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Bleaching
Within the context of this work, the author(s) may use as examples specific manufacturers
of equipment. This does not imply that these manufacturers are the only or best sources of
the equipment or that T APPI endorses them in any way. The presentation of such material
by T APPI should not be construed as an endorsement of or suggestion for any agreed upon
Principles
and Practice
...
CarltonW.
and
Douglas W. Reeve
Library of Congress
AtJanta, Georgia
@ 1996
U.S.A.
College of Environmental
TAPPI
;:)1996 by:
TAPPIPRESS
Technology Park/Atlanta
P.O. Box 105113
Atlanta, GA 30348-5113
Dence
action.
Editors
Cataloging-in-Publication
Data
~
TAPPI PRF.SS
it
specific
base fee
Center,
$.50 pp.
TABLE OF CONTENTS
Acknowledgements
Preface
vii
Section I: Introduction
11:Introductionto the Principlesand Practiceof PulpBleaching
25
59
II 3: Bleaching Chemicals:
Hydrogen Peroxide,
71
and Brightness
PulpComponents
Reversion
91
113
125
161
183
213
IV 2: Chlorination
241
261
291
IV 5: Ozone Delignification
321
347
363
379
395
IV 10:HydrogenPeroxideBleaching
411
443
Iii
457
491
513
537
569
597
625
647
of Bleached Pulp
675
695
717
Section
749
767
VIII 3: Dioxins
799
821
VIII 5: Environmental
835
Regulations
Subject Index
847
iv
Acknowledgments
As is usually the case in any major undertaking, many individuals worked behind
the scenes in a variety of capacities to help create this book. In particular, we acknowledge with thanks the efforts of those who contributed a substantial amount of
time in serving as referees for specific chapter manuscripts: Terry Adams, Terry N.
Adams Consulting; Chad Bennington, PAPRICAN; Dennis Borton, NCASI; Bruce
Fleming, Boise Cascade; Raymond Francis, SUNY College of Environmental Science
and Forestry; Maurice Hache, Morton International, Inc.; Bruno Marcoccia, Kamyr,
Inc. ;Thomas McDonough, Institute of Paper Science and Technology;Anil Mislankar,
University of Toronto; Esa Vilen, University of Toronto, and Paul Wollwage,
Weyerhaeuser Company.We also wish to express our appreciation to the many companies and institutions for the "loan" of their employees for the purpose of contributing to this book and to TAPPI PRESS for their patience and support in this project.
As editors and contributing authors we individually wish to acknowledge those
who have been involved with us on a more personal level in the production of this
book.
Doug Reeve:
First and foremost, I am very grateful to my partner in this project, Carlton Dence.
He has been his usual self: capable, energetic, insightful, meticulous, thorough, reliable, and feisty through these many, many long months.A better partner I could not
have wished for.
.
I am grateful to my colleagues at the Pulp & Paper Centre for their steady and
capable support: in particular, Mimee Cheung, David Goring, Bruce McKague, Kate
Reeve, linda Staats, Cindy Tam, Esa Vilen, and KathyWeishar.
Finally, I wish to express my heartfelt thanks to my family for their support and
encouragement and most especially to my wife, Melanie, who tolerated my occupation of the dining room well beyond the originally agreed-upon six-month period,
often with fiery forbearance.
Carlton Dence:
The scope and detail of the material found in this book required the participation
of a co-editor whose educational background and experience complemented
my
own. By providing the chemical engineering expertise and an extensive practical
knowledge of commercial bleaching operations, Doug Reeve filled that requirement
to perfection and I sincerely acknowledge his pivotal role in determining the content and quality of this book.
I am also indebted to Elizabeth Elkins and James Williamson of the Moon Memorial library staff at the SUNY College of Environmental Science and Forestry for
providing me with copies of journal articles and for corroborating reference citations. Thanks also are due Sarah Remon for her careful work in transferring the
manuscripts for my chapters to diskette. Financial support from TAPPI as reimbursement for out-of-pocket expenses incurred in connection with this book is noted
with gratitude.
In conclusion, I wish to acknowledge the efforts of my wife, Frances, whose vicarious suffering in this literary odyssey took the form of frequent manuscript-burdened trips to Sinclair Office Supply, Mail Boxes Ine. and local post offices in the
vicinity of Hendersonville, N.C. on my behalf.
I'
Pulp Bleaching
Principles and
Practice
Preface
This edition of theTAPPI Bleaching Monograph is the fourth in a series of such books
published
in 1953, 1963, and 1979, all
projects of the TAPPI Pulping Bleaching
committee.
In a radical departure from the format of
previous monographs, the contents of this
edition have been organized under eight
major headings (designated by Roman numerals) to highlight what we perceive to
be the main subject areas for any discussion of contemporary pulp bleaching. By
this device, we have sought in particular to
give subjects relating to bleach plant engineering, bleaching chemistry, and environmental issues a more distinct identity than
in the past.
NC, USA
Doug Reeve
Toronto, ON, Canada
February, 1996
vii
SEcnON I:
Introduction
Chapter 1:
Introduction to the Principles
and Practice of Pulp Bleaching
Douglas W. Reeve
Department of Chemical Engineering and
Applied Chemistry and Pulp & Paper Centre
University of Toronto
Toronto, Ontario
1. What is bleaching? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1 A general description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Objectives and critical parameters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7. Trends
in pulp bleaching.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
23
Chapter I 1:
Introduction
to the
Principles and Practice
of Pulp Bleaching
Preface
Since the first bleaching monograph in
texts
1953 (1) two other comprehensive
have been published on pulp bleaching, in
1%3 (2) and in 1979 (]). Thorough treatments of pulp bleaching also appear as
chapters in other texts (4,5) and in the annual TAPPI Bleach Plant Operations Short
Course Notes.
In this chapter, the foundation concepts
of pulp bleaching are introduced including
the objectives, economics, history, chemistry, and engineering of pulp bleaching systems. In the other chapters in this text,
these concepts are described in greater
detail, and more penetrating explanations
and fuller descriptions are provided. There
are many places in the introductory chapter where reference might have been made
to more detail elsewhere in the text. This
has not been attempted;
however, the
reader is encouraged to seek greater detail
through the use of the table of contents and
the index.
1. What is bleaching?
1.1 A general description
Bleaching is a chemical process applied
to cellulosic materials to increase their
brightness. Brightness is the reflectance of
visible light from cellulosic cloth or pulp
fibers formed into sheets. Bleaching processes are applied to cellulosic textiles,
woven articles made from conon or linen,
and cellulosic pulp, in the form of aqueous
suspensions of individual fibers separated
from wood or non-woody materials such as
straw, reed, jute, sugarcane (bagasse), and
bamboo. Bleaching increases the capacity
of paper for accepting printed or written
images and so increases its usefulness. It
also is a means of purifying pulp, thereby
extending its application, increasing its sta-
droxide), and for mechanical pulp bleaching only, a reducing agent, sodium hydrosulfite (sodium dithionite). These chemicals
are mixed with pulp suspensions and the
mixture is retained at prescribed pH, temperature, and concentration conditions for
a specified time period. The bleaching reactions that occur are highly complex due
to the complexity of lignin and the wide
variety of reactive bleaching
species
present. The progress of bleaching reactions is monitored by measuring pulp lignin content, pulp brightness, and residual
chemical.
Bleaching chemicals are frequently applied sequentially with intermediate washing between treatments (stages),
because it is not possible to achieve sufficient removal or decolorization of lignin by
the action of anyone chemical in a single
treatment or stage.
To carry out these reactions, appropriate process equipment is required for mixing steam with the pulp to control the
temperature, mixing chemicals with the
pulp, pumping or otherwise conveying the
pulp, and washing the pulp after the reaction is complete. Reaction times for bleaching chemicals are generally in the range of
a few minutes to several hours, requiring
the construction of large towers (reactors)
to provide an adequate retention (t. e., reaction) time. Bleaching processes are monitored by on-line sensors and process control
algorithms devised to achieve product quality targets with efficient use of chemicals
and energy.
1.2 Objectives and critical parameters
The prinicipal objective of pulp bleaching is to achieve a high brightness with secondary objectives, for particular end uses,
being high brightness stability, high pulp
cleanliness (freedom from colored particles), and a high cellulose content. These
objectives must be achieved without compromising the strength of the final product;
cellulose degradation during bleaching can
lead to significant loss of strength in product paper sheets.
Bleaching costs must be appropriate to
the value added by the process. Variable
Chapter I I: Introduction
or alkaline soils (lime) followed by washing and exposure to the sun. Buttermilk or
juices of berries were used for acid treatment. This practice continued almost unchanged until 1800.
Bleaching was a serious matter in medieval times. At one point, regulations forbade the use of lime and violators paid the
ultimate penalty: "any bleacher who used
improper materials was adjudged to be
guilty of felony and to suffer death" (6).
Cloth was laid out on bleaching-greens
(grassy meadows) for exposure to sunlight;
the process was sometimes referred to as
"grassing." Thefts from bleaching-greens
were a serious problem, so a Society of
Bleachers was formed for protection against
such thefts. Thieves were sometimes executed.
In 1784 Scheele, in Sweden, discovered
chlorine and its ability to destroy vegetable
coloring matter. At that time, chlorine was
called depholgisticated
marine acid gas because it was thought to be produced by
removing phlogiston frOm muriatic acid. In
France in 1785, Berthollet discovered that
chlorine could be dissolved in a solution of
vegetable ash, potash, and gave it the name
"eau de Javelle." Several English scientists
became involved in further developments.
Davie showed that the new gas was an element and gave it the name "chlorine" from
the Greek word "chloros" meaning green.
In 1798, Charles Tennant of Glasgow found
a less expensive alternative to vegetable ash,
namely a suspension of lime, and used the
suspension to absorb chlorine gas and make
calcium hypochlorite.
This chemical became the standard bleaching agent for the
next century. At first it was used in combination with grassing and was able to dramatically decrease the time of exposure to
sunlight from many weeks to a few days.
Experiments in which chlorine gas was
added directly to water led to tragedy in
several instances; there are accounts of wellknown scientists dying immediately, or
years later, from exposure to chlorine.
Up until the second half ofthe nineteenth
century, paper was made from cotton and
linen rags. However, with the industrial
~-~-~
--~
revolution
and the advance of reading
among an increasingly larger public, the
demand for papermaking fibers for printing, publishing, and commerce outstripped
the supply of rag fiber. Wood fiber, initially
obtained from groundwood pulping and
later from kraft and sulfite pulping, was increasingly used for papermaking.
The
groundwood and sulfite pulping processes
produced fiber that was weaker than rag
fiber and of moderate brightness. The soda
and then the kraft processes produced
stronger but substantially darker pulps. One
or two hypochlorite bleaching stages were
used; the hypochlorite treatment had to
be very severe to produce even moderate
increases in kraft pulp brightness.
This
proved to be very expensive and caused
considerable damage to the pulp which increased the incentive for finding a way to
bleach wood pulp without incurring fiber
damage.
It is interesting to note that throughout
this early history, the issues of bleaching
effectiveness, cost, product quality, brightness, and strength were as important to
bleachers as they are today.
In the first 30 years ofthe twentieth century, several important
bleaching techniques were developed.
One was the
multi-stage bleach plant where hypochlorite (H) was applied first, followed by an
alkaline extraction stage (E) and then by
another hypochlorite
stage, the HEH sequence.
This approach, together with
interstage
washing, greatly decreased
chemical requirements. Ways were discovered to use gaseous chlorine (C) instead of
hypochlorite, and further savings resulted
from application of the CEH bleaching sequence. Also, in the period 1900 to 1930,
new equipment was developed to make
bleaching
more efficient.
The Belmer
bleacher permitted pulp consistency to be
increased from 3 to 6%. About the same
time, high-density bleaching was developed, which enabled bleaching to be conducted at 12% consistency. These methods
led to considerable savings in steam.
Large-scale chlorine dioxide manufacruring and chlorine dioxide bleaching (D) were
first practiced in the 1940s. This led to the
3. Significance of bleaching in
the paper industry
Bleaching plays an important role in the
economics of the paper industry. Global
bleached fiber capacity in 1994 was 93 million tons as shown inTable 1 (8). This tonnage is dominated by bleached chemical
pulp, in particular kraft pulp together with
a small fraction of sulfite pulp. Although
only 2.3 million tons of bleached chemithermomechanical
pulp is reported in this
table, it should be noted that a large amount
of mechanical pulp is produced for newsprint which may require only modest, partial bleaching.
An important
distinction
is made in
Table 1 between market bleached fiber and
integrated
bleached fiber. The market
bleached fiber is sold as an end product,
and this usually imposes higher quality standards in terms of brightness, cleanliness,
strength, and uniformity. In integrated mills,
the bleached fiber is sent as a suspension
directly to papermaking operations and so
does not face the more stringent market
demands. This distinction is an important
factor in bleach plant design and operation.
32.2
1.9
2.3
Kraft
Sulfite
BCTMP
42.6
4.0
Total
Annual
Growth
Rate, %
74.8
2.5
5.9
2.3
o
7.5
5
Deinked pulp
1.1
9.2
10.3
Total
37.5
55.8
93.3
BCTMP
=Bleached
chemithermomechanical
pulp.
Chapter
I 1: Introduction
to Principles
& Practice
of Pulp Bleaching
Pulp Bleaching
- Principles
and Practice
u
u
'0:: :E
S
~u
..c::
:;:::
'50
'"
\0
0
CI)
~r<"\
0
CI)
Softwood
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1.8
Canada
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EQ
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'SS
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~~..c::
uu
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ket pulp
duction
spruce,
50% of
hardwoods,
properties that are in demand on the mar~ketoThere is relatively little market for unbleached kraft pulp, the bulk of production
":
~\0
going directly
into the manufacture
of
linerboard.
It is also apparent
from Table 2
~that Japan, Germany, France, and the United
~States must import
pulp to be able to
0\
countries
to create
a product
with
0..
-;
in these
r<"\
0..
ct
~...
U
::;
reached
mainly
(US) $1000
eucalyptus.
products including writing and publicationgrade paper, tissue and sanitary papers,
absorbent products, and board for packag-
U
rJJ
2.4
~...;
~~~"3
13.8
8.7
softwood. In Canada, the dominant hardwood species is aspen poplar; in the United
States oaks, maple, and gum predominate.
Market pulp production in Europe is dominated by the Nordic countries where pine
is the dominant softwood and birch is the
dominate hardwood. In Latin America and
Asia, production is dominated by tropical
the production
-0
0
:is
c::
~u ::J
EQ
N
""
2 (9). The
kraft pulp
Japan, Finproducers
~0..
-0
-0
-8
U
U
S
..c::
vi
0..
0\
bleached
fiber are given in Table
leading producers
of bleached
~~arethe United States, Canada,
land, and Sweden; the leading
(11)
13.8
0\
CI)
~~~r<"\ I'oci
0\
-0
~0
r<"\
0\
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~...
...
...
~I::!
00
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~~~1
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-E
it
2.5
Asia
United States
'"
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3.8
1.4
~oci
u
-0
4.5
Millions ofTons
&S
1S.
4.8
Europe
~LatinAmerica
""
~ee ""-
...
10.7
-a
c::
'"
.....
0
c::
'"
Hardwood
North America
c::
S
of bleached
packaging
accounts
and
4. Pulp composition,
and terminology
properties,
4.1 Composition
The properties of pulp are the result of
the properties of its principal components
cellulose, hemicellulose, and lignin.
Cellulose, a carbohydrate, is a linear polymer of anhydroglucose and constitutes 4050% of most wood species. However, by
acid hydrolysis or a combination of oxidation and alkaline hydrolysis, the chemical
bonds in a cellulose chain can be broken.
The strength of paper is due in part to the
strength of individual cellulose chains and
in part to hydrogen bonds formed between
adjacent cellulose moleeules, within fibers,
and between fibers, which are responsible
for the strength of paper sheets. Cellulose
has a great capacity to form hydrogen bonds
and, as a result, has a great affinity for
water.
Cellulose is essentially colorless and does
not require bleaching. However, during the
bleaching of pulp fibers to decolorize other
components, cellulose degradation can occur. This can lead to cellulose fragments
being dissolved and to a lower pulp yield.
Further, if cellulose degradation is sufficiently severe, pulp strength will decrease.
Although the strength of pulp sheets is a
complex property, the degradation of cellulose during pulp bleaching can be an important factor in determining overall pulp
strength.
To determine the extent of cellulose degradation, the average length of the cellulose
molecules is determined.
To do this, the
pulp is dissolved in a cellulose solvent and
the viscosity of the solution, which is a function of cellulose average chain length, is
measured. Pulp viscosity, as this is known,
is often used as an indicator of cellulose
degradation during bleaching and to indi-
10
the residual lignin after pulping is oxidatively fragmented to lower the molecular
weight to a point where dissolution takes
place. In high-yield pulps, lignin bleaching
is achieved by decolorization with an oxidizing or a reducing agent. This is termed
"lignin-retaining bleaching."
lignin content must be measured during
chemical pulping and bleaching. Because
of its complex structure and relatively low
concentration in chemical pulp, lignin is difficult to measure directly and therefore relative lignin content
is measured
by a
standardized reaction of potassium permanganate with pulp. permanganate
reacts
with the lignin in pulp but not with the
carbohydrate components. In this test, the
conditions for the reaction between permanganate and pulp (pulp concentration
in the reaction mixture, permanganate
charge or concentration,
acid concentration, time, and temperature) are carefully
controlled so that a consistent, reproducible though still relative, measure of lignin
content is obtained. Several variations of
this test are available, so it is important to
know which set of standard conditions are
used. One test is referred to as the"k number" (sometimes called the "p number" or
"permanganate
number"); another test is
termed "kappa number." Conditions used
for the kappa number test are slightly more
rigorous than those for the k number test
and provide a more linear relationship between kappa number and lignin content;
Ttlble 4. ComposIIImI
aU propertks
Pulp
of different
however it requires more time. The "k number" can be approximated by multiplying
the kappa number by 0.66. Lignin content
(in weight percent) is approximated
by
multiplying the kappa number by 0.15.
Thus, an unbleached sofrwood kraft pulp
might have a kappa number of 30, which is
approximately equal to a k number of 20
and a lignin content of 4.5%.
The properties of different pulp types are
shown in Table 4. Values for the groundwood pulp reflect the relative concentrations of cellulose, hemicellulose, and lignin '
initially present in wood. Without bleaching, the pulp has a brightness of 62. However, mechanical damage occurs in the
fiberization process with the result that the
tensile and tear strengths are low. Acid
sulfite pulping provides pulp having a lower
lignin content and a significantly higher
strength than groundwood; however, the
yield is significantly lower. Acid sulfite
pulping does not decrease pulp brightness
significantly, and this type of pulp is readily
bleached to 90 brightness.
Unbleached kraft pulp at 50% yield provides a much stronger pulp sheet, although
the kraft process leads to significant darkening of the lignin and therefore to lower
brightness. Kraft pulp can be bleached to
a high brightness with high strength retention.
Another component of pulp that must
be taken into account are the extractives.
Extractives are wood chemicals that can be
removed by extraction with neutral solvents
sjmlce pulps
(14).
Groundwood
95
42
31
27
62
2.5
40
75
55
56
71
22
17
22
6
60
63
7.5
9.5
60
70
55 (50)'
82
18
90
10
70
Kraft, unbleached
50
79
17
20
11.5
130
Kraft, bleached
,
Bleached yield
50 (47)'
82
18
90
11.5
130
Chapter
I 1: Introduction
to Principles
& Practice
of Pulp Bleaching
11
feed a rotary drum filter which, in turn, increases the consistency to 12-14%, (medium consistency).
To obtain higher
consistency
pulp, pressing is required;
presses produce pulp consistencies of 3045% (high consistency).
Oven-dry
Fiber Water,
%
%
Humidity - 5% 98.6
- 50"A>90.7
- 80% 87.0
Air-dried pulp
90
Newsprint'
1.4
9.3
13
10
Press discharge
40
60
Gas-phase bleaching
(high consistency)
30
70
12
88
97
99
0.5
99.5
12
R.,.
=1 + (k/S) - -J(k/S)'
+ 2(k/S)
[11
where:
Roo
reflectivity of an "infinite"
pile of sheets
absorption
scattering
coefficient,
m2/kg
coefficient,
m2/kg.
III
III
Q)
c
OJ
.t:
bletUbiJfg.
13
In pulp
bletu:hlng.
14
Pulp
Type'
Advantages
Disadvantages
Effective,econonUc~
delignification; good
Organochlorine formation;
highly corrosive
Oxidant
Function
Chlorine
Hypochlorite
Chlorine
dioxide
1) Oxidize, decolorize,
and solubilize lignin
2) In s~
amounts with
Cl;" protects against
cellulose degradation
Oxygen
Hydrogen
peroxide
Cor
M
Easy to use;
low capit~ cost
Ozone
Effective; provides
chloride-free effluent for
recovery.
Reductant
Hydrosulfite
Easy to use;
low capit~ cost
Decomposes readily;
linUted brightness gain
~Xylanase
Ca~e
xylan
hydrolysis and aid in
Easy to use;
low capi~ cost
limited effectiveness;
cost
particle
remov~
lignin remo~
~Sodium
hydroxide
Hydrolyze chlorolignin
and solubilize lignin
Darkens pulp
Chelants
EDTA or
DTPA
Improves peroxide
selectivity and efficiency
Cost
'C = chenUc~;
M = mechanic~.
Chapter I 1: Introduction
15
16
- Principles
Pulp Bleaching
Table 7. Dnerlptioll
and Practice
of bletrel1i"g cbemktds.
Stage
Designation
Manufacture
By electrolysis of NaCi
solution; shipped as liquid
under pressure
By reaction of CI with
NaOH (or for Ca(OCI) with
Ca(OH),}; usually on site
Pressurized gas
On-site by reduction of
chlorate
By separation from air;
shipped as cryogenic liquid
or separated on-site
By reduction of oxygen via
organic intermediates;
Shipped as 50% solution
Pressurized
gas mixture.
up to 12% OJ in 0,
Solution
By electrolysis of NaCi
solution; shipped as
50% solution
Solution, -10%
Name
Formula
Chlorine
CI,
Hypochlorite
NaOCI
Chlorine
dioxide
Oxygen
ClO,
0,
Hydrogen
peroxide
H,o,
Owne
O~
Hydrosulfite
Na,S,o.
Enzymes
Sodium
hydroxide
NaOH
Pressurized gas
Solution, 2-5%
Solution
Table 8. Oxldizi"g
equitJlllents
Oxidant
Formula
Weight
(g/mole)
Electrons
Transferred!
Molecule
Equivalent
Weight
(g/mole electrons
transferred)
Equivalent
to
50 kg of CI, (kg)
71
133'
2
2
35.5
66.5
94
67.35
13.5
19
32
34
4
2
8
17
II
24
48
II
Chlorine
Sodium
hypochlorite
Chlorine
dioxide
Oxygen
Hydrogen
peroxide
Ozone
of differnt
bletrel1i"g agenls.
Amount of
Chemical
-"._~---
Chapter I 1: Introduction
17
18
Table'.
Oxidizing
e'l.drllllerUs
Chemical
Applied'
(kg/metric ton
of pulp)
Chlorine
60
Chlorine
23
dioxide
Oxygen
30
'To 30 kappa unbleached
ofbleacltlng
agerUs.
Equivalent
OXEI
Weight Metric Ton
(g/mole)
of Pulp
35.5
13.5
8
1700
1700
3750
softwood
Cost and selectivity are two very important aspects of establishing the proper sequence of bleaching chemicals. Chlorine
is less expensive than chlorine dioxide, so
chlorine should be used earlier in the sequence where more lignin is present and
more chemical is required. Thus, for great.er
economy, the preferred sequence is CEO
instead of DEe. Also, chlorine is less selective than chlorine dioxide, so the former
should not be used at the end of the sequence where the lignin content is low and
the possibility of degrac:fmg carbohydrates
is greater. Thus, to achieve greater for selectivity, the preferred sequence is CEO instead of DEe.
Bleaching sequence designation is specified by TAPPI Information Sheet TIS 060621. The letter designated for each chemical
is used to describe a stage of chemical application followed by washing. Thus, CEO
refers to the application of chlorine (C) followed by washing, then sodium hydroxide
for alkaline extraction (E) followed by washing, then chlorine dioxide (D) followed by
washing. When washing is omitted between chemical applications, letters indicating the chemicals in that portion of the
sequence are enclosed in parentheses. For
instance, C(EO)D refers to the sequence
chlorine, washing, sodium hydroxide addition, oxygen addition and washing, chlorine
dioxide and washing. If the chemicals are
added simultaneously, in this case alkali
and oxygen, the sequence is designated
C(E+O)D.
Examples
of bleaching
sequences are shown in Table 10. It is noteworthy that, in chemi-mechanical
pulp
bleaching, a single application of one chemical is most common.
sefJ'll!'fUS.
Sequence
Comment
CEH
cmrditforrsfor
bleacbing
softwood
kraft jmlp
In an OD(EO)DED sequerru.
(EO)
8
,-5
3.5
70
180
12
5
10.6
70
60
12
Chemical applied,
kg/t
30
l
CIOl
NaOH
End pH
Temperature, C
Tune, min
30
11+
95
30
12
Consistency, %
10...J
8i
~
:g
0.1-
"0
en
5
15
25
10.6
70
60
12
3
60
30
3
5
4
70
180
12
~:
~c
0.01-
0.001
0.01
0.1
10
of bleacltlng
gases.
are
(EO)
delignification
30%
12%
19
20
extraction
12%
Water
NaOH
6. Bleaching flowsheets
There are a number of ways in which
bleaching can be represented in flowsheets.
One example is given in Fig. 5, a block diagram showing the application of chemicals
in each of four bleaching stages. Water is
added to each bleaching stage for washing,
and in most bleaching stages steam is added
to increase the temperature. Effluent from
the oxygen stage is sent to the recovery
system of the kraft mill, but acidic and alkaline effluents from the remaining bleaching stages are discharged, usually after
passing through biological treatment systems.
CI02
CI02
NaOH
Water &
steam
O2
Water &
steam
Unbleached
pulp
EO
Effluent
to recovery
Acidic
effluent
Alkaline
effluent
Mixer
Bleached
pulp
Reactor
Washer
Washed
pulp to
next stage
Washed
pulp from
previous
stage
02 gas
Water
Consistency
Mixer
000000
000000
~~~g~~~~~6~6~
o~o~ooooooooo
Chemical
Effluent
I"
pulp bletU:bI"g.
Within each of these stages, there is usually a series of unit operations as depicted
in Fig. 6. There are often several mixing
stages where steam and chemical are applied to the pulp. The mixture of chemical
and pulp suspension then passes into a reactor which provides sufficient retention
time for bleaching reactions to occur. Pulp
exiting the reactor passes through a washer
before continuing to the next stage.
1\.wide variety of equipment is available
to accomplish the unit operations in each
of the various stages used for bleaching
chemical and (chemi)mechanical
pulp.
Traditionally,
rotary drum filters have
been used as washers between bleaching
towers as illustrated in Fig. 7. Several
other examples of process equipment for
bleaching kraft pulp are shown in Figs.
8-10.
Further details on the chemistry, processes and equipment used in pulp bleaching are found in the chapters that follow.
7. Trends in pulp bleaching
In the last decade there has been an extremely rapid evolution of processes for
production of bleached pulp. Much of this
technological activity has been environmentally driven. There are several important
emerging technologies for manufacture of
bleached pulp: extended, in digester delignification; oxygen delignification; "elemental chlorine-free" (ECF) bleaching, bleaching
with chlorine dioxide, and "totally chlorine
free" (TCF) bleaching, bleaching with oxygen, ozone, and hydrogen peroxide.
Over the last decade various changes
have taken place that will influence bleaching technology for the next decade. There
have been dramatic shifts in fiber supply.
Forest utilization, particularly preservation
of old-growth forests is now much higher
on the public agenda than in the past.
Sustainability of forests is under closer scrutiny than ever before. Increasing restriction
of wood supply and increasing wood cost
must be expected over the next decade,
certainly in a number of important pulp
manufacturing regions. These factors will
require increasing emphasis on maximizing
yield in pulp manufacturing processes. In
the past ten years, extensive legislation on
recycling of paper has been enacted causing significant restructuring, in terms of fiber supply, in the newsprint industry.
In the early 199Os, markets were highly
competitive. There was an oversupply of
pulp which caused significant cutbacks in
production, low prices, and in many cases,
heavy financial losses. This situation stimulated marketing based on environmental
quality criteria. The demand for so-called
"environmentally superior" pulps, particularly those having lower quality and higher
cost, will undoubtedly
suffer in times of
tight markets.The market for the long term
will surely favor competition based on performance, cost, and other traditional criteria for industrial products.
The age and size of pulp and paper
mills is an element in the development
of
technology
that is often forgotten. The
average age of kraft mills in the United
States was twenty years (in 1994) (16).
For example, a mill started up in 1974 may
Pulp
in
(Slo~ge
nots~own)
Pulp
out
..
Fig. 7. Example
::r
"0
'"
~....
......
uslllg rotary
drum
fJtU:Ullm filters.
a0c:
P-
o'
:;)
8
"tI
S'
,.,
:0'
'"
Ro
;y
Pr:;"
Ib
0....,
Pulp
~out
"0
1:1:1
n,.,
'"
::r
5"
rJQ
Fig. 8. Example
for an (OO)D(EO)(DN)D
drum
washers
and diffusion
washers
(Ahlstrom
N
......
Kamyr).
N
N
~"0
,.,
~'"
e:
~Pulp
out
"tI
S'
,.,
:0"
n
'"
8"tI
(EOP)
R
r:;"
Ib
Pulp
out
Pulp
in
Fig. ,.
Examples
ofproeess efjlllpmtnrtjlowsbeets:
Deflbrator
botb using wash presses (SII'"
Upper) aflber
Inc.).
llnefor
bakb pulping
llnefor
23
vironmental campaigns on particular subjects such as industrial use of chlorine. dioxins from pulp bleaching, and old-growth
forestry.The complexity and sophistication
of environmental
criteria have increased
dramatically in the last ten years. Toxicity
testing of bleach plant effluents previously
was limited in Canada to the acute toxicity
test for rainbow trout. Now there is a very
wide array of biological response tests.
There has been a significant increase in the
scope and restrictiveness of environmental
regulations in the last decade; for example,
in 1984 dioxin and AOX were unknown
terms in the pulp and paper industry. Certainly in the next ten years more testing will
be required to meet even stricter regulations.
An important trend in bleaching technology development is the renewed effort to
devise ways to decrease discharge by recycling, concentrating. and burning effluents.
for instance by recycling kraft bleaching
effluents to the kraft black liquor system
for destruction in the recovery boiler. Com-
(ON)
24
plete elimination of kraft bleach plant effluents was originally proposed by in 19(i6
and attempted on a commercial scale in
Canada in 197684(17).There
are also currently several developmental
projects to
eliminate kraft mill bleaching effluent by
independent evaporation and burning.Two
bleached chemithermomechanical
mills in
Canada operate with no aqueous effluent;
all spent liquors are concentrated
and
burned (18). Over the next decade there will
be increasingly less material discharged
from bleaching processes as such processes
are progressively implemented.
of Pulp.
S.A.. Pulping
Processes.
Publishers, New York, 1%5.
a D(EOP)(DN)D
sequence
using
compaction
baffle
10. Stefan,v.Pulp
(1995).
1994.
14. Rydholm. S.A., Pulping
Processes,
Interscience Publishers. New York. 1965.
p.1156.
15. Grundelius. R., "Oxidation equivalents.
OXE
References
4. Rydholm,
Interscience
58(8):38(1995).
9. Brennan. w: Pappens.
37(7):19(1995).
- an
alternative
to active
chlorine."
1991 International
Pulping Bleaching Conference Proceedings.
SPCI. Stockholm. p.
49.
16.}ohnson.
A.. Trepte. R.,Gleadow.
P.. and
Herschmiller.
D
Directions
in the
Fiberline". presented
at the Pulping Horizons Seminar.Washington,
DC. September.
1994.
17. Reeve. D.W:. Pulp
(1984).
18. Evans.T
Startup of MillarWestern's
Discharge BCTMP Mill in Meadow
1992 Pulping Conference Preprints.
PRESS.Atlanta.p.1167.
Zero
Lake."
T APPI
SECTION II:
Raw Materials
Chapter 1:
Production of Unbleached Pulp
James L Minort
USDA Forest Service
Forest Products Laboratory2
Madison, Wisconsin
1. Fiber component. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.1 Fiber sources and characteristics. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
1.2 Fiber supply. . . . . . . . . . . . . .'. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
2. Pulping process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
2.1 Classification of processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33
2.2 Chemical pulping. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
2.3 Mechanical andchemimechanical pulping. . . . . . . . . . . . . . . . . . . . .. 41
2.4 Pulping of recycled fibers
43
3. Composition and properties of unbleached pulps . . . . . . . . . . . . . . . . ..
3.1 Chemical pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.2 Mechanical and chemimechanical
pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.3 Recycled fibers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
44
44
50
52
, The
Forest Products Laboratory is maintained in cooperation with the University ofWisconsin. This article was written and prepared by U.S. Government employees on official time,
and it is therefore in the public domain and not subject to copyright.
25
Chapter n 1:
Production of
Unbleached Pulp
1. Fiber component
Pulp can be derived from wood fibers,
nonwood fibers, and secondary or recycled
fibers.The supply of fiber also varies, changing with availability, fiber production, and
consumption.
1.1 Fiber sources and characteristics
Fibrous material from plants, such as papyrus, wood, bark, and bamboo strips, have
been used as a source of writing materials
since the earliest civilizations. Papermaking,
the formation of paper from separated nbers, originated in China in 105 AD. Its development is credited toTs'ai-Lun, a servant
of the Imperial Court, who used flax, mulberry bark, and rags as his source of fibers.
At that time, parchment was used in Europe,
but during the Middle Ages, it was supplanted by paper made primarily from rags
and rope. The use of wood as a source of
papermaking fiber was not commercially
applied until the mid-1800s. However, because of availability, economic factors, and
technological advances, wood became the
dominant source of papermaking fiber in
North America and is presently the original
source of 99% of the pulp fiber produced
in the United States.
Wood fiber
Although virtually any wood can be
pulped by some process, certain tree species are commonly used for pulp because
of their fiber quality, ease of pulping, availability,and because they may not be as suitable for other wood products. The most
frequently
used pulpwoods
in North
America are listed in Table 1.
The advantages of wood relative to other
renewable plant fiber sources include yearround availability rather than ~a5onal harvest, relative stability when stored as logs
or chips, the ability to serve as a waste resource from other wood products opera-
27
28
i"
North America.
Softwood
Dominant
Secondary
Hardwood
Dominant
Secondary
Spruce, fir,
white pine
Hemlock,
tamarack
Hickory
South
Yellow pines
Cypress
Oaks, gums
Northwest
Douglas-fir,
western
hemlock
True firs,
spruce
Red alder
Lake states
Jack pine,
White pine,
red pine
Red oak,
tamarack
Birch
aspen, maple
Douglas-fir,
western hemlock, spruce,
lodgepole pine
Western red
cedar. true firs
Aspen,
cottonwood,
red alder
Hybrid
poplars
Aspen
Balsam fir
Region
United States
Northeast
Canada"
British Columbia
Oak aspen,
other poplar,
maple, birch
Prairie region
Spruce, pine
Ontario
Jack pine,
spruce
Balsam fir,
larch, red pine
Aspen, beech
Birch, maple
Quebec
Black spruce,
jack pine,
balsam fir
White spruce
Aspen,beech
Birch, maple
Maritime region
Spruce,
balsam fir
Eastern hemlock,
eastern white
pine, red pine
Aspen, birch
Beech, maple
a Reference
(1)
Fig. 1. SebemIItk
IrtIcbelil;
of wood'
Hardwoods
Softwoods
42-49
41-46
O-acetyl-4-0-methyl-
gIucuronoxylan
20-30
O-acetylgalacto-
gIucomannan
Glucomannan
16-20
2-3
4-O-methylglucuro-
noarabinoxylan
Pectin materials
Arabinogalactan
GaIactoglucomannan
Starch
lignin
Ash
Trace
Trace
Trace
20-26
0.2-0.8
8-11
1
2-3
Trace
26-31
0.2-0.4
Extractives
3-8
10-25
Uronic anhydride
3-5
3-4
IPercentageof weight of extracted wood, except
extractives analyses
Lw, IIItewood;
29
30
TR,
Fig. 2. Scbenultk
sectllln of krdwood.
AP, lIXiIIl ptlreru:bymtI; F, wood ftber; EIlI, etlrlywood;
6RB, grollltb ring bollndsry; P, pit; WR, wood ray; and SC SC41arlform plllte.
LIlI, latewood;
N'onwood fiber
The quality of nonwood fiber varies. The
strength of fibers from some bast fiber
plants, such as hemp, jute, and flax, exceeds
that of softwood fibers. In general, however,
the stalk or core fibers from cereal grains,
grasses, and other "straw" pulps are closer
to hardwood fibers in their characteristics.
Nonwood fibers are a major fiber source in
some parts of the world, notably in much
of Asia where wood resources are limited.
At present in the United States,nonwood
fibers are used primarily for specialty paper grades. Cotton fibers, in the form of rags
or cotton linters, are used in rag-content
bond paper and various specialty grades
such as onionskin, maps. charts, and blueprint papers.
Hibiscus cannabinus (kenai) is used in
Asia as a source of papennaking fiber. It has
been studied extensively as a potential fi-
31
40
1000
(/)
Q)
c
c
0
800
600
'C
Q)
E 400
c
~200
o
1952 1962 1970 1976 1976 1986 1990 2000 2010 2020 2030 2040
Year
Sawlogs
Veneer logs
1952-1986,
Pulpwood
Misc.products
Fuelwood
of dem4rul
to 20f0.
Data
from (4).
ber-producing
crop in the United States
because it can be grown in the South and
in areas where wood is not abundant. largescale trials have been conducted, but there
is no commercial
kenaf pulp mill in the
United States at present.
Secondary
fibers
and wood
residues
The term "secondary fibers" refers to recycled papers. Secondary fibers are categorized according
to a single industry-wide
classification
scheme that has been maintained for many years by the Institute for
Scrap Recycling
Industries
(lSRI). These
categories (of which several dozen are in
use commercially)
are aggregated into five
principal
groups that are also recognized
by industry trade associations and by the
U.S. Department
of Commerce. For statistical purposes,
these categories
are Old
Newspapers
(ONP), Old Corrugated Containers (OCC), Mixed, Pulp Substitutes, and
High-Grade
Deinking. ONP is commonly
reconverted
into newsprint
and therefore
requires bleaching. It may be used for paperboard or non-paper products that do not
require bleaching. acc are also reconverted
to their original products and do not require
bleaching.
However, some mills upgrade
OCC to bleached printing and writing papers (2,3). Mixed papers, as the name implies, contain a variety of fiber types, some
of which may be bleachable. Pulp Substitutes are clean wastepapers such as envelope cuttings, tabulating
cards, and other
converting
wastes. Although
Pulp Substitutes may include colored papers, the white
papers are used with no further bleaching.
The High-Grade Deinking category includes
coated and fine papers that are bleachable.
The rate of recycling and use of secondary fibers in the United States has increased
substantially in the 1990s.A record 26 million tons of secondary
fibers were consumed by the U.S. industry
in 1993. The
secondary fiber input represented
about
30% by weight of the final production.
In addition to recycled paper, a substantial portion of the total pulp fiber input is
obtained as wood residues, primarily from
sawmills and plywood
mills. Wood chips,
shavings, sawdust, and other residues accounted for roughly 40% of the approximately 100 million
cords of pulpwood
consumed
Mmllillly
by U.S. mills in the e:J.fly
1990s; the remaining
60% of pulpwood
consumption
was obtained almost entirely
from domestic pulpwood
harvest.
Pulp Bleaching
-Principles
and Practice
the rate and increase pulp yield. Such processes have not been applied commercially
in the United States, but they may appear
in new procedures presently under development (see following text).
pulping
41
42
water temperature in the pit to rise to 70 90C to achieve a higher grinding rate,
lower energy consumption, and higher pulp
strength than are possible at lower temperatures.
Presteaming
of wood is practiced in
Europe to add moisture and to soften the
lignin. The procedure is especially advantageous with some hardwoods. In the late
1970s and early 1980s, it was demonstrated
that pressurizing the region surrounding a
stone grinder to 100-300 kPa (1-3 attn) markedly improves the strength and fiber integrity of the pulp. This process retains the
advantages of low energy consumption and
high opacity (42). Recently, the pressure has
been increased to 450 kPa, with continuing improvements
in properties. This is
called the Super Pressure Groundwood process (43).
Refiner mechanical pulping
The conventional groundwood process
requires bolts of roundwood as raw material. In the 1950s, the refiner mechanical
pulping (RMP) process was developed,
which produced a stronger pulp and utilized various supplies of wood chips, sawmill residuals, and sawdust. However, the
energy requirement of RMP is higher and
the pulp does not have the opacity of stone
groundwood pulp.The refiners are rotatingdisk attrition mills. The plates are paired
face-to-face with a small interval between
them. Either one disc rotates against a stationary disc or they both move in a
counterrotating
manner. The chips are fed
through channels near the shaft in one of
the discs and move toward the periphery
while undergoing attrition. They emerge
from the periphery as single fibers or fiber
fragments, including ribbons and fibrils that
are formed by the unraveling of the spiral
fiber walls of individual fibers.This process
is termed fibrillation. These thin, flexible
elements considerably improve the bonding properties of mechanical pulps.
Th~rm()m~chanical pulping
the refiner bars. Refining can also be performed under pressure. This modification
is called thermomechanical
pulping (TMP).
If the presteaming time and temperature are
limited, higher steam pressures can be used
in the refiners without reducing the pulp
quality. The heat can then be recovered for
other uses such as paper drying At temperatures from 100C to about 150C, wet lignin softens but does not flow.When the hot
chips are fiberized in a refiner at high consistency, whole individual fibers are released; separation occurs in the S1 layer of
the cell wall, and the same ribbonlike material described for RMP is produced. The
amount of fibrillization depends on the refining conditions and is critical to the properties of the pulp. Much less fiber
fragmentation occurs in TMP pulps than in
groundwood pulps or in those produced by
RMP. The production
of TMP pulps increased dramatically after its introduction
in the early 1970s because they could be
substituted for conventional groundwood
pulps in newsprint blends to give a stronger paper. Therefore, smaller quantities of
the more expensive, lower yield chemical
pulps were required for reinforcement.
Unfortunately, the TMP process consumes
considerably more energy than does RMP.
Combinations of mechanicaland
chemical pulping
Chemicals may be added to the wood or
fiber in any of the mechanical processes to
improve strength properties, reduce mechanical energy, reduce the shive content,
or bleach the pulp. Very often there is a
trade-off in properties or benefits obtained,
and each process is optimized to minimize
costs for the particular properties desired.
Frequently, chemical treatment lowers the
yield and decreases the optical properties
of brightness, opacity, and light scattering.
Chemithermomechanical
pulping
The strength properties
of thermomechanical pulps can be increased by a mild
pretreatment with 1-6% sodium sulflte at pH
9-12.The chips are impregnated with chemicals, steamed to 130 - 170C, then refined.
The refining can be at atmospheric pressure
recycledftbers
(CMP). The regular CMP process for softwoods uses sodium sulfite, 12-17% on
wood, 10 - 60 min at 130 - 170C, and twostage refining at atmospheric pressure (44).
Variations include using bisulfite at lower
pH, longer pulping time, and vapor-phase
pulping. Mechanical pulps can also be upgraded by sulfonating the oversize reject
fractions obtained by screening mechanical pulps. This fraction contains long fibers
that can be chemimechanically
pulped to
produce a stronger reinforcing pulp for the
main mechanical pulp production.
Semichemical pulping
Semi chemical pulping (see Table 3) is
chemical pulping that has been terminated
at a higher yield and lignin content than full
chemical pulping.These pulps typically are
used unbleached in corrugated boxes.
2.4 Pulping of recycled fibers
Recycled fibers have previously been
pulped by one of the existing wood pulping
processes. Hence, the equipment used to
slurry wastepapers back into a pulp form is
called a repulper, or if it is understood that
recycling is being discussed,
simply a
(45).
Function
Unit operation
Bale de-wirer
High-density
pulper
Wastepaper
consistency,
High-density
cleaners
pulped to approximately
chemicals added
Coarse screens
Fine screens
Remove spherical
Washing
Belt press/screw
press
Thru-flow
Thickens
15%
Flotation
cleaners
43
Forward-flow
cleaners
Remove nonattached
High-intensity
dispersion
ink specs
OAF clarifier
Bleach towers
Provide residence
stripping
and color
44
Pulping process
Kraft
Pulp yield
Lignin
Glucan
Mannan
Xylan
50
5
6.5
4
<;
37
8.6
5.8
50
5
5
4
36
36.6
79
8
18
9
6
3% Polysulfide
Spruce (48)
7% Polysulfide
Kraft
Polysulfide
55
Acid sulfite
Aspen (49)
Beech (50)
Kraft
55
58
Acid sulfite
64
Sulfite
45
Kraft-AQ
50
ASAM'I
ASAMn
51
3
6
73
77
11
5.5
80.1
12.8
5.3
2.2
78
1.9
87.5
1.7
9.6
10.8
3.2
1.9
1.8
53
75.5
24.5
76.7
23.3
25.7
74.3
and methanol
pulper. Repulpers may be of various designs, but the function is to re-swell the fibers and to gently break up the paper
structure with minimum damage to individual fibers. Repulping may be done at different
consistencies
and pH levels
depending on the starting material and the
desired outcome.Various chemicals such as
surfactants and bleaching agents may be
added at this stage. The major treatment of
recycled pulp is contaminant removal, including the deinking of printed papers.Various screening and cleaning techniques are
employed to remove the wide variety of
contaminants that may be present. An example of a sequence of unit operations for
pulping and cleaning recycled papers is
given inTable 4 (45).
Deinking can be particularly problematic
and, because of its importance, special processes have been developed. Historically,
two major techniques of deinking have
been used: washing and flotation.The washing process is similar to laundering where
detergents are used to wash the contaminants from the fibers. Flotation is a method
of removing hydrophobic
contaminants
such as oil-based inks. It is based on the fact
that such materials selectively cling to air
bubbles passing through the aqueous sus-
processed
ened.
or treated
50
'"
~'" 40
if 30
o
'" 20
~
:>
10
10
20
30
Kappa number
40
and CE
chemical composition depend on the conditions employed. For example, in the kraft
process, both dissolved hemicelluloses and
lignin reprecipitate onto the fibers, esp~cially if there is a decrease in alkalinity at
the end of the pulping. In wood, the xylans
in hardwoods and the glucomannans in softwoods are substituted with acetyl groups.
Saponification of these esters under alka.
line pulping conditions
leads to lessbranched structures,
which are readily
accommodated onto the surface of the linear cellulose microfibrils. The higher alkalinity in extended
pulping
serves to
minimize the reprecipitation
of lignin, but
the reprecipitation of the hemicelluloses is
also decreased. Another factor that influences the chemical composition of kraft
pulps is the use of pulping additives, such
as anthraquinone
or polysulfide, which
leads to increased pulp yields through
greater retention of the hemicelluloses.
The chemical composition of pulps from
various chemical pulping processes is given
inTable 5. More than 98"10of the pulp weight
is usually accounted for by the summation
of lignin and the five major wood sugarsglucose, mannose, xylose, galactose, and
arabinose. In summative analyses, the sugars are calculated as if they were in the polymeric (i.e., anhydro) form. Additionally,
hemicelluloses contain uronic acid units;
for example, the uronic acid content of pine
kraft pulp is about 1% (46). For many purposes, pulps may be chemically characterized by analysis for glucose, mannose, and
xylose. The glucose analysis provides an
45
estimate of cellulose after making a correction for glucomannan based on the mannose content.The xylose analysis represents
the amount of xylan. Galactose and arabinose are present primarily as substituent
groups on the major hemicellulose chains.
There are exceptions to this general rule
as,for example, in the arabinogalactan from
larch.
The exact chemical composition
of
chemical pulps is not as important in influencing the physical properties of the pulps
as are other factors such as morphological
differences. However, the lignin content is
important to bleaching and optical properties. Carbohydrate analyses provide information on pulp yields and the relative
selectivity (removal of carbohydrates compared with removal of lignin) of the pulping
process. The proportion of glucose in the
total carbohydrate analysis provides an indication of the weight percent yield of the
pulp because, as a first approximation, the
cellulose content of pulp can be considered
to be constant on a wood basis throughout
pulping, and therefore, for a given degree
of pulping, differences in yield are due to
differences in hemicellulose retention.
During delignification, the pulp fibers
become more flexible and malleable, and
on application of relatively low pressures,
delignified pulp fibers can be flattened to
form strong, well-bonded papers (Fig. 9).
Interfiber bonds consist primarily of hydrogen bonds, and the extent of bonding of a
fiber is proportional to the surface area of
the fiber in physical contact with other fibers. Although the location of hemicelluloses and their contribution to fiber strength
is not completely understood, an increased
hemicellulose content generally correlates
with increased fiber bonding.
The ash content is a low percentage of
the pulp weight, but the trace metals in pulp
can have a significant influence on bleaching. Metals may affect the bleachability of
unbleached pulps by forming colored complexes with organic pulp constituents, particularly with phenolics such as lignin.
Heavy (transition) metals also interfere with
oxygen-based bleaching agents such as oxy-
46
Pulp Bleaching
-Principles
Fig. ,. Electrort
and Practice
micrograph
of softwood
gen, hydrogen peroxide, and ozone by catalyzing their decomposition and often initiating the formation of intermediate
free
radicals such as the hydroxyl radical, which
degrade the pulp. Metals are initially present
in wood and are also introduced from the
process water and equipment. Of the common transition metals, copper and iron are
often harmful. Manganese can sometimes
show positive effects with oxidative reagents depending on conditions (51).
The results of some ash analyses performed at the Forest Products Laboratory,
USDA Forest Service (52,53) are shown in
Table 6. Ash analysis data are very dependent on local processing conditions as well
as the wood source. For example, kraft
pulps produced at the Forest Products Laboratory tend to be high in copper and low in
manganese compared with pulps from
other sources. Mills often use chelating
agents or mineral acids to reduce the heavy
metal content of pulps. Iron is particularly
difficult to remove by any means. Some resultS of pulp treatment with the chelating
agent, diethylenetriaminepentaacetic
acid
pentasodium salt (DTPA), are also shown
in Table 6.
Properties
Pulp physical properties that affect the
bleaching operation include fiber strength,
kraft /JtIJW1'.
47
Pulp'
Spruce groundwood
Untreated
Treated
Loblolly pine groundwood
Untreated
Treated
Aspen groundwood
Untreated
Treated
Loblolly pine kraft
Untreated
Treated
Aspen kraft
Untreated
Treated
Commercial pine kraft
(untreated)
Laboratory-made
pulps, except
Metal (ppm)
Zn
K
Ca
Mg
Na
286
<60
1,530
1,240
329
270
185
<60
9
3
117
<60
572
504
111
96
1,410
238
2
2
16
4
158
<50
1,190
1,040
165
144
<50
<50
49
37
66
24
14
4
<50
<50
2,470
1,730
465
329
<50
<50
4
2
13
12
63
30
19
7
<50
<50
3,600
2,950
767
645
<50
65
73
33
Mn
Fe
Cu
85
18
11
10
2
5
105
13
46
16
29
28
3
5
30
2
18
16
20
6
as noted.
48
been utilized to measure the pore size distribution of pulps (58,59). As wood fibers
are pulped, the size of the lignin fragments
that diffuse out increases, indicating that the
size of the pore openings is increasing.
Researchers have observed that treatment of unbleached pulps with hemicellulase enzymes improves the bleachability of
the pulps (see Chap. IV 7). Removal of some
hemicelluloses
apparently improves
the
accessibility of residual lignin to chemical
bleaching agents. One explanation is that
the accessibility is restricted by xylan readsorbed on the kraft pulp during the
pulping process (60) and that the enzymes
act to remove this restriction. The issue of
whether the hemicellulose hydrolyzed by
the enzyme is re-adsorbed hemicellulose has
not been resolved, but data showing that
the cell wall pore sizes are larger after the
enzyme treatment (61) certainly suggest
that hydrolase enzymes do remove restrictions to inner cell wall penetration.
Heterogeneity
The heterogeneity
of the unbleached
pulp has a strong influence
on pulp
bleachability and, together with product
specifications, influences bleaching strategy
(62). Because of the heterogeneity of wood
and the topochemical nature of the pulping
Pt:Ocess, unbleached pulp is composed of
fibers having a distribution of lignin con.
tents. A specified average lignin content,
as determined by kappa number or K number, is the usual goal of pulping operations.
In the pulp mill, it is difficult to consistently
reach the same average value, let alone to
produce a pulp in which all fibers have the
same lignin content.
Mter the pulped chips are defibered,
knots and incompletely
delignified chip
fragments remain unfiberized. Unbleached
pulp is screened before bleaching, but even
after screening, small fiber bundles (shives)
are still present. Shives are especially
troublesome because of their relatively high
lignin content, density, and color. For these
reasons, they are not as easily bleached as
free fibers. For some products, a very low
shive content is desired. If shive removal is
an objective of bleaching, the severe treat.
49
50
20
01
~-C\J
16
100
12
15
80
(J)
"0
.5
....
CO
(J)
90
14
70
12
10
60
10
6
I3
o
o
10
20
30
Tensile
40
50
60
index, kNmlkg
70
80
Klason
lignin
%
Fig. 11. Comparlsrm
Bleachability
Bleachability
refers to the ease with
which pulps from different processes or
after different pretreatments can be brightened. The result is expressed as the final
brightness
obtainable
with a specified
bleaching sequence or by the amount of
chemical required to reach a target brightness. In this case, each laboratory selects
its own control bleach sequence as a benchmark for comparison. A general bleachability test has been proposed by which
different bleaching chemicals or different
pu1p samples can be compared (6]). The
decrease in lignin content and brightness
increase are both determined. The oxidation equivalence of various reagents is based
on their reaction with iodide.
In industrial practice, the term bleachability, when used for a given pulping process, refers to the amount
of lignin
remaining in the unbleached pulp. Therefore, application of standard delignifying
bleaching chemicals is proportional to the
residual lignin content as determined by
reaction with oxidizing agents. Test meth-
40
30
20
10
54
52
50
48
46
90
35
30
25
20
15
10
5
50
of various
Hypo
Kappa
number
number
lipi"
determ/ruJttOff
Mechanical
pulps
and chemimechanical
Permanganate
number
Unbleached
pulp yield
%
methods.
of the original wood (see Table 2).The material dissolved or released during pu1p production has been identified
as lignin,
lignans, hemicellu1oses, and lipophilic extractives (67). Ash analyses of some groundwood pulps are given in Table 6. The
transition metal content of high yield pu1ps
is especially important because these metals catalyze the decomposition of hydrogen
peroxide, a bleaching agent frequently applied to high-yield pulps.
The main contributor to physical property differences between chemimechanical
and chemical pu1ps is lignin. One function
of lignin in plants is to impart stiffness and
cohesiveness to the fibers and the cell wall
components. Thus, high-lignin content fibers are stiff and tend to retain their cylindrical shape during the drying and pressing
steps in papermaking.
Compared
with
delignified pu1ps, high-yield pulp fibers do
not flatten and "conform" to each other.
Therefore, papers from high-yield pulps
have a lower degree of interfiber bonding
than those from kraft pulps. An electron
micrograph of newsprint composed of 75%
spruce groundwood and 25% spruce su1fite
pulp is shown in Fig. 12. Although the ends
of some fibers are closed because of the
action of the razor blade used for cutting,
mlcrogrtlpb
of newspri"t
cmrsUU",
of 75% sprwe
51
g1'Ollllllwooll.
52
Pulp Bleaching
-Principles
and Practice
11 R~tYdad fib~R
Composition
The major problem in any type of recycling is removal of contaminant<;.These can
53
54
chromophoric
group, a smaller, water-insoluble fragment and a charged, watersoluble fragment may result. Some insoluble
fragments may retain a slight yellow color.
The acid anthraquinone
dyes are problematic because reduction to hydroquinones imparts a yellow or brown color, and
the dyes are easiIy reoxidized to the quinone
state. In the ionic state, hydroquinones are
more water-soluble and the dyes are then
amenable to removal by washing before
they are reoxidized to their quinone form.
Fiber-reactive
dyes that are covalently
bonded are very difficult to remove and
often contain a quinone function.
Color stripping
Because of the chemical constitution of
the common dyes, oxidative agents alone
usually cannot adequately remove color
from dyed recycled papers.Therefore, color
stripping is generally a separate operation
as part of recycled paper bleaching (Table
4). If hydrogen peroxide is used in the
pulping or deinking stage and alkali yellowing is avoided, a single subsequent reductive bleaching stage with sodium dithionite
(NaZSZ04, also called sodium hydrosulfite)
may be sufficient. A two-stage "post-bleaching" with hydrogen peroxide, followed by
dithionite or formamidine sulfinic acid (FAS,
H1NCNHS01H, also called thiourea dioxide), may be used for high brightness. Obviously, the chemicals in the two stages are
incompatible, and residual peroxide must
be washed out or destroyed before the reductive stage. Dithionite is also subject to
air oxidation. The sequence of oxidant followed by reductant is usually recommended
because the effects of reduction of chromophores are more easily reversed than are
those of oxidation (79). However, in at least
one published example (80), bleaching
with FAS followed by hydrogen peroxide
improved brightness significantly compared
to reversing the order of these operations.
The chemical classification of the Colour
Index number system (81) combined with
the known analytical reactivity of many dyes
toward dithionite has been used to estimate
the stripping characteristics of most identifiable dyes (82). Dithionite can effectively
Acknowledgment
I am indebted to John Hatton, PAPRICAN,
and Peter Ince, USDA Forest Service, for
providing some of the information fOlmd
in the text, figures, and tables comprising
this chapter.
References
1. Hatton,].
v., personal
communication.
2. Nguyen,
X. T., Shariff,
P. E, Earl, Earner,
(1993)
55
19. Greenwood,
B. F., "Extended
Delignification, a Bleaching Stage?," Bleach Plant
Operations
Short Course Notes, TAPPI
PRESS, Atlanta, 1992, p. 41.
20. Cyr, M. E., Embley, D. F., Macleod,].
TapPiJ. 72(10):157
(989).
21. Dillner,
(1993).
M,
56(2):35
6. McGovern,].,
in Pulp
Chemical Technology
eOO., Wiley-Interscience,
Vol. 1, Chap. 3.
Paper, Cbemistry
O. P. Casey, Ed.) 3rd
New York, 1980,
Gratzl,).
D. A. I.;
S., Wood
Pulp
Pap.
Sci.
C-
17. Johansson,
B., Mjoberg,].,
Sandstrom, P.,
Teder, A., Svensk Papperstidn.
87(0):30
(1984)
18. Kubes, G. J., Fleming, B. I., Macleod,
].
M., Bolker, H. I.,J Wood Cbem. Tecbnol.
3(3):313 (983).
(982).
B. F., Phillips,].
450):19
(992).
27. Blain,T.].,
76(3):137
TapPiJ.
(993)
Sym54(4):52
38. Cronlund,
M. and Powers,).,
"Bleaching
Responses ofALCELL Organosolv Pulps using Conventional and Nonchlorine
Bleaching
Sequences,"
TAPPI
Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, 1991, Book 2, p. 547.
39. Schroeter,
M. C. and Dahlmann,
G.,
"ORGANOCELL
Simplifies
the Solvent
Pulping Process," TAPPI Pulping Conference Proceedings,
TAPPI PRESS, Atlanta,
1991, Book 2, p. 646.
40. Gottlieb, K., Preuss,A.W, Meckel,]., Berg,
A., "ACETOCELL Pulping of Spruce and
Chlorine-Free
Bleaching," Solvent Pulping
Symposium
Notes, TAPPI PRESS, Atlanta,
1992, p. 35.
41. Poppius-Levlin,
74(3):113
(1991).
K., Mustonen,
R., Huovila,
L., TapPiJ
34. Kleppe,
T.,Sundquist,].,
28. McDonough,T.J.
and Herro,].
65(9):117 (1982).
56
Pap. 54(6):76
(991).
(1980).
F., Tappi
48. Rydholm,
S. A., Pulping
Processes,
Interscience,
New York, 1965, p. 1156.
49. Springer, E. L., Tappi 54(12):2059
50. Kordsachia,
O. and
41(7):3400987).
Patt,
(1971).
R., Papier
J. D.,
Pulps
- Comparison with Hydrogen Peroxide,"TAPPI
Pulping Conference
Proceedings,
TAPPI
PRESS, Atlanta, 1986, p. 671
D., Tappi
Pap.
C.
60. Kantelinen,A.,
Hortling, B., Sundquist,].,
Linko, M., Viikari, L., Holzforscbung
47(4):318 (1993).
61. Yu, X., Minor,]. L., Atalla, R. H., Labbauf,
M. M., Farrell, R. L., "Effect of Hemicellulase on Unbleached
Softwood Kraft
Pulp," International
Pulp Bleaching Conference Proceedings,
Technical
Section,
Canadian
Pulp and Paper Association,
Montreal, 1994, p. 63.
62. Hamlin,M.P.,"Impact
of Unbleached
Pulp
Quality on the Bleach Plant Operations."
Bleach Plant Operations
Short Course
Notes, TAPPI PRESS, Atlanta, 1992, p. 31.
63. Wartiovaara, I. and Toikkanen,
68:630 (986).
Pap. Can
0.,
66. Misra, D. K., in Pulp and Paper, Cbemistry and Cbemical Tecbnology O. P.Casey,
Ed.) 3rd edn., Wiley-Interscience,
York, 1980 Vol. 1, p. 553.
New
~--
62(12):803
57
80. Heimburger,
S. A. and Meng, T. Y, Pulp
Pap. 66(1):79 (1992).
81. Colour Index, 3rd edn., Society of Dyers
and Colourists, Yorkshire, England, 1971.
Barton, R. W., Tappi 45(2): 178A (1 %2).
69. Axelson,
P. and Simonson,
R., Svensk
Papperstidn.
85(15):RI32
(1982).
83. Troemel,
104(2):74
70. Leask, R.A., in Pulp and Paper Manufacture (M.]. Kocurek R. A. Leask, Eds.) 3rd
edn., McGraw-Hill, New York, 1987, Vol.
2, Chap. 11, p. 157.
84. TAPPI
Pulp
CA#94060608.
71. Adler,
E. and H:iggroth,
S., Svensk
Papperstidn.
53(11):287,
321 (1950).
Pulp Pap'.
75. Joachimides,
T. and Hache, M., Tappi j.
74(1):211 (1991).
.
76. Allen,]., Tappi 45(2): 170A (1962).
77. Risser Associates, "The Magazine Wastepaper Stream: Addressing
the Challenge;
Background
report for Magazine Publishers of America, Magazine Publishers
of
America, New York, 1990, p. 28.
78. Freeman,
Claxton,
(1991).
G., Wochbl.
(1976).
Papierfabr.
Bleaching
Committee
85. Heimburger,
S. A. and Meng, T. Y., Pulp
Pap. 66(2): 139 (1992).
87. Shackford,
L.,Pulp
Pap. 66(2):75
88. Angulo,].
E., Tappij.
74(8):135
(1992).
(1991).
N.,]
Pulp
90. Abadie-Maumert,
E A., and Soteland,
Ozone Sci. Eng. 7(3):229 (1985).
N.,
S.,
"A Non-Chlorine
RepulpingAide
for WetStrength Destruction," 79th Annual Meeting Proceedings, Technical Section, Canadian Pulp and Paper Association, Montreal,
1993, p.A62.
93. Walsh, P. B., Hill, R.T., Dutton,
Pap. Recycl. 3(1):9 (1993).
D. B.,Frog.
SECTIONII:
Raw Materials
Chapter 2:
Bleaching Chemicals:
Chlorine Dioxide
Maurice C. Fredette
Sterling Pulp Chemicals, Ltd.
Toronto, ON
Canada
1. Properties.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Process chemistry.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
61
62
3. Generation systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 62
3.1 Atmospheric processes
63
3.2 Vacuum evaporator processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 64
4. Testing.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . ..
5. Safety hazards
67
67
59
Chapter n 2:
Bleaching Chemicals:
Chlorine Dioxide
1. Properties
The properties
of chlorine dioxide,
shown inTable 1,influence its manufacture
and storage. Because chlorine dioxide is
unstable as a gas and can only be stored as
a solution of approximately
1% in water
[Fig. I (1)], it must be generated on-site at
the pulp mill. All production, handling, and
storage systems control the concentration
of chlorine dioxide in the gas phase.
Most processes use air or a combination
of steam dilution and vacuum to keep the
partial pressure of chlorine dioxide below
100 mm Hg (1). At this vapor pressure
and at typical process temperatures of 4070eC, the gas is stable for at least five seconds (1); in commercial
processes, the
time to convey chlorine dioxide from the
generator to the absorption water is 0.5
seconds. Once in solution, chlorine diox5eC in
ide is stable and can be kept at
the dark for several months with little
change in concentration providing the container has no gas space.
20
18
16
(.)
14
12
C
o
:;:;
:c
(.)
4
2
0
20
40
60
80
100
120
of eblorlf8e
140
mmHg
_ CI- + 3 HP
[11]
2. Process chemistry
C103' + 6 H+ + 6 e'
Steps must be taken to minimize this reaction by careful choice and control of reaction conditions.
The mechanism of chlorine dioxide formation has been extensively studied and is
described in detail elsewhere (3, 4). In all
mechanisms, chloride plays a crucial role
as evidenced by its presence in all chloratebased reaction media and by the trace
amounts of chlorine in the chlorine dioxide formed. No chlorine dioxide is formed
if chloride ion is not present in the reaction medium. Chloride ion is introduced
into the system by reduction of chlorate to
chloride (reaction [11)) or by addition of
chloride in the feed. Rapson (5) proposed
the following mechanism where chloride
ion is the reducing agent:
CI03'
[1]
ClO;
-- CIO,
[2]
+ e'
The choice of reducing agent for chlorine dioxide generation from chlorate has a
great bearing on optimum reaction conditions, by-products, and economics. Production from chlorite (CIO,-) is uneconomical;
reaction [2] is reversible and chlorite is usually synthesised from chlorine dioxide.
Commercially used reducing agents for
production of chlorine dioxide from chlorate are sulfur dioxide (SO,), methanol
(CH30H), chloride ion (Cn, and hydrogen
peroxide CHP,). Their half reactions are
as follows:
+ HP
_ HCOOH
[3]
+ 4 H+ + 4 e- [4]
[5]
[6]
+ 4 H+
_ 4 CIO,
+ HCOOH
+ 3 HP
[8]
[9]
Fig. 1. Equilibrium
62
4 CI03-
~"iS. 10
-001
'x
8
o
'0
6
~
';::
61
HCI03 + HCI-
HCIO, + HClO
_
2 CIO, + HP
HCI03 + HClO,
[12]
HCIO + HCI-
[14]
CI, + HP
[13]
3. Generation systems
In this section, commercial chlorine dioxide generation systems are described in
a sequence which closely follows the order
of their adoption by the pulp industry. The
evolution of the technology has been dictated by the changing ability of pulp mills
to effectively utilize the by-products and
also by the need for larger and more reliable chlorine dioxide plants. Changes have
63
64
3.1 Atmospheric
processes
[15]
Vent
Chilled
water
To help avoid this problem, enough sulfuric acid is fed to the Mathieson generator
to create a 450-500 g/L acid concentration
(9-10 N H2S04)' The acid (2-2.5 tit ofC102)
overflows from the generator and must be
used for tall oil acidulation, recovered with
black liquor for makeup sulfur, or neutralized and discharged. Some unreacted s0dium cWorate also leaves the generator with
the acid; this, and the contribution of reaction [16], limits the yield to about 87%.
The Solvay process uses methanol as the
reducing agent, also in a 450- 500 g/L sulfuric acid solution. The reaction, based on
equation [8], is
4 NaCIOj + H2S04 + CHpH
2 Na2S04 + HCOOH + 3 HP
-> 4 CI02 +
[17]
Cl02
absorber
C102 and Air
CI02
solution
...
QI
Cooling
water
a.
a.
";:
.....
Air
& S02
Spent
acid
Air
Fig. 2. Flowsbeet
of cblorine
tUoxUk
In tbe Matblesofl
proeess.
V\
by-product
93%.
As pulp mills decreased sodium and sulfur losses and also increased their use of
chlorine dioxide, sodium/sulfur
by-prod-
65
66
Pulp Bleaching
Purchased
+ 1/2 CI2
1/2C12 + 1/2S02 + HP
Generator
Excess
HCI + 1/2H2S04
(21)
HydrocWoric acid processes can be operated independently (R5, SVP-HCI) or integrated with an on-site cWorate plant (R6,
Lurgi, Chemetics, and Day-Kesting processes) as shown in Fig. 4 (22-26).
The
key reactions are:
(a) chlorine dioxide is made by reaction [22]
Chlorine
& air to
scrubber
& vacuum
Generator
evaporator
crystallizer
CD
"-
H2SO4
8
u
L
tank
Cl02 + 1/2
(20)
NaCI
Jltg. 4. DUlgram
of I"tegrwletl
CD
"-
-e
0
fII
.Q
c(
cblorl~
NaCi + 3 HP
Filter
cake
mix
CI2
and Practice
Chilled
water
Filter
-Principles
NaClO, + 3 H2
(23)
CI02 + 2 H2
(25)
These processes produce no sodium sulfate. The integrated plants burn 0.7 t of CII
t of CI02 (reaction [24]) to make the required hydrocWoric acid and therefore contribute
to balancing
the NaOH/CI2
purchases of the mill. Integrated plants require significantly more capital and space
compared with other chlorine dioxide
plants.
I"-CD
::I:
The R8/SVP
NaG109
+ reducingagent
may be represented
of t:blort~
dioxide
I"
tbe R au
SW series processes.
as
~ 3 Cl02
(26)
The stoichiometry
based on equation
(26) does not take into account the 0.03 t
of CH,OH/t of CI02 which leaves the generator unreacted in the gas phase and dissolves in the chlorine dioxide solution.
Some of the formic acid (HCOOH) reacts
further
HCOOH ~
C02
+ 2 W + 2 e-
[27]
Na3H(SO)2 ~ Na2S04(solid) +
NaHS04 (solution)
[28]
[29]
+ Na2S04
NaCI03 + HP
NaOH + HCI03
[30]
[31]
with a lowering
due to extended
bleaching, may
ing processes to
requirements.
67
4. Testing
Analysis of chlorine dioxide solution and
generator liquor is required for efficient
plant operation.
Most tests for chlorate,
chlorite, chlorine, and chlorine dioxide involve the oxydation of iodide ion to iodine
which is titrated with a reducing agent such
as sodium thiosulfate or sodium arsenite
(35). pH is used to control the reaction and
differentiate the chlorine species involved:
CI2+ 21-~
[32]
ClO; + 4 r + 4 W
pH,
- 1 N)
CI- + 2 HP (acidic
[34]
5. Safety hazards
Because chlorine dioxide gas is unstable
(3), it must be handled carefully and within
accepted limits. Generators are designed
to withstand chlorine dioxide puffs up to
200 mm Hg of chlorine dioxide. A puff (1)
is the name given to the decomposition of
chlorine dioxide:
2 CI02 ~ CI2 + 2 02 + heat
[36]
68
References
1. Paulet, G., and Desbrousser, S.,Archives des
Maladies Professionnelles,
de Mededne du
Travail et de Securlte Sociale (Paris) 33:59
(1972); 35:797 (1974); 31:97 (1970).
2. Haller, ].E, and Northgraves,
39:199 (Apri11955).
WW,
Tappi
W.H., Can.]
6. Woodside,
V., and Macleod,
Trade] 137(8):26 (1953).
K.S., Pap.
9. Partridge,H.D.,
(1%1).
10. Atkinson,
(Oct
Rapson,WH.,
Tappi 44:698
PRESS, Atlanta,
p. 169.
12. Fredette,
M.C., "New ClO, Generation
Capacity" I 990TAPPI Bleach Plant Operations Short Course Notes, TAPPI PRESS,
Atlanta, p. 159.
13. Sepall, 0., and Buser. R.C., U.S. Pat. No.
3,347,628 (Oct. 17, 1%7).
14. Read, R.}., Pulp
T506 (1%7).
15. Partridge,
H.D., Atkinson,
E.S., Schulz,
A.C., Tappi 54:1484 (1971).
16. Partridfje,
H.D., Schotpflt,
D,<;,)" :)~h\llil,
(Oct.
and
69
30. Fredette,
M.C., U.S. Pat. No. 4,473,540
(Sept. 25, 1984) and 4,627,%9
(Dec. 9,
1986).
31. Eka-Nobel, "Methanol-Based
SVP-Lite Reduces By-Product
Chlorine,"
Pap. Ind.
Sept.-Oct.
1990:7 (1990).
32. Szell, M., and Fredette, M.C.," The Development of the ERCO RIO Process"CPPA
Annual Meeting Proceedings, Tech. Sect.,
CPPA, Montreal, 1994, p.A211.
33. Isa, I., Yamamoto, H., Shindo, S., Shibuya,
M., Can. Pat. 1,170,019 (July 3, 1984).
34. Sokol,j.C.,and
Conkle,j.,"Peroxide
Based
CIO, Process," CPPA Annual Meeting Pr0ceedings,
Tech. Sect. CPPA, Montreal,
1990, p. B47.
22. Hatherly,D.G.,Can.
29, 1974).
(Oct.
35. Standard
Testing Methods, Tech. Sect.,
CPPA, Montreal, Method No.]14P
Pap.
36. Fredette,M.C.,"CWorine
Dioxide Solution
Strength Losses in Storage" Spring Conference Proceedings,
Tech. Sect. CPPA,
1988, Session 3-2.
T.D., Pulp
G., Pulp
Pap. Can.
81(4):30
(Sept.
Foot Notes:
1. ERCO R3, R3H, R5, R6, R7, R8, RIO, Rll,
R12, R13 are trademarks owned by Sterling Pulp Chemicals and Sterling Canada
Ltd.
2. SVP, SVP HCI, Svp, (HCl), SVP(MARS),
SVP(MeOH) and SVP-HP are trademarks
owned by AKZO-Nobel.
~_.,
~-~
~-
-- .----
SECTION ll:
Raw Materials
Chapter 3:
Bleaching Chemicals:
Chlorine, Sodium Hydroxide, Hydrogen Peroxide,
Peroxy Acids, Oxygen, and OZone
Dennis Owen1
John
R. Anderson1
Gordon Homer3
Canadian Liquid Air Ltd.
Vancouyer, BC, Canada
1. Chlorine and sodium hydroxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.1 Chlorine: properties, safety, and materials
of construction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.2 Sodium hydroxide properties, safety, and
materials of construction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.3 Manufacture of chlorine and sodium hydroxide. . . . . . . . . . . . . . . . ..
1.4 Chlorine storage and handling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.5 Sodium hydroxide storage and handling . . . . . . . . . . . . . . . . . . . . . . ..
73
2.Hydrogenperoxide
2.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . ..
2.2 Manufacture of hydrogen peroxide . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2.3 Storage and handling of hydrogen peroxide
77
77
78
79
73
73
74
76
77
3.Peroxyadds.
79
3.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . .. 79
3.2 Manufacture of peroxy acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 80
3.3 Storage and handling of peroxy acids
80
4. Oxygen . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .,
4.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . ..
4.2 Manufacture of oxygen
4.3 Transportation and handling of oxygen. . . . . . . . . . . . . . . . . . . . . . . ..
81
81
82
84
5. OZone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85
5.1 Properties, safety, and materials of construction. . . . . . . . . . . . . . . . .. 85
5.2 Ozone manufacture. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 85
~--,-_.
Chapter n 3:
Bleaching Chemicals:
Chlorine, Sodium
Hydroxide, Hydrogen
Peroxide, Peracids,
Oxygen, and Ozone
Preface
This chapter concerns the properties, manufacture, and safe handling of the bleaching chemicals chlorine, sodium hydroxide,
hydrogen peroxide, peroxy acids, oxygen,
and ozone. Chlorine dioxide properties and
manufacture have been covered in the preceding chapter; this material has been.
placed in a separate chapter for editorial
convenience. Hydrosulfite properties and
manufacture are covered in Chap. V 2.
'.
safety, and
materials of construction
liquid chlorine is amber in color and has a
saturated liquid density of 1.467 g/cm3 at Oe.
