TKS 32504

Teknologi Pulp dan Kertas

(Pulp and Paper Technology)

Kuliah 8 – Bleaching Pulp

Semester Genap 2019/2020
Prodi Sarjana Teknik Kimia Universitas Riau
INTRODUCTION

• Bleaching is the treatment of wood (and other

lignocellulosic) pulps with chemical agents to
increase their brightness.
• Bleaching of chemical pulps is achieved by lignin
removal.
• Bleaching mechanical pulps is referred to as lignin-
preserving.
INTRODUCTION

• Sometimes bleaching mechanical pulps is called

“brightening” to distinguish it from bleaching of
chemical pulps.
• Brightness is a term used to describe the whiteness
of pulp or paper, on a scale from 0% (absolute black)
to 100% (relative to an MgO standard, which has an
absolute brightness of about 96%) by the reflectance
of blue light (457 nm) from the paper.
INTRODUCTION

The approximate brightness levels of some pulps are as

follows:
INTRODUCTION

• Bleaching stages are carried out at consistencies from

3% to 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
MEASUREMENT OF LIGNIN CONTENT

• The measurement of lignin in chemical pulps is a vital

tool to monitor the degree of cook (extent of
delignification during pulping) or to measure residual
lignin before bleaching and between various stages
of bleaching to monitor the process.
• Lignin is easily measured indirectly by measuring the
amount of an oxidant (such as chlorine or potassium
permanganate) consumed by lignin in a sample of
pulp of known mass.
MEASUREMENT OF LIGNIN CONTENT

• Methods based on consumption of potassium

permanganate (Kappa and K numbers) are the most
common ones used.
• The idea (Fig. 19.2) is to treat the pulp with an excess of
permanganate ion (or chlorine for Roe or C number) for a
specified period of time to oxidize the lignin.
• After the specified reaction time, the residual
permanganate (or chlorine) is determined by indirect
titration.
Kappa Number

• 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
KMnO4 consumed by 1 g of pulp in 0.5 N sulfuric acid
after a 10 min reaction time at 25oC (77oF) under
conditions such that one-half of the permanganate
remains unreacted.
Kappa Number
• 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 T 236 is based on this procedure.
• The Kappa number test can be used on bleached
pulps, unbleached pulps, and high yield chemical
pulps by use of a single scale.
Kappa Number

• Klason lignin is considered to be essentially the same as

the actual lignin content.
• Alander, Palenius, and Kyrklund (1963) give the following
relationship for sulfite and kraft chemical hardwood
pulps: Klason lignin, % = 0.15 Kappa number.
• This relationship is approximately correct for softwoods
as well. Chiang et al. (1987) found the coefficient of 0.159
for Douglas fir and 0.168 for western hemlock.
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 (Fig. 19.2), 75 mL, or 100 mL (for high
yield pulps) of permanganate.
• Guillory (1982) gives the relationship in the equation:
log(Kappa number) = 0.837 + 0.0323 (40 mL K number)
• Therefore a 40 mL K number of 10 corresponds to a Kappa
number 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 Cl2 consumed by 100 g dry pulp at 25oC
(77oF) in 15 min.
• 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 (Sulfit)
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 method for determining lignin
directly in woody materials, for example, by TAPPI
Standard T 222.
• Wood meal or pulp is treated with 72% sulfuric acid
at 20oC (68oF) for 2.0 h followed by dilution to 3%
sulfuric acid and refluxing for 4 h. The lignin is filtered
in a tared crucible, washed, dried, and weighed.
Klason Lignin, Acid-Insoluble Lignin

