6-20%.
• Hydrogen peroxide with sodium
• The formation of the perhydroxyl ion
is as follows:

• Some carbohydrate degradation

occurs and is responsible for about
half of the peroxide consumed.
• Pine and fur are difficult to brighten.
• Color reduction occurs by altering
chromophoric groups such as ortho-
quinones.
• The pulp is sometimes subsequently
treated with SO2 to neutralize OH-
 Chemical pulp bleaching process
• The use of three to seven stages increases the
efficiency of bleaching by reducing the amount of
chemical required.
• This is due to the complex nature of lignin; each
bleaching chemical is going to react differently with
lignin.
• Lignin is a complex molecule with different types of
linkages,
• The use of different chemicals will break various
types of bonds.
• For example, a large increase in brightness is
achieved by using relatively small amounts of Clo2. in
a later stage that could only be achieved using
massive amounts of additional Cl2 in stage 1;
• Use of large amounts of chlorine in stage 1 would
also cause much carbohydrate degradation.
 Chemical pulp bleaching process
• Lignin removal is accompanied by significant
losses of pulp yield and strength of the
individual fibers.
• However, the strength of fiber-fiber bonding
increases after bleaching.
• Oxygen and chlorine are relatively
inexpensive, but not particularly selective for
lignin removal.
• These chemicals are used in the early stages of
bleaching to remove most of the lignin.
• Residual lignin is removed in later stages with
expensive, but highly selective bleaching
agents like chlorine dioxide, hypochlorite, and
hydrogen peroxide.
• Table is a summary of conditions
used in various bleaching stages.
• Typical sequences are CEH to a
brightness of 84-86% or CEHD or
CEHHD to a brightness of 92%.
 Classification
• Single stage Bleaching
• Multistage Bleaching
 Single Stage Bleaching
• Single stage bleaching with
hypochorite is one of the oldest
processes.
• Hypochlorite react readily with
unbleached pulps to whiten or
bleach.
• In this process either calcium or
sodium hypochlorite is used.
• Many pulps, especially produced by
the sulphite or soda process, can be
bleached to a brightness value of 78
• Usually single stage is not so good
for sulphate or high yield pulps,
unless a low brightness is desired.
 Results of single stage bleaching
• A minimum of purification.
• A maximum chemical cost per unit of
brightness obtained.
• A maximum strength loss per unit of
brightness.
• The possibilities of reversion of color
in the bleached pulp.
• A minimum investment per unit of
brightness.
 Steps of Multistage Bleaching
• A typical, five-stage multiple-
bleaching sequence would then
comprise
– chlorination with chlorine,
– alkaline extraction,
– hypochlorite bleaching,
– a second alkaline extraction,
– and, finally a chlorine dioxide
treatment.
• Multistage bleaching, which made it
possible to obtain white kraft pulp,
– consists of two steps:
• first, removing lignin and its by-products;
• second, bleaching after these color-
producing substances have been eliminated.
During the earlier stages, lignin is progressively
removed. Bleaching then removes or decolorizes
the remaining substances to expose the inherent
whiteness of the cellulose fibers.
 Chlorination stage(C stage)
• Cl2 +H2O HOCl + H+ + Cl-
• HOCl H+ + OCl-
• The three chlorine species Cl2, HOCl
and OCl- exerts varying affect on the
carbohydrates and lignin of the pulp.
• Reaction of chlorine with lignin:
Addition, Substitution and oxidation
Reaction of cholorine with lignin
Reaction of chlorine with
carbohydrates
 Alkaline Extraction (E stage)
• In acidic medium cellulose
degradation takes place during
bleaching.
• So alkali is added to reduce
degradation.
• In this process chlorinated lignin is
removed as they will consume the
oxidative bleaching agent.
• Normally NAOH is added in this
stage.
• The alkali displaces chlorine and
 Hypochlorite stage (H stage)
• 2Ca(OCl)Cl = Ca(OCl)2+CaCl2
• Ca(OCl)2+2H2O = Ca(OH) 2+2HClO
• 2HClO = 2HCl +2[O] (Nascent)
• Ca(OH) 2+2HCl = CaCl2 +2H2O
Second alkaline
treatment(E)
Chlorine dioxide addition (D stage)
• The D stage involves bleaching with
chlorine dioxide.
• Chlorine dioxide is relatively
expensive, but highly selective for
lignin.
• This makes it very useful for the
latter bleaching stages where lignin
is present in very low
concentrations.
• The D stage is useful for reducing
shive contents.
Final Treatment
 P stage
• Bleaching with hydrogen peroxide,
H2O2, is not common for chemical
pulps. (But this is changing
somewhat as mills look for chlorine-
free systems).
• It is usually used for brightening
mechanical pulps, but when it is
used to bleach chemical pulps it
appears as the last stage of a
sequence such as C-E-H-P or C-E-H-
D-P.
• It is an expensive bleaching agent,
• But may be used more frequently as
the use of elemental chlorine
decreases.