At atmospheric
pressure
it boils at
-34e. Chlorine gas is greenish-yellow and has
a saturated gas density 2.48 times greater than
air. Under standard conditions, the weight of
one volume of liquid chlorine equals the
weight of 456.5 volumes ofthe gas.
The solubility of chlorine in water is dependent on temperature as shown in Table
1 for a partial chlorine pressure of 750 mm.
Below 1000C,chlorine combines with water, forming crystalline hydrates (1).
Table 1. S61ubilily of cblorlfle gtIS,,, lHIer /II4ifferetlt tempetYllrl"S '.
Temperature
("C)
10
20
30
40
,
Chlorine
partial pressure
Solubility
(g/L)
9.65
7.29
5.80
4.77
of 750 mm.
73
74
Cl2 + H2
[1]
Anode
Membrane
Cathode
Saturated
brine
__ NaOH
Depleted
brine
Fig. 1. Sbettultk
aolution
4i11grt1m of typk411llelllbrrlfle
Water
of eblorlfle
cell for
""'''''f'''"
11114soill"m
by4roxitle.
Impurity
Unit
Amount
NaCI
Ca+Mg
Sr
Si02
I
Ba
Al
Na2S04
Fe
Ni
g/L
ppb
ppm
ppm
ppm
ppm
ppb
ppm
ppm
ppm
280-305
20
0.5
5
0.4
0.4
50
5
0.5
0.05
Hg
T.O.c.
F
ppm
ppm
ppm
0.04
1
1
75
76
clad steel and, where activated nickel surfaces are used for lower voltage, require
replacement or recoating every five years
(12).
Chlorine and hydrogen are produced in
the electrolyzer at slightly greater than atmospheric pressure. The sodium hydroxide discharged from the cathodic side of the
electrolyzer, after separation from the hydrogen, flows to a catholyte tank where it
is cooled before being recycled to the
electrolyzer. Sodium hydroxide concentration is controlled at 32-34% by recycling the
catholyte and varying the amount of deionized water used for makeup.
Hydrogen, scrubbed to remove residual
sodium hydroxide, may be used as an auxiliary fuel in the pulp mill lime kiln or
burned with chlorine to make hydrochloric acid. Care should be taken to avoid creating an explosive mixture of hydrogen,
chlorine, and oxygen (25).
Chlorine recovery
Chlorine is recovered by cooling, drying,
compression, and liquefaction. It is stored
and transported as liquid chlorine which is
ultimately vaporized to supply chlorine gas
to a chlorination stage.
Chlorine produced by the electrolyzer is
saturated with water vapor at high temperatures. The chlorine gas is first cooled but
temperatures less than 1000C(1) should be
avoided to prevent the formation of chlorine hydrate crystals. The cooled chlorine
gas then flows to sulfuric acid drying towers. The upper limit for moisture remaining after drying is 50 ppm (-48"C dew point)
(26). A sulfuric acid-sealed, liquid-ring reciprocating compressor can be used to compress the gaseous chlorine.
Single-stage
liquefaction units are not designed to liquefy more than 90-95% of the chlorine. A
three-stage reciprocating compressor is capable of producing the chlorine gas pressure required in the chlorination
stage.
About half ofthe chlorine is liquefied (27).
The gas flows directly to the chlorination
stage. Should the plant demand exceed the
gas flow, liquid chlorine is fed from the storage tank through a vaporizer. This system
requires only one liquid chlorine storage
tank (28). To minimize the adverse consequences of tank rupture, the minimum
quantity of liquid chlorine should be stored
on-site. All chlorine-contaminated
streams
should be safely vented through emergency
scrubbers (29).
77
approximately 60% hydrogen peroxide. Hydrogen peroxide has a slightly pungent odor
most often detected if aerosols are formed
at a nozzle during unloading or transfer.
Table 3. Properties of bydrogtm peroxiIle.
Properties
of 50"10solution in water
1.19
Freezing point
-52"C
at 25"C
13.5 rnrn Hg
Boiling point
Most pulp mills receive sodium hydroxide as a 50% aqueous solution in tank cars,
tank trucks, barges, or pipelines. Tank cars
contain 25 or 50 tons of sodium hydroxide
at 50% concentration (50 or 100 total tons).
Sodium hydroxide tank cars are equipped
to be unloaded by pump or air pressure;
they can be unloaded from the top or bottom of the tank car or truck. The unloading area should be designed to confine and
collect any sodium hydroXide lost from the
unloading system. Because 50% sodium
hydroxide solution freezes at 16C, it is
stored in a heated tank. Storage tank areas
need to be diked because sodium hydroxide is designated as a hazardous material.
Sodium hydroxide is diluted to 5 or 25%
in a continuous dilution system as required.
The dilute sodium hydroxide storage tank
level controls the flow of dilution water to
a mixing tee and coil. The dilute sodium
hydroxide concentration can be measured
by a conductivity cell or density gauge.
2. Hydrogen peroxide
2.1 Properties, safety, and materials of
construction
Hydrogen peroxide is a clear, colorless
liquid which is available commercially as an
aqueous solution in concentrations ranging
from 30% to 70%. It is completely miscible
114"C
78
Pulp Bleaching
-Principles
and Practice
Recycle
2.2 Manufacture
of hydrogen peroxide
Most of the hydrogen peroxide used today is produced by the anthraquinone process shown in Fig. 2. This is a cyclic process
wherein a working solution containing an
alkyl anthraquinone is sequentially hydrogenated, oxidized, subjected to an extraction process, and recycled back to the
hydrogenation step.
In the hydrogenator, alkyl anthraquinone
reacts with hydrogen in the presence of a
catalyst. The resulting solution containing
hydrogenated alkyl anthraquinone is filtered
to remove the catalyst and is fed to the oxidizer. It reacts with air or oxygen to form
hydrogen peroxide and regenerate the alkyl
anthraquinone. In the extraction step,demineralized water is added to extract crude
aqueous hydrogen peroxide, leaving the
alkyl anthraquinone
working solution for
recycle to the hydrogenator.
The crude
hydrogen peroxide is purified and concentrated.
working solution
o:)Cr
I
-..;;::
-..;;::
::
R-Anthraquinone
(RAQ)
Contaminants
+H2---'
CAT
~
1
H
o
:: " ::
-..;;:: R Hydrogenated
::
R-Anthraquinone
(HRAQ)
OH
Compressor
Low strength "crude" peroxide
[2]
79
3. peroxy acids
3.1 properties, safety, and materials of
construction
A peroxy acid, or peracid, is an acid that
contains a perhydroxyl group ("OOR) in
place of the hydroxyl group of its parent
acid. Peroxy acids are described in more
detail in Chap. IV 10. Percarboxylic acids
(e.g., peracetic acid) are weaker acids than
their parent acids. The peroxy acids of primary commercial interest are peracetic
acid, CH COOOH, and Caro's acid, monopers.c
acid or HzSO,. Caro's acid is a
dibasic acid. The ionization constant of the
perhydroxyl proton, pKz, is much higher
than the p~ for sulfuric acid; therefore, t~e
Caro's acid anion is a much weaker aCid
than the parent acid.
The principal hazard of peroxy acids is
their corrosive nature, which causes severe
burns to skin, eyes, and body tissue. Contacted areas must be washed immediately
with large volumes of water to avoid tissue
damage.
Peracetic acid has a sharp, pungent odor.
It has a boiling point of 103C and a vapor
pressure of 20 mm Hg at 25C. Exposure
to the vapor causes lachrrmation and possibly lung damage. Long-term exposure to
peracetic acid can lead to liver damage, decreased white blood count, and lung tumors
(42). Personal protective equipment should
include a respirator in addition to splashproof goggles, rubber acid suit, and rubber
gloves. Caro's acid, peracetic acid, and
mixtures of these two peroxy acids are not
shock sensitive. However, some mixtures
of 70% hydrogen peroxide and glacial acetic acid are detonatable if present in. the staichiometric molar ratio 4-HP z:l-CH3COOH.
Mixtures of 50% hydrogen peroxide and
glacial acetic acid are not detonatable.
80
Pulp Bleaching
-Principles
and Practice
4. Oxygen
4.1 Properties, safety, and materials of
construction
Oxygen is a gas under normal atmospheric conditions. It is indispensable for
the maintenance of life and for combustion..
Oxygen is a colorless, odorless, tasteless gas
that is slightly heavier than air. It accounts
for 20.94% by volume ofthe air components
heavier than air. At atmospheric pressure
and temperatures below -183"C, oxygen is
a transparent
pale blue liquid, slightly
heavier than water. Some properties of
oxygen are listed Table 4 (49). Oxygen is a
highly reactive gas which combines directly
with most elements to form oxides. Certain
elements, for example, phosphorus
and
magnesium, ignite spontaneously in oxygen
(or in air); noble metals are only slowly oxidized at very high temperatures. Oxygen is
liable to react violently with organic substances.
Oxygen does not burn but vigorously
supports combustion.
In fact, many mate-
Density
Density
Density
of liquid at boiling
point
81
and 1 atm
= 1)
1.1053
31.329 kg/m;
4.475 kg/m;
1141.0 kg/m;
-183.00"C
213 kJ/kg
0.9li kJ/kg
0.653 kJ/kg
0.001162
0.031
82
Air
4.2 Manufacture
of oxygen
Air is a mixture of the following components: oxygen (21% by volume), nitrogen
(78%), argon (less than 1%) and trace quantities of carbon (350 ppm), neon (18 ppm),
helium (5 ppm), krypton (1 ppm), and xenon (0.08 ppm). Depending on the ambient air quality, other components such as
hydrocarbons,
nitrogen oxides, carbon
monoxide, hydrogen, ozone, SO x,dust, and
Year of Invention
Cryogenic distillation
1902
Adsorption
1965
Membrane separation
1975
At present, only distillation and adsorption are commercially viable for oxygen
supply to the pulp and paper industry. The
commercial cryogenic separation of air into
its component gases entails cooling air until it liquefies and the fractional distillation
of each component. Adsorptive separation
consists of passing a feed gas (air) over a
suitable adsorbent such as a zeolite molecular sieve which selectively adsorbs one or
more components of the feed gas (nitrogen),
thereby producing a gas enriched in remaining components (oxygen).
Liquid 02
Fig. 3. Plowsheet
for cryogenk
separation
of oxygen.
83
Separation by adsorption
Adsorption is a very simple process that
produces gaseous oxygen at purity levels
up to 95%. Because no liquid is produced,
liquid oxygen must be supplied from an outside source and stored on-site as back-up.
The process consists of a cyclic sequence
in which 1) nitrogen is absorbed by molecular sieves at high partial pressure, forming
a purified oxygen stream and 2) desorption
at low partial pressure to regenerate the molecular sieves. Several process options are
available:
1) PSA (pressure swing adsorption):Adsorption under pressure, regeneration at
atmosphere pressure
2) VSA (vacuum swing adsorption):Adsorption near atmospheric pressure, regeneration under vacuum
3) VPSA(vacuum pressure swing adsorption):
Adsorption under pressure, regeneration
under vacuum.
In the oxygen systems in use today, the
adsorbent consists of a two-bed system with
a sparger vessel or a three-bed system. The
84
4.3
System
Compressor
Adsorption
Separation
Product manifold
Adsorber
beds
./'...
Exhaust
Exhaust
manifold
Vacuum
pump
shows
Adsorber A - oxygen production
is extremely
cold (-183"C)
Cryogenic
Separation
-190C
Purchased
liquid
-190C
Operating
temperature
Ambient
Maximum purity
Up to 95%
Up to 99.9%
Up to 99.9"10
Usual purity
90 or 93%
98 or 99.5%
99.5%
Pressure (psig)
Atmospheric with
additional compression
From 10 to 200
without additional
compression
Up to 225 from
vaporization
Flexibility
in operation
Instantaneous
startup
From 100% to 0%
From 100% to 0%
liquid production
No
Yes
N/A
265
300
25 x 35 m
30 x 35 m
Thmdown flow
phase
phase
not shown
Site size
JO
Vaporization only
site (kwhft)
6x30m
~-
Metals
85
Glass
Grease
Halocarbon, Crytox'"
LOX -8'"
Teflon@, Goretex@,
Gylon"VitonA",
Silicone
Joint Sealant
Seals and Gaskets
5. Ozone
5.1 Properties, safety, and materials of
construction
Ozone is a bluish gas under normal atmospheric conditions. It is a powerful oxidizing agent, is toxic, and has a pungent
odor. Ozone exists in the atmosphere in
very low concentrations (0.025-0.045 ppm
by volume) and is a contributor to photochemical smog. It can be stored almost indefinitely at -50C but, at room temperaturer
is 50% decomposed in several days, liberating oxygen. Ozone is sparingly soluble in
water.
Ozone has a very high electronegative
oxidation potential, 2.07 .ev, second only
to that of fluorine. This high oxidation p0tential has made ozone both a good bactericide for air and water and a potent oxidiant
in chemical pulp bleaching.
Ozone is a toxic, irritating gas, with good
odor-warning properties (the odor threshold is 0.01-0.015 ppm). It is unlikely that
people people will stay in an area in which
ozone concentrations are as high as 10 ppm
because of its irritating character. Nevertheless, ozone is very toxic. Ozone should
be monitored continuously
and, should
critical levels be exceeded, the system
should be shut down. Ozone, unlike chlorine dioxide, cannot be stored and is produced only when power is applied. All
ozone relief vents should be piped to an
ozone destruction system.
All handling and safety procedures that
have been adopted for the use of oxygen
(described in the previous section) also apply to ozone. These procedures include as
a minimum, "cleaned for oxygen service,"
no smoking in the area of use, and correct
m1terials
selection.
86
Pulp Bleaching
-Principles
and Practice
the introduction
of non-glass dielectrics
having selected properties and optimized
geometries has led to a significant decrease
in energy consumption and cost and to a
significant increase in ozone concentration,
unit capacity, reliability, and operational
flexibility (52).
Most commercial systems currently in
use are horizontal, dielectric tube exchangers. Feed gas passes through the gap between the dielectric shells and the electrode
receptacle; water flows outside the tubes
to remove the heat generated by the process. The generators are self-<:ontained,
each having individual power systems and
controls to allow each to be an independent production unit.
Energy and cooling systems
Cooling in an ozone system is achieved
by a coolant circulating in the generator
shell and, if required, in the ozone liquidring compressor.
Power requirements decrease and unit production increases with
decreasing cooling water temperature. The
water flow requirements for system cooling are substantial, but the temperature rise
(3"C) is small. Depending on the temperature of cooling water available at the mill, a
chiller or cooling tower may be required.
Outer
electrode
Cooling
water
Pulp
02 gas
to recycle or
Dialectric coated
inner electrode
reuse
Fig. 5. Ozone systemsfor
pulp
bleaebillg.
Fig. 6. ScbemtJtie
diIIgrtI1II
of ozone
generwtioll
discbarge
gap.
87
A. Once through
Exhaust
and/or
02 usage
B.Shortloop
Exhaust
C.
Long loop
Fig. 7. AltertUltives
for oxygen
reuse in 0%_
bleaching
systems.
Ozone destr.
Exhaust
02 purificat.
02 compress.
and/or
02 usage
88
The properties,
generation, handling,
storage, and safety concerns of sodium hydrosulfite are found in Chap. V 2 as part of
the description of hydrosulfite bleaching
technology.
In parallel with ozone generation development work, optimized oxygen-ozone systems have been developed as illustrated in
Fig. 7.
Once throueh systems are effective when
there is a sizable oxygen demand in a pulp
mill that reuses a significant portion of the
vent gas (Fig. 7A).
Short loop systems recover oxygen before the
gas mixture reacts with the pulp and avoid
the need for extensive gas cleanup but require a second carrier gas such as dry air
or nitrogen (Fig. 78). The principal methods for ozone separation are adsorption!
desorption (silica gel, molecular sieves, and
dissolving/stripping of the gases from an
aqueous medium). It is also possible to
increase ozone concentration with these
techniques. Work is continuing in this area,
including the possible use of membranes
to separate oxygen and ozone.
Lone loop systems recycle the oxygen after
reaction with the pulp. Impurities are produced from the products of reaction of
ozone with pulp (Fig. 7C). It is necessary
to reduce the concentration of these impurities in the recycle gas to a level that
ozone generators can tolerate. The steps
involved are dilution, chemical conversion,
and separation. The most recent example
is a system that incorporates a combination
of ozone and hydrocarbon destruction
(conversion) compression, purge (dilution)
and drying (separation) (57).
In current commercial practice, ozone is
delivered by long loop and once through
systems at applications of 5- IO kg per metric ton of pulp. For a 1,200 metric ton/day
pulp mill, the ozone supply therefore var-
ies from
References
1. Perry, R.H. and Green,
Engineering
Handbook,
Hill, 19843.102.
D.W., Cbemical
6th edn., McGraw
Insti-
3. Pampblet
63, The CWorine
Washington,
D.C., 1990.
Institute
Inc.,
4. Pampblet
74,The CWorine
Washington,
D.C., 1991.
Institute
Inc.,
5. Pampblet
85, The CWorine
Washington,
D.C., 1992.
Institute
Inc.,
6. Pampblet
73,The Chlorine
Washington,
D.C., 1993.
Institute
Inc.,
7. Cbemical Safety Data Sbeel SD-9 Manufacturing Chemists Association Inc.,Washing. ton, D.C., 1968.
8. Caustic Soda Solution
Handbook,
Dow
Chemical Company, Midland, MI, 1986
9. Pampblet
10, The CWorine
Washington,
D.C., 1993.
10. Perham,
D.A.,Appita
Institute
39(5):391
Inc.,
(1986).
11. Brown,D.R.,"Current
legislative and regulatory
developments
affecting
the
chloralkali
industry," Plant Operations
Seminar,The Chlorine Institute Inc.,Washington, D.C., 1989, p. 5-1.
12. Wilson, R.D., "Advances
in design for
higher current density cells;' Plant Operations Seminar,The Chlorine Institute Jnc.,
Washington,
D.C., 1989, p. 3-1.
13. White I.f. and O'Brien, n, in Modem
Cblor-alkali Tecbnology, Elfevier Applied
Science, London, 1988, Vol. 4.
28. Pampblet
5, The Chlorine
Washington,
D.C., 1982.
89
Institute
Inc.,
29. Pampblet
89, Edn 1, The Chlorine
tute Inc., Washington,
D.C., 1991.
insti-
30. Pamphlet
79, Edn 1, The CWorine
tute Inc., Washington,
D.C., 1984.
insti-
31. Pamphlet
66, Edn 1, The CWorine
tute Inc., Washington
D.C., 1979.
Insti-
32. Pampblet
49,The CWorine
Washington
D.C., 1989.
Institute
Inc.,
33. Pampblet
60,The CWorine
Washington,
D.C., 1990.
Institute
Inc.,
34. Pamphlet
6, The CWorine
Washington,
D.C., 1989.
Institute
Inc.,
35. Pamphlet
9, The CWorine
Washington,
D.C., 1987.
Institute
Inc.,
Institute
Inc.,
38. Pamphlet
65,The Chlorine
Washington,
D.C., 1988.
Institute
Inc.,
39. Pamphlet
IB/C, The Chlorine
Inc., Washington,
D.C., 1983.
Institute
40. Hydrogen
Peroxide
(20-60%) Material
Safety
Data Sheet, CAS# 7722-84-1,
DuPont Canada Inc., Mississauga,
ON,
1994.
Cbem.
Eng.
Inc.,Washington,
D.C.,
42. Peroxyacetic
acid (35%) Material Safety
Data Sheet, E.I. du Pont de Nemours
&
Co.,Wilmington,
DE, 1994 (based on FMC
Corporation
MSDS dated 3/9/90).
43. Amini, B., DuPont Pxa;
High Conversion Pero.xyacids, DuPont Techncial Bulletin H-57651, E.I. du Pont de Nemours
& Co., Wilmington, DE, 1994.
44. Reichert, D.L., "Corrosion
behaviour
of
hydrogenperoxide
bleaching
solutions,"
CPPA Pacific and Western Branch Annual
Meeting
Preprints,
Tech. Sect., CPPA,
Montreal,
1995.
90
51. Armengaud,
B., Schmid, E., Thonnelier,
).Y., Nicolas,). E, and Lang, H., Proceedings of the 1993 11 th World Ozone Congress Proceedings,
lOA, San Francisco.
52. Wiegart,
N., 1993 Air Liquide/Ozonia
Ozone Symposium Notes, Helsingor, Denmark, available from Air Liquide, P&P/
Ozone Division, Paris.
47. Anderson,).R,Amini,
B., and Wilkinson,
W,"On-site generation and use ofperoxyacids in chemical
pulp bleaching;
81st
CPPA Annual Meeting Preprints,
Tech.
Sect., CPPA, Montreal, 1995, p. B59.
48. Seccombe,
R, Hill, R., Martens, H., and
Haakana, A., "Practical
mill experience
with the use of Caro's acid to produce
high brightnessTCF
pulps," Non CWorine
Bleaching Conference Proceedings, Miller
Freeman, San Francisco, 1994.
49. Encyclopedie
des Gaz Air Liquide, L'Air
liquid, Elsevier Scientific Publishing Company,Amsterdam,
1976, pp. 1079-1118.
50. Canadian
available
Montreal,
SECTIONm:
The Chemistry of Bleaching and
Brightness Reversion
Chapter 1:
Chemical Structure
of Pulp Components
G. Gellerstedt
Royal Institute of Technology
Stockholm, Sweden
106
2. Carbohydrate
106
constituents
3. Extractives in pulps.
in pulps
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
91
. . . . . . . . . . . . . . . . . . . . ..
93
93
96
99
108
108
Chapter m 1:
Chemical
Structure Of
Pulp Components
In pulp bleaching, all chemical reactions
involve fiber constituents that have been
chemically modified as the result of mechanical and chemical treatments of wood
material. In the following survey, an attempt
is made to describe the chemical characteristics of the pulp components, particularly lignin, in (chemi)mechanical
and
chemical pulps.
The information presented below originates from a variety of analytical methods
applied to lignin, cellulose, and hemicelluloses. Nevertheless, our present knowledge
of the chemical structure of the residuallignin in chemical pulps is far from complete.
Available analyses are better developed for
polysaccharides than fo~ lignin, but information about lignin-carbohydrate
linkages
and molecular weight distribution and their
possible change during refining or pulping
is, to a large extent, still Jacking.
CHlOH
I
CH
II
Q
OH
p-Coumaryt
alcohol
Fig. 1. Lipi" precursors.
CHlOH
I
CH
II
~
V~
OH
Coni/eryt
alcohol
93
94
5-5
CHlOH
&
II
CH,O~
OH
Sinap~
alcohol
Fig.Z.l"'erw,,i,li_ges
ill lipi..
c
b
c
b
99
,/
,/
95
96
Pulp Bleaching
-Principles
and Practice
0i0
I
a-t
<9Y~
0
r.<
L
<D = Lignin
O:>nWeraldehyde
structure
~~A
o
1.2
lignin in unbleached
high yield pulps
and bleached
Quinone
structures
TypeA
I"
_lifI#Jlipl".
Unbleached
pulps
The structural changes occurring in lignin. when wood is converted to mechanical pulp by grinding
or refining
are
apparantly small (20, 21) .The phenolic content does not change to any noticeable
extent (Table 2) nor does the relative distribution of different types of lignin sub-structures. Analysis of lignin end groups
(b) =Lignin
Linkage type
Dimer structure
~-0-4
a-0-4
~-5
~-1
Phenylpropane ~-arylether
Phenylpropane a-aryl ether
Phenylcoumaran
1,2-Diarylpropane
50
2-8
9 -1 2
7
60
7
6
7
5-5
4-0-5
Biphenyl
Diaryl ether
~-~
Lignan-like
10 -11
4
2
5
7
3
Type B
Fig. 3. ForrruIHoII
of II slilHMfrum
II ~-1 stnu:lrm!.
During the biosynthetlc process and during tree aging, the acidic environment in a
tree promotes
condensation
reactions
within or between the lignin macromolecules which lead to the formation of new
carbon-carbon
linkages between adjacent
lignin chains (7). Furthermore, some lignin
(3).
lip''''
Phenolic
groups!
100 phenylpropane units
Wood flour,
Wood flour,
Wood flour,
Wood flour,
TMp, spruce
CTMP,
spruce
pine
birch
aspen
spruce
Reference
10,13
13,12
7
10
13
12
9,11
10,11
11
11
20
12
12
98
Pulp Bleaching
-Principles
and Practice
chain. Under these reaction conditions, several new phenolic structures, formed simultaneously by hydrolysis of alkyl-aryl ether
1inkages, undergo sulfonation with the result that degrees of sulfonation are obtained
far above that expected based on the original free phenolic hydroxyl content. It has
also been noted that, under these sulfonation conditions, lignin undergoes other
profound chemical changes, notably condensation reactions, which presumably lead
to cross-linking of the lignin network (20).
suI/_ie
Tllble 3. CIIrIJoxyI
various pulps
""" (67).
Pulp
group COtItefll of
Sulfonate,
mmol/kg
Unbleached (TMP
Bleached CTMP
Unbleached kraftb
Unbleached sulfiteb
Bleached kraft
.
b
Total
capacity' ,
mmol/kg
-~!
80-11 0
150-250
Unbleached TMP
Bleached TMP
Gellerstedt, unpublished
97
40-70
40-70
120-180
190-320
100-120
60-80
150-180
10-25
acid groups
Bleached pulps
The bleaching of high-yield pulps is usually conducted
with alkaline hydrogen
peroxide and/or sodium dithionite (hydrosulfite) under nearly neutral conditions.The
latter chemical is a reducing agent used to
produce small or moderate increases in
pulp brightness (less than 10 brightness
units). In dithionite bleaching, lignin chromophores typified by simple quinones (Fig.
5) are rapidly eliminated without any further chemical modification of the lignin
(27).
Hydrogen peroxide, on the other hand,
can be used to increase the brightness of
high-yield pulps to values of around 80%
ISO for spruce and 85% ISO for aspen. The
chemical changes occurring in lignin are
again minor and the bulk of the polymer i~
seemingly
unchanged structurally.
The
most important reaction in peroxide bleaching is the oxidative elimination of conifer-
ConiferyI
alcohol
structure
slnU:tures
I" IIgnl"
""ri"g
allulllne
pulpi"g.
99
20
40
60
80
Delignification, % on wood
100
of ~-Q-4 strru:IIIrf!S
Fig. 7. C'-"t.e
lIS
". lip'"
fuctIott of tbe degree of dellpljktlltorll.
"
llraft Jndpt",.
Phenolic hydroxyl content
The cleavage of an alkyl-aryl ether
<IH>-4. a-0-4, or ~5) linkage in lignin leads
t.othe formati.on .ofa new phen.olic hydroxyl
end group that is i.onized under the alkaline conditi.ons prevailing in the digester.
The phenolic hydroxyl group content of the
lignin is of great importance because, except for a ornall nwnbtr of carboxyl groUP1!,
this is the .only type .offuncti.onal group conferring water (alkali) S.olubility to the lignin
in kraft pulping. During the c.ourse .of
100
Pulp Bleaching
-Principles
and Practice
dissolved
lignin
pulp lignin
~
,
o
20
40
60
80
Delignification,% on wood
100
"futU:llraft
Condensed
structures
The alkaline conditions prevailing in kraft
pulping favor a variety .of c.ondensati.on reacti.ons between lignin units and between
lignin and carb.ohydrates. Several such reacti.ons have also been identified in m.odel
compound studies (43-45). Whether c.ondensati.on reactions actually take place in
the polymeric material is, however, still a
debatable issue. Four main modes of ligninlignin condensation
reactions have been
identified on the basis of model compound
studies (43).
Table 4. c.rbtm "toms II
10 CIIrbtm "rulbytlrognl/l00 C4rbtm "toms I. Is6lt1tetlllplllS.
(Dat" btrse4 0fI ClJNMR """'ysls by tH DEPT
~.)
Type of
carbon
Aliphatic CH
Aliphatic CH2
Aliphatic CH3
Native
lignin
(MWL)
2.9
2.0
Kraft pulping to
kappa no. 3D.5
Residual
lignin
Dissolved
lignin
3.3
4.8
2.3
5.2
8.4
2.4
In the first of these, styrene- or stilbenetype structures react with a quin.one methide S.o as to form a carb.on-carbon
linkage
between two lignin side chains. This reacti.on leads t.o the f.ormation
.of methine
carbons in the lignin. However, as shown
in Table 4, the number of methine carbons
is not significantly
different in native and
kraft pulp lignins. In an.other type .of condensati.on, aromatic rings add to a quinone
methide forming a diarylmethane
structure
(Fig. 9, reacti.on A). Again, an increase in
the number of methine carb.ons W.ould result if this reacti.on occurred t.o a meaningful extent.
Chapter
III 1: Chemical
Structure
of Pulp Components
102
Pulp Bleaching
2
OCH.!
Table 5. S}lifk
peru:e.)
Typeof
carbon
l~
CtlrIHnI
<9 =Ugnin
and Practice
Native
lignin
(MWL)
CH:zC)
- Principles
Aliphatic
carbonyl
structures
present
in
lignin side chains are reaction
sites for the
third suggested
type of condensation.
The
amount
of carbonyl
groups in lignin is low,
however,
(Table 5) and, despite the fact that
this reaction
accounts
for the observed
increase in methylene
groups, it is reasonable
to assume that condensation
reactions
of
this type are of minor importance.
4-
101
Carbonyl
Carboxyl
Olefinic +
aromatic Cq
Aliphatic CHx-OR
Methoxyl
Aliphatic CHx
Kraft pulpi'1% to
kappa no. .5
Residual Dissolved
lignin
lignin
0.8
0
0
2.1
0.3
1.5
39
54
39
23.6
11.2
4.9
9.5
9.1
10.4
10.1
8.9
16.0
103
104
OH
0--
=Cerbohydrate
+
a-I:!S-
(a-I:!Sa-I:!)
C0 =Lignin
Thus,
increased
carbohydl".lte
con-
CH:IOH
tt-OH
tt
(;lI
@ ~
oc:H3
CH:I
OH
OH
~~----
105
Pulp Bleaching - Principles and Practice
106
phase. Sugar analysis has revealed that arabinose and xylose are the predominant
structural units. Similar analysis of the lignin dissolved in an oxygen bleaching stage
has again revealed the presence of carbohydrates with xylose once again a major
component (57).
On the other hand, analyses of the residual polysaccharides in lignin isolated by
enzymatic hydrolysis of kraft pulps have
provided divergent results. In one study, the
results suggest that the residual lignin is
mainly bonded to cellulose (58) and that
these lignin-<:arbohydrate bonds to a large
extent are generated during pulping according to the reaction outlined in Fig. 11. The
results of another study in which a similar
analytical technique was used suggest, however, that the lignin-<:arbohydrate linkages
are predominantly native and bond lignin
to the hemicelluloses, that is, to glucomannan and arabinoxylan
(59). It was also
noted that the number of linkages between
each individual polysaccharide
chain and
lignin is low (about one);
Molecular weight distribution
Gel permeation chromatography
of lignin isolated by enzymatic or acid hydrolysis of kraft pulp provides molecular weight
distribution curves indicating that the apparent molecular weight of this material is
higher than that of dissolved kraft lignin (38,
60, 61). However, the differences are not
of such a magnitude, nor do other analytical data differ sufficiently, to suggest that a
completely different solubility behavior
should be expected. Nevertheless, the linkage of residual lignin in the fiber wall to
polysaccharides
by alkali-stable chemical
linkages substantially increases its molecular weight and molecular size distribution.
This, in turn, makes diffusion of lignin fragments through the pore system and out of
the fiber wall much more difficult. By applying a high temperature to facilitate the
diffusion of lignin molecules, a "leaching"
effect can be observed for both kraft and
high-yield pulps over long periods of time
(62). Consequently, the efficiency of the
pulp washing stage is of great practical importance in later bleaching reactions be-
enhanced,butfernou~/ferncion~can
that condensation reactions involving aromatic rings take place in the lignin (65).
Such condensation
reactions
are wellknown and may lead to cross-links between
lignin chains. Nevertheless, industrial sulfite
pulps having very low kappa numbers and
good bleachability are routinely obtained,
indicating that the structure of the residual
lignin closely resembles that of native" lig"
nin and therefore is reactive toward oxidative bleaching agents.
2. Carbohydrate constituents
pulps
in
(Q
C
vF~H
CQ(J
OH
HO:/,
OH
Metasaccharinic
~oo
OH
@
= Carbohydrate
chain
~so
DIssoIIIed
glucoisosaccharinic
acid
107
108
~~OO
OH
0." M.ecH
9O"C,"
r:>:
o
+
0
I
OH
OH
and others
of fIIWIhItwINl
t:OtII/JOIIIUI8 f017llell
of gl_
in tN al""'me trelJlJJIeIJt
lose.
or :!tY-
3. Extractives in pulps
Wood extractives, for the most part, are
dissolved in alkaline pulping liquor directly
by soap formation or indirectly by micelle
formation caused by the presence of ionized resin and fatty acids. In softwoods especially; which contain only small amounts
of neutral components, the amount of extractives remaining after kraft pulping is low
and approximately 0.1% for pine and 0.20.3% for spruce. Neutral components such
as sterols and sterol esters predominate, but
smaller amounts of resin and fatty acids are
also present (72).
In hardwoods (e.g., birch), on the other
hand, the extractives are comprised of large
amounts of neutral components
making
them much more difficult to remove during pulping (Fig. 14). Despite the addition
of an emulsifier, tall oil, to the kraft pulping
liquor, the remaining amount of extractives
in the unbleached pulp, is about 0.5-1.0%
but may vary widely depending on such
variables as wood species and debarking efficiency (72).
Several of the extractives in unbleached
kraft pulps contain one or more double
bonds making them extremely reactive toward bleaching agents such as elemental
Squalene
tXHIIUtkms
Additive
Brightness
of resulting
pulp, %
HO
80.1
None
Milled wood
lignin
Birchxylan
Spruce
(69).
glucomannan
65.6
69.5
72.2
S~osIerol
Fig. 14. Examples of extrGdi_
tN IHIrlI.)
Betu~nol
preSMt ", "tlbletu:bed bircb iraft JIIIlp (BetflliflOl orlglfllJtes exclflSively Iff
109
110
Type of carbon
Aldehyde
Carboxyl
Aromatic + olefinic Cq
Aromatic + olefinic CH
Aliphatic CH-OAliphatic CH2-OMethoxyl
Aliphatic CH
Aliphatic CH2
Aliphatic CH3
carbon
atoms
MWL
Kraft Pulp
After 0
0.8
0
39
32
15
9.1
11
2.9
2.0
0
0
2.1
54
21
5.5
4.0
9.1
3.3
4.8
2.3
0
3.5
52
21
6.4
3.9
8.2
3.7
6.5
3.1
After 0-0(1
OO)-EOP
0
10
47
14
9.4
5.7
5.4
2.6
7.7
3.6
Kemisk
Tidskr.
56:124
80:279
(1973).
S., Svensk
G., Acta
Chern.
D.A.I.,
13:
Can. j.
II
valuable
criticism
of the
14. Pew,].c.,
(1971).
and Connors,W.j.,
I.,] Wood
19. Polcin,).,
and Rapson, WH., Pulp
Mag. Can. 73(1):86 (1972).
References
1. Adler, E., Svensk
(1')68).
0.,
and Practice
Acknowledgments
and to Dr. Adrian EA. Wallis,
- Principles
16. Manouchehri,
M., and Samuelson,
Svensk Papperstidn.
80:381 (1977).
Department
Pulp Bleaching
1.lIplas
B., Svensk
Pap.
Matsuoka,
M., Lee, D-Y.,
M., Mokuzai
Gakkaishi
37:164 (1991).
Sumimoto,
24. Suckling,
I.D.,
"The
Effect
of
Coniferaldehyde
Sulfonation on the Brightness
and
Absorption
Spectra
of
Chemithermomechanical
Pulps," 1991
International
Symposium
on Wood and
Pulping Chemistry Proceedings,
Appita,
Parkville, Victoria, Australia, Vol. 1, p. 587.
25. LuValle, ).E.,j.
(1952).
Am. Chem.
31. Gel!erstedt,
G., Hardel!, H-L., lindfors,
EL., Acta Chem. Scand. B34:669 (1980).
32. Teder,A.,
(1981).
Svensk
Hartler,
N., Pap.
Papperstidn.
35. Gellerstedt,
G., and lindfors,
Pulp Pap. Res.]. 2:71 (1987).
36. Gellerstedt,
63:315
73:571
E-L., Nord.
Soc. 74:2970
Imsgard,
K.,] Wood
K., Northey,
3:87 (1988).
E, Pettersson,
I., Appl.
D.,] Pulp
27. Polcin,].,
(1976).
28. Gellerstedt,
G., Pettersson,
I., Sundin, S.,
"Chemical Aspects of Hydrogen Peroxide
Bleaching",
1981 International
Symposium
ceedings,
SPCI, Stockholm,
29. Gellerstedt,
Chem.
Scand.
Chemistry
Pr0-
Vol. 2, p. 120.
c.,
87:R61
(1984).
23. Wu,
R., Acta
S., Holzfor-
Wood
N.,
.
--"-
Wood
0., Acta
Set. Tecbnol.
Chem.
19:289
Gellerstedt,
Holzforscbung
E-L.,
Mokuzai .
E-L., Tappi J.
S., Holz/or-
59. Minor,}. L., "Chemical linkage of Polysaccharides to Residual lignin in Pine Kraft
Pulps," 1983 International
Symposium on
Wood and Pulping Chemistry
Proceedings, }TAPPI, Tokyo, Vol. 1, p. 153.
60. Hortling, B., Ranua, M., Sundquist,}.,
Pulp Pap. Res.}. 5: 33 (1990) .
Nord.
61. Gellerstedt,
G., and lindfors, E-L., "On the
Structure
and Reactivity of Residual lignin in Kraft Pulp Fibers," 1991 International Pulp Bleaching
Conference
Proceedings,
SPCI, Stockholm, Vol. I, p. 73.
62. Favis, B.D., Willis:}.M., Goring, D.A.I.,j
Wood Cbern. Tecbnol. 3:1 (1983).
63. Gellerstedt,
537 (1976).
G., Svensk
111
PaPPerstidn.
79:
N., Tappi
65. Gellerstedt,
G., in Metbods
in Lignin
Chernistry
(S.Y. lin, C.W Dence, Eds.),
Springer, New York, 1992, p. 322.
66. Meller, A., Holzforscbung
19:118 (1965).
Svensk
69. Theander,
Carbobydr.
(1988).
70. Forsskahl,
Carbobydr.
0.,
B.I., Holz/or-
75. Gellerstedt,
G., lindfors, E-L., Pettersson,
M., Sjoholm, E., Robert, D., "Chemical Aspects of Chlorine Dioxide as a Bleaching
Agent," 1991 International
Symposium on
Wood and Pulping Chemistry
Proceedings, Appita, Parkville, Victoria, Australia,
Vol. 1, p. 331.
----
SECTION m:
1. General considerations
. . . . . .. .
. . . .. . . . . . . . .. . .. .. . ..
reactions
in pulp
agents
. ... .. ... ..
115
115
. 115
bleaching
118
4.1 Electrophilic
substitution
and oxidation of
aromatic structures.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 118
4.2 Addition
reactions
of olefinic
strucrures
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 120
121
of hydrogen
atoms
...
124
113
ChapterID 2:
Reaction Principles
in Pulp Bleaching
1. General considerations
A precise and comprehensive description
of every chemical transformation
taking
place during pulp bleaching is not available.
lbis deficiency, in part, is attributable to the
large number and complexity of the bleaching systems currently in use. Bleaching system complexity is expressed not only by
the number of chemicals involved and the
sequence in which they are applied, but
because an individual bleaching chemical
may give rise to additional, intermediate reactive species throughout the course of the
bleaching treatment.
An additional handicap encountered in
attempting to characterize the principal
chemical transformations occurring during
bleaching is the lack of a clear understanding of the structure of the components that
constitute various unbleached pulps, particularly lignin. As was indicated in the previous chapter, information
about the
structure of lignin in unbleached
pulps
ranges from good to incomplete depending on the type of pulping process used and
on the process conditions. Moreover, with
each successive stage in a multi-stage bleaching sequence, the structural features of the
residual lignin become increasingly less distinct until a point is eventually reached
where it is no longer possible to correlate
structural changes in the lignin with the
bleaching response of the pulp.
In an attempt to address the problems
outlined above, Gierer (1-4) has developed
a concept in which the complex chemical
reactions observed in pulp bleaching are
classified according to common mechanistic types. Using this approach, the fundamental similarities and differences inherent
in the action of various bleaching agents are
highlighted. Because this concept provides
a useful background for the discussion of
the chemistry of individual bleaching stages
in the following chapters, it has been
adopted as the basis for the organization
and discussion
chapter.
115
2. Classification
of bleaching
reaction types
116
Table 1. Reactive
Reactive
species
cbemlcal
species
I. blHcbl.g.
Name
Type
E'orN'
Function in
Cl+
ct.
octCIO,
cWoronium ion"
cWorine radical
hypochlorite ion
cWorine dioxide
cation
radical
anion
radical
E
E
N
E
pH range
initial reaction
oxidant
oxidant
reductant
oxidant
acidic
acidic
alkaline
acidic
.00.
00"
HOO.
HOOHO.
OH+
+000-
oxygen
superoxide
anion radical
hydroperoxide
radical
hydroperoxide
anion
hydroxyl radical
hydroxonium ion
ozone
HS03-
sulfur dioxide
radical anion
bisulfite anion
diradical
radical
anion
oxidant
all
oxidant
alkaline/neutral
radical
oxidant
acidic
anion
radical
cation
cation
N
E
E
E
reductant
oxidant
oxidant
oxidant
alkaline
all
acidic
acidic
reductant
reductant
all
acidic
(dithionite)
radical
anion
anion
bleaching
N
N
hydroxide ion
anion
alkaline
E = Electrophile; N = Nucleophile
Derived
--
117
118
(Non-<:onjugated
units)
(Ring.oonjugated
chemi-
The reactions of cationic bleaching species with the residual lignin in chemical
pulps are among the most important and
well-documented of all bleaching reactions.
The general sequence shown in Fig. 2 is
comprised of three distinct pathways: electrophilic substitution at an unsubstituted
ring carbon, electrophilic substitution of the
units)
+X
-CI
-C-R
_c-
.~-~--
Main Attack
--
Minor Attack
'~-~OCH3
+H:10
--_
(Non-conjugated
units)
(Ring-<:onjugated
units)
~/
:~~OH
.2H'"
-ROO
.2H'"
-ROO
(8) ,,,dls.
AtliIptedfrom
H-zO
:~~oo
~o
o
Gierer (1-4).
R=H.alk~.oraryi
/
luther electrophtlic
attack by cations
X=CI.HO
polymerization
through attack
andlor degradation
by nucleophiles
119
120
cleavage of
ortho-quinonoid
rings
As noted by Gierer (3), cationic bleaching species are unable to oxidatively cleave
aromatic rings or o-quinonoid intermediates. Instead, ring rupture is proposed to
occur following the coupling of an initially
formed phenoxyl radical (upper sequence)
X-C-R
~I
.....
-.:
..
/(fOCH,
,
.'
OH ]
/0+[
.#'
()cH3
[
,........0 OH]
C-R
II
/~
[
+:;/
>v
!
,........0
OH]
+X~
A
/~ o
A
~ *
+
.-
"'"
OH
X-C-R
I
CH
.'
+ C-R
>(1
+Y'
0
H, lv, Olv
X=C1, H)
Y =a, H)
Fig. 4. AdllilUm
or Alk
~/~~
,........0
[ OHJ
.#'
.'
,........0
(3).
()cH3
[O~J
R = Alkyor
Aryl
121
122
x.
OI-r
.~"'
HO
.~
RO0
+
HClO
HelO or H2o
x= 00,..
or H2O
0, OH or OOH
A
Ftg. 6. Free radkilis
coupUrrg of pberrol-derltJf!d
rtUlkills.
--C-R
I
H~OH
...
"
'...
OCH,
0+
-<;:-R
of ini-
of the
- TYPE
124
123
STRUCTURES
Hydrogen atom abstraction from both lignin and carbohydrates by free radicals has
been postulated (2). For lignin, the hydrogen atom may be directly and preferentially
removed from the alpha (i.e., benzyl) carbon atom of the side chain as illustrated in
Fig. SA (3,9). In this process, a benzylic
hydroxyl group is converted (i.e., oxidized)
to an a-keto group. Alternatively, an a-keto
group may arise following abstraction of a
hydrogen atom from the benzyl carbon of
a cationic radical or cydohexadienonyl
radical (3). The a-keto group activates the side
chain in reactions with nudeophiles in later
bleaching stages.
The mechanism by which secondary alcohol groups in glucopyranose
units are
transformed to keto groups is illustrated in
Fig. SB. The introduction of keto groups
into hemicellulose and cellulose chain units
makes them susceptible to S-elimination
(t.e.,"peeling") reactions which often translate into losses in pulp yield and fiber
strength.
Comparison of the proposed sequences
for lignin and carbohydrate units illustrates
a parallelism that frequently is duplicated
in other pulping and bleaching reactions as
well 0,3, 10, 11). That both lignins and carbohydrates react competitively with reactant free radicals bears on the issue of
selectivity in lignin-degrading bleaching reactions. This important topic is dealt with
specifically in Chap. III 3.
..
x = 0: (unconjugated)
X
= 1:
= 2: quinonemethides
=3: extended
conjugated
carbonyl
carbonyls
groups
in side
chain
quinonemethides
8 - TYPE STRUCTURES
4.7
Addition
carbonyl
carbonyl
X = 1: para-quinones
X = 2: stilbenequinones
X = 3: vinylogous
stilbenequinones
N-=nucleophile
Fig. I). Gerlerdl sequences
of nueteopblles
cariJonyl structures
(4).
to
References
1. Gierer,].,
Hol:iforschung
2. Gierer,].,
36(2):43
(1982).
20:1 (1986).
3. Gierer,].,Holzforschung
44(5):387
(1990).
4. Gierer,J.,Hol:iforschung
44(6):395
(1990).
5. Sarkanen,
K.Y., and Dence,
Chern. 25:715 (1960).
6. Horspool,
(1%9).
WH.,
Quart.
C.W,J
Rev.
Org.
23(2):204
20:1 (1986).
X = 0: ortho-quinones
of nucleophiles
and conjugated
groups
J., Wood
K., Holzfor-
Sci. Technol.
14:241
SECTIONm:
The Chemistry of Bleaching and
Brightness Reversion
Chapter 3:
Chemistry of
Chemical Pulp Bleaching
Carlton W. Dence
Professor Emeritus
College of Environmental Science and Forestry,
State University of New York
Syracuse, NY
1. Introduction
.......
. 127
127
2.1 Chlorine
2.2 Chlorine dioxide.
....
"
............................................
"
2.3 Sodium hydroxide in alkaline extraction. . . . . . . . . . . . . . . . . . . . . . . . . . .
"
2.4 Molecular oxygen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
127
2.5 Ozone
144
3. Reactions of carbohydrates
with bleaching
132
138
141
150
152
4. Reactions of extractives
with bleaching
. . . . . . . . . . . . . . . . . . . . . ..
agents . . . . . . . . . . . . . . . . . . . . . . .. 153
125
127
128
Chapter m 3:
Chemistry
of Chemical
Pulp Bleaching
1. Introduction
Multi-stage bleaching sequences are customarily divided into delignification and
bleaching segments. In a typical delignification sequence, the bulk of the residual
lignin in a chemical pulp is degraded and
solubilized by a single oxidant or combination of oxidants such as chlorine, chlorine
dioxide, oxygen, hydrogen peroxide, and
ozone in conjunction with joint or sequential alkali (NaOH) treatments.
Oxidative
processes invariably lead to the formation
of acidic groups (carboxylic, phenolic and
enolic) that lend enhanced water and alkali
solubility to the lignin fragments to which
they are attached.
Depending
on the
bleaching chemical and. the residual lignin
content of the pulp, some bleaching may
accompany delignification.
In the bleaching segment of a multi-stage
bleaching sequence, oxidants such as chlorine dioxide, sodium hypochlorite, and hydrogen peroxide are used to remove the
remainder of chromophore systems initially
present in the lignin and those formed
in preceding
pulping and prebleaching
treatments.
Because at this juncture of a
multi-stage
bleaching
sequence
the
concentration
of non-carbonhydrate
material in the pulp is relatively low, it is essential that the bleaching (oxidizing) agent
selectively eliminate chromophore residues
while leaving the carbohydrate components
relatively intact to preserve pulp strength
and yield.
Any attempt to describe delignification
and bleaching phenomena by a set of welldefined chemical reactions is of necessity
limited by the meager amount of information available dealing with the structure of
lignin in unbleached pulps or in partially
delignified or bleached pulps. The situation
is further complicated by the fact that most
of the oxidant systems used to delignify or
Cl, + HP
+->
HOCl + W + Cl
tion pH enhances the delignification of softwood kraft pulp by increasing the proportion of elemental chlorine (2).
Other reactive species that may play a
role in chlorination are chlorine radicals (3)
and dichlorine monoxide (4). The proposed minor involvement of chlorine radicals in bleaching is based on the detection
of a dimeric coupling product after the chlorination of guaiacol (5) and on the effect of
known radical scavengers such as chlorine
dioxide and sulfamic acid in controlling the
viscosity loss (6) proposed to result from
attack of chlorine radicals on cellulose (7).
Dichlorine monoxide is formed by the
dehydration of hypochlorous acid (4):
2 HOCI
+->
qo
[2]
HP
tal chlorine and the O-CI bond in the conjugate acid of hypochlorous acid:
[1]
the overall reaction comprising the chlorination process may vary significantly depending on the reaction conditions. For
example, a decrease in the initial chlorina-
+ CI+ [3]
Substitution reactions
Hydroxyl- and alkoxy-activated aromatic
nuclei in lignin undergo rapid and extensive substitution by chlorine. Thus, in the
chlorination of a softwood kraft pulp, substitution of nearly 2 CI/C9 unit has been
observed after only five minutes' reaction
(9). Most, if not all, of this chlorine uptake
can be attributed to aromatic substitution.
:ru~ reaction is portrayed mechanistically
III FIg. lA. The number and location of ar0matic chloro substituents in chlorinated lignin depend on the amount of chlorine
applied and the number and type of substituent groups initially present.
Uncondensed guaiacyl nuclei in softwood lignin
have three unsubstituted sites available for
chlorine substitution; syringyl nuclei, typical of hardwood lignin, have but two. An
additional chloro substituent can be introduced into each of the foregoing ring types
by electrophilic displacement of a suitably
substituted side chain (see below). Under
conventional chlorination conditions, chlo-
-w
H. Alkyl, Aryl
=
R1 = H or rest of lignin molecule
W.
~~
/yoc~
/0
R,
Fig.1. ReactUmsequem:esfor aromstk sabstl",tlon and side chal" displacement Irycbloronillm Ums.
129
Pulp Bleaching - Principles and Practice
130
rine uptake by aromatic substitution in the
range 1.5-3.0 CVC9 units has been reported
for softwood kraft pulps (11-13). Chlorine
uptake by lignin becomes increasingly restricted with each successive introduction
of a chlorine atom because of the deactivating effect of the electron-withdrawing
chloro substituents on aromatic substitution
reactions (9).
The relative reactivity
of the three
unsubstituted
ring sites in uncondensed
guaiacyl units during chlorination is determined by the combined and overlapping
o,p-directing effects of the hydroxyl and
alkoxyl substituents.
Steric hindrance by
the side chain and alkoxyl substituents also
may have an effect in detennining the preferred site(s) for chlorine substitUtion (9).
The results of studies of the chlorination
behavior of guaiacyl-type lignin model compounds (14-16) and softwood lignin (13,
14) indicate an order of preference for ring
monosubstitution
of 6>5>2 (see Fig. 1 for
ring numbering system).ln syringyl nuclei,
the 2- and 6-positions are equally activated
by the two para methoxyl groups with the
result that monosubstitution
may occur
with equal ease at either site.
The solubility of chlorinated lignin in
water is decreased by the substitution of
(hydrophobic)
chloro substituents on the
aromatic ring. However, to the extent that
these substituents are replaced by hydroxyl
groups in following alkali (NaOH) treatments, both alkali and water solubility of
the lignin may be enhanced (see Sect. 2.3).
The formation of chloroaromatic structures
during the chlorination of lignin has great
environmental significance because the observed toxicity and mutagenicity displayed
by a large number of compounds identified
in spent chlorination effluent can, in part,
be attributed to such groups (Chap.VIllI).
Aromatic substitution of lignin also occurs by electrophilic displacement of the
side chain by chlorine as illustrated by sequence B in Fig. 1 (15,17). Although the
substitution reactions shown in the figure
occur simultaneously, reaction A has been
estimated to occur at about 10 times the
rate of reaction B (17). Side chain displace-
As was the case with aromatic substitution, the initial step in the addition of chlorine to olefinic groups is an attack of a
chloronium ion on an electron-rich carbon
as pictured in Fig. 2(3). The resulting intermediate undergoes attack by a weak nucleophile such as chloride ion or water forming
a vicinal dichloro unit or a chlorohydrin,
respectively. The formation of a chlorohydrin from ring-conjugated
ethylenic
structures has the effect of introducing a
hydroxyl group on the a-position of the side
chain, making the side chain susceptible to
displacement by chlorine (Rg. 1, sequence
B).
Although chlorine addition is invariably
included in lists of the types of reactions
occurring when chlorine reacts with lignin,
there is almost no direct evidence that such
reactions have any relevancy in the chlorination of pulp. However, in a recent study,
a chlorohydrin was reported to be formed
from an intermediate chloro-o-quinone in
the aqueous chlorination
of trichloromethylcatechol (32). The effect of chlorine
addition reactions on the solubilization
of lignin during pulp chlorination is, in all
C-R
II
HC
'
_0
Y:[ ]
ocH3
o OH
cblorlfU! or hypocblorous
arid to ring-conjugated
etb-
--------------.~---
131
132
R = Alkyl
Ct. = Chlorine atoms at
unspecified ring sites
Catechol
unit
/~
o
+7
Q-Ouinone
Unri
Degradation
products
Muconlc acid
Unri
Fig. 3. RetU:U018S6q_es
for cleavllge of IIIIlyI aryl etllers (.tdllylatftm)
benzoq,"_
Irrterrrretlllltes by cblorlflt! In IItJfIJfISffIt!tlitl.
of 0-
deHgnification
because it leads to the
splitting of a lignin interunitary bond. Because some B-aryl ether structures are
present in the residual lignin in kraft (26)
Pulp Bleaching
- Principles
and Practice
+ 5 e- ~ CI" + 4 OR"
[4]
"--~
~_._-
[6]
133
134
rine substitution. These reactions are discussed below as they apply individually to
phenolic and non-phenolic units and ringconjugated ethylenic groups.
Phenolic units
Several of the proposed sequences for the
overall reaction of phenolic lignin units with
chlorine dioxide are outlined in Fig. 4 (3,
49, 57-59). The initial reaction in all instances is the formation of the phenoxy radical (IA) and its mesomeric radical forms
(lB-ID) by a one-electron oxidation. The
coupling of these various radicals with additional chlorine dioxide leads to the formation of chlorous acid esters (Fig. 4,
lIB-lID). On decomposition, the latter structures are convened to o-benzoquinones or
the corresponding catechols (49, 57, 60),
p-benzoquinones
(49, 59, 61, 62), and
muconic acid mono methyl esters (38, 49,
57) or their lactonized forms (49, 57, 59,
62) with release of chlorous acid or hypochlorous acid in one- or two-electron oxidation reactions.
The conversion of guaiacyl nuclei to
muconic acid monomethyl esters and their
cyclicized (i.e., lactonized) forms (Fig. 4,
IIIBI) is an important degradation reaction
in chlorine dioxide bleaching because it
leads to increased water and alkali solubility of the residual lignin. Muconic acid
structures and their corresponding lactones
are also subject to funher oxidation reactions in which dicarboxylic acid fragments
are formed (63-65).
The most prominent reaction of those
shown in Fig. 4 is oxidative demethylation
(57,59). The prevalence of this reaction is
indicated by the high yields of methanol
found in the reaction mixtures following
treatment of lignin model compounds (59)
and lignin (37, 62) with chlorine dioxide.
The initial product of oxidative demethylation is an o-benzoquinone derivative (Fig.
4, lIB). The latter is not convened to a
muconic acid derivative by chlorine dioxide, but instead undergoes dimerization and
polymerization reactions (57) that have a
retarding effect on delignification.
Conversely, funher oxidation and degradation
of o-quinonoid units through the proposed
_A
R=HorSldeChain
.-~~
Biphen)i
Structures
OH I
+clO'l-
/~ o
HCIO,
IB
/~o lIB
'I -
+H,o
+H,o
_
HOCI(CI.)
Lactone
esters
+H,o
-HCIO,
HCI02
CHpH
Condensation and
reduction products
135
136
R,==
R,
Side chain
Alkyl or aryl
Aryl
of
aroxyl
lCIO,
,I- ,==()
==,~
.- YOCH,
'-R~OCH'
/O+
R
IB
I'"
.- TOCH,
IC
R/O
ID
["t']!
[+]1"
-C-R,
R
000
COH
"'"
t>-
..-
~0cH,
,Q,
RP
/0
R,
.-
j'-HCIO
- CH,OH
-w
cf
/~
OCH,
000
.-' '
/0+
R,
lIB
IIA
HC-OH
[,
- HCIO
OCH,
/0
R,
["'
-w
IIC
lID
["'
instances once
atom/aromatic
applications of
ring is then oxi-
dized
Chapter
m 3: Chemistry
of Chemical
Pulp Bleaching
137
138
H, aryl, or araxyl
ij
..,
80
80
60
60
ij E
.~ '"
~E-o
e <Ii
"'<z:
0"';:;~c: 40
o <Ii
:E-o.U
'0 20
"#
0
/~~
/0
Hi
/0
40
80
60
Cl02 Substitution, %
40
a.-.g
.~
~.c
20
E:'::
00
..( ,0
C'
0
100
V
CI02
a-C-R
I
/~~
/0
20
'g
=>1:1
~-0'"
e
a-C-R
I
/~
100
100
C-R
VI
Fig. 6. Seqrmu:e for tbe reaction of chlorhre dioxIde with ri.g-conjugated etbylenic groups
(3,68,69).
.ClO + CIO, + H,O + ClO;- + HOCI + H+
Either of these two chlorinating
agents
[7]
may,
c:
'"
o
..c
o
o
]
E
Z=>
o
o
20
40
60
CI02 Sulmitution,
80
100
or ethylenic carbons
RCOOH
Carboxylic
(R
=
Aryl
or
Carboxylate
acid
anion
Alkyl)
\
Phenol
C-QH
II
He
Phenolate
C-O-
HO-
He
I
Enol
f).
Enolate anion
NeuIrfllizllHoll
tioruIl
+ H2O
II
Fig.
anion
grtnI/JS
of lignill-tIerlreti
i. prebk4ebetl
addle jilrreJItIlps.
139
(i.e., 1,2-dihydroxybenzenes)
appear to be
dominant in the extraction effluent of a
chlorinated pulp but, in the corresponding
effluents of oxygen- and chlorine dioxidepretreated pulps, the guaiacyl-type prevails
(70).
Enol groups arise from carbonyl groups
adjacent to carbon atoms containing an ahydrogen. Although this structural requirement is met by lignin in unbleached and
prebleached pulps, the contribution of enol
groups to lignin solubilization in alkaline
treatments has not been established.
Base-catalyzed
hydrolysis of organically
bound chlorine
A large fraction (ca. 60-70"10for kraft pulp)
of the organically bound chlorine in chlorinated pulp is removed in the ensuing extraction stage (72-74). In a study of the
base-<:atalyzed hydrolysis of aromatic and
aliphatic chlorine-substituted
lignin model
compounds under simulated alkaline extraction conditions, loss of chlorine invariably
was found to occur although to widely varying extents (75). Chlorine bound to aliphatic structures, for example to the lignin
side chain and to aromatic ring oxidation
products
such as o-benzoquinone
and
muconic acid derivatives, is extensively
removed. Although less susceptible to alkaline hydrolysis than the foregoing structure-types, even chloroaromatic derivatives,
particularly phenolic moieties, sustain a significant loss of chlorine on treatment with
alkali.
The removal of chlorine from lignin during the initial alkali extraction stage may be
described mechanistically as a nucleophilic
displacement reaction in which a chlorine
atom is replaced by a hydroxyl group. Two
types of displacement reactions are illustrated by the sequences in Fig. 10 (3). As
shown in the right-hand sequence, chlorine
attached to a side chain may be displaced
through attack of a neighboring alkoxide
group to form an oxirane and, ultimately, a
glycol structure. In the left-hand sequence,
the end-product of chlorine replacement
from an o-quinonoid unit displacement may
be viewed as a vinylogous enolate ion
(Fig. 9, bottom sequence). In each of the
140
~
~
-C-CI
I
HOC-
HO-
-H+!
+ HO-
-c-o
-o-c-
"
.--""-
0-
Joc
I
-OOH
1~
O~
.--yo
0Fig. 10. Sequ1u:es for tH lHrse-catillyze4 elimitUlo
titm of Mg..leally bormII cblorltle (3).
141
142
OH
HO
H
---A
O2
- e, H~
HOO-
pKa
tl
4.8
OCH3
- e, H~ HOOH - e. H+.
HO' + -OH - e. H+. 2 H20
I.
H+ + -00'
tl
10.5
tl
11.3
I.
I.
W + -OOH
W + -0'
[9]
[10]
(M=transition metal)
C
Fig. 11. Seqrumce for tbe j'ormstion
wltb aliI/IIi.
of eondenseJl structures
143
R = H.alkyl,arylor aroxyl
..-y~
0-o~
Alphatic
degradation
products
.II
ofpbellolk
"
IIpl"
"
I
C-R
-c
144
C
,,"Ils 10 oxIrrme (A), tmICOIIk add (B), aIId
II(
,
YOCH3
,'00
,x
YOCH3
o
R = Side chain
M Trans~ion metal
=
carbonyl groups
Ring-<:onjugated carbonyl structures in
lignin react with oxygen under alkaline conditions in a series of steps (Fig. 15) which
lead ultimately to the cleavage of the Co-C.
bond in the side chain (3, 89, 105, 106).
Key steps in the sequence include the formation of a hydroperoxide anion followed
by the intramolecular attack of this nucleophile on the carbonyl carbon atom to form
a four-membered (dioxetane) ring structure
2.5 Ozone
Ozone is a triatomic, non-linear allotrope
of molecular oxygen that can be viewed as
a resonance
hybrid of four mesomeric
forms:
~O,
/0",
_ _
_
/0,
+ /0,
c=o
+OH-
OCH,
CfI~
.--
/0
02
OCH3
/0
= H. alkyl.
tbe retldlon
aryl
OCH,
.--
HOO-(02')
+ 02
O=C-R +
O
~C=O
OCH,
/0
6 ~
OCH3
OCH3 ~
--H20,.-0
/ 0[OH] 0
.--""'- 0
o
/
-lOH]0-0
:;n
:;n
+H 0
+H 0
CH,H.--
with CIIrlxmyl-eonj"gatetl
[11]
+ HO. (12)
[14]
[15]
strllctrlres
OCH3
0
/ 0[OH] 0
OCH,
/0
C-R
II
o
or aroxyl
[13]
-+
~C-O-
/0
ofoxygen
HO;
Cf1- cf1-
03
O-C-R
~C=O
1-
.--
O-C-R
c=o
146
Lignin
JC-R
He-R
145
(3).
R=ArorOAr
R
aryl or aroxyl
aryl ethers and stilbenes, are readily degraded by ozone (3,119). In the sequence
outlined in Fig. 16B, the initially formed
ozonide, a 1,2,3-trioxolane,
decomposes
and is reformed into 1,2, 4-trioxolane (secondary ozonide). On hydrolysis of the latter, the ethylenic double bond is ruptured
and the ethylenic carbons are converted to
carboxyl groups.
Alkyl aryl ethers, represented by B-aryl
ethers in lignin, undergo ozone-induced
cleavage (118). Cleavage of the ether linkage can result from attack of ozone at the
alkyl or aryl end of the linkage. In the first
instance, ozone initially attacks the B-hydrogen-carbon bond and a 1,~ipolar insertion
reaction leads to formation of a hydrotrioxide (Fig. 17, right-hand sequence).
Following the loss of a hydroperoxide radical,
Ca-C. cleavage occurs and the ester fragment is ultimately converted to creosol.
Electrophilic attack of ozone on the aryl
component ofthe B-aryllinkage leads to the
cleavage of the aryl-oxygen bond and formation of a diol with accompanying release
of the B ring as an o-quinone (Fig. 17, left.
hand sequence).
-02
- CH30H
1-000.
HC +
'~_'
/~o
0
/0
H20
1
r3
<>-0
I
Threo
Isomer
~/
y
. .))
.-y~
CH3
1+ H.<'
t - CH3COOH
.~OH
(18).
147
148
3. Reactions of carbohydrates
with bleaching agents and
alkali
Although the chemistry of pulp bleaching mainly involves the reactions of lignin
with bleaching chemicals, carbohydrates
nevertheless undergo concurrent transformations during bleaching that often have
an important bearing on the strength properties and yield of the resulting pulp. The
impact of these reactions becomes increasingly more significant as the lignin content
of the pulp decreases. The reactive sites
for attack by electrophilic bl~d1ing s~ecies
on carbohydrates
are shown in Fig. 1(B)
(Chap. III 2); nucleophilic sites in carbohydrates include acetal (glycosidic) linkages,
--'-'----
149
o
o I?O
11 C
0Me
'"
H.z9/0'CH
1
I
HC-CH
I
1
He,
CH:2
RH + CI2
O-OMe
K,F
HCOH
o=c
HCOH
~
6
tiOCt\>
HC
HC-O
MeO-:
~
B
H'
o=c,
OMe
C-OMe
C II
II 0
0
CH,OH
I
HCOH
II
C-OMe:o
W
I
o lI'o-C-HC
o
I'
HOCK,
"
O-W
o
d'
OMe
OH
of OZOlUlted soft.
GI-f2OHo
GI-f2OHO
R
'0
+CI.
-HCI
D
OH
R. + CI. + HCl
CI2
.R-\OH-CI.
OH
<;:H"OH0
0,
-ROH R
R-,OH
a
+2H.o
OH
IOH
X ~
Cellulose
GH.oHo
R
\
O
OH
-02
R
H
~
OH '0
0
residues
seqaeru:es
0
C
+0,
4:r
H20
-ROH
co-o-o'")
[16]
-C-CH,OH
,
A'"
II C
IF~?
o""y ~
cleavage
R, OH
0
COOH
OH
of glycoslilk
IIniages
In cell"lose
150
Pulp Bleaching
- Principles
and Practice
- Alkoxy
of alcohol
groups
elimination
+
(C)
1-"
Oxidation
of Ketol B
ROH
~t' 0
-----
->
RCI + HO.
[17]
[18]
151
152
R-C-OH
II
R-
O-O-Q-H
.-----------.------..----------------------.------.--.-----.--------.--------.----------------.-------.----.-----..--COOH
/
B
-1-
H
(f)
o
It
HCOH
'c
I
-C=O
I
-C-
(9)
Step-wise
depolymerization
COOH
I
HC-QH
I
-C-
of carlJol1yllrtlte
redtIdIIg
end groups
with bleaching
chemicals.
Compound
Veratrylglycerol-B-guaiacyl
of bydl'O:ltJI rtJdkllls
IIIItb lip'"
tIrUl Ctlrbobydrtlle
Veratrylglycol
1.5 X 1010
ether
153
1.7 X 1010
Methyl B-D-glucopyranoside
3.2 X 10'
Methyl B-D-xylopyranoside
2.6x
10'
model
rom-
154
Pulp Bleaching
-Principles
and Practice
OH
A'V~
>=<
B
o
2 -!!oH
9Q:...
CIO:!, 00-
!
CIO:!
/''1''-
.......
2,;;c=o
+ C1:1 (HOCI)
OH
~
Fig. 22, Reaclkms
of "leaebi"g
.g"""
11II1"elbyl""k
grtn'ps
,,, exIrtu:UfJf!:S.
References
1. Hise, R.G., "Chlorination
of Pulp," Bleach
Plant Operation Short Course Notes, 1992
TAPPI PRESS, Atlanta, pp. 69-77.
2. Russell, N.A., Tappi 49(9):418
3. Gierer,}.,
(1966).
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Chemical
Technology
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and
Chemical
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7. Fredricks, P.S., lindgren, B.O.,Theander,
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12. Erickson,
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79(10):316
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32. McKague,
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55. Lindgren,
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78:66 (1975).
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34. Dence,
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27. Gellerstedt,
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G., Tappi
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PJ., McDonough,
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}., Holzfor24(10A):671
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28(lOA):V9
Pap. Mag.
Can.
SECTIONill:
The Chemistry of Bleaching and
Brightness Reversion
Chapter 4:
Chemistry of
Mechanical Pulp Bleaching
Carlton W. Dence
Professor Emeritus
College of Environmental Science and Forestry,
State University of New York
Syracuse, NY
1. Chromophores
in unbleached
1.1 Coniferaldehye-type
(cheml)mechanical
structures.
units.
1.5 Stabilized
complexes.
free radicals.
.........
163
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
164
methideintermediates
1.4 Metal-catechol
pulps.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Chemistry
167
of dithionite
(hydrosulfite)
bleaching.
. . . . . . . . . . . . . . . . . . . . . ..
176
161
Chapter m 4:
Chemistry
of Mechanical
Pulp Bleaching
Carbonyl group
163
Ethylenic group
164
Pulp Bleaching
-Principles
and Practice
J:
N
I
1. Chromophores in unbleached
(chemi)mechanical pulps
The objective in the bleaching of (chemi)mechanical pulps is to selectively remove
color-contributing groups (chromophores)
while simultaneously preserving pulp yield.
In current practice, this involves mainly the
use of bleaching agents such as hydrogen
peroxide and sodium dithionite (sodium
hydrosulfite).
Notwithstanding
the enormous importance of chromophore
structures in dictating the ultimate extent to
which (chemi)mechanical
pulps can be
bleached, the origin and identity of the entire array of color-contributing structures in
these pulps remain to be'.convincingly established in many instances.
The color of wood itself is variable, exhibiting dependence
on such factors as
plant species, growing conditions, composition, and microbiological breakdown (1).
On storage, wood may become further discolored through the influence of air, heat,
light, and fungal activity. In the refining
and grinding operations used to produce
(chemi)mechanical
pulps, the combination
of mechanical action, heat, added chemicals, and transition metals may also contribute to discoloration (2). Although every
principal component of wood -lignin,cellulose, hemiceUuloses, and extractives
has the potential for contributing to the
overall color of wood (3), lignin is generally singled out as the constituent having
the greatest direct influence on the color
of wood (2, 4-6). Because wood components are largely retained in the production
of (chemi)mechanical
pulps, lignin or
chemically modified lignin is also regarded
J:
N
+
Aromatic ring
J:
N
I
J:
N
+
J:
I
9J:
+
J:
N
I
J:
+
'"
J:
N
I
J:
N
+
-{)-oj
\
structures
165
166
--9=,
OH
1-
+2
Fig.3. Structurtd ~
cateebol complex.
(H\
'l
of IIferrtnlSlron-
1.6 Leucochromophores
Leucochromophores
comprise a class of
structures that, although nominally colorless, are readily converted to chromophore
systems through dehydration or dehydrogenation reactions as illustrated in Fig. 2.
Transformations of this type have the potential for significantly affecting pulp brightness. For example, the ease with which
hydroquinone (1m) and catechol (lIm) derivatives are oxidized to their chromophore
counterparts is a distinct disadvantage in
reductive bleaching where brightness gains
may be partially offset by successive re-conversion by air oxidation of the leuco (colorless) form to the quinonoid (colored)
form.
Inclusion of the stilbenequinone, VIB, in
the group of leucochromophores
is based
on the finding that structures of this type
are formed when diarylmethane-type lignin
model dimers are subjected to mechanical
action in a ceramic ball mill or a disc re-
1
Resonance-stabilized
radicals
Fig. 4. 6e1wral retU:tltm seqrunu:e for pberwxy
c4l f0rm4tKm
I.. lip''',
rtUU-
HOO- + H20
[1]
This ion is a strong nudeophile, exceeding the nucleophilic reactivity of the hy-
10.0
10.5
11.0
11.5
Initial pH
12.0
12.5
JIll ad flul
bletlcbi.g of
[2]
[3]
167
168
[6]
Chromophore
elimination
reactions
The reactions of side chain enone structures with hydroperoxide ions are outlined
in Fig. 6. Coniferaldehyde
units (A) are
present in softwood lignin to the extent of
4-5/100 phenylpropane
units (4]). Enone
structures of the type represented by B in
the figure are not initially present in native
lignin but may be formed from phenacyl-<xaryl ether units on treatment with alkali
(44) alone or by hydrogen peroxide in alkali (45,46). The initial step in the reactions of these two enones, a conjugate
addition of hydroperoxide ion, is formally
a reduction process (47). Succeeding rearrangement and oxidation reactions lead to
the rupture of the n-S bond in the side chain
and formation of aromatic aldehydes for Atype structures (48,49) and aromatic carboxylic acids for B-type structures (45,46).
In the process,
the conjugated
chromophore systems of enone types A and B
(Fig. 6) are interrupted with the result that
the absorption maximum of each is shifted
from the near-visible to the UV spectral region, that is, "bleaching" occurs.
The aromatic aldehydes formed by reaction of contferAldehyde.type strUCt\IJ.'rS(A)
with alkaline hydrogen peroxide may, in
turn, be converted to p-benzoquinonoidtype chromophores by the Dakin reaction
as described below. The formation of phenolic end groups in the reaction of B-type
enones with hydroperoxide ions (Fig. 6) also
has important implications with respect to
the generation of new chromophore systems.
0- and p-quinonoid rings are comprised
of dual enone elements which offer multiple sites for attack by hydroperoxide ions
as illustrated, in part, by the sequences in
Fig. 7. The common feature of all these sequences is the destruction
of the chromophoric
systems terminating
in the
formation of carboxylic acids (50-54). Relatively simple carboxylic acids have, in fact,
been detected in the effluents from peroxide-bleached mechanical pulps (52,53).
When the quinonoid rings are condensed,
that is, linked to adjacent lignin units by
carbon-carbon or stable ether bonds, carboxylic acid fragments remain attached to
the lignin network as evidenced by its increased carboxyl content (51,55). Besides
carboxylic acids, methanol invariably is
formed from methoxyl-substituted phenolic
and p-quinonoid rings during the reaction
of lignin (52,53,55) and lignin model compounds (46, 50, 51, 52, 56, 57) with hydroperoxide ions.
Hydroxide ions, the other major nucleophile present initially in alkaline peroxide
bleaching system (Table 1), in principle may
attack enone units in quinonoid structures
in a manner analogous to the much stronger hydroperoxide ions. As an example, the
conjugate addition of a hydroxide ion to an
o-quinonoid ring is outlined in the left.hand
sequence of Fig. 8. The hydroxylated catechol dianion formed (41) is a leucochromophore (see Fig. 2) and is readily reoxidized
to a hydroxyquinone
structure by molecular oxygen, hydroxyl radicals, or specific
metals in the appropriate valence state as
described below in Subsect. 2.2. In the
right-hand sequence in Fig. 8, attack of a
hydroxide ion on the carbonyl group of an
o-benzoquinonoid
ring is pictured as giving risc (Q a ring contr.lctlon by a benzylic
acid-type rearrangement with accompanying
partial destruction of the chromophore system (41).
169
170
Conjugate
addition
HCOO+
l-~'
1
~oo
roo
~-o-
~o
. ,
~~HO<r
"
./
~-HO
OCH;,
~~o
0-
./
/0~
l-w
HCOO+
ROH
+
I
Carboxylic acid
fragments
coo-
/~./
--~:
~~o
o
0-
HOD-
HO
IH~
~1-=
1
GartJoxyllC
Carboxytic
Fig.6. ElIml1Ul1lonof _
oxide lOllS(41.42).
acid
fragments
sUIechain cbromo'/Jbore smu:"'res IryreflCtltmwltb Irydroper-
Fig. 7. ElIml1Ult1tm
of 0- find p-qrdrunwlll
cbromopbore
IIdd
fragments
Carboxytic acid
fragments
systems
Ions ( 41).
Nucleophiles
0/-0,-)
HO-
HOO'
HO'
0,'
171
172
l~
-- \::0
~
Stilbenequinone-type
~f~l,
o
1
Fig. 8. Eltml",,1ttm
of fJIIltIOfUJitl cbromopbof'f!