• The isolated lignin in this manner is degraded

considerably; nevertheless, it corresponds (by
weight) closely to the original amount of lignin in the
sample.
• Some of the lignin, especially in sulfite or hardwood
pulps, remains soluble (called acid-soluble lignin) and
can be estimated spectrophotometrically in the UV
region.
BLEACHING CHEMICAL PULPS
• The cellulose degree of polymerization in low yield pulps
and bleached pulps is very important as these processes
lower the degree of polymerization of cellulose to the
point where the paper strength properties are adversely
affected.
• Cellulose viscosity is measured by dissolving the pulp in
cupri-ethylene-diamine solution and measuring the
viscosity of the solution (TAPPI Standards T 254 and T
230).
BLEACHING CHEMICAL PULPS
• Chemical pulp bleaching is accomplished with various
compounds containing chlorine or oxygen and alkali
extractions in several stages.
• 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.
BLEACHING CHEMICAL PULPS

• Bleached chemical pulps are insensitive to color

reversion, but high temperatures may induce some
color reversion.
• Lignin removal is accompanied by significant losses of
pulp yield and strength of the individual fibers.
• However, the strength of fiberefiber bonding
increases after bleaching.
BLEACHING CHEMICAL PULPS

• Bleaching of chemical pulps involves the use of

chemicals which are more specific to lignin removal
than to carbohydrate degradation compared with the
chemicals used in pulping.
• Bleaching is much more expensive than pulping for a
given amount of lignin removal.
C Stage, Chlorine

• Normally, chlorine is the first bleaching stage, where

unbleached pulp is treated with elemental chlorine, Cl2,
that is either gaseous or in solution, at a pH of 0.5 - 1.5.
• Bleaching is carried out with a pulp consistency of 3% -
4%, ambient temperature as the reaction is quick, and a
retention time of 0.3 - 1.0 hours.
• Chlorine application is 6% - 8% on softwood kraft pulps
or 3% - 4% on sulfite or hardwood kraft pulps.
C Stage, Chlorine

• Chlorine is manufactured concomitantly with sodium

hydroxide by electrolysis of sodium chloride; as these
two chemicals are produced together, one often
speaks of the chlor-alkali industry.
• The production of chlorine is summarized as follows:
C Stage, Chlorine

• The chlorine reacts with lignin by substitution of

hydrogen atoms for chlorine atoms (particularly on
the aromatic ring), oxidation of lignin moieties to
carboxylic acid groups, and, to a small extent,
addition of chlorine across carbonecarbon double
bonds.
• The substitution reactions (Fig. 19.8) are probably
the most important in the ultimate lignin removal
CD Stage

• The CD stage is a modification of C stage bleaching,

where some of the chlorine is replaced with ClO2.
• Substitution of 10% of the chlorine with chlorine
dioxide is used to prevent over-chlorination.
• Substitution of 50% or more of chlorine with chlorine
dioxide at many mills is becoming common to reduce
production of dioxins and other chlorinated organic
chemicals.
E Stage
• The E stage is extraction of degraded lignin compounds,
which would otherwise increase the chemical usage in
subsequent bleaching stages, with caustic (NaOH)
solution.
• It follows the C stage and sometimes other stages of
bleaching.
• When it follows the C stage (E1), it is used at 2%-3% on
pulp, often with a downflow tower because of the HC of
pulp (10%-18%), with a temperature of 50-95oC (120-
200oF) and a reaction time of 0.75-1.5 h.
E Stage

• High temperatures and alkali loading up to 5% are used

to remove hemicelluloses for dissolving pulps or
absorbent pulps.
• In later E stages, alkali is used at less than 1% on pulp.
• The alkali displaces chlorine and makes the lignin soluble
by reactions such as:
H Stage

• The H stage consists of bleaching with hypochlorite

solution, usually as the sodium salt NaClO; this is the
same chemical found in household liquid bleach.
• This stage is carried out at 4%-18% consistency, 35-
45oC (95-113oF), 1-5 h, and pH 10.
• The process is often controlled by measuring the
oxidation-reduction potential.
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.
• It is used at consistencies of 10%-12%, 60-80oC (140-
176oF), for 3-5 h at a pH of 3.5-6.
• It is used at 0.4%-0.8% on pulp.
D Stage

• The D stage is useful for reducing shive contents.

• Chlorine dioxide may react in two steps. In the first
step ClO2 is formed; this then reacts under acidic
conditions to form Cl. Thus

• It reacts by oxidation; one reaction is shown in Fig.