• Peroxide oxidizes carbonyl groups of
carbohydrates (produced by
oxidants such as hypochlorite) to
carboxylic acid groups.
• Its use with chemical pulps is fairly
similar to that with mechanical
pulps, except for a higher
temperature.
 O stage, oxygen pulping and bleaching
• Oxygen bleaching or pulping is the
delignification of pulp using oxygen
under pressure (550- 700 kPa or 80-
100 psi) and NaOH (3-4% on pulp).
• Oxygen bleaching has been used
commercially since the late 1960s.
• This is an odorless, relatively
pollution-free process used prior to
chlorination at high consistencies
(20-30%) or medium consistencies
(10-15%).
• Delignification is carried out at 90-
 O stage, oxygen pulping and bleaching
• The key to the use of O2
delignification was the discovery
that small amounts of magnesium
ion (0.05-0.1 % on pulp) must be
present to protect the carbohydrates
from extensive degradation.
• This is the most inexpensive
bleaching chemical to use, but also
the least specific for lignin removal.
• A considerable decrease in cellulose
viscosity accompanies this process.
 Bleachability
• The amount of bleach required in the
bleaching operation.
• This serve as a guide and control for the
cooking operation.
• Low bleachability
– means the pulp is highly purified and will not beat
as readily as the same type of pulp containing more
hemicellulose matter.
• If the bleachability is extremely high,
– the pulp is said to be hard cooked and as a rule will
not develop strength on beating.
• An intermediate bleachability value is most
desirable for easy beating of pulp.
 The identification types
• The process to asses the bleachability
– Kappa no.
– Permanganate number, K number
– Roe number
– Chlorine number
 Kappa no.
• The kappa test is an indirect method for
determining lignin by the consumption of
permanganate ion by lignin.
• The kappa number is the number of milliliters of
0.1 KMn04 consumed by one gram of pulp in 0.5
N sulfuric acid after a ten minute reaction time
at 25°C (77°F) under conditions such that one-
half of the permanganate remains unreacted.
• The 50% residual permanganate is titrated to
determine the exact consumption.
• Experimentally, 30-70% excess is common with
factors to convert this to 50%.
• TAPPI Standard T236 is based on this
procedure.
 Kappa no.
• The kappa number test can be used
on bleached pulps, unbleached
pulps, and high yield chemical
pulps by use of a single scale
• With bleached pulps always giving
low numbers and unbleached pulps
giving high numbers, unlike the K
number.
• A variety of lignin contents are
accommodated by varying the
amount of pulp used in the test, but
keeping the amount of KMn04
 Permanganate number, K number
• The permanganate (or K) number, is really four
different tests.
• A constant amount of pulp is used with either 25 ml
(for bleached pulp), 40 ml, 75 ml, or 100 ml (for high
yield pulps) of permanganate.
• Results of the 100 ml K number test are not easily
compared to the results of the 75 ml (or any other) K
number test, so there is no continuum or results for
all types of pulps as with the kappa test.
• Guillory (1982) gives the relationship in the equation:
log (kappa no.) = 0.837 + 0.0323 (40 ml K no.)
• Therefore, a 40 ml K number of 10 corresponds to a
kappa no. of 14.5, 20 (40 ml K number) corresponds
to 30.4 kappa number, and 30 (40 ml K number)
corresponds to 64.1 kappa number.
 Roe number
• The Roe number is a measure of lignin
content by the number of grams of gaseous
Cl, consumed by 100 grams dry pulp at 25 °C
(77 °F) in 15 minutes.
• TAPPI Standard 202 (now withdrawn) was
one method.
• Alander, Palenius, and Kyrklund (1963) give
the following relationship for hardwood pulps:
• Roe number = 0.158 x kappa - 0.2 (kraft)
• Roe number = 0.199 x kappa + 0.1
(sulfite)
 Chlorine number, C, hypo number
• The chlorine number is a test
method similar to that of Roe, except
the ClO2 is generated in situ (on site
)by acidification of sodium
hypochlorite.
• TAPPI Standard T 253 uses this
method to determine a hypo number.
• The following empirical equation
relates the chlorine number to the
Roe number.
• Chlorine number = 0.90 x Roe
 Klason lignin, acid insoluble lignin
• Klason lignin is the residue obtained after total
acid hydrolysis of the carbohydrate portion of
wood.
• It is a gravimetric (concentration of a substance)
method for determining lignin directly in woody
materials, for example, by TAPPI Standard T
222.
• This method is not used for routine quality
control in the mill, but has uses in the
laboratory.
• Wood meal or pulp is treated with 72% sulfiiric
acid at 20°C (68°F) for 2.0 hours followed by
dilution to 3% sulfiiric acid and refluxing for 4
hours.
• Papers are bleached to whiteness for
several reasons:
– printing contrast improves as the
whiteness of paper increases;
– whiter papers are aesthetically
desirable;
– colored papers become more brilliant
when made from whiter pulps;
– bleaching contributes to the chemical
stability, purity, and permanence of
chemical pulps;
– and bleaching is necessary for sanitary
reasons (for example, in food-packaging
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