Kms.
tems by f'f!tICIUm wit" bydroxtde
sys-
~--
~~~b_
#
" ~0- C>CI'\
173
#
"
~,HO..orM+
HOO1
~~-
!{
~"
"
~C>CI'\
~C>CI'\
j-HO-
j
J/OH
~-
--9-000
"
C>CI'\
~,
b=a
~,
I I
"
1-~
"
~C>CI'\
~
~II
C>CI'\
HO-
--~-"'-l~
~--~~
l-oow
OH
Reduction
(Proton donor)
~,HO.,orM+
Oxidation
"
~C>CI'\
--~
0
Fig. 10. FomJIItkm of'l,dtUmOiIl cbronwpbore arulleru:ocbrrnrropbore systems by reactiorr witb diff-t
ffucleopbiles arul electropbiles.
174
= H,
Aryl,
175
<;:HzOH
b-R1
/~
It'
l-~-
Stilbenequinone
chromophoresystem
arrtl slilbeae
'1'11-
clmnrwpllore
systems
or Alkyl
R1 AryIoxy
Conjugetedenone
chramophoreaystem
176
very
fry base-eatJJlyzeti
few exceptions,
unavail1ble.
One such
Oxidanl
(b)
(e)
(eJ
Fig. 12. Sfldflres resistteatto degnulatkm frybydro/J6f'fdIk Was arrtI tbe deeompositkm
protlru:1s.
502 + 5022-
[8]
520l- + 2 H20
2 HS03- + 2 W + 2 e- [9]
Under bleaching
conditions,
sodium
dithionite is unstable, particularly in the
presence of oxygen, and undergoes oxidation and auto-oxidation-reduction
reactions
leading to the formation of complex mixtures of inorganic species that includ~
sulfite, sulfate, thiosulfate, and polythionate
ions (85-87). These decomposition
reactions are described in greater detail in Chap.
V 2. Apart from bisulfite ions which have
found limited use in the bleaching
of
groundwood and disc refiner pulps (88),
dithionite decomposition
products other
than sulfur dioxide appear to have no
demonstratable
role in chromophore
removal.
177
178
H
R-C=~-CH.10H
A
H
AC=C-a-tO
H
HS03-
of f/IIi-imu.
arul COIIifemltlebyde-type
chemimechanical
pulping (97-99). In all
four examples shown in the figure, the reactions lead to the partial reduction of the
chromophore system and the displacement
of absorption maxima from the visible region to the near-UV spectral region.
Under pulp bleaching conditions, a-aryl
ketone-type structures are generally unresponsive toward reduction by dithionite
(90,91,93).
At higher temperatures and
in mixed solvent systems, aliphatic and aromatic aldehydes and ketones are reported
cbromoJlbores
H
R-C-~-CHO
I
saz-
H
R-C=C-C-H
H
OH
I
I
S03OH
H
R-C-CHz-C-H
S03-
I
I
503-
~-
References
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54. Gierer,].,
and Imsgard,
Scand. B31:546 (1977).
G.. Acta
62. Gierer,
]., Yang,
E., Reitberger,
Holzforschung
46(6):495 (1992).
44(5):387
Pearl,
61. Agnemo,
R., and Gellerstedt,
Chern. Scand. B33:337 (1979).
Wood
Sci.
71. Nonni,
A.J.,
HolzJorschung
and
Dence,
42(1):37 (1988).
C.W.,
P.].,
Appita
lpn.
and
Sumimoto,
M.,
45(Suppl.):15
(1991).
78. Ericsson,
B., and Malinen,
Chern. Technol. 8:327 (1974).
79. Isbell, H.S., and Frush,
Res. 59:25 (1977).
80. Larsen, B., and Smidsrod,
Scand.
R., Cellul.
H.L., Carbohydr.
0., Acta
Chern.
21:552 (1%7).
]., Holzforschung
44(5):387
Symons, M.CR.,
W.H.,
Tappi
Pap.
92. Pokin,].,
and Rapson, WH., Pulp
Mag. Can. 72(3):T1l4
(1971).
Pap.
93. Pokin,].,
S.-L.,]
Org. Chern.
181
(1973).
P.,] Pulp.
46(26):5457
Chern.
98. Gellerstedt, G., and Zhang, L., "On the Behavior of Reactive lignin Structures
in
High Yield Pulping," 1991 International
Symposium on Wood and Pulping Chemistry Proceedings,
APPITA, Parkville,
Victoria, Vol. 1, p. 81.
99. Suckling,
I.D.,
"The
Effect
of
Coniferaldehyde
Sulfonates on the Brightness
and. Absorption
Spectra
of
Chemimechanical
Pulps," 1991 International Symposium on Wood and Pulping
Chemistry Proceedings,APPITA,
Parkville,
Victoria, Vol. 1, p. 587.
100. DeVries, ].G., Van Bergen, T.]., Kellogg,
R.M., Synthesis 1977:246.
101. Minato,
H., Fujie,
S., Okuma,
K.,
Kobayashi, M., Chern. LeU. 1977:1091.
SECfION ill:
The Chemistry of Bleaching and
Brightness Reversion
Chapter 5:
Chemistry of Brightness Reversion
and Its Control
Cyril Heitner
The Pulp and Paper
Research Institute of Canada
Point Claire, Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Experimental
yellowing.
. . . . . . . . . . . . . . . . . . . . . ..
185
185
185
. . . . . . . . . . . . . . . . . . . .. . . . . . . .. . . . . . ... .. . . . .. . . . . ..
186
187
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 188
yellowing..
. . . . . ... . . . .. .. . . . . . . . . . . . . . . .. . . . . .. . . . . . . ..
4.1 Chromophoreformation
4.2 Role of oxygen in light-induced yellowing.
190
190
. . . . . . . . . . . . . . . . . . . . . . . . . .. 1%
5.Summary
209
183
Chapter m 5:
Chemistry of
Brightness Reversion
and its Control
1. Introduction
Ugnin-containing pulps, thermomechanical (TMP) and chemithermomechanical
(CTMP), are used primarily for the production of newsprint, advertising inserts, directory paper, and some catalogue papers
all short-life products. These pulps can be
bleached to an ISO bdghtness level of about
80% using two alkaline hydrogen peroxide
stages or an alkaline hydrogen peroxide
stage followed by a sodium dithionite stage._
At this brightness level, these pulps can be
used in furnishes for the manufacture of
business forms, copy and reprographic papers, tablet and writing papers, and highgrade publication
papers for books, all
long-life uses. However, papers made from
bleached TMP and CTMP turn yellow during use, a property which restricts their use
to short-life papers. It has been suggested
(1) that, if the time taken for light-induced
yellowing of these papers could be increased by 3-36 months, the potential market for bleached TMP and CTMP would be
expanded by 0.6-2.2 million tons per year.
If the tendency to yellow, termed brightness reversion,
could be prevented,
bleachedTMP and CTMP could be included
in furnishes used to manufacture
highbrightness papers (2).
Brightness reversion may be classified
according to the following two processes:
185
(l-Rj/2R.
[1]
= 100{(k/S)attt<a_(k/S)bdo",_}
[2]
186
of chro-
and mechanical strength) decreases with deceasing temperature (6). These results suggest that accelerated thermal aging not only
increases the rates of reactions occurring
under ambient conditions, but also initiates
color-forming reactions that occur only at
elevated temperatures. Therefore, accelerated thermal yellowing at temperatures of
80-1OOC may lead to uncertain conclusions
about
the extent
to which
paper yellows in the dark at room temperature.
The use of IN-rich light to accelerate
light-induced yellowing can produce results
comparable to those obtained under ambient conditions (i.e., under natural or artificial daylight),
provided
the emission
spectrum of the IN light source has a similar wavelength range and light intensity distribution as the IN region of the ambient
light.
3. Thermal yellowing
Thermal yellowing of lignin-containing
paper is caused by storage in the dark under warm and moist conditions, for example, during paper roll storage in the
manufacturer's or customer's warehouse or
during storage in an office filing cabinet.
Excessive yellowing due to thermal reversion often causes the brightness of the
paper to decrease below contracted specifications leading to increased costs to the
16
Jack pine
heartwood
14
....
Q)
.c
E
:]
c:
10
0
(5
0
en
0
a..
12
Jack pine
sapwood
~Westernhemlock
heartwood
Western hemlock
sapwood
1
2
~Peroxidecharge, % on pulp
~_._--_.
Chapter III 5: Chemistry of Brightness Reversion and its Control
187
188
Species
/JIIlp (7).
Thermal reversion
(&em' m2/kg)
Softwood
Cedar
Balsam fir
Black spruce
White spruce
Larch
Jack pine
0.6i1.0
0.9:1:0.3
1.110.1
1.210.1
2.010.5
2.510.6
Hardwood
Birch
Poplar
1.310.8
1.210.2
30
o Unchelated
100C,
70
III Chelated
o Unchelated
ED Chelated
23C, 50% R.H.
60
0% R.H.
C>
.:JI!. 20
N"
E
,::.
It)
:2 10
<1
C>
50
.:JI!.
N" 40
J<1
~30
20
10
o
SGW
TMP
HYB
TMP or RMP
SGW
Pulp type
Fig. 1. Yell_Ing of stone gt'OfIn4uJood (SGW), t~kal
under 4IXBlertdell aging corulttlorts (11).
HYS
Pulp type
JIIIlp (TMP), IIIUlblgb yklil S8lfth! (HYS)
(SGW), tbermomeclHmkal
189
190
1.5% Peroxide
...
~
5% Peroxide
c:::
Ambient
conditions
OH
~ 10
E
::J
~
6-
1 % Dithionite
...
o
"0
o
-IoI)
a.
Sebeme1.
the lower extent of yellowing of peroxidebleached HYS pulp compared with that of
unbleached HYSpulp.
.:.:.
-C\I
o Unbleached
Peroxide-
bleached
23C, 50% R.H.
Dithionite-
bleached
40
E 30
~II)
v 20
.:.:.
<I
10
0
SGW
TMP
HYS
Pulp type
Fig.4. Yellowlllgof ~-
IlUbkmUe-bletIcbetl
SWlle~
(SGW),tbermtnrleelHm,"1
pulp
(TMP),
blgb-yNlIl s"lflte
""" (HYS) "ruler tlf!lerwIetI IIgllIg WIIIlIHmu (7, 18 ,19). No"'"
IIf)/dltlble
"""for tbe yellowlllg of tUtlmmite-bletlcbell HYSpulp.
tWe
100
200
Aging time, h
(18).
"""
300
400
roII-
4. Light-induced yellowing
Photochemical reversion or light-induced
yellowing of lignin-<:ontaining paper can
lead to brightness decrease of more than
30 points in a short time (6-8 months).
Under identical conditions, light-induced
yellowing of bleached kraft pulp (i.e., a lignin-free pulp) causes only about 3-points
loss in brightness. As a result, kraft pulp is
used in the manufacture of produ<.:ts where
long life is important.
Early studies led to the conclusion that
thermal- and light-induced yellowing are
attributable to chemical changes in the lignin,specifically the oxidative demethylation
of aromatic methoxyl groups (24-28). Further progress in elucidating the yellowing
reaction pathway was hampered by lack of
knowledge about the structure of lignin.
-~~
191
192
12
Unbleached
....
....
CD
1 % Dithionite
-+-
1.5% Peroxide
.......
.c
E
:J
C
....
o
(5
o
1i)
;:R.
-+-
'S;
:g
Q)
:;:::
Q)
....
Q)
o
a..
>
..as
Q)
a:
20
60
50
30
40
Aging time, h
..
85
80
75
Relative reflectivity
R(irradiated)lR(initial)
250
x 100
20
....
Q)
-+-
.a
350
400
450
500
550
Wavelength,
nm
600
650
300
350
400
600
650
125
[3]
(R=Reflectance)
Unbleached
~
1.5% Peroxide
300
tIfIlfIrwIfIfl
25
:J
c
~90
70
10
95
5% Peroxide
1 % Dithionite
i-
~120
'S; 115
..0
Q)
110
:;:::
Q) ~105
..>
as 100
Q)
a:
95
90
-+-
250
5% Peroxide
.......
450
500
Wavelength,
nm
550
15
....
'0
0
UJ
0
a..
10
5
Fig.7.
100C, 0% R.H.
10
20
30
40
Accelerated aging time, h
..
~tblolllte-iIIfIGebM
m1HI1IIul
90
JIfIIp "ruler
tIfIlfIratetl
C)
~(:;j-
194
Pulp Bleaching
-20
I
I
I
I
I
CL
-40
~I-
;r
/'"'"
'-/
\
\
~-60
t>
;r
,t, I
/
I
-Principles
and Practice
40
/,...,--
CL
193
I
I
C)
Na2S03 Charge,
% on wood
-1
---
~
.......
C\I
20
'.L
<I
-80
350
400
Wavelength,
300
250
450
nm
500
550
260
340
420
500
Wavelength, nm
580
O-lignin
Scheme 2. Pbo/~
","."".
sodium periodate and that of vanillin irradiated with near-UV light are nearly identical, suggesting that photooxidation
of
vanillin produces a quinone similar to that
known to be formed by sodium periodate
oxidation.
Solid state 31p NMR spectroscopy of mechanical pulp derivatized with trimethyl
phosphite has provided more direct evidence for the formation of o-quinones in
light-induced brightness reversion (33).
When applied to refiner mechanical pulp
(RMP), this derivatization treatment led to
a decrease in the specific absorption at 457
nm before and after UV irradiation (fable
2), indicating that trimethyl phosphite had
reacted with chromophores in unirradiated
and irradiated pulp resposible for most of
the color. The chemical shift in the solid
Q
"'"
OMe
O-Lignin
Scheme 3. AJl411Umof sodl_
.""
(30).
O-Lignin
O-Lignin
Sample
Untreated
4. RHcIIorI
49
13
186
RMP
~o
~o
o_rl__OMe
O_P.
/~o
MeO
MeO/'-OMe
31p NMR CHEMICAL
SHIFT, -45 ppm
Scheme
RMP
6'"
(MeOhP
O-Lignin
group 'It II COftifemlllebytle
Specific
Absorption at
457 nm (cm2/g)
Lignin
Lignin
O~
oftrimetbyl
pbopbIIe
wllb 11fto-tl'IItU1IWId
31 P NMR CHEMICAL
SHIFT, 11 ppm
lIpl"
.""
(33).
42
195
1%
40
Untreated
C)
20
-20
.::t:.
.....
C\I
C)
E -40
.::t:.
.....
C\I
-60
E -20
~
<! -40
TMP brightness
Unbleached
-80
Bleached
57"k
C=O
in BTMP
I
77%
/"
NaBH4-reduced
'/
-60
-100
320 - 330 nm
-80
250
300
350
400
Wavelength,
Fig. 12.f/t of~
C=Ofrom
irradiation
550
250
300
coe.fllcie18t (i(tl).j,_)
ofTMP (31).
(t.e.,
MI:
= 0)
as seen
in Fig. 13
o;
HC=O
H""",oOH,-OOHI
,
OMe
Q-Lignin
350
400
450
500
550
600
Wavelength, nm
nm
500
450
H
HOCH2C=O
OMe
wood
O-Lignin
tWbu:1fmI 018tbe cbtmge hi IIgbt absorplfml coe.fllcie18t (MI) of}letYJ#Fig. 13.Ejft of so4I8m ~
Ide-bletu:bed, pbotoyellouJeil TMP (35).
(36).
lignin
(MWL)
in methyl
cellosolvel
water. Under vacuum, this solution produced no color; but, when opened to air
and irradiated, it produced the same amount
--
--s$l _ -Q
~
ROO.
OMe
198
. . hU
Ligmn
197
ooR
'.:::::-
OMe
II
(1)
+ RooH+ MeOH
0
(2)
RO-
H or alkyl
L = Lignin
Sebeme
hv
6. O$Id4tknr
of II pI1etwxy
rtUlktll
to
O-lfIIlrumoid
IIpm
by pnwty
."It
rtUlktIls
""
..
RH + 02
L=Lignin
.
ROO-
ROO- + RH
Rhv or!!.
-CZ
Mn+
RO _
+ HO
RO -
+ -OH +M(n+1)+
(3)
OMe
+ ROOH
_
M = Transition metal
Had oxygen been able to completely penetrate the fiber wall, phosphorescence
should have been fully quenched. Therefore, some photochemical
reactions may
occur in pulp fiber in the absence of oxygen.
In a study of the reaction of guaiacoxy
free radicals with ambient oxygen (43), it
has been found that the formation of yellow chromophores
from phenols occurs
only in the presence of carbon-centered free
radicals, molecular oxygen, and phenoxy
free radicals.
LO~L
= Photo-excited structure
R = H or alkyl
SebertIe8. FomuItW8of ~
rtUlIt:Mstlmnlgb direct tIIUIlrullrectllgbt-Irulltcedhomolytic elHvage of II
pbetwlk by""-,yl grotIJI.
HOO - + R -
R- + 02
ROOH
OH
(43).
*0
9) account
tIIUI1I~1
rtUlktlls.
of the phenoxy
free radical:
1. Direct absorption of light by phenolic chromophores
(Scheme 8, reaction 1) (44)
2. Abstraction
of a hydrogen atom from the
phenolic hydroxyl group (Scheme 8, reaction 2)
3. Abstraction
of a phenolic hydrogen atom
by a triplet excited state carbonyl group
(Scheme 8, reaction 3)
4. Cleavage of the g.Q..4 aryl ether bond of
the singlet and triplet excited state of the
phenacyl aryl ether group (Scheme 9, reaction 1)
5. Abstraction
of a benzylic hydrogen atom
to form a ketyl free-radical followed by the
facile cleavage of the s-o-4 aryl ether bond
(Scheme 9, reaction 2).
Phenolic
units as chromophore
precursors
199
200
MeO
MeO
MeO
The failure of etherification or esterification of the phenolic groups in lignin to totally inhibit
light-induced
yellowing
ultimately led to the identification of two
additional pathways involving non-phenolic
guaiacyl propane-s-0-4 aryl ether structures
containing a<arbonyl and benzyl alcohol
groups (reactions 1 and 2 in Scheme 9) that
account for most of the light-induced color
formation.
MeO
M~J?
~M~
MeO
'60
MeO
MeO
4
Fig.14. Up'" __I
~M~
J9l"2
flew- (46).
served
when solutions
containing
a
non-phenolic
aromatic aldehyde (3,4,5trimethoxybenzaldehyde
or veratraldehyde)
and a phenolic compound (syringyl alcohol, vanillyl alcohol, catechol, or phenol itself) were irradiated with near-W light.
Separate irradiation of the aldehydes or
phenols did not produce any free radicals
or yellowing. The inability ofthese phenols
to absorb W light at the wavelengths used
in this experiment (jOO-4OO nm) suggests
that phenoxy free radicals produced by the
abstraction
of hydrogen from phenolic
groups by photo-excited
carbonyl struc-
tures may play an important part in the lightinduced yellowing of lignin. Brunow and
Sivonen (52) have obtained similar results
using a phenolic lignin model compound,
ethyl guaiacyl carbinol. This compound did
not undergo oxidation when irradiated with
near-UV light until p-methoxyacetophenone, a triplet sensitizer, was added to
the solution. When the molar ratio of pmethoxyacetophenone
to ethyl guaiacyl
carbinol was increased from 0 to 0.32, the
rate of photooxidation
of this benzyl alcohol also increased. The above results are
consistent with the mechanism of light-in-
8-0-4 structures
containing
a-carbonyl
groups
Gierer and liD (46) have shown that the
non-phenolic
phenacyl-a-O-aryl
ethers,
a-guaiacoxyacetoveratrone
[1], a-guaiacoxy3,4-dimethoxypropiophenone
[~], and
a-guaiacoxy-B-hydroxy-3,
4-dimethoxypropiophenone
[3.] (Fig. 14), are rapidly
discolored after irradiation with near-W
light. Irradiation of these lignin models
produced
the corresponding
ketones,
(acetoveratrone and dimethoxypropiophenone) and ketols,(a-hydroxyacetoveratrone
and a-hydroxydimethoxypropiophenone)
from 1 and ~ and, in all cases, guaiacol. The
formation of these products can be explained by the light-induced cleavage of the
B-aryl ether bond to produce a phenacylphenoxy free radical pair, as shown in reaction 1, Scheme 9. Guaiacol and the aketone are produced through hydrogen
atom abstraction
by the guaiacoxy and
phenacyl free radicals; the ketols are formed
by reaction of the phenacyl free radical with
ambient oxygen. The corresponding structural isomers, B-keto-a-O-aryl ether [1] or
a-keto-yO-aryl ether [2], shown in Fig. 14,
are unaffected by irradiation with near-W
light. The formation of guaiacol, ketones,
and ketols as monomeric products of lightinduced cleavage of the a-aryl ether bond
of phenacyl-a-O-aryl ethers in solution and
!ldsorbed on cellulose have been confirmed
byVanucci and co-workers (53).
Because light-induced cleavage of the aaryl ether bond of the phenacyl aryl ether
moiety of lignin is a pathway to paper yellowing, it is essential to understand the effects of chemical and physical environment
on the extent of bond cleavage and the relationship of bond cleavage and yellowing.
The effect of protic as against aprotic solvents on the photochemistry
of the
phenacyl aryl ether bond has been determined using a-guaiacoxyacetoveratrone
as
a model. The cleavage of the phenacyl aryl
ether bond occurred through both the singlet and excited states of the carbonyl chromophore (54-58). In aprotic media the
triplet excited state of the phenacyl aryl
ether is unreactive; only the singlet excited
state undergoes aryl ether cleavage (54-56).
Aryl ether cleavage occurs in a protic environment through both singlet and triplet
excited states (54-56). This result is significant because the fiber wall in wood and
pulp, which is composed of cellulose,hemicellulose, and lignin, is highly protic.
8-0-4 structures containing benzyl alcohol
groups
Sequential reduction and alkylation of
TMP (59) and peroxide-bleachedTMP
(35)
effectively lowers the light-induced yellowing of these pulps. However, photostabilization is incomplete and only temporary
so that, with continuing
irradiation,
photoyellowing ultimately occurs (35). Although the forgoing results confirm the
roles of aromatic carbonyl and phenolic
hydroxyl groups in the initial stages of lightinduced yellowing, they also indicate that
other structures may contribute to yellowing as part of another reaction pathway.
One such possibility is illustrated by reaction 2 in Scheme 9.
The steps in this reaction sequence consist of the formation of a peroxyl free
radical from the combination of a carboncentered lignin free radical and oxygen, a
typical first stage in the oxidative degradation of polymeric materials (see Scheme 7).
The peroxyl radical then abstracts a benzylic hydrogen atom from a guaiacylglycerol-i?raryl ether forming a ketyl free
radical and the hydroperoxide.
The ketyl
free radical is converted to an aromatic ketone with accompanying elimination of a
201
202
(2)
~L
OMe
ROO-
/~OMe
OL
. =Excited state
L = Lignin
phenoxy free radical. This reaction pathway accounts for the light-induced formation of aromatic carbonyl groups that cause
an increase in specific absorption at 330 nm
for both unmodified, bleached TMP and
sodium borohydride-reduced,
bleached
TMP (31, 35). Also, analysis of mechanical
pulp photodegradation
products indicates
the formation
of 3-hydroxypropioguaiacone, an expected product of f?rO.4-aryl
ether cleavage (60). The proposed formation of ketyl free radicals by abstraction of
a hydrogen atom from a benzylic alcohol
group followed by f?rO.4-aryl ether bond
cleavage is further supported by results
obtained by Scaiano (61) showing that the
t-butoxy free radical generated by the photolysis of t-butyl peroxide abstracts the
benzylic hydrogen atom of l-phenyl-2phenoxyglycol
to produce the ketyl free
radical which in tUrn undergoes B-aryl ether
cleavage yielding acetophenone
and phe-
- Principles
and Practice
CH20H ,
H?-0-1
Pulp Bleaching
bomolytk
is prevented.
Reduction of aromatic carbonyl groups:
Carbonyl groups were recognized at the
early stages of research on light-induced
r.ulic'Als
203
204
lytic hydrogenation,
hydroboration
with
diborane,or reduction with diimide may not
have completely
eliminated the vinylic
double bonds in the pulp fiber.
Sequential reduction of carbonyl groups
and etherification of phenolic hydroxyl
groups.
That both carbonyl and phenolic hydroxyl groups may play a direct role in lightinduced yellowing has led to the strategy
of preventing light-induced yellowing by
sequentially reducing carbonyl groups and
etherifying phenols in lignin. Tschimer and
Dence (59) found that sodium borohydride
reduction of spruce TMP followed by complete alkylation with dimethyl sulfate, propylene oxide, or diazomethane completely
prevented light-induced yellowing for up to
2 hours. This series of treatments has been
proposed as two segments of a three-stage
process designed to inhibit light-induced
yellowing (70). The three-stage treatment
is composed of reduction with sodium borohydride followed by hydroxypropylation
(i.e., etherification) with propylene oxide.
The treated sheet is then coated with a fluorescent inorganic material.
Paper thus
treated shows a decrease in the extent of
light-induced yellowing after an undisclosed
time of exposure to near-UV light.
Although a combination of etherification
of phenolic hydroxyl and reduction of carbonyl groups delays yellowing for up to 2
hours no information is available on the
effect'of long-term exposure of treated paper to UV light. Figure 15 shows the effect
of reduction and methylation of bleached
TMP on the change in specific absorption
at 420 nm (35). Reduction and methylation delays yellowing for 1.5 hours, results
that are similar to those of Tschimer and
Dence (59). However, after 1.5 hours of
near-UV irradiation, yellowing, as measured
by ~420' increases at about the same rate
as that for untreated paper. As illustrated
by reaction 2 in Scheme 8, cleavage of the
B-O-4-aryl ether bond in the guaiacylglycero\-P.-ary\ ether lignin. unit produces
phenoxy free radicals which in turn are
oxidized to colored chromophores.
This
means that reduction of carbonyl groups
and etherification
of phenolic hydroxyl
groups in lignin only delay yellowing for a
short time or until phenoxy radicals are
formed in the ether cleavage reaction. Successfullong-term inhibition of light-induced
yellowing requires a method that prevents
cleavage of the B-04-aryl ether bond and
oxidation of the resulting phenoxy free
radical.
Addition of Inhibitors
listed in the following sections are various types of paper additives that affect the
degree and rate of yellowing caused by exposure of paper to near-UV light.
UV Absorbers
mtraviolet absorbers, that is, compounds
that absorb UV light and dissipate the light
energy by a non-yellowing mechanism,have
been used extensively to prevent the lightinduced degradation of a wide variety of
polymers. It was recognized at the start of
research on this subject that compounds of
this type, decrease light-induced yellowing,
when added to a paper surface.
The effect of UV-absorbing additives on
the light-induced yellowing of groundwoodbased paper was first reported by Nolan
(71). In this study, sheets treated with
Eastman Ultraviolet Sensitizer required
twice the amount of UV exposure as untreated sheets to undergo a given brightness
decrease.
Hydroxybenzophenones
have been
widely used as UV light absorbers (72). This
type of compound absorbs UV light and
forms an o-quinonemethide
which dissipates the light energy
as heat by
tautomerizing
to the starting material as
shown in Scheme 10. Kringstad (73) has
found that the addition of 2-2'-dihydroxy-4methoxybenzophenone
or 2,2',4,4'tetrahydroxybenzophenone
to bleached
groundwood-based
paper decreases lightinduced yellowing.
Similar results have
been obtained by Gellerstedt et al. (74)
using 2,4-dihydroxybenzophenone
and by
Fomier de Violet et al (75) who used a series of 2-hydroxybenzophenones.
However,
achievement of 93% stability requires more
than a 4% charge ofUV absorber,an amount
too large and expensive for commercial use.
------
205
Polymeric inhibitors
Polyethylene glycol has been used to prevent light-induced yellowing of wood surfaces and paper (76, 77). Its effectiveness
in inhibiting light-induced
yellowing increases as its degree of polymerization increases from 2 to 90 (78). Although the
mechanism of polyethylene glycol inhibition of light-induced yellowing is not well
understood, it has been suggested that it
inhibits yellowing by excluding air from the
paper fibers (77).
Polyvinylpyrrolidone
(I>VP), used to improve the whiteness and gloss in paper coatings, as an additive in inks to prevent paper
slippage, and to improve the dimensional
stability of wood, also reduces light-induced
yellowing (79). The monomer, n-vinyl-2pyrrolidone,
and the lowest molecular
weight (molar mass 104) PVP are the most
efficient. It is has been proposed (79) that
the phenolic hydroxyl forms strong hydrogen bonds with the amide group ofPVP and
prevents
its oxidation
by alkoxyl and
peroxyl free radicals.
(Fig.
-Principles
and Practice
50
.
of
Pulp Bleaching
it to an o-quinonoid
206
40
!if
N"
E
<5
C\I
Untreated
Reduced + methylated
Methylated + reduced
30
20
<!
10
o
0.1
10
100
time, h
Irradiation
J?
..
RSH
qSR
/1
HO
OH
II
(B)
RSH+
Qri"g
R"
0
"-
,/
R
II
_uv
Thiols
Aromatic thiols such as mercaptobenzothiazoles,
mercaptobenzimidazole,
Snaphthyl thiol, and alkyl thiols such as
dodecylmercaptan,
have been used effectively as stabilizers for a wide variety of
polymers (86). The fll"Stthiols used to inhibit light-induced yellowing of lignin -containing papers was sodium thiopropionate
(65). In a preliminary study, Janson and
(A)
~o
ftJf7l/lltttm
III
C=CH-C-R
...
II
R-S-C-CH-C-R "'
I.
R
(B).
207
208
45
3
C)
~
C\J
35
--
C!
N-
~25
s:::
c\I
:; 15
~<I
o Untreated
.D
CO
o
;;:::
0.01
0.1
1
Irradiation time, h
ng. 16.E.I1eet
of IISeOrlJkIICUIIlMlUort 011t:itrrnIuJp/Ior
blMll Sj1rIIeeTMP (34).
10
4rIrhIg _UV
100
IIgbt I~
. Ascorbic acid
'0Q)
. Na2S03
a.
en
-5
tmM-blMdJetl
o
+a.
...
of/')
o
o
of JIn'
4
Irradiation
6
time, h
of~-b'MCIJM
fortlUltiOll
10
""rmg
18e"r-UV IIgbt
5. Summary
The aging of lignin-containing pulps in
the dark is very likely caused in part by the
autoxidation of hydroquinonoid groups in
lignin. This explanation accounts for the
higher brightness reversion of dithionitebleached mechanical pulps compared with
unbleached or peroxide-bleached
pulps.
Dithionite
bleaching
occurs primarily
through the reduction of quinoid groups to
hydroquinones
(8) which are susceptible
to autoxidation leading to brightness reversion (17).
Thermal yellowing of peroxide-bleached
pulps during aging under ambient conditions, or after less than 16 hours of accelerated aging, occurs to a lesser degree than
that of dithionite-bleached
pulps. Peroxide bleaching oxidizes quinone groups to
carboxylic acids and lactones (20) which
contribute only slightly to thermal yellowing. The lower thermal yellowing of peroxide-bleached pulps compared with that
observed for dithionite-bleached pulps may
be attributed to the low amount of residual
hydroquinones in peroxide-bleached
pulps
available to undergo autoxidation to colored
quinones.
Treatment of pulps with chelating agents,
ethylenediaminetettaacetic
acid (EDTA) or
diethylenetriaminepentaacetic
acid (DTPA),
decreases thermal yellowing. This result
suggests that the presence of transition
metals promotes thermal yellowing. In particular, the presence of femc (Fe3+) ions
appears to promote the thermal yellowing
of unbleached
and peroxide-bleached
pulps. Apparently, dithionite-bleached
pulps have an abundance of easily oxidizable groups, (i.e., catechols) with the result
that Fe3+-cata1yzed autoxidation contributes
only minimally to the overall thermal yellowing of dithionite-bleached
pulps.
209
210
and
Swan,
B.,
67(5):177 (1%4).
Pulp
9. Polcin,J,and
Rapson,WH.,PuljJ
Can. 72(3):TI14
(1971).
Svensk
Chem.
G. and Pettersson,
B., Svensk
83(11):314
(1980).
18. Abadie-Maumert,
EA. and Loms, v:,
vueATLE
31(9):334 (1977).
Re-
Skogtnd.
20. Gellerstedt, G., Hardell H.-L., lindfors, E.L.,Act. Cbern. Scand. B34(9):669
(1980).
21. Abadie,E,RevueA.TLE41(9):493
(1987).
Pap.
Mag.
Can.
References
50:17 (1967).
51(6):257
(1968).
K.P.,
Norsk
G., Svensk
Papperstidn.
Pap. Mag.
Pap. Mag.
79
Cbem.
McDonough,
DR,].
Pulp
--
211
212
34. Schmidt,
J.A. and Heitner,
C.,J
Chem. Techno! 11(4):397 (1991).
Wood
35. Schmidt,
J.A. and Heitner
C.,)
Chem. Technol. 13(3):309 (1993).
Wood
36. Reeves,
48(2):121
R.H. and
(1965).
Pearl,
LA.,
Tappi
51. Kringstad,
53(12):2296
K.P. and
(1970).
Lin,
S.Y., Tappi
M., Pap. Puu
53. Vanucci, C., Fornier de Violet, P., BouasLaurent H., Castellan, A.,) Photochem.
Photobtol., A:Chern. 41:251 (1988).
I., Olkkonen,
e., Tylli, H.,)
Photobiol.
43:337 (1988).
(1966).
S.Y.,
(1972).
Stlensk
N., Nourmamode,
D., Davidson R.S.,
Chem.
Technol.
48. Holbom,B."Analysis
of Chemical Changes
Caused by Bleaching and Light-Induced
Yellowing of Spruce Groundwood;
First
European Workshop on Lignocellulosics
and
Pulp
Proceedings,
HamburgBergedorf,
1990, p. 272.
49. tee, D.-Y., Matsuoka, M., Sumimoto,
Holzforsbung
44(6):415 (1990).
50. Adler, E. and Lundquist,
Scand. 17:13 (1963).
K., Acta
M.,
Chem.
nology, Development
Eds.)
55. Schmidt,j.A.,
Berinstain,A.B.,
de Rege, E,
Heitner, C, johnston,
I..j.,. Scaiano, j.e.,
Can.) Chern. 69:104 (991).
56. Schmidt,j.A.,
Goldszmidt, E., Heitner, C,
Scaiano, j.C., Berinstain A.B., johnston,
L.J., in Photochemistry
of LtgnoceUulosic
Materials,
(e. Heitner and j.e. Scaiano,
Eds.) ACS Symposium Series 531, American Chemical Society, Washington,
D.e.,
1993, p.122.
57. Palm, W.-U. and Dreeskamp,
H., )
Pbotocbem.
Pbotobiol.,
A: Cbemistry
52:439 (1990).
58. Palm,W-U. , Dreeskamp H.,Bouas-Laurent,
H., Castellan, A., Ber. Bunsenges
Pbys.
Chern. 96 (1):50 (1992).
59. Tschirner,
36(4):338
U. and Dence,
(1988).
CW,
Pap. Puu
60. Holmbom,
B., Ekman, R., Eckerman,
C,
"Degradation
Products
Formed During
Light and Heat-Induced
Yellowing
of
Spruce Groundwood;
1989Tappi Fifth International
Symposium
on Wood and
Pulping Chemistry
Proceedings,
TAPPI
PRESS,Atlanta,445.
61. Scaiano,
j.C.,
Wintgens,
v.,J
59:265 (1991).
Netto-Ferreira,
J.C.,
Photocbem.
Photobiol.
e., Schmidt,
9(3-5):263
(1994).
65. Andrews, D.H. and Singh, R.P., Can. Pat.
No. 810,571 (April 15, 1966).
(Tappi
Section)
Oxidation
and
New York, 1965,
(1969).
74. Gellerstedt,
G., Pettersson,
I., Sundin,
Svensk Papperstidn.
86:R157 (1983).
75. Fornier
de Violet,
P.,Nourmamode,
A.,Colombo,
N., Zhu, j., Castellan,
CeUu! Chern.Technol.
24:225 (1990).
76. Minemura,
N., Mokuzai
24(8).'587 (1978).
77. Minemura,
Kobunkazai
S.,
A.,
Gakkaisbi
N. and
Umehara,
K.,
no Kagaku 31:55 (1986).
R., Kamiya,
81. Wan,j.K.S.,YatTse,
M., Heitner e.,]
Cbem. Tecbnol. 13(3):327 (1993).
Wood
82. Fridovitch,I.,
In Free Radicals in Biology
(W.A. Pryor, Ed.), Academic
Press, New
York, 1976, Vol. 1, p. 239.
83. Kwon, B.-M., Foote, e.S., Khan,
AmCbem.
Soc. 111:1854 (1989).
S.I., )
84. Agnemo,A.R.,
International
Patent Application PCT/SE91/00798,
Publication
No.
WO 92/09745 Oune 11,1992).
85. Ragauskas, A.J., Cellul.
28(3):265 (1994).
Chem.
Tecbnol.
for
K.V., Tappi]
G.W.j.
90. Lee,
D.Y.
Holzforscbung
(1991).
91. Ragauskas,A.J.,
Pulp
and
Pap. Sci.12(4).:J129
Sumimoto,
45 (Supplement):15
Tappi]
76(12):153
M.,
(1993).
J.. Vtikari,
M., Tappi]
SECTIONIV:
The Technology of
Chemical Pulp Bleaching
Chapter 1:
Oxygen Delignification
Thomas J. McDonough
Institute of Paper Science and Technology, Inc.
Atlanta, Georgia
1. Introduction
1.1 History
1.2 Process overview .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3 Advantages and dissadvantages of oxygen
delignification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
215
216
216
217
232
232
233
233
234
236
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
213
237
Chapter IV 1:
Oxygen
DeHgnification
1. Introduction
Oxygen delignification can be defined as
the use of oxygen and aIkaIi to remove a
substantial fraction of the lignin in unbleached pulp. The process is usually conducted under pressure, and delignification
is normally in the range of 35-50%. Oxygen
is usually applied to kraft wood pulps but
can also be used for sulfite, secondary fiber, nonwood, and other pulp types. In this
chapter, oxygen bleaching is considered
to be synonymous with oxygen deligni- .
fication.
The main benefits of oxygen bleaching
are environmental.They derive from the fact
that both the chemicals applied to the pulp
and the materials removed from the pulp
are compatible with the kraft chemical recovery system. This enables the recycling
of oxygen-stage effluent to the recovery
system by way of the brown stock washers, decreasing the potential environmental impact of the bleach plant.The decrease
is roughly proportional to the amount of
delignification achieved in the oxygen stage.
This applies not only to chlorinated organic
by-products, but also to other environmental parameters associated with bleach plant
effluents, including BOD, COD, and color.
The decrease in color, however, is larger
than expected on the basis of the lignin removed in the oxygen stage.
The industrial application
of oxygen
bleaching has expanded very rapidly in recent years.The first commercial system was
not started up until 1970 and total world
capadtyin 1980 was only about 10,000 tons
per day. By 1992 the number of operating
systetns stood at 155, with a total capacity
of about 85,000 tons per day, as illustrated
in Fig. 1 (1). Furthermore, this rapid growth
is likely to continue. As trends away from
the use of chlorine and chlorine-containing
compounds intensify, both technical and
economic considerations will mandate the
use of oxygen. Ozone, for example, though
it possesses certain advantages over oxygen,
will probably see application only in conjunction with oxygen. Oxygen will be used
to predelignify pulp to the point where the
necessary ozone charge becomes small
enough to be economical and selective.
1.1 History
The gestation period of commercial oxygen bleaching was a long one. It began in
1867 with the patenting of an "Improvement in Bleaching of Paper Pulp" by Joy and
140
~120
c:
~100
"C
ni
0
0
0.....
80
-:0
II
Single-stage systems
Two-stage systems
60
~40
'u
CtS
Co
CtS
c;)
20
0
1970
Fig. 1. WorUwUIe
prodlletlorl
1975
alJNldty
1980
of oxypn-tiBllpifled
215
1985
pulp.
1990
1995
216
NaOH
Steam
O2
Vent
gases
Wash
water
Pulp to
further
bleaching
Filtrate to
washing unbleached
pulp (recovery system)
of
The chief advantages of oxygen bleaching are related to its beneficial effects on
environmental parameters, although there
are also some operating cost advantages.
Its chief disadvantages are capital costs and
increased demand on the mill recovery
system.
ment translate
217
advantage
2. Fundamental aspects of
oxygen delignification
Before considering equipment configurations and process variable effects in oxygen bleaching, it is worthwhile to review a
number of its fundamental aspects. This
provides a logical framework for understanding the design and behavior of the
process, and for predicting the effects of
changes in hardware or mode of operation.
The basic aspects of oxygen bleaching can
be organized under the headings of chemistry and process fundamentals. Important
chemical considerations include the chemistry of oxygen, reactions of lignin and carbohydrates, and the related concepts of
218
Pulp Bleaching
- Principles
and Practice
.
+8,- H+. HOOH +8, H+. HOH + .OH +8.- H+~ 2 HOH
1l
11
4.8
11.8
11.9
11
II
II
pKa
H+ + o~
Flg.3. SleJniMe
that, because of their parallel spin, are unpaired. Each of these electrons therefore has
an affinity for other electrons of opposite
spin. In other words, oxygen is a free radical. Although less reactive than other free
radicals, it shares their tendency to react
with appropriate substrates at regions of
high electron density. The result is the initial step in a four-step process in which
oxygen is reduced to water and the substrate is oxidized. Figure 3 illustrates the
process. The product of the first step is a
negatively charged ion, called the superoxide anion, 0z"' which can combine with a
hydrogen ion to form the hydroperoxy radical HOO~ However, because this radical is
a weak acid (PK.=4.8), the anion remains
uncombined under the alkaline conditions
of oxygen bleaching.
Both the superoxide
anion and the
hydroperoxy radical have higher oxidation
potential (affinity for electrons) than their
parent oxygen. In principle, therefore, each
can readily acquire another electron to
form, respectively, the peroxide dianion,
ot, and the hydroperoxide
anion, HOO-.
In reality, the dianion is probably not sufficiently stable to form in appreciable
amounts. The hydroperoxide
anion is the
dissociated form of hydrogen peroxide.
Because hydrogen peroxide is a weak acid
(PK. = 11.8), both it and its anion are present
~ofoqgM.
H+ + .OOH
II
H++ 0:
Initiation
ROo + 02.
(1)
R. + H02
(2)
R02
(3)
R02H + R.
(4)
ROR
(5)
Propagation
Termination
PIg.4. Steps'n tbe m/Mnism of ~
ROo + R.
219
220
Lignin reactions
Two general approaches have been used
to learn about the mechanisms of lignin
removal during oxygen bleaching: Model
compound studies beginning in the 1960s
(23) and continuing up to the time of writing (24) have provided considerable insight.
More recently, studies of the effects of the
process on structural features of both residual and dissolved lignins have led to increased understanding of the chemical and
physical aspects of the mechanism (25).
The review articles already mentioned are
a good source of information on these studies.A brief summary of the major findings
is presented here.
blueblng.
-L
I
in appreciable
amounts under oxygen
bleaching conditions.
The third step in the stepwise reduction
of oxygen occurs whe11, hydrogen peroxide accepts an electron to form a hydroxide ion and a hydroxyl radical, HO.. The
hydroxyl
radical is also a weak acid
(PK,,=11.9) that exists in equilibrium with
its anion, -0.. Finally, the hydroxyl radical
can acquire another electron to form hydroxide ion or water. The occurrence of
hydroxyl radicals in this process is particularly significant because they are extremely
reactive and indiscriminate, attacking cellulose as well as lignin.A final point worth
noting about Fig. 3 is that a variety of reactions may occur between the species shown
(13).ln some of these, entirely new species are formed, such as the hydrotrioxy
radical, HOOO., and singlet oxygen, 102'
The complex oxidation processes that
occur in the oxygen bleaching reactor include radical chain reactions involving a
variety of organic species derived from both
lignin and carbohydrates. Figure 4 shows
likely initiation, propagation, and termination steps. Oxygen in its normal state is a
weak oxidizing agent, so it is necessary to
promote its reaction either by raising the
temperature or by providing a reactive substrate. In oxygen bleaching, the substrate
is activated by providing alkaline conditions
quently, m~Mgement
of tree tt'!l.ngttion
metals concentration
is an important consideration in achieving selectivity in oxygen
bleaching.
R=H,OAr,Ar,orAIk
.'
.~
'('~,
o
-L
=1:/
7 ..;1)
.
r~'
-Y-R
~.
7):
I
-Y-R
7;X:
0-
0CH0
221
222
I
-Y-R
".;;::
09
HO
._~
oci
I
-Y-R
/~
.
0..,,0
--90
- ,~
0-
...~
I
O=:Co-R
.--9-0-
Fig.6. RetU:tknIsoflfllermetlWe~.
radical is a resonance hybrid of structures
in which the odd electron formally resides
at the phenolic oxygen, at one of several
different carbon atoms in the aromatic ring,
or at the S-carbon atom of the side chain.
All of these positions are therefore potential sites for the next step of the reaction,
conversion to a hydroperoxide. The other
reactant can be molecular oxygen, the superoxide anion radical, or the hydroperoxy
radical. Figure 5 illustrates these steps.
In the alkaline environment of the oxygen bleaching process, the hydroperoxide
intermediate
exists, in pan, as the corresponding anion, which can subsequently
undergo an intramolecular nucleophilic reaction at an adjacent site. This may be the
carbonyl carbon of the quinone methide, a
ring carbon conjugated with it, or an adjacent side chain carbon, depending on the
location of the hydroperoxy function.These
reactions, illustrated in Fig. 6, lead to the
I
-Y-R
-OO---Y-R
o 0"
I
-Y-R
fOnnation of oxirane, muconic acid, and carbonyl structures. The last corresponds to
breakage of a bond joining two lignin monomeric units and therefOre leads to lignin
fragmentation. The others correspond to
introduction of hydrophilic groups, impaning polar character. Both types of reactions
may be expected to enhance the solubility
of the lignin in the alkaline medium.
Pathways are also available for similar
reactions of unionized hydroperoxides,
and for conversion of the hydroperoxides
to onho- and para-quinones. The resulting
quinones are susceptible to nucleophilic
attack by the hydrogen peroxide anion.
Figure 7 illustrates these routes. These reactions lead to opening of the quinone ring,
and the formation of muconic acid and
other acidic structures that ionize and impan solubility to the lignin. Hydrogen peroxide is present as a result of oxygen
chain are both structural features that enhance reactivity. A methoxyl substituent in
the aromatic ring also increases the reaction rate. On the other hand, a carbonyl
group in the a-position of the side chain or
an interunit linkage at the 5-position of the
aromatic ring decreases the rate.
Studies employing pulp or lignin instead
of model compounds have, to a large extent, confirmed the conclusions drawn from
the model studies. Gellerstedt and co-workers (28) investigated the structure of the
lignin in oxygen-bleached
pulp and concluded that oxygen bleaching
reduces
the content of free phenolic units. In contrast, the lignin remaining in the pulp
after oxygen bleaching was enriched in
biphenyl-type condensed structures and
p-hydroxyphenyl-type
lignin units. Both
observations are consistent with the results
of earlier model studies. In a later study
(29), it was confIrmed that the number of
phenolic hydroxyl groups in the pulp lignin decreased and the number of carboxylic acid groups increased.
Pulp lignin
structural studies have also shown that
diphenylmethane-type
condensed
structures are panicularly resistant to oxygen
bleaching.
A fInal point concerning the chemistry
of lignin reactions during oxygen bleaching concerns the role of covalent linkages
between lignin and one or more of the car-
223
224
C~H
1T
OH
R1-<P ~-
O'
0-R2
in the
MgS04
(moleslton
pulp)
,
,,
eo
40
20
,.i
'
".""
"
o~
10
20
Kappa number
30
Ion 011
225
226
the pulp mass (mass transfer), while chemical factors govern the rate at which the pulp
and bleaching chemicals react with one
another once they are in contact (chemical
kinetics).
Mass transfer
Mass transfer is an important consideration because most oxygen bleaching stages
are three-phase systems. Oxygen must cross
the gas-liquid interface, diffuse through the
liquid film surrounding the fiber, and finally
diffuse into the fiber wall before reacting.
Depending on the conditions, the rate of
oxygen transport can limit the rate of the
overall process because of the inherent
slowness of the diffusion phenomena involved (47).
The mass transfer problem is aggravated
by the low solubility of oxygen in aqueous
sodium hydroxide (48, 49). Typically, 24
times as much oxygen is consumed during
bleaching at 15% consistency as can be
present in the liquid phase at anyone time
and, at 27% consistency, 50 times as much.
Obviously, a viable process must facilitate
the transfer of oxygen into and through the
liquid phase.This can be done by ensuring
that the partial pressure of oxygen in the
gas phase and the gas-liquid interfacial area
are both sufficiently large.
Kinetics
Several studies have examined the rate
dependence of delignification and carbohydrate degradation reactions on reactant concentrations and temperature (50, 51).The
lignin in the pulp appears to be of tWo different types that differ with respect to the
ease of their removal by oxygen. The first
type is removed within about the first 10
minutes in a rapid initial phase. Removal
ofthe second type proceeds at a rate that is
proportional to the amount oflignin remaining at any given time. This means that the
lignin content can be reduced to any desired level by allowing the reaction to continue for a sufficiently long time. In practice,
the extent of reaction is limited by the availability of aIkali.The rates of removal of both
types of lignin increase with increases in
alkali concentration,
oxygen partial pressure and temperature.
Depending on reactor type and conditions, the delignification rate may be determined by the intrinsic chemical reaction
rate or by the rate of mass transfer of oxygen or alkali to the fiber. In the limiting case,
where mixing is so good that oxygen and
alkali are equally available to all fibers, the
rate is equal to that of the chemical reaction. Empirical models are available for predicting this rate and can be used to evaluate
mixing in a given reactor (52). They indicate that high-shear mixers are capable of
achieving very good mixing of alkali and
oxygen with pulp at medium consistency.
2.3
- 14,000
kJ per metric
(11).
Chemical consumption
The stoichiometry of oxygen bleaching
is such that, for each unit of kappa number
decrease, about 0.13% NaOH (o.d. pulp
basis) is required for softwoods and about
0.16% for hardwoods (54). In high-consistency systems, alkali consumptions in this
range are realized in mill-scale bleaching.
Medium-consistency
systems tend to consume slightly more alkali because the alkali
concentration is lower at a given charge in
these systems. The alkali is usually supplied
in the form of oxidized white liquor, which
can often be made available at lower cost
3.1 Medium-consistency
processes
As a1ready mentioned, the low water solubility of oxygen makes it necessary to 1)
have a very large amount of water present
Ilelipi,/bl1orl
Medium Consistency
High Consistency
10-14
25-28
50-60
30
Initial temperature, C
85-105
1()()'1l5
7()().800
415-600
450-550
415-600
Delignification, %
40-45
45-55
4().1l 0
30-50
40-1BO
75-175
35-45
40-50
Alkali consumption,
18-28
18-23
20-24
15-24
kg/t
228
3. Processes
and equipment
The factors discussed above influence
equipment
design for oxygen delignification. In particular, the relevant reaction
kinetics determine the size of the reactor;
mass transfer considerations determine the
configuration of the reactor and the provisions for efficiently contacting the pulp with
oxygen. The factor that most clearly distinguishes the available process types is pulp
consistency, but most systems being installed currently are of the medium-consistency type. High-consistency
systems
constituted the majority of those installed
during the first fifteen years of commercial
oxygen bleaching, beginning in 1970. Both
types have advantages and continue to be
available, and a few high-consistency
systems have been installed recently. Typical
operating data ranges for the two types are
given inTable 1 (54,56).
Consistency, %
227
Oxygen
blowtank
to dissolve all the oxygen needed for delignification, or 2) use a smaller amount of
water and provide conditions that facilitate
continual replacement of the dissolved oxygen by oxygen from the gas phase.This generally means providing
a very large
interfacial area between the liquid and gas
phases. One way of doing this is to dewater the pulp to high (20-27%) consistency
and fluff it to separate the fibers before
bleaching to create a dispersion of fibers in
a continuous
gas phase. When oxygen
bleaching was first introduced, this was the
only feasible method. Operating at medium
consistency was not feasible because of the
unavailability of equipment for intimately
mixing a very large volume of gas with the
pulp suspension (57). This problem was
solved when medium-consistency
mixing
technology became available in the late
1970s. The new high-shear mixing devices
make it possible to efficiently disperse oxygen as very small bubbles in 10-14% consistency pulp. After the oxygen is dispersed,
the pulp is tr.lnSferred to a reactor, where
the delignification reaction is allowed to
continue. The dispersion is relatively stable
and the buoyancy imparted by the trapped
229
230
Pulp Bleaching
-Principles
and Practice
feeder or thick-stock pump, which maintains a seal against the reactor pressure. At
the bottom of the reactor, the pulp is diluted
to 5% consistency with recycled oxygenstage filtrate. Discharge is accomplished by
a rotating conical screw and agitating arms.
The system is exemplified by those in
operation
at Eddy Forest Products
in
Espanola, Ontario (67), and at the Franklin,
Virginia, mill of Union Camp Corporation
(68). Figure 13 (54) is a generic flowsheet
of the process. Washed unbleached pulp is
dewatered to a consistency of about 30%
in a twin-roll press. Alkali, usually in the
form of oxidized white liquor, and steam
are added and the pulp is transferred to the
reactor by a thick-stock pump or plug screw
feeder. Steam is added at the top of the reactor to maintain the desired temperature.
Upon entering the reactor, the pulp passes
through a fluffing mechanism and falls onto
the bed. A nuclear gauge senses the bed
level, which is controlled by changing the
flow rate of the leaving pulp suspension.
Oxygen is added at the top or bottom of
the reactor to maintain the desired partial
pressure. A small gas phase stream is con-
Fig. n.
MoDo-CH
rwwltw.
Vent
Post oxygen
washer
Steam
Post oxygen
filtrate
FIG
Oxygen reactor
FIg.14. Bottom stKmofrHetor
J1rocas.
Bottom
231
section
ruMfor
StIJNW
232
4. Process variables
The response of an oxygen bleaching
system to changes in process variables is a
40
....
CD
.c
. Original pulp
o Temperature
85C
. Temperature 100C
V Temperature 115C
t!. Temperature 130C
30
~
c:
as
2: 20
as
~
10
1
Reaction
2
time, h
~-_._--
30
Temperature
110eC
pp02 0.68 MPa
1% NaOH
25
.D
20
15
as
0.
0.
3.5% NaOH
10
15
80
60
30
Time,m
011
Fig. 16. Effeel:l of lime, .0..11 eJHnre,
~
"*
tkllpljklltiolt
of IIlWftwooillnwft
JItIlp.
~
234
Pulp Bleaching
-Principles
and Practice
2.5% NaOH
233
/uIJIPtI---'"
1M
1100
Consistency 825% 07%
Temperature 11oec
Pp02 0.68 MPa
1% NaOH
45
2.5% NaOH
3.5% NaOH
25% consistency
IJ
'C
;Eo 1000'0
o
o
15
30
20
900U
en
40
60
I
15
I
20
Time,m
Fig. 18. Bffeel:l ofbliu:lI
121
44
Bleck
Iiquo<
Numberof
Addition
Recirculations
Kgs DSIBOMT 0 1 2 3
UJ
'5O
80
121
25
5
oxygen stage
If an oxygen stage is to be used for
predelignification, it is most logically integrated into the brown stock washing system. Good upstream washing is essential,
because black liquor solids consume oxygen and may adversely affect selectivity.
Good downstream washing is necessary to
fully realize the pollution abatement potential of the stage. Oxygen-stage washer ftltrate is used as wash liquor in the brown
stock system and therefore finds its way
back to the recovery system. Oxygen-stage
washer losses enter the chlorination stage
and become unrecoverable.
The effects of pre- and post-oxygen washing efficiency have been the subject of several studies (56, 64, 76, 77). The dissolved
solids entering the oxygen stage arise from
two different sources, the digester and the
oxygen stage, and the effects of each are
dependent on the consistency of the oxygen stage. Oxygen-stage solids find their way
back into the oxygen stage because it is part
of a closed countercurrent washing system.
This is necessary to capitalize on the environmental benefits obtainable by prevent-
ti:s
~
60
C)
~
M-
UJ 40
E 35
;Eo
'0
o
~ 30
:>
Ilq80r
ClJrtyooer
"""
8444
V'f"'''
IJI2lIiI.
I
25
Kappa
number
dlssolved
IWlltls reclmlllllUm
011 oxygen-stllge
selectivity
235
1200
C)
'C
1100
'w
8rn
Block liquor
of
Recirculalions
-.
KgsDS.9OMT 0 1 2
20
64"-
'>
Z
() 1000
40
V".
eo
en
[J~.
100
OC)8
4-?
15
20
..,
~-' _
}nIlp).
200
30
50% delignification
C)
~
;;;-
25
Kappa number
III
[J
160
'C
:Z 120
.Q
~ 80
'w
o
urn
:> 40
Z
(S
0
en
Pulp
<:ons-.cy
10%
25%
20
40
COD
"",."""."k
in liquor
to el6stlre (so~
after
.o
WlOl8drculatlon
With r&eircu8ation
[J WIO 18dn:ulation
.__Iion
60
O2 (gIl)
80
lnwft JIfIlp).
Greenwood (64) has reported data obtained by the laboratory bleaching of softwood kraft pulp at 25% consistency in the
presence of systematically varied amounts
of dissolved solids (Fig. 18). At each level
of black liquor addition, the oxygen-stage
was repeated four times. In each experiment, a fresh sample of pulp was diluted
with filtrate from the previous experiment,
simulating oxygen stage solids recirculation,
and fresh black liquor was added, simulating carryover from the brown stock washers. Apparently,
in the absence
of
236
recirculation
of oxygen-stage
solids,
carryover of as much as 60 kg/t black liquor
solids has no effect on selectivity. On the
other hand, combinations of the two types
of dissolved solids, as would occur in practice, have a detrimental effect.
Experiments of the same type at 10%
consistency provided the data shown in Fig.
19. In this case, combinations of recirculated solids with up to 40 kg/t black liquor
solids were tolerated without loss of selectivity, but higher levels had a detrimental
effect. The higher tolerance of the mediumconsistency system for dissolved solids suggests that the important parameter is their
concentration in the liquor, not the ratio of
their dry weight to the dry pulp weight. To
test this possibility, liquors were removed
from the pulps after the oxygen stage in experiments conducted at both consistencies,
with and without recirculation, at different
levels of black liquor carryover. Figure 20
shows the results of determinations of their
chemical oxygen demand (COD), a surrogate for total organic dissolved solids concentration, plotted against the viscosity loss
in excess of that observed when fully
washed pulp was bleached. A definite relationship is apparent, despite scatter in the
data, which suggests that viscosity loss is
incurred when the COD concentration is
higher than about 20 g/L.
Greenwood (64) has performed calculations to demonstrate the practical implication of these phenomena,
namely that
highly efficient washing after the oxygen
stage, essential for environmental reasons,
requires an increase in the efficiency of the
brown stock washing system before the
oxygen stage to keep the COD levels in the
oxygen stage below that at which viscosity
is affected. In the ideal case, represented
by perfectly efficient brown stock washing,
the dissolved solids entering the oxygen
stage consist only of recirculated oxygen
stage solids. This emphasizes the importance of good washing before oxygen
bleaching. Greenwood's calculations demonstrate the desirability of three washing
stages before, and an additional three washing stages after, the oxygen stage.
5.3 Implications
system
6. Pulp quality
The strength equivalence of conventionally bleached pulps and pulps that have
been oxygen delignified to an extent of
about 50% before conventional bleaching
iswell-documented(66,78,
79). Although
the viscosity of the oxygen bleached pulps
may be lower (as much as 4 mFa-s on the
TAPPI T230 scale), their tear factor at a
given tensile strength is generally the same
as that of conventiona11y bleached pulps.
The effects of oxygen bleaching on pulp
cleanliness, pitch, brightness stability, and
refining energy requirements are at least
neutral and in some cases slightly beneficial. The effect on cleanliness may be indirect inasmuch
as oxygen bleaching
is
usually followed by short bleaching sequences consisting of high concentration
chlorine dioxide stages, which are known
to improve pulp cleanliness. Refining energy requirements have been observed to
decrease upon installation of an oxygen
stage (79).
237
l.}ohnson,A.P.,Pulp
Pap. 67(3):103
(1993).
(1954).
(1971).
10. Arhippainen,
B. and Malinen, R., "Cost
Competitiveness
of Oxygen Bleaching,"
1987Tappi International
Oxygen Delignification Conference
Proceedings,
TAPPI
PRESS, Atlanta, p. 23.
11. Greenwood,
B.E and Hallenbeck,
Private communications,
1995.
M.R.,
Papter
46(10A):Vl
(1992).
Pulp Bleaching
-Principles
References
4. Harris,G.e.,
238
Papier
E, Svensk
41(3):120
Papper-
(1987).
17. Gierer,}.,
20:1 (1986).
18. Theander,
0., in Cbemtstry
of Deltgnt-
ftcaUon
and Practice
e.,.Al1P
Rev
21.Hise,R.G.,"A
Critical Review of the Chemistry and Technology
of Oxygen-Alkaline
Delignification," Department
ofWood and
Paper Science, North Carolina State University, Raleigh, 1983, pp. 6-17.
22. Gratzl,}.S., "Reactions of Polysaccharides
and Lignins in Bleaching with Oxygen and
Related
Species,"
1990 Tappi Oxygen
Delignification
Symposium Notes, TAPPI
PRESS, Atlanta, p. 1.
23. Kratzl, K., Gratzl, }., Claus,
Chern. Series 59:157 (1966).
P., Adv.
in
G., Gustafsson,
K., Lindfors,
Pulp Paper Res.]
1(3):14
(1981).
32. Samuelson,
Pappersttdn.
33. Robert,A.
(1971).
34. Gilbert,A.E,
Pavlovova,
Tappt 56(6):95 (1973).
37. Parthasarathy,
YR., Sundaram,
YS.M,
}ameel, H., Gratz!, }.S., Klein, R., "Hydrogen
Peroxide-Reinforced
Oxygen
Delignification of Southern (Loblolly) Pine
Kraft Pulp and Short-Sequence
Bleaching,"
1989 Tappi Pulping Conference
Proceedings,TAPPI PRESS, Atlanta, p. 539.
38. Colodette,}.L.,
Campos,A.S., Gomide,}.1.,
"Attempts
to use White Liquor as the
Source of Alkali in the Oxygen
Delignification
of Eucalypt Kraft Pulp," 1990
Tappi Oxygen Delignification
Symposium
Notes, TAPPI PRESS, Atlanta, p. 145.
39.Yethon,A.E.,
5, 1980).
40.
(Feb.
Abrahamsson,
K., Lowendahl,
L.,
Samuelson,
0., Svensk
Pappersttdn.
84(12):RI52
(1981).
TapptJ.
68(6):92
(1981).
62(12):43
J.S., AICbB
J.
and Benefits
-An
G.B.,
PRESS,Atlanta,
Overview,"
Bleach-
p. 245.
EA., Tappt J.
B.,
239
Coetzee,
75(6):T223
B., Pulp
(1974).
- High
Pap.
Bleaching
Mag.
Can.
of Kraft Pulp
PRESS,AtIanta,
p. 61.
SECfION IV:
The Technology of
Chemical Pulp Bleaching
Chapter 2:
Chlorination
Ronnie Rise
Westvaco Corporation
Covington, Vlfginia
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. Role of chlorine
as adellgnifyingagent.
244
3. Chlorination chemistry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
'.'
3.1 Chlorine-water equilibrium
.......................
3.2 Reactions of chlorine with lignin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Reactions of chlorine with carbohydrates . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Reaction kinetics
4. Impact of chlorination
4.1
4.2
4.3
4.4
4.5
243
process variables
245
245
246
247
247
248
Chlorine charge
Temperature and time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Consistency
pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chlorine dioxide substitution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
249
250
251
251
251
5. Process equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.1 Stock dilution. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . .
5.2 Blending and consistency control
5.3 Chemical injection and dispersion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Mixing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
252
253
253
253
254
6. Process control.
254
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7. Effect of chlorination
and dirt removal
8. Environmental
on shives
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
aspects of chlorination.
255
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 255
741
Chapter IV 2: Chlorination
Chapter IV 2:
Chlorination
1. Introduction
In the early 19005, practical means were
developed for handling liquid chlorine. This
was a key step leading to the use of chlorine as the first delignification stage after
pulping. Previously, hypochlorite was used
to continue the delignification
process.
Chlorine came to be preferred because of
its lower cost and improved selectivity for
reaction with lignin compared with cellulosic materials. At present, the use of chlorine for bleaching is decreasing rapidly. Its
decline can be attributed to concerns about
the formation of chlorinated organic compounds - mainly fragments of degraded
lignin as by-products of the delignification
process. Government regulations and market pressures in the early 1990s have led to
the virtuaI elimination of molecular chlorine for bleaching in Sweden, Finland, and,
to a large extent, Canada, as well. Proposed
legislation will effectively eliminate the use
of molecular chlorine in the United States
for the bleaching of kraft pulp by the year
2000 if not sooner.
243
.....
\I)
.I
c:
='
as
a.
a.
as
~
Fig. 1. Uplll
~s.
_,,1
",,,g
244
2. Role of chlorine as a
delignifying agent
The chlorination and first alkaline extraction stages generally are viewed collectively
as a continuation of the delignification process that began in the digester in contrast
to later bleaching stages which mainly serve
to bleach the pulp. Lignin removal is more
selective in the chlorination and extraction
stages than in the pulping process. Wood
chips contain 2().30% 1ignin on a dry-weight
basis depending on the species. Pulping to
a bleachable grade removes over 90% of the
original lignin, but, because portions of the
cellulose and hemicellulose are dissolved
d111'ingpulping, lignin still comprises about
4-5% of the dry weight of unbleached pulp.
Chlorination, combined with an ensuing
alkaline extraction stage, removes 75-90%
.of the lignin remaining in unbleached kraft
~,ul~!I. The lignin remaining in the fibers
after chlorination and extraction, usually
leSiSthan 1.5% by weight, can be removed
or decolorized in one or more bleaching
stages. Various aspects of chlorine bleaching are well covered in the literature (1-7).
More selective and expensive chemicals
must be used to preserve pulp yield and
strength as the lignin content of the pulp is
further decreased. Therefore, the importance of the chlorination stage is emphasized by the fact that inadequate
chlorination leads to hlgh chemical demand
in later bleaching stages. Excessive or
poorly controUed chlorination may result
in unsatisfactory pulp quality and yield loss.
Equally important of late, the formation of
highly chlorinated by-products such as chlorinated dioxins, may increase as chlorine
consumed increases.
Another important function of the chlorination stage is to smooth out variations in
unbleached kappa number and to insulate
the remaining bleaching stages from any
black liquor carryover which may accompany the pulp after the brown stock washing and screening operations. In this regard,
chlorine has been a nearly ideal first-stage
bleaching agent following pulping.
Chlorine may be described as a very"user
friendly" bleaching agent compared with
other well-known chemicals. For example,
chlorine reacts with pulp rapidly and selectively over a broad range of pH values, over
a wide range of temperatures, and at low,
medium, or high consistency. Because of
the high reaction rate, in-line sensors can
be used effectively to obtain real-time information for controlling the process with
a short feedback loop. Chlorine is also effective in bleaching "dirt" and shives (fiber
bundles) (see Section 11 in this Chapter).
Chapter IV 2: Chlorination
HOCI + HCl
[I]
Both hypochlorous and hydrochloric acids (on the right side ofEq. 2.1) dissociate
in water to release a hydrogen ion (H+).
Hydrochloric acid is completely dissociated
at the normal chlorination stage pH levels,
but hypochlorous acid is only slightly dissociated according to the equation below:
HOCl ~
W + ocr
[2]
The concentrations of these chlorine species can be calculated based on the law of
mass action:
K, = [HOC;h[~+]
2
[OCI"] [W]
1(,=
[HOC1]
[CI"]
- 3.94 x IQ4
at 25C [3](8)
[4)(9)
= 5 .6 x W" at 25C
where Kl and Kz are the equilibrium constants for these reversible reactions (8, 9).
From these known relationships, predictions can be made on how changes in process variables affect the distribution
of
246
20
b80
0
.,,60
I:
as
HOCI
0'''40
~0
20
400
0
J:
6O~
80
CI2
100
023456789
3. Chlorination chemistry
Cl2 + HP
100
pH
-Principles
245
dllo-
reactive species in the chlorine-water system and therefore affect the reactions that
occur in the chlorination stage. Operating
the C stage at a lower consistency, for example, causes the equilibrium to shift to the
right in [I]. A similar effect is observed as
the temperature is increased and the system becomes enriched in hypochlorous
acid relative to molecular chlorine.
Probably the most important process
variable controlling the form of chlorine
present in the C stage is pH. It is clear from
[I] and [2] that an increase in hydrogen ion
concentration forces the equilibrium to the
left which facilitates reactions involving
molecular chlorine. Increasing the pH (decreased hydrogen ion concentration) shifts
the equilibrium to the right and enhances
the formation of hypochlorous acid and finally hypochlorite ions [I] and [2]. This
effect is illustrated in Fig. 3 (10). As the
temperature is increased, and the system
becomes enriched in hypochlorous
acid
relative to molecular chlorine.
The type of reactive species present in
the chlorination stage is significant because
hypochlorous acid reacts with pulp components by different mechanisms than does
chlorine.
Hypochlorous
acid reacts less
selectively with lignin than chlorine and loss
of pulp quality and yield may result from
attack on carbohydrates.
Reactions of hypochlorous acid with lignin are mainly oxidative, but reactions with chlorine involve
oxidation, substitution, and addition. All of
these reactions contribute directly or indirectly to the breakdown of the lignin !mC-
Pulp Bleaching
and Practice
does not proceed in a step-wise manner for
the system as a whole: even under the relatively homogeneous reaction conditions existing when model compounds are treated
with chlorine, the reaction mixture often
contains unsubstituted as well as polychlorinated phenolic materials.
It was noted earlier that the main function of chlorination stages is to continue the
removal of lignin from unbleached pulp in
a more selective manner than is possible
during pulping. Oxidation, substitution,
and addition reactions with various reactive
species in the chlorine-water system lead
to the breakdown and removal of most of
the residual lignin from the cellulose matrix. These reactions are described in detail in Chapter III 3. Some lignin is dissolved
in the acidic chlorination filtrate as was
noted earlier. The dissolved lignin consists
of relatively low molecular weight carboxylic acid-containing
organic compounds.
Various chlorine-containing
compounds
such as phenols and fatty and resin acids
also are dissolved in this ftltrate (13, 14).
lignin not dissolved in the acidic C-stage
nevertheless is modified extensively by re-
~:}
I
A
~ }
H-C! oR
Ugni'(
-LVdn
/A
~. 8q.
~nln
I
,C.
H 0
-lJg~
~}
I
COOH
~
o (O-Benmquinone
=Aromatic sub8tltutlon
= Electrophlllc
= Oxidation
displacement
C
Clx= Chlorine substltuent(s) at
unspecified ring slte{s)
derIv8tIve)
Ox.
Red .
1
CIx~
DiC8rt1oxy1lc
hgmen18
~OH
OH (C8techoI
deriv8tllre)
FIg.4. 1)e rt!fIetWruof cblorllw IIIIIb ~fllive
"grd" ftwgmeat.
"
8Cid
Chapter IV 2: Chlorination
actions with chlorine (15). Oxidation reactions destroy aromatic ring structures,
generating
hydrophilic
carboxylic acid
groups (Fig. 4). Substitution and addition
reactions lead to the incorporation of chlorine atoms into the structure
of the
residual lignin. In the following alkaline extraction stage, much of the chlorine-substituted lignin is solubilized and removed by
alkaline hydrolysis reactions, a topic discussed in greater detail in Section 4. Studies have shown that some organically bound
chlorine remains with the pulp and cannot
be removed with organic or inorganic solvents (16).
In theory, conditions in the C stage can
be manipulated to favor substitution or oxidation reactions but, in practice, only a few
mills change chlorination-stage variables in
this stage for this express purpose. It has
been shown, for example, that formation
of highly chlorinated phenolic and chlorinated dioxin and furans (products of substitution
reactions)
can be decreased
dramatically by operating the chlorination
stage at a higher pH and splitting the total
charge of chlorine among multiple addition
points (17, 18). The effects of other selected process variables on these chlorine
reactions are listed below:
Change in Bleaching
Conditions and
Putp Cofi\POSition
Effect on
Bleaching
Reaction
Higher temperature
More oxidation
More oxidation
Higher pH
More oxidation
Higher chlorine
concentration
More substitution
More substitution
More condensed
More oxidation
lignin
(20).
Van Heiningen
247
248
Pulp Bleaching
-Principles
and Practice
of the chlorination
1. Amount
of chlorine
stage:
applied
and consumed
3. Reaction
time
4. Chlorine
concentration
5. Temperature
o
o
12
16 20 24 28
Time, S
32
36
40
44
6. pH
7. Pulp consistency
8. Degree of chlorine dioxide substitution.
Fig.5. 1lJIIe
remorHIll. tile mUUI s~
of"""
of1nwft }HIIp eblorllUllitm.
some of the residual lignin is resistant to
removal by chlorination and extraction (2427).
In one study (25), for example, a 2minute chlorination (denoted CRin Fig. 6)
was followed by alkali extraction, a second
2-minute chlorination and extraction, and
finally a third chlorination and extraction.
The CE K number was reduced substantially
each time, but the repeated chlorinations
and extractions
failed to completely
delignify this softwood pulp. Thus, some
of the lignin remaining after kraft pulping
is highly resistant to removal by chlorine
and alkali alone (25).
30
...
aCE
c CAECE
25
l>.CAECAECE
CA : 2 min., 5.74% CI2 on o.d. pulp
CD
.Q 20
::J
c:
as 15
a.
a.
as 10
~W
()
5
0
0
10
20
40
30
50
Time, min
Fig. 6. Effects
of re}letded
eblorllUllitm
tmd extraetiorl
08 IIg1".
removal,
lIS measured
IIap/JII
.umber.
Chapter IV 2: Chlorination
Molecular
chlorine
4.5
24
22
35
40
ffi
"
CEHDED
0.15
0.20
Kappa factor
0.25
cblorine IlJlPlka-
0.32
C-stage brightness
%GE
8
<Q
as 25
Q.
E
'iii
0
(J
20
:>
w
5'
15
0.22
11
~~3QC
o 40.C
. 50.C
rn
0.24
[J 60C
Il 70.C
V BO.C
5
5
0.16
22
24
26
28
30
C-stage brightness,
32
34
,""nber,
Ing of a softwood
In tbB 14bomtory
ImIft Jnllp.
36
20
40
60
80
100
120
bleaeb-
6
7
8
9
CI2 applied, % on pulp
I
I
I
I
0.160 0.192 0.224 0.256
Kappa factor
OJ.
4.2 Temperature
and Time
Chlorination stages may be conducted at
various temperatures ranging from ambient
to 70C. As is shown in Fig.ll, viscosity
loss is independent of temperature; for the
most part, given sufficient reaction time, the
extent oflignin removal also is independent
of C-stage temperature. However, temperature does affect reaction rate. Increased
efforts to close the system and conserve
water have led to the recycle of chlorination and chlorine dioxide stage filtrate and
use of paper machine or similar process
waters instead of fresh water for dilution of
unbleached pulp. The result of such filtrate
recycle is an increase in C-stage temperature. The use of recycled filtrate may be
limited by the material of construction
in
pumps, piping, and unbleached pulp storage chests. As is discussed later, it is important to maintain a constant temperature in
this stage to facilitate control strategies and
reduce variability in the post-extraction K
30
::;;
2.5
IIonsfor MrloIISbleaebhlg~.
26
30
25
Kappa number
28
20
0.10
0.2
'3
u
CI>
0 0.18
,-....... /
30
15
:2
u
(,)3.5
[5]
32
W
CJ
~0
u;
In
..
C
E
C>
'C
.Q
..
C>
as
7ij
'C
0
0.3
'3 0.28
E
.. 0.26
C
multiple
..
15.
250
~
W
249
Fig.
11.
Bffect
of cblorine
10
I
I
0.288 0.320
Chapter IV 2: Chlorination
number. Knowledge of expected temperatures is critical in choosing sites for mounting on-line brightness and residual chlorine
sensors.
Most chlorine is consumed within the
first few minutes of reaction, even at room
temperature.
Most delignification occurs
in this same period as was noted earlier.