19.8.
P Stage
• Bleaching with hydrogen peroxide, H2O2, is not common
for chemical pulps.
• 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 used at 10% consistency, 60-70oC (140-160oF), pH of
8-10, for 2-4 h.
• It is an expensive bleaching agent but may be used more
frequently as the use of elemental chlorine decreases.
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).
• This is an odorless, relatively pollution-free process
used before chlorination at high consistencies (20%-
30%) or MCs (10%-15%).
• Delignification is carried out at 90-130oC (195-266oF)
for 20-60 min.
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.
• Many mills have considered using an oxygen
delignification step after pulping but before the
traditional chlorination first step of bleaching.
O Stage, Oxygen Pulping and Bleaching

• There are two main methods of oxygen bleaching: MC and HC.

• The HC process is at 30% consistency and 90-110oC (195-
230oF) in a pressurized reactor.
• In the MC process pulp at 10%-15% consistency (the normal
consistency as it comes off the drum washers) is used.
• The temperature of oxygen bleaching is important to the
selectivity of the process with better selectivity at 100oC
(212oF) than 130oC (266oF).
Ozone Bleaching

• The development and utilization of ozone treatment

technology in the bleaching process in the pulp and paper
industry has allowed recycling of waste streams from the
bleach plant.
• Ozone can be used in both chemical and mechanical pulping
and has enabled many pulp mills to improve product quality,
environmental, and process performance.
• It is found to efficiently delignify all types of chemical pulps
and is used either at medium or high pulp consistency in ECF
and TCF bleaching.
Ozone Bleaching

• Charges of ozone typically used are lower than 6-7

kg/t of pulp.
• It is a highly competitive bleaching chemical that,
when compared at equal bleaching power, is typically
1.2-1.5 times less costly than chlorine dioxide.
• ECF sequences combining ozone and chlorine dioxide
are economically competitive with sequences using
chlorine dioxide only.
Ozone Bleaching

• It is used either at medium or high pulp consistency

in ECF and TCF bleaching sequences.
• Charges of ozone typically used are lower than 6-7
kg/t of pulp.
• The effluent from ozone pre-bleaching can be used in
brown stock countercurrent washing and taken to
the chemical recovery system, providing its acidic
nature is taken into account.
Peroxy Acid Bleaching

• A peroxy acid, or peracid, is an acid that contains a

perhydroxyl group (-OOH).
• Typically, the delignification conditions for peracetic
acid are given: initial pH 6-7; temperature 70-80oC;
reaction time 60-180 min at MC.
• In this application, 1-2kg per-acetic acid per ton of
pulp is sufficient to increase ISO brightness by 1.5-2.5
units.
Elemental Chlorine-Free Processes

• The focus on reduction in adsorbable organic halides

(AOX) in bleach effluents has promoted ECF and TCF
bleaching processes.
• ECF bleaching is a chlorine-free process in that no
elemental (molecular) chlorine is used in the bleaching
sequences.
• Although the term ECF does not specify it, typically
chlorine dioxide is the principal bleaching agent for these
processes.
Elemental Chlorine-Free Processes
Totally Chlorine-Free Processes

• The TCF bleaching processes do not use chlorine dioxide

or any other chlorine containing chemicals.
• In the TCF process, only oxygen based chemicals are
used.
• These are oxygen molecules, hydrogen peroxide, ozone,
and peroxy acids.
• The TCF technology is often used in combination with
extended delignification in the pulping process.
Totally Chlorine-Free Processes
Totally Chlorine-Free Processes
Enzyme Bleaching
• Two different strategies have been developed in using
enzymes for chemical pulp bleaching:
1. hemicellulases (particularly xylanases) as a
pretreatment for enhancing the chemical removal of
lignin in multistage bleaching sequences.
2. ligninases or laccases for direct delignification.
• The main goals have been directed toward reducing the
charge of chlorine-containing chemicals in the bleach
plant and lowering the AOX content of the bleach
effluent.
question