Even so, allowing extra time for the slower
phase of the chlorination reactions to be
completed significantly improves the economics for attaining a high final brightness.
Pulp quality, as measured by pulp viscosity,
does not suffer as retention time increases
(36). Additional retention time also provides flexibility for handling upset conditions and production rate changes.
4.3 Consistency
Most pulp chlorination stages are conducted at relatively low (2.5-4.0"16) consistency. Several mills now operate mediumconsistency
(8-15%) chlorination
stages,
utilizing recently develQped medium-consistency pumping and mixing equipment.
There are limitations in the volume of gas
that can be mixed into a medium-consistency slurry (37, 38). Laboratory studies
have shown some benefits in selectivity and
efficiency of delignification accruing from
medium-consistency
chlorination (39,40).
However, because of the higher concentration of chlorine, more chlorinated organics
would be expected to be generated at medium consistency (17,41). The operation
of in-line sensors may also be adversely affected by changing from low to medium
consistency.
4.4 pH
The pH of the pulp suspension influences chlorination reactions by controlling
the relative amounts of chlorine or hypochlorous acid present as discussed previously. Organic acids and hydrochloric acid
are generated as by-products as chlorine
reacts with lignin causing the pH to drop
as the chlorination proceeds. The bleach
plant operator can control the pH in only a
few ways. Recycle of chlorination washer
(or chlorine dioxide washer) filtrate for
major or minor dilution of unbleached pulp
251
252
32
co
30
28
(fJ
a,
~24
~..~20
:> 16
22
18
o
o(fJ
234
567
End pH in the first stage
'S;
W
U
points
26
Q..
E
'ii)
12
Optimum
CIO2 addition-
30%
14
30C
10
I 1/ I I"
10 5 I
300
..-
60 3020
Seconds before
5. Process equipment
Chlorinatlon equipment varies considerably at different mills, but many of the system components are common. The diagram
in Fig. 1 shows the following components:
Brown stock pulp dilution
Blending and consistency control
Chemical injection and dispersion
mechanisms
Pulp washing.
Seconds
60
300
after.......
dioxide for chlorine to achieve viscosity protection and delignification. The impact of
chlorine dioxide substitution on environmental parameters has also been reported
in recent years (44). The timing of chlorine dioxide addition relative to that of chlorine is an important consideration for pulp
quallty as shown in Fig. 13. When used in
relatively small quantities in softwood kraft
pulp bleaching, chlorine dioxide should be
added with or slightly after the chlorine
(45). Chlorine dioxide may be entirely consumed if added too far ahead of the chlorine, resulting in poor viscosity protection.
Similar curves have been developed for
hardwood (46).
Mixing
5 10 2030
Chlorine added
--Chapter IV 2: Chlorination
Fillers, clays, other additives which that may
interfere with optical sensors
Inorganic compounds which buffer pH and
create scale or deposits
The choice of the dilution water source
must involve these and perhaps other considerations. For low-consistency chlorination stages, the C-stage water balance is the
highest volume filtrate/effluent
system in
the bleach plant. A purge from this system
to the wastewater treatment plant is required because corrosiveness due to the
presence of chloride ions and the low pH
preclude countercurrent
use of this filtrate
for screening or brown stock washing.
5.2 Blending and consistency control
Stock is diluted to a fixed consistency in
the 2.5-4.0% range and pumped out ofstOrage to an agitated blend chest. This step
helps smooth out fluctuations in the lignin
content of the unbleached pulp and consistency.
Elimination of short-term variations in
these two variables facilitates control of
chemical addition and improves the uniformity of chlorinated pulp. This procedure
has taken on added significance with the
recent concerns raised about formation of
chlorinated organics that can occur in cases
of excess chlorine application. Dilution is
generally controlled at two points: out of
storage (major dilution) and out of the blend
chest (minor dilution).
5.3 Chemical injection and dispersion
The goal is to treat each fiber in the pulp
suspension
uniformly with the proper
chemical charge. Injection techniques and
mixing devices are used to disperse the
chlorine gas because more chlorine is generally required than can practically be dissolved in the water, throughout the slurry.
In low consistency applications, this goal
generally is achieved by dispersing the gas
in water in the form of small bubbles using
venturi devices or static mixers. High-shear
mixers are used in low- and medium-consistency chlorination systems, because of
the importance of good mixing for lowering the formation of chlorinated by-products (39). The effects of water temperature
253
on chlorine gas dispersion have been studied in the laboratory (47). Hot water was
shown to facilitate coalescence of small
bubbles into larger ones in less than 0.25
second. These findings have practical significance for the design of chlorine injection systems: the chlorine gas dispersion
should be formed and injected into the
slurry with as little "dead time" in the pipeline as possible and should be mixed with
the pulp slurry immediately following injection.
Maintaining an adequate water flow to
the dispersion device has also been shown
to be important. At least 60 kg of water per
kg of chlorine is required to form a stable
dispersion and prevent plug flow (47).
Adding chlorine gas without prior dispersion can be practiced on low- or mediumconsistency
systems when high-shear
mechanical mixers are used. Because no
injection water is used, check valves are recommended to prevent plugging chlorine
addition ports by pulp during interruptions
in the chlorine flow.
Chlorine dioxide solution should be
added together with the chlorine dispersion, upstream or downstream depending
on chlorine dioxide substitution (Fig. 13).
Because chlorine dioxide is added as a solution, the mixing requirements are less rigorous and static mixers are often used.
5.4 Mixing
Diffusion of chlorine in pulp slurries has
been shown to be slow relative to the rate
of reaction of chlorine with pulp (47).
Good mixing is therefore important to avoid
pockets of over-chlorinated and under-chlorinated pulp. Proper performance of in-line
sensors depends on uniform mixing of
chemicals with pulp. Symptoms of poor
mixing may include dirty pulp (shives, bark
particles) after the chlorination stage, loss
of pulp viscosity, and varying levels of residual chemicals in the washer vat. Local
over-chlorination may result in formation of
highly chlorinated by-products even at relatively low chlorine dosages.
Several general types of mixers currently
are used in chlorination stages, each having advantages and disadvantages.
254
6. Process control
The objective of a chlorination stage control strategy is to produce a uniform pulp
exiting the C-stage washer regardless of incoming pulp variations in kappa number,
black liquor carryover, consistency, temperature, or flow rate. In part, this implies
maintaining a constant ratio of chlorine
consumed (not applied) to mass flow of lignin through the pipe line. In practice, this
goal can be achieved by good feedback control of chemical addition based on in-line
sensor measurements of the degree of chlorination at a point downstream. Sensors can
detect variations in pulp brightness (reflec-
tance), temperature, pH, and level of residual chemical(s). Control room personnel and the computer control system can
then use this information, together with
consistency
and flow measurements,
to
adjust chemical flows in response to detected variations. Sensors can be located a
short distance after chlorine/chlorine
dioxide addition points, after the retention
tower, in the washer vat, or in all of these
locations (49).
Another technique for controlling chemical addition to the C stage is to measure Cstage washer pulp brightness and extracted
pulp K number. These tests are still widely
used today as a longer term set point to
adjust pre-tower sensor set points. Other
manual tests that are commonly performed
are chlorine residual in the washer vat and
vat pH.
Reflectance of light by the chlorinated
pulp slurry is an indication of lignin content. Several optical sensors use this principle to estimate the degree of chlorination
by illuminating the flowing stock at a specified wavelength.
As noted earlier, paper
machine additives such as titanium dioxide
can give false indications of delignification
progress by increasing the reflectance of the
stock slurry. Aiso, the relationship between
chlorinated pulp brightness and post-extraction K number shown in Fig. 7 changes with
changes in chlorine dioxide substitution
level. Practically, this means that brightness
setpoints must be adjusted or sensors must
be tuned as the degree of substitution
changes.
Two basic types of sensors are used to
measure chemical residuals (49): one is
based on measuring the "ORP" (oxidationreduction potential) and the other type depends on polarography. The signal from a
polarographic sensor indicates the voltage
required to reduce chlorine at an electrode
which is directly proportional
to the residual chlorine concentration. The ORP sensor measures the potential
difference
between a platinum and reference electrode
immersed in the solution. The signal is
markedly non-linear, however, and rises
sharply as the chlorine residual increases
from zero but levels off at higher residuals.
Chapter IV 2: Chlorination
7. Effect of chlorination on
shives and dirt removal
The chlorination stage has played an important role in the bleaching of coarse particles derived from the woody starting
material, for example fiber bundles (shives),
bark specks, and particles from ground up
knots. Bleaching has relatively little impact
on other extraneous particles, such as sand,
pitch particles, and rust that may be present.
Removal of these materials, collectively
known as "dirt; is an important goal of
bleaching, in addition to brightness development. The presence of dirt in the final
paper or board products can cause a variety of quality defects. A significant observation is that particle reduction during
bleaching is a statistical operation; ev~n
though the percent reduction may be acceptably large, when more particles enter
the bleach plant, more leave the bleaching
operation intact (50, 51).
According to extensive laboratory studies conducted by AxegaId and co-workers,
bleaching eliminates most of the shives,
leaving the bark and knot particles and inorganic materials relatively enriched among
the remaining particles. Given that the relative rate of chlorine bleaching of dirt particles is much lower than that for fibers,
several principles have been proposed for
improving the cleanliness of the final pulp
(52). These include maintaining high concentrations of chlorine and operating the
chlorination stage at lower temperatures to
ensure a chemical residual for a longer period of time. These same principles apply
to chlorine
dioxide and hypochlorite
bleaching, but not to oxygen and ozone
bleaching. In these latter cases, the kinetics of bleaching particles and fibers are similar so that little can be done by way of
process modification to enhance dirt removal dirt.
Even with partial chlorine dioxide substitution, higher chlorine charges lead to
improved dirt bleaching (50). Clearly,with
the trend toward decreasing use of chlorine
for bleaching, it becomes increasingly advantageous to take steps to prevent dirt
particles from entering the bleach plant.
255
256
8.
Environmental
aspects of
chlorination
Lignin represents about 4.5% of the dry
weight of unbleached softwood kraft pulp
at 30 kappa number. Perfectly selective
delignification would therefore lead to a
4.5% yield loss across the bleach plant.
Actual values are estimated at about 7%, or
70 kg/ton of unbleached pulp, depending
on the bleaching process and the final
brightness target. Because most of the residuallignin is degraded and removed in the
chlorination and extraction stages, the chlorination-stage filtrate is a major contributor
of organic loading to the bleach plant effluent stream. Because, in most cases, chlorination is conducted at low consistency, the
volume of filtrate in the overall water balance is large in comparison
with other
bleaching stages operated at medium consistency unless recycled filtrate is used for
dilution. In most existing bleach plants, a
large purge to the waste treattnent plant is
required because of the corrosiveness of
chlorination filtrate. The degree of recycle
of this filtrate plays an important role in determining the temperature and pH of the
chlorination stage and affects the quantity
and type of chlorinated organics that are
formed.
The lignin remaining in the fiber after
pulping still contains aromatic structures,
but differs from "native" lignin in that it
contains more carbon-carbon inter-unit linkages and fewer labile inter-unit ether linkages (53). Reactions in the chlorination
stage lead to substantial depolymerization
oflignin; carboxylic acid groups are formed
and chlorine atoms are introduced.
Most
of the aromatic rings are destroyed by oxidative cleavage reactions. Some of the degraded material is dissolved and removed
in the acidic chlorination stage filtrate, but
t
5%
Mw< 1000
30%
Mw < 25000
C-stage
Jlig.14.
Mo'-"'"
mgllt
E-stage
most of the degraded lignin and carbohydrate fragments are solubilized in the following hot alkaline extraction stage. It has
been estimated that of the 70 kg/ton that is
removed during bleaching:
about 50 kg
originates from lignin, 19 kg from carbohydrates, and 1 kg from extractives (54).
About 90% of the chlorine used for
bleaching is converted to chloride ion,
which contributes to salinity and corrosivity
but has no harmful effect on the receiving
streams at the concentrations encountered.
The balance, about 10%,is bound to organic
molecules or high molecular weight material. The organically bound fraction is measured asAOX (adsorbable organic halogen).
AOX is used world-wide as a basis for estimating the discharge of chlorinated organics, and has in some cases been used in
establishing effluent discharge limits for
pulp bleaching operations. Details on the
significance of this sum parameter for characterizing effluents are covered in Chap.
Vlll, Sects.I and 2.
Dence andAnnergren initially compiled
much of the relevant information that has
been generated regarding the chemical
composition
of the chlorination
filtrate
(55). Kringstad and Lindstrom provided an
update in 1984 on the nature and identity
of compounds in the C- and E-stage filtrates
(56). Through the use of membrane separation techniques, it has been shown that
about 70% of the organically bound chlorine in the chlorination
stage filtrate is
present as high molecular weight material
If blMdmIg stIIges.
C
"'
"""
Chapter IV 2: Chlorination
Component
Amount
kg/ton bleached pulp
Methanol
4.6
Formic Acid
1.2
Acetic Acid
0.1
Non-volatile acids
0.3
Carbohydrates'
0.4
Chlorophenols
2.3 x 10'3
'present as polymers
Some organically bound chlorine remains
with the pulp and cannot be removed even
by exhaustive extraction with water or organic solvents (16). The ecological significance of this type of organically bound
chlorine has been compared with that of
polyvinyl chloride (PVC), a common plastic, in which the chlorine is part of the structure of the polymer itself and quite inert.
Chloroform is one of the volatile by-products of pulp chlorination which is proposed
for regulation in bleach plant ffitrates in the
United States. A number of structures found
in pulp can react with chlorine to yield chloroform, including carbohydrates and lignin
(63). Although chloroform is found in largest amounts in hypochlorite
bleaching
stages, it is also detected in C, E, and D
stages (14,64-67). The source of the chlo-
257
References
1. Dence, C.W and Annergren, G. E., in Tbe
Bleaching
of Pulp (R. P. Singh, Ed.) 300
eOO.,TAPPI PRESS,Atlanta, 1979, Chap. 3.
2. Loras,V., in Pulp and Paper Chemistry and
Chemical Technology Q. P. Casey, Ed.) 3rd
eOO., Wtley, New York, 1980, Vol. I, p. 670.
3. Smook, G.A., Handbook for Pulp & Paper
Technologists
(M.}. Kocurek, Ed.), TAPPI
PRESS,Atlanta,
1982, p. 160.
4. Singh, R. P., Handbook
of Pulp and Paper
Technology, 2nd eOO., Reinhold, New York,
1970, p. 249.
258
C. W., Tappi
14. Kringstad,
K. P. and Lindstrom,
K.,
Environ. Set. Tech. 18(8):236A (1984).
Dence,
C. W., Tappi
72(12):121
Pulp
(1989).
(1992).
C. W, Tappi
Pap. Set.
(1966).
B.
6. Rydholm,
Intersdence,
R., Pulp
25. Berry,
R. M. and
Fleming,
HolzfiJrschung
41(3):177 (1987).
S. A., pulping
Processes,
New York, 1965, p. 916.
Tappi
8. Rydholm,
Interscience,
S. A., pulping
Processes
New York, 1965, p. 916.
27. Grangaard.
I.,
(1956).
37. Bennington,P.}.,
Tappij.
76(7);77
(1993).
T., Pulp
(1978).
Chapter IV 2: Chlorination
45.
46.
Macas, T. S. and
tion Strategy:
Kraft Softwood
ing Preprints,
Montreal, 1985,
D. W and Davis,].
Practice
in North
Pulp
c., "Chlorina-
America
Part
I:
259
E, Svensk.
F., Svensk.
60. Lindstrom,
Holzforscbung
K.
and
Osterberg,
39(3):149 (1985).
F.,
50. Axegard,
P., Lindblad,
P.-D., Popke, I.,
Puukko, M., "The Matrix for Softwood
Pulp Quality and Effluent
Kraft Pulp
Load," 1991 Tappi Bleach Plant Operations
Short Course Notes,TAPPI PRESS,Atlanta,
p.21.
52. Axegard,
P. and Bergnor,
E., "Bleaching
- An Overview,"
1991
G.E., unpublished
results.
SECTIONIV:
The Technology of
Chemical Pulp Bleaching
Chapter 3:
Chlorine Dioxide in Delignification
Douglas W. Reeve
Department of Chemical Engineering
and Applied Chemistry
Pulp & Paper Centre
University of Toronto
Toronto, Ontario, Canada
1. Introduction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2. DeUgnificationchemistryandkinetics
2.1 Definitions.. . . . . . . . . . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2 Reactions during chlorine dioxide delignification
.....
2.3 Delignification kinetics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. ~tlonefEkiency..
...
3.1 Degree ofsubstinItion and mode of addition.
3.2 Alkali required for extraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Brightness development. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4 Chlorate formation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Process flowsheet and delignification conditions . . . . . . . . . . . . . . . . . . . . . . ..
4.1 Flowsheets and equipment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Chemical charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. 3 Timing of chlorine dioxide addition.
4.4 Time and temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5 pH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6 Chloride ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.7 Consistency
4.8 Carryover from brown stock washing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
263
263
263
264
265
266
266
268
269
271
273
273
273
274
275
276
278
278
5. Pulp quality .. .. .. .. . .. .. .. .. .. .. . .. .. .. . .. .. .. .. . .. .. .. . .. .. .. ..
5.1 Brightness stability. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2 VIScosity and strength. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Cleanliness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Extractives and organochlorine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.5 Dioxins in pulp. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6. Effluent properties. . . . . . . . . .. . . . . . . . .. .. . . . . . .. . . . . . . . .. . .. . . .. . . . . ..
278
278
279
280
281
282
282
6.1 Dioxins
278
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
Economic
and other
effects.
parameters:
factors.
organochlorine
compound5
..... .......,....
. . ~61
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 285
color, chlorate,
BOD, COD.
. . . . . . . . . . . . . . . . . . . . . . . . . 286
.................................................
261
286
"
Chapter IV 3:
Chlorine
Dioxide in
Delignification
1. Introduction
"Euchlorine," a mixture of chlorine dioxide and chlorine generated from the reduction of potassium chlorate by hydrochloric
acid, was first described by Davy in 1811
who noted that it destroyed the color of
vegetable dyes (1). Watt and Burgess patented the bleaching of soda wood pulp with
chlorine, euchlorine, and sodium hydroxide in 1854 (2). In the 1920s,Schmidt and
co-workers demonstrated that chlorine.dioxide does not react with carbohydrates
(3). In the 1930s, the Mathieson Chemical
Corp. introduced a process for bleaching
in which sodium chlorite was added to a
pulp suspension and ~ous
chlorine was
added to "activate" the. chlorite, that is, to
generate chlorine dioxide. The first industrial processes for continuous generation
and use of chlorine dioxide for pulp bleaching began in 1946 with almost simultaneous, though independent, developments
in Canada and Sweden (4, 5). In one early
application, chlorine dioxide was used as
the sole bleaching agent, replacing chlorine
for delignification and, in later stages for
bleaching, to facilitate resin removal and for
the preparation of pure alpha cellulose from
sulfite pulp (6).
However, from 1946 on into the 1980s,
chlorine dioxide was not used extensively
for delignification but was mainly used for
bleaching in the final stages. Chlorine dioxide was more expensive than chlorine or
calcium hypochlorite, but it enabled production of high brightness kraft pulp without loss of pulp strength. Indeed, it was
these advances in pulp bleaching technology and chlorine dioxide generation which
stimulated the growth ofthe bleached kraft
industry.
Industrial use of chlorine dioxide to replace chlorine was at first only a means of
protecting the strength of the pulp; 5-10%
263
of the chlorine was replaced with equivalent chlorine dioxide (7). However,in 1963
it was reported that substantial substitution
of chlorine by chlorine dioxide resulted in
a synergistic effect so that delignification
efficiency was greatly improved (6). Further improvement was achieved when the
chlorine dioxide and chlorine were added
sequentially, chlorine dioxide first, with 50%
substitution having the greatest efficiency
(8). This technique did not gain wide acceptance until the late 1980s when environmental
concerns
about chlorinated
dioxins and other chlorinated organic materialled the industry to decrease chlorine
use and adopt substantial, and later complete, replacement with chlorine dioxide.
In this chapter, the subjects discussed are:
process chemistry, flowsheets, and variables; pulp qualities such as brightness,
strength, and cleanliness; dioxins in pulp
and effluent; effluent qualities such as organochlorine content, toxicity, and color;
and finally, economics. There have been several reviews on chlorine dioxide delignification in which these issues are discussed
(9-14).
[1]
264
C103-
CI02
_
--
C102:
1
2
8 9 10
J
L_-t~HCIO
3--.
Cb ~l~
CI- .,--4
-1
6 4 5 7
Organochlorine
Lfactor
Lkappa
number
[2]
Pulp Reactions
"\.0 X0."\0 =
and
5.0 x 0.50
/ 2.63
5.0";6equivalent chlorine
on pulp
50 kg equivalent chlorine per
metric ton of pulp
100 Ib equivalent chlorine
per short ton of pulp which
would be made up of
2."j% chlorine on pulp
= 0.95%
chlorine
on pulp.
dioxide
265
.'
100
....
<1J
E
~"
'x
0 . (D+C)E
l::,. .... DE
<1J
7 .J:J
E
::::I
6 c:
::.!
::::I 60
en
c:
20
4
-----
~::.!
5
4
50C
0
40
80
120
160
tlloxlM
of sojlrrJootlltrwft
40
::::I
...
<1J
7 .J:J
6 c:
c: 40
8
E
....
. CE
<1J
...
::::I 60
en
c:
0
U
....
c: 40
JIll
~~9
'* 80
,,'
DE
.........-.-.-JIIl
100
(D+C)E19
'*
,,' 80
266
/JfIlJIllt
80
120
Retention time, min.
upc.
tion of oxidant and the rate of delignification are extremely high. Even at the
relatively low temperature of lOoC, 90% of
the cWorine and 60% of the cWorine dioxide are consumed in only ten minutes (Fig.
2), while at 500c virtually all of either chemical is consumed in ten minutes (Fig. 3). At
l00c, the rate is low enough so that cWorine can be observed to react faster than
cWorine dioxide; both the rate and extent
of delignification with cWorine dioxide are
significantly less. At 500C, the rates of cWorine dioxide consumption
and delignifi.
.
cation are indistinguishabl e fro m th oseo f
cWorine; a SO/50 mixture of cWorine and
cWorine dioxide (D+C) reacts almost as rapidly as cWorine.
Extensive kinetic studies by Germgard
show that the rate of delignification with
cWorine dioxide is fifth order with respect
to kappa number (18):
-!.!K
dt
K5
[4)
3. Delignification efficiency
3.1 Degree of substitution and mode
of addition
Although the use of mixtures of cWorine
dioxide and cWorine to bleach pulp had
been described in the literature on numerous occasions (2, 22, 23), it was not until
1963 that it was shown that when cWorine
dioxide was substituted
for chlorine
delignification efficiency increased signi:
ficantly (6). This was confirmed in other
20
[5]
[l
-0,
where
determined
after
to K 4,
{)
Oxygen bleached
n...
where
= bleaching time
K =pulp kappa number
160
pulps
_ _
Kappa
number
[l" - - {] 22.4
unbl;'ched
23.8
o
o
1
Time, hr
267
268
9
17 Kappa birch kraft
(CD)E /:,.
(D+C)E
~E 4
c:
"
Kappa factor
(DC)E
~7
0.15
"
c:
Q. 6
'"
Q.
'"
~w
21 Kappanumbersoftwood kraft
o
o
20
FIg. 5. MoMs
40
60
CIO, Substitution,
o
80
dllorlIIe ~
100
'"
20
40
60
CIO, Substitution,
80
etnIIlmuIHtnu
~S
100
11M
8
19 Kappa oxygen
delignified
softwood
kraft
20
40
60
CIO, Substitution,
Fig. ,.
MtmM
IIIJtINI ftu:lor
for unbleached
o
o
20
FIg. 6. MoMs
40
.60
CIO, Substitution,
of IlMltimI
of dllorI8e
100
'"
MtmM
11M
-oqgn-bllplJW
cIJlorI8e~
soJlw1oo4 nft
80
JIIIlp.
reports (17,24,25,26).
Further, it was discovered that when the chlorine dioxide and
chlorine were added to the pulp sequentially, the chlorine dioxide first, the benefit
was even greater (8). Maximum delignification efficiency was achieved when the fraction of chlorine dioxide was between 40
and 60% (8, 27-29). When chlorine was
added first, delignification efficiency was
worse. This is illustrated in Fig. 5 for softwood kraft pulp (30), in Fig. 6 for oxygendelignified softwood kraft pulp (31), in Fig.
7 for birch kraft pulp (32), and in Fig. 8 for
oxygen-delignified
eucalyptus kraft pulp
(33). In the case of oxygen-delignified softwood pulp, birch pulp, and most dramatically, for oxygen-delignified
eucalyptus
pulp, the final kappa number is higher for
100"16chlorine dioxide compared to 100%
chlorine, illustrating the relative difficulty
in delignifying these pulps with chlorine
dioxide. In going from softwood to hardwood and from unbleached kraft to oxygen-
20
40
60
CIa, Substitution,
80
100
naIlYftI8snft JIIIlp.
~ CIO,
kraft pulp
= k [H+]-o"'ln
(KjK)
= k [W]-o
[6]
kraft pulp
(K-os - Ko-oS)
[7]
where
~ CIO,
=ClO,
consumption
to reach target
kappa number, K
k = a constant (influenced by pH, [Cn, the
type of pulp, and the extraction stage
conditions)
Ko= kappa number of the starting pulp
K
= kappa
number
of the treated
pulp
af-
'"
011soJlw1oo4nft
80
100
/J8lp Ullpfte4Htm.
to temperature, pulp and chemical concentration, chloride ion concentration, and the
responses of oxygen-delignified
and unbleached pulp. With a 50/50 mixture, pH
had no influence between 1.5 and 2 but, at
pH greater than 2, the chemical requirement increased (36).
CII
270
0.6
Oxygendeligni/iedsoftwoodkraft
~30
269
95
Kappa 35
0
~...
"2't
Eu 0.4
C.-~c
0-"
~uU
Ig~",,0.2
1f 20
E
C
8 10
90
(D+qEDED
"*
~S
z]>
~Q;
0
0
10
20
Kappa number reduction
30
20
60
40
CIO, 5ubstitution,%
80
85
-e--
.-e_e-e-e-e-.
after
aging --e_e
80
100
75
55
"* 3
"2'
E
~
C
ou
I
a
z'"
o
"*
80
30
100
Fig.11. WI_11y4rozIM ~
lit tIJeuIrYIIItm st.ge follmlllag tlellpljietlllqa ","b
eombl".tloru of eblorl"e dioxide ."d
eblorlu.
38) and hardwood pulps (26). Figure 11
shows sodium hydroxide consumed in the
extraction stage, for three softwood kraft
pulps (28). Figure 12 indicates the sodium
hydroxide consumed per equivalent chlorine consumed in the first stage, as a function of chlorine dioxide substitution, for
both softwoods and hardwoods (26). As
an example, in the delignification of softwood kraft pulp having a 30 kappa number,increasing the percent chlorine dioxide
in the first stage from 10 to 50 to 100 would
decrease the sodium hydroxide required
(not including acid carryover in the filtrate)
from 2.4 to 1.8 to 1.2% on pulp (24 to 18 to
12 kg per metric ton of pulp).
3.3
Brightness
development
60
40
Substitution,
80
100
45
i>
as 35
40
60
CI02 Substitution,
20
Fig. 14. fte brlgbtua ofJnllPufler three tIrIdfive sltlges ofbletu:Wag of sojlwJood lmIfI
pulp
","b eblorirle tIrId eblorirle dIo:xIiIe.
50
S40
20
Cia,
70
34.8
15
.10
Kappa number
chemical requirement is achieved with 3050% chlorine dioxide substitution. Optimization for lowest chemical cost was also
studied and was usually close to the optimal conditions for lowest overall equivalent
chlorine. For unbleached softwood pulp,
the lowest chemical cost was at 30% chlorine dioxide substitution.
Increasing substitution to 70-90% required a significant
increase in chemical and led to a significant
increase in cost. The results of a similiar
study on optimization
of (OC)(E+O)O
bleaching of oxygen-delignified eucalyptus
are summarized inTable 2 (33).
To decrease the cost at 70-90% chlorine
dioxide substitution,
for bleaching softwood kraft, consistency was increased from
3-8%, chloride ion was added, and the interval between 0 and C was increased from
2 to 4 minutes; a 5% decrease in cost was
reported (40). These changes in process
conditions had no influence on costs at 3050",,(,chlorine dioxide.
Another optimization study, for (OC)E
(HO) bleaching to 86 ISO brightness,found
minimum costs at 30% substitution independent of kappa factor in the range 0.20 to
0.27 (46). At 90% substitution the lowest
cost was at 0.20-0.24 kappa factor; costs
increased at 0.27 kappa factor. At 50% chlorine dioxide for the same sequence bleaching to 90 ISO brightness,
cost was
minImized at 0.16-0.18 (47).
271
272
ISO MI,,,,-.
80
Optimal charge in
first bleaching stage,
kappa factor
Kappa number
after extraction
0.20
30
50
70
90
0.20
0.18
0.17
0.14
6.4
4.8
5.1
5.6
8.7
0.17
0.17
0.17
0.14
6.1
4.9
5.8
8.1
0.29
0.27
0.25
0.28
0.30
0.17
0.17
0.17
0.16
0.16
4.3
4.1
3.7
4.4
5.4
40
60
CI~ Substitution, %
100
80
10
10
30
Chlorine dioxide applied, kwtonne
FI,. 17. C61ort1tfJ.for'mH
m, ~
frmrt e61or1u
.,...
tI'-Itle
lrfJ"'-Ia.ftnm4lt1
VGrl-
OIlS sllulla.
0.28
1.0
0.27
0.25
0.28
0.31
o
:to.8
*-
10
0.27
0.26
0.26
0.27
0.31
Pulp
J'
"i' 0.6
E
..2 0.4
S
~
0.1
U
Optical and
residual
sensor
10
40
60
Cia, Substitution, %
80
100
Mix
tank
Chlorination
tower
Iow-etnlSlsIf!fU:J
(DC) .11181.
./b1Um.
0.37
0.35
0.34
0.36
0.42
0.24
0.17
0.17
0.24
0.24
0.29
0.24
0.26
0.28
0.32
0.17
0.17
0.15
0.15
0.20
'Sequence (C+D)EDED
Some mills using only chlorine dioxide
in the first stage have had difficulty in reaching high brightness (90 ISO); the addition
of peroxide to the second extraction stage
has helped to overcome
this problem
(48, 49).
TIIbk
2. optImIzetI
(DC)(B+O)D
6lMe1mtf
0112.0
bpJJtI
tI_'-
0xyffJtI-6IfJGC6fJtI_lyptus
""p
10"
30
0.15
0.15
0.22
0.21
50
70
~
OJ7
0.17
QB
O,~l
0.25
Q~
'Sequence (C+D)EDED
(33).
0.15-0.25
kappa factor
Chlorine dioxide
charge:
25-100% of the
total
Temperature:
30-60C
nil up to 5 min.
Time between
D and C:
Total time:
20-60 min.
End pH:
1.5-3
Consistency:
3-4%
273
charge
274
Pulp Bleaching
-Principles
and Practice
10
Chlorine
gas
Pulp
.~
~~:::--~:
t
Pulpto
tower
DE
(C~+D,JE
MC
pump
CIO,
Optical and
residual
sensor
JIIg.If). ~tftn'mftiam~(DC)de.
IIpljlaltlml.
creases. There is merit in limiting the charge
of chemical to the range in which it is most
effident, that is, an amount corresponding
to the steep part of the curve. As the cWorine dioxide in the first stage increases
above 500A"the curve flattens at a higher
extracted kappa number. Optimal chemical charge must be determined in the context of the overall bleach plant as discussed
in Section 3.3.
4.3 Timing of chlorine dioxide addition
Chlorine dioxide, added in advance of
the cWorine, reacts with the pulp before
cWorine is added and is more effident than
when cWorine and chlorine dioxide mixtures are used. The logical extension of this
finding is therefore that delignification effidency is maximized when all the chlorine
dioxide is consumed before the chlorine is
added. The time required for complete reaction of the cWorine dioxide is a function
of temperature,
consistency, and kappa
factor.
Early laboratory wode:, by Hatton (8), on
the timing of sequential delignification was
done only at 200C with hand mixing and
chlorine dioxide was limited to 50% substitution. It was found that a 3-minute chlorine dioxide
reaction
time at this
temperature was insuffident to give maximum benefit; 5 minutes gave greater
delignification and higher brightness (8).
Hatton also used a 5-minute chlorine dioxide reaction time at 200C; delignification
was not increased at 10 minutes and, in fact,
was poorer at 15 minutes' reaction (27).
O-{D"C.,JE
4
Chemical consumed,
cblorlu.
wltb
6
% equiv. CI, on pulp
cblorine
dWxUle
"""
With effident laboratory mixing, incorporating a stirred tank reactor at low consistency, it was shown that at 300C and with
30% substitution, 30 seconds was suffident
to obtain almost maximum delignification
(61). However, in the same study, it was
shown that if 60 seconds or more were
used, pulp viscosity suffered because all the
cWorine dioxide had disappeared before it
could be useful in protecting
the pulp
against cWorine. Further discussion of this
topic is found in Chap. III 2 on chlorination (125). To avoid viscosity loss, where
the combination of time, temperature, and
amount of added chlorine dioxide lead to
complete consumption of protective chlorine dioxide,it is recommended that a small
amount of chlorine dioxide (5-10% of the
total charge of equivalent chlorine) be
added with the chlorine. In another study,
it was found that 60 seconds was required
to obtain maximum delignification at 400C
18
D(C+D)
Delignification
. 2 min between
D and (C+D)
10
20
40
Clo,
60
Substitution,
80
100
')(,
CI02 in first
stage, % of
total equivalent
chlorine
275
Temperature, C
20
35
50
14
11
11
conditions:
kappa
8
6
5
5
4
2
1.5%
276
Pulp Bleaching
-Principles
and Practice
Tune to zero
residual, min
(EO)
(EP)'
5.8
5.5
6.4
6.2
180
82
34
19
7.0
6.8
7.9
7.6
5.9
6.1
6.7
6.8
30
60
155
16
8.3
9.6
7.5
8.2
3.0
12
8]
E
6
"
:;;
Q.
Q.
'* 0.5
o
5
pH in D stage
Fig. 22. De IffI/HId of JIll 011tlellp'.fktlt"m
.,."" cbIurl1Ie
~
278
14
.!j-Q.
" 5:E
u c:
0 2.5
CIi
"t:J
cra .5
(5 2.0
.!j~"5
..Qc 1.5
CIi
--"u!:
~ 'S 1.0
"t:JCT
Q,)
"in
&!
277
a4
jomItItitm
of35/u1pJ111
__
9
of dllorl~
a4
dllmwle
SDftrDootllmlft
JHIlp.
kraft pulp of 22.4 kappa number with chlorine dioxide indicated a steadily decreasing
DED brightness with decreasing initial pH
in the first D stage from 8.3 "natural pH" to
1.5; this range corresponded to end pH values ranging from approximately 2.5-4 to 1.5
respectively (72). Another study provided
supporting evidence indicating that the
maximum delignification efficiency and DE
brightness occurred at a pH slightly below
4, a value consistent with the minimum loss
of chemical in the form of chlorate and chlorite (73).
The kinetics of chlorine dioxide/chlorine
delignification are affected by pH in a manner complicated by the chloride ion concentration. With chlorine dioxide alone,
increasing the pH from 2 leads to a steady
increase in delignification rate. In the presence of 0.1 M sodium chloride (5.8 g/L),
the delignification rate is higher at all pH
levels but a distinct minimum appears at pH
3 (18). When mixtures of chlorine dioxide
and chlorine are used, the delignification
rate is again lowest at low chloride ion concentration but increases substantially with
increasing chloride ion concentrations
up
to 0.50 M at all pH levels. The delignification
rate decreases from pH 2 to pH
in the
" from
absence of chloride ion but increases
pH 2 to pH 4 in the presence of chloride
ion (20).
5. Pulp quality
5.1 Brightness stability
Bleached pulp darkens with age. This
"brightness
reversion" is a function of
chemical structures in the pulp. It is possible to accelerate aging by elevating the
temperature and, for light-sensitive structures, by exposing the pulp to light. Until
recently, there has been no standard procedure for measurement of brightness stabil-
5
w
U 35
'ifci
'"
-: 30
6-
~
.~ 25
5
20
o
20
40
60
ClO, Substitution. ')(,
Fig.23. 1IoeImJNIdofcblorlu ~
- so~
80
100
-/I JnIlJI
"'-11].
of cbltJrlu ~
1125
1135
1115
of cblorl_ ~
and Practice
of so~
Starting Pulp
(oxygen-delignified)
16.0
10.7
Viscosity, dm3fkg
10
50
90
-Principles
Starting Pulp
(unbleached)
33.3
Pulp Bleaching
Ttlble6. r-fl-
Kappa number:
280
(C+D)EDEDset[fImU.
00,,%
279
920
935
950
740
745
745
-/I Jnllpbleacbed",
(C+D)EDEDset[fImU.
ClO" %
Kappa number:
Starting Pulp
(unbleached)
33.3
"
Starting Pulp
( oxygen-delignified)
16.0
Tear index,Nm'/kg
10.7
10
14.6
13.4
11.0
50
90
13.4
13.0
11.5
13.4
13.3
11.5
900
2000
2500
50
90
1000
2000
2300
1000
2000
2400
= k [ClO,]07
[particles]l
dt
where
= shives,
particles
k
= rate
The particle concentration decreases linearly with time, and so this is a first-order
equation. This is distinctly different from
the concentration of1ignin which decreases
very rapidly initially and then more slowly.
Thus, particle removal is favored by prolonged retention at a given concentration
of chlorine dioxide. The Arrhenius activation energy for chlorine dioxide reaction
with paniclc~, jj :t j kJ/mol ({J5), compares to a value of 60 kJ/mol for reaction
with lignin as measured by kappa number
decrease. Thus, lower temperature
in a
281
400
Substitution.
o
0
jb
Substitution,
o
0
.. SO
70
300
300
. 90
o 100
~c:
-"<Ii 200
:i5
.in
CEDED
:>
100
.o 100
90
lJ
oc:
<Ii 200
"'"
:i5
.in
:>
.. 50
70
100
o
o
75
80
85
Brightness, % ISO
90
Sllbstitutton
measured
70
80
90
100
110
Chemical consumed. kg equiv. CI, /tonne
282
6. Effluent properties
6.1 Dioxins
Substitution of chlorine dioxide for chlorine has a profound affect on the formation
of chlorinated dioxins as is discussed in
more detail in Chap. VII 3 (125). It was
established in 1989 that increasett chlorine
dioxide substitution is one means by which
the formation of chlorinated dioxins and
furans can be reduced; at substitution
greater than 50-70%, TCDF and TCDD are
no longer detectable in pulp (91-93).
Because of their very low concentration
and limited solubility in bleaching effluent,
chlorinated dioxins and furans are difficult
to detect and measure with the result that
little information
about them has been forthcoming from laboratory
studies. However,
several mill studies have shown that,as chlo-
mg/kg
Nonextractable
Birch kraft
O(C+D)(EO)DED
OD(EO)DED
650
120
250
100
Softwood kraft
O(C+D)(EO)D(E+P)D
OD(EOP)D(E+P)D
270
110
230
100
&
283
200
Kappa no.
Unbl.
30.0
o (E+O)
23.5
t>. (E+O+ P) 20.5
00
16.6
284
6.3 Chlorophenols
150
<11
t::
t::
S
0.,100
x'
o SW
Lab
0"
o HW, Lab
10
100
20
30
CI. k&'tpulp
ClO, Substitution, %
of AOX Jonrtft
bkbi.,toe~
tN (DC)""p.
~(a)..
40
o
o
0
I.
(DC)E
I.
20
40
&0
CIO, Substitution, %
80
100
Fi,. 27.AOX~irf(DC)E~tlSlI.frMc'
tin of .MIH4:Nl
soJtfllool "rIIJt pip
lrNtMMIal
bJI/M """.,.,
IS
0.8
i<110.6
Ii:
"<11
0.4
.S
x
~ 0.2
o
0.1
0.12
0.14
Kapp~ tartar
0.22
Fi,. 2'.
o
~
50
0.24
infi~ 0 ~~
D(EO)IJ(EOP)D 61MeW"g
Fig. 28. AOXfortrllltilm
I"
of 1311t1ppt1..-Hr
GXYIfI"-llelig,dfld
Super B4tcIr softwootl.
3
4
5
&
AOX, kgltonne pulp
BOX tIS IIfnctiorc
of AOXfor
6lNdn.,
9
ef-
fl.-b.
chlorine compounds
Several types of chlorophenolic
compounds are generated when chlorine dioxide is used in combination with chlorine to
de1ignify pulp. Formation is strongly dependent on the amount of molecular chlorine
(C~ used; some compounds, particularly
those which are highly chlorinated, are not
formed when chlorine dioxide alone is
used. Chlorine-substituted
phenolic compounds,
that is, catechols,
guaiacols,
vanillins, and syringols are formed from the
lignin remaining after pulping and may have
from one to five chlorine atoms per aromatic ring. The most abundant ring type is
guaiacol
~ = ~ = H).
OH
Phenol
Catechol
Guaiacol
Syrlnvol
Vanillin
Rs
H
H
H
H
CHO
I"
E6
."
~5
"8 4
.~
'" 3
~
(;
_0
2
:E
U 1
,
'
,,
,,
. 0...
4,5,6trichloro
tetrachloro
,,
o
o
20
40
60
80
CIa.,Substitution,%
100
285
286
Pulp Bleaching
- Principles
and Practice
color, chlorate,
scat-
7. Economicfactors
The greatest economic consideration in
the use of chlorine dioxide in delignification is the chemical cost. The relatively high
cost of bleaching chemicals is basically a
function of percent chlorine dioxide and
the price ratio of chlorine dioxide and chlorine as illustrated in Fig. 32 (31). This is
typical of many similar studies in which the
lowest cost is obtained in the range of 3050% substitution with the cost being rela.
tively insensitive over this range. As 100%
substitution is approached, the chemical
cost increases sharply.
The cost of increasing chlorine dioxide
substitution has been estimated from the
results in numerous mill trials. In 1%7, a
trial on a hardwood kraft pulp indicated that
increasing chlorine dioxide substitution to
about 50% does not influence cost (53). A
study made in 1973 showed that, at 25%
substitution, chemical costs were decreased
by 10% in one mill but were unchanged in
another (54). More recent mill studies and
mill surveys have examined 100% chlorine
dioxide substitution and have reported a
significant increase in bleaching chemical
cost (48, 49,56, 57).
Another factor, sometimes discussed in
connection with chlorine dioxide substitution economics, is pulp yield. This question was thoroughly
examined
by
McDonough in a 1985 review where it was
concluded that, based on literature published up to that time, chlorine dioxide
160 27 Kappa softwood
150
140
"*
Tt
u 130
.~ 120
~
110
100
90
20
40
60
80
ClO, Substitution, %
100
Acknowledgments
Sterling Pulp Chemicals has provided financial support for chlorine dioxide bleaching research to the University of Toronto.
Paul Earl and Ulf Germgird reviewed this
chapter and provided helpful comments.
References
1. Davy,
H., "On
a Combination
of
Oxymuriatic
Gas and Oxygene Gas" ,Philosopbical
Transactions,
Royal Society of
London, 101:155 (1811).
2. Watt, C. and Burgess,
11,343 Only 18, 1854).
3. Casciani,].,
(1953).
Paper
Trade
4. Woodside,
V. and Macleod,
TradeJ 137(8):26 (1953).
136(10):21
K.S., Paper
5. Rapson,
WHo and Strumila,
G., in ~
Bleachinv of Pul!)" (R. P. Singh, Ed.), TAPPI
PRESS, Atlanta, 1979, Chap. 6.
6. Rapson, WH., in The Bleachin~ of Pulp,
(Rapson,WH.Ed.),
TAPPI PRESS, New York,
1963, Chap. 8.
7. Rapson,WH.,
(1958).
287
11. McDonough,
T,J., Berry, R.M., Betts, ].L.,
Du Mano~].R,
Reeve, D.W,'furnbull,}.K.,
"Chlorine
Dioxide in the Chlorination
Stage
A Summary of Existing Published
Information;
1985 Tappi International
Pulp Bleaching Conference
Proceedings,
TAPPI PRESS, Atlanta, p.143.
12. McDonough,T.]."Chlorine
Dioxide in the
Chlorination
Stage: A Survey of Existing
Published Information;
71 stAnnual Meeting, Tech. Sect., CPPA, Montreal, 1985, p.
B283.
13. Pryke, D.C., Tappi J, 72(10):147
(1989).
14. Folke,J.,"Chiorine
Dioxide in Pulp Bleaching - TechnicalAspects
and Environmental Effects; Duoplan Oy, Helsinki, 1993.
15. Kolar, J.]', lindgren,
B.O., Pettersson,
Wood Set. Technol. 17:117 (1983).
16. Ni, Y., Kubes, G.]., Van Heiningen,
J Pulp Pap. Set. 19(1):Jl (1993).
B.,
A.RP.,
(1982).
20. Germg3rd,
(1982).
21. Germgard,
V., Teder, A. Tormund,
Tappi 65(5):124 (1982).
22. Vmcent,G.P.,
18, 1939).
23. Stone,WA.,
10, 1956).
D.,
Only
Pap.
Mag.
Can.
288
31. Axegard,
(1986).
P.,]
Pulp
32. Germgard,
33. Germgard,
V. and Vannfalt,
43(4):305 (1990).
C., Appita
34. Axeg3rd,P',"Effect
ofCIO,Substitution
on
Bleaching
Efficiency
and Formation
of
Organically Bound Chlorine," 1984 Tappi
Pulping Conference
Proceedings,
TAPPI
PRESS, Atlanta, p.353.
(1982).
Rapson,
W.H.,
Tappi
R.-M., Pap.
41. Germgard,
V. and Karlsson,
Puu 67(11):655
(1985).
R.-M., Pap.
M.,Appita
28. Hatton,].v.
and Eade, B., Pulp Pap. Mag.
Can. 68(9):T420 (1967).
29. Hatton,
J.V., Pulp
68(4):T181 (1967).
Pap.
Mag.
Can.
"VCVelop-
ments in Chlorine
Dioxide Bleaching;
1980Tappi
Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, p.403.
E., Germgard,
U., Kolar, J.]',
B.O., CeUul. Chern. Tech. 21: 307
H.C., Pulp
0%7).
Pap.
S.,
'/rans.
C43,
Tech. Sect.
].A., personal
Kiiskila,
D., Pap.
E., Tappi
communication,
K.M., Tappi
1., Pap.
C.B., Tappi
Puu
64(0):581
U., Apptta
71. Basta,J.,Andersson,
L., Blom, c., Forsstt
m, A., W ne, G., Johansson,
N.-G., "New
and Improved
Possibilities
in DI00
Bleaching," 1992 Tappi Pulping Conference Proceedings,
TAPPI PRESS, AItanta,
p.547.
R.W: and Wrathall,
S.H., Appita
45(5):3360992).
.
73. Basta, J., Andersson,
1., Blom, C.,
Holtinger, L., Hook,}., Appita 45(1):29
(1992).
74. Liebergott, N., Pulp Pap. Mag. Can.
720):109 (971).
75. Reeve, D.W:,Weishar, K.M., li. L.,"Process
Modifications to I>ecrease Organochlorine
Formation During Chlorine Dioxide Delignification", 1994 Tappi International
Pulp Bleaching Conference Proceedings,
Tech. Sect., CPPA, Montreal, p.283.
76. Reeve, D.W:, Anderson, C.B., Rapson,
W:H.,Pulp Pap. Can. 81(6):Tl42 (980).
77. Maples, G., Ambady, R., Caron, J. R.,
Stratton,S.,VegaCanovas,R"BFR-A
New
Process Toward Bleach Plant Closure," International Pulp Bleaching Conference
Proceedings, Tech. Sect., CPPA, Montreal,
1994, p.253.
78. Kutney, G.W:, Macas, T.S., Donnini, G.P.,
Pulp Pap. Can. 86(5):Tl35 (985).
79. Grundelius, R, Mitchell, K.A., Rankin,}.P.,
Pulp Pap. Can. 92(4):T87 (991).
80. Howard, E.}. and Histed, }.A., Tappi J
47(1):653 (964).
81. Fergus, B.}., Tappi 56(1):1140973).
82. Fossum, G. and Marklund, A., Tappi J
71(1):79
83. Axeg:ird,
84. Basta,
P., Svensk
(980).
(1988).
P., TapptJ
69(10):54
J., Andersson,
(1986).
Papperstidn.
P.O., Tappi
K.M.,J
Pulp
74(2):123
Pap.
P., Pulp
(991).
L., Cbemosphere
97. liebergott,
N., van lierop, B., Nolin, A.,
Faubert, M., Laflamme,J., "Modifying the
Bleaching Process to Decrease AOX Formation," 76th Annual Meeting,Tech.
Sect.,
CPPA, Montreal 1990, p.B229.
98. Earl, P.F. and Reeve,
72(0):183
(989).
D.W.,
99. Sangster,
1971.
communication,
M.C., private
communication,
Tappi
290
70. Asplund,
C. and Germgard,
44(2):950991).
72. Allison,
85. Axegard,
83(0):284
289
1994.
101. liebergott,
N., van lierop, B., Nolin, A..
Faubert, M., Laflamme,}., Pulp Pap. Can.
92(3):T70 (991).
102, Histed,]., and Vega Canovas, ft.."Dccrea~
ing the Usage of Chlorine and Caustic in
Bleaching," 1989 Tappi Pulping Conference Proceedings,
TAPPI PRESS,Atlanta,
p.85.
Pulp Pap.
112.Earl,
P.F. and Reeve,
730):179
(990).
D.W.,
Tappt
D.W.,
Tappi
116. O'Connor,
B.I., Kovacs, T.G., Voss, RH.,
Martel, P.o., van Lierop, B., Pulp Pap.
Can. 95(3):T99 (1994).
117. Crawford, R}., Dallons,V.}. ,Jain,A. K.,Jett,
S.w., TapptJ 74(4):159 (1991).
118. Donnini,
(1983).
119. Eriksson,
K.,Svensk
SECOON IV:
The Technology of
Chemical Pulp Bleaching
Chapter 4:
(Oxidative) Alkaline Extraction
Richard Berry
Pulp and Paper Research Institute of Canada
Pointe Claire, Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.1 Development of alkali use in bleaching.
2. Role of extractlon in bleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2.1 Solubilization and reactivation of lignin
2.2 Alkali-consuming reactions
',' . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
2.3 Lignin dissociation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3. Factors affecting aIkaJi consumption.
................................
"
3.1 Carryover
3.2 Addition of oxygen and peroxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.3 Substitution of chlorine with chlorine dioxide. . . . . . . . . . . . . . . . . . . . . . ..
4. Effect of extraction on extractives and carbohydrates.
.................
"
5. Effect of extraction on reversion.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.First extraction stage
6.1 Kinetics
6.2 Chemical concentration (charge and consistency) . . . . . . . . . . . . . . . . . . . ..
6.3 Consistency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.4 Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.5 Time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.6 Pulp type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.7 First-stage oxidant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7. Oxidant-reinforced
extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7.1 Development of oxidant addition. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
7.2 Oxygen
,
7.3 Peroxide
8. Seomd extraction stage . . .. . . .. .. .. . . .. . .. . .. .. . . . .. . . . . . . . . .. .. . . . ..
8.1 Kinetics
8.2 Chemical concentration (charge and consistency) . . . . . . . . . . . . . . . . . . . ..
8.3 Tune. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
8.4 Temperature. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
8.5 Rapid extraction
8.6 Added oxidants
9. Other aIkalles. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
? 1 Chlorine-tO"5Odium hydroxide ratio
9.2 On-site sodium hydroxide generation
9.3 Conversion of chlorine to chlorine dioxide. . . . . . . . . . . . . . . . . . . . . . .,
9.4 Alternative alkali sources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ." . . . . . . ..
9.5 Papricycle process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .,
291
293
293
293
293
296
296
297
297
297
297
297
298
299
299
302
303
304
305
305
305
305
305
306
310
312
312
313
313
313
313
314
314
j 14
314
315
315
315
Chapter IV 4:
(Oxidative)
Alkaline Extraction
1. Introduction
1.1 Development of alkali use in
bleaching
The use of a1kali has remained one of the
few constants in the evolution of pulp
bleaching. However, the way a1kali has been
used has changed significantly since the first
recorded alkaline bleaching stage using
potassium hypochlorite for bleaching textile fabrics was described in 1789 (I). In
the intervening 200 years, a1kali has been
used to achieve several objectives in the
bleaching process. In the first application
cited, a1kali was used to provide an optimum reaction pH for the hypochlorite and
simultaneously to provide the conditions
under which the reaction products could
be hydrolyzed and solubilized. It was later
recognized that chlorine is more effective
under acidic conditions and so the oxidation step, chlorination (C),and the hydrolysis/ solubilization step, extraction (E), were
separated. This led to the development of
multiple-stage bleaching processes, such as
CEH and CEDED, where the oxidation and
hydrolysis steps are separated. In modem
bleaching, the distinction between an alkaline oxidizing stage and an extraction stage
is blurred by the now routine addition of
oxidants to the latter stage. A distinction
can be made between the two by considering that a stage having a final pH higher than
IIIssoI""
293
a-Cellulose,
%
NaOH,
% on o.d. pulp
Tune,
min
Temp.,
C
Consistency,
%
89-90
0.5-2
120
50-SO
10
<]0-93.5
2-6
45-150
80-125
10-22
93.5-96
6-15
15-240
95-145
10-22
>96
to
30-60
30-40
294
-Principles
Pulp Bleaching
and Practice
30
~
Q)
J:j
25 -
20
E
::J
Rapid phase
/'
c:
15-
a.
CO
~
10
W
c..>
Slow phase
5-
..
,
I
10
20
30
I
40
50
Time, min
Rg.l.
CII_gell,
CE lIIIJIIItt amber
IIIUII/:b1orlfUllttm
to further
oxidation.
This theory,
it_forti
softwood
28.8)(3).
295
296
o
II
C-OH
CI-b-O-Ug.
CI.
H
Blocking
-Principles
Group
2.2 Alkali-consuming
Ug.
Ltg.
"*"
C, C):~ H
Cl...... ....c....~~b
~O
CI.
HOOCH.
~OH
Lig.
C, J~
~~C
Blocldng Group
Lig.
"*"
HOOCH.
loll
Ltg.
"*"~o
CI
C~
-------
"*"
CI 0
OCH.
OR
~C1z
Ho'H
Blocking Group
Lig.
H
b~OH
H
CI/ 'C
OCH.
OR
BlocktlgGroup
Pig. Z. Prop0se4
frmutlml
o
II
C-OH
I
CI-C-o-Ug.
I
C-oH
II
o
!'IaCL C...C~ H
cv
H b~o
fio
blocih8g
01....'"'
NIIOH
Blocking
groups
(3, 7).
NaCI
+ Na2C03
HO-Llg
HaCI
+ Ha2C03
Activated Lignin
NIIOH
~
NaCI
+ Na2C03
+ Activated Lignin
CI
OR
Furta Oxidation
~Productl
reactions
pulp that was is caused by hydrolysis of organically bound chlorine in the pulp. Most
aliphatic organically bound chlorine and
heavily chlorinated aromatic compounds
are susceptible to alkaline nucleophilic substitution reactions (Fig. 3). Sodium carbonate formation
is caused
by another
hydrolysis reaction which occurs with activated carboxylic acids (Fig. 3).All these reactions activate the remaining lignin to
funher oxidation.
A funber small amount of the sodium hydroxide is consumed in forming sodium
salts of insoluble organic acids which remain with the pulp. These insoluble acids,
particularly if phenolic in nature, probably
represent a portion of the reactivated structures. Some residual sodium hydroxide also
is present to ensure a sufficiently high pH
for full extraction of the pulp.
2.3 Lignin dissociation
The solubilization of the oxidized material is largely caused by the greater water
solubility of the sodium salts of otherwise
insoluble organic acids. However, the alkaline environment also decreases the degree
of association of lignin molecules and decreases their hydrodynamic volume which,
in turn, increases their ease of removal from
the fiber wall.
Ug.
LIII.
CI
Group
N80H
and Practice
FUItIMr OIdd8lon
Produclo
b-OH
Pulp Bleaching
Ct
CI
NeOH
OCH1
NaCI
+
CI
*
OR
OH
OCH1
234
297
50
a.
:;
a.
40
~30
0"'"
c:
Precipitable
~Fraction
~20
Z
0
10
....I
11<
*_
0
0
Fraction
7
~~.
10 11 12
pH
298
Pulp Bleaching
-Principles
and Practice
In most circumstances, the degree of viscosity change is too small to affect the
strength of the paper made from bleached
pulp. However, one method of eliminating
most of this viscosity loss is to use a reductant such as sodium borohydride (23). It is
also possible to stabilize carbohydrates by
oxidizing the carbonyl groups to carboxylic acids with a selective oxidant such as
sodium chlorite (23). Neither of these
methods is practised on a commercial scale.
CEHD control
81.3
83.1
82.7
82.7
30
30
60
Extraction
Extraction
Unbleached pulp:softwood
Water soak: 48C
Extraction: 48OC, 10.5 pH
Thermal Reversion,
% ISO Brightness
ISO Brightness,
%
pulp
Water soak
4.6
4.3
3.3
3.1
kraft
3.5
3
Residual
sodium hydroxide
2.5
2
1.5
0.5
Sodium chloride
o
o
Time,
min
Treatment
00
00
100
of.flrst
Sllbstltrltltm
Off sodI.m
11Me:drtletltmof MlftfIJOOtllnwft
jnIlp (1uIppa".mber, 29.5).
balmlee
ill
OXYgert-rel"forced
""
"1,,,,-
299
300
- Principles
Pulp Bleaching
and Practice
20
(1~~ ~~
~~~
0 0
HO
011
IKIfIoC
HO
IKIfIoC
011
HO
000
I
IKIfIoC
-~~-
CD
.0 15
E
::J
c:
CO
0.. 10
011
0..
+OH13
HO
~W
()
~~--
-0=---
o
o
0
8
IKIfIoC
011
~
0
000
I
S
IKIfIoC
O
.
011
H:zO.
0
IKIfIoC
+OHS
2!}.5)(25).
00
~
Time,h
.t . CONSt""t
~
100
1~
1~
UmCOtfeet8lrrJtUm
for. softwoolllmJft
18
16
Chlorine charge
....
CD
FIg.7. ~ofOJdlUzM~
'-I'sgto
dM", t:1MHge""""'g""'*-~
.0
14
E
::J
c: 12
CO
0..
0.. 10
CO
~W
8
()
(15).
O.15'Kappa number
O.20'Kappa number
O.25'Kappa number
6
4
FIg.!}. JlJIteof ~
.rlsg
10
20
30
40
Time, min
50
60
70
=K.-K.
o ,
eblorlu mulUples
intercept
=the
extrapolation
kf
=
=
of the reverse
of the linear
slow phase with the Y-axis.
the fast reaction rate constant
Af.e('390001R1)
= 1.5
min.1.mol-oz
at 6O"C
=
=
Chapter
IV 4: (Oxidative)
Alkaline Extraction
301
302
14
12
13
...
....
~12
CD
.c
10
~11
c:
c 8
as
a.
a.
6
::I
~10
0.
as
~W
()
9
8..1
J2
04~.
-...........
w
()
4
10
20
30
40
Time,
Rg. 10. 1J.ffect
ol,,'IMlI,,'ty
""ted
softwood
Inwft pulp
50
60
70
min
tlecretue ariftg
"lIulil.
(25).
extrtldlort
14
12
::I
c:
as
10
0.
0.
as
8J
w'-.
~------
~W
()
6
30
01" cblorlftllted
dK;dt
= -kfI.[OH-j02.K,-~'[COtjLO.K.
[2]
dK/dt
where
10
20
30
40
50
Time, min
60
Rg. 11. 1J.ffect01 temperatrwe 011tile me 01 bpJM ""mber tlecretue 48rl"g tIlIMll.
utetl softwood Inwft pulp (25).
70
2.1
=
exIrtIctUm 0111eblorl-
40
50
!tJInIllqIwr011tbeme 01bpJM
-'Inwft pulp (25).
softwood
...
<D
20
60
Time, min
R,. 12. Effect
01tIllMI.
16
..c
10
01" eblorl-
kf2
= the
=1
k" =
k'2 =
0'
arl",,,,IMl.
'e(-~9000IR1)
fast carbonate
reaction
rate constant
ij6.e(-4I4001R1)
This analysis allows more precise modelling of the extraction stage and predicts the
performance of the extraction stage when
all the sodium hydroxide in the extraction
stage is consumed and only carbonate remains to continue the extraction process.
This analysis also allows the prediction of
results when sodium carbonate alone is
used as the extractant (28). In particular,
the rate constants for the carbonate reac-
6.2
Chemical concentration
(charge
and consistency)
The kinetic analyses show that, although
the hydroxide concentration
has a much
larger effect on the fast phase than on the
slow phase of extraction, both phases benefit from a high concentration
of sodium
hydroxide. There is, however, a practical
constraint on how much sodium hydroxide can be applied. A balance is achieved
between the amount of sodium hydroxide
used and the amount of oxidant required
in the following stage. Figure 13 shows that,
with increasing sodium hydroxide charge,
the CE kappa number decreases to an asymptotic limit which is lowered as more
oxidant is applied in the first stage of bleaching (29, 30). In a first stage in which only
303
20
c:
0
:;::; 18
0
as
... 16
)(
Q)
...
Q)
1ij
...
Q)
.D
14
Kappa
factor
12
10
E
::] 8
c:
as 6
0.
0. 4
as
~2
0
JIIg.13. E.fIeeto/s0M88
~
In"IIftJnIlp (IuIppII-.6er,
234
5
6
NaOH, % on o.d. pulp
dNIrp '"t6e.extrwetloll
31.')} (29).
from the bleaching first stage. The time delay in such a control feedback loop is large,
corresponding to the retention time of the
stage but, because the degree of change in
the caustic charge caused by variations in
normal operation is small, this control system functions adequately. The extraction
stage control system can be refined to include a feed forward signal from the cWorination stage control system (30). In this
strategy, the caustic charge is ratioed to the
oxidant addition. When this approach is
combined with final pH control, both shon
and long period variations can be managed.
6.3 Consistency
In practice, bleaching at higher consistencies decreases the amount of steam required
to achieve
a given reaction
temperature and also decreases the retention time which determines the size of the
bleaching tower. Bleaching at lower consistencies generally allows better mixing
which in turn ensures more uniform and
complete reaction.
Theoretical considerations can also be
incorporated into the determination of optimum consistency. The kinetic analysis
shows that increasing the alkali concentration by increasing the consistency improves
the degree of delignification achieved in the
304
Pulp Bleaching
- Principles
and Practice
Consistency,
%
Steam,'
kg/t
40
400
760
1334
667
400
266
10
10
10
40
60
80
60
60
60
60
3
6
10
15
and washed
pulp is 38C.
erature than those of the slow-phase reactions.Again, practical considerations determine the eventual configuration
of the
system. The temperature in an extraction
stage without oxygen carried out in a conventional downflow tower cannot exceed
95C. Temperatures higher than 95C are
achievable in retention vessels built to withstand pressure but, even in extraction systems that include
both oxygen
and
peroxide, a temperature of 95C is rarely
exceeded in present bleach plant configu-
8.5
8
...
Q)
.D 7.5
E
::]
c:
7
as
0.
0.
as 6.5
~w
U
6
Time, min
15
5.5
2
6
8
Consistency,
10
%
12
14
16
305
also now being used in several mill installations (32).As with the other oxidants, extraction of ozone-treated pulps improves
the efficiency of a sequence in which ozone
is used by decreasing the kappa number and
improving the further bleachability (33,
34). Some advantage may be obtained by
eliminating the wash step between highconsistency ozone (Z) stages and the following E stages; peroxides, carried over
from the ozone stage, become active in the
alkaline environment
of the extraction
stage.At medium consistency, however, the
amount of acid in the carryover substantially
increases the caustic (NaOH) requirement
of the extraction stage.
7. Oxidant-reinforced
extraction
7.1 Development
of oxidant addition
Before 1980, oxidants were used sparingly in the extraction stage. Sodium hypochlorite and hydrogen peroxide were
added to overcome specific problems such
as shortfalls in the availability of chlorine
dioxide, the need to produce a very high
brightness grade, or the need to decrease
the color of the extraction stage effluent.
Since 1980 there has been a rapid implementation of oxygen reinforcement in the
alkaline exttaction stage.
The potential of using less expensive
oxygen in oxygen-reinforced alkaline exttaction to replace more expensive chlorine di-
306
Pulp Bleaching
-Principles
and Practice
16
c:
0
:u
x
a>
14
~12
....
a> 10
1ij
....
a>
.c
E
~c:
as
a.
a.
as
x:
I(E~)I
8
6
4
2
0
1
2
3
4
NaOH charge, % on o.d. pulp
(IIIpJM nlllber,
", plltntbesa
tained from the oxygen applied in the exttaction stage than when chlorine dioxide
is applied at a high active chlorine multiple
(44). In some cases, the degree of oxidation of the first stage pulp can be so high,
for example when using ozone, that a negligible benefit is obtained from the application of oxygen (45) .These results show that
not only the stage but the sequence needs
to be optimized to ensure the maximum
benefit from the use of the lowest cost
chemical. In general, both softwood and
hardwood furnishes and pulps produced by
the kraft and sulfite processes all respond
well to the application of oxygen in the
extraction stage (fable 5) (43).
Thekappanumberdecreaseob~Nedin
oxygen-reinforced alkaline extraction does
not accurately represent a corresponding
Ttlble4. Chlorltle IIlonu Sllvltlgs 'Itrough usltlg
oxygetl- or JH!t"fJXlU-mtiforcetl "lI"dltle
extrtlctton (30).
Stage
(EO)
(EP)
Cost of Oxidant,
$ per metric ton of pulp
5 kg 02 in E1
saves
0.75
3 kg C102 in D.
3.00
1.5 kg Hz02 in E2
saves
3 kg CI02 in D.
1.65
3.00
Net saving
2.25
Net saving
1.35
"",..
Post
Post
&kappa (EO}kappa
1st
Stage
Softwood
kraft
C90+D10
D7OC30
5.8
4.6
3.4
3.3
Hardwood
kraft
C90+D10
D7OC30
3.4
2.7
2.2
2.1
Softwood
sulfite
C90+DI0
2.6
1.2
Unbleached
Softwood
Hardwood
Softwood
pulps:
kraft; kappa
number,
kraft; kappa
sulfite;
kappa
33.9
number,
17.7
number,
30.5
number;
20 min at sooC;
decrease in the lignin content of the extracted pulp because the remaining lignin
is more oxidized and therefore consumes
less potassium permanganate in the kappa
number test than a conventionally extracted
pulp (Fig. 16) (9). However, kappa number is still the critical indicator of the chlo-
307
308
Pulp Bleaching
-Principles
and Practice
50
(C90+D10)EDED
[J
cD
"C
'x
(D3OC70)EDED
<>
(D5OCSO)EDED
40
Q)
(D7OC30)modEDED
.~
(D70C30)convEDED
.
.
30
~~
(..)E
(D9OC10)modEDED
--
"C
Q)
rn
c:
o
U
(D9OC10)convEDED
20
10
2
4
567
8
E-stage kappa number
Q) 6
.D
E
:J
c: 5
as
a.
a.
as 4
27.0
"C
Q)
as
10
Pressure02
I-....~ PSIG MPa
10 0.07
~(211.8)
~2b 20
0.14
~50 0.50
(27.2)
~UJ
o 1 2 3 4 5 6 7 B 9 10
60
2
0.4
0.6
0.8
1.2
1.4
1.6
1.8
KlIIstm lipi.
"'"'
t:tmIe8i i. CMI_Uo1uIl
~-ret..
"'"'
309
co
a.. 0.4
~cD
....
::J
en 0.3
en
Q)
"..................
\',
....
c..
Q)
0) 0.2
::J
CO
0)
c:
Q) 0.1
0)
>.
x
0
\ \ .".
\'
g-J.................
. :
I
\:
\:
oftbe
..
~:
\~~,
:'
\
Kappa number
shown in circles.
..................
' , ........
o
Fig. If). ComptIrlstm
............
..........
.\
I
I
\:
':\
",
..
..........
....
.........
"\
.........
........
............
2
3
4
5
6
7
8
9
Oxygen treatment time, min
effect ofgrw4lullly
Mctwsmg
10
0.35 MP. tMYfM Jna$8re
to .tmospberk ad tbe effect of tlUd"tldttUrg. wutllflt Jna$8re of 0.14 MP. lit VlJrWusm,refl
Ire"",,",t times. Tbe reSJIltiltg1uIJIPII bers lire cIrr:W Tbe Iiotmlilfle reJIrWefItstbe expected
to tbllt obtllifled Iry~g
. wutll"t
Ire"",,",t (5 ",.tes) rel/fdred to glfJII. result t:OIIIJNII'fIble
Jna$8re of 0.14MP. _ 3 ",I""tes (46).
be well distributed throughout the pulp
mass for uniform reaction to occur. The
advent of high-intensity mixers allowed the
successful application of (EO) (36). Other
less expensive mixer designs (for example,
static mixers) may be used, (47, 48) but
the decreased rate of reaction of pulp with
oxygen because of poorer gas distribution
must be compensated for by using higher
pressure and extending the reaction time
at pressure. This type of installation represents an option for those mills using upflow
extraction towers.
Most of the operating conditions in oxygen-reinforced alkaline extraction are similar to those of conventional extraction.Time
and temperature are generally in the same
ranges. The kinetic models described earlier in Equations [1] to [3] are still relevant
in the context of oxygen-reinforced alkaline
extraction.
It is perhaps significant that
there is a correspondence between the time
required for pressurization in (EO) and the
time span of the rapid phase described in
the model. This correlation suppons the
conclusion that the rapid phase is the period during extraction when most of the
chemical reactions occur with the pulp.
-Principles
and Practice
7.3 Peroxide
.............
Pulp Bleaching
c~.....
\~\ "\,
\ \
310
One operating
condition
that does
change is the sodium hydroxide charge
which, for oxygen-reinforced
extraction,
must be 0.5% on pulp higher than in conventional extraction if the stage is controlled
to the same final pH (9). The reason for
this increase, as stated earlier, is the increased formation of sodium carbonate occurring during oxygen-reinforced
alkaline
extraction.
The oxygen charge applied is commonly
0.5% on pulp, most of which is consumed.
Generally, the amount required is determined by the point at which no further
benefit is obtained in terms of kappa number reduction or cWorine dioxide savings.
Some analyses of the residual gases have
been made (49); however, mills do not routinely measure the oxygen content of the
off gases. For the limited amount of oxygen added, it is judged not worthwhile to
control the oxygen addition more closely.
Although some carbon monoxide and hydrocarbons are produced in oxygen-reinforced alkaline extraction
stages, the
concentrations
are not high enough to cre.
ate an explosion or fire hazard (50).
One negative aspect of oxygen-alkali extraction is that when residual gas is en-
in the absence of the necessary cWorine dioxide generator capacity to provide for the
alternative strategy of increasing the cWorine dioxide substitution, this approach allowed some mills to promptly decrease the
fIrst-stage cWorine multiple (52). Alternatively, by applying peroxide in either or both
of the extraction stages, chlorine dioxide
could be made available to increase the
degree of cWorine dioxide substitution in
the first bleaching stage (53).
As in oxygen-reinforced alkaIine extraction, the effect of the oxidant, in this case
peroxide or both peroxide and oxygen, is
superimposed on the effect of the alkali on
the pulp. Figure 20 shows the change occurring in the extracted kappa number
when different oxidants or combination of
oxidants are applied to a softwood kraft
pulp (54). There is much debate, and no
definitive answer,about how to achieve the
maximum bleaching effect from the peroxide addition, particularly when oxygen is
also being applied to the extraction step.
One configuration commonly being used is
shown in Fig. 21 (39). However, it is difficult to obtain the full value from the peroxide in an (EOP) stage. If the full value of
the oxygen is obtained,llitrate-peroxide
reactions tend to dominate. If, on the other
hand, the full value of the peroxide is ob-
0.26
~ 0.24
c..
:;:::::
'3 0.22
~
.;::
o
0.2
:c
0.18
o
~ 0.16
13
<C 0.14
0.12
2
2.5
3.5
4.5
CE kappa number
FIg. 10. XiIpJM".mber
bludmtg of. so~
311
312
Caustic (NaOH)
Retention
tube
(EOP)
bleach
tower
Oxygen
Pulp to
E-stage
washer
Thickstock
pump
= kE2.[HO'Jo.t.to.3.e.f/RT
k02
[4]
where
~=
the E"stage
reaction
rate constant
= the
E2'stage reaction
= the
apparent
activation
temperature
energy
stage reaction
in "K
of the E 2
= 15 k]lmot.
95
Hydrogen peroxide
90
ill... ~-retnfim:e4
.IWiIIe
~0
iii
(/)
85
Q)
c::
62
..c:
C)
.;::
D
#.
c::
o
60
'U
as
'U
58 ~
~Qj 3.6
75
~70
Q)
~...Q)
56
65
0.05
!jto
rJ)
rJ)
.c
80
54
3.2
c::
as
a.
a.
as
~
2.8
0.1
0.2
0.3
0.4
0.5
EC)
52
15
50
0.2
0.25
dioxide, mmol/g
0.3
0.6
E-stage
NaOH,
mmoVL
~1
90
0
89
iii
(/)
0.15
chlorine
o(/)
0.1
Consumed
IIlU"ne
Q)
c:: 88
..c:
.~ 87
D
0 86
en
85
84
0.02
0.025
0.03
0.035
0.04
Consumed chlorine dioxide, mmol/g
cmu:nJtrtltItm
chlorinedtoxftleCOlJSllmptton
(58).
0.045
brightness
.nd
Chapter
IV 4: (Oxidative)
Alkaline Extraction
313
314
Pulp Bleaching
92
and Practice
93
92
~90
~0
iii
II)
Q)
c: 88
iii
II)
Q)
E-stage
c:
time,min
sC)
=.
.;::
.D
0
-Principles
sC)
=.
.120
86
-;::
.D
0
. 60
~o 30
o 0
84
20
40
60
D-stage
Fig. 25. Effect of t'I'J'-"-
tI_
I" tile ~
~tIoft
80
retention
100
120
140
8.4 Temperature
(charge
8.3 Time
89
88
86
0
20
40
time, min
This kinetic equation shows that the caustic (NaOH) concentration, time, and temperature in the E2stage each affect the rate
of bleaching achieved in the O2 stage.
and consistency)
Figure 24 (58) shows that the alkali concentration used in the E2 stage determines
the brightness obtainable in the O2 stage
and determines the amount of chlorine dioxide required to provide this brightness.
In the extreme case, if no alkali is used in
the second extraction stage, the final brightness will be significantly lower (two points
in this example) than when a proper alkali
charge is used.
E,stage alkali charge is controlled by pH.
The charge is much lower than that of the
first extraction stage, typically 0.5% NaOH
on pulp (30), because of the decreased
amount of alkali-consuming
material remaining in the pulp after the previous oxidation stage.
90
~87
82
0
91
80
60
D-stage
1ft tile ~
9. Other alkalies
hydroxide
120
140
9.1 Chlorine-to-sodium
100
time, min
ratio
Most alkaline chemicals have been evaluated for use in bleaching (63), but sodium
hydroxide is the alkali of choice because of
low cost, high solution concentration, high
--
Sodium carbonate
-+-
I!!
X 15
...
CD
316
Sodium silicate
Chemical in
E-Stage
CE
Kappa No.
NaOH
Na2C03
NaHC03
HP
4.6
7.0
9.1
11.9
WMe liquor
Sodium sulfide
10
Sodium
~Xide
.c
E
~c:
5
as
0.
0.
as
~0
Unbleached
C stage:5.6%
and Practice
c:
0
Of50ftrtItHM
X
CD
ImIft
rine dioxide. In the integrated chlorine dioxide process (74), chlorine is burnt with
hydrogen to produce hydrochloric acid
which is then used as the reducing agent in
the generator.
alkali sources
The third approach is to use an alternative alkali source. Some alkali replacements
that have been considered are sodium silicate (63), sodium sulfide (75),oxidizedand
unoxidized white liquor (76, 77), sodium
carbonate
(78), and calcium hydroxide
(23). The comparative efficiency of these
different alkalies is shown in Fig. 27. None
of these alkali sources is as efficient as s0dium hydroxide on a weight basis but, by
increasing the charge and time and temperature of reaction, sodium carbonate, for example, can be made to give comparable
results (fable 6). There are also concerns
with scaling and reactions with added oxidants with some of these alternative alkali
sources.
...
CD
1ij
...
CD
Strategy
Increase
time by 2 h
Increase
temp. by 20"C
Capital Cost,
$ million
Operating
Cost', $/ton
0.41 - 0.81
- 4.00
Na.c03
Na-Organics
NaHC03
NaCI
0.95
0.51
0.46
0.92
0.79
0.74
1.78
1.88
pulp:black
spruce kraft; kappa number, 28.0
02 on o.d. pulp; 45 min at 25C; 3.5% consistency
02468
9.4 Alternative
-Principles
Pulp Bleaching
Calcium hydroxide
(J
CD
...
CD
1ij
315
.c
E
on o.d. pulp
(except
10% consistency.
14
~12
10
Na2C03
NaOH
~c:
as
0.
0.
90 min at 70C;
N~C03
NaOH
~4
2.50
c:
0
2
3
Charge, % on o.d. pulp
16
~14
...
X 12
CD
...
NaOH+Ca(OH)2
CD
1ij 10
...
CD 8
.c
c:
as
0.
0.
NaOH+N~C03
~6
'"NaOH
4
~2
0
ejJfdnrey of~
CllrlHnMle (63).
317
NaOH Charge,
% on o.d. Pulp
CE
Kappa No.
D,
3.0
2.0
1.0
5.4
6.1
9.0
81.0
76.7
56.5
84.6
Conventional
Recycle
(with no wash)
3.0
2.0
1.0
5.5
5.8
8.4
81.4
76.6
60.7
89.6
87.9
85.5
Recycle
Followed by washing
(Papricycle)
3.0
2.0
1.0
5.1
5.3
5.8
82.2
81.7
79.6
89.9
89.6
88.7
No recycle
pulp:black
ISO Brightness. %
D2
89.5
Sewer
The extraction
with 3% NaOH
Type of E,
Effluent Recycle
Unbleached
318
effluent used
on o.d. pulp.
for recycling
was produced
by extracting
pulp
'-;
Sewer
Kimtloops mill (
Iv. IlItISber', 1:,
ST,UIIltMdI)(79).
'
Na organics +
[5]
Na organics +
[6]
Na organics
[7]
Na2COj + HP
NaHCOj
[8]
[9]
hydroxide removes any sodium bicarbonate or carbon dioxide and allows use of the
residual alkalinity in the filtrate to reduce
the caustic charge required (fable 8). This
process requires an extra washing step.The
cost depends on whether an extra washer
is available, as is the case in a six-stage sequence where the hypochlorite stage has
been removed, or if a new washer has to
be purchased. One of the simplest process
designs is shown in Fig. 30. In this case
only two pipe lines were added to an existing installation. The process is now being
used with differing degrees of implementation complexity in twelve bleach plants in
Canadian mills. The process can also provide further savings by decreasing
the
amount of chlorine
dioXide
required in the
References
1. Larsen, L.H. and Partridge, H. deV., in The
Bleacbtng
of Pulp (R.P. Singh, Ed.) TAPPI
PRESS,Atlanta,
1979, p. 101.
2. Wayman, M., in Tbe Bleacbtng
of Pulp
(WH. Rapson, Ed.)TAPPI PRESS, New York,
1963, p. 67.
3. Berry, R.M. and
scbung 41(3):177
Fleming,
(987).
54
5. Pugliese
III, S.c. and McDonough,
T.].,
"Kraft Pulp Chlorination:A
New Mechanistic Description,"
1988 International
Pulp
Bleachlng Conference
Proceedings, TAPPI
PRESS,Atlanta, p. 139.
6. Matsumoto, Y, Thneda, T., IShizu,A., Chang,
H.-M., Bhattacharjee,
S.S., "Roll of Sugars
Remaining in R.esidual Lignin,"International
Symposium on Wood and Pulping Chemistry, Poster Presentations,
Paris, 1987, Vol.
2, p. 285.
10. Loeschbrandt,
Sulfatzellstoff,"
2-4 (1939).
B.I.,]
Pulp
E, "Das Bleichen
Karnyr Nacbrlcbten
Rapson,
12. Germgard,
U. and Karlsson,
Puu (11):627 (1984).
W.H.,
R.-n.,
Pap.
von
No.
Tappt
Pap.
Wood
14. Meller,A., Brin, K.W, Singh, R.P., in Handbook of Pulp and Paper Tecbnology, 2nd
eOO., Van Nostrand Reinhold, New York,
1970, p.263.
15. Meller,A.,
Tappi
16. Wayman,
(1958).
M., Can].
48(4):231
(1965).
C"l'ap.
10:450
(956);
19. Richtzenhain,
Abrahamsson,
Papperstidn.
H., Lindgren,
B.O.,
B., Holmberg,
K., Svensk
57:363 (1954).
G.N.,Pulp
22. Corbett,WM.
(1958).
B. Svensk
D.,
Papperstidn.
].M.,J
82(12):
74(3):224
319
Pap. Res.]
Dence,
C.W., Tappi
39. Althouse,E.
Strunk,W,
PIMA Mag.
320
Pulp Bleaching
-Principles
and Practice
R.,
51. Andersson,
L., Hook, J., Basta, J., Wallin,
S., Holtinger, L., "The Use of Hydrogen
Peroxide for Bleaching of Chemical Pulp",
1985 TAPPI Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, p.445.
52. Reid, D.W., Billmark, G.G., Sutton,
Tappi] 74(7):99 (1991).
53. Robitaille,
89(12):167
M.A.,
(1988).
Pulp
Pap.
54. Carmichael,
] 69(11):90
C,J.,
Can.
E. B., Tappi
Pulp
60. Histed,
(1984).
Pulp Pap.
Pap. 58(10):140
K., Pulp
Pap.
(1984).
37(6):22
J.A., Pulp
Pap. Can.
85(6): 114
Pap.
Nordisk
Cellulosa
BJ.
P. Tappi]
76(3):99
(1993).
74. Hughes,T.D., "Chemetics' Integrated Chlorine Dioxide System," 1979 TAPPI International Pulp Bleaching Conference
Proceedings, TAPPI PRESS, Atlanta, p. 167.
75. Richter,
(1955).
I., Pulp
Pap.
Can.
81(1):24
Trade]
79. Berry, R.M., Fleming, RI., Berndt, G., Williams,G., Tappi] 72(2):109 (1989).
so. Berry, R.M. and Fleming,
Sci. 14(5):121 (1988).
81. Berry, R.M. and Fleming,
43(6):426 (1990).
82. Berry, RM. and Fleming,
Sei. 15(5): 165 (1989).
BJ.,)
Pulp Pap.
B.I., Appita.]
B.I.,)
Pulp Pap.
SEcnON IV:
The Technology of
Chemical Pulp Bleaching
Chapter 5:
Ozone Delignification
B.
van Uerop
Paprican
Pointe Claire, Quebec
A. Skothos
Noranda Technology Centre
Pointe Claire, Quebec
N. Uebergott
liebergott &Associates Consulting Inc.
Laval,Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 323
325
326
326
328
329
329
331
6.Carryover
336
336
337
338
339
7.t:nvironmentalconsideratlons
310
321
Chapter
IV 5:
Ozone
Delignification
1. Introduction
Ozone is a powerful oxidizing agent
which reacts readily with most organic
materials, including lignocelluloses. Its oxidizing potential (+2.07 electron volts) is
exceeded by that of only a few compounds,
among them fluorine, atomic oxygen, and
perhydroxyl radicals (1). Ozone is used in
commercial oxidation processes to bleach
textiles, waxes, and starches, and to disinfect air and water (1). Although ozone itself is highly reactive, its application)s
restricted because it is generated in low
concentrations
diluted with a carrier gas,
usually oxygen or, less commonly, air. The
reactivity of ozone, therefore, is not only
defined by its own properties but also by
those of the carrier gas: The main impediment in ozone utilization is its low solubility in water (0.98 g of Oil of water at room
temperature
and atmospheric
pressure).
This limits its reactivity in aqueous systems
where ozone must transfer from the gas
phase into water to react. The mass transfer of ozone into the liquid phase, and hence
to the reactive site, can be improved by increasing the concentration of ozone in the
carrier gas and by compressing the gas mixture.The early generators produced only 4%
ozone by weight in an oxygen-ozone mixture, but generators are now being designed
to produce concentrations
of 12-14% by
weight (2, 3). Although ozone generators
are limited to operating pressures of about
2 atm, auxiliary compressors can achieve
10 atm.
Ozone is toxic in small amounts, but its
odor can be detected at only 0.01-0.015
ppm. The accepted maximum allowable
concentration
for a daily 8-hour exposure
is 0.1 ppm (4).
A patent tracing the application of ozone
in the bleaching of fibrous substances used
to make paper was issued in 1889 (5); the
process conditions best suited for ozone
323
2. Fundamental aspects of
ozone bleaching
2.1 Ozone reactions with lignin and
cellulose
The strongly electrophilic character of
ozone promotes its reaction with functional
groups in the lignin remaining after pulping
and other deligniflcation
processes (see
Chap. ill 3). Aliphatic double bonds conjugated to the aromatic rings in stilbene, styrene, and enol ether structures react with
324
. Carboxylicacid
. Total hydroxyl group
o Phenolic hydroxyl group
. Methyl ester
o
Fig.1. F8fI(;tiouigrtJfIp~
30
60
Time of ozone treatment,
",/nwft IIpl" tlftn _
90
min
tretlIrMrII
titJIll7 (29).
bleaching (31). Ozone itself is approximately 1<f' times more reactive toward lignin than toward carbohydrates (32), but the
by-products from these reactions react more
readily with carbohydrates
(33-35). Two
such intermediates are hydroxyl (HO.) and
perhydroxyl (HOO.) radicals formed by direct decomposition
of ozone in water or
indirectly by the reaction of ozone with an
organic substrate
(26, 32, 36-39). The
strongly electrophilic hydroxyl radical, in
particular, has been shown in model compound studies to attack lignin structures
only 5-6 times faster than carbohydrate
structures (35). The susceptibility of carbohydrates to react with ozone-reaction byproducts
restricts
the de lignification
capabilities of ozone in a pulp bleaching
process.
Most of these studies, as with others
aimed at gaining an understanding
of the
chemistry underlying
the ozonation
of
wood pulps, were performed on model
compounds instead of on pulp. Linking
these findings with ozone-pulp reactions
where the pulp substrate is highly variable,
presents contradictions. Because of the vigorous reaction of ozone and lignin, and because of the slightly greater reactivity of the
hydroxyl radical with lignin than with carbohydrates, it can be speculated that highlignin pulps are less likely to sustain a
325
3. Process conditions
In ozone delignification, the main process variables that influence the ozone-pulp
reactions, pulp properties, and commercial
viability are pulp consistency, ozone charge,
pH, time, temperature, chemical additives,
effect of metal ions, carryover of residual
dissolved organic matter to the ozone stage,
and pulp treatment before an ozone stage.
It is crucial to identify the conditions that
induce rapid and efficient transfer of ozone
to the appropriate fiber constituents and
thereby enhance ozone-lignin reactions in
326
Pulp Bleaching
-Principles
Ttlble 1. EJfti_S$,
selecti"'ty
pine Inwft Jnllp' (49).
and Practice
tItUl reaetivlty
0lozone
I"
tbe blHcbtng
01 tm oxygn-dellgnlftetl
Pro.Perties after ZE
Z-stage
Con-
sistency (%)
3
(% consumed)
Ozonation
Yield
(%)
Kappa
No. (K)
Viscosity(V)
(mPa.s)
rvul14M
re&POnse
30
0.35
0.5
98.9
98.3
'5.5
4.5
13.3
11.2
0.29
0.49
0.85
98.5
97.8
97.8
6.3
3.8
2.4
13.6
11.4
10.4
59
55
57
1.9
1.6
1.1
0.67
0.77
0.83
0.25
97.0
7.0
16.8
0.51
97.7
3.9
13.2
0.73
95.4
1.9
11.6
'Kappa number, 11.7; viscosity, 21.7 mPa.s
b% reactivity
ozone consumed/ozone applied x 100
56
58
55
1.9
1.5
1.3
0.96
0.92
0.97
1.5
re-
d,
Ozone
(gas)
Fiber
as an Oxygen/ozone gas mixture and its solubility in water is a function of its partial
pressure (2). The low solubility of ozone
in water and the large gas volume required
in bleaching processes restricts the physical transfer of ozone through the water layer
to the pulp fiber. Increasing the ozone concentration and gas pressure not only improves its solubility but also lowers the
volume of gas charged to the pulp. The
accessibility of the fiber to ozone has been
considered the rate-detennining step in the
ozone-fiber reaction instead of the reaction
between ozone and the fiber itself (52,53,
55).
To achieve effective mass transfer between the gas phase and the liquid phase,
ozone bleaching processes are designed for
high transfer rate. Dispersion of the gas in
the fiber suspension is a key component and
the process design is dictated by the amount
of water in the fiber suspension, that is, pulp
consistency.
Other variables, such as pH
and temperature, figure prominently in facilitating ozone solubility in the water surrounding the fiber and the reaction itself.
Mobile
Immobile
Water
Water
Fig.2. MIISShYmIIlM'jn'rJu$S In ozone bt"tlebtng
(5Z).
bleach-
ing focused on low (0.;-3%) and high (3040%) consistency because of limitations in
pulp mixing equipment. In low-consistency
bleaching, vigorous stirring of very dilute
327
ozone-containing
bulk gas with reactive
sites in the fiber (See also Chap. VI 4): 1)
transfer of ozone from the bulk gas phase
to the floc surface,2) transfer of ozone from
the floc surface to the fiber surface, 3) transfer of ozone from the fiber surface to the
reaction site, and 4) chemical reaction. The
essential components
of reactor design
which enhance these steps include pulp
consistency approacWng fiber saturation
point to decrease the water surrounding the
fiber, small-sized flocs adequately fluffed for
bleaching uniformity, and efficient pulp
agitation to ensure intimate contact of pulp
with ozone gas (60).
Laboratory comparisons of high- and lowconsistency ozonation indicate that higher
pulp viscosity and strength are obtained at
low consistency
(25, 49), especially as
delignification increases (Fig. 3) (25). The
heterogenous nature of high -consistency reactions may cause localized overexposure
of fibers to ozone and create zones of a low
lignin content, making the carbohydrates
vulnerable to attack:by ozone with the result that pulps of inferior strength are produced. Interest in low consistency
as a
viable commercial technology has dwindled
because of the large volumes of fresh water required (57).
Reports of selectivity differences between medium- and hlgh-consistency systems are less conclusive;
evidence
is
available which shows no change in
strength properties (2, 59,61, 62),greater
selectivity at high consistency (49, 58), or
greater selectivity at medium consistency
(62). The weakness of these comparisons
in selectivity differences may be due to an
effect of the pulp-ozone mixing apparatus
used at the different consistencies instead
of a direct consequence of consistency (2).
Viscosity is often used as a criterion of
selectivity, but its measurement
is influenced by the treatment history of the pulp
and may not necessarily correlate with the
strength of pulp bleached at different consistencies and made by different processes
(2, 49). The tearlbreaking length plots of
data from medium-consistency
pilot plant
ozonation and hlgh-consistency laboratory
328
Pulp Bleaching
-Principles
and Practice
3.3 Effect of pH
The most efficient de lignification for
ozone bleaching occurs near pH 2 (Fig. 5).
The pH effect has been established in several studies (8, 9, 12, 26, 46, 58, 64-67),
confirming that lowering pH from neutral
enhances delignification.
The viscosity
shows only a slight improvement (Fig. 5),
or none at all (41, 46, 58) depending on
the treatment before the ozonation. The
combined effect of delignification and viscosity, however, results in an overall selectivity advantage at low pH. ThIs effect has
been demonstrated for hlgh- (8, 12, 41, 46,
24
Kappa
number
4.9
3.0
6.3
3.4
22
~20
C\I
E 18
Z
E 16
ViscOSity
(dm3/kg)
1120
695
735
580
xQ) 14
'C
.5 12
...
as
Q) 10
I8
6
40
Fig. J. ""Ip
JnIl/I (25).
'-,
60
80
100
Tensile
index, Nmlg
strMgtll j1roJIerHa IIfm' /otv- tm4 I1Igb-amslstertcy OZOfNtrHtrrm8I of IIJII- irIIft
22
20
CI
E
Z
E
X
Q)
'C
.5
...
as
Q)
I-
AIIMO
AlterOZE
~18
MC Z. pilot
plant
16
HC Z. laboralOry
14
% 03 Kappa Viscosity.
inZ no. mPa-9
- 16.9 21.6
.0.35
11.3
~0.53 10.1
. 0.30 11.0
.. 1.00 3.4
17.0
15.7
18.4
11.6
12
10
8
6
4
8
Breaking
Fig. 4. PrIIJI
10
12
14
length, km
IIrrdI1Igb-emrsIstertcy OZOfNtrHtrrm8I of II soft-
~..
~
3.5 Additives
Considerable research effort has been
directed toward identifying an additive or
pulp treatment capable of preventing ozone
from reacting with the carbohydrate fraction of pulp and thus promoting its reaction with lignin. This goal is linked to several
approaches. One is to restrict the physical
availability of ozone to the carbohydrate
fraction (55,76-78). Another approach is
based on suppressing the formation or scavenging activity of secondary reactive species, such as hydroxyl radicals, considered
20
~ 19
~
18
a
0; 6
.c
E
::>
c:
though some results indicate that temperatures as low as OC offer the best selectivity
(55,74,75).
At high temperatures, delignification efficiency decreases (8,58,61,73), mostly as
a result of accelerated ozone decomposition
(45,68). Figure 6 shows that an ozone treatment at 20C offers an advantage of lower
kappa number and less viscosity loss
compared to the treatment at 60C (58),
indicating the desirability of low ozonation
temperatures.
Most bleaching stages are operated at elevated temperatures. Oxygen and peroxide
stages are more effective at temperatures
approaching or even exceeding 100C. Because an ozone stage requires much lower
temperatures, steps must be taken to cool
the pulp before it enters the stage. Therefore, when incorporating an ozone stage in
a bleaching process, the temperature prome of the sequence and the implications
for energy consumption are important considerations.
III
<is
W 8
329
117
e!i
2
4
6
.~
16
III
og
:>
1.5
Ozone, % on O.D. pulp
15
1.5
2
Ozone,
% on O.D. pulp
Fig. 5. Effect of pH 0fI hppa ,,,,,,,her IIU IJiseosiIy ill tbe OZOM treatmerIt of""
rrood "raft pulp (8).
oxygerr-tkUgnified
soft-
330
Pulp Bleaching
-Principles
and Practice
950
5.5
N
o
Z-stage temperature, C
.60
.40
020
4.5
~
0;
.c
c:
Z-stage, C
-20
~:
:3'900
E
N
a
0; 850
4
3.5
1ij
~800
g
c.
..
~ 2.5
:>
750
0.4
0.5
0.6
Ozone consumption
0.7
0.8
in Z, % on O.D. pulp
0.9
2.5
Fig. 6. 1jfft of t~
OfITuIJI/M1I8Ml1er1lllll1Jiseosi1y i" metH_
pi_ AS.4MoxygM-tkllg,dfW
jnIlp (58).
3
3.5
Kappa number
etmSistlm9
4
4.5
after OZ
OZOM blMcW"g of II
(% on pulp')
Kappa
Number
no prior
treatment
2.25
2.25
1.3
1.3
16.9
4.9
2.7
0.5
3.0
0.7
1045
1120
645
630
695
675
Z-mge
Sequence
0
(CD)(EO)
OZ
OZD
OZE
OZED
332
03Applied in
331
NaBH.
reducedd
775
680
675
ISO
tensile index eNmllz) of
Brightness
70
90
(%)
35.2
42.4
70.2
88.1
58.8
84.1
14.2
15.5
14.0
13.0
14.8
14.0
10.2
12.1
10.3
9.5
10.5
10.3
31, 88-90) or the (ZD) (3, 91) configuration is proving to be an attractive solution
to decrease the chiorine dioxide requirement and, subsequently, AOX formation.
Several mills have incorporated this stage
in their ECF bleaching sequence (3). Dillner
and TibbIing (88) has shown that 6 kg of
ozone applied 5-20 seconds after chiorine
dioxide at pH 4 in a medium-consistency
(DZ) stage of the (DZ)(EOP)D(ED)
sequence replaced 9.7 kg of chlorine dioxide
in the D(EOP)D(ED) sequence.Whether the
(DZ) or (ZD) combination has a synergistic
effect on delignification is unclear.
Pulp Source
Kappa number
Viscosity, rnPa.s
Sequence
OZD
OZED
0.5
1.0
1.0
03, % in Z'
NaOH, % in E'
CIO" % in D'
% in pa
HP"
Kappa number
OZEP
0.5
1.5
2.0
6.8
5.7
6.8
5.8
ISO Brightness, %
DorP
83.4
89.2
76.1
85.1
Viscosity, rnPa.s
ZorZE
DorP
18.9
16.7
17.2
15.4
23.4
21.6
24.8
22.8
ZorZE
-z stage: 40 % consistency;
ambient temperature;
2.5 end pH; E, D and P stages,
E: 60 or 70C, 90 min; P: 10 min, 80C; D stage, 180 min, 70C.
10% consistency;
Ozone delignification
as a replace-
333
334
Pulp Bleaching
-Principles
and Practice
40
35
(/)
cis
30
a...
;i'0
0
0
(/)
:>
25
PO)
20
15
10
5
0
15
10
20
25
30
35
Kappa number
Fig. 7. ~IecUlJity
of"
bigb-cmrsIsteru:y
oz_
rine-free (fCF) processes (fable 4). Considerable variation in the sequence configuration is apparent.
Medium-consistency
ozone stages are included in 9 out of the 13
installations reported in 1995. An example
of how an ozone stage is integrated into a
TCF bleaching sequence is shown in Fig. 9.
In all commercial sequences, the ozone
stage is placed after an oxygen delignification treatment.
Some sequences are
arranged with an ozone stage even later in
the sequence, following a peroxide stage.
Final brightening is accomplished with peroxide (fCF). cWorine dioxide (ECF), or
both. Chelation is appropriately situated
in the sequence to improve the bleaching
efficiency of the ozone or peroxide stage.
25
25
89.9
90
0>
1;;20
'"
N
iD
(/)
CD 70
Initial
Initial
10
c
as
Q.
51- 5
~
77.9
~80
uj
ti 15
~
Krait pulp 22.4
After 0
15.8
After 0
AlterO
0.5
1.5
15.8
11.7
AlterO
0.5
11.7
1.5
c:
.s=
C)
60
'C:
.c
0
P2
Z
P2
P1
P1
P1
50
~40
83.9
P2
OQPP
FII. 10. Brlgbtrum of uo.tt-H
OZQPP
OQPZP
111III
~
(110).
Tok 4. 0z0M
335
blMelml6 ,lIStIIlilltUms'.
Company
Process
Z-Stage
Sequence
Consistency
Ozone
Process
Supplier
Owne
Generator
Manufacturer
LenzingAG
Hwdb sulfite
MCC
(EOP)ZP
Kvaerner
Schmidding
Union Camp
Franklin, VA, USA
HCC
OZ(EO)D
Soods
Ozonia
SOdraCell
Monsteras,
Sweden
Lenzing, Austria
MC
OQZP
MC
O(DZ)(EOP)D(EP)D
01JQ(EOP)P
Kvaemer
Ozonia
MC
OQPW
OQPZP
AhlstromKamyr
Ozonia
Kvaemer
rrailigaz
Stora Billerud
Skogha1l,
Sweden
MoDo
Husum,
Sweden
WJSafurest
Pietarsaari,
Finland
ECF,rCF kraft
Swd ECF,
rCF kraft
Hwd ECF,
rCF kraft
Metsii-Botnia
Kaskinen,
Finland
Peterson Seffle
Siiffle, Sweden
Sulfite
Swd and hwd
rCF kraft
Swd and hwd
ECF kraft
Recycled
fiber
Swd kraft
rCF
SCA Ostrand
rinui, Sweden
SAPPI
Ngodwana, SA
Ponderosa~rs
Memphis,
Metsii-Rauma
Rauma, Finland
Consolidated Papers
Wisconsin Rapids
WI,USA
O(ZD)(EO)(ZD)(EP)D
MC'
OQ1JQ(EOp)ZP
O(ZD)(EOP)(ZD)(EP)D
MC
OQZlQ(EOP)ZP
AhlstromKamyr
rrailigaz
Schmidding
AhlstromKamyr
Ozonia
MC
ZEP
Kvaemer
Schmidding
HC
OPZEP
Ozoma
HC
O(W)(EO)D
MC
ZPZP
MC
OZPZP
Soods
AnOOtz
Sunds
AhlstromKamyr
AhlstromKamyr
Schmidding
HC
OZEDD
Sunds
Ozonia
Ozoma
Ozonia
Hwd
= hardwood;
MC = medium
Swd
= softwood
consistency;
HC
= high
consistency
336
Pulp Bleaching
-Principles
and Practice
.. IIrlfImras ofllOfttr004
T"bk 5. KiIJIPII
."""- blMeW", TCF~
lnwft"uJl'
COItpi
III'.'", (1',1!',flll1lll sIIIgtIS(110).
Kappa
number
Brightness,
% OSO)
OZ
OQP
9.9
7.1
46.7
71.1
OQPP
OZQP
OQPZ
OZQPP
OQPZP
5.9
3.6
2.7
77.9
77.5
77.6
2.8
nde
83.9
89.9
Sequence
5. Process equipment
Process equipment for ozone delignification of pulp is designed to achieve the
desired degree of delignification
and to
maximize selectivity and pulp uniformity
while minimizing ozone usage. The process
of ozone bleaching of pulp comprises several fundamental steps: pulp washing to
minimize carryover of organic material to
Pulp in
337
338
Pulp Bleaching
- Principles
and Practice
(EO) filtrate
Flutter
Preheater
Chilled
water in
Scrubber
r:
1Liiiiii]}
Pulp to
(EO) stage
;:
Pulp in
at medium
consistency
~
1
Discharger
jlJ-~
L1iJ
Exhaust
Destructor
II
I
19
Pulp out
'-I
Acid
Ozone
reactor
Pump
Pump
Filtrateto!
O-stagewasher
Fig.
11. Flowsbeetfor
!
m
Wgb-coruisteru:y 0_
Z filtrate
mm
bletIebhtg systMrt
m..........
-..
Ozonein
(lhIw.
CimIp
Corp.)
(112).
1
I
Compressor
I,".) (116).
3.5
c:
o
'5.
EO.as 2.5
~o.
II) as 2
c:.>o:
8~
C')~ 1.5
O"M
.!:!0
~CI
&!.>o:
0.
en
Fig.
13.
EjJeet
10
of CtI1TJOfJ6f"frmrt oxygm
340
In", (112).
Effluent Loading
kg/ODTP"
Bleaching Sequence
kg/ADTBP"
Color
BOD
COD
0.25
0.8
0.6
0
15
12
12
6
10
6
6
3
33
17
14
12
1.7
2.4
1.6
0.3
0
53
69
57
35
27
13
16
15
13
12
52
35
34
32
30
Hardwood kraft"
D,oo(EO)DED
O(D50+C~O)DED
0(070 +C~O)DED
OZ(EO)PY
Softwood kraft"
D,oo(EO)DED
0(050 +C~O)DED
0(070 +C~O)DED
OD,oo(EO)DED
OZ(EO)PY
'Air-dry metric ton of bleached
"Oven-dry metric ton of pulp
'Unbleached
"Unbleached
pulp
effect of COD carryover on ozone bleaching show a high degree of variability (57).
For example, a COD carryover of 10 kg/ton
of pulp from the oxygen stage was reported
to increase the specific ozone consumption
by 20% (113), 47% (59), and as much as
100",1,(63).
Ozone bleaching is more sensitive to
carryover from an oxygen stage than to
carryback from Z-stage filtrate (59). Carryback from the Z stage has been shown to
improve selectivity (113, 120).
The effect of the carryover to the ozone
stage is less sensitive at high than at medium consistency because six times more
water is removed from the pulp ozonated
at high consistency (18, 59,121).
7. Environmental considerations
0.5
339
corurImJJtIorI
12
(63).
14
0
.n
C\I
S:2
100
Stage
C12:C102
80
(C+D)
(DC)
90:10
50:50
0:100
~D
341
60
40
16. Schwarzl,
K., "Pulp Bleaching
Using
Ozone,"Workshop
on Emerging Pulping
and BleachingTechnologies
Proceedings,
North Carolina State University. Raleigh,
NC, 1991.
32. Gierer,}., and Zhang, Y, "The Role of Hydroxyl Radicals in Ozone Bleaching Processes," Seventh International
Symposium
of Wood and Pulping Chemistry
Notes,
CTAPI, Beijing, 1993, p.951.
20
0
342
19. Gotlieb,
P.M., Nutt, W.E., Miller, S.R.,
Macas,TS., TapPiJ 77(6):117 (1994).
(DC)E
DE
Bleaching
References
1. Rice, R.C. and Netzer, A., Handbook
of
Ozone Tecbnology
and Application,
Vol.
1, Ann Arbor Science Publishlrs,
Ann Arbor, MI, 1982.
2. Berry, R.M., Barclay, H., Prins,}., Sacciadis,
G., Skothos,A. ,Ayala, v., Magnotta, v., Breed,
D., Rounsaville,}.,
Shackford, L., Pulp Pap.
Can. 96(9):T324 (1995).
3. Homer,
G., Muguet,
M., Epiney,
M.,
Johnson, S., "Oxygen, Ozone, and Chlorine
Dioxide," 82ndAnnuai
Meeting,Tech. Sect.,
CPPA, Montreal, 19%, p. A297.
4. Sax, N.I. and Lewis, R.}. Sr., Dangerous
Properties on Industrial
Materials,Vol.
ill,
7th eOO.,Van Nostrand Reinhold,NewYork,
1989.
), Drin,A. and Drin, L.Q., U.S. Pat. No. 396,3Z5
Ouly 17.1889)
6. Brabender, G.}., Bard, }.W, Daily, }.M., U.S.
Pat. No. 2,466,633 (April 5, 1949).
ODE
OQP
20. Helander, R., Nilsson, B., Bohman, G., "Development and Progress in Ozone Bleaching at the Skoghall Mill", International
Pulp
Bleaching Conference
Paper Session Proceedings,
Tech. Sect. CPPA, Montreal,
1994, p.289.
OZEP
sequence
7. Gellman, I. "Delignification
and Bleaching
of Chemical Pulps With Ozone: A literature and Patent Review," NCASI Technical
Bulletin No. 619, National Council of the
Paper Industry for Air and Stream Improvement, New York, 1991.
8. Uebergott,
N., van lierop,
TapPiJ 75(1):145 (1992).
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N., van lierop,
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B., Skothos,A.,
Pap.
Mag.
Can.
22. Sote1and,
75(4):T153
Pap.
Mag.
Can.
N., Pulp
(1974).
23. Karnishima,
H., Fujii, T.,Akanatsu,
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25. lindholm,
C.-A., Nord. Pulp
5(1):22 (1990).
B.}.. Tappi J
14. Funk,
E.. Szopinski,
R., Munro,
F,
Vtlpponen,A.,"Espanola
Ozone Bleaching
Pilot Plant: Status Report",
1992 TAPPI
Pulping
Conference Proceeding~, TMPI
PRESS, Atlanta, p.1091.
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Hendel, P.,PaPier 45(10):610
(1991).
A.,
Pap. Res.]
44(6):405
(1991).
27. Gupta,
M.K. and Eckert,
R.C., "OZ
Prebleaching:
Influence on VISCosity and
Sheet Strength,"
1984 TAPPI Oxygen
DeIignification
Symposium
Notes, TAPPI
PRESS,Atlanta, p.133.
28. Gierer,}.,Holz/orscbung
(1982).
I.,ja-
11. liebergott,
N. and van lierop, 8. ,"The Use
of Ozone in Bleaching and Brightening
Wood Pulps, Part I. Chemical Pulps," 1978
TAPPI Oxygen/OzonelPeroxide
Pulp
Bleaching
Seminar Notes, TAPPI PRESS,
Atlanta, p.90.
12. Singh, R.P., Tappi 65(2):45
21. Procter,
A.R., Pulp
75(6):T21O (1974).
36(2):43
(1982).
D.S., Holz-
Wood
Cbern.
C-A., Nord.
(1988).
Pulp
Pap. Res.]
42.}acobson,
B., lindblad,
P., Nilverant,
N.,
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International
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Vol. 2, SPCI, Stockholm,
1991, p.45.
43. Sonnenberg,
L.8. and Poll, K.M., "Studies
on High Consistency
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national
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1994, p.lOl.
Sect.,
K.,
C-A., Pap.
Puu
69(3):211
Z. and
(1963).
Schuerch,
c.,
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TAPPI,Montreal
and Atlanta, 1989,p.425.
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A.R.P.,
"The Development
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and
Lignin-ceUulose
Selectivity During Ozone
Bleaching,"
81st Annual Meeting, Tech.
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343
69(7):84
344
H., Akamatsu,
(1986).
73. Dillner,
B. and
74(9):720 (1992).
58. Oltmann,
E., Gause, E., Kordsachia,
Pan, R.,Papter
46(7):341 (1992).
0.,
0.,
-Bleaching
Sequences
and Pulp
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Proceedings,
Tech. Sect.
CPPA, Montrea1, 1994, p.187.
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B.E, and Szopinski,
R.,
"Ozone-bleaching
Technology,"
International Non-Otl.orine Bleaching Conference
Proceedings,
Miller Freeman, San Francisco, 1992, Session V.
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T., Vilpponen,
A.,
Munro, E, "Espanola Ozone Bleaching Pilot Plant: Progress Update," 47th Annual
General Conference,
APPITA, Parkville,
Victoria, Austra1ia, 1993, p.217.
64. Hosokawa,].,
Kimura,Y,]apan
Kobayashi,
T., Kubo, T.,
Tappt 30(4):226(1976).
65. Lindholm,
C.-A., Cellul.
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66. Wang,
D.L.K. and
38(6):245 (1984).
Chem.
Patt,
Technol.
R.,
Papier
D.,]
Pulp
Pap.
70. Parthasarathy,
V.R. and Peterson,
R.S.,
"Ozone Bleaching, Part I.The Decomposition of Ozone inAqueous Solution - Influence of pH, Temperature,
and Transition Metals on the Rate Kinetics of Ozone
Decomposition,"
1990 TAPPI Oxygen
Delignification
Symposium Proceedings,
TAPPI PRESS,Atlanta, p.23.
71. Pan, G., Chen, C., Chang, H., GratzI, ].S.,
] Wood Chem. Tecbnol. 4(3):367 (1984).
Peter,
W., Pap.
!.,jaPuu
92. Lindholm,
16(6):]190
C.-A.,
(1990).
Pulp
Pap.
Set.
Pap. Res.]
94. Lindholm,
(1992).
74(3):224
95. Lindholm,
(1992).
C.-A., Pap.
74(9):738
96. Lindholm,
19(3):JI08
!.,ja-
M., ] Pulp
36(1):42
(1982).
Gierer,J.,Holzforschung
85. Henricson,
K. and Lindholm,
Puu 75(3):133 (1993).
C.-A., Pap.
(Sept.
C.-A.,
(1993).
J.
Puu
Pulp
Pap.
Set.
97. Liebergon,N.,
van Lierop,B.,Garner,B.C.,
Kubes, G.]., Tappi] 67(8):76(1984).
98. Sundin,]., and Hartler, N., Nord. Pulp Pap.
Res.] 9(3):140 (1994).
99. Hartler, N., Granlund,V., Sundin,].,ThbekLindbolm,A., "Ozone Bleaching of Chemical Pulps," International
Pulp Bleaching
Conference
Proceedings,
Vol. 2, SPCI,
Stockholm,
1991, p.75.
100. Kordsachia,
0., Oltmann,
D.L.K., Patt, R., Wochenbl.
7:251 (1990).
E., Wang,
Papierfabr.
101. Liebergott,
N., "Peroxyacids
used in
Bleaching Sequences," 1995 TAPPI Workshop on Emerging Pulping and Bleaching Technologies,
TAPPI PRESS, Atlanta,
Section 3-1.
102. Lachenal, D. and Nguyen-Thi, N.B., "TCF
Bleaching - Which Sequence to Choose?,"
1993 TAPPI Pulping Conference Proceedings, TAPPI PRESS,Atlanta, p.799.
103. Rothenberg,
Johnsonbaugh,
(1975).
S., Robinson,
D.H.,
D.K., Tappi 58(8):182
International
Non-Chlorine
Bleaching
Conference Proceedings, Miller Freeman,
345
116. Henricson,
K., "MC Ozone Bleaching:
Machinery
and Pulp Reactor; International Non-Chlorine
Bleaching Conference Proceedings,
Miller Freeman, San
Francisco, 1994, Session 4-1.
N., Norsk
Skogtnd.
32(9): 199
K.]., Tappi
SECfION IV:
The Technology of
Chemical Pulp Bleaching
Chapter 6:
Hydrogen Peroxide
as a Delignifying Agent
D. Lachenal
CfP
Grenoble, France
1. The dual role of hydrogen peroxide in
delignifying and bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . .. . . .. . .. 349
2. Hydrogen
peroxide
delignification
Processes
. . . . . . . . . . . . . . . . . . . . . . . . . .. 351
delignification
treatments
353
353
355
355
355
356
. . . . . . . . . . . . . . . . . . . . . . . . . .. 356
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
of peroxide
delignHied pulp.
8.En~nmentdf.actors
358
. . . . . . . . . . . . . . . . . . . . . . . .. 358
359
347
Chapter IV 6:
Hydrogen Peroxide
as a Delignifying
Agent
1. The dual role of hydrogen
peroxide in delignifying and
bleaching
Alkaline hydrogen peroxide is widely
used in the pulp industry to bleach ligninrich pulps to brightness levels of 80-83% ISO
without any substantial dissolution of lignin. The bleaching effect of hydrogen peroxide has been attributed to its ability to
react with various colored carbonyl-containing structures in lignin. Its use in chemical
pulp bleaching has long been limited to the
final stages to improve not only brightness
but also brightness stability (1). The commercial use of hydrogen peroxide as a
delignifying agent for kraft pulp was reported in the late 19705 (2). More recently,
some Swedish, Spanish, and Canadian mills
(3, 4) started the commercial production
of bleached kraft pulps using sequences
containing at least one extensive peroxide
delignification stage. A similar development
has been observed in the sulfite pulp industry, especially in Germany (5). The advantages of delignification
with hydrogen
peroxide are low investment cost and the
accompanying strong bleaching effect.
The action of alkaline peroxide as a
bleaching agent has been explained through
the reactions of the hydroperoxide anion,
HO~, formed in an alkaline medium according to the equilibrium:
HP2
= 11.6
+ HP
[1]
at 25C.
This anion is believed to be the principal active species involved in the elimination of chromophores in lignin structures,
349
pulp by hydrogen peroxide has been essentially explained by this mechanism even
though it has been claImed recently that
peroxide decomposition products such as
the hydroxyl and superoxide anion radicals
('OH and 0>" respectively) may participate
in the bleaching mechanism, at least to a
small extent (7) .Whatever their form, these
bleaching reactions proceed with only minor amounts of material being dissolved and
cannot explain the delignification observed
with hydrogen peroxide in the processes
described below. It has been shown that,
under alkaline conditions, hydrogen peroxide is unable to attack phenols of the type
present in lignin (B).This finding was confirmed recently in a study on the modification of the lignin in a mechanical pulp
during peroxide bleaching (9,10). No degradation of the phenolic rings was observed.
These considerations indicate that no significant degradation of the residual lignin
in kraft pulp by hydrogen peroxide should
be expected. Indeed, there is no apparent
reason why residuailignin would be more
reactive than the original lignin. On the contrary,residual kraft lignin is more condensed
(11) and does not contain easily cleavable
ether bonds. Despite this, delignification
does in fact take place when a kraft pulp is
treated with alkaline hydrogen peroxide
(12). A temperature of 90C is usually required to produce a substantial decrease in
kappa number. Higher temperatures (e.g.,
110C) lead to increased delignification,
comparable to that occurring in a conventional oxygen delignification process (13),
Studies on the behavior of lignin in kraft
pulp during hydrogen peroxide delignification at 90C indicate that some depolymerization
of lignin occurs (11) and
carboxyl groups are created (11,14).
A comparison of peroxide and conventional oxygen bleaching shows that the
brightness is higher (13,15) and the resulting viscosity is lower for a peroxidebleached pulp than for a corresponding
oxygen.IJleached mt't pulp of the EIlC li~nin content; that is, the selectivity is lower
for peroxide delignification. The selectivities of chlorine, oxygen, and hydrogen
350
Pulp Bleaching
-Principles
and Practice
1600
40
Fe
Mn
'",
/0
:&1400 CE
o
(0)
b 30
u;S>
..20
~
:a
a;
"
~1200
'E
~/
1000
5
10
15
20
Kappa number
25
30
o'"
~"
a:
8DTPA
added
10
0.285
0.150
0.213
0.285
Metal ion concentration,
mM
+ .OH
+ 02 + OM"
,,, tile
_t,d
351
352
Pulp Bleaching
-Principles
and Practice
To evaporation plant
and recovery plant
Sequence
Pulp type
PC ED ED
OPDED
PPDED
Op,OPP'
OPD
PDp,PDPD
PHDH
PCHH
(PO) (PO)
(EOP) P
PPacP
OPZ
OPZP
(EOP) Z P
Reference
Softwood
kraft
Softwood
kraft
Softwood
and hardwood
Hardwood
kraft
Softwood
sulfite
Softwood
sulfite
Softwood
sulfite
kraft
Softwood
and hardwood
Softwood
sulfite
Hardwood
kraft
Hardwood
2,12,42
13,18,29,30
Softwood
Softwood
kraft
39
4,57
9
24
5,25
5
31
52
58
9
59
52
kraft
sulfite
kraft
and softwood
sulfite
AQ, anthraquinone;
Pac, peracid; Z, ozone
. Semi-bleached
(70-80% ISO for softwood and 75-85% ISO for hardwood)
b
,.------...
To evaporation plant
and recovery boiler
_~ l-_-:_~
:Brownstock:
washing ,
:
J
.------.
I
: Pulping :
:I Pulping :,
L:
:-~~~~!~t=k:
washing
-...
~--
: Stage:
O2 +
NaOH
'--+--'
:Washing 1
I
---'
r-------...
I
I
: Bleaching:
I
L
I
J
Water
Water
353
also
and
To evaporation plant
and recovery boiler
: Pulping
:
iuTuJ
t____..
:Brown stock:
washing
'
,-------...
: Bleaching:
I
I
I
I
J
Fig.5. FIort1sbHtoftlle~osygM-~
peroxIik dellg,dJbtloft
process.
3.1 Metals
Decomposition
of hydrogen peroxide
under alkaIine conditions is greatly influenced by the presence of specific inorganic
substances that act as catalysts or stabilizers. Among the catalysts, transition metals
such as Fe, Cu, and Mn have been studied
extensively (28, 36, 37). On the other hand,
magnesium salts and sodium silicate are
well-known peroxide stabilizers According
to some studies, the key to optimum hydrogen peroxide delignification is to control the metal profile in the pulp before
hydrogen peroxide treatment in such a way
that the concentration of transition metals
is as low as possible and that of alkalineearth metals (essentially Mg) is sufficient (28).
In other studies (3637), it has been
shown that not all transition metals are detrimental. For instance, addition of manganese has been found to be effective in
retarding carbohydrate degradation (36).
Although the ideal metal profile is not
known, a beneficial effect is observed when
a pretreatment
with a chelating agent is
used. For example ethylenediaminetetraacetic acid (EDTA) is best used at pH 5-7, as
shown in Figs. 6 and 7 (28). Other preferred
conditions in the pretreatment are 90C for
60 minutes at a consistency
of 10%. A
charge of 2 kg EDTA per ton of pulp is sufficient. After EDTA pretreatment, not only
is hydrogen peroxide delignification
improved, but bleaching is enhanced and cellulose degradation is less. At the same time,
peroxide consumption
is lower (9). It is
probable that other complexing agents applied under similar or different conditions
lead to the same improvements.Thus,DTPA
in the presence of sodium sulfite provides
about the same benefits (38)Acid pretreatment with sulfur dioxide or sulfuric acid
improves peroxide delignification (11, 39,
40) but not to the same extent
as
complexing agents (41).
Therefore, it appears essential to limit the
effect of metal catalysts even though
delignification involves the decomposition
354
Pulp Bleaching
- Principles
and Practice
70
400
E
Q.
Q.
Ci
~
200
en
~60
:Z
CD
C
-,5O
'C
m
11
pH
11
11
11
pH
80
E
Q.
Q.
c:
~40
o
1
11
pH
5
pH
20
950
C>
E
Q.
~925
E
'0
': 10
CD
LL
. , .EDTA
~900
o
>875
pretreated
o
1
I
7
850
I
11
pH
7
pH
of-Ws
rIIIIrMtM .. ED1'A-JlretrMtM
sojlrt1ootl
"' prdJts (18).
nft
j
c:
products of hydrogen peroxide. This suggests that the radicals and oxygen have to
be formed slowly to actively participate in
delignification process without any detrimental effect on cellulose.
The effect of stabilizers on delignification
has been investigated.
Sodium silicate,
organophosphonates,
and polylactones do
not lead to any significant improvement
when added in a peroxide stage (5,12,39,
42).Although addition of magnesium sulfate does not seem to improve delignification either, its effect on cellulose
degradation is favorable (4, 13).
~E 15
.,::>
c
N
<&
:I:
10
5
1
.-
.
5
pH
EDTA
pretreated
11
355
-.e.
::i
~Z
20
40
60
Time. m
80
100
0.5
120
1.0
1.5
H202. %
4
(EDTA
~Z
0.5
1.0
1.5
H202. %
On.ce the peroxide stage has been successfully stabilized with optimal pretreatment, the reaction time should be as long
as practically possible. Figure 8 shows that
oxide charge, there exists an optimum s0dium hydroxide charge. At sodium hydroxide charges above the optimum,
the
effectiveness of hydrogen peroxide is reduced and brightness reversion is observed
(41).The trend is similar for softwood kraft
pulps although the adverse effect of high
alkalinity is not always observed (42).Therefore, there is no incentive for increasing the
sodium hydroxide charge beyond an optimum level. This level is a function of the
hydrogen peroxide charge and has been
estimated from previous studies (fable 2).
::i
3.3 Time
-.e.
Jlr81ret11rf8erat)
3.2 Temperature
Hydrogen peroxide 'decomposition
is
strongly influenced by temperature. Thermal decomposition
occurs by homolytic
cleavage of the peroxide bond. Temperatures as high as 120C have been used in
peroxide de1ignification (I3, 43). However,
it has been shown that a decrease in temperature from 120C to 100C improves
pulp quality without affecting lignin dissolution. Again, it seems that too rapid peroxide decomposition
(which occurs at
120C) has a detrimental effect on selectivity. A temperature of 90C represents a good
compromise because the rate of delignification is still relatively high and cellulose
depolymerization does not take place to any
appreciable extent provided a complexing
pretreatment is used (41,42). Furthermore,
no pressurized
equipment
is needed.
Higher temperatures may be used, for instance, when hydrogen peroxide is added
in an oxygen delignification stage (31).
356
0fI1uIpptI
Fig.,. If/fed of BP, tI8IlNtIOII~
...""- tI8Il ""81_ DP I. lbe perozUe
.'iptjktllWfl of IIbtIt*JootIlmfftJI8lJI(a22, DP 15(0) (11)
bktlt:betl UJIIHI
--'t:OfISlsUfIt:y.
CoIuIItiou
: Btl'C,
1'beoJIM.-
120""'"
2O'X.
0/1"- t:OfIIlI-
H202' % on Pulp
1
1.5
2
3
4
NaOH, % on Pulp
Operating
90C, 2 h, 1(}"15%
consistency
3.5 Consistency
Increases
conditions:
2-2.5
2-3
2-3
2.5 - 3.5
3-4
in consistency
from
1 OOAi
to 25%
have a positive effect on the extent of peroxide delignification (41, 42).Trials at higher
consistency (30%) have shown a further
improvement
in peroxide delignification
(41). Whether high consistency should be
used, however, is questionable considering
the higher investment cost required to dewater the pulp. In most mills performing
hydrogen peroxide delignification, the consistency is about 10%.
4. Modified peroxide
delignification treatments
In some cases, peroxide delignification
has been carried out under nonconventiona! conditions at laboratory, pilot, or full
scale. For example, delignification
using
hydrogen peroxide and oxygen under acidic
conditions has been investigated (44).The
mechanism of delignification is completely
different from that previously described for
reactions in alkaline media. In acidic me-
-~~_.
% on pulp
0Z'
Kappa no.
19.5
14.6
Cellulose
1065
1300
Conditions:
DP
12.01410
Activation of hydrogen peroxide is another possibility for enhancing delignification. As mentioned previously, some
transition metals likely act as activators in
peroxide delignification treatments. Other
substances have also led to positive results,
at least in some cases. Among them, cyanamide, (NHzCN) was found to enhance the
peroxide delignification of sulfite pulps substantially without negatively affecting the
cellulose (52-54).
357
problem indicate that titanium is not corroded under conditions existing in alkaline
peroxide bleaching (55). A conventional
downflow extraction tower can be used
without any modification. However, the
desired retention time is generally greater
than that of a regular extraction stage which
may require the use of two towers in series.As a general rule, the peroxide should
be introduced at a point as distant as possible from where other chemicals (e.g.,
sodium hydroxide)
and live steam are
added. Inadequate mixing may lead to unproductive
peroxide decomposition
in
pockets of extremely high alkalinity or temperature. Several peroxide
application
points are indicated in Fig. 10.A good application point is the throat of an MC pump.
Peroxide addition in a mixer just before the
bleaching tower is another possibility. The
use of a high-shear mixer is not required
because hydrogen peroxide is very easily
mixed with pulp. However, chemical consumption may be reduced by instantaneous
and thorough mixing. Although not recommended, the addition of peroxide can be
made following washing. In this approach,
hydrogen peroxide and sodium hydroxide
are sprayed onto the mat exiting the decker.
The two chemicals must be added separately because of the poor stability of hydrogen peroxide
in sodium hydroxide
solutions.
5. Processequipment and
flowsheets
The process flowsheet of a typical hydrogen peroxide delignification is given in Fig.
10. A peroxide stage can be carried out in
whatever alkaline peroxide-compatible
equipment is available. Alkaline peroxide
is normally incompatible with carbon steel
and titanium. This is of particular concern
where existing chlorine dioxide stages are
being considered for replacement by peroxide in non-d11orine bleaching sequences.
However, actual mill operating experience
has shown that alkaline hydrogen peroxide
has only a moderate effect on titanium
equipment elements. Recent studies of this
358
hydrogen
peroxide
- oxy-
7. Characteristics
of peroxidedelignified pulp
Implementation
of peroxide delignification in kraft pulp mills is still too recent
for much published data on pulp yield, pulp
quality, and cost to have accumulated. From
laboratory studies there is evidence that
peroxide-<:ontaining sequences give higher
pulp yields. A comparison
6. Process control
Because
For mills in which the peroxide delignification process is combined with a metal
complexing stage, few bleach plant modifications are required (30). The C tower can
be used for the pretreatment
with the
per-
of APPDED
(A
8. Environmental
factors
Because peroxide bleaching is a chlorinefree process, the resulting effluent can theoretically be burnt after it is recycled back
to the brown stock washer.This strategy has
been followed on a mill scale for many years
(2). As a consequence, a potential reduction in pollution load can be achieved which
is roughly proportional to the kappa number drop during the peroxide stage. As an
example, it has been shown that, if the
CEDED sequence is replaced by APPDED
(50% delignification after APP) and the effluents from the peroxide stages are recycled, reductions of over 90% in color, 40%
in BOD, and 65% in TOC can be obtained
(39). Compared
with oxygen delignification, peroxide delignification appears to
provide better color abatement because of
the specific action of hydrogen peroxide on
chromophores.
359
The AOX issue has been the major incentive for the development of hydrogen peroxide delignification as a complement to
oxygen delignification.As indicated above,
it is possible to achieve a 50% further kappa
number reduction using about 25-30 kg
HP/t
of pulp provided that the oxygenpredelignified softwood kraft pulp is given
a proper chelating pretreatment.
Pulp
treated in this way can be easily bleached
to a full brightness in three stages without
molecular chlorine, while generating substantially less than 0.5 kg AOXlt of pulp in
the total mill effluent (30). The development of extended pulping has made it possible to reach a brightness higher than 80%
with both hardwood and softwood kraft
pulps using the totally chlorine-free OQPP
sequence in which noAOX is formed (57).
The ultimate goal in such sequences is to
bum the effluent. One intermediate step
would be to use the alkaline effluents for
brown stock washing and to dispose of effluent from the acidic Q-stage. However, an
effluent consisting of sequestered transition
metals and excess sequestrant may not be
environmentally
acceptable. The Q-stage
effluent could be concentrated and burnt.
If the effluent was burnt in the recovery
boiler, the metals would be carried forward
to the green liquor clarifier where they
would precipitate. A modem kraft pulp mill
must dispose of about 10 to 30 tons of metal
residues annually which would have to be
passivated if used for landfill (41). Another
problem arising from burning the Q stage
effluent might be the sequestrant itself.The
sequestrants proposed to date are EDTA and
DTPA, and the burning of such nitrogencontaining compounds is likely to generate
NOx although the extent of this problem is
unknown. The best choice of sequestrant
is one which, on combustion, yields only
carbon dioxide, water, and sodium for recovery (41). Another solution to the transition metal problem is to inactivate the
metals and to leave them in the puIp (41).
This area has yet to be studied extensively.
The effluents from Q and P stages of the
OQP sequence have been tested for toxic-
360
References
1. Owins, R.W, Strunk, W.G., Meng, T.Y., Pulp
Pap. Can. 86 (9):79 (1985).
2. Carlos,j.E., Lemoyne, H., Logan, WR., "Peroxide
Delignification
of Unbleached
Chemical
Pulp by Minox Process;
1980
TAPPI Alkaline Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, p. 325.
3. Basta, j., "Practical Experiences
with Peroxides, Organic Peroxides and Peracids" ,
1993 Workshop on Emerging Pulping and
Chlorine-Free
BleachingTechnologies
Proceedings, Dept otWood and Paper Science
North Carolina State University, Raleigh,
N.C.
4. Van Lierop, B., Liebergott,
N., Faubert,
M.G., "Using Oxygen
and Peroxide
to
Bleach Kraft Pulps; 1993 Annual Meeting
Technical
Section CPPA Preprints, Tech.
Sect., CPPA, Montreal, Vol. B, p.81.
5. Siiss, H.U. and Kruger, H., Pulp Pap.1nternational (6):60 (982).
6. Pan, X., Lachenal, D., Lapierre,
B.,J Wood Cbem. Tecbnol.
(993).
7. Hobbs, G.c. and Abbot,}.,]
Tecbno! 11 (2):225 (991).
8. Gierer,
}. and
Imsgard,
Pappersttdn.
(6):510
(977).
c., Monties,
13 (2):145
Wood
E,
Chem.
Svensk
D. and Papadopoulos,}.,
Teclmol22
12. Lachenal,
P., TapptJ
D., Lapierre,
Cbem. Tecbnol.
C.,
12
CeUul.
(5):537 (1988).
D., de Choudens,
c., Monzie,
63 (4) : 119 (980).
A.j. and
42 0):37
Dence,
(988).
C.W., Holzfor-
17. Agnemo,
R. and Gellerstedt,
G., Acta
Cbern. Scand. B 33 (5):337 (979).
18. Gierer,j.,Yang,E.
Reitberger, T.,"The Role
of Superoxide
Anion Radicals
Oz: in
Delignification;
1993 International
Symposium on Wood and Pulping Chemistry
Notes, CTAPI, Beijing, p.240.
19. von Sonntag, c., "Free Radical Reactions
of Carbohydrates
as studied by Radiation
Techniques;
Advances
tn Carbohydrate
Cbemtstryand
Btocbemtstry,
37:7 (1980).
20. Singh, A., "Delignification
Mechanisms
Using Oxygen and Hydrogen Peroxide;
1990 TAPPI Oxygen Delignification
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p.53.
21.Gess, j.M. and Dence,
(7):1114 (971).
22. Lindgren, B.O., Svensk
(3):57 (1971).
C.W., Tappt J 54
Papperstidn.
74
Kruger,H.,Papter
35 OOA):
K., Wocbenbl.
Papterfabr.
(977).
A. and Mulcahy,
(992).
j.P., Apptta
V.R., Tappi].
75 (9):2.43
Pap. (10):113
(1990).
35. Lachenal,
D., BoursQn, L., Muguet, M.,
"Reducing AOX in the Bleaching of Magnesium Sulphite Pulp," 1989 TAPPI International Sulfite Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, p.91.
36. McDonough,T.].,
Kirk, Re., Backlund, B.,
Winter, L., "Catalysis in Peroxide
Delignification,"
1987 International
Oxygen
Delignification
Conference
Proceedings,
TAPPI PRESS, Atlanta, p. 165.
37. Smith, P.K. and McDonough,
T.]., Svensk
Papperstidn.
(12):R 106 (1985).
38. Gellerstedt,
G. and Penersson,
1.,] Wood
Cbern. Tecbnol. 2 (3):231 (1982).
39. Ruhanen,
M. and Dugal,
(9):107 (1982).
H.S., Tappi
67
Choudens,
e.,
of Bleaching
as First Stage,"
Pulp Bleaching
TAPPI PRESS,
361
Heimling,0.,Papier40
(6):
0., Papier
41
Tappi].
71
D., de Choudens,
C. , Monzie,
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(17):494 (1980).
Wocbenbl.Papteifabr.(10):423
55. MacDiarmid,].A.
and Reichert, D.L., "Corrosion and Materials Engineering Considerations in Hydrogen Peroxide Bleaching,"
1992 TAPPI International
Symposium on
Corrosion in the Pulp and Pdper Industry
Notes, TAPPI PRESS,Atlanta, p.97.
56. Makkonen,
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(1992).
Pulp
Pap. Int.,
T., Paper
34 (3):50
and Bleaching
SECTIONIV:
The Technology of
Chemical Pulp Bleaching
Chapter 7:
Enzyme Treatments of Pulp
Roberta L Farrell
Biotech division of C1ariant Corporation
Lexington, MA, USA
and
University ofWaikato
Depanrnent of Biological Sciences
Hamilton, New Zealand
Uisa Viikari
VIT Technical Research Centre of Finland
Espoo, Finland
David Senior
ICI Canada Inc
Mississauga, Ontario
1. Introduction
. . . . . . . . . . . . . . . . . . .. . .. . . . . . . . . .. . . . . . .. . .. .. . ..
365
mechanism
of enzyme action
366
4. Hemicellulose-degrading
enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 367
4.1 Enzyme sources. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
4.2 Enzyme activity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
S. Process aspects of enzyme treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 368
5.1 Effects of enzyme treatments in multi-stage
bleaching sequences. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
5.2 Environmental effect of enzyme treatments. . . . . . . . . . . . . . . . . . . . . . . . . . . 371
6. Enzyme treatments In the bleach plant. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
6.1 Process flowsheets
6.2 Economic factors in xylanase treatments. . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.3 Effect of conditions external to the bleach plant
6.4 Benefits in bleach plant operations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7. ~tureprospects
"
363
,.,
372
372
373
374
375
375
Chapter IV 7:
Enzyme Treatments
of Pulp
1. Introduction
The traditional, effective approach of
using chlorine-containing
chemicals as
bleaching agents has been challenged, first
by environmental groups and then by consumers. In response to these pressures, alternative bleaching technologies have been
developed to partially or completely replace
these chemicals, particularly elemental chlorine (Cl). Enzymatic processes have been
developed
as one of these alternative
bleaching technologies.
The primary goal of chemical pulp
bleaching is to remove lignin from the pulp
while retaining the carbohydrates
in the
pulp. Two different approaches using enzymes have been followed since the early
1980s to accomplish this goal, but only one
has led to a successful commercial mill-scale
process. The main focus of this chapter is
to discuss the use of such enzymes, called
hemicellulases (specifically xylanases) for
enhancing the chemical removal of lignin
in multi-stage bleaching sequences. This
process, sometimes termed "bleach boosting" (1), has been successfully used in pulp
mills throughout the world. An alternative
approach, direct delignification, using enzymes called ligninases or laccases which
act directly on lignin, is still in the exploratory stage and awaits possible future commercialization.
Environmental, customer, and regulatory
concerns have favored the investigation of
enzymes in bleaching because they are
readily biodegradable and do not contribute to organochlorine formation.
Enzymes are catalysts of highly specific
reactions.
In their capacity as catalysts,
enzymes are not consumed and only a small
amount is required to bring about a particular reaction. Enzymes consist mainly of carbon, oxygen, hydrogen, and nitrogen and
are classified as proteins, molecules made
by living organisms. Enzymes are often
365
366
Pulp Bleaching
-Principles
and Practice
3. Proposed mechanism of
enzyme action
Hemicelluloses are polysaccharides associated with cellulose and lignin in plants.
The two most common hemicelluloses are
xylans and mannans. Not only do the relative amounts of these two polysaccharides
vary in hardwoods and softwoods, but their
chemical composition as well (25).
Extensive modification of hemicelluloses
takes place during pulping processes. During the initial heating period in kraft
pulping, when the alkali concentration
is
comparatively high, the xylan is partially
depolymerized and stripped of substituents
such as acetyl and arabinosyl groups. As
pulping proceeds, the a1kali concentration
decreases and degraded, short-chain xylans
precipitate in a more or less crystalline form
on the surface of cellulose microfibrils (26).
Overall, xylan constitutes over 90% of the
hemicelluloses in hardwood kraft pulp and
50% in softwood pulp. Because of the
reprecipitation, hemicelluloses are concentrated on the fiber surfaces of microfibrils
although a part remains at its originallocation in the fibers.
One of the predominating hypotheses for
the mechanism
of xylanase activity in
bleaching is that these enzymes catalyze the
hydrolysis of reprecipitated
xylan on the
surface of the pulp fibers making the lignin
fragments in and on the fiber easier to
remove in the following bleaching and
alkaline extraction stages (27,28). This hypothesis is not supported by the results of
experiments in which pulp was delignified
under high alkalinity conditions which precluded xylan deposition. In that situation,
xylanase treatment lead to a reduction in
Optimum
pH'
Optimum
Temp. ("C)'
Supplier
Product
Trade Name
Primalco
Ciba-Geigy
(collaboration with Genencor
International Inc., U.K.)
Ecopulp'"
Irgazyme to'"
Irgazyme 40'"
4-7.5
6-7
7-8.5
55
60
50-70
ICI
(collaboration with Primalco)
Ecopulp
4-7.5
55
5.0-7.7
5.2-7.8
~
7-8
45-57
40-62
55
55
3-5.5
7-10
40-55
50-70
50-80
40-65
45-65
X-200'"
Iogen
Pulpzyme
Novo-Nordisk
HA
'"
Pulpzyme HB'"
Pulpzyme HC'"
CartazymeHS'"
Sandoz
Cartazyme ps'"
~e
sa'"
3-5.5
Solvay
Xy1anase 18000'"
Zeneca
Ecozyme'"
'Optimum
conditions
4. Hemicellulos@-d@grading
enzymes
The two main enzymes which depolymerize the hemicellulose backbone are
6-8.5
6-9
because
367
endo-l,4-g-D-xylanase
(EC 3.2.1.8) and
endo-l,4-g.D-mannanase
(EC 3.2.1.78), referred to generally
as xylanases
and
mannanases, respectively. Xylanases and
mannanases are produced by many species
of bacteria and fungi. Xylanases, the enzymes applied in commercial bleaching, are
available from several different sources.The
most thoroughly studied bacteria sources
include several Bactllus species and actinomycetes such as Tbermonospora fusca; the
most weU-studied fungal sources include
Tricboderma
sp., Aspergtllus
sp., and
Aureobasidium
pullulans.
Mannanases
have been studied in several laboratories (3133) and are available for commercial use.
368
this reason, often have correspondingly different properties. Typically, the properties
which vary among different xylanases are
related to stability, the number of catalytic
cycles occurring per enzyme unit, which
determines dosage, and the pH and temperature range required for activity.
As reported in Table I, enzymes are catalytically active over a specified pH and temperature range. Most of these enzymes are
active at neutral pH, although some function under alkaline or acidic conditions. In
mill operations, the pH of the pulp is typically adjusted with acid (usually sulfuric
acid) to a range suitable for the selected
enzyme to function.
ECF
TCF
XCEDED
X(CD)EDED
XDED
OXDED
OX(CD)ED
X(EOP)D(EOP)D
X(EP)P
ZX(EP)
XZ(EP)
OXQPZP
OXZP
OX(EP)ZP
OXDP
on kappa
number
Two aspects of the effect of enzyme treatments on kappa number are important to
bear in mind: First, the effect of the starting kappa number on the overall benefit
derived from enzyme use and second, after
enzyme use, the significance of kappa number in terms of the amount of chemical required to bleach a particular pulp.
The magnitude of the effect of enzymatic
treatments depends on the pulping process
and starting kappa number. In general, the
greater the residual lignin content of the
pulp,(i.e., the higherthe initial kappa number), the greater the effect ofaxylanase
treatment in bleaching sequences.
An example of this trend has been shown
by laboratory
experiments
in which
xylanase treatments were performed on
different softwood kraft pulps made by eX-
369
370
environment,
but also for some mills
through cost savings or increased pulp production capacity through expansion of the
chlorine dioxide generator capacity.
Enzo-Gutzeit was first to patent a process
for the reduction of chlorine bleaching
chemicals through use ofaxylanase
treatment (21).The introduction of an enzyme
treatment before a D<)OC1oE
sequence had
the effect of reducingAOX from 1.0 to 0.6
kg/ton of pulp and the COD from 55 to 40
kg/ton of pulp.
Xylanase-treated pulps respond to varying chlorine dioxide substitution differently
than do untreated pulps (37). The traditional untreated pulp shows a concave
curve when total chlorine charge (% on
pulp) is plotted against chlorine dioxide
substitution and the characteristic
minimum charge requirement corresponds to
40% substitution
(38). Xylanase-treated
hardwood pulps bleached at 10% chlorine
dioxide substitution levels surprisingly require less total chlorine than at other substitution levels. A possible explanation for
this effect may be the sensitivity ofxylanasetreated pulps to the addition of chlorine and
chlorine dioxide.
Although savings in chemicals are also
obtained when enzyme treatments precede
the multi-stage bleaching of hardwood kraft
pulps, the economic benefit is larger for
softwood. Undoubtedly this is because the
lignin content of softwood pulps ls higher
and therefore they benefit more than hardwood pulps from delignification-promoting
enzymatic treatments.
du Manoir and Dubelsten
(39) have
shown that kraft pulp can be more effectively delignified and bleached in sequences
that include an oxygen delignification step
and a xylanase treatment.This combination
allows bleaching to be performed with
lower amounts of chlorine-containing
bleaching agents or in the absence of elemental chlorine (in an ECF sequence). Preferred processes consisting of oxygen and
xylanase treatments include an OXC/OED
or OXDP sequence. The results in Table 3
show the favorable effect on final bright-
ness ofaxylanase
treatment after oxygen
delignification of northern hardwood kraft
pulp (22). In addition, the kappa number
was reduced by about 60",.(,following oxygen delignification and xylanase treatments.
The chemical charges applied to the oxygen-delignified and xylanase-treated pulp
in the subsequent C/O, E,and D stages were
significantly less than those required to
reach the same or even higher final brightness using a C/OEDED, OC/OED, or XCI
CED sequence.
Tultl 3. IIl/tlCt of O:JrYIIIIItkllpiflctltwII
tlrut tI
trntrrumt 011softwood lnwft Jnllp
xy"""propertks.
Treatment
None
(unbleached
pulp)
0
X
OX
OX(C+D)ED
Kappa
Number
Viscosity Brightness
(% ISO)
(mFa's)
14.1
8.3
10.8
49.1
5.3
26.6
55.9
25.7
90.5
34.3
Bleaching
sequence
371
CWorine
% on Pulp
CWorine Dioxide
%on Pulp
Brightness
%
Yield
%
91.9:t0.7
(1)
(CD)(EO)DED
2.6
0.5
88.8
(2)
(CDXEOP)D(EOP)D
2.6
88.8
(3)
X(EOP)D(EOP)D
0.0
0.3
1.1
89.0
92.2:t1.2
(4)
(EOP)D(EOP)D
0.0
1.8
87.4
93.7:t1.0
(5)
X(EO)D(EOP)D
0.0
0.9
86.3
(6)
(EO)D(EOP)D
0.0
2.2
87.0
'Unbleached
on pulp.
bleached
quences
ozone to
kappa number:
372
Pulp to
final
bleaching
14.5
6. Enzymetreatments in the
bleach plant
As indicated above, the use of enzymes
can reduce bleaching chemical requirements and preserve or enhance pulp quality while maintaining equivalent yield at
comparable final brightness. Before introducing an enzyme treatment in the bleach
plant, it is useful to address the following
questions:
1. What is the driving force for enzyme usage (environmental, reduction of bleach-
373
374
Pulp Bleaching
Ttlble 5. DeserlptUm
Pulp to
final
bleaching
Fig. 2. SebelluUk
oflyJtlall
Mzyme
at pH 3.5.
Acidification of unbleached kraft pulp to
a pH range appropriate for enzyme activity
can be achieved with various acids; typically, sulfuric acid is used in most mills although C-stage filtrate or chlorine dioxide
generator waste acid may also be used.
Aqueous sulfur dioxide has been used successfully in mills to acidify pulp before a
xylanase treatment, but its use is not recommended because of its high corrosivity
and potential for consuming chlorine dioxide in later bleaching steps if it is not adequately washed from the pulp. Caution
must be taken at pH levels below 5 to ensure that the acidity selected is compatible
with the metallurgy and the high-density
storage tower lining and grouting.
Enzyme dispersion, as determined
by
tracer tests, ls significantly better with a
shower bar than with other addition systems. Enzymes typically are mixed with
water before being added to the repulper
side of the brown stock decker by a shower
bar. The pulp is allowed to react with the
enzyme in the high-density storage tank for
at least two hours before being conveyed
to the next stage of the bleach sequence.
-.11$
and Practice
Mill
Trial
Enzyme
Pulp
Bleaching
Sequence
Pulpzyme HB
Hardwood
OX
Albazyme 10
Softwoods
XD(E+O+P)DED
Cartazyme HS
Eucalyptus
X(E+O+P)D(E+P)D
logen Xylanase
Unknown
X(DCXE+O)DED
Ecopulp
Softwood
(MCCb)
XD(E+O)D(E+P)D
Result
18%decrease
in bleaching
chemical usage
ACM' decreased
by 28.3%;
15%decrease
inCIO,
Brightness
increase of 5-7 pts
23% decrease in
equivalent chlorine
ACMdecreased
by 26%;
16%decrease in
CIO, usage
Reference
50
48
43
49
I. TCF seqwru:e.
range
"
2. Proportionately
pulp
tm4
-Principles
apply enzyme
to the
Effect of conditions
bleach plant
external
to the
375
7. Future prospects
Pulp and paper mills are presently facing
formidable regulatory pressure to reduce
the discharge of chIoIDQrganic substances
(as represented byAOX) and other wastes.
The industry is assessing various technol~
gies to identify means for achieving less than
0.2 kg ofAOX/ton of pulp in effluents. This
target is achievable using extended pulping,
oxygen delignification, pulping additives
(i.e., anthraquinone),
and ECF bleaching;
however, older mills are faced with meeting the targets without the advantages of
capital funding to install this equipment.
Mill data suggest that xylanases may be an
important factor in helping such mills meet
the AOX discharge limits.
The eventual significance of enzyme
bleaching in the pulp and paper industry
remains to be detertnined.The
technology
is relatively new and the mechanisms of
enzyme action are not fully understood.The
commercial xylanases currently available
offer the advantages of reduced bleaching
chemical requirements'for
high brightness
pulp, relatively low cost, ease of application, and great selectivity. Researchers continue to isolate new xylanases and to
investigate the effect of other hemicellulases and ligninolytic enzymes such as lignin peroxidase, laccase, and manganesedependent peroxidase on pulp bleaching.
References
1. Pedersen, L., Elm, D.D., Nissen, A.M.,
Choma, P.P.,"Bleach Boosting of Kraft Pulp
Using Alkaline Hemicellulases," International Chlorine-Free Bleaching Conference,
Stockhoim Proceedings, 1991, Vol. 2, p.
107.
2. Eriksson, K.-E., Blanchette, R.A.,Ander, P.,
in Microbial and Enzymatic Degradatiotl
of Wood and Wood Components
(T. E.
Timell, Ed.) Springer-Verlag, Heidelberg,
1990, Chap. 2.
3. Kirk,T. K. and Cowling, E. B., in The ChemistryofsolidWood.(R.M.Rowell,Ed.)
Adv.
Chern. Ser. 207, American Chemical Society, Washington, D.C., 984, pp. 455-487.
376
221:661
Rev. of
1987,
p. 325.
L.,
K-E., Hallmark,
74:32 (1972).
B.
Wood
Chem.
D. J., Hamilton,
(1992).
J.
Pulp
Pap.
33. Biely, P., and Farrell, R. L., Sixth International Conference on Biotechnology
in the
Pulp and Paper Industry
Proceedings,
Technische
Universitat, Vienna, 1995.
34. Suurnakki, A., Kantelinen, A. Buchert,}.,
Vrikari, L. Tappi J 77(11): 1 II (1994).
35. Skerker, P.S., Farrell, R.L., Chang, H-m.,
"Chlorine
Free
Bleaching
with
CartazyrneTM HS Treatment," International
Pulp Bleaching Conference
Ptoceedings,
SPCI, EUCEPA, Tech. Sect., CPPA, TAPPI,
Stockholm,
1991, vol. 2, p. 93.
36. Farrell, R.L., Skerker, P. S. in Xylans and
Xylanases,
O. Visser,
Ed.) Elsevier,
Amsterdam,
1992, p. 315.
37. du Manoir,}.R., Hamilton,}.,
Senior, D.}.,
Bernier, }.E., Moser, L.E., Dubelsten,
P.,
"Biobleaehing
of KraffPulps
wtth CeUulase-Free Xylanase,"
International
Pulp
Bleaching Conference
Ptoceedings,
SPCI,
EUCEPA, Tech.
Sect.,
CPPA, TAPPI,
Stockholm,
1991, Vol. 2, p. 123.
38. Senior, D.}., Hamilton,}.,
"Xylanase Treatment for the Bleaching of Softwood Kraft
Pulps:The Effect of CWorine Dioxide Substitution," 1992TAPPI Pulping Conference
Ptoceedings,
TAPPI PRESS,Atlanta, p. 19.
39. du Manoir,}. R., Dubelsten,
P., U. S. Pat.
No. 5,179,021 Qanuary 12, 1993).
40. Ledoux, P., Detroz, R., de Buyl, E., Shetty,
)., Troughton,
N., Presley, }. R., "Use
of Bacterial Xylanase in Chlorine
Free
Bleaching Sequences," 1993 TAPPI Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 1057.
377
J 75:95 (1992).
43. Luers, M., "Biobleaching
at Skeena Cellulose," 1993 TAPPI Pulping Conference Pr0ceedings, TAPPI PRESS,Atlanta, p. 12.
44. Scott, B.P., Young, E, Paice, M.G.,
Pap. Can. 94(3):75
(1993).
Pulp
p. 1049.
47.Tolan,}.S.,"Using
Enzymes in Pulp Bleaching," CPPA Bleaching Course Manual,Tech.
Sect., CPPA, Montieal, 1993.
48. Turner,}.
c., Skerker, P.S., Burns, B.).,
Howard,}.C.,Alonso,
M.A., Andres,). L.,
TapptJ 75:83 (1992).
49.)ean, P., Hamilton,), Senior, D.}., Pulp Pap.
Can. 95:126 (1994).
50. Vaheri, M., Miiki, K, Jokela, v., Kitunen,
v., Salkinoja-Salonen,
M., "Bleaching
of
Kraft Pulp Without Formation of Dioxins."
Ninth International
Symposium on CWorinated Dioxins and Related Compounds
Notes, NCASI, Corvallis, OR/Environrnent
Onario, Rexford, Ont., 1989.
-------._-
SEcnON IV:
The Technology of
Chemical Pulp Bleaching
Chapter 8:
Chlorine Dioxide in
Bleaching Stages
Douglas W. Reeve
Department of Chemical Engineering
and Applied Chemistry
and the Pulp & Paper Centre
University of Toronto
Toronto, Ontario
1. Introduction.
......................................................
381
"
381
381
382
383
383
385
388
390
391
391
392
4.E~eerbmgconsiderations
4.1 Mixing
4.2 Chlorine dioxide solution heating
392
392
393
5. Pulp quality
.. .. .. .. .. . .. .. .. .. .. .. .. .. .. . .. . .. .. .. .. .. .
6. Environmental factors
393
393
379
Chapter IV 8:
Chlorine Dioxide
in Bleaching Stages
381
portant chemicals used for bleaching chemical pulp because it reacts readily with lignin
and does not react to any significant extent
with carbohydrates.
It can be used to
achieve high brightness and is also extremely effective in bleaching particles.
Chlorine dioxide bleaching has been essential to the manufacture of strong, stable,
clean, high-brightness kraft pulp. Economical means of manufacture and use of chlorine dioxide were developed in the 1940s.
This technology
was essential for the
growth of the bleached kraft pulp industry.
Until very recently, all mills manufacturing
bleached kraft pulp of brightness greater
than 80 had to use chlorine dioxide.
An interesting survey' of chlorine dioxide bleaching in North America was published by Rapson in 1958 (1). Chlorine
dioxide stages in operation grew from 1 in
1946 to 9 in 1953, and to 43 in 1957; 60%
of the mills employed only one stage of
chlorine dioxide in the bleach plant and
40'>,1,
used two stages; 74% of chlorine dioxide bleaching stages were in kraft mills and
20% were in sulfite mills; 58% of the chlorine dioxide generators were Mathieson and
34% were Solvay generators.
From that
time, chlorine dioxide bleaching stages
grew to be universal in kraft mi1ls producing bleached market-grade kraft pulp. There
are a number of comprehensive references
on chlorine dioxide bleaching beginning in
1953 (2-6).
In this chapter, the use of chlorine dioxide to brighten pulp in the latter stages of
bleaching sequences is discussed, including
chemistry and kinetics, process flow sheets
and process conditions,
bleaching
se-
the chemical added is lost. Further, the intermediates formed by reaction with the
pulp react with one another to form chlorate ion (CI03'). Chlorate ion does not react
1. Introduction
CWorine dioxide is one of the most im-
382
CL
],
0.15
--E0
""
pH 2
CWorate Formed
(mole % of Cl02 added)
pH
pH 3
E 0.10
11'
E
.E
S 0.05
oi!
:2
u
0.10
0.2
0.3
0.4
ClO, consumed, mmoll g pulp
38
28
17
(Ref. 17)
28
15
(Ref. 19)
0.5
= the
light absorption
coefficient
at
457 nm
(k457)~
= km
chromophores
This equation describes the elimination of
chromophores as being very fast initially but
slowing as the absorption
coefficient
(brightness) limit is approached. This equa-
383
384
20
Vapor
to
scrubber
NaOH
54
10
Steam
Water
67
11
::; 1.0
;;
..z
82
"#
JCD
CI02
aH
89
CEHDE
0.1
Pulp
in
stage
Pulp
out
94
Effluent
Reaction time, h
E
c:
o
0.2
n'
a'
0.072
0.058
0.078 (km)o
0.042
0.010 (km)o
1.6
1.0
2.3
1.3
2.0
Iii!
o'"
Vents to
scrubber
0.1
i3
0
o
10
15
20
NaOH
Wash
water
-ACk. m2/kg
Fig. 3. Wed
01 eblorllte 4Io:dM t:OIISImIptlml 0fI
tbe
tM ell"d""tImI
01 elmnrro/lllores
I"
IHau:ImIg o/preIrNIM
so.flrroo4lm1ft In'',,.
and
sequences
Pulp
out
/i3uImpIes
of eblorl1le
tUoziM
94
bletlebhtg
~.
92
385
Post-l990
(DC)(E+O)D
O(DC)(E+O)D
OD(E+O)D
OZ(E+O)D
CEDED
90
88
'*
~86
.s 84
..c
00 82
~80
80
75
70
W
o 65
*::60
~ 55
CEDED
cm
50
as 4S
40
35
78
76
o
386
0.2
0.4
0.6
0.8
1.0
1.2
Cia, applied in the final stage, % on pulp
effective (23).
40
6"
..,
c:
<II
35
92%ISO
'. c: 30
og
c:.....
'~6
25
Qo
u~
aJ 20
E
i;1
c:
15
S
"!
{?
50
75
25
% Cia, consumed in the D, stage
100
100
..- E,D.
-E,D,
'D,
~110
'D,
.."
sible to increase
brightness
further.
However, when the DJ stage is followed by
an alkaline extraction treatment and a second chlorine dioxide stage, an additional
brightness gain can be achieved as shown
in Fig. 7.
Another way of describing this effect is
illustrated in Fig. S (23), To achieve a particular brightness, optimal use of chlorine
dioxide is obtained when 20-30% of the
selected amount is applied in a second (D)
1A!i
iii)
DIC-OE
40
DIC-E
20
10
20
30
40
50
IJfIeei0foxyga
irwft JIrIIJI.
errrlebmerJt
Oft IN fir,,"
brlgbtrfess
of (I so~
387
388
2.00
12
fiN' B..........
90 ISO
.9-1.50o &.
c: .
1:i
1.00-
1:!'>
Q~
u
0.50:is
o
,
I
2
10
1.9
Eucalyptus (32)
3.4
Birch (33)
4.5
:r
Q.
NaOH added.
onpulp
"
t
0.4
0.0
I
3
4
5
Post E, kappa num~
DI!D *Ja
/I
, ,,
,, ,
Pulp (Reference)
, , , , , Etalyptus
,
, 5oltwood
, ,, , ,
,,
,
,
, ,, , , , , , ,
, ,
~ j
Ii
, Birch "
I
7
I
6
o 10
60
120
1110
01..
~20
'j 15
~
'i'5. ~ 10
~~
8j
4
Post
Fig. 11.
of
5 6
7 8
[, kappa number
9 10
JIfIlps.
at the end of the stage to prevent a darkening of the pulp corresponding to approximately 2 brightness units. Maintaining a
certain concentration level of cWorine dioxide throughout the bleaching stage provides a continuing
driving force for
brightness increase and, more importantly,
for particle bleaching as is discussed in
Chap. IV 11. However, minimizing the residual is desirable for decreasing washer
corrosion, emission of cWorine dioxide into
the air, and complications in systems closure. An analysls of low residual cWorine
dioxide bleaching shows that this approach
is more economical and produces higherquality pulp (36).
CWorine dioxide residual is usually measured at the washer vat following a cWorine dioxide stage and typically is in the
range 10-50 mg ClOIL (10-50 ppm). A 10
mg aOIL residual in the vat corresponds
to 1 kg of cWorine dioxide per metric ton
of pulp.
Some mills add "anti-<:Wor" at the end of
a cWorine dioxide tower to minimize the
negative effects of large concentrations of
residual cWorine dioxide. The "anticWor"
dioxide
and elimi-
-1.0
~5
0
NaOH.
05
1~
15
2.0
% on pulp
3.3 pH
When cWorine dioxide reacts with pulp,
organic and hydrocWoric acids are formed
and the pH decreases. The rate of pH decrease is extremely high with most of the
change occurring in the first 10 minutes of
reaction as is illustrated in Fig. 12 (37).
Sodium hydroxide is added to the pulp be-
Chapter
IV 8: Chlorine
Dioxide
in Bleaching
Stages
389
1.0
..
1.4
'0
~.!!:1.2
!fs.
c
'C
0 0
1.0
:e II!
~80
1
Iii
0.8
75
15 'C
t~
70
3
End
4
pH
in
5
the
Dt
1.2
1.0
~
u
~ 0.8
~
0.6
5
~ 0.4
~
0.1
z
o
'I
:;
6
pH
14
~ 6
c:f 4
2
I .
3.0
4.0
D,
tower
5.0
terminal
6.0
pH
10
jJtIr-
stage
tmtl ebWrlte
"l
?d
Practice
0.2
11
- Principles and
. .
12
~>Q; 10
":fj
0.5 .!! ..
~';
0.4 6
Pulp Bleaching
22
20
1: 18
16
8
1.8
85
390
tmtl eblorwte
j'ormIItWrI.
to the steam
mixer
to achieve
60
6
..J
......
(5
650
~
~
4
(\j
70 u)
I1J
Q)
c:
75 '5
.;;::
o 2
J:
a.
80m
90
60
120
Bleaching
Fig. 17.
qfI
of"-
ness.
time,
180
min
391
392
Pulp Bleaching
-Principles
and Practice
1
""
coeffi-
5
10
15
2(
00, applied, kg / metric ton pulp
Fig. 1'). Efft 01 mlxlag ~./JfdMey 011eblorl_ 111O#IM resIilul I". eblorl_ llloxUe bletleb-
'''g st.ge.
40
Fig. 10.lffft
10
15
CIO, applied. kg / metric ton pulp
01 mlzl..,
. eblorl_ ~
~./JfdMey 011brlglllrrns
bletleblrtg
st.ge.
I"
100
~
-110
is quantified
s/'i.
o
4.1 Mixing
mixing
0,,"
:> 2
4. Engineering considerations
mathematical
40"
~;;
.~
.11:
"'60
..c
';;
60"
:::6
0
.~
t4
~ 40
20
CIO, applied,
10
15
kgl metric ton pulp
Fig. 11.lfffeet
01 mlxlag ~./JfdMey 011sblve rmrolJld
. eblorl_
llloxUe 6lMebl..,
slilge.
I"
2(
5. Pulp quality
CWorine dioxide provides pulp of high
brightness and low brightness reversion and
is extremely effective in particle elimination. Chlorine dioxide does not react extensively with carbohydrates although some
oxidation of cellulose does take place (50).
In addition, if the cWorine dioxide stage is
very acidic, some acidic hydrolysis of cellulose can take place. Although viscosity loss
in cWorine dioxide bleaching stages is usually very low, under aggressive conditions,
such as pH 2, at temperatures greater than
80"C, or when the chlorine concentration
equals that of cWorine dioxide, some carbohydrate degradation can take place.
6. Environmental
393
factors
Some chlorinated
organic matter is
formed during cWorine dioxide bleaching
stages. AOX in the amount of about 0.1 kg!
metric ton pulp in the combined D, and D2
stages has been reported (15, 51). AOX
from these stages may increase if the lignin
content of the entering pulp increases.
Chlorine dioxide emission from chlorine
dioxide-stage towers and washers can also
occur. Emission rates and control strategies
are described in Chap.VIlI 4.
Acknowledgments
Sterling Pulp Chemicals
has provided
financial support for cWorine dioxide bleaching research to the University
of Toronto.
References
1. Rapson, W H., Pulp Pap. 32(1):46
(1958).
2. Casciani,].,Pap.Tradej
(1953).
136(10):21
1963,pp.13O-179.
Svensk
A. and Robert,
16:77(1982).
10. Wartiovaara,
(1982).
Papperstidn.
A., Cellul.
I., Tappij
Chern.
64(11):680
M., Bull.
Soc.
69(2):82(1986).
13. Nilsson,
T. and Sjostrom,
L., Svensk
Papperstidn.
77(17):643
(1974).
14. ~pson,
CPP.4
(1977).
Pulp Pap.
394
D., Pap.
17. Bergnor,
E., Ge, rmgard
D., Kolar, ).J.,
lindgren, B.O., Cellul. Chern. Technol. 21:
307 (1987).
18. Van der Merwe,AJ.W,VlIjoen,
FJ.,Thom,
B.D. Lourens, G.]., Tappi 63(8):94 (1980).
19. Kutney, G.W and Mallais, M.M., Svensk
Pappersttdn.
86(12):RI35
(1983).
20. Teder, A. and Tormund, D., CPPA Trans.
Tech. Sect. 3(2):TR41 (1977).
21. Teder,A. and Tormund, D., "Mathematical
Model for CWorine Dioxide Bleaching and
ItsApplications;
AlChE Symposium Series
No. 200, Vol. 76, 1980, p. 133.
22. Reeve, D.W, in Pulp and Paper Manufacture,
Vol. 5 - Alkaltne
Pulping
(T.M.
Grace, E.W Malcolm, MJ. Kocurek, Eds.),
3rd eOO. JointTextbook
Committee of the
Paper Industry,
CPPA (Montreal)
and
TAPPI (Atlanta), 1989, pp. 390469.
23. Axegaro, P., Jansson, U., Teder, A.,j
Pap. Sci. 10(1):JI (1984).
Pulp
24. Histed,J.A.andVega
Canovas,R.,"Decreasing the Dsage of CWorine and Caustic in
Bleaching; 1989TAPPI Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, p. 85.
25. Carre, G., Nasman,
L., Annergren,
G.,
lindstrom,
L.-A., "Oxygen Alkali Extraction,A Versatile Tool Towards a Simplified
Bleaching Technique;
1982 TAPPI International Pulp Bleaching Conference
Proceedings, TAPPI PRESS, Atlanta, p. 17.
26. Axegard,P.,"Effect
ofCl02-Substitution
on
Bleaching
Efficiency and Formation
of
Organically Bound CWorine; 1984 TAPPI
Pulping Conference
Proceedings,
TAPPI
PRESS, Atlanta, p.353.
27. Germgard,
D. and Karlsson,
Puu 66(11):627 (1984).
R.-M., Pap.
28. Germgird,
D. and Karlsson,
Puu 67(11):655 (1985).
R.-M., Pap.
M., Appita
c., Appita
33. Asplund,
44(2):95
D., Appita
34. Axegard,
C. and Germgard,
(1991).
P., "ClO.-Substitution
Reduces
C.B., Tappi
Pulp
Pap.
Pappersttdn.
E.S., Pulp
Pap.
54(10):152
D., Tappi
6I
Blom, C.,
SECTIONIV:
The Technology of Chemical Pulp Bleaching
Chapter 9:
Hypochlorite and Hypochlorous Acid Bleaching
J.A. Histed
M.M. Hurst
Quantum Technologies
Twinsburg, OH
Inc.
1. Introduction
... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 397
1.1 History of hypochlorite bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 397
1.2 Evolution of hypochlorite bleaching
397
1.3 Modification of bleaching conditions in
response to changing control methods
397
2. Process variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 398
2.1 Chemical charge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
2.2Time
399
2.3 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
2.4 Consistency
,.,
399
2.5 pH . . . . . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 399
2.6 Conditions affecting viscosity loss. . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . 400
3.Reaction kinetics. . . . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 400
3.1 Kinetics equations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 400
3.2 Effect oftemperature
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
3.3 Effect of consistency. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
3.4 Effect of pH. . . . . . . . . . . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
4. Process equipment . , . . . , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 402
'
4.1 Flowsheet of hypochlorite
stage
402
4.2 Effect of bleaching temperature on equipment design . . . . . . . . . . . . . . . . . . . 403
4.3 Use of towers or flow-through tubes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
5. Particle b
h1ng with hypochlorite.
. . . . . . . . . . . . . . . . . . . . , . . . . . . . . . . . . .. 403
6. Hypochlorite bleaching ofdJssolving pulp. ... .. . . .. . . ... . . ... . . . .. . . . ... 403
7. Washing of hypochlorite-bleached
pulp .. . .. .. . . .. . . . .. .. .. .. . . . .. . .
404
8. Modern process control.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 404
8.1 Sensors. . . . . . . . . . . . '. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
8.2 Sensor location. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404
8.3 Response of optical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
8.4 pH sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
9. ~nomlcconskieratlons
406
10.EJ1vDnDnmmentdas~
...
407
11. Chlorine monoxide bleachIng of pulp . . . . ... .. .. ... . . . ... . . . . . . . . . .. .. 407
11.1 Background
407
11.2 Effect of pH. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 408
11.3 Process conditions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
11.4 Bleaching responses. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
11.5 Environmental aspects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 409
11.6 Hypochlorous acid generation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 410
395
Chapter IV 9:
Hypochlorite and
Hypochlorous
Acid
Bleaching
1. Introduction
1.1 History of hypochlorite
bleaching
Following the discovery ofJavelle water
(chlorine dissolved in caustic soda) in 1789
and bleach powder (calcium hypochlorite)
in 1799, hypochlorite
was the preferred
bleaching agent for cloth and wood pulp to
1946 when chlorine dioxide became commercially available. Because bleach powder
could be made in dry form and shipped long
distances in wooden kegs, it was the preferred bleaching agent and became the standard oxidant against which the oxidizing
power of all other bleaching agents was
measured.
Hypochlorite stages are in the process of
being phased out of commercial bleach
plants for environmental reasons including
the perceived hazard of hypochlorite as a
chlorine compound and the documented
role of these chemicals in the formation of
chloroform during pulp bleaching.
1.2 Evolution of hypochlorite
bleaching
Initially, soda and sulfite pulps were
bleached at 3%-4% consistency in a series
of vertical tanks. In 1895 the Bellmer brothers in Germany introduced a new type of
bleacher which operated at 7% consistency.
TIlls was a horizontal oval tub divided into
compartments
by two interior walls. Pulp
flowed from the outer compartment to a
pumping element which returned the pulp
to the central compartment (1). Bleach was
added into the circulating pulp until the
desired brightness was reached in a single
stage.
During World War I, a need developed
for large quannties ofhighly purified sulflte
wood pulp for nitrocellulose production.
This pulp was prepared using a three stage
HEH process with inter-stage washing.Wlth
397
the commercial introduction of the chlorination stage in 1930, hypochlorite lost its
position as the sole oxidizing agent in pulp
bleaching and became part of a multi-stage
CH or CEH sequence capable of producing
high brightness (about 88 ISO) sulfite pulps
having improved strength and brightness
stability.
Only a few kraft mi1ls produced bleached
pulp before the advent of chlorine dioxide
in 1946. These mills used multi-stage sequences such as CEHEH to produce pulp
of about 82 ISO brightness. One variation
of this sequence
was a hypochlorite
prebleach which preceded chlorination,
(HC), with no interstage wash. The advantage of this modification was that the total
dose of chlorine chemicals was split thus
decreasing the amount of chlorine gas that
had to be dispersed in the slurry by the rudimentary mixing equipment available at
that time. Another variation of the sequence
was the inclusion of small amounts of hypochlorite in the high-pH second extraction
stage (E+H).
After becoming available in 1946, chlorine dioxide received rapid commercial
acceptance
by the kraft industry which
was then able to compete with companies
producing high brightness sulfite pulps.
Sequences such as CEHD and CEHED came
into use for bleaching pulp to 82-85 ISO
brightness and a CEHDED sequence was
used to produce pulps of 90+ ISO brightness.
398
,,-,
20
~0
15
:>.
0
c:
Q)
::J 10
c:r
\./
\
\
I
I
I
68C
\
I
I
I
I
~u...
5
0
52
56
60
Brightness,
64
68
72
% Elrepho
2. Process variables
2.1 Chemical charge
The chemical charge required to achieve
a given hypochlorite stage brightness is di-
rectly proportionll
399
,j
"'cO
oo .
>
:::::J C\I
0)'5
:t::CT
0)
J:~
0
o
o
2
10
mathematically
where H= hypochlorite
B
K
=
=
hypochlorite
ofilypodlWrite
by the equation:
= 14.7113-0.4196(B)-
and Practice
2) pH
expressed
-Principles
Co
>:r:
Pulp Bleaching
The pH of the stage is normally determined by mixing caustic with the hypochlorite immediately before the point of addition
of chemical to the pulp. pH can be controlled using a feedback loop from in-line
pH probes located between the thick-stock
pump and the tower. Alternatively, a liquor
extractor may be used to provide a liquid
sample for an external pH probe.
0)
E
400
0.778500
+ 0.OO2873(Bi
+ 0.0163(BxK)
[1]
consumed, % on pulp
brightness
treatment
The relationship has a correlation coefficient r' of 0.996. A similar relationship can
be derived for E-stage pulp.
Figure 2, generated from the above equation, shows the linear relationship between
(EO)-stage kappa number and hypochlorite
consumed in reachIng brightness values between 65 and 80.
2.2 Time
A hypochlorite stage can be as shon as 8
minutes at 8O"C or as long as 90 minutes at
the more conventional 35"C.Mills that have
converted from a low-temperature to a hightemperature hypochlorite stage incorporating a 9O-minute retention downflow tower
can decrease the retention time by lowering the operating level in the tower.
2.3 Temperature
Temperature in the hypochlorite stage
may be as low as 3O"C for a conventional
9O-minute stage or as high as 8O"Cfor a stage
having an on-line feedback control system.
2.4 Consistency
The hypochlorite stage normally is operated at a consistency only slightly lower than
the discharge consistency of pulp from the
extraction-stage washer. This general principle takes into account dilution due to the
chemical charge, condensed steam, and any
seal-water leakage. Consistency may be limited on the high side by limitations of the
thick-stock pump. The consistency
may
range from 9-14%. However, at 14%, there
is a risk of non-uniform mixing because the
stock directly in contact with the chemical
at the point of application may adsorb more
than its share of chemical.
2.5pH
The initial pH at the point of pulp-bleaching liquor contact is usually 11 or higher to
maintain a final pH of 9.5 or,preferably,10.
The risk of viscosity loss is less at the higher
pH; below pH 9.0 the viscosity loss for a
given hypochlorite addition may be severe
(7).
3. Reaction kinetics
l1 Kinetic equations
Histed and co-workers (6) have carried
out kinetic studies in a stirred tank reactor
in which kraft pulp was bleached with hy-
pochlorite at varying temperatures and consistencies. The results of this work showed
that the rate of disappearance of hypochlorite is governed by two kinetically distinct
mechanisms:
1) At high hypochlorite concentration (i.e.,
at the beginning of the reaction), the reac,
tion is zero order.
2) At low hypochlorite concentration (i.e., at
the end of the reaction), the reaction is
first order.
The rate equation for the consumption
of hypochlorite in this situation is:
-dfNaOCIl
dt
= -k1 fNaOCIl
[2]
1+k2[NaOCI]
= k,'
[ClO,]06 . [OR].() 1.
km3'
[3]
(it
The stoichiometry of chromophore
removal is not affected by the temperature or
alkalinity, but the concentration
of hypochlorite has a significant effect.The lower
of hypochIorite
ions, the
-d rocr!
kz'---L..
dk457
km11
[4]
~Q.
E"5
~
c::
8~
(I)
~
o
401
402
-oQ.
(1)_
E
:JQ.:J 0.8
II) c::
c:: 0
~ 0.6
8(l)U
~>
.Q'S 0.4
.c::c:r
g (I) 0.2
g;?f.
J:
o
3%
10
1.0 % on pulp
50C
100
1000
Time, min
FI,. 4. E/fect of cmuIsIftu:y Oft tile rwU of bypoeblorlt~ t:OIISfIIII/Itk i.. tile bluebl..,
PMlp.
3.4 Effect of pH
The rate of chromophore removal increases slightly with decreasing pH but the
rate of cellulose degradation increases significantly with decreasing pH (8).
4 Process equipment
4.1 Flowsheet of hypochlorite
stage
In a conventional low-temperature
hypochlorite stage, the hypochlorite and alkali are normally added at the re-pulper of
the E-stage washer. The pulp is then dis-
of tI so,ftrtitHMTwtIft
NaOCI
NaOH
0.8
~
0
D-- --------
U 0.6
Pulp
Sen8Ol'8
1. Temperature
2. pH
3. Brightness
.->-
:c 50.4
(I)
e-?f. 0.2
J:
o
1
10
100
1000
Pump
Time, min
Fig. 3. Effect of temJHmltrtre on the f'tIt~ of typocblorlte _mptItm
PM'p.
Pulp
403
6. Hypochlorite bleaching of
dissolving pulp
Hypochlorite
stages are normally required in the manufacture of dissolving
pulps for the viscose process. Hypochlorite is used to control cellulose degradation
to achieve a desired viscosity level and to
further purify the pulp by oxidizing and
solubilizing non-cellulosic components.
Control of the hypochlorite stage bleaching conditions must be maintained to produce a pulp of uniform viscosity and
reactivity. This goal is best accomplished
with a carefully defined bleaching strategy
using state-<>f-the-art process control technology. Typically, only one hypochlorite
stage is required for viscosity control, and
it is normally located after the first alkaline
extraction stage.
The major variables in effective control
of the process are pH, consistency, tempera-
404
ture, and hypochlorite application. One effective strategy is to operate at fixed consistency and temperature and at a fixed pH
above 10. The viscosity reduction is then
controlled by varying the hypochlorite application.
Overbleaching may occur if the pH is
below the optimum, if an excessive dosage
of hypochlorite is applied, or if the temperature significantly exceeds the preselected
maximum. In each case, the rates of bleaching and viscosity loss are both significantly
increased. Overbleaching is evidenced by
a decrease in viscosity and alpha-cellulose
levels.
pH is ordinarily the most important variable in hypochlorite bleaching. For control
purposes, it is normally kept above 10.0
because the degradation reactions leading
to viscosity decrease become much faster
and less controllable as the pH decreases.A
higher pH favors a lower and more controllable bleaching rate. The pH of the hypochlorite stage also affects the aging of the
a1kali cellulose in the viscose process.
The first steps in the viscose process are
mercerization of the pulp with caustic soda
(NaOH) followed by pressing to a constant
cellulose-to-caustic
ratio. The cellulose is
then shredded and aged at constant temperature in the presence of oxygen. During the
aging step, the cellulose depolymerizes at a
rate governed by the carbonyl content of
the cellulose. Because carbonyl formation
during hypochlorite bleaching is low above
pH 10 but increases significantly as the pH
decreases to 7.0 (9), the aging rate is greatly
dependent on hypochlorite stage pH.Variation in hypochlorite
stage pH probably
accounts for much of the variability in solution viscosity in the viscose process.
When the kappa number of the pulp leaving the first extraction stage washer is 4.5
or lower and when good washing is provided on the first extraction stage washer
to minimize lignin carryover, a washing step
between the hypochlorite stage and chlorine dioxide stage is not required. Indeed,
the carryover of alkaline salts of weak organic acids formed in the hypochlorite stage
is beneficial because these materials act to
control pH in the following chlorine dioxide stage. This alkali source maintains the
D-stage pH in the optimum range and minimizes viscosity and strength loss in a strong
final chlorine dioxide stage (10).
405
406
80
70
60
c 50
OJ
'00
a; 40
a;
88
en
U)
A
Hypochlorite
:;::: 30
Final
pH
10.6
10.5
10.6
11.3
applied, % on pulp
A
0.45
B
0.7
C
1.03
D
1.03
20
10
0
0
10
15
20
CD
C
Rnal
brightness, % ISO
58
71.2
76.7
74.7
25
30
.s::.
86
OJ
'C
m
35
84
1.5
2.5
3.5
4.5
pochlorite (6).
90
~~0
(.)
a.
0
92
i. lbe bktu:lmlg of tI
Fig. 7. Brlgbtrlas
resJHnIU of (W)E .'lgrdftetl
sIIIga oftbe (W)E(DIEID)
tIIUI (W)E(HID)
9. Economicconsiderations
In general, to be cost effective, hypochlorite should be less expensive than chlorine
dioxide on an oxidizing equivalent basis.
Figure 7 shows that, on an equivalent chlorine basis, the (DIEID) stage pulps of a simplified (CD)E(DIEID) sequence have higher
brightness and a higher brightness ceiling
than the same extraction
stage pulps
bleached by the (CD)E(HID) sequence. This
is true for pulps chlorinated at 0.157 or 0.22
kappa factor. Therefore, the (CD)E(DIEID)
sequence is more cost effective than the
(CD)E(HID) sequence unless the chlorine
dioxide generator produces by-product hypochIorite which would require disposal.
Figure 8 shows that pulp bleached in a
(CD)E(DIEID) sequence has better brightness stability than that bleached
in a
(CD)E(H/D) sequence. However, if the
grade of pulp being produced requires low
viscosity, or rapid strength development
during beating, the hypochlorite sequence
would be favored.
bletlt:'-l
,.
Some mills use lime bleach (calcium hypochlorite) because lime is a less expensive
alkali than sodium hydroxide. However, use
of a calcium base may be disadvantageous
for a variety of reasons. When sodium hydroxide is added for pH control, lime is precipitated onto the fiber. Lime carryover into
a following chlorine dioxide stage may lead
to low brightness because of the high pH.
Also, lime bleach cannot be used in countercurrent washing because of problems
associated with lime scale formation.
The use of a hypochlorite stage necessitates the inclusion of an additional wash
before the D, stage in a CEHDED sequence.
A 1978 survey of Canadian mills (11)
showed that six-stage bleacheries used an
average of 6.8 kg of CIO /metric ton of pulp
compared with 17.7 kg ofCIO/metric
ton
of pulp used by five-stage CEDED bleacheries. This difference in chlorine dioxide
consumption cannot be explained by the
10 kg of Cljtonne of pulp normally used in
the hypochlorite
stage. Poor extractionstage washing is suspect as the cause of
much of the high chlorine dioxide consumption in the D, stage of the CEDED sequence. Most bleachery washers remove
only 85% of the solids generated in the extraction stage. This amount increases to 97%
removal after two stages. The waste of chlorine dioxide in the D, stage was confirmed
0
0
407
C>
':
CC
90
~~88
86
~
c:
1:
C)
82
22
80
20 '(jj
0
u
I/)
80
18 :>
78
76
78
84
86
88
Initial brightness,
90
92
a.
u
;i.
82
':
III
24
w
~
cf?84
u)
cii
c: 86
'en
as
...
Q) 84
=as
I/)
I/)
Q)
c:
408
16
2.0
3.0
% ISO
4.0
5.0
6.0
pH
11.Chlorinemonoxidebleaching
of pulp
11.1 Background
Chlorine monoxide (CIP) is a reddish
yellow gas which was first synthesized in
1834 by the French chemist Belard. A comprehensive review of the chemistry of this
compound has been published (18).
Uebergott and Bolker (19, 20) used chlorine monoxide to delignify unbleached kraft
pulp in the first stage of a high<onsistency
bleaching sequence. Chlorine monoxide,
2%, was applied to the pulp at 30",1,consistency in a I-minute treatment. The resultant pulp had a lower kappa number (4.3
compared with 7.6) than pulp delignified
in a conventional chlorination stage (5.9",(,
Clz on pulp at low consistency). By bleaching at high consistency, it was a1sOpossible
to replace cWorine dioxide with chlorine
monoxide in the latter stages of a multi-stage
bleach sequence and produce pulp of comparable brightness and strength.The bleaching characteristics
of chlorine monoxide
have also been studied by Christiansen and
Friedt (21).
Hypochlorous
acid (HOCI) is the hydrated form of cWorine monoxide. It is also
formed in the cWorine-water or hypochlorite-water systems by pH adjustment. In
such systems, hypochlorous
acid is the
dominant species present between pH 3
and S. Hypochlorous acid is a very powerful oxidizing agent with a standard reduction potential of 1.63 volts. However, it has
generally been considered to be destructive
82
~80
en
78
en
Q)
409
~~~24
22
20
(C+D)(E+O) H
a.
76
18
~u
72
+ 70
~w
68
CJ
66
64
16
:g
c:
~~? 74
.;::
.r::.
C)
~+O)M
a:!
14
~12
10
0.8
1.0
1.2
1.4
1.6
1.8
IJrlgblrJess
410
Pulp Bleaching
-Principles
and Practice
11.6 Hypochlorous
acid generation
Hypochlorous acid is not stable and has
to be generated at the mill site. The raw
materials are water, alkali, and chlorine.
When Monox-L is used, a nitrogen-containing viscosity protector is also added. The
materials of construction for the hypochlorous acid generator must be such that they
can tolerate the acidic (pH 4.5), strongly
oxidizing medium. Such materials include
titanium, Hastalloy, and some plastics.
11.5 Environmental
aspects
Hypochlorous acid bleaching has significant environmental advantages over chlorine or hypochlorite bleaching.To maintain
these advantages, the pH of the hypochlorous acid stage should be between 3.0 and
4.5. If the pH decreases much below 3, the
fraction of chlorine (Clz) present in the system increases (see Chap. IV 2, Fig. 3). Chlorine undergoes substitution reactions with
lignin more extensively than does hypochlorous acid which reacts oxidatively. As a result, the quantity of chlorinated organic
compounds increases dramatically in lower
3.5) pH regions. As evidence of this, mill
data have shown that tetrachlorodioxin
is
non-detectable when hypochlorous acid is
used as a bleaching agent and that AOX levels can be reduced by 30-60% compared to
when chlorine is used (27).
Chloroform formation is also heavily influenced by pH and is enhanced under
alkaline bleaching conditions. By maintain-
References
1. Hatch, R.S., The History
of Bleaching,
Monograph
No. 27, (WH. Rapson, Ed.),
TAPPI PRESS,Atlanta, 1963, pp. 1-7.
2. Milne, P.T.,"High Temperature
Short Retention Hypochlorite
Bleaching; International
Pulp Bleaching
Conference,
Preprints,
Tech Sect. CPPA, 1979. Montreal, p. 189.
3. Devoe, P.,"Crofton's Experience with High
Temperature
Hypochlorite
Bleaching", intern. Pulp Bleaching Conference Preprints,
Tech Sect. CPPA, 1979, Montreal, p.185.
4. Histed, J.A. and Nicolle,
EM.A., CPAR
Project Report 47-4,(copies
available from
Environment Canada library, Place Vincent
Massey, 251 St. Joseph
Blvd. Hull QC
Canada KIA OH3), 1974, pp. 3-20.
5. Histed, J.A. and
59(3):75 (1976).
6. Histed,J.A.,
Inc.
private
7. Rapson,WH.,
Nicolle,
EM.A.,
file courtesy
Tappi 39(5):284
Tappi
of Avenor
(1956).
8. Axegard,
P. and Tormund,
D., Svensk
Papperstidn.
88(3):R36 (1985).
9. Rapson, WH., Anderson,
Tappi 41(8):422 (1958).
10. Histed,
(Dec.9,
No. 4,238,281
Exam.
23(2):
of fI
Rev.
19. liebergott,
N. and Bolker, H.I., U.S. Pat.
No. 3,619,359 (Nov.9, 1971).
20. Bolker, H.I. and liebergott,
N., Pulp
Mag. Can. 73(11):T332
(1972).
Pap.
21. Christiansen,
C.B. and Friedt, R.D., Paper
Trade] 159(19):44 (1975).
22. Larson, L.E. in Handbook
of Pulp and Paper Technology @ritt, K.W,Ed.) 2nd eOO.
Reinhold, New York, 1970, p.272.
23. Larson, L.E., U.S. Pat. No. 3,177,111
6, 1954).
(April
M.M.,
Tappi]
27. Klykken, P.G. and Hurst, M.M., "Molecular Chlorine Free Bleaching with MonoxL," 1991 TAPPI Pulping Conference
Proceedings, TAPPI PRESS, Atlanta, p.523.
28. Yant, R., Smeds, U., Hyvarinen,
H., 76th
Annual Meeting Proceedings,
Tech. Section, CPPA, Montreal, 1990, p. 315.
SECfION IV:
The Technology of
Chemical Pulp Bleaching
Chapter 10:
Hydrogen Peroxide Bleaching
J. Ross
Anderson
B. Amini
E.I. DuPont de Nemours & Co.
Wilmington, Delaware
U.S.A. 19898
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
413
415
415
416
417
417
421
422
422
424
428
428
429
429
5. Pulp
5.1
5.2
5.3
414
quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 430
Brightness stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 430
Strength
431
Cleanliness
431
6. Process Oowsheets
7. Environmental
8. Economics
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
considerations
of hydrogen
432
434
peroxide bleaching.
. . . . . . . . . . . . . . . . . . . . . . . . . . .. 434
agents.
. . . . . . . . . . . . ..
435
411
Chapter IV 10:
Hydrogen Peroxide
Bleaching
1. Introduction
The use of hydrogen peroxide ("peroxide") as a wood pulp bleaching agent has
been well documented since its introduction for mechanical pulp bleaching in 1940.
The literature dealing with the early development of hydrogen peroxide bleaching has
been comprehensively reviewed by Beeman
and Reichert (1) and later by Holladay and
Solari (2). The more recent review of hydrogen peroxide bleaching by Andrews and
Singh (3) includes examples of its applif,;ation to chemical pulps.
Before the widespread use of cWorine
dioxide, a typical use of hydrogen peroxide was in short bleaching sequences, of the
type CEHP, for producing brightness levels
in the range of 75-85% ISO. The introduction of cWorine dioxide led to the division
of old multi-stage processes and the development of many short sequences. The addition of a final hydrogen peroxide stage in
such a sequence contributes to a gain in
brightness and brightness stability while
preserving high viscosity and pulp strength.
Similar benefits are seen with the substitution of hydrogen peroxide for sodium hypocWorite.
The proliferation in the late 19508 and
1960s of five- and six-stage bleach plants
using cWorine dioxide in multiple bleaching stages led to a general shift to high
brightness (>89% ISO) and high-strength
market chemical pulps. Hydrogen peroxide
was used in the final bleaching stages to
achieve higher brightness P-<)2% ISO) and
improved brightness stability for specialty
pulps (4). Over the years, the versatility and
relative ease of use of peroxide has led to
applications that overcome the inherent
limitations of existing bleach plant equipment and chemicals. A typical application
of peroxide involves reinforcement of an
alkaline extraction stage, which transforms
it from a simple extraction or washing stage
413
414
...~,
~-
+ HO- ->
HOO.
+ HP
[1]
415
Hydrogen
peroxide
416
[3]
[4]
decomposition
reactions
Hydrogen peroxide decomposition
is
catalyzed by metais normally present in the
bleaching solution and pulp. Martin (21)
established that hydrogen peroxide decomposition, as well as the bleaching reaction,
is first order with respect to hydrogen peroxide concentration. Tests also showed that
hydrogen peroxide consumption increases
as the pH is increased from 9 to 12; this
was attributed to an enhanced reaction of
hydrogen peroxide with the pulp.Although
the rate of hydrogen peroxide decomposition also increases with the increasing pH,
decomposition can be minimized by addition of stabilizers.
To utilize alkaline hydrogen peroxide as
an effective lignin-retainin bleaching agent,
precautions should be taken to minimize
peroxide decomposition. Some decomposition products, however, may be necessary
for delignification and bleaching of kraft
pulps with hydrogen peroxide (18 and
Chapt IV 6). In conventional bleaching sequences, decomposition of hydrogen peroxide can be controlled by:
Using mild alkaline bleaching conditions
Stabilizing the hydrogen peroxide (by the
addition of magnesium sulfate and s0dium silicate)
Removing transition metals from the pulp
(by pretreatment with an acid or chelating agent).
Despite these measures, Gellerstedt et al.
(22) showed that hydrogen peroxide decomposition will occur to some extent.The
principal decomposition products studied
are hydroxyl radicals, HO', and, to a lesser
extent, superoxide
anion radicals, 02;
(23,24). The generation of hydroxyl radicals occurs primarily by the transition metal
(M) ion<atalyzed decomposition of hydrogen peroxide (23,24):
bleaching
process.
Gellerstedt
and
Pettersson (26) have shown that efficient
control of transition metals in chemical
pulps and control of pH and temperature
conditions make it possible to use hydroge~ peroxide to substantially increase pulp
bnghtness and remove a major portion of
~e re~iduallignin without decreasing pulp
VISCOSity to an unacceptable
level.
of
[5]
=perhydroxyl
anion concen
, tration,
= gas constant,
Ko = rate constant,
T = absolute temperature,
E, = activation energy, and
D = transfer coefficient from liquid
to pulp phase.
According
to this model, the highest
rate
of brightness
increase is obtained with
1) The highest practical
temperature.
Temperature is limited by the homolytic cleavage. of hydrogen
peroxide into hydroxyl
radicals (approximately
130C)(28).
2) A high concentration
of perhydroxyl
anion. This is affected by the amount of hydrogen peroxide applied, the alkali charge
to the
pe~hydroxyl
anion), and the rate of peroXide decomposition.The
optimum alkali
charge is not necessarily the highest practical charge but pH must be sufficiently
~--~---_....--
417
418
Pulp Bleaching
and Practice
H202 charge:
90
88
0
86
~84
~0
82
en
I/J
Q) 80
c:
-C)
35 kg/metric
ton
Consistency: 10-12%
78
.r:
.;::
76
CD 74
72
70
4
Retention
time,
10
-Principles
delignifW
90
H202 kg/metric ton
40
30
o
C/)
85
20
rft.
en
I/J
Q)
.E
C)
.;::
Temperature: 90C
80
11 %
ConsistencYi
.r:
CD
75
ft
6
Retention
10
time,
FIg.2. JJffeel
of ~
ciNll'p OIl tH rille of blelleblflg of till ~.del""ifW
(IuIpJM No. 11) blelleW with 6ytIrogen ~
(32).
12
14
IMrdttIootllmlft
}mlp
__ _'___~_'_'__'___n_____
into an existing
bleach
419
420
Pulp Bleaching
-Principles
Tllbk 1. Effect of P, I~
(O+P)Q(E+O+P)P(JI+P)P
application
and Practice
setpIBfIU.
Mill results
(E+O+P)
PI
0.6
2.5-3.0
14-17
4-10
65-77
plant, time
and temperature are normally the two parameters that are difficult to change. This
is because water flow and heat transfer generally limit the change in pulp temperature
from one stage to the next and the tower
size determines the pulp residence time for
a given production rate. When the temperature is below the optimum value of about
90C (atmospheric
towers), the performance of a hydrogen peroxide bleaching
stage is often disappointing. Table 1 shows
the brightness results for a TCF sequence
in a mill producing an oxygen-delignified
softwood kraft pulp using conventional
bleaching equipment.
For reinforcement of an existing extraction stage, process conditions in most pulp
mills are generally adequate to effectively
utilize the added hydrogen peroxide. To
obtain the maximum effect from oxygen
and added peroxide, however, the oxidative extraction stages are currently being
designed to operate at temperatures
of
90C or higher and at pressures exceeding
75 psig (31).
To prolong the retention
time and
achieve a higher brightness, several bleaching towers can be combined in a single stage
(32). Figures 1 and 2 show, however, that
the brightness increase is modest even after an extended (> 10 hours) retention time
(17,32). Figure 1 also shows the impact of
temperature on brightness response.
For an atmospheric pressure peroxide
stage, 90C is normally the maximum operating temperature (10, 19,33,34). Even at
90C, however, the time required to attain
the desired brightness may be longer than
most mills can achieve in their existing towers and it may be economically difficult to
justify building additional towers. The retention time to reach a target brightness can
be dramatically shortened, however, by increasing the temperature of the peroxide
stage. The plots in Fig. 1 show that for an
oxygen-de lignified softwood
pulp, an
equivalent brightness is achieved in only 2
hours at 110C compared with 6 hours at
90C (17). Other workers have presented
(O+P)Q
Stage:
",0" %
0.5
19-20
60-65
<120
40
Kappa no.
Temperature, C
Tune, min
Brightness, % ISO
45-48
uboratory
P, Temperature, C
(E+P)
65
i"
""
0.6
P,
2.;
66-69
72-79
evaluation"
P, Brightness, % ISO
77
88
77b
77.6
80.0
82.3
(E+P) replaced
peracid
solution),
as %
",0,
85
0
~80
~0
en
en
Q) 75
c::
.C)
c
'C::
III 70
65
10
Hydrogen
(IMpJM
no.
12.5)
peroziM
20
30
peroxide charge,
Off IH me of bletwbi",
40
kg/metric ton
of II" o:rygen-tieUpiftetl
softwood In'IIft
(17).
similar results (11, 16, 27, 29). These findings are the basis for the design of pressurized hydrogen peroxide stages.
The application of pressure is an engineering device to maintain control of a hightemperature stage and avoid boiling. The
benefits can be higher brightness and decreased hydrogen peroxide charge (17)
(Fig. 3). Some researchers have reported
brightness improvement when oxygen, instead of nitrogen, is used to provide the in-
Peroxide Bleaching
421
422
65
Conditions:
Cf)
8 kg H202/metric
<f.
en
II)
Q)
c:
'5
.;::
.t:I
Q)
C)
co
0
SQ
~0
ui
II)
60
Q)
c:
.C)
l:
.;::
CD
II)
I
H202 Change,
85
84
83
82
81
80
79
kg/metric
40
o
ton
20
78
Kappa number of oxygen-delignified
(PO) stage: 100C, 2 h
77
76
fL
o
~
and Practice
pulp: 9
75
55
10.8
11.0
11.2
(EOP)
ng. 4. ReWUmsblp behtJeM flul
pulp (/ItIJ1p8110.
2')).
-stage
pH hi 1m (EOP) 81.ge
pH
The pK, for formation of perhydroxyl
anion is 11.6 at 25C. Equation 6 predicts
that: when the applied hydrogen peroxide
is 50% dissociated ( [HOO-]
[HP2] ), pH
and pK, will be equal. When the pH is de.
creased to 10.6, the hydrogen peroxide will
be only 10% dissociated to perhydroxyl
anion according
to Eq. 6. Because the
perhydroxyl anion concentration is essen.
tial to brightness development, it is not surprising that as pH decreases, brightness also
decreases as shown in Fig. 4. In a peroxide
bleaching stage, alkalinity must be optimized to balance
the formation
of
perhydroxyl anions with the formation of
colored compounds attributable to alkali
darkening (10). The previous history of the
pulp may also govern the optimum pH. For
example, softwood kraft pulps tolerate a
wide range of alkalinity, when the P stage
is preceded by a vigorous chelation stage
(10). This effect is shown below in Fig. II.
Consistency also has an impact in determining the optimum alka1inity level. At medium consistency (9-12%), depending on
other process parameters, the optimum
molar ratio of caustic soda (sodium hydrox.
ide) to hydrogen peroxide is approximately
1:1. In high-<:onsistency (20-30%) bleaching, the best results are obtained at a so-
"""
10
11.4
final pH
brlgblJlas hllbe bletrcblttg of IIOjI1IJootl
""'fl
= pK, +
20
25
Pulp consistency,
15
log
[HOO']
mo-
[6]
IHPz]
and
When a conventional
chlorine bleaching
sequence for kraft pulp is converted to an
ECF sequence, many mills find that total
chemical charge for bleaching is higher than
ng..s.
30
Effeel of pulp ~
OIIlbe brlgblJlas of"" oxygn-tleliplfletIlIOjI1IJootl
9) bletu:bedhl" pre!l88rl%etl~81"ge
(17).
35
%
""'ft
pulp (/ItIJ1p8No.
3.4 Carryover
Carryover of liquor containing dissolved
organic fragments usually increases consumption of hydrogen peroxide. The peroxide is expected to have free access to the
dissolved organic fragments in the bleaching liquor, but its access to the lignin residue of the pulp (which is bound to the
carbohydrate)
is somewhat
restricted.
Therefore, it is expected that peroxide is
423
90
85
10% consistency
85
424
-09-
0
~80
ui
IJ)
75
-c:
70
0)
'C
IJ)
QP
.s:::.
0)
. (EOP)QP
'C
.Q
CD
0)
tU
. D(EOP)QP
h. A(EOP)QP
(where, A= dioxirane)
o A(EOP)QP
o O(ZE)QP
65
10 12 14 16 18 20 22 24
Post-oxygen
kappa number
5.7
o
~
5.7
80
12.5
15
CD
c:
.s:::.
.g'
IJ)
70
- - - -
25% consistency
12%consistency
Postage: 90C, 4h
60
f
2
3
4
Hydrogen peroxide charge, kg/metric ton
35 kg H202/metric
ton, 90C,
4 h, pH 11-12
10
12
Q-stage pH
90
-09ui
IJ)
Postage:
55
__OIIlbe
fIIIIb~
IJ)
65
ci..
60
024
75
CD
c:
..OOP
CD
.s:::.
ui
IJ)
~Legend:
softwoodltrwftJnllp
softwood
"""/1
Jnllp (/uIpJM110:
Metal Content,
Before chelation
After chelation
aQ-stage conditions:
't:I
Fe
Cu
300
11
47
0.6
500-1000
120-280
6-8
<5
0.1.Q.2
Initial metal
68
<fl.
en 66
en
Q)
c::
&
levels
(ppm)
Mn
70
Mg
220
Ca 2300
Na 2900
CD
No DTPA
in Postage
62
Postage: 25 kg H202/metric
ton, 90C. 4h
60
20
Legend:
Sodium
~uo.~100
25
hydroxide
30
in P-stage,
kg/metric
50
75
Postage: 25 kg H202/metric
ton, 90C, 4 h
o
0
~
2
Acid treatment
en
en
Stlftrrood InYIft
Q)
c::
~
01
'C
P.lp (37).
The plots in Fig. 9 show that significant removal of magnesium, calcium, and sodium
ions can occur in an acid wash-stage together with the manganese (37).
Pulps exhibit ion exchange properties
because they contain weakly acidic groups.
Neither chelation nor an acid wash removes
all of the transition metals. Iron is particularly difficult to remove because
it has an
affinity for phenolic
groups in lignin and
can also exist as a counter-ion to carboxylic acid groups in the pulp. Such acid groups
also bind many other transition
and alkaline earth metals (37). This may explain
why acid pretreatment
is less effective than
chelation. In a peroxide bleaching stage,
the metals bound to the pulp may be released and reduce the effectiveness of the
70
EDTA in Q,
% on pulp
A
1.2
65
0.6
60
0.2
<fl.
pH
ton
g!
:;:::~
.!!! 0
0
oen
1:
0164
250
't:ICD
C\JCD
O-!!!..
'0 E 150
-0.
co. _
~~g
Mn
'C
..0
~:g
c CD
~CD_:?200
.!!11ij
.!!!...
1400
426
p.lps.
ppm
Mg
Ca
425
..0
a..
o
o
55
50
. ----.
OP
45
15
20
Sodium
hydroxide
25
in P-stage,
30
kg/metric
ton
brighmess
of a StlftwootIhft
P.lp
(lappa
110.32.5)
in a following
427
o
~
90
#.
88
iii'
I/)
Q)
c:
86
azp
Z-stage: 0.5% 03, pH 2
Postage: gooc
82
Hydrogen
Fig. 12. IUfects of ebe'-t
10
15
peroxide
20
25
consumption,
30
35
40
kg/metric
""""mbletWbetll" ~
ImIft I"dp (i4pJMno.
""" B)
Pulp Bleaching
t:fnII/Iosedofoz_"""~
ton
meygen-tieliplftM
I16j'trtJoot1
stllge5(39).
-Principles
and Practice
90
0
0
u)
80
~H202added to (E+O)
~",,/
~70
I/)
Q)
60
50
c:
C)
.t:
CD
,/
40
P '"
'"
~/
(E+O)
Stages
peroxide
IIMUImrm." (E+O)stage011brlgblrlns
consumption
in bleach sequence
bleaching of chemithermomechanical
pulps
(CfMP). Similar to magnesium, the silicate
complexes the transition metals through
oxygen or hydroxyl bridges (43,44). The
formation of the complex changes the catalytic activity of the transition metal and its
ability to decompose the hydrogen peroxide (36). Despite a previous chelation or
acid-wash stage, metals may be released
from the pulp during hydrogen peroxide
bleaching and addition of silicate to the
bleaching liquor can decrease the negative
impact of these metals on bleaching performance. This benefit is particularly apparent in high-consistency
hydrogen
peroxide stages (11, 35,49). Forexample,
the addition of 2% silicate in a high-consistency stage has been found to decrease the
hydrogen
azap
"5> 84
.t:
CD
428
(91 % corn-
'"
tbe _
4. Typicalhydrogen peroxide
bleaching sequences
4.1 .Conventional.
Hydrogen peroxide is generally applied
as a reinforcing chemical in an existing extraction stage. The combined delignification and bleaching effects of hydrogen
peroxide allow the kappa factor for addition of chlorine and chlorine dioxide to be
reduced and thereby decrease their consumption. Peroxide addition in an extraction stage may also help a mill achieve
environmental objectives (lower AOX) and
maintain pulp production capability when
the mill's chlorine dioxide capacity is limited (8, 9). Some mills may make changes
in their process conditions to optimize the
peroxide-reinforced extraction stage as previously described. In most cases, however,
because the applied peroxide charges are
low and performance
expectations
are
modest (often, to overcome a specific sequence constraint), the mills are inclined
to accept whatever benefits they can get
without incul'1'iJ1g additioMl ~rocess optimization costs.
The primary objective of a reinforced
extraction (E+O+P) stage is to improve lig-
0
.c.
c.
429
92
91
~90
iIi
89
::!!
0
ui
88
(/)
Q)
-c::
.c.
OJ
.;::
.c
DO
W
U
87
86
85
84
80
82
84
86
88
90
Fig.14. BrlgbtruJSSglli.
softwood iIrIIftJnllp (50).
. ft'""
92
i. tbe bktu:bi.g of"
4.2 ECF
ECF bleaching sequences currently dominate the production of bleached kraft market pulp in Canada and Scandinavia (52).
A typical ECF bleaching
sequence
is
D(E+O+P)DD.The conversion of sequences
from "conventional" to ECF often is hampered by limitations in cWorine dioxide
generating
capacity and by bleaching
equipment capacity and configuration. Hydrogen peroxide reinforcement of the ex-
4.3 rCF
430
5. Pulp quality
5.1 Brightness
stability
Carbonyl groups are known to be responsible for photo sensitizing heat-induced (56)
and photochemically- induced (57) brightness reversion of bleached pulps. Hydrogen
peroxide is effective in eliminating carbonyl groups (33) and a final P stage leads to
excellent brightness stability in TCF sequences even when the bleached pulp has
a relatively high residual lignin content. For
example, the brightness reversion was only
2-3 points for samples of softwood and hardwood sulfite pulps (kappa numbers, 2-4)
that W8re bleached in TCF sequences (49).
The initial brightness range for the pulps
was 81-88% ISO and the reversion was measured at 100C for 2 hours using the standard TAPPI heat-aging test. The reversion
was 3.5-4 points after a 3-<iaylight-induced
yellowing test. Results for softwood kraft
pulps were similar. Figure 15 shows the
comparative brightness reversion of pulps
bleached in OZP and OPZ sequences after
exposure to heat at 105C (33).
The primary benefit of a peroxide application in the final stage of a conventional
bleaching sequence such as (CIDXE+O)DP,
is brightness stability. Reversion for a fully
80
0
~::!! 75
0
ui
(/)
Q)
c:: 70
.c.
OJ
.;::
II)
65
60
12
24
36
Heat exposure
Pi,. 15. 'l'bemuIl
slllbilily
tnMOQPZ~
of...
oxygert-."piftetl
(33).
48
60
72
time, h
i. OQZP
431
432
Pulp Bleaching
-Principles
and Practice
5.3 Cleanliness
6. Process flowsheets
High-performance
TCF bleaching sequences presuppose
effective screening
and washing. The low kappa numbers required for achieving a high final brightness
ensure a low shive content in the incoming
pulp. Therefore, pulp cleanliness is not an
issue in most pulp mills that have an established TCF pulp bleaching process. Hydrogen peroxide is not as effective as chlorine
dioxide for bleaching shives and dirt. Mills
attempting to produce TCF pulp through
the application of high charges of hydrogen peroxide, but without having made the
investment in adequate pulp preparation,
do not achieve the expected pulp brightness and cleanliness.
When hydrogen peroxide is used to reinforce the oxidative extraction stage in an
ECF sequence for the purpose of reducing
the kappa factor, attention must be given
to adjusting the conditions of the chlorine
dioxide stages to maintain pulp cleanliness
(9). Although some of shive removal may
take place in the (E+O+P) stage, it is important to reduce the pH in the Dl stage
for shive control. The chlorine dioxide
charge in the first stage may also have to be
increased to completely remove shives.
(a)
Q
20
Z-stage: 0.5"1003, pH 2
PO-stage: 30 kg H:p~metric ton
includes Mg addition
0>
C\I
Z
E
15
(b)
xCD
"C
.S
....
10
<U
CD
~5
60
80
100
Tensile index, Nm/g
:ro~
120
(c)
ImIft "",p bluebetl
", IICF111MTCF
ft1r TCFbluebirJg seqrmrces sullilble for refittl"g I"to exlstl"g bleaeb pl",,16 (32).
433
EOP
PO
ZQ
cially at the tile edges (32). A potential exists for titanium corrosion at sufficiently
high temperature, pH, and peroxide charge.
Effective inhibitor species for preventing
titanium corrosion include calcium, magnesium, and silicates (63,64).
Brightness control in a hydrogen peroxide bleaching stage may be difficult if the
lignin content of the pulp varies over a wide
range. Most processes can be controlled by
maintaining a uniform low kappa number
for the incoming pulp. Brightness thresh-
Degassing
Standpipe
MC-pump
Fig. 19. Processflowsbeetfor
Diffuser
washer
MC-pump
a pressurized
Pulp Bleaching
-Principles
and Practice
NaOH
EDTA
434
(Kvaemer)(28).
7. Environmental considerations
The main environmental consideration
associated with peroxide bleaching is the
role of this oxidant in facilitating the recycle
of bleach plant effluents to the recovery
cycle. Effiuent recycling can help to reduce
water use in a mill and may ultimately lead
to elimination of effluent discharge to waterways. Other considerations, such as the
drive to eliminate dioxin and reduce AOX,
have led to the concept of ECF bleaching.
Such sequences use a low kappa factor in
the initial chlorination stages (5,6,9). The
benefits of an ECF process, with inclusion
of hydrogen peroxide, are lower AOX in the
bleaching effluent and, more particularly,
lower AOX in the pulp (10,65). When a
mill's capacity to produce chlorine dioxide
is limited, the use of hydrogen peroxide may
allow the mill to convert to an ECF process
and yet maintain its pulp quality and production rate (7,8).
Hydrogen peroxide reinforcement of the
oxidative extraction stage can be used to
decrease the color of mill effluent (9). Hydrogen peroxide has also been used to control odor by treatment of reducible sulfur
compounds in the mill effluent.
The major incentive for the development
of TCF bleaching sequences has been the
elimination of AOX. Reduction of AOX may
be required by regulation, due largely to the
public's concerns about the Impact of chlorine on the environment even though there
8. Economics of hydrogen
oxide bleaching
per-
peroxide
activators
= NH
OOH
[7J
strong nudeophile
that .reacts selectively
with chromophores
and lignin to increase
pulp brightness. The nitrilamine is consumed in the bleaching reaction and converted to urea.
The use of tungstate and molybdate catalysts to activate acidic hydrogen peroxide
in bleaching reactions has also been investigated aO). Similarly, transition metal-substituted polyoxometalate duster ions have
been proposed
primarily
for use as
delignifying agents. Polyoxometalate cluster ions are inorganic analogs of the organic
platfonns known to control the activity of
transition metals in enzymes that selectively
catalyze the oxidation of lignin (71).
Application of a silicon-tungsten-manganese-based
cluster ion to an oxygendelignified softwood kraft pulp at 125C for
2 hours decreases the kappa number from
35 to 5 and produces only a small reduction in viscosity (from 34 to 27 cP) (71).
The polyoxometalate cluster can be re-oxidized, after reaction with the lignin, for recycle and reuse. Air and hydrogen peroxide
have been used to re-oxidize the catalyst.
To be viable economically, the industrial
application
of these polyoxometalate
435
clusters would undoubtedly require an extremely high recovery of the polyoxometalate catalyst.
Heteropolyoxometalates,
which can be
produced from relatively inexpensive reagents, have also been proposed as catalysts
for delignification of pulps (72). They are
added directly to the P stage to improve the
effectiveness of the peroxide application.
For example, the addition of a polymeric
silicoperoxomolybdate
leads to significant
improvements in delignification in a peroxide stage and improves brightness development in the following stages (72).
The formation of carbonyl groups, which
the perhydroxyl anion effectively attacks,
may be considered a form of activation. It
has been shown that a peroxy acid pretreatment enhances the performance of a following hydrogen peroxide bleaching stage.
The effect surpasses the simple finding of a
decrease in kappa number or the carryover
of residual hydrogen peroxide from such a
stage to a subsequent
peroxide
stage
(15,59). The mechanism for this performance enhancement has not yet been determined.
9.2
Hydrogen
bleaching
peroxide-derived
agents
II
R - C - OH
Carboxylic acid
II
R-C-OOH
Percarboxylic acid
For Peracetic acid,
R
II
HO-S-OH
II
Sulfuric acid
=CH3
II
HO - S
II
OOH
PeroxymonosuHuric
acid
Caro's acid
436
Pulp Bleaching
-Principles
and Practice
rllbk 3. ~JIoInUMlsof~
(59).
Oxidation Potential
(e', V)
03 + 2 H+ + 2 e- -+ 02 + H20
H202 + 2 H+ + 2 e- -+ 2 H20
HCI02 + 3 H" + 4 e" -+ C.- + 2 HzO
HOCl + H" + 2 e" -+ C.- + HzO
HSOs- + 2 H+ + 2 e" -+ HSO;
+ H20
2.07
1.78
1.56
1.49
1.44
1.36
1.15
1.06
0.90
0.87
0.78
0.40
HOO' + HP
+ 2 e' -+ 30H-
Function
viscosity and strength comparable to ECF control (conventional TCF sequence showed a
3) Lower
cost:
5-10"10strength
agent
agent
The bleaching
performance
of peroxy acids has been evaluated in pulp mill trials and
the results have duplicated
the laboratory
findings (13,59).
Activation of hydrogen peroxide stage together with oxygen under acidic or mildly alkaline conditions (15,59)
Activation of a following hydrogen peroxide bleaching stage
(15, 59, 82, 83)
Bleaching agent in later
oxidizing stages
438
Pulp Bleaching
-Principles
and Practice
[8]
The acetone acts essentially as a catalyst
and is regenerated following the oxidation
of the pulp with DMD. Elucidation of the
pulp reaction mechanisms remains a subject of research activity. The practical application of this technology depends on the
extraction and recovery of acetone from the
bleaching effluent. In any commercial use
of DMD, the Caro's acid would likely be
produced on site as a product of reaction
of sulfuric acid with hydrogen peroxide.
loss)
Application
Delignification
Activation
437
for a chlorine
dioxide
stage (14,
References
1. Beeman, L.A. and Reichert,
J.S., in The
Bleaching of Pulp,TAPPI PRESS, New York,
1953, p. 210.
2. Holladay,P.C.and
Solari,R.]., in The Bleaching of Pulp (W.H. Rapson, Ed.), TAPPI
PRESS, New York, 1%3, p. ISO.
3. Andrews,
D.H. and Singh, R.P., in The
Bleaching
of Pulp (R.P. Singh, Ed.), TAPPI
PRESS,Atlanta, 1979, p. 211.
4. Robitaille, M.A., "Hydrogen Peroxide - A
Versatile Bleaching Agent," 74th CPPA Annual Meeting Preprints, Tech. Sect., CPPA,
Montreal, 1988, p. B1.
5. Berry, R.M. Fleming, RI., Voss, R.H., Luthe,
C.E.,Wrist, P.E., Pulp Pap. Can. 9O(8):T279
(1989).
6. Liebergott,
N., van Uerop, B., Nolin, A.,
Faubert, M., Laflamme,].,
"Modifying the
Bleaching Process to DecreaseAOX Formation," 76th CPPAAnnual Meeting Preprints,
Tech. Sect., CPPA, Montreal, 1990, p. B229.
13. Basta,].
Holtinger,
L., Hallstrom,
A-S.,
Lundgren, P.,"Peroxo Compounds
in TCF
Bleaching," 1994 TAPPI Pulping Conference Proceedings,
TAPPI PRESS, Atlanta,
p.953.
439
K., Holzfor-
26. Gellerstedt,
G. and Pettersson,
Chern. Tech. 2(3):231 (1982).
I.,J Wood
15. Liebergott,N.,"Peracid
Delignification and
Bleaching," 1994 TAPPI Pulping Conference Proceedings,
TAPPI PRESS,Atlanta,
p.357.
17. Germgard,
U. and Norden,
S., "OZPBleaching of Kraft Pulps to Full Brightness," International
Pulp Bleaching Conference - Papers Preprints, Tech. Sect"
CPPA, Montreal, 1994, p.53.
18. Gellerstedt,
G. and Lindfors, E-L., "On the
Structure
and Reactivity of Residual Lignin in Kraft Pulp Fibers," International
Pulp Bleaching Conference
Proceedings,
SPCI, Stockholm,
1991, p. 73.
19. Lachenal, D., Femandes,].C.,
Froment, P.,
"Behavior of Residual Lignin in Kraft Pulp
During Bleaching,"
International
Pulp
Bleaching
Conference-Papers
Preprints,
Tech. Sect., CPPA, Montreal, 1994, p.41.
20. Hobbs, G.c. and Abbott, J., "The Role of
Radical Species in Peroxide Bleaching
Processes," 46th Appita Annual General
Conference Proceedings, Appita, Parkville,
Victoria, Australia, 1992, p. 99.
21. Martin,
(1957).
22. Gellerstedt,
G., Pettersson,
I., Sundlin, S.,
International
Symposium
on Wood and
Pulping
Chemistry
Notes,
SPCl,
Stockholm,
1981, Vol. 2, p. 120.
23. Gierer,J.,Jansbo,
K.,Yeng, E.,Yoon, B-H.,
"On the Participation
of Hydroxyl Radicals in Oxygen and Hydrogen Peroxide
Bleaching
Processes,"
6th InternatioanI
Symposium on Wood and Pulping Chemistry Notes, Appita, Parkville,Victoria,Australia, 1991, Vol. I, p. 93
24. Tatsumi,
K., Murayama,
K., Terashima,
N.,
Pulp
Bleaching
Conference
Papers
Pre-
1994,
Pap. (6):125
(1993).
440
42. Colodette,
J.L., Rothenberg,
S., Dence,
C.W,J Pulp Pap. Sd.: 15(2):J45 (1989).
34. Basta,]., Holtinger, L., Hook,]., "Controlling the Profile of Metals in the Pulp
BeforeHydrogen
PeroxideTreatment,"
6th
International
Symposium
on Wood and
Pulping
Chemistry
Notes,
Appita,
Parkville, Victoria, Australia, 1991, p. 237.
35. Kappel, J., Neubauer,
G., Petschauer,
F.,
"High-Consistency
Peroxide Bleaching for
Chemical Pulps," 77th CPPAAnnuai Meeting Preprints, Tech. Sect.,CPPA, Montreal,
1991, p.A333.
36. Lapierre, L., Bouchard,].,
Berry, R.M., van
Uerop, B., "Chelation Prior to Hydrogen
Pc;roxidc; Bltachin/5
of Kraft Pulps: An
Overview," 81st CPPAAnnuai Meeting Preprints, Tech. Sect.,CPPA, Montreal, 1995,
p. B233.
48. Johansson,
N-G., Johnson,
S.E., Biggers,
8.W., Clark, EM., Bergeron, M.P., Jean, P.,
"Metal Management
in ECF Bleaching and
the Effect on Peroxide Efficiency in the
EPO Stage," 1994 TAPPI Pulping Conference Proceedings,
TAPPI PRESS, Atlanta,
p. 1345.
Pulp
Paper.
Scf.
17(1):JI0
45. Heimburger,
S.A., Pool,J., Knight,J., "Stabilization
of Hydrogen
Peroxide
to Improve TCF Bleaching of Kraft Pulp," 1994
TAPPI Pulping Conference
Proceedings,
TAPPl PRESS,Atlanta, p. 935.
46. Xu, C.,Jameel, H., Chang, H-m., Hoekstra,
P.M., "New High Efficiency
Peroxide
Bleaching Process and Its Use for ECF Sequences," I 994TAPPI Pulping Conference
Proceedings,
TAPPI PRESS, Atlanta, p.
1331.
47. Bryant, P.S. and Edwards, L.L.,"Manganese
Removal
in Closed Kraft Mill Bleach
Plants," 1993 TAPPI Pulping Conference
Proceedings, TAPPl PRESS, Atlanta, p. 43.
E.B., Bostwick,
D., "Summary
of AOX
Survey
55. Nimmerfroh,
N., Suss, H.U., Bottcher, HP., Luttgen, W, Geisenheiner,A.
"The GermanApproach
to the Closed-CycJe Sulfite
Mill: Development
and Implementation,"
International
Pulp Bleaching Conference
-Paper
Preprints,
Tech. Sect.,CPPA,
Montreal, 1994, p. 247.
56. Edwards,].O.,
Peraxide Reaction Mechanisms (J.O. Edwards, Ed.) Interscience,
New York, 1962, p. 67.
57. Argyropoulos,
D., "Fundamental
NMR
Studies in Lignins: Emerging Answers to
Issues of Concern in Relation to Pulping;
TCF Bleaching and Yellowing," 81st CPPA
Annual Meeting Preprints,
Tech. Sect.,
CPPA, Montreal. 1995, p. A209.
E.B., Tappi
R., personal
communication.
63. Reichert,D.L.,"Hydrogen
Peroxide Bleaching in Titanium Equipment," International
Pulp BleachingConference
- Posters Preprints, Tech. Sect.,CPPA, Montreal, 1994,
p.73.
64. Schutz, RW and Xiao, M., "Practical Wmdows and Inhibitors
for Titanium Use in
AlkalinePeroxide
Bleach Solutions,"NACE
International
Corrosion
Meeting Notes,
NACE International,
Houston, 1994, Paper
No. 427.
65. Pageau, G.,"ECF andTCF Pulp Production
at Howe
Sound
Pulp
and Paper;
(Roundtable
audio recording)
81st CPPA
Annual
Meeting,
Tech.
Sect.,CPPA,
Montreal, 1995.
p.207.
Chem.
75. Atnini,B.,DuPontPxa~:High
Conversion
Pero.xy adds, DuPont Technical BuUetin
H-57651,E.I.du
Pont de Nemours & Co.,
Wilmington,
DE, 1994.
76. Poljak,A.,
77. Leopold,
Angew.
441
(1%1).
C.W,
Tappi
Rapson,WH.,Wayman,M.,
Tappi 48(2):65 (1%5).
Anderson
C.B.,
Poppius-Levlin,
K., Toikkanen,
1..,
Thominen, I., Sundquist,]., "Chlorine-Free
Bleaching of KraftPulps,"
International
Pulp Bleaching Conference
Proceedings,
SPCI, Stockholm,
1991, vol. 3, p. 103.
442
Pulp Bleaching
-Principles
and Practice
83. Anderson,
].R., Webster, ].R., Amini, B.,
Wang, S., Chang,
H-m., Jamee1,
H.,
"Peracids:A Further Step in the Evolution
to TCF Chetnical
Pulp Bleaching," 47th
Appita Annual General Conference
Proceedings, APPITA, Parkville, Victoria, Australia, 1993, vol. 2, p.461.
84. Springer, E.L. and McSweeney,].D.,
J 76(8):194 (1993).
Tappi
87. Devenyns,J.,Troughton,
N.A., Desprez, E,
"Strategies for High Brightness, Low Effluent TCF Bleaching of Sulfite Pulps," 1994
TAPPI Pulping Conference
Proceedings,
TAPPI PRESS,Atlanta, p. 481.
88. Lee, C. L., Hogikyan,
R., Skothos,
A.,
Sacciadis, G., Wearing,].T., Oloman, C. W,
Amini, 8., Teetzel, W. W., Carmichael,
D.
L., Fetissoff, P., Trench, L. Harper, S., "Ac-
Agent for Chemical Pulps, Part IY.TotallyChlorine-Free Bleaching: Pilot Trial and
Process Designs," International
Pulp
Bleaching
Conference
Papers
Preprints,
1994, p. 273.
SECfION IV:
The Technology of
Chemical Pulp Bleaching
Chapter 11:
Bleaching Shives and Dirt
Peter Axegird
and
EUsabeth Bergnor Gidnert
Swedish Pulp and Paper Research Institute
P.O. Box 5604
50114 86 Stockholm, Sweden
1. Background
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 445
2. PartlcIemmeasuremment...
3. RelatIonship
445
between cIeanllness
and brightness.
of particles
448
stages . . . . . . . . . . . . . . . . . . . . . . . . .. 450
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 450
8. ~ndelIgnificatIon
9. ChlorinatIon.
. . . . . . . . . . . . . . . . . . . . . .. 445
. . . . . . . . . . . . . . . . . . . . . . .. 445
..,
450
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 451
(ECF) bleaching
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 452
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 454
443
445
2. Particle measurement
Chapter IV 11:
Bleaching Shives
and Dirt
1. Background
446
Comment
Method
8-150
c:
::0
o
'\
~ 100
is
'\
'\
"
50
......
--
o
85
87
89
Brightness,9/,
91
93
95
SCAN
fur"
t:tntrmet'C1iII
fIS-
(Z).
Most common
method
C) Determination
of particle
elimination during bleaching
after the addition of larger
amounts of particles to the
pulp before bleaching
(3)
D) light microscope
examination
of
single particle before and after
bleaching
(4)
E) Determination
of particles
bleaching
of size distribution
before
F) IN microscopic
lignin gradients
(5)
and after
determination
after bleaching
G) Continuous
monitoring
contaminants
of
(6)
of
1) on paper strip
H) Determination
of type and
structure of residual particles
(scanning electron microscopy,
(1)
(7)
2) in pulp suspension
3) by on-line plastic
dectector
200
of pulp
T 213 om-85
The concentration
of shives and other
bleachable particles decreases significantly
during bleaching. However, a large reduction in the number of particles does not
necessarily yield a clean pulp because particle elimination is a statistical operation.
This means that an increase in the number
of particles entering the bleach plant leads
to an increase in the number of particles
exiting the bleach plant.
For a given bleaching sequence, a typical relationship exists between cleanliness
and brightness as shown by the example
shown in Fig. 1. Cleanliness improves with
increasing brightness up to a critical brightness above which it changes only slightly.
The critical brightness is often higher than
the brightness needed for a particular paper. Bleaching in the pulp mill is often targeted to the critical brightness to obtain a
sufficlently clean pulp.
Reference
A) Pulp screening
B) Visual inspection
250 ......
tlU!lJS#remenI.
(1)
(8)
SEM)
and there is a relative enrichment of particles, knots, bark (mostly stone cell aggregates from spruce), and inorganic material.
A small quantity of knot particles and stone
cell aggregates in an unbleached kraft pulp
may become the predominant residual particles in a pulp bleached to high brightness.
Furthermore,
particles
evident in the
bleached pulp cannot be observed in the
unbleached pulp: pitch, pollen, and insect
fragments (9, JO).
To determine the relative bleachability of
different particles during bleaching, welldefmed kraft pulped particles have been
bleached in a CEDED sequence (9,lO).The
Fig.3.
SeIJImIrtg eltrrnr
mlemgrwpb
oJ" blMebetl
#mot JItIrlIek
447
(11,13).
448
Pulp Bleaching
Low
b1eachability
and Practice
-Principles
Knots,
compression
wood
.....
. .
0.5
o
0.1
0.2
OJ
0.4
05
Thickness,mm
0.0
0.7
449
Partially bleached
450
1j
~ 01
j
20
10
:~
E
*'
iIJ'
>
.~
.;;;
""
7. Extended delignification
New pulping processes make it possible
to prolong delignification during pulping
(Chap. II I).The result is greater selectivity
with respect to delignification and a much
smaller formation of rejects (Fig. II) (19,
20). In Super Batch pulping, the depth of
delignification in a shive at a given kappa
number has been shown to be about I mm
deeper than in a shive pulped conventionally (19).
8. Oxygen delignification
In laboratory studies, it has been found
that, when an oxygen stage is included in a
bleaching sequence, cleanliness at a particular final brightness may decrease or increase
50
20
..:
'"
10
120min
80 60
40"C
5
0.2
0.2
I
93
92
0.5
I
1
2
k457. m2/kg
I
10
I
0.5
2
k.,,, m'lkg
20
10
67 61 76
64
54
Calculated brightness. % ISO
67
6Z
Flg.!J.
Effect of
brightness.
20
)4
64
76
Calculated
Fig 7. Estl",.tetlllgnlll
~
III IIff 0%_tkllgnlfted }HIrtkle IU IIJuctIoft of cross-stkm tUstllru:efrom tbe }HIrlkle SJlrftree (15).
0.1
0.3
0.1
0.2
Cross-sectiondistance, mm
and Practice
100
-<
-Principles
100
"#. 50
~-
E
c:
c
NO.2
'"
@)
Pulp Bleaching
% ISO
-"""g
tUozIde blellCbIttg
at fllll'Ylflg temperIIlflres tIffd times (9,16).
softtrood
chlorlffe
'5000
100
;f.
50
t,oooo
.f
~..
CII
10
.~
c::
'2
.
a:
!5000
OEIJED
1
0.5
2
m2&g
k057'
87
".".g
s/1IH$ft!r
__trYItimIS-
10
20
64
% ISO
54
O(C+D)IJ-6lHeIIH sofl-M
Ittwft pIIq"'fterell/qrlfUJ
of eIIIorIINtUoxIikfor tlIfferl8g U-
(9,16).
9. Chlorination
Annergren and lindblad (2) have studied the effect of C-stage conditions
on clean-
'00
,..
...
,.
40
SllbstttJllUnl
(2).
more chlorine dioxide in OED final bleaching improved cleanliness. They concluded
that an alternative to hlgh chlorine charge
in the first bleaching stage is to bleach at
economically
optimized conditions to a
higher brightness, mainly by increasing the
chlorine dioxide charge in the final bleaching. In any event, the choice is dictated by
local economic considerations.
10
E
'"'"
t,oooo
8
f
'5000
1
0.1
for WIorwtory
'c
'iij
20
0.0
... <
JI
tltonM
... SCAN
~- 20
'5000
2.0
0.'
of s/1IH$ OJIlIrlgillrlns
clllorIIN
82
76
CalcuIaIBd blighb_.
1'0
6IHd1M sofl-M
92
"
1IIigI8I88.
0.2
452
451
0.2
0.5
10
20
k4571m2Jkg
1\)
7'
80
..
90
.,
93
92
87
82
Calculated
64
76
brightness,
54
%150
Brightness
Fig. 15. Effect ofb~
IJIIrl4bIes011tbe ,."WioIIship behtJetm dellalifIBss llrut brlgbtflBss
(27).
453
454
Pulp Bleaching
-Principles
and Practice
o 0
[J OZ
... OO(EO)IJED
20000
Knot-free chips
Knot-containing
chips
Ca
Na
Fe
Mn
690
32
32
10
3070
1.0
13
390
12. Mixing
High-shear mixers are attractive from an
economic point of view. It is well established that, in most cases, they lead to a reduced chlorine dioxide requirement which
in turn makes it possible to lower the
bleaching temperature (36, 37).
The effect of mixing on cleanliness is not
straightforward. In a study based on a computer simulation of the Dl stage, it was concluded that more efficient mixing decreases
cleanliness at a specified brightness and
temperature (Fig. 17) (38). If the temperature is decreased, the effect is less and, at a
sufficiently low temperature, and in the
presence of a relatively high chemical residual, cleanliness is improved.
. OZP
o
~
00
m
ro
~%ISO
Fig. 16. Effects of shives 011 brlgbtfIBss
W-blucbetl pulps (32).
100
80
60
.c
""
" 40
.n;
E
20
o
40
50
60
70
Brightness, % ISO
80
Pappersttdn.
P.O., Tappi
Pappersttdn.
83(10):
Pap. Can.
6. Axegard,
P. and Jonsson,
V.,
Pappersttdn.
82(10):310
(1979).
7. Karlsson, H., STFI Sweden,
results, 1993.
8. Treiber,
E., unpublished
Svensk
unpublished
results,
Pappersttdn.
1973.
83(14):
Papperstidn.
81(14):
83(12):
i56
15. Germgard,
Pappersttdn.
32. Norden,
S. and Germgard,
V., Svensk
Papperstidn.
96(2):26 (1993).
References
455
6(11):723
(1979).
22. Lindqvist,
B., Marklund,
L.A., Norden, S.,] Pulp
(1986).
A., Lindstram,
Pap. Set. 12(6)
R.V., "Optimum
Part I
S., Carre,
G.,
28. Germgard,
68(4):307
29. Annergren,
V, and Sjagren,
(1986).
T.A., "Ef-
fect of Peroxide
Bleaching on Dirt and
Shives in TMP," International
Mechanical
Conference
Preprints, Tech. Sect, CPPA,
Montreal, 1979, p.145.
unpublished
35. Moldenius,S.,"Mill-scale
operation ofTEF
Bleaching at SOOra's Monsteras Mill, Sweden," International
Non-Chlorine
Bleaching Conference
Proceedings,
Miller Freeman, San Francisco, 1993.
36. Sinn,S.,PulpPap.
58(6):1190984).
37. Kolmodin,
H., Svensk
87(18): 8 (1984).
Papperstidn.
SECTION V:
The Technology of
Mechanical Pulp Bleaching
Chapter 1:
Peroxide Bleaching of
(Chemi)mechanical Pulps
J.R. Presley and R.T. Hill
Solvay Interox
Houston, TX
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 459
2. Peroxide bleaching
2.1 Composition
2.2 Stability
solutions.
. . . ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 459
459
460
3. General description
of peroxide bleaching
4. Peroxide bleaching
chemistry.
processes
. . . . . . . . . . . . . . . . . . . .. 460
. . . .. . . . . . . . . . . . .. . . . . . . . . . .. . .. . . . . . . .. 461
461
462
477
478
480
484
462
463
468
474
477
8. Non-conventional
peroxide bleaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 485
8.1 Refiner bleaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 485
8.2 Alkaline peroxide chemithermomechanical
pulping. . . . . . . . . . . . . . . . . . . . 485
9. Heat- and Ught-stability of peroxide-bleached
pulps
. . . . . . . . . . . . . . . .. 487
9.1 Factors affecting light and heat reversion.
487
9.2 Strategies for controlling reversion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 488
10. Environmental
impact.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 488
457
Pulps
459
Chapter V 1:
Peroxide Bleaching
of (Chemi)mechanical
Pulps
1. Introduction
2.1. Composition
Hydrogen peroxide can dissociate through
ionization or radical reaction mechanisms
as shown by the examples listed in Table 1.
[IJ
[2J
[3J
HP2 -+ 20H.
[4J
(hydroxyl radical)
-N
0
C\I
;;.
+
1.0
0.8
g.....
0.6
460
2.2 Stability
Hydrogen peroxide readily decomposes
under bleaching conditions according to the
overall reaction
[6J
Although the decomposition process is often viewed as a base<atalyzed reaction having the overall form,
HP2
+ HOO' -+ 02 + HO- + HP
[7J
results reponed by Colodette et al. (3) indicate that peroxide decomposition can be
more accurately described as a transition
metal<atalyzed process whose main reactions are illustrated by the sequence shown
in Table 2.
The transition metal-induced decomposition of hydrogen peroxide during bleaching is generally believed to be undesirable
because it leads to a loss of perhydroxyl ion,
a species believed to react with and eliminate chromophores of the type present in
(chemi)mechanicals pulps (see Chap. III 4).
For this reason, control of the transition
'J: 0.4
0
Q.
~
m
0.2
H202
HOO'
0
8
10
11
pH
of #JytIroga perodtIe (1).
12
13
14
Mn+ -+
M(n+l)+
M(n+l)+
+ HO'
+. OH'
+ OH.
-+ Mn+ + HlO + 0>,
M(n+l)+
0>,
+ 2' -+ 02 + Mn+
+ HO. -+ 02 + HO'
(M
= transition
[8J
[9J
[IOJ
[llJ
metal ion)
Pulps
461
462
Table 3. l!1IblMcbetll1rlgbmess
Wood Species
Eastern larch
Balsam fir
Lodgepole
pine
Eastern hemlock
57.3
61.1
White pine
Red pine
5.2.1 Groundwood
and
pressurized ground-
wood
Groundwood pulping processes employ
pulp stones which are covered with an abrasive grit. Debarked whole logs, cut to a uniform length, typically about four feet, are
pressed against the revolving stone and individual fibers and fiber bundles are peeled
away. Although the grit does not cut the
wood as this would produce an excess of
debris (shorter fibers and fines), grinder
pulps nonetheless do have higher levels of
debris than do refined pulps. This is not a
totally undesirable characteristic of groundwood pulps because the high debris helps
contribute to making a smoother, more
opaque sheet, particularly when hardwoods
SGW
PGW
TMP
80
59.4
59.5
41.6
54.5
56.7
45.2
Black spruce
Jack pine
85
Unbleached TMP
Brightness, %150
75
~~70
en
HCOO.
I/J
Q)
-c:
Bleaching
65
C)
.;:: 60
conditions:
3% silicate
.s::.
55
50
0
234
H202,
Flg.3. hlfl-
ofp,dfrl"g}tl'flass
% on pulp
(cbemi)mecbtmklll
jItIlps (8).
Pulps
463
464
etmImt of tIJOOII
sJIks (13).
Wood Species
Metal Content,
Iron Manganese
Hemlock, western
Hemlock, eastern
Aspen, midwest
Spruce, eastern
115
20
55
17
105
110
4
136
ppm
Copper
14
1
5
1
in peroxide
con-
sumption
can be important
in situations
where bleach liquor is reclaimed at the end
of the bleaching treatment and recycled to
a previous bleaching stage.The response of
the PGW sample to pretreatment was much
less pronounced, suggesting the need to determine if pretreatment
was necessary in
this case. Figure 4 also provides an example
of a pulp (CfMP 2) where DTPA pretreatment had no significant effect on brightness
response or peroxide
consumption.
In the
Pulps
465
78
466
o
-a.
Q) 72.0
....
iIi
cfl 71.0
en
(/)
Bleaching conditions:
2% H202, 1.4% NaOH
3% silicate
68aC. 120 min.
20% consistency
Q)
c:
E 70.0
OJ
.;::
III
69.0
0.0
76
0.6
0.8
1.0
1.2
DTPA, % on pulp
PGW
~74
~0
en 72
III
Q)
c:
.E 70
OJ
.;::
CD
68
0
0.2
0.4
DTP A, % on pulp
0.6
0.8
0.6
0.8
100
c..
a.
as 90
0
~0
80
r::
0
70
EE
60
CTMP1
:J
III
c:
0
()
50
C\I
40
0
C\I
:I:
CTMP2
30
0
0.2
0.4
DTP A, % on pulp
Spruce:
CTMP:
3% H202.
0.4
Cl'MP (8).
1.5% NaOH.
2% silicate
OIl brlgbtllt!ss
development
PGW:
2% H202. 2.5% NaOH,
3% silicate
and peroxide
OOtISUmptitm
In the bleaebing
respmue of a peroxide
content (8).
Pulps
467
20
c
16
'c
:J
14
CI)
CI)
Q)
12
~OJ
.;::
III
-Principles
and Practice
CI)
Pulp Bleaching
18
'(ij
OJ
468
10
8
6
0.0
0.5
1.0
1.5
2.0
2.5
3.0
35
30
c
'(ij
whose use is favored in pretreatment applications.The use of organic stabilizers is not,
however, common beca,use of both performance limitations and economics: It is difficult to fmd a more cost-effective stabilizer
than silicate.
5.3.2.2.1 Mechanism of sodium silicate stabilization in the peroxide bleach
ing of (chemi)mechanical pulp
Several theories about the role of silicate
in the peroxide
bleaching of (chemi)mechanical
pulp have been suggested.
These roles include silicate acting as a peroxide stabilizer, metal ion sequestrant, buffering agent, and metal surface passivator.
For stabilization, metal sequestration and
metal surface passivation are two important
silicate functions. Indications of silicate activity as a sequestrant or metal complexing
agent have been reported (15). Experience
has also shown that, even with inclusion of
a pretreatment
to eliminate some of the
metals, the addition of silicate to the bleach
liquor leads to a higher brightness for the
same peroxide application.This is illustrated
in Fig. 6 where the bleaching response at
varing silicate applications for chelated and
unchelated groundwood pulp is shown.
Peroxide residual is also increased by silicate addition (15), suggesting that peroxide decomposition
is reduced, probably
through metal control. There is also evidence indicating that the amount of silicate
applied should be increased with higher
peroxide applications (14) as illustrated in
Fig. 7 (B). The brightness response at varying silicate addition levels is somewhat flat
at low peroxide applications 1%). At intertnediate peroxide applications (3-5%),
the brightness response levels off at 3% silicate addition and, at elevated peroxide application levels (8%), the addition of high
sillcate charges further improves the brightness response.
The inclusion of silicate also allows the
use of some types of mild steel equipment
in peroxide bleaching. Mild steel is not normally used in peroxide service and any
equipment used for bleach liquor storage
or transport of bleach liquor must be made
of compatible materials such as stainless
steel or aluminum. Silicate, however, coats
equipment surfaces, presenting a non-reactive surface for the alkaline peroxide bleach
liquor to contact. This allows the safe and
efficient use of mild steel equipment such
as stock mixers and pumps.
CI
CI)
25
'c
:J
20
0-
CI)
CI)
CD 15
C
CI
-;::
CD
[}.-
---<J
/1
/1
~10
/1
5
0
Silicate,
UMIimI OIIlJrlg"'-
% on pulp
It'bI tit Mff-t
UMlimIlevela (8).
85
80
0
5!2
0
TMP
75
~70
u)
CI)
Q)
Bleaching conditions:
65
3%silicate
~SO.C. 180 min,
CI 60
'i:
CD
20% consistency
55
50
o
Fig.8. Hjfeetof I1yt/t'ogM
~
234567
H202' % pulp
tl/lPlktIIImI011tile IJrlg"'of" sprvee (el1eml}mlHmkt" lnllp (8).
= % NaOH
% Total Alkali
+ [0.115
x %
the relationship
Pulps
469
470
80
Bleaching
~~0
conditions:
3% silicate
60C, 180 min, 18% consistency
u)
70
II)
CD
c:
.s:::.
01
'1::
ID
60
1.0
1.5
(NaOH + 0.115 Na2Si03)/H202
Fig.10. /"fl-
70
0
.s:::. 68
70
W
0
u) 68
II)
CD
c:
.s:::.
01
'1::
ID
,,
u) 62
II)
CD 60
c:
E 58
66
65
0.5
1.0
1.5
2.0
NaOH, % on pulp
resptmse
m tbe peroxIiIe
60
2.25%
NaOH
50
3% silicate
70C, 14% consistency
40
30
~01
.;: 56
ID
54
0.0
80 0..
a.
70
~~2.5%H202,
Bleaching conditions:
90 "C
.9,!
,,
W 64
,,~I
,,
,,
67
CD
.... 66
2.5
bletu:bI",
3.0
TMP(8).
100
-----
--~---------------
, ,.......:=J
I
,I
a.
,
,,
~69
0/ ~
20
10
lIS
'0
0
(ij
:I
"C
'w
N
0
N
:I:
Time, h
Fig. 11. Rellltlmlsblp
beIwJeerJ IJrlgblrless
pille JlMlp (8).
tlerJeloJmltlflt
I"
tbe bletu:bI",
0/ Soutberrt
Pulps
471
Consistency
472
8-10 points
2% HP2
14-16 points
3% HP2
18-20 points
= -k
dC/dt
[HPzror]067[ORj023Ck2.2
[13]
where
~
o
C.
= light
absorption
coefficient
at
= bleaching
[HPzror]
64
I"
tbe peroxIile
bletU:bl"g
= [HP2]
= sum
+ [OOR]
of undissociated
peroxide, mole/L
H202, % on pulp
Fig. 12. EDed
time, min
and dissociated
(8).
= kinetic
rate constant.
Chapter VI:
80
!:Q
473
includes alkalinity levels which, as mentioned previously, vary to some extent with
time and temperature.
Pulps
45C
5.1
75
65C
4.8
70
85C
4.5
474
Pulp Bleaching
-Principles
and Practice
65
iii
(/)
CD
c:
60
.C)
c:
.;::
II)
55
~Total
groundwood-containing
pulps by deinkers.
In addition, peroxide is very versatile for
these applications because it can be used
in the pulper, in a tower as a dedicated post
bleach, or in a disperser operated under
alkaline conditions.
alkali,
% on pulp
4% H202. 5% silicate
30% consistency
To cleaning,
screening,
deinking,
and bleaching
50
o
Pi,. 13.~ eJfeetofl~
(8).
30
60
90
120 150
Time, min
011tIIe"*
ofbrlflllrless
180
210
240
Low temperature
Medium temperature
(1408-175F; 6o-79C)
. Medium alkali
Medium retention
time (2-3 h)
(95'-120F;
35-44C)
. Med. - high alkali
Long retention
time (4-6 h)
\ /
.
.
.
Dump/soak
chest
SJWrIceTMP
Fig. 15. ~I
70
0.4%, DTPA, 2.5% silicate
65
43C. 8% consistency
!:Q
~0
iii
(/) 60
CD
c:
.C)
c:
.;:: 55
II)
High temperature
(ZocrZ10F;S3-S6G)
Low alkali
.""
0.5
Short retention
50
.lWiIIUy.
H202.
1.0
% on pulp
Pi,. 16. Brlglllrless response to jIero%iM applW i.. IN pulpet' of. 70130 ONPIOMGdelnJr slid
(8).
rule 5 ~
H202'
%
unbleached
I
4
~,..
TAl
~ 02
0.8
0.8
3
j
475
The limiting factor in the brightness response of recycled mechanical pulps is ink
removal: even under optimum bleaching
conditions
and with a fresh (under 6months-old) furnish, if the ink is not thor.oughly removed, it can mask brightness
gained in bleaching.An example of bleaching response
in a post-de inking tower
bleaching application based on laboratory
bleaching data is given in Table 5.
Another difference between recycled and
virgin pulps is the alkalinity demand in the
peroxide stage. The alkalinity demand of
recycled fiber is much lower than that of
virgin pulp because most of the wood acids in the fiber were neutralized or removed
when the fiber was first processed into paper. Consequently, the ratio of total a1kaIi
to peroxide necessary for efficient bleaching of recycled fiber is lower than that for
virgin pulps. This is critical to groundwood
pulps which can alkaline-darken if all the
peroxide is consumed before the end of the
bleaching stage.
As in the peroxide bleaching of virgin
mechanical pulps, metals control is essential for effective peroxide perfonnance.This
can be very difficult because of the diversity of fiber sources and contamination from
trash and dirt (ink, particles, soil, tramp
metal) that often finds its way into bales of
waste paper. Aluminum may also buildup
in the pulp mill water loop because the
alum or sodium aluminate that deposited
on the paper during the papennaking process is freed from the fiber during
repulping. The aluminum itself does not
decompose peroxide in the bleaching stage
but, in high concentrations, it can complex
m-r(post-b~
Silicate,
%
Pulps
II[IJIlIeIdImI
(8).
Bleaching
Time, m
Brightness,
% Hunter
120
...49. 5
59.6
60
63.3
476
0
~60
~0
qj
(/)
Q)
c:
-C) 55
J::
':
50
0.5 (0.50)
H202
Fig. 17. Dro-sIIJp ~lfUe
and
0.75 (0.55)
(NaOH),
lllaebi..,
% on pulp
with most or all of any chelant added before the stage. This leaves transition metals
which can decompose
the peroxide,
uncomplexed.
Peroxide stages are often incorporated
into sequences with sodium hydrosulfite or
formidiline-sulfinic acid (FAS). This is especially the case for post-bleaching wood-free
deinked stock. The peroxide stage almost
always precedes the hydrosulfite or FAS
stage and can be economical
if higher
brightness levels are required or if residual
color is present on the fiber. The peroxide
stage provides an initial brightness increase,
while the hydrosulfite or FASstage destroys
the color or gives an additional brightness
increment (Fig. 17).
5.5.4 Peroxide applied in a disperser
Kneader and disc-type dispersers, operated under alkaline conditions, are another
application point for hydrogen peroxide.
The disperser is an excellent mixer and the
high temperature and consistency, up to
90C and 30%, are well-suited for peroxide
bleaching. The disperser can function in
place of the traditional high-consistency
mixer, and the pulp exits the disperser directly into a bleach tower. Even if the additional retention after dispersion is short,
peroxide bleaching in the disperser can
produce a significant brightness increase.
The alkaline peroxide bleaches the pulp
1.0(0.60)
Pulps
477
DTPA
478
Washer
Bleaching
Unbleached
pulp
(H20,
Twin wire
press
liquor
NaOH,
Na2Si03'
H202)
28% BD
peroxide
tower
H.D.
storage
10%BD
Bleach tower
10-15% cons.
12Q-170F
2-4 h
Bleached
Dilution
8%BD
pulp
4.5% BD
Fig. 18. Flowsheet
for st.gle
stage, medl.",
etmslstnu:y,
jIet'rdIk
blueb
plll.t.
4%BD
To paper machine
Pulps
479
mechanical
pulp bleach plant offers a
greater range of brightness response and a
much more efficient bleaching environment
than does a medium-consistency
bleach
plant (see Sect. 7.3).
7.1.3 Two-stage medium-high consistency
bleach plant (with recycle)
The most prevalent (cheml)mechanical
pulp bleach plant configuration for achieving high brightnesses is shown in the flow
sheet in Fig. 20. The first stage is run at
medium consistency to permit the uti1ization of the highest volume of recycled (recovered) filtrate (further discussion see
Sect. 7.3).
I
CD
"0
II:
480
description
50%
23.5
70%
32.9
-52
-63-40
40
Boiling point,
c (76Omm Hg)
of
Density, g/mL (20C)
Ib/gal (68F)
114
237
1.20
9.98
Bleach liquor makeup systems have undergone changes over the past decade.
There has been a movement away from the
traditional cascade makeup systems as described by Andrews in his 1968 survey of
existing (chemi)mechanical
pulp bleaching
technology
(24). Although the cascade
mixer (see Fig. 22) still has utility in bleach
liquor makeup systems, it is not always the
makeup system of choice. In state-of-the-art
(chemi)mechanical
pulp bleach plants, the
cascade mixer has given way to in-line (see
Fig. 23) and/or combination makeup systems. This is largely because bleach plants
have shifted to continuous liquor makeup
Water
Bleached
pulp
4%
cons.
Utilization
t
Fig. 21. FlofllSbut lor II two-stllge peroxIM-byIlf'OSfllftte b~
Na2S04
JmH:eSS.
systMI.
125
258
1.29
10.75
Pulps
481
To
process
NaOH solution
~
Fig. 23. 1.-11_ blMeb llfrwr
"""fI/J
Static mixers
sysm..
482
Pulps
483
484
hydrogen
peroxide
from the mill's
whitewater system. Other chemicals commonly used to acidify peroxide bleached
pulp include sulfuric acid and sodium
bisulfite; however, sulfuric acid does not
destroy residual hydrogen peroxide.
Brightness
Gain
Required,
Points ISO
gain required. The other main species-related impact is the metals content of the
pulp which, in some cases, may require a
special removal or stabilization treatment.
Several common bleach plant configurations in conjunction with the usual brightness gain produced are shown in Table 7.
In general, if the brightness gain desired
exceeds 12-15 points or if the peroxide
application required to produce the desired
gain exceeds 2.5%, then bleach liquor recycling and/or two-stage systems should be
considered
to optimize bleaching economics. It is also possible to perform twostage bleaching without two conventional
towers, for example, by using refiner
bleaching or alkaline peroxide chemithermomechanical pulping system as a first stage
(see below). It should also be recognized
that the recycling of bleach liquor around a
single stage can lead to significant savings
in bleaching chemicals.
01_
Number
of
Stages
bIMdI"""
8. Non-conventional peroxide
bleaching
8.1 Refiner bleaching
Peroxide bleaching can be conducted
etnIftprYltllnrs.
Consistency,
%
Recycle
Wood
Type
Advantagesl
Disadvantages
8-10
10-15
No
HWD or
SWD
10-16
10-15
No
HWD,
easy
8-20
18-25
No
SWD
8-20
18-25
Yes
HWD or
SWD
15,30
Yes
HWD or
SWD
l;-~O
HWD =hardwood,
SWD =softwood
Pulps
485
486
on an intermittent
(campaign) basis and
requires only a peroxide bleach liquor
makeup and delivery system.
chemithermo-
mechanical pulping
Alkaline peroxide chemithermomechanical pulping offers an opportunity to obtain not only a chemithermomechanical
pulp having a higher brightness, but also a
pulp with enhanced physical properties.
The process is flexible enough to be used
in a variety of applications. For example,
alkaline peroxide chemithermomechanical
pulping can be installed in a greenfIeld mill
for the production of market BCTMP. Alternatively, it can be used to upgrade the physical properties of a lower-grade newsprint
TMP, relieving brightness limitations or improving the strength characteristics of the
paper sheet to reduce kraft usage. In either
case, this process can be implemented without the same capital constraints of a conventional
two-stage
bleach plant. An
additional benefIt of the process is the potential for energy reduction resulting from
refIning alkaline impregnated
chips. The
basic process involves impregnation with
an alkaline peroxide bleach liquor in one
or more steps, followed by refining, atmospheric or pressurized. The number of impregnation steps used depends on the final
Chip washing
and
presteaming
Impregnation
Refining
Screening Bleaching
(Single- or (atmospheric)
and
two-stage)
(Single- or cleaning
two-stage)
H202
H202
+
bleaching
NaOH
liquor
DTPA
Rg.
25.
FlmlJsbeet.fur
t.
",.,.
jJerrJzIM cbemitberr1unrrbtmktll
brightness and pulp quality desired. Different variations of the alkaline peroxide
chemithermomechanical
pulping process
may be referred to as alkaline peroxide
pulping, alkaline peroxide
mechanical
pulping and bleached chemithermomechanical pulping. An outline of the process is shown in Fig. 25.
lf the goal is fiber development and only
a moderate (8-10% ISO) brightness increase,
a one- or two-stage impregnation process, in
which low levels of chemicals are applied,
should be evaluated. The results of a moderate two-stage impregnation
on hemlock!
lodgepole pine chips followed by two stages
/1fIIpirtg
process.
in Table
9.
Pulp
1IIbkB. ~o/,,~jJrllJlbkllcW"'''IrIJo-slllge''''''''.~cbMrlt~
~1JIIrtg
ro
H202
bleaching
liquor
process (26).
H202
bleaching
liquor
49.9
Opacity, %
96.6
Freeness, CSF
Bulk, cm3 / g
110
3.05
2.1
41.6
Stretch, %
2.I4
T.E.A.,] / m2
32.4
10.2
Pulmac shives, %
Fig. 24. FIoIlJsbeet 1M' reft-
bletreW"g.
Control
Brightness, %ISO
1.5%
HP2'
1.7% NaOH,
1.92
2.5% Na2Si03,
APaMP
62.8
88.7
114
2.85
2.0
9.4
42.9
2.30
36.3
1.3
Tule,. ~ofIN~of'-efUl
,,",6'bIM:I:
~
palps
ebe"dmeeblllliall
8CfMP
AP CfMP
80
80
245
244
3.4
3.2
9.9
9.7
57
56
Scattering
m'/kg
47
50
0.6
0.1
Brightness,
Freeness,
Shives, %
%ISO
CSF
coefficient,
Pulps
487
hydroxyl groups generating phenoxy radicals which are the precursors of quinonoid
structures
(4,28). Chelation
improves
brightness stability if the complexed metals are washed from the pulp following the
reaction.The chelation and wash stages that
normally precede bleaching therefore serve
to improve color stability.
Peroxide bleaching irreversibly removes
some of the chromophore
systems from
pulp thus reducing the potential for color
reversion. In practice, however, peroxide
bleaching produces, as well as destroys, lignin species that are prone to revert. As a
result, bleaching may have little net effect
on light stability (30). Bleached and unbleached groundwood papers suffer substantial brightness losses even after short
exposure to sunlight. For this reason, highyield pulps, some of which can be economically bleached to mid-80 brightness levels,
are generally unsuitable as a sole furnish for
high-quality papers which traditionally are
made from chemical pulps.
Peroxide-bleached
(chemi)mechanical
pulps are generally more resistant to color
reversion than are similar pulps bleached
with reducing agents because many reduced chromophores
(leucochromophores) are easily re-oxidized in air to their
colored form.
9.2 Strategies for controlling reversion
To date, the most effective means of controlling the reversion of papers made from
high-yield pulps is through the use of fillers
and coatings. Fillers reduce the fiber content in the sheet whIle increasing the visible light-scattering properties of the sheet
(31). Coatings prevent damaging UV light
from contacting the fiber and/or mask the
yellowed fiber (32). Calcium carbonate, titanium dioxide, and bentonite clays are effective for reducing the light-induced
reversion of high-yield pulps.
radicals (OH) by way of a Fenton-type reaction (30). As stated above, hydroxyl radicals abstract hydrogen atoms from phenolic
488
attractive to mills in areas where water discharge regulations are very restrictive.
References
1. Martin, D.H., Tappi 40(2): 65 (1957).
2. Gierer,J.,
20:1 (1986).
3. Colodette,
J.L., Rothc:nberg,
S., Dence,
C.W,] Pulp Pap. Set. 14(6):JI26
(988).
4. Gierer, J., Jansbo, K., Yang, K., Yoon, B.-H.,
Reitberger,
T., J Wood Chem. Technol.
13:561 (1993).
5. Gierer,J.,Yang,
E., Reitberger,T.,
"The role
of superoxide
anion radicals
(0 .;<:) in
delignification," Seventh Internatioo:..
Symposium on Wood and Pulping Chemistry
Proceedings,
CTAPI, Beijing, 1993, p.240.
6. Dodson,
M.G., Bohn, W.L., Meyrant,
P.,
Kouk. R.S., "Impact of sulfonation
level on
hydrogen peroxide bleaching response of
hardwood and softwood high-yield pulps,"
Pulping Conference
Proceedings,
TAPPI
press,Atlanta,
1987, p. 479.
7. Leask, R.A. and Kocurek, M.J., Pulp and
Paper Manufacture,
Vol. 2 Mechanical
Pulping, TAPPVCPPAJointTextbook
Committee,
TAPPI press,
Atlanta,
CPPA,
Montreal, 1987, p. 149.
8. Unpublished
ton, TX.
Hous-
E., Advan.
M.,
Svensk
Pappersttn.85(15):
1968.
25. ReferenceAbitibi description from bleach
plant paper -1985 Quebec Int. Pulp
Bleaching.
26. Sabourin, M.J, and Presley, J.R., "Low
chemical
slkaline
peroxide
TMP
489
29. Gellerstedt,
G. and Petersson, B., Svensk
PappersUdn.
83(11):314
(1980).
Pulps
N., Pulp
Pap.
61(10):139
SECTION V:
The Technology of
Mechanical Pulp Bleaching
Chapter 2:
Hydrosulfite (Dithionite) Bleaching
Michael E. Ellis
Hoechst Celanese Corporation
Charlotte, North Carolina
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 493
495
495
499
500
500
. . . . . . . . . . . . . . . . . . . . .. 501
501
501
502
504
pulp types
510
bleaching.
. . . .. . . . . . . . . .. .. . .. . .. . .. .. . ...
491
511
Chapter V 2:
Hydrosulfite
(Dithionite) Bleaching
1. Introduction
As used in this chapter, the term "hydrosulfite" refers to sodium hydrosulfite or,
more correctly,
to sodium dithionite
(Na2S20~) because this compound is a salt
of dithionous acid. Because the name "hydrosulfite" is found more frequently in the
context of commercial pulp bleaching, it is
used preferentially throughout this chapter.
The recommended
pulp bleaching stage
designation for sodium hydrosulfite is Y.
The use of hydrosulfite as a bleachittg
agent in the pulp and paper industry began
with its addition to groundwood
pulps.
Following the development
of thermomechanical pulping processes, hydro sulfite
was used to bleach thermomechanical
pulp
(fMP) and became the bleaching agent of
choice for all (chemi)mechanical
pulps,
especially in situations where a brightness
increase of 4-14 points was required. The
use of hydrosulfite in pulp bleaching grew
significantly as more TMP was produced to
meet the growing demands for newsprint.
Paper destined for news applications was
bleached to significantly higher brightness
levels as new printing practices (especially
color printing) were developed.
Mechanical pulps, by nature of their processing, contain all the components initially
present in wood and therefore are classified as high-yield pulps. This means that
most of the cellulose and hemicellulose,
together with lignin and smaller amounts
of lower molecular weight organic and inorganic material, remain in the unbleached
pulp. Carbohydrates are essentially colorless; lignin, the other main component of
wood, contains
chromophoric
groups
which impart color to the pulp. In contrast to the bleaching of chemical pulps, a
purification
process in which residual
chemically modified lignin and other materials are removed from the cellulose fiber
at the expense of decreased pulp yield, the
493
objective in chemimechanical and mechanical pulping is to selectively eliminate colorcontributing groups while maintaining pulp
yield.
Many factors affect chromophore formation in mechanical pulps: wood species and
age, storage conditions after cutting, and
exposure to light and oxygen all play a role.
The pulping process itself provides an excellent environment for newly created fiber surfaces to interact with metals and
other chemicals. Groundwood pulping is
known to produce relatively high-brightness pulp. With the onset of thermomechanical
pulping, unbleached
pulp
brightness decreased. It is now generally
understood that the two most significant
causes of this brightness decrease are elevated stock temperature and retention of
metals in the pulp.
The following sections include a detailed
discussion of the factors influencing the
brightness response of (chemi)mechanical
pulps to hydrosulfite, various aspects of
commercial hydrosulfite bleaching including the handling of hydro sulfite in solid and
solution forms, the various modes of its
application to pulp and its effect on the
brightness of different types of pulp and
recycled paper. The chapter concludes with
an analysis of the future directions hydrosulfite bleaching are likely to take.
2. Chemistry of hydrosulfite
bleaching
Sodium hydrosulfite is classified as a lignin-retaining bleaching agent, that is, it selectively
converts
color-contributing
structures (chromophores) in pulp to their
corresponding colorless Oeuco) forms without simultaneously degrading and solubilizing the 1ignin where the color-<:ontributing
structures are concentrated. In contrast to
alkaline hydrogen peroxide, which is an oxidative bleaching agent, hydrosulfite functions as a reducing agent in pulp bleaching.
Hydrosulfite characteristically reacts with
lignin or lignin-derlved carbonyi-<:onjugated
structures typified by those found in orthoand para-quinones, quinone methides, and
the side chain of coniferaldehyde units. The
494
Pulp Bleaching
-Principles
and Practice
0\ J
II
C-~ "
-W
"""
0\
S~H
C-N
N= N
-0-
&"
OH
0II
J
"'
S03H
"""
__
-.
S~H
'-
&"
~
N-~
~H
'-
v
H-("("'(H
(Dihydrazo
Intermediate)
OH
I
N-N -V
&"
~S~H
N-~~
&"
(Amine Fragments)
Fig. 1. l'roJIO$M ~
ftw tile rMtIdImt of" direct dy~ (DIrect Dye 81) IlIitb sodl_
in which
bydrostIlftt~.
Composition
solutions
of hydrosulfite
bleach
[IJ
This radical ion may give rise to sulfur
dioxide and a sulfoxylate dianion, both of
which are reducing agents (2):
S02
SO;>
[2]
Other
sulfur-containing
compounds
present in hydrosulfite bleaching solutions
are introduced
as minor impurities
during
the synthesis of hydrosulfite
or are formed
from the hydrosulfite
during bleaching:
BleachedPulp
2 NaHS03
495
[3]
NaHS03
or by decomposition:
496
+ NaHSO.
(8]
(4]
application
Temperature
Retention
[9]
[6]
2-20Ib.ofpwp~on
(1% by wt)
HydrosWfite
[7]
This compound may have a buffering effect on the bleaching pH but does not participate in bleaching reactions.
Hydrosulfite bleaching solutions usually
contain additives such as anti-oxidants, pH
buffers, chelants/sequestrants (for metal
control), and alkali to obtain the optimum
pH level required for a particular bleaching
application. Although these additives have
no direct role in eliminating color-contributing (chromophore) groups in the pulp
during bleaching they are essential for maximizing the bleaching efficiency of hydrosulfite.
reducing
agent and must be used in a manner which
allows for complete
reaction with all materials capable of being reduced.
Each variable or operating parameter produces a
time and
40-100'C (higher
in pressurized refiners)
30-60 mIn
time
pH
4.5-6.5
Consistency
3-30 %
Chemical charge
The amount of sodium hydrosulfite or
hydrosulfite-contalning
bleaching solution
added to a pulp stock varies from mill to
mill, from wood species to wood species,
and according to type of equipment used.
Generally, 0.1 to 1.0% or 2 to 20 pounds of
bleach per ton of pulp is used. (It should
be noted that a 1% addition refers to a
weight percent addition
based on the
weight of chemicals added per weight of
oven- dry pulp. Therefore, a I % addition
corresponds to adding 20 pounds of chemical to 2,000 pounds of oven dry pulp. This
is more commonly referred to as 20 Ibs/ton
in most North American mills.) As seen in
Fig. 2, there is a limit (ceiling) to the brightness gain that can be achieved by increasing the amount of hydro sulfite applied to a
particular pulp. In the example shown, the
upper limit is about 10 points. Once the
brightness plateau is reached, any excess
hydrosulfite may decompose
to sodium
thiosulfate and sodium bisulfite (see reaction 151 in the previous section).
Temperature
The ideal temperature range for bleaching mechanical pulps with hydrosulfite is
45-6O"C. The temperature range commonly
used to bleach pulp at 3-5% consistency in
12
c:
10
'co
CI
UJ
c:
'0
a.
UJ
UJ
Q)
c:
~CI
'C
Temperature: 60C
Consistency: 3.3%
pH: 5.9
4
2
m
0
0
ng.2. Ilrl&""'- ~
0.2
1.4
1.6
497
Pulp pH
The relationship between pH and the stability of hydrosulfite solutions is well recognized: Lowering the pH leads to a
decrease in hydrosulfite stability; for example, at pH levels < 4, immediate decomposition occurs. Conversely, when the pH
is increased to near 11, hydro sulfite solutions are stable for weeks, provided the temperature remains low and contact with air
is minimized.
Although sodium hydrosulfite has a much
higher reduction potential in alkaline media than in acidic media, mill experience
has confirmed that higher brightness levels are achieved when hydrosulfite bleaching is performed
under mildly acidic
conditions (pH 4.5-6.5). However, hydrosulfite bleaching also can be successfully
conducted under slightly alkaline conditions provided additional bleaching chemical is added to offset the apparent negative
effect of alkali darkening at the higher pH(6).
Retention time
The optimum retention time for hydrosulfite bleaching is 30.60 minutes. As shown
by the plot in Fig. 4, most bleaching typically occurs within the first 10-15 minutes
following hydrosulfite addition. However,
to fully utilize the reductive capacity of the
bleaching agent, sufficient additional retention time must be provided to allow com-
498
Pulp Bleaching
-Principles
c:
'(ii
C>
!/)
c:
'0
0..
!/)
Hydrosulfite:
Temperature:
Consistency:
pH: 5.5
!/)
CD
c:
.c:
C>
.;::
c:
'(ii
C)
!/)
o
o
c:
'0
0..
,/
c::
.t;j
C>
J9
c::
'0
0..
!/)
!/)
CD
".""
".
/' ,.,','
,I,,"
C>
'C:
on brigbtness
tlellelopmertt
pH= 6.0
pH=5.0
pH=4.0
."
0.2
Hydrosulfite,
of ,,,""'1/,,11,
bytlroSfllftte (4).
Consistency:
pH: 5.0
Consistency:
Temperature:
4%
60C
0.4
0.6
0.8
% on pulp
0.6
m tbe blellebl"g
of _them
4%
0.8
Hydrosulfite, % on pulp
Fig. 3. E.I1t of temperature
Stllftte (3).
-',-'
I,,'/"
I""
c::
Fig.5. E.I1t
0.4
0.2
70
time, min
_-".,,,._.>..,'
.,'
".".,,,,,,'"".",."
0
0
60
50
a:I
40
50C
/ ,,' "
I ,I'
1',1'
,I,"
,
/,,'
!/)
!/)
CD
c:
.c:
C)
.;::
./ ,,,'
"
",,'-
30
10
.---------------------.
./''/
20
Retention
./,- 60C
,./
10
Fig. 4. E.I1t of retention tbne on brigbtness tlellelopment I" tbe bletU:blngof smahem pine TMPflJUb bytlroSfllftte (4)
-----------.
0.5%
60C
4%
a:I
m
8
and Practice
pine
has a
499
500
12
c:
'(ij
C>
II)
"E
'0
a.
8
7
10
10% consistency
J::
C>
'C:
m
II)
c:
'0
a.
Temperature: 60C
pH: 5.5
II)
II)
Q)
"
,,
,,,
J::
C>
'C:
m
"
0.2
0.4
0.6
0.8
Hydrosulfite,
011 brl,,,,-
1.0
1.2
TMP bytIro.
""'"
Goodmixing
II)
c:
'0
a.
--- --
c:
J::
C>
'C:
m
""
-- --
"
,I"
"
0.2
0.4
Hydrosulfite,
FI,.7.If/feetof~
Temperature: 60C
Consistency: 4%
pH: 5.5
"
/"
0.2
0.4
0.6
Hydrosulfite, % on pulp
",,. 011brl,,,,-
~loJtrt-I'.
-1fUe (4).
discussed
_-------------------
,,/'--,
II)
II)
Q)
,,"
tion is increased.
Mixing principles and
technology, as they apply to bleaching, are
10
effldaey
~1fUe(4).
011brlt"'-
leveloJtrt-l
responding to low-consistency
bleaching
can be obtained over a wide range of by.
drosu1fite applications (Fig. 6). The benefit accruing
from higher-consistency
hydrosulfite bleaching offers mills the option of reaching the same brightness in less
time with smaller bleaching towers.
0.8
0.6
% on pulp
ill.
of~
pirie TMP
""t"
in detail
...-----------_.
/,'
12
c:
1.4
of 6tnIII1erw pirie
tN W-:"""
_---------
,/,'-,
% on pulp
leveloJtrt-ll.
air
-- "."' ,.
'(ij
C>
Without
c:
,,
Fig.6. B.Jft of ~
-file (4)
'(ij
C>
CD
c:
c:
//---/_.
II)
II)
_---
#'------------------------
in Chap.VI
2.
Hydrosulfite bleaching solutions are usual1y introduced through the suction side of
a stock pump in which the impeller serves
as a mixing device. Pump malfunctioning,
often indicated by noise and vibration, may
imply that poor mixing is occurring.
In
such instances, a brightness loss may be
observed. This problem can be resolved by
the institution of a preventative pump main.
tenance program.
Some mills use in.line mixers following
the addition of the bleaching solution. In
this case, there is concern that dewatering
may actual1y negate anticipated gains from
their use. The recommended solution is to
use a pump which is designed to accom.
modate the addition of chemicals into the
pulp. Such a pump would fluidize the pulp
and enhance the dispersion of the added
chemical introduced into it.
tN "luc6lltg
of_tlJer.
0.8
pirie TMP
""t"
IIytlr'O.
501
66
64
o
~
62
............
......
---- ......
~
Ethylenediaminetetraacetic
'::::.---------------- ---
?f.
U;
rJ)
Q)
60
c:
.C)
c:
'C
CD
acid
------- ~"'.......
Diethylenetriaminepentaacetic
-------acid
.............
...
58
Sodium
tripolyphosphate
56
100
200
300
Iron added,
500
400
ppm on pulp
~
of _Ibent
~u
TMP
CtnI"'''''''g
fMJryiIIg
4, Effect of hydrosulfite
properties
502
it forms a dihydrate that reacts almost instantaneously with oxygen. The solubility
of sodium hydrosulfite in water is about 18%
at 20"C. A 1% solution of commercial sodium hydrosulfite has a pH of 6.5 +/- 1.
Sodium hydrosulfite can decompose when
exposed to air, moisture, heat, or oxidizing
agents. Its decomposition produces both
heat and oxygen; the heat generated can
be sufficient to cause a fire.
Solutions of sodium hydrosulfite are clear
liquids at varying concentration levels. For
long-term stability purposes, the liquid
products are cooled to about 7"C, stabilized
with alkali, and maintained in an oxygenfree environment.
The aerobic and anaerobi~ecomposition of hydrosulfite solutions is described
by reactions [8] and [9] (Sect. 2.2). Although the aerobic decomposition
of sodium hydrosulfite occurs in a relatively short
3'_
I~ICI
on pulp
quick
2'
dloconnecl
GIll.
"'s.>
2XIK:
3X2 -
5, Commercial hydrosulfite
bleaching operations
1*
2.truck
unloedlng
lJnloedll1!J""-'"P
Fig.10.St:bemIIIkIUagrwM
for ~
"-"
ptlmpo
aU slorwgeof
l1y4msulfltesol.1imI
Toproceso
503
H2SO. -+ 4 Na2Sp.
+ NaB02 + 6 H20
[10]
504
NaBH. + 8 NaHS03 -+
4 Na2Sp. + NaB02 + 6 HP
[11]
The sodium borate remains in the hydrosulfite solution, but the hydrogen gas must
be carefully vented to the atmosphere.
Addition Point
4-6
8-10
2-6
9-14
Refiner (single-stage)
Tower (single-stage)
Stock chest (single-stage)
Refiner and Tower (two-stage)
Refiner bleaching
A process for bleaching lignocellulose
material (pulp) with a reducing bleaching
agent in multi-stage refiners was patented
Sodium
borohydrlde
solution
BIn
BIn
Vent
Water
'" Oeuas
IXlJ
Sodllm
blsumt.
To
t
t
)(()(IJI
lank
(jJ
t
t
Static mixer
Sulfuric
acid
I
L
I
I
I
I
J
1L
Caustic
soda
solution
DlnoMng
tank
i
'
L
~
lie
,nrr
pHI
pll".'
tUtlgrwm of II maUap
systtlm
for
soM_
~lftle
bktldmtg
sol.tItms.
gnreraU18g sysltlm.
To storaaelProcess
(11)
tion.
The addition of sodium hydrosulfite
bleaching products into the refining zone
of a TMP refiner was commercially undertaken in North America in the early 1970s
by Bowater Corporation to increase pulp
brightness. With respect to the bleaching
effect of hydrosulfite, the following factors
are critical: pulp temperature, pH, alkalinity, bleaching chemical charge, and effective chelation (12).
Refiner bleaching provides mills with the
opportunity to obtain incremental brightness gains without having to rely on a singlestage hydrosulfite addition step to attain the
brightness objective. In refiner bleaching,
50-95% of the total brightness gain required
is typically obtained.
Refiner bleaching,
combined with a following second-stage
bleach treatment in an upflow tower, can
provide the desired brightness at reduced
cost under more easily controlled bleaching condition than does tower bleaching
alone. An operator needs only to reduce
hydrosulfite addition in the tower to reach
the target brightness.
Hydrosulfite
505
506
Bleaching
Solution
centrifugal
stock pump preceding
an
upflow bleaching tower (Fig. 14). The pulp
moves through the upflow tower in a plugflow condition and is not mixed or aerated.
The tower is sized according to the consistency of the pulp used and the time required
to complete the bleaching reaction. Most
towers are tile-lined and provide a retention
time of 30 to 40 minutes. Brightness gains
from the use of hydrosulfite in tower bleaching typically range from 8 to 10 points.
Stock chest bleaching
Bleaching in a stock chest is similar to
tower bleaching but the bleaching response
is not as favorable. Stock storage chests do
not possess the upflow character of bleaching towers; therefore, it is not possible to
properly regulate the retention time or to
ensure that the bleaching chemicals react
uniformly with the pulp. Because of their
design characteristics, pulp storage chests
usually do not prevent air from contacting
the pulp. As a result, air entrained in the
pulp can consume any unreacted hydrosulfite and cause oxidative brightness reversion of the pulp. Hydrosulfite bleaching
Steam
Upflow
tower
Temperature
r:::J
o confrol
I
1-2 houre
retention
time
Pulp
I
PrInwy
SecondBry
Ratio
control
Ter1I8y
Level
control
Refiners
.......
Latency Chest
Fig. 13. Flowsheet
for refiner
bletu:btng
wltb bytlrrJSIIlflte.
nleached stoc~
to
Level
chest
Fig. 14. Flowsbeet
for bytlrosfIlflte
blellCbtng
paper
In an upflow
tower.
machine
507
gl
508
Pulp Bleaching
- Principles
and Practice
25
r ,--........
c
'Cij 20
C>
UJ
---
Pulp
--1-'
C
'0Q.
UJ
UJ
Q)
C
..._ CIw8t
hydrosulfite addition:
10
"
.-,
Fig.17. Brlgblrlns ~
1
2
Hydrogen peroxide, % on pulp
of,."
system (5).
Up.Iow
,,-Pulp 10
Blond
O.1_8-~~~:-_.
"""".......................
15
.J::.
C>
.;::
II)
Second-stage
BIo8ch
Tower
Cho8I
16
14
C
'Cij
C> 12
UJ
C
'0Q.
UJ
UJ
Q)
C
C>
'C
II)
Refiner
10
S
6
,.-- - -- --
---------
addition
1%
FeraKIde
Bleac:hlng
System
-----------------------------.
"""""'0.5%
::',/,
R_
will
appropriate
resldU81
neulnllzatlon
4
2
0
0.2
Hydrosulfite
0.4
applied
0.6
0.8
in tower, % on pulp
Hydrosulfite
Bleach Solution
Pulp to
Paper
Machine
Blind Chili
509
Because peroxide bleaching is terminated before the peroxide is totally consumed, the residual
oxidant
is first
destroyed so that it does not consume hydrosulfite in the following stage. Sulfurous
acid (82S03)' formed by dissolving sulfur
dioxide in water, or sodium bisulfite
(NaHSO,) is generally used for this purpose.
The neutralizing
agent is automatically
added as called for by in-line pH sensors.
Sulfurous acid both reduces residual peroxide and lowers the pH from the alkaline levels used for peroxide bleaching to the
slightly acidic levels required for optimized
hydrosulfite bleaching. .If sulfuric acid is
added to make this pH adjustment, as is
sometimes done, a separate reducing agent
must be added to destroy the residual peroxide. Although the addition of these two
chemicals may achieve the desired effect,
this approach is more costly than when
'0
a.
U)
U)
Q)
c:
ofslllgle-color}Hl/ler
StI1IIJIles to sodium
35.3
83.4
92.2
94.6
-13.4
-0.8
46.2
2.5
Blue
None
Hydrosulfite
75.0
82.0
83.1
93.4
-4.6
-2.1
-10.6
1.6
6. Application of hydrosulfite to
secondary (recycled)fibers
Red
None
Hydrosulfite
42.5
84.7
73.3
94.6
32.3
0.0
3.2
1.6
Green
None
Hydrosulfite
51.6
68.5
81.3
93.7
-22.3
-6.0
7.8
13.0
50C
3.5%
Color
Chemical
Yellow
L. = Yaxis
a*= Xaxis
b. =
Z axis
.L:
C)
7. Typicalhydrosulfite bleaching
responses for representative
pulp types
'C:
CD
0
0.2
0.4
Hydrosutfite,
resptmse
of dellIied
old -sJIrlllt
(4).
None
Hydrosulfite
Temperature:
Consistency:
pH: 6.5
bydrosuljite
a.'
-c:
Table 1. Resptmse
L"'
'6
C)
U)
Brightness
(% ISO)
c:
'(ij
510
0.6
0.8
1.0
% on pulp
(ONP) pulp
(3).
solutions
Pulp Description
TMP
Spruce
Aspen
Douglas-fir
Hemlock
Balsam
Pine
Hardwoods
+++
+++
+
++
+++
+++
++
Northern
Western
Cottonwood
Pine
Spruce
Hemlock
Northeast
Northwest
SprucelFir
?
++
+++
+++
++
++b
++b
Secondary Fiber
Mechanical Pulp-Containing
Mechanical Pulp-Fn:e
Northern
Western
Southern
Groundwood
CTMP
Other
Bleaching Response
Southern
Kenaf
511
++
+
+
512
References
1. Cotton, EA. and Wi1kinson, G., Adt'anced
Inorganic
Chemistry,
4th edn. WileyInterscience,
New York, 1980, p.535.
2. Atkins, P.W., Horsfield,A.,
pollutants.
Biological oxygen demand
(BOD) and chemical oxygen demand (COD)
incn:ases caused by lignin decomposition
an: not seen because sodium hydrosulfite
modifies but does not degrade or solubilize
lignin in its pulp bleaching process.
M.R.C.,
Hoechst
Celanese
6. Ducharme,
N.R. and Nye, J.E, "Optimum
Conditions
for Bleaching Totally Chlorine
Fn:e Kraft Pulps with Hydrosulfite;
1993
TAPPI Pulping Conference
Proceedings,
TAPPI PRESS,Atlanta, p. 777.
7. Hart, R., Pulp Pap.
8. Hart, R., Tappi
9. Ganguli,
Symons,
55:138
(1981).
64 (3):43 (1981).
54:108
(1980).
10. Voelker,M.H.,The
Bleaching of Pulp CR.P.
Singh, Ed.), TAPPI PRESS, Atlanta, 1979,
p.342.
11. West, W B., US Pat. No. 3,467,574
16, 1%9).
(Sept.
(1987).
SECfION VI:
Bleach Plant Operations,
Equipment and Engineering
Chapter 1:
Pulp Pumping and Hydraulics
Jeffrey lindsay
Institute of Paper Science and Technology
Atlanta, GA
(Currently at Kimberly-Clark Corp., Neenah,WI)
Johan
Gullichsen
Department of Forest Products Technology
Helsinki University of Technology
Espoo, Finland
1. Overview of pumping
Maintenance
........................................
Control and stability issues . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Startup. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Flow metering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
513
521
521
522
526
528
529
530
530
530
530
531
531
531
532
532
532
532
533
533
534
Chapter VI 1:
Pulp Pumping
and Hydraulics
1. Overview of pumping needs
and trends
No other non-Newtonian fluid is pumped
in larger volumes than wood fiber suspensions,and yet these suspensions remain one
of the least understood industrial flows. In
the past, pulp operations at low-consistency
(less than 6%) were commonplace. In the
bleach plant, chemical addition and mixing,
pulp discharge from storage towers, and dilution and washing historically were done
at low-consistency. Conventional centrifugal pumping strategies were usually adequate.Where pulps of higber consistencies
had to be pumped, positive displacement
pumps were the standard, but significant
pumping at elevated conSistencies was generally avoided.
Now, however, there are strong incentives to operate at higher-consistency
wherever
possible. The advantages
of
higher-consistency
include lower energy
costs to pump and heat water, less capital
equipment when diluting and thickening
operations are eliminated, more compact
equipment and facilities, chemical savings
when less diluting water is present during
bleach addition, and decreased effluent
volume (a major environmental
and economic consideration).
Since the late 19505, many bleaching and
transfer systems have employed mediumto high-consistency (10-18%) pumping to
decrease water use, energy use, and pulp
storage space. These "thick stock" systems
accept the various sized lumps of wet stock
and air and displace them into a pipe for
mixing, heating, bleaching, refining, or
transport to storage. In the past decade, a
need has developed to process the higherconsistency pulps at pressures up to 1.4
MPa (200 psi) and with significantly less air
content as newer bleaching processes replace cWorine bleaching.
515
Pulpcurve
516
Pulp Bleaching
-Principles
(~)D
c
I
I
I
I Water curve
(turbulent
flow)
Log velocity
Fig. 1. ~of'-"IossCllroesftwWtllertmil
II /IfIlp SfU/IeIISUm.
and Practice
[1]
4'td
compared
with a dimensionless
( Y'PZI1 )
velocity tenn,
1/6
[2]
't3dD
flows
[4]
519
520
Flow rate
RI.5. '/)JIIaIlmfIrl./ilpl JHItIIP~~.
Centrifugal pumps tend to be inexpensive, reliable, and easily repaired. They are
the mainstay of most processes
in the
chemical process industries, including the
pulp and paper industry.
Centrifugal pumps cannot perform well
when large amounts of gas are in the system unless some strategy is applied to remove the gas. likewise, startup requires that
the pump be primed with liquid to create
suction to pull in fluid into the impeller.
Self-priming pumps, which must be IDled
with fluid before the first operation, are
available.
-Principles
and Practice
(a)
'U
as
Q)
Pulp Bleaching
E
~20
~ 10
o
o
8 10 12 14
Consistency,
%
16
18
20
when Gullichsen and Harkonen (18) discovered that these suspensions can "fluidize" at high shear rates, behaving almost like
water.This is demonstrated in Fig. 3, which
shows data from a rotational shear tester. It
was found that the disruptive shear stress
at which fluidization occurs was a simple
function of consistency, and no obvious
change in mechanisms occurs as consistency increased.
This work laid the
foundation
for centrifugal
pumping of
medium-<:onsistency suspensions (19,20)
which is described below.
Friction calculations in general are done
in the same way as for low-<:onsistency. For
example, some pump manufacturers rely on
a modified form of the Bodenheimer equation (21) which can also be used for lowconsistency flow:
H
= 482
F, F2 F3 C2.33 1""5
. Complete turbulence
D-13
[3]
..:..
0)
~
cD
::3
517
518
pumps
eO
t-
1000
Revolutions, rpm
2000
Fig. 4. Cross uetIlm of" emIrl/rIgtIl pump showing
Fig. 3. RolfillotuIl
pulp
(18).
Irwpeller
In IN ClUIng.
523
524
(a)
(b)
(c)
(d)
FIg. 8. FtnwtX1lllrlln'l:W
3500, (c) C8mmt
"""-consIsteney
S
Defilnwtor
rentrlfuglll
pump
pumps:
(eM Series),
(II)AblstromMC"
(d) ellrller
S"W
521
ered. Positive-displacement
pumps tend to
be more expensive than centrifugal pumps.
The cost may be higher by 50% or more for
a given application. The higher purchase
cost must be weighed against the lower
costs achieved by higher efficiency, less
peripheral equipment, and simpler operation.
If a positive-displacement
pump is damaged by foreign objects or other problems,
repairs can be expensive (on the order of
$30,000 for a typical pulp pump) because
of the precise machining and small tolerances required. In some pumps, small
changes in clearances caused by wear may
significantly decrease pump performance
so maintenance tends to be more frequent
than for centrifugal pumps. Actual service
needs vary widely depending on the type
of pump, the application, and the preventative maintenance program.
4. Pumping
of pulp
4.1 Low-consistency
pulp
Flow disturbances before the pump inlet such as elbows or bends increase the
likelihood of cavitation and increase the
true NPSHR beyond the manufacturer's recommendation. Poor layout of the inlet piping to a pump is a common problem in the
pulp and paper industries, contributing to
the widespread occurrence of pump cavitation. Careful consideration of inlet pressure requirements is essential to designing
a good pumping system. In designing a
pump system, the highest possible pulp
temperature that might be encountered in
the line should be used in calculating the
vapor pressure for NPSH estimations.
Horo and Niskanen (27) found that
NPSHR values or centrifugal pumps were
often not reliable for pulp suspensions because the head required to avoid cavitation
did not follow the expected trend as fluid
temperature was changed. They found that
a higher suction head is needed for pulp
than for water and that the additional head
required increases with consistency. Users
of centrifugal pumps for stock should inquire how the NPSHR value was determined: If it was determined in water flow,
522
Medium-consistency
pumps
centrifugal
Design principles
The advent of modern medium-<:onsistency technology for the bleach plant came
with the development
of Kamyr's Me'''
pump (now made by Ahlstrom) which combined pulp fluidization,
degassing, and
pumping in a single-shaft tower discharge
unit. Gullichsen et al. (18,19) have outlined
the path taken to achieve this goal. The
manufacturer's
current MC"" pumps are
claimed to operate at consistencies up to
16%. Other centrifugal pumps for mediumconsistency
pulp are now marketed by
Goulds Pumps and Sunds Defibrator. These
pumps are described below.
consistency.
Pulp flow out of the pump can be controlled by regulating the pump's rotation
speed with the limitation that the speed be
above the minimum required for network
disruption. Many instalIations use throttling
for flow control. The choice of control valve
is important: Ball sector or v-sector ball
valves are preferred to guarantee stable operation. Full bore ball valves or disc valves
may provide unstable operation. The control valve should be mounted as close as
possible to the pump discharge and have
the same free diameter as the pump discharge.
Centrifugal pumps for medium-consistency pulp generally require few repairs
largely because they are designed to have
large enough clearances to tolerate foreign
materials that might be introduced with the
pulp. They are generally built of stainIess
steel or titanium and can be mounted with
the shaft horizontal or, for tower discharge,
vertical.
The flow velocity in medium-consistency
pipelines is typically near 0.2 m/s. In some
cases, this is not enough to avoid stick/slip
motion or pulsations in the flow, and op-
525
526
Pulp Bleaching
-Principles
4.3 Positive-displacement
and Practice
for the
pumps
Positive-displacement
pumps for medium-consistency have predominantly been
of two types, rotary screw pumps and gear
pumps. Most rotary screw or progressing
cavity pumps for medium-consistency pulp
are twin-screw pumps, but single-rotor progressive cavity pumps are also found in
some installations.
Twin-screw pumps
Twin-screw pumps carry fluid in the
spaces between screw threads. The fluid
moves axially as the threads rotate and mesh
inside a closely fitting housing.The required
pressure gain occurs as the volume between
the threads progressively decreases because
of an axial increase in shaft diameter or an
increase in thread thickness. The decreasing volume pressurizes the fluid.The major
producer of twin-screw pumps for mediumconsistency pulp has been Warren Pumps.
Figure 6a shows an example of such a
pump. Twin-screw pumps were the most
common means for pumping thick stock
before the development of centrifugal medium-consistency pumps in the 1980s and
are still widely used.
Perhaps the main advantage claimed for
twin-screw pumps over centrifugal medium-consistency
pumps is the ability to
handle higher ranges of pulp consistency.
Current technology permits pumping stock
up to 18% in consistency, according to
manufacturer claims, and pumps that will
handle up to 25% consistency are planned
for the near future. Typical week-to-week
variations in pulp consistency do not have
a dramatic effect on pump performance.A
significant benefit for the bleach plant is the
high flow uniformity possible with twinscrew pumps.
Other potential advantages of twin-screw
pumps for medium-consistency
include
lower energy costs and the ability to handle
high gas content in the incoming stock.
Unlike the centrifugal medium-consistency
pump, positive displacement pumps do not
depend on high shear to create fluid-like
behavior in the stock, a process that requires substantial power. This accounts for
part of the energy savings with positive displacement pumps. Because degassing ofthe
stock is not needed, a vacuum pump and
the associated control equipment need not
be purchased with the pump. However,
for some bleaching processes (especially hydrosulfite bleaching), the presence of air is
harmful, so degassing may be needed in any
case. If the pulp is pumped with some air
content, further energy savings may be
achieved because of the friction-lowering
effect of air in medium-consistency
pulp
(30). Apparently, the air acts as a lubricant
between the pulp and the pipe wall, lowering friction. At 14% consistency, for example, the energy savings due to decreased
pipe friction may be on the order of 50%
compared to pumping degassed pulp. One
mechanism that may be important in achieving this friction reduction is the relatively
long dwell time the pulp suspension has in
the twin-screw pump. The shear in the
pump folds in and disperses the air in the
pulp. Much of the air is removed from the
pump by an air bleed valve, but a portion is
still present in the discharged pulp. If the
air is not well dispersed, slug flow and large
pulsations can occur.
Capital costs for twin-screw pumps are
40-100% higher than medium-consistency
centrifugal pumps. Although the pulp is
usually free of harmful foreign objects in
the bleach plant, there may be high maintenance costs if damage occurs. (Foreign
objects that might cause problems are usually the result of poor maintenance; for example, damaged repulper blades that are
not replaced can eventually fail and enter a
pump, or damaged screen straps from a
washer drum may break off and fall into the
pulp.)
Positive displacement pumps tend to do
much less mixing of the pulp than do centrifugal pumps, which is not necessarily a
disadvantage unless the chemical mixing
systems of the bleach line are marginal.
The design of the feed system for a positive displacement
pump is important. If
proper guidelines are not followed, bridg-
527
528
dertsltySlortlp t_
]I1ImJlsfor blgb-
disekrge (Ahlstrom).
a)
:B
~
(b)
0.8
~0.8
0
to
.,...
'(0
>
as -.E 0 .6
-00
as C\I
~ 0.4
c::
o
. 0.6
000
~::I
529
~0.4
:CE
as
Q)
I
0.2
U)
0.2
0
10
12
14
16
Consistency,
18
%
20
500
1000
ADT per day
1500
530
Pulp Bleaching
-Principles
and Practice
531
= Q6P
- 11
[5]
532
Pulp Bleaching
-Principles
and Practice
5.8 Seals
5.11 Maintenance
Pumps used in the pulp and paper industry have some of the highest mean time between failures of all available industrial
pumps, permitting continuous operation
for many months. However, failures still oc-
~ul~ 1~~lic1tions where dilution is undesirable; however, these are associated with
efficiency losses typically on the order of
3% (36).
poorly. It is advisable to keep a spare rotating assembly for every pump to ensure that
pump failures result in minimal down time.
cur, especi1lly
signature analysis.
'.
533
Positive-displacement
pumps do not require regulation and must not be regulated
by a valve.
The principles of pump control and stability are presented in the Pump Handbook
of Karassik et ai. (40).
5.13 Start-up
For pumps with heated fluids, it is wise
to warm up a pump before startup to prevent misalignments or high stresses due to
strong thermal gradients. Garay (p. 124)
advises that all parts of a pump should be
held within 25C of each other. Pumping
hot fluids (fluids hotter than the pump by
35C or more) with a cold or partially
warmed-up pump may damage the pump
severely.
Water hammer can occur during pump
startup, and needs to be carefully considered. When a surge of fluid forcefully impacts an empty elbow or valve, a shock
wave can be generated that can damage the
pipeline, even rupturing
components.
When a pump is turned off, pulp may drain,
resulting in evacuated regions that can contribute to hammering. A solution is to gradually increase the flow on startup, beginning
with closed discharge valves that are slowly
opened manually or by installing automatic
ramping valves on discharge piping. (positive-displacement pumps must not have discharge valves.) Variable-speed
drives, if
available, can be used to ramp the start-up
velocity.
5.14 Flow metering
Magnetic-flux meters, or simply magmeters, are generally preferred for measurement of flow rates in pulp suspensions and
other slurries. These meters do not interfere with the flow, offer high accuracy (0.5%
of full scale is commonly claimed), and can
remain accurate over a wide range of consistencies (low- and medium-<:onsistency
flows).The reading from magmeters is proportional to the velocity of the conductive
fluid (water) passing through a magnetic
field; it does not directly measure the mass
or liquid volumetric flow rate. If there is a
significant amount of gas in the flow, the
534
Acknowledgment
Many individuals and companies provided assistance for this chapter. Special
thanks are due to Elliot Blackwell and Ray
Barufaldi of Warren Pumps; Bruce Conner
of Goulds Pumps; Frank Steffes and Paul
Flickinger
of Sunds Defibrator;
Jeff
Rounsaville
of Ingersoll-Rand;
Kaj
Henricson of Ahlstrom Machinery; Mike
Chervenic of ABS Pumps; Elton Krogel of
Durametallic Seals; Dave Evans of Peak Instruments; John O'Brien of Controlotron;
Tom McDonough of IPST;Thomas Hagler,
Jr., and G. R.Addie of Georgia Iron Works;
Geoff Duffy of the University of Auckland;
Ben Thorpe of James River; and Karol
Kocourek of James River.
References
1. Lee, P.F.W. and Duffy,
22(4):750 (1976).
G.G.,
AIChE
J.
Parker,].,
Tappt
50(5):237
G., Tappt
G., Tappt
6. Norman,
B.G., Moller, K., Ek, R., Duffy,
G.G., "Hydrodynamics
of Papermaking
Fibers in Water Suspension,"Transactions
of
the Fundamental
Research Symposium
at
Oxford. BPBIF, London, 1977, p. 195.
7. Kerekes, R.J and Gamer, R.G., Trans. Tech.
Sect., CPPA 8(3):TR53 (1982).
8. Lee, P.F., "Predicting
Local Velocities
and
Pressure Gradients in Thrbulent Fiber Suspensions,"
International
Symposium
on
Papermachine
Headboxes,
McGill Univ.,
Montreal. 1979, p.36.
9. Moller, K.and Sullivan,
57(3):165 (1974).
M.].O.,
Tappt
535
16. Higgins,
65(3):131
33. TIS 0420-10 "Horizontal End Suction Centrifugal Stock Pumps," TAPPI PRESS, At-
D., Tappt
E., Tappt
E., Niskanen,
V.B., South.
Pulp
T.,
Pap.,
Tappi 61(1):67
1anta' 1988.
34. Homer,
E, PaPier
33(3):93
(979).
communication.
E.T., Pulp
Pap.
SECTION VI:
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
2. General principles.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 539
2.1 Goals of mixing and mixing scales
. . . . . . . . . . . . . . . . . . .. 539
2.2 Pulp suspension rheology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 540
2.3 Mixing gases intI) pilip suspensions
542
3. Mixing in pulp bleaching
3.1 Mixing quality.
3.2
Mass transfer,
544
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 544
reaction
after mixing
rate.
. . . . . . . . . . . . . . . . . . . . . . . . . . 544
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 545
4. Mixersusedforpulpbleachlng
4.1 Low-<:onsistency mixers
4.2 Medium-<:onsistency mixers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3 High-<:onsistency mixers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Mixing Practice.
546
546
549
554
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 554
. . . . . . 554
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 557
5.3 Estimates
quality.
of mixing
of improved
5.7 Troubleshooting.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
mixers
562
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 563
mixing.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
537
Chapter VI 2:
Mixing
and Mixers
1. Introduction
Good mixing is a critical requirement for
effective pulp bleaching.This principle has
been demonstrated in many mills and laboratories where more efficient mixing has
been observed to reduce chemical consumption and improve pulp quality (1-13).
Together, these benefits provide an important economic incentive for achieving good
mixing in bleaching operations.
A discussion of mixing theory and principles can be found in several books (1"423). The fundamentals of mixing in pulp
bleaching operations have been reviewed
by Bennington et ai. (24); a description of
older pulp mixing equipment is available
in an book chapter coauthored by Perkins
and Doane (25) and pulp agitation has been
discussed by Yackel (26).
Many types of mixers have been used in
pulp bleaching applications over the years.
Mixer design has progressed as a result of
practical experience and with increasing
knowledge of mixing principles and pulp
rheology. In addition, as bleaching processes have evolved, so have bleaching
chemical
mixers. For example, the increased use of gaseous chemicals in bleaching has necessitated
development
of
efficient gas-pulp mixers. This chapter reviews these developments as well as the
current technology and understanding of
mixing in delignification and bleaching operations.
2. General principles
2.1 Goals of mixing and mixing scales
The objective of any mixing process is
to commingle two materials to produce a
uniform distribution of one in the other. For
pulp bleaching, exposure of each fiber to
the correct amount of bleaching chemical
must be ensured. To achieve a well-mixed
state, nonuniformities must be eliminated.
539
540
Tllbk
St:llles
I" In"p
blHcbl"g.
Mixing
Dimension
Scale
Designation
Approximate
Size (mm)
Large
Macroscale
>10
Small
Fiber-scale
0.05 - 10
Very small
Microscale
< 0.05
Mixing Achieved
Primarily by
Bulk motion
Laminar and turbulent
shear, diffusion
Diffusion aided by
small-scale fluid motion
Concentration
(8)
Small-acala
(b)
Fig. 1. Process flOflJS Htle etmt:tmlrtltUm
flru:llulof St:llles or tItstUms IHI SJMfI . spec""""
and by diffusion
- molecular
dients. Because fiber suspensions are discontinuous over small distances, it is useful
to define two small scales of mixing: a fiber-scale to represent nonuniformities having a size comparable to fibers and flocs,
and a microscale to represent nonuniformities approaching the molecular level. Although uniformity on the latter scale is
attained by molecular diffusion, it is aided
by clump breaking and stretching (produced by relative fluid movement) which
greatly increases the surface area available
for diffusion. Table 1 summarizes these mixing scales.
The nonuniformities to be removed by a
mixer can be considered the "mixing load."
They may originate in flows external to the
mixer, for example, as flow or concentration fluctuations in the incoming pulp and
chemical streams, or they may be imposed
by the mixing geometry. This latter case is
illustrated in Fig. 2 by two configurations
for chemical addition to a mixer. A scale of
nonuniformity is introduced in both cases
at the point of chemical addition by the distance over which the added material must
be transported to contact and mix with all
of the pulp stream. In the second configuration [Fig. 2(b)] ,the distance is smaller and
therefore imposes a smaller "load" on the
mixer. Consequently, less mixing is required
to attain a desired level of uniformity. It is
important
to recognize
that, although
nonuniformities entering a mixer are caused
by external factors, the mixing load imposed by the positioning of the chemical
addition point is controllable by the designer. Mixing can often be improved by
lowering the mixing load instead of increasing mixer capacity.
rheology
Chemical Addition
Pulp
MIXER
(8)
Chemical Addition
Mixer
(b)
Fig. 2. Ntm-U"iformUies
III' I04tl
tbllt COIfIrIhte
1,,1rfHlMcetl
to tbe ",ix-
lbe
__ I"
ronlaetetl. Tbe
(b).
541
=7.7
32 (I-X)3.4
X 105 C m....
A06
[1]
';42
Pulp Bleaching
- Principles
and Practice
= 7.5
X 103 Cm25
[2]
blMcItIffl
operatltms.
Bleaching Stage
Qperating Conditions
Suspension
Pressure Temp.
Consistency
kPa
C
%
(Absolute)
Cm'
Air content of kraft pulp [28]
10
101
25
15
101
25
20
101
25
Chlorination of kraft pulp
(7.2% equivalent chlorine on pulp)
C~
3
Cwo
12
12
C,J)""
Oxygen delignification
12
(2.2% 02 on pulp)
30
Oxidative extraction
(0.5% 02 on pulp)
(E+O)
12
350
350
3';0
30
50
50
0.18
0.49
0.33
0
0
0
750
7';0
100
100
0.26
0.49
0.26
0.48
450
70
0.11
0.10
700
10
0.6j
0.84
0.62
1100
40
0.23
0.50
0.22
0.49
Ozone bleaching
(1.0%
0;
on pulp,
7"(0
q in OJ 10
30
available
10
30
to dissolve
0.84
543
544
phase mixtures can be created under turbulent conditions as illustrated in Fig. 3(a)
(45). Here it is difficult to identify the gaseous phase although small pockets of gas
can be seen moving in the flow. Increasing
the gas phase above that which can be
handled by the mixer leads to phase separation and poorer contact between the gas
and suspension as shown in Fig. 3(b).
Energy input is required to create interfacial area and maintain a mixed state.Thus,
the quality and extent of mixing depends
on the rate and duration of energy input.
As gas is added to a pulp suspension, the
power that can be applied by a mixer decreases as shown in Fig. 4. In this figure,
the ratio of the power drawn under gassed
conditions (P) to that drawn by water under ungassed' conditions (po..J is plotted
against the gas void fraction for a laboratory mixer operated in batch mode. The
graph shows a rapid decrease in energy input to medium consistency suspensions
with increasing gas content. The upper gas
handling ability of a mixer is dictated by
geometry and is approximately 13% by volume (0.13 gas fraction) in this case (45). In
industrial settings, maximum gas void volumes of around 30% have been reponed
(46-48).
..1.0
D-
e 0.5
c;;
plpBllIIe~",
0.4
0.6
Gas fraction, Xg
0.8
1.0
ps fIII:t-
poeIu!t
(11IIUuted
by lbe
(b)
movIllg wIIb the SIISJIefISItm flow.
"rrow)
A C = 12'J(,SIISJIefISItmwltb X = 0.20 sbows
The
contact
action.
phase
to jn'fH/IIetlon
""'e
of 477 tidily. Tbe ps tUltUtIon" rwte eorresporuIs
IJOItlftwetlon
ofll-3%
t:OIIf/NItWbk
to
COIIto"
f!eIIttoul
~-rellI.foreM
e3drtletlon.
1.') meters
O.lj.
=14.1
.. =12
=14
. =16
""
dm/m.strNm
of the mIIIrVl V4lve follollJlrsg gtIS
sl1IIerN metlll sptIt'ger. Tbe
tUltUtIon flSlllg
vIewIrsg wlruImIJ " Is ').2 em III tiUlmeter. Afully
blellebM lnwft pulp lIt C
WIIS flow-
Cm.'"
0=6
C =8
.6. = 10
tar system is a function of the rates of chemical reaction, mass transfer resistances, and
mixing. In the general case of a three-phase
(gas-water-fiber) reacting system, a number
of mass transfer steps are involved in the
bleaching process. However, one step often controls the reaction rate, and this controlling step must be determined for each
system. Bleaching reactions are complex
and the net bleaching rate may change during the course of reaction or be different in
different pieces of equipment. For example,
the rate-limiting step in pulp chlorination
has been reponed as being chemical reaction (51-54), diffusion through the liquid
film ~urrounding the fiber1l (JJ),and diffusion through the fiber wall (56,57).
Mixer design should take mass transfer
resistances into account. For example, if
diffusion to the center of a floc has been
545
546
(a)
(b)
(c)
(Ntu:letlr
Mtlpetk~)
, ,,'"
_ tuJotIIlMIISIoIIIIlslka (2-3
"""
11M")
IlmnIgb I. CMtM
SJlberk4llydiffus"""
01"'"
trtu:er. lire IrtIar /IHr5 flIbire I.
'"I
'"
'_1ft, lllbik I. urt lI~tIS II~ InIbbles
trrIpJJetllllllblll
SfIS/IeIIsIotI.lIre ermtllhler
boItIIIII I. /'8lp"'" Is spberleIIllI"" 40
tllllmeler. l_ges nuuIe lifter (II) 38, """
(b) 82
'"
(e) 660
""".
"""
tial degree of segregation and chemical concentrations, diffusion distances may be limited to fractions
of a millimeter. This
indicates that flocs should be disrupted in
the flow-through mixers and that assess-
547
548
sIm''''r
11Ch~mical
In
of supasitm
Impeller
tip zone
tbe
""t
"'~ zorres ,.. aeeruII..g order of sbe/Ir:
11IIotlwee
hili, tmpeller,
Bulk
flow
tmpeller tip.
"""
is divided into three zones in ascending order of shear: the bulk, impeller, and impeller tip. Power dissipation in the impeller
tip zone (accounting for only 0.5% of the
vessel volume) is fifty times that of the
mean.The significance ofthis for pulp mixing may be illustrated by examining the av-
High
shear
Pulp
out
to tlMt of /I CST.
Fig. 8. Rototlon
Pulp
in
tmpeller
"'rge-set"e
reclt'CfI"""'g
sel /15 well /15 sbe/Ir
"""
fIJIIIIe of rototl..g I1l1Uies.
bleaching
Dynamic
reagent.
mixers
mixpulp
549
';50
(a)
mixers
Peg mixers
Mixing in medium-consistency
pulp suspensions has conventionally been achieved
by peg mixers. These are tubular vessels
having one or two shafts, with attached
pegs, that rotate between stationary elements attached to the mixer casing as
shown in Fig. 12. As pulp is conveyed
through the mixer, the rotating bars shear
the suspension against the stationary elements. This shearing action creates transport through the suspension and exposes
new fiber surface. Chemicals may be added
ahead of the mixer (as in the Ingersoll Rand
mixer) or distributed
inside the mixer
through appropriately
located injection
ports (as in the Dorr-Oliver steam mixer).
Peg mixers have also been used, to a limited extent, in gas-mixing applications. In
the "swept area" mixer shown in Fig. 13
(77), the design aim is to achieve a target
value of area swept out by the rotating pegs.
In so doing, a given area of fiber surface
per metric ton of pulp is exposed. The
swept area required for different applications has been determined in pilot-scale
studies and found to depend on the bleaching chemical used (50).
(b)
Cblorine
dloxUk
High-shear mixers
In high-shear (high-intensity)
mixers,
chemicals and pulp are mixed during passage through zones of intense shear. The
high shear is created by imposing high TO-
mixer,
shaft
slHm
mixer
551
';52
Pulp inlet
Pulp Bleaching
-Principles
and Practice
Chemical in
~
(a)
Chern.
Fig. 13. Beloit
PUlp out
through a number of bleaching stages' alters pulp properties only very slightly (the
changes in tear, tensile, burst, and freeness
are less than 5-10%). Consequently, the
pulp appears only slightly pre-beaten. In
laboratory batch operntions, the energy
exposure is generally substantially higher
and may need to be considered when evaluating the outcome of bleaching. '
Gas contacting is also carried out with
high-shear mixers. In this situation, the volume of gas to be mixed with the pulp is
(b)
Pulp in
Pulp out
<:).
Pulp out
(c)
Chemicalin
Mixingpin
.-
Rotor
mbIy
Pulp in
(d)
m:izers: (II) AIIIstrom All/mix, (6) Ahlstrom Me Jnlmp (c) Be/oit-Rtlutrltl R Series F
. dJ
J"get'SOlI-RmuI
Hi-SbetIr.
'
""
553
554
Pulp Bleaching
-Principles
and Practice
Pulp out
(t)
Pulp in
(g)
be noted that the Ahlstrom pump is included in this figure. The decaying turbulence produced in fluidizing pumps is often
utilized for mixing purposes.
Mixing in pipe contractions and expansions
Thrbulence can occur wherever a fluid
is subjected to intense power dissipation.
For example, turbulence may oecur during
flow through centrifuga1 pumps or in the
wake of any flow element that causes
boundary layer separation (e.g., partially
closed valves or sudden expansions in process lines). These are flows of decaying turbulence because the power dissipation
required to maintain the turbulent flow is
not sustained. Fluid motion in a pulp suspension diminishes very quickly in decaying turbulence.
For example,
at 3%
consistency, cessation of inter-fiber motion
leads to refloeculation approximately 0.005
second after the turbulence maximum is
attained (27). This refloeculation time decreases dramatically as the consistency is
increased.
Despite the rapid loss of mixing action
in decaying turbulence, it can be used for
mixing in the low- and medium-<:onsistency
ranges. For example, in oxygen-reinforced
extraction, oxygen bubbles from a sintered
metal sparger are mixed into the discharge
flow from a Kamyr MC pump just before
passage through an orifice plate and control valve with good results (81). Indeed,
Cirucci et aI. (82) conclude that this method
permits oxygen to be mixed into mediumconsistency pulp as efficiently as with highshear mixing. While decaying turbulence
from the medium-<:onsistency pump is a key
factor in this mixing, the shear and turbulence induced by the orifice plate and pipe
expansion contribute to the good mixing.
4.3 High-consistency
mixers
Pulp suspensions at high mass concentrations have very little free water present.
Mixing can be achieved by creating surface
area within the suspension to facilitate con-
Fig.
15. High-shear
mixers:
(e)
Kamyr
MC, (j)
S,,1UIs
SM arul
(g) S,,1UIs
T.
5. Mixing practice
5.1 Equipment use in mills
In the 1970s static mixers replaced CST
and dynamic mixers in low-<:onsistency operations; medium-<:onsistency
operations
relied on peg mixers (25). In the early and
mid-1980s, replacement of existing C- and
D- stage mixers with high-shear mixers proceeded rapidly in a quest for chemical savings and increased product quality (13).
High-shear mixers are now common in
medium-consistency
operations. In lowconsistency operations, static mixers continue to be widely used. However, a wide
range of mixing equipment is found in mills.
Mixer installation is highly site-specific and
a wide range of configurations are possible
as illustrated by Pryke (75).
:,
..
!"
..~
i,.
~1
!i
~l
~~ii
"c
it
-6'
:i'
r!~..
~!
~Ir
z
CD
I
... ca
C')
n ~~.
~~CD
nCD
C')
CD
1:"[
~l~
C')
-:r
it.....
_.CD
~3
n.
It
0-.I:
os
tI
:;;
CD 0
AI
~:::
~:
c?1
_c
[
:::~.
Ci1
!!.
i':..
~!-
~VI
VI
VI
Mixer
type
CST
Low
( l.()
.Various
configurations
and
residence times
Comments
%
High
(20-40)
Medium
(8-16)
. In-tower mixers
In-tower mixers
STATIC
.Widely used
. Some applications
turbulent
mixing.
DYNAMIC
Agitated vessels
.Various
.Short residence times
configurations
Peg mixers
High-shear
mixing of pulp
.
.
times
.
.
Fluffers/Shredders
Kneaders
PIPE
CONTRACTIONS
and EXPANSIONS
. Decaying turbulence .
generated by flow
through valves.
Turbulence
created
Expose fiber
surface area
Squeeze liquid
from floes
in MC
...
.
.
cycles of compression
and
and decompression.
557
Pulp Bleaching
-Principles
and Practice
(a)
..
Pulp in
(b)
"In
Che!1'iC81
Fig.17. Hlgb-eonsIstem:ym~
558
Pulp
out
TheKIImyrMDR(II)II1IdS"rulsRotomlxer (b).
I
~
M = sIX
.
L~=1
(Xi
n-l
- X)2
[~
x
where s is the standard deviation of the
measured quantity and x is its mean value.
Other indices have also been used.
Torregrossa (5) used the concept of "charge
deviation," which assumes a rectangular
distribution of chemical in the suspension,
to quantify mixing. For a given mixing quality, the charge deviation reported is smaller
than the value of M.
Before comparing the results of different
studies, the sample volume used in determining the mixing index should be known.
Figure 18 shows a set of test results in which
M was determined as a function of sample
size and mixing time in a batcb-operated
laboratory mixer (89). This figure shows
that sample size affects the value of the
mixing index measured. Therefore, sample
0.1
"'"
'0
5
C>
c:
'x
:E
8
9m.min
0=2
0=5
6.= 10
. =20
0.01
10
Sample
100
size, cm3
Regardless of the sample size or the mixing index used, the literature reports large
differences in macroscale mixing quality as
shown in Table 4. This table shows that
macroscale mixing varies within a particular mixer group and that mixing can be significantly improved by using high-shear
mixers in place of static, peg, and tower
mixers. This observation seems to contradict the earlier statement that high-shear
mixers do not achieve macroscale mixing.
However, the improved macroscale mixing
occurs because of the reduction in mixing
load resulting from improved chemical addition, akin to that illustrated in Figs. 2(a)
and 2(b). Direct evidence for this view has
been provided by Breed (85) who demonstrated that the macroscale mixing efficiency of an Ingersoll-Rand Hi-Shear mixer
could be substantially improved by optimizing the point of chemical addition.
Fiber-scale mixing assessment
At the fiber-scale, 0.05-10 mm, a number of techniques have been used to measure mixing quality. Paterson and Kerekes
(90) developed a method to assess fiberscale mixing using a micro-sampling technique. The test was developed
for
chlorinated pulp suspensions at low consistencies and consists of removing a series
Chapter
559
560
Pulp Bleaching
Ttlble 5: 111t'_ml
-Principles
of fiber-sult'
and Practice
mLnllB """Illy.
Intensity
e::
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p.,
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e::
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two static
0.12
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Mill I
0.12
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~~'-"
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~~.c:U
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t~iI
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~The results
50, I, M.
==
of mill measurements
tained by Paterson
and Kerekes
Teodorescu
and Liebergott
(93)
ob-
(92) and
are sum-
energy expenditure
as expected.
However,
as shown in Table 5, the measured
segregation values were higher than those found
previously
for the low-consistency
suspen-
ficulty
.....
..~~<:!
.~
o.
~~C
~:;
~'"
'"
0.27 - 0.45
~'"
~~~R
p.,~ ~~00p.,
- 0.11
- 0.22
- 0.24
- 0.83
- 0.58
'0IU
'"
p.,
~~~..
e::
~~'0
~IU
t-.....
0.00
0.00
0.00
0.23
0.09
'Mixing Index, M.
.!:S
E5
~..;0 ~.8~
0.00 . 0.30
1.15
1.48
0.48
900 rpm
:E ..
0.09 - 0.18
0.03 - 0.11
0.25
0.14
High-consistency suspensions:
Kamyr MDR (Frotapulper) (94)
Hobart lab mixer (94)
30 s mixing
60 s mixing
240 s mixing
~laboratory high-shear (105) 1800 rpm
00
IU
~p.,
ON
$
0
0.12-0.14
0.00 - 0.23
IU6
0.09
I,
Range of Results
0.0
0.67
'
0
e::
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'"
of Segregation,
Average
,Q
~'3
00
~E
:8
~~~:;E
0.07-0.16
which
may be
poor mixing
was sus-
fiber-scale
mixing
in high-
of creating
fiber-scale
uniformity
as
~suspensionconsistency is increased.
Microscale mixing assessment
Chemical reactions are affected by mixing at the microscale level. The turbulence
rate at which
reaction
proceeds
561
562
Pulp Bleaching
-Principles
and Practice
Tuk~~m-~m~u~m~~~~M~
Mixer
Laboratory mixers
Hand mixing
High-shear (37)
Quantum mixer
(256 g pulp, 2600 rpm)
Fluffer
Hobart (94)
Industrial mixers
Stirred tank (CST)
Agitation vessels
Static
Static
(Komax)
Peg
In Tower, Radial (5)
Ahlstrom, AhImix (106)
Beloit-Rauma, R-Series
Ingersoll-Rand, Hi-Shear
Kamyr MC
Soods SM
SundsT-25
Kamyr MC pump
(pilot plant) (49)
Valve and pipe expansion
(pilot plant)(49)
Power Dissipation
(W1m3)
Energy
(M]lt)
2xlO'
5 x 10'
1.8 x 10.
4.5 x 10'
1.1 x 1()6
2.2 x 1()6
1.2- 1.6 X 105
7.7 x 10'
120
90
180
63
160
310
50 - 200
II -86
Consistency
(Cm,%)
Residence
Time (s)
3
10
10
5
10
15
25-40
28
180
180
10
10
10
10
40 - 200
30 - 240
2-3
4
2-3
10
10 -12
8 - 12
8-20
10
9-16
9 -14
9 -14
18 (max)
150- 400
3-5
4
10-12
8
0.03 - 0.2
2-4
-.05
0.2-0.9
0.025 - 0.05
0.05 - 0.2
8-11
0.3 - 0.5
4-5xl()6
13 - 18
8 - 11
0.3 - 0.4
1 - 3 x 1()6
9 - 11
600
2 - 4 X 10'
3 X 10'
5-9
1 X 105
8 - 11 X 10'
1.7 X 105
1-6xl()6
4 x 1()6
4
11- 15
13
2-6
13- 28
8 - 15
14 - 43
9 -18
3-6
5.5
6-12
4 - II
5
x 107
x 1()6
X 107
X 107
ABNiIson
20-35
3-6x
25 - 50
3 - 7 X 107
(94)
26 - 27
25 45
107
8.6 - 17 x 10'
60-90
22 - 65
400 - 700
70 110
'To convert to horsepower days per metric ton multiply by 0.0155. Unless indicated otherwise, the data
for this table were obtained from reference (24). estimated through consultation with equipment suppliers, or measured directly.
t = 12.7;/ Q.l/E)
= 0.4
s but varies
locally
throughout the mixer. Taking again the example of pulp chlorination and using t as
t , in both cases t It 1 and mixing rate
at this scale will ~ot mcontrol the outcome
of bleaching.
563
tinued agitation even though the net reaction rate is lower for shives than for pulp.
Shives are isolated regions of great chemical demand within the suspension; they
deplete the chemical supply in their vicinity and diffusion alone cannot meet the demand. Continued
mixing maintains
a
uniform chlorine concentration throughout
the suspension which aids shive removal
without affecting pulp quality.
In medium-consistency
oxygen bleaching, there is a need to maintain a homogeneous gas-fiber mixture for the duration of
the reaction. Premature cessation of mixing leads to phase segregation, loss of contact between the oxygen and the pulp, and
reported poor bleaching. In this case, prolonged gentle agitation improves bleaching.
Finally, ozonation is a rapid reaction. In
this case, once mixing of sufficient intensity (rate) and duration are supplied, increased mixing does not improve bleaching.
Mixing also plays a role in the outcome
of bleaching reactions where multiple products may be formed. Earl (37) measured the
formation of AOX during laboratory chlorination using manual and high-intensity mixing. He found that the formation of AOX
was reduced when high intensity mixing
was used. This may be attributed to the increased rate and/or quality of mixing produced by the high-shear mixer.
Although laboratory studies provide indications of what may be expected in mill
situations, laboratory mixing generally uses
more energy and consequently
achieves
better mixing than in the mill. Studies made
under conditions closer to that experienced
in the mill are needed to confirm the relationships indicated above.
564
Pulp Bleaching
-Principles
and Practice
mixing
quality
can be reported
as M
=0.30.
improving
mixing
to M
=0.10
14
12
~10
CD
D
E
OJ
c:
to
a.
a.
to
8
M
0.60
0.50
0.40
0.30
02(J010
~6
o
357
565
Acknowledgments
References
1. Schlumberger,
(1%1).
't
566
18:8
7. Pattyson, G.W:,"Kamyr MC Mixer for Chlorine Dioxide Mixing at Great Lakes Forest
Products, Thunder Bay, Ontario;
1984
Annual Meeting Preprints, Tech. Sect.,
CPPA, Montreal, p. A63.
8. Pettersson, B., "Bleaching is Improved by
Efficient Mixing in the Chlorination Stage,"
1985 Annual Meeting Preprints,Tech. Sect.,
CPPA, Montreal, p. A105.
9. Reeve, D.W., GuIlichsen,].,
Pu, C.M.,
Magued, A., Earl, P.F., Rapson, w:o., "Medium Consistency Chlorination in a laboratory Mixer; 1985 International
Pulp
Bleaching Conference Proceedings, CPPA,
Montreal, p. 193.
10. Abercrombie, D.A., "CD and 01 High Intensity Mixers Reduce Bleaching Costs at
Westar;Pacific Coast Branch Spring Meeting Preprints, Tech. Sect., CPPA,Montreal,
1986.
11. Cameron, M.,"Sunds High Intensity Mixer
Performance on CD and 01 Stages," Pacific Coast Branch Spring Meeting Preprints, Tech. Sect., CPPA, Montreal, 1987.
12. Robitaille,
M.A., Pulp
88(4):Tl09 (1987).
Pap.
Can.
and Appli1975.
Atlanta,
p. 721.
0..
Tech.
Svensk
E., Tappi
36. Bennington,
c.P.]., "Mixing Pulp Suspensions," Ph. D. thesis, The University of British Columbia, Vancouver, BC, 1988.
37. Earl, P.R, "The Chlorination
of Softwood
Kraft Pulp in a High-Intensity
Laboratory
Mixer; Ph.D. thesis, The University
of
Toronto, Toronto, ON, 1990.
38. Bennington,
].R., Can.]
39. Gullichsen,].,
Harkonen, E., Nishaneni,T.,
Tappi] 64(9):113 (1981).
40. Harkonen, E.]., "Variables Influencing
the
Power Consumption
in Medium Consistency Mixing," 1985 TAPPI Medium Consistency
Mixing Seminar Proceedings,
TAPPI PRESS,Atlanta, p. 45.
41. Scallan,
A.M., Carles,
Pappersttdn.
75(17):699
].E.,
(1972).
Sliensk
42. Bouchard,].,
Nugent, H.M., Berry. R.M.,
Tappi 78(1):74 (1995).
43. Munro,
(1987).
RC., Pulp
Pap.
Can.
88:228
4<;.Bennington,
(1993).
c.P.]., Tappi
J 76(7):77
46. Greenwood,
B.F., and Szopinski,
R.,
"Ozone Bleaching Technology
'92," 1992
Non-Chlorine
Bleaching Conference
Pro-
Miller Freeman,
San Francisco.
47. Henricson,
K., "Modem Bleaching Technology," 1993 Non-Chlorine
Bleaching
Conference
Proceedings,
Miller Freeman,
San Francisco.
48. Miller, B., Shackford,
L.D., Minami, S.,
"Oxygen, Peroxide
and Ozone Process
Equipment," 1993 Non-CWorine Bleaching
Conference
Proceedings,
Miller Freeman,
San Francisco.
49. Francis,
(1993).
D.W, private
communications
50. Meredith,M.D.,"Application
of Swept Area
Mixers," 1985 TAPPI Medium Consistency
Mixing
Seminar
Proceedings,
TAPPI
PRESS, Atlanta, p. 39.
51. Chapnerkar,
Y., "A Kinetic
CWorination
of Unbleached
Ph.D. thesis,
University
Gainesville, FL (1%1).
Study of the
Kraft Pulp,"
of Florid~,
L.L.,
C.B., Tappt
E.G., Tappi
Tappi
R.]., Tappi
Pulp Pap.
64. Nienow,A.W,
and Elson, T.P., Chem. Eng.
Res. Des. 66:5 (1988).
65. Walker, 0.]., and Cholette,
Mag. Can. 59:113 (1958).
A., Pulp
Pap.
(1%6).
567
72. Bates, R.L., Fondy, P.L., Fenic,}.R., in Mixing, Vol. 1, (Y.W Uh1 and ].B. Gray, Eds.),
Academic Press, New York, 1%6,pp.lll178.
73. Chen, S.]., and Wong. c., "Improved Pulp
Bleaching by an Inline Motionless Mixer,"
1973 International
Pulp Bleaching Conference, CPPA, Montreal, p. 25.
74. Cybulski, A., and Werner,
Eng. 26(1):171 (1986).
75. Pryke, D.C., Tappi]
72(6):143
(1989).
76. Swenson,
P.A., "High Consistency
Pulp
Bleaching
with the Static Mixer Unit,"
1976 TAPPI Alkaline Pulping and Testing
Conference, TAPPI PRESS,Atlanta, p. 175.
77. Torregrossa,
L.O., Bentue!zen,
j.M.,
Crosby, G.D., Meredith, M.D., Bepple, H.,
U.S. Patent 4,298,426 (Nov. 3,1981).
78. Bennington,
c.P.j., and Seth, R.S., "Response of Pulp Fibers to MechanicalTreatment During MC Fluidization," Transactions of the Ninth Fundamental
Research
Symposium
(C.F. Baker
and V.W.
Punton,Eds.),
Mechanical
Engineering
Publications,
London, 1989, Vol 1, p. 87.
79. Seth,
R.S., Francis,
C.P.].,APPITA
46(1):54
D.W., Bennington,
(1?93).
<;68
(1984).
90. Paterson,A.H.].,
and Kerekes,
Pap. Sci. 11(4):108 (1985).
91. Dankwerts,
(952).
P.Y., Appl.
R].,J
92. Paterson,A.H.].
and Kerekes,
Pap. Sci. 12(3):)78 (1986).
93. Teodorescu, G., and Uebergott,
communications,
1987-1988.
94. Francis, D.W., and Kerekes,
Pap. Sci. 16(4):JI30 (1990).
R.}.,J
R.J.,]
%. Bennington,
c.P.]., and Thangavel,
Can.] Cbem. Eng. 71:667 (1993).
j.R.,
Cbern.
Eng.
Pulp
N., private
97. Bourne,
(1983).
Pulp
Sci.
Pulp
Cbem.
Y.K.,
38(1):5
98. Liebergott,
N., Trinh, D.T., Poirier, N..
Crotogino,
R.H., "CWorination
of Pulp
The Effect of Mixing Intensity, CWorine
Concentration
and ReactionTemperature.
Part I: CWorine Water -Pulp System," 19R4
TAPPI Pulping Conference
Proceedings,
TAPPI PRESS, Atlanta, p. 359.
99. Hsu,].C.L., and Hsieh,J.S., "Mass Transfer
and Kinetics of Oxygen Delignification
at
Medium
and Low Consistencies
with
High-Shear
Mixer," 1989 TAPPI Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 223.
100. Hurst, M., Tappi]
76(4):156
(1993).
].K., private
R.]., Tappi]
communication,
Consistency
Corporation.
Mixer Bro1991.
570
SECTIONVI:
Bleach Plant Operations,
Equipment and Engineering
Chapter 3:
Washing and Washers
Authors
571
2. Fundamentals
of pulp washing.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 571
2.1 Dilution/extraction
and displacement
washing.
. . . . . . . . . . . . . . . . . . . . . . . 571
2.2 Washer performance
parameters
'. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 572
3. Washing equipment
3.1
3.2
3.3
3.4
3.5
3.6
3.7
.............
Vacuum drum washers.
.......
Pressure washers.
............
Wash presses.
...............
Atmospheric
diffusers.
...... ..
Pressure diffusers
............
Comparison
of washer efficiencies.
Proper sampling around a washer
.
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575
575
578
579
580
581
582
582
6. Control
of bleach
washers.
..............
..............
plant. . . . . . . . .
bleaching stage.
and pitch
9. Defoamers
and drainage
10. Washing
bleached
.
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585
585
585
585
585
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
7. Material selection
for bleach washers.
...
7.1 Oxygen delignification
washers.
.....
7.2 Chlorine/chlorine
dioxide washers
7.3 Alkaline extraction
washers.
........
7.4 Hypochlorite
washers.
.............
7.5 Hydrogen peroxide washers.
........
7.6 Electrochemical
protection
for stainless
7.7 Manufacturing
considerations.
8. ExtractIves
....
....
....
...
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 586
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 587
587
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 588
steel equipment
. . . . . . . . . . . . . . . . 588
588
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 589
aids
mechanical
591
and high-yield
569
pulps
. . . . . . . . . . . . . . . . . . . . 592
contributed
in the following
P.A.Turner:
LH. Allen:
S.L Allen:
S. Clarke:
R.W. Cunningham:
E. Dylke:
C. Hastings:
T. Picaro:
N.A. Poirier:
R.C.Reid-Bickne~
equipment,
Extractives
and pitch
Defoamers
and drainage
Material
Washing
washing,
selection
areas:
Control
of bleach
aids
for bleach
washers
equipment,
Brown stock
Bleach plant washing
and post-oxygen
delignification
washing
and high-yield
pulps
bleached
Fundamentals
mechanical
of pulp washing
washers
de lignification
Chapter VI 3:
Washing
and Washers
havior of
defoamers
followed
bleached
pulps.
571
The primary objective of all pulp washing operations is to remove soluble organic
and inorganic materials. Dissolved material carried with the pulp to delignification
and bleaching stages can be deleterious by
impairing the delignification or bleaching
and by consuming costly bleaching chemicals with the result that the end product
may be a pulp with lower brightness or
lower strength.
It is necessary for the reader to possess a
basic understanding of the principles and
definitions of pulp washing before equipment design, operation, and optimization
can be discussed. Parts of the section which
follows are taken from a paper by Crotogino
etal. (1).
2.1 Dilution/extraction
and displacement washing
Dilution/extraction and displacement
washing are the two basic operations that
take place when pulp is washed (Figs.1 and
2, respectively). All pulp washing equipment described in this chapter performs
Clean
pulp
\ !
...
...
... "
...
"
Dirty
. water
...
Mix
Fig. 1. Sebem4tk dUlgrtlm of dtl"tltntlexlrlletton
Drain
wabt"g.
Clean
water
Clean
pulp
,-:f
Clean
water
1. Introduction
Dirty
pulp
572
Press
I '
,--,,"1,
I
Dirty
pulp
I_~::_,,_~-~_~?~
wabt"g.
one or both or these basic operations. Commercial washers that depend on dilution!
extraction alone include presses for washing chemical pulp and screw presses and
twin-wire presses for washing (chemi)mechanical pulp. Washers that use a combination
of dilution/extraction
and
displacement washing include pressure and
atmospheric
diffusion washers, vacuum
drum filters, wash presses, and pressure
washers such as the Compaction Baffle Filter (CBF) and the Drum Displacement (DD)
Washer.
In dilution/extraction
washing, an unwashed pulp slurry is diluted and thoroughly mixed with clean wash water or
weaker wash liquor and then thickened by
filtering or pressing (Fig. 1). The washing
efficiency depends primarily on the consistency to which the pulp is diluted and thickened. The amount of soluble organic and
inorganic material remaining in the thickened pulp can be easily calculated if it is
assumed that the solute is split in the same
proportions as the liquor although deviations from this simple picture of dilution!
extraction washing can be caused by incomplete mixing. Efficiency also depends on
the extent to which solute has been sorbed
onto the fibers and the time required for
solute to diffuse out of the fibers (1).
''''''1'-'
I_';'_~_-=--~--'-
DIrty
water
In displacement washing, the liquor in a
pulp mat is displaced in a piston-like fashion with weaker wash liquor or clean water (Fig. 2). Mixing at the interface between
the wash liquor and the liquor being displaced should be minimized to achieve ideal
displacement washing. If no mixing takes
place, it is possible to remove all of the solute by displacing one volume of the liquor
in the pulp pad. In practice, thorough washing cannot be achieved using the principle
of displacement
washing alone because
there is always some mixing at the interface between the liquor in the pulp and the
wash liquor and because some solute is
trapped within the fibers. Variables such
as displacement velocity, pulp pad thickness, pulp pad consistency, and temperature have been shown to have an effect on
displacement washing efficiency (2-7).
Filtrate
573
Wash water
574
_ V.. YI
~Vz,Yz
Lo,Xo
Washer
L., X1_
p
Fonnula'
Dilution Factor, DF
DF =V,-L,
Washed pulp
pulp
filtrate stream, metric tons of liquor/oven dry (o.d.) metric ton of washed pulp
pulp stream, metric tons of liquor/o.d. metric ton of washed pulp
Yt, Y,=
concentration
concentration
Fig. 3. ScbemiIIk
W=VtlLo
WashYie1d,Y
Table 1 lists the three most common Rarameters used to describe the amount of
wash water used and the efficiency of solute removal in pulp washing operations. Of
these, dilution factor (DF) is the only one
that is defined in tenns of the weight of pulp
being washed. DF represents the amount
of water that is added during washing over
and above the volume of water in the pulp
pad and provides an indication of the evaporator load attributable to brown stock and
post-oxygen washing and the effluent volume from open washing stages in the bleach
plant. For displacement
washing, a DF
equal to zero implies that the liquor in the
pulp pad was displaced by an equal amount
of wash liquor. When pulp is washed with
less water than the amount leaving with the
pulp, the dilution factor is negative.
The wash liquor ratio (R) is defined with
reference to the liquor leaving with the
pulp. R equals V 2 IL, which is the ratio of
shower water applied ' on the washer to the
flow of filtrate leaving the washer with the
washed pulp. For displacement washing,
an R equal to 1 implies that the liquor in
the pulp pad was displaced by an equal
amount of wash liquor. The weight liquor
ratio (W) relates the filtrate flow rate to the
liquor entering the washers with the pulp.
Rand Ware approximately
equal when
there is no change in pulp consistency
through a washer.
Table 1 lists the two ratios commonly
used to describe the amount of solute re-
R =V/Lt
= 1- !b
Loxo =
Loxo
Ratio, DR
DR
Est=
log (1+
(1
- EDR)
and ICF =
XI
y,
x" -
log !:Y(Xo - Yt )
L, x, -y,
where
Displacement ratio for standard inlet consistencyof 1% and discharge consistency of 12%
= Xo -
- Cst
where Lst = 100Cst
~)
= (1
- DR)
DCF
(DCF)
(ICF)
100 C
7.33 (C~
99 (Ll + DF)
LI (99 + DF) - L. (99 - L,) (1 - DR)
:VI,VZ = filtrate stream, metric tons of liquor/oven dried (o.d.) metric ton of washed pulp;
pulp stream, metric tons of liquor/o.d. metric ton of washed pulp;
Lo' Lt
concentration
of dissolved solids in pulp stream, kg of dissolved solids/metric ton of liquor;
XO,x\
concentration
of dissolved solids in liquor stream, kg dissolved solids/metric ton of liquor.
Y1,Y,
=
=
performance
in terms of a hypothetical
washer operating at 12% discharge consistency that has the same dilution factor as
the actual washer. Loss from the hypothetical washer must be the same as that from
the actual washer. Loss in this case is dermed as the difference between the weight
of dissolved solids leaving with the washed
pulp stream and the weight of dissolved
solids entering with the wash liquor.
Both E and EDR are useful tools for comparing th~ performance of washers or wash-
Efficiency Factor,
E"
1.2 - 2.5
0.58 - 0.77
Decker/rewasher"
Compaction baffle filter
0.9 - 1.5
0.50 - 0.58
4.5-4.6
0.80 - 0.85
6.5-8.3
0.95 - 0.98
Rotation
Face wire
~,
/.,
/"
3.0-3.7
0.76 - 0.90
Two-stage atmospheric
diffuser
5.9 - 7.4
0.92 - 0.96
0.87- 0.92
~.
pipes
4.5-6.0
~\,~..
Internal
Pressure diffuser
for service
~ Worm drive
..;i~
Drop leg
'""" Valve
/?""7'J
Trunnion
"- Drum
One-stage atmospheric
diffuser
0.83 - 0.86
Wash press'
576
Corrugated
Equivalent Displacement
Ratio,EDR
Modified Norden
Equipment Description
575
in an unbleached
softwood
solids as the
basis. Dilution factor 3. (Infonnation courtesy SandweU Inc. and H.A. Simons Consultants Ltd.).
bA decker/rewasher is a simple vacuum decker, or thickener, that bas been converted to a washer by the
addition of shower bars. It functions much like a vacuum drum filter except that the consistency of pulp
leaving the drum is generally lower.
,
Values of E. for wash presses are very low because solute removal is achieved mostly in the final
dewatering step.
ing systems (Table 2). EDR is easier to understand because it is directly related to the
fraction of solute removed; E ,on the other
hand, expresses performan;e
in terms of
an equivalent number oftheoretica1 stages.
One advantage ofE" over EDR is that the E..
for the overa1l wash system can be easily
calculated from the E.. values of the indio
vidual stages.
3. Washing equipment
The five most common types of washers
used in oxygen delignification systems and
in bleach plant operations are described in
this section in the following order: vacuum
drum washers, pressure washers, wash
presses, atmospheric diffusers,and pressure
diffusers.
It is important to emphasize that wash.
ing equipment
should be selected only
when its design specifications meet the requirements for a particular operation. The
capital and installation costs of washing
equipment are important when consider.
ing a purchase, although several factors can
outweigh the importance of capital cost
(fable 3). Typical loading factors, operat.
ing consistencies, and drum dimensions of
tlHlt'''flT""k 3. FtICIOrS
BtJI"pmnd.
.
.
Intended service
.
.
.
.
Washer Type
Loading Factor"
(admt/d/m')
Vacuum drum
washer
GasFree filter (GFF)
Compaction baffle
filter (CBP)
Drum displacement
(DD) washer
Wash press
8.0.8.5
< 12
-30
Consistency
Feed
Discharge
(% a.d.)
(% a.d.)
Drum Dimensions
Diameter x Length
(m x m)
1.0-1.3
16-18
4.1 x 9.1
0.5 - 2.0
14 -17
4.0 x 7.0
3.5 . 4.0
13 -15
3.0 x 4.0
< 15
3.0 - 5.0 or
10.0 - 12.0
12 - 15
4.0 x 6.0
< 27
3.5 - 4.0
28- 35
1.2 x 5.0
(x 2 rolls)
25
Capital cost
Operating
Operational
Down-time
routine
Availability
.
.
.
accessibility
for routine
and non-
maintenance
of spare
parts
and factory
support
to accommodate
of the equipment
'Design values for a modern greenfield softwood kraft mill producing 1000 admt of pulp/day. (H.A. Simons
Consultants Ltd. and SandweU Inc.).
"Loading factor is defined as the drum loading capacity in admt of pulp/day/square meter of drum surface
area.
systems
577
578
1.8
Airlift take-off
Hood pr_ure
throttle back
to blower _a...-
~u
01
=..
0.6
E
..
~ 0.4
"S.
..
is Dol
0.0
4
Fig. 6. Gaerwl
~
0
1
DUution Factor
rflltllHnrsblp
betllJen
tUl"Utm
flU:-
__
tur"""~rwIIofortl"""'"
tJ/IC'fYIIIlm (H.A. Simorrs
ConsrllltItIls
U41.).
Division
Grid
COII-
..
1. Cake forming
2. Flat washing
3. Second washing
4. Cake discharging
..
FIltrate /'
no. 2 out
Fig. 9. Sebem4t1c
Washed
pulp
Unwashed
pulp
Filtrate
Fig. 7. C"t-tlwtly
KiImyr Inc.).
FIltrate
no. 1 out
Pulp out
air emissions from the washer. This increases the efficiency of the drop-leg and
provides a higher mat discharge consistency.
Compaction
Baffle Filter
KiImyr Inc.).
579
580
Hood
Doctor
HydrauUc
Moton
Filtrate
Oul
Fig. 10. ScbeIruItk
tile"..".
Slott
oil
51ock1.
3.4 Atmospheric
diffusers
The atmospheric diffuser (Fig. 11) is essentially a displacement washer. It can be
installed as a single-stage washer in the
bleach plant or as a single- or two-stage unit
for washing brown stock or oxygen-delignifled pulp. A medium-consistency
storage
tank is often located below the washer
when the washer is used in the brown stock
area. The diffuser is mounted on the top of
a bleach tower when used as a bleach
washer (Fig. 11).
A two-stage diffuser is typically 16 meters
high (elevation difference between pulp
inlet and wash water inlet, including cone
section) and 6 meters in diameter at the
dt/ftlser
581
approximately
5 seconds and is then
downstroked
rapidly in approximately
1
second.
The advantages of an atmospheric diffuser for washing bleached pulp include low
energy requirements because the pulp is
not diluted and rethickened. Space requirements are minimized because the diffusers
are normally located above a high-density
storage tower or a bleach tower. The diffuser is totally enclosed, minimizing the potential for air entrainment in the pulp.
The entire screen assembly undergoes a
regular, vertical stroking cycle to remove
pulp from the surface of the screens and
prevent plugging. The upstroke speed is
adjusted so as to be slightly greater than the
pulp flow rate through the diffuser. The
diffuser is held at the top of its stroke for
approximately
5 seconds and is then
downstroked
rapidly in approximately
1
second.
The advantages of an atmospheric diffuser for washing bleached pulp include low
energy requirements because the pulp is
not diluted and rethickened. Space requirements are minimized because the diffusers
are normally located above a high-density
storage tower or a bleach tower. The diffuser is totally enclosed, minimizing the potential for air entrainment in the pulp.
3.5 Pressure diffusers
The pressure diffuser (Fig. 13) is a displacement washer. It is built to operate at
digester pressure and is most commonly
positioned directly after a digester or an
oxygen delignification
tower. This is a
pump-through device and the pulp is discharged with sufficient pressure to flow to
the next operation. A unit for a 1000 admt/d
mill is 3 meters in diameter and 18 meters
high. The complete system, including a filtrate tank, occupies a floor space of 4.5
meters by 12 meters. Pulp residence time
in the diffuser is about 3 minutes.
Pulp at medium consistency is fed to the
bottom inlet of the pressure diffuser. The
pulp passes up through the annulus between the wash baffles on the outer shell
582
diffuser
----
"' ---
Pulp
w nozzle
Screen
--,
supportcytlnder
Fig. 14. CaI-"fIHIJ'dUlgrtmI
of pressure
tU/ftIser
cross-set:lltm
(Ahlstrom
KAmyr lrre.).
ion.
It is important to know which solute variable was used to calculate washer performance parameters before attempting to
interpret results. For example, an alkaline
extraction stage vacuum drum washer in a
bleach plant was found to have a DR of O.54
based on conductivity measurements and a
DR of 0.83 when total dissolved solids values were used (information courtesy of
Ingersoll-Rand).
583
and composited to ensure that a representative sample is obtained. The top and bottom of the mat and the quantity of pulp from
each location should be weighted equally
in the final composite. likewise, samples
should be collected and composited along
the length of a washer vat.
Tllbte5. YIIriIIItmrs ~
/HIlpwruistmrey
'"
crnullletlfJlty
.'Off' tbe l""tb of .
.""
fJIICfI_ tltw,. fIIIISber.
Sample location
on the drum
Left
Mid-left
Center
Mid-right
Right
,
Consistency
(%)
10.74
10.40
11.65
10.87
11.50
Conductivity'
(mS/cm at 25C)
0.88
1.09
0.87
1.33
1.00
Simple material balances based on water, fiber, and solute concentrations can be
calculated using washer data as a validity
check on the sampling program. All calculations should balance when sampling is
conducted during a period of stable operation. The accuracy of flow meters should
be verified because the calibration of these
instruments can change.
584
585
586
fication washing. Feedback control strategies used in brown stock washing (24,26)
would be simple to apply in bleach plant
washers if the required sensor existed. The
carryover of a specific contaminant from
the washing stage can be monitored using
the appropriate sensor and shower water
rates can be manipulated automatically to
maintain the cleanliness of the pulp at a
predetermined
setpoint.
Washer operation can be improved only
marginally at mills where bleach plant washers are overloaded because shower water
flow rates cannot be increased to the degree necessary. Periods of overwashing can
possibly be eliminated, however, which can
lead to reduced water consumption in the
pulp mill.
Cl- + 4 OH-
[2]
the
[3]
Even short duration exposure to high residual oxidant levels can cause severe corrosion, especially in acidic stages. Generally,
other environmental
parameters such as
pH, temperature, and chloride ion concentration are less important.
Major advances have occurred in the
development of materials of construction
for washers over the last twenty years. This
has been a result of changing conditions in
the bleach plant. The introduction of wash
water recycling and widespread use of chlorine dioxide gradually led to washer condi-
-.sbI.g
slllges
Alloy
0
P
P
P
D+C
NR
NR
B
P
P
P
NR
P
B
P
B
316L
3171
904L
6% Mo alloy
(e.g., 254 SMO)
"'"'
587
P
B
P
NR
P
P
P
B
P
P
NR
B
P = Premium material: Material resists corrosion even when exposed to aggressive bleach filtrates.
E.,
P
P
P
P
P
P
B
B = Budget material: Material resists corrosion in many applications but may corrode prematurely when
exposed to agressive filtrates.
NR
= Not
recommended:
Material
may experience
rapid degradation.
';88
7.6 Electrochemical
protection
for
stainless steel equipment
To improve the resistance of a C+D- or
D- stage washer made from a lower alloy
8. Extractives
and pitch
589
590
Pulp Bleaching
Table 7: EffectitJ_
Washer
Location
-Principles
and Practice
of Extractives
Extractives
Removal
in Washing
in Mill
On fiber surfaces (moderate
Dispersed (large amounts)
Dissolved (large amounts)
(C+D) Stage
E, Stage
Very effective
D, Stage
amounts)
Very effective
Unbleached pulp
screen room
Very effective
E, Stage
D, Stage
there is usually very little or no pitch deposition in the bleach plant. There are, however, several factors which can lead to
deposit problems.
The use of defoamers at any point in the
bleachery should be avoided because they
can form deposits (46,54).A high application (greater than 1.5 kg/t) of defoamer to
the knotters, brown stock washers or, especially, to the brown stock screen room
or o-stage washers can similarly cause deposits in the bleach plant. This problem
may be exacerbated if most of the defuamer
is added at the brown stock decker or postoxygen washers.
Kraft mills using hard water may experience scale deposition on the E-stage washers. There is evidence that this kind of
deposition can be accelerated by the presence of residual defoamerin the stock (53).
Talc has proven to be a useful additive for
sorbing defuamer residues (54,55). In addition, it acts as a de-tackifier to suppress
formation
of deposits
on equipment
(54,56). Soft water such as stripped evapo-
Effective when
3 < pH < 6
Very effective
591
592
for
Types of defoamers
There are several types of specially formulated defoamers on the market that are
well-suited to the high pH, high temperature conditions of brown stock washing.
Oil-based, water-extended, water-based, and
water-based/oil-free
defoamers, as well as
new defoamers
and drainage aids, are
briefly discussed below.
Oil-based defoamers consist of amide
wax and hydrophobic silica particles suspended in mineral oil and have traditionally been the most effective. The deposition
of oil and wax which can occur (64) may
lead to inferior paper properties (e.g. ,lower
strength, cleanliness, and printability) if the
defoamer is carried over into the paper mill.
The use of some low-quality oils has been
linked to formation of chlorinated dioxins
and furans (65). This problem has now
been eliminated by the use of oils free of
the precursors of these compounds (66).
Oil-based defoamers are the industry standard against which other types of defoamers and drainage aids are compared.
Water-extended defoamers are oil-based
defoamers in which some oil is replaced
with emulsifIed water, resulting in a lower
unit cost. This translates into savings only
when the effectiveness is the same as that
of the oil-based defoamers. Although it has
been claimed that water-extended defoamers lead to decreased deposition and paper
deterioration, there are few supporting data
available.
Water-based/oil-free defoamers are aqueous emulsions of concentrated
oil-based
defoamers with a lower unit cost compared
to oil-based defoamers. Again, there are few
data to support the claim that these defoamers lead to reduced deposition and deterioration of paper properties,
and savings
occur only if the efficiency is equal to that
of oil-based defoamers.
Water-based/oil-free
defoamers
are
emulsifiable silicone oils, or silicone-inwater emulsions and may contain hydrophobic silica. Deposition of silicone oil may
occur (67), leading to inferior paper properties if the deposit is carried over"into the
paper mill. Silicone-containing defoamers
are more expensive than oil-based products
and have a variable cost effectiveness. Originally, these were better drainage aids than
defoamers, but newer formulations
are
claimed to be equal or superior to oil-hased
products for foam control. The performance of silicone-containing
defoamers
may be optimal in combination with oilbased defoamers. Some new defoamers and
drainage aids containing neither mineral oil,
silicone oil, silica, or amide waxes (67,68)
have undergone limited testing. Paper machine defoamers and drainage aids are ineffective at high temperature and pH.
593
594
Pulp Inlet
~
FIg. 16./Hilgram
+
Pulp Outtet
Fig. 15. Cut-away diagram 01-
press (HymtU:/I1"",e).
References
1. Crotogino, R.H., Poirier, N.A., Trinh, D.T,
Tappi J 70(6):95 (1987).
2. Griihs, L.E., Svensk Papperstidn.
79(4): 123
(1976).
3. Lee, P.E, TappI62(9):75
(1979).
K., Pulp
Pap.
Pap.
9. PhiIlips,JR.
78(6):T123
and Nelson,],
(1977).
22(7):481
8.,
16. Berry, R.M., Fleming, B.I., Berndt, G., Williams, G.]., Tappi J. 72(2): 109 (1989).
(1983).
~--
].R, AIChB J,
Rochard,
(1988).
24. Han,Y.and
(1988).
Edwards,L.,
L., Dorn,W,
TapPiJ.
TapPiJ. 6(71):101
595
27. Gamer,
(1981).
A., Pulp
Pap. Can.,
82(12):109
Steels
N.].,
38. Bishop,
(1992).
TN.,
Pulp
Pap. Can.
Pap.
93(6):62
Performance
29
M.I.,
and
Re-
596
Pulp Bleaching
-Principles
and Practice
Wood
46. Dunlop-jones,
N. and Allen, L.H.,j
Pap. Sri. 15(6):J235 (1989).
Pulp
47. Granum,E.Hasvold,K.,
Loras,V:,Soteland,
N.,]. Pulp Pap. Set. 10(2):]25 (1984).
48. Allen, L.H., Pulp
(1988).
63(2):81
Papperstidn.
(1980).
63(17):556
(1977).
52. Allen, L.H., TapPiJ
71(1):61
(1988).
M.,j
Pulp
Pap.
57. Teodorescu,
G., Dunlop-jones,
L.H., Liebergott,
N., Pulp
92(9):T209 (1991).
N., Allen,
Pap. Can.
(1989).
64. Dorris,G.M.,Douek,M..Allen.L.H.,jPulp
Pap. Set., 11(5):JI49 (1985).
65. Allen, L.H., Berry. R.M.. Fleming,
B.I.,
Luthe, e.E., Voss, R.H., Chemosphere
19(1-6):741
(1989).
66. Voss, R.H., Luthe, e.E., Fleming,
B.I.,
Berry, R.M., Allen, L.H., Pulp Pap. Can.
89(12):151
(1988).
67. Wilson,].,
Jr., "Results
from Improved
Brown
stock Washing,"
1993 TAPPI
Pulping Conference
Proceedings,
TAPPI
PRESS, Atlanta, p.155.
68. Pelton, R. and Grosse, B., "Toward New
Brown stock Washing Technology," CPPA
Pacific Coast andWestern
Branches Spring
Conference
Proceedings,
Whistler, 1993.
69. Froass, W.e., Omori, S., Francis, R.e.,
Dence,C.W,
TapPiJ 76(11):111
(1993).
70. Wearing,J.T,
Barbe, M.C., Ouchi,
Pulp Pap. Sri. 11(4):J113 (1985).
71. Thornton,].,
Ekman,
Eckerman,e.,Pap.Puu
M.D.,
R., Holmbom,
B.,
75(6):426 (1993).
--..----
SECTIONVI:
Bleach Plant Operations,
Equipment and Engineering
Chapter 4:
Towers and Reactors
David E. White
Union Camp Corporation
Princeton, NJ
Rune Larsson
Sunds Defibrator AB
Sundsvall, Sweden
1. Introduction
2. General
599
principles
and fundamental
considerations.
and reactor
2.4 Rheology
kinetics
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 601
. . . . . . . . . . . . . . . . 601
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 603
criteria
for reactors.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 604
4.2 Medium-<:onsistency,
high-intensity
contacting
bleaching
mixer/reactors.
reactors.
towers.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 609
609
- examples.
(low-<:onsistency)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
5.1 Upflow
towers
610
towers
5.5 Medium-<:onsistency,
5.6 High-<:onsistency
6. Case study.
7. Troubleshooting.
. . . . . . . . . . . . . . . . . . . . . 608
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 608
599
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 599
considerations
of pulp suspensions
3. Contactors.
4. Design
and chemical
considerations
towers
E and P stages)
(high-<:onsistency)
high-intensity
contacting
reactors.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 610
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 611
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 612
mixer/reactors.
. . . . . . . . . . . . . . . . . . . . . 614
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 616
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 617
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 619
597
Chapter VI 4:
Towers
and Reactors
1. Introduction
Industrial chemical processes are designed to economically produce a desired
product from a variety of starting materials
through a succession of treatment steps as
shown in Fig. I (1). In pulp bleaching, this
overall process concept involves I) mixing:
the initial physical treatment, designed to
prepare the pulp for the chemical reaction
step, including dilution, temperature adjustment, and mixing of pulp and bleaching
chemicals; 2) reaction in a bleaching tower,
contactor, or other type of reactor; and 3)
washing, an additional physical treatment
step to obtain the final product from a
bleaching stage. Mixing and washing operations are covered in Chaps. VI 2 and
VI 3; bleaching reactor design engineering
is discussed in this chapter.
The overall objective of the pulp bleaching reactor is to delignify or bleach the pulp
in a particular stage, with minimum operating cost and maximum selectivity. Additional requirements,
depending
on the
position of the treatment in the bleach sequence, may include adding enough bleaching chemical
to react with incoming
contaminants
(bark, shives) and with dissolved carryover and carryback solids.
To design a reactor to accomplish these
objectives, the thermodynamics
(heat liberated or absorbed; maximum possible extent of reaction) and chemical kinetics (rate
of reaction) must be evaluated (1-5). These
analyses generally require detailed labora-
Raw
Materials
599
tory and pilot plant evaluations to understand the fundamental physical and chemical principles which are especially relevant
to pulp bleaching where the reactions are
heterogeneous
(two or three phases are
present). These evaluations allow the correct reactor to be identified and designed,
resulting in maximuni product quality and
optimal capital and operating economics.
In this chapter, the principles and design
concepts used for low-, medium-, and highconsistency delignification and bleaching
reactors for kraft pulps are reviewed in Sect.
2. Section 3 contains a discussion
of
contactors used in pulp bleaching. Tower
and reactor types and design criteria are reviewed in Sect. 4; reactor examples are provided in Sect. 5. A case study is detailed in
Sect. 6 as an example of how fundamental
principles are applied in reactor specification and design. Finally, troubleshooting
approaches for reactor evaluation are reviewed in Sect. 7.
Chemical
treatment
steps
Physical
treatment Products
steps
Recycle
Fig. 1. Scbemllllc rej1reseff1ll11off of typkIIl
cbemklll
process,
reprlfftJobft
(1).
600
.............
.' .
(1)/
.......
fi fi
J .fII'
. e...
fi'......
".
fi
Pulp floes
'. '.
'.
From
(1) Bulk gas phase
@ Surface of floc
@) Surface of fiber
@ Chemical reaction
.......
Fiber cross section
To
Surface of the floc
Surface of fiber inside floc
Reaction site
bled-
601
05
'0%_
5O'C.7.5%0,'"<>:.
Balm
0.4
.,
CD
o'"
0.3
--
f! 0.2
""
~;:, 0.1
'5
>
oo
0.'
0.2
0.4
0.5
Ozone, % on pulp
0.6
0.7
IIIIIlIIIIIU of
602
Pulp Bleaching
-Principles
and Practice
Temperature
Temperature affects reactor design because of its effect on reaction rate and selectivity. Temperature is important in both
diffusion-limited and kinetically controlled
bleaching reactions because it affects both
diffusivity
and chemical
kinetics
in
Arrhenius-type rate expressions. Because
the activation energy is significantly higher
for chemical reactions than for diffusion,
kinetically controlled reactions are more
sensitive to the effect of temperature on
overall reaction rate. In addition, the usual
inverse relationship between temperature
and gas solubility must be taken into account in design (Chap. I). The process thermodynamIcs (heat liberated or absorbed)
must be taken into account so the proper
strategy for temperature control can be identified. For most bleaching reactions, the
amount of heat liberated is not significant
relative to the mass of the water present.
Retention time
The retention time (how large the reactor or tower must be from the point of pulp
and chemical mixing to the point of pulp
dilution following the bleaching reactor)
depends on the reaction kinetics, production rate, effective reactor volume, consistency, and, when there is a continuous gas
phase in the reactor, the degree of packing
(14). Stagnant regions within the reactor
can cause nonuniform residence time and
over- or under-bleaching.
Residence time
can be on the order of less than 1-2 minutes in ozone bleaching and up to hours in
chlorine dioxide bleaching.
Reactor design for variable retention time
is also important for optimal chemical use
and product quality. Variable retention time
can accommodate changes in production
rate and in feedstock properties (lignin content, variation in carryover or carryback
solids, seasonal temperature variation, startup, and wood species).
Pressure
Pressure affects reactor design because
it affects gas solubility and therefore the
amount of gas which can be contacted and
reacted with the pulp in a single mixertower at a particular reaction rate. The initial dissolution step and the diffusion rate
are functions of the bulk liquid phase con-
603
3. Contactors
Efficient chemical mixing and contact
with the pulp are essential at any consistency with gaseous or liquid bleaching
agents. Inefficient mixing can lead to overor under-bleaching, compromising chemical efficiency and the ability to meet pulp
quality targets (strength, kappa or brightness, and dirt) (18). Mixers are discussed
in detail in Chap. VI 2.
Chemical mixing before the tower or reactor can be done in a static or high-intensity mixer -depending
on mixing
requirements which are a function of the
bleaching agent phase consistency, and the
degree of mass transfer control of the chemical system. Medium-consistency pumps are
sometimes used to mix chemicals, and can
lead to capital savings at the expense oflimited flexibility in controlling mixing parameters. liquids such as caustic soda (NaOH)
solutions can be added into the fluidized
zone on the suction side of a pump; moderate amounts of gases can be added using
a porous sintered metal sparger built into
the discharge shear plate (19). (Pulp suspension properties and pumping are discussed in Chap. VI 1.)
Addition of a gas phase bleaching agent
to low- or medium-consistency
stock requires very effective mixing to provide
uniform solubilization and dispersion of fine
gas bubbles in the stock to establish a stable,
dispersed gas-water-pulp mixture. Mediumconsistency, high-intensity mixers - a relatively recent development
operated
within the proper gas-suspension volume
ratio range are very effective for dispersing
gas into pulp suspensions at 8-18% consistency. Medium-consistency
chlorination,
oxygen delignification, and ozone bleaching are examples of processes based on the
use of such mixers (Chap. VI 2).
Keys to the design of high-intensity mixers are an efficient means to initially disrupt
the continuous gas phase to create high interfacial surface area, efficient distribution
of the gas into the pulp suspension, high
energy input in the mixing zone, and a small
mixing volume to minimize overall energy
consumption (20). The incoming pulp sus-
604
criteria
605
Chemical
Pulp
out
Pulp
in
IofHr
(13).
Chemical
606
Pulp Bleaching
-Principles
and Practice
Inlet devices improve distribution, prevent channeling, and facilitate plug flow of
the stock in the tower, leading to closer
control of residence time and improved
uniformity. In an upflow tower, an agitator
will be used for low-consistency bleaching
(e.g., in chlorination).
In a larger diameter
medium-consistency
upflow tower, a rotating stock distributor is used at the tower
base to promote uniform pulp feed across
the cross-section of the tower. A distributor may also be used to add chemical at a
point of relatively high shear, but distributors are inefficient mixers compared with
modem high-intensity mixers.
In upflow tower discharge, scrapers are
used to facilitate flow and to allow better
control of reactor residence time (Fig. 7).
Scraper blades on rotating arms feed the
pulp to the sides of the bleach tower. In
wet discharge, the pulp is collected in a
chute with dilution water introduced at the
top of the chute. The tower may also have
a dry discharge, that is, with no dilution, in
which pulp, directed by a rotor to the edge
of the tower, is collected and transported
around the periphery to a chute.
Pulp
out
Fig. 5. ~
Pulp
out
Fig.
6.
Seberrullt4:
4IiIgrwm
ofupflOllJ-tloumflOllJ
tower
(13).
607
608
Pulp Bleaching
-Principles
and Practice
a)
---__.
:~:J
I--
:=..~
t.-Dilution
-===-
':-~~=--"---T+r---
---
Pulp
Non diluting: inlet and outlet consistency
= 8-13%;
Diluting: inlet consistency
13-25%: outlet consistency
b)
8-1j'Jf.; OIl"",,,:
~-----
Pulp
FIt. 7. Topmwpersjor flJlfI- '-~
(S"'DejUmllfJr,")
Ilry "",,,
to 12%emulstnu:y b) 'l'mHr6aWJIerto ~
Discharge design for a high- or mediumconsistency downflow tower must provide
for even pulp flow out of the tower to a
low- or medium-consistency transfer pump.
In medium-consistency
downflow towers,
the wall friction is generally too low to disrupt the fiber network, allowing stagnant
pulp to collect on the reactor walls near
the discharge unless discharge is designed
properly (16). Conical or hemispherical
bottom designs with rake or scraper-type
bottom dischargers are used (e.g., in high-
'l'mHr6aWJlertotUsebM,UJfJtIn"".
to 1001B'Yoemulstnu:y.
""
and medium-consistency
downflow towers) to improve circulation and facilitate
even discharge without channeling to a
medium-consistency
pump (Fig. 8). Dilution can be carried out using a diluting
scraper or a series of pressure-actuated
nozzles to induce internal circulation, break
up and dilute the underside of the pulp
plug, and ensure uniform transition to a
lower consistency (21). Circulators inside
the tanks or reactors are also used for mixing in the dilution zone. The height of the
dilution zone can be regulated using an in-
max
'- Cf1IISIstaey
,tIlet
= 13%
= 13-25%, 08tlet
etnUIstmey
= 13%_.
609
Pulp In
Pulp Out
(CD)(EO)
WulUalace
Dlapla"emenl
Tower
PI,. ,. 'nro-s,.
KiImyr)
1l1sJl'-'
wee
Wi"ine
Pump
61Hd11ag1_
(D1)(EJ)
WulUalace
Dlapla"emenl
Tower
wee
Wi"inc
Pump
~ Relentlon
Tower with
Diffuaer
If..bine
W~
Slorace
Tank
610
PuJp Out
(Ahlstrom
(28).
fluffer, the reaction being completed afterward in a tower (24, 25). This development
was in part based on studies showing the
impact of fluffing on bleaching performance.
ers (medium-consistency
towD- and
(EO)-stages)
Medium-consistency
upflow
or upflow-downflow
towers are used in
chlorine
dioxide
stages to maintain
hydrostatic pressure head at the point of
chemical
addition.
Chlorine
dioxide
611
Medium-c:onsistency oxygen-enriched
extraction stages
Oxygen-enriched
extraction (EO) was
commercialized in Sweden in 1980 following the introduction of medium-consistency
(8-16%) high-intensity
mixers (43). An
(EO) stage employs conditions similar to
those of conventional a1kali extraction with
the exception of three additional process
variables: oxygen addition rate, oxygen
pressure, and time at pressure (44). An
additional requirement is an upflow tower
or an upflow retention
leg ahead of a
downflow tower to provide the hydrostatic
head. This increased pressure keeps the
oxygen, which has a relatively low solubility in aqueous alkaline solution, at a higher
concentration
and keeps the undissolved
oxygen bubbles small (45). Typical upflow
preretention tube conditions for (EO) include a relatively short retention time requirement of 15 minutes or less (44, 46).
For a 1000 admtpd production rate, the
upflow tube dimensions would be 2.2 m in
diameter x 21 m high.
The (EO) upflow tube can be pressurized using a back-pressure valve to allow
additional oxygen to be charged at a higher
temperature, for example, at a pressure of
0.3-0.4 MPa at the top of the upflow leg
and a temperature of 85-90C (10, 47).
The pressurized upflow leg can lead to additional delignification or can be used to
compensate for a short upflow leg height
in a retrofit. Oxygen is added to a highintensity mixer or through a sparger inunediately after a medium-consistency
pump.
An (EO) stage can also be conducted in a
displacement bleach plant (45).
E and P stages)
612
Pulp Bleaching
-Principles
and Practice
hydrogen
peroxide
stages
Hydrogen peroxide bleaching can be
conducted
in a separate downflow
or
upflow tower or in a high-density pulp storage tank although use of a separate tower
favors improved control of retention time,
temperature,
pH, and consistency
(50).
towers
(high-c:onsistency)
614
Twln-roll
Press
Clove-Rotor
613
..
Pump
02 Reactor
Discharger
Dftuted
stock
out
Peroside
Reactor
P-Stale
W..her Filtrate
Flg.12. Hlgb~
JIetWdM bletU:WrlgretU:tor
(S._
DejUmllor).
..
615
after mixing are so numerous that gas coalescence and tower channeling occur (10).
To drive the reaction, medium-consistency
oxygen delignification is normally designed
for pressurized operation (0.5-0.6 MFa).
After the mixer, the tower provides sufficient residence time (45-60 minutes) to
achieve delignification in the 40-45% range,
above which selectivity deteriorates (64).
To prevent channeling and maintain plug
flow, pulp consistency in the tower must
be above 10%; a rotating distributor is used
in the inlet and the tower has a relatively
high aspect ratio (10) (Fig. 13). (Typical
tower dimensions for a 1000 admtpd production rate are 4.5 m in diameter by 24 m
high.) The stability of the pulp-gas dispersion is also aided by the buoyancy imparted
by the trapped oxygen which reduces the
likelihood of bed compaction. At the top
of the reactor, a fully submerged rotating
scraper- type discharger prevents plugging
and channeling
and directs the pulp
through a blow valve to the blow line and
the blow tank where the pressure is relieved.
More demanding operations
for example, those involving a larger kappa number reduction, softwood delignification, or
higher entering dissolved solids levels
may lead to oxygen depletion. Efficient prewashing minimizes black liquor carryover,
which can otherwise cause cellulose degradation and consume oxygen and alkali,
and allows higher delignification levels to
be achieved (20).
Multiple stages are required to reach the
same degree of delignification as that obtained in high-conslstency operation. This
is a result of the lower reaction rate in medium-consistency
bleaching caused by
lower alkali concentration at a given charge
and possibly by mass transfer constraints
leading to localized oxygen limitations (30,
65). To increase the total oxygen charge,
two mixer/reactor units may be used in series followed by a single blow tank (Fig. 14).
The first stage (tower or retention tube)
typically has a shorter residence time (about
10- 20 minutes) and the second, a residence
time of about 45 minutes (66).
FIg.13. Me"'
(KJJamIer
eo.stste.ey
P81p18,
o:ryle8 reactor
TeeIntologIes).
616
Medium-consistency
ozone stages
A related process concept is used for
medium-consistency ozone bleaching. Pulp
(acidified and, in some cases, chelated) at
10-14% consistency is pumped to a highintensity mixer where the compressed gaseous bleaching
agent (ozone/oxygen
mixture) is added and where high pressure
and relatively high ozone feed concentration are used to decrease gas volume and
increase gas solubility. The ozone/pulp suspension is then fed into an upflow tower
where the reaction is completed (11, 67).
Discharge is through a pressure control
valve to a gas/pulp separator.
As was the case in oxygen delignification,
pilot studies have demonstrated that effective mixing and reaction take place as long
as the gas:pulp suspension volume ratio is
below a certain critical level (68, 69). An
increase in suspension gas volume led to a
decrease in applied power, indicating a reduction in mixing efficiency, bubble coalescence, poorer mass transfer, and an
increasingly unstable suspension flow following the high-intensity mixer and in the
ensuing upflow tube (11,70) (Fig. 3). Compared with oxygen delignification, the overall reaction time in orone bleaching is much
shorter. The upflow tower where the reaction is completed has a retention time no
higher than 1-3 minutes (11,67, 71) (Fig.
15). Laboratory studies showed that most
of the bleaching occurs within and immediately after the high-intensity mixer (reten-
transferred to a downflow tower to complete the reaction (24, 25). In a pilot plant
study, about 60% of the ozone consumption
and at least half of the kappa number reduction occurred in the fluffer with remaining reaction occurring in the tower (24, 25).
6. Case study
The attractiveness of ozone bleaching
from an environmental standpoint led to
intensive experimental work to quantify the
benefits and to identify the proper reactor
design for the process. Early on, ozone
bleaching was investigated at low consistency because of process simplicity and the
availability of larger amounts of water for
ozone dissolution (75, 76). In this work,
the need for suitable contacting to minimize
the mass transfer limitation was recogmzed.
Use was made of static mixers (laboratory
scale) and a pilot-scale reactor consisting
of a vertical, agitated upflow tower, a
hydrocyclone, in which ozone was introduced through an interniil porous tube, and
617
Scrubber
,,
618
ducted on a pilot scale following an approach similar to that used in high-consistency oxygen delignification. This consisted
of a combination of dewatering, fluffing,
and reaction in a downflow tower designed
for co<urrent
ozone feed. However, the
downflow bed design was found to lead to
brightness nonuniformity in the fast-reacting ozone system because of variation in
bed density and uneven gas flow down the
reactor (6). This led to uncertainties, not
only on the pilot scale, but also in reactor
scale-up.
As a result, a fundamental analysis was
made of the rate-limiting steps in high-consistency ozone bleaching. Characteristic
times were calculated for each mass transfer and chemical reaction step necessary to
accomplish ozone bleaching (Table 1). This
analysis showed that all three mass transfer steps - bulk gas phase mass transfer,
diffusion through the floc, and diffusion
through the water layer and the fiber wall
are important in determining the overall
c.. Out
PIltnte
In
tl'8te
Ou
o
o
Pulp out
Pulp
'"
0'16111!
111
7 1't %
150 PSIG
...Medlum Consistency
Ozone Reactor
Out
- Pulp
In
cHrrriaJlrHdlorl
2. Floc penetration
3. Diffusion through
and into fiber
4. Chemical
"-
Characteristic
619
time (s,/
(6).
Affected by
2-5
1-4
PIiIp agitation
1-3
Consistency
Fluffing
< 0.01
7. Troubleshooting
A satisfactory, predictive reaction model
for a bleaching stage cannot only facilitate
design, but can also be a significant aid in
reactor troubleshooting.
As an example, a
model for oxygen delignification kinetics
has been incorporated into a complete oxygen-stage model which can be extended for
stage optimization
and control (57).
lithium (6, 18) or radioactive tracer methods are commonly used in troubleshooting
reactor performance to characterize both
mean residence time and the range or van-
of 4%
620
References
I. Levenspiel, 0., Chemical
Reaction
Engineering, Wiley, New York, 1972, pp. 1-4,
349-355.
2. Froment, G. E, and Bischoff, K. B., Chemical Reactor Analysts
and Design, WlIey,
New York, 1979, p. 191.
3. Levenspiel,
0., Tbe Chemical
Reactor
Omnibook,
Oregon State University Book
Stores, Inc., Corva1lis, Oregon, 1989, pp.
11.1-11.10.
4. Hill, C. G., Jr., An Introduction
to Chemi-
(1993).
7. Bennington,
C. P.}., Kerekes, R.}., Grace,}.
Ar.'-Mixing in Pulp Bleaching," 1991 TAPPI
Bleach Plant Operations
Short Course
Notes, TAPPI PRESS,Atlanta, p. 45.
9. Gullichsen,}.
and
64(6):69 (1981).
Harkonen,
E., Tappi
C.-A., Pap.
c.,
Mfr. 32(9):42
v: B., Southern
Pulp
Pap.
(1969).
-~------
621
24. Kappel,).,
Diehold, M., Brauer, P., "High
Consistency BleachingTechnology
forTCF
Pulps," 1993 EUCEPA Conference
Proceedings, EUCEPA, Paris, p. 161.
42. Backlund, B., and Parming, A. M., "A Kinetic Study of Inhomogeneities
in Bleaching; International
Pulp Bleaching Conference
Preprints,
Tech.
Sect.,
CPPA,
Montreal, 1985, p. 155.
43. Lindstrom,
L.A., Norden,
Tappi 64(6):91 (1981).
C 8., Tappi
S. Carre,
G.,
28. Torregrossa, L. 0., "Kamyr Bleaching Systems; 1989TAPPI Bleach Plant Operations
Short Course,TAPPI PRESS,Atlanta,p. 223.
45. Kortelainen,
V.A.,
Sipilainen,
Arhippainen,
B., Gullichsen,).,
65(12):69 (1982).
T., Pulp
R. P.,
R. H., Van
Pap. Set.
R. P.,
Tappi
CPPA Trans,
(1980).
40. Kolmodin,
H., Svensk
87(18):8 (1984).
Papperstidn.
).,
Tappi
Pulp Bleaching
papper-
52. Basta,)., Holtinger, L., Lundgren, P., Fasten, H., "Reducing Levels of AOX. Part 3.
Lowering
of Kappa No. Prior to CIO,
Bleaching,"
1991 International
Pulp
Bleaching Conference Proceedings,Swedish Association
of Pulp and Paper Engineers, Stockholm, Sweden, Vol. 3, p. 23.
53. Basta, j., Andersson,
L., Hermansson,
W,
"UGNOX and Complementary
Combinations; 1992 Non-<:hIorine Bleaching Conference Proceedings,
Miller Freeman, San
Francisco.
-Principles
and Practice
66. Kondo,
S., "Two Stage
MC-Oxygen
Delignification
Process and Operating Experiences;
Pan-Pacific
Pulp and Paper
Technology
Conference
Proceedings,
Tokyo, 1992,p.23.
0.,
27. Gullichsen,).,
in Tbe Bleaching
of Pulp
(R. P. Singh, Ed.) 3rd edn., TAPPI PRESS,
Atlanta, 1979,Chap.
10.
30. McDonough,
T. }., "Oxygen
Delignification; 1991 TAPPI Bleach Plant Operations Short Course, TAPPI PRESS,Atlanta,
p.57.
622
M. R. and
72(9):215
Edwards,
L. L., Tappi
(1989).
58. Miller,W:,"ProcessTechnology,Machinery,
Advantages and Disadvantages;
1992 NonChlorine Bleaching Conference
Proceedings, Miller Freeman, Inc., San Francisco.
59. Ali, 0., Eachus, S. W:, Seiter, D. E, "Use of
Ozone for Bulk Lignin Removal: Effect of
Feedstock Quality; ESPRA Spring Meeting,
Invited Papers, Empire State Paper Research Institute,
Syracuse,
New York,
1993, p. 25.
60. Liebergott, N. and van lierop, B. ,"The Use
of Ozone in Bleaching and Brightening
Wood Pulps. Part I. Chemical Pulps; 1978
TAPPI Oxygen,
Ozone, and Peroxide
Pulping and Bleaching Seminar Proceedings, TAPPI PRESS, Atlanta, p. 90.
61. Norden,
S. and Simonson,
0., "Ozone
Bleaching of Sulfite Pulp
A Pilot Plant
Study; Proceedings
of World Pulp and Paper Week - New Available Technologies,
SPCI, Stockholm,
1984, p. 118.
L.-K.,
68. Dillner,
B. and
74(9):720 (1992).
Peter,
w.,
Pap.
Puu
69. Szopinski,
R. and Stromberg,
B., "High
Brightness
Using Totally Chlorine
Free
(TCF) Bleaching Sequences,"
1993 NonChlorine Bleaching Conference
Proceedings, Miller Freeman, San Francisco.
70. Bennington,
(1993).
C P. )., Tappi
J 76(7):77
71. Greenwood,
B. F. and Szopinski,
R.,
"Ozone
Bleaching
Technology
'92,"
1992 Non-<:hIorine Bleaching Conference
Proceedings,
Miller Freeman,
Inc., San
Francisco.
72. Oltmann,
E., Gause, E., Kordsachia,
Patt, R., Papier 46(7):341 (1992).
0.,
A.,
43(1):14
(1990).
623
SECl'IONVI:
Bleach Plant Operations,
Equipment and Engineering
Chapter 5:
Sensors and Process Control
J. Willems
ValmetAutomation (USA) Inc.
Norcross, Georgia
M. Williamson
Freelance technical writer
Thornhill, Ontario
1. Introduction
627
627
630
630
632
632
633
634
3. De1ignIficationandbleachlngcontrol
3.1 Traditional C-stage control. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 DC- and D-stage control
3.3 Oxygen-stage control
3.4 Brightening D-stage control
3.5 Peroxide-stage control
4. Optimization
ofcontrolloop
performance.
634
. 634
636
637
638
639
. . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
analysis
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
625
Chapter VI 5:
Sensors and
Process Control
627
1. Introduction
Chemical pu1p bleaching is an extension
of the fiber delignification process started
in the digester. As an integral part of the fiber production line, bleaching is a continuation of the delignification process which
is comprised of sequential steps or stages.
Besides further delignification, unit operations in the bleach plant lead to the development of pulp quality as expressed by
brightness and cleanliness.When operating
conditions are properly managed, pu1p fiber degradation and the formation of environmentally
harmful by-products
are
minimized. For the pu1p manufacturer, it has
become a challenge to maintain pu1p or
paper quality targets and to decrease the
environmental impact of bleach plant emissions in balance with bleaching costs.
Environmental concerns and the pressure to increase production rates have created major changes
in the chemical
processes used in delignification and bleaching, the types and amounts of chemicals
applied, and the process conditions under
which chemical reactions take place. Chlo-
80
0
0
~~60
u)
II)
CD
-c:
40
In
20
1% lignin
28% lignin
.s::.
C>
'L:
------~,'
\5% lignin
Digester G
E
Delignification
Fig. 1. Delipl/ktUlon
qrumce.
tUUl brigbtness
developmerll
D
profile
E
0
Bleaching
of softwootl
lnYIft pulp
628
through
lig-
630
ImJH1t1tmIl,,-IIM~.
Measurement
Pulp brightness
Quality development
Reaction progress
Chemical residual
Kappa number
Temperature
50
Reaction progress
Chemical demand
0
CD
(..)
x flow
dioxide concentration
....--.........
'.
I
I"
CD 20
:;::
CD
a:
10
Consistency
~40
"
,,'
c: 30
as
I
(..)
Reaction rate
pH
Chlorine
629
,,'
,
:'.....
:',
I
I
...,"'<
,'/
/
/
...~'
" --
"...
'...:- ,"
'-'
.........
~~~~
'
2ndD
1st D
,-.... ,
~~~~~
...............
'.
1st E
C stage
Brown
stock
0
dioxide
400
600
800
Wavelength,
n,.2.
Re.fkcttmu
CfltWS of."bletlt:bM
1000
1200
nm
MUlJMrtUllly bl/lllebed""/l
pnlps.
Experience has indicated that,after chlorine dioxide addition in D stages, a solid residue may build up on the probe windows
when oxygen has been included in the previous extraction stage.To eliminate residue
buildup in such cases, the sensor may be
situated before the chlorine dioxide addition point and used to measure the incoming brightness level which in turn can be
used to control the chlorine dioxide flow.
Ultrasonic cleaning of the window also
solves this problem (4).
631
(c)
(a)
Light
Detector for
source reflected light
Electrical
connections
.',},
Fibre
optics
Electrodes
,. ,
.I
_'
~'_
'
"
..~;~,;,'--:VC:1~~;~_,~~~'~.1~2\\;""
'
'-:':p~if> s~~~,nsion':-"
Current flow
proportional
to chemical
concentration
Potential
set for species
to be measured
2;.\;~5<\',,~;:; }/<,.,~;';:,-->:-~p'uipsuspe_nsio~:/,
- \,'
",-
,',
- '. '.
',-,-
632
Reference electrode
reading (4). Depending on the analyzer configuration, sample preparation and measuring sequences require from 2-8 minutes per
analysis.
Kappa number measurement is based on
lignin's characteristic absorption of ultraviolet (UV) light at specific wavelengths.
Figure 5 illustrates the operating principle
in which the absorption and scattering of
UV light is measured simultaneously. Another measurement corrects for any variation in the light source intensity.
Some kappa analyzers also measure relative fiber length. This is a useful measurement in mills whose fiber lines alternate
between hardwood and softwood grades.
This measurement is used to automatically
adjust the calibration of the sensor for hardwood or softwood fibers. Also, the chemical charge may be adjusted specifically for
each fiber type as it enters the delignification and bleaching process.The detection of fiber size transitions may aid bleach
plant operators in delivering the right fiber
to the correct storage towers, with a minimum of transition-quality pulp.
One analyzer also measures dissolved lignin in the pulp suspension as an indication
of carryover from the brown stock washers (3,5). This carryover lignin consumes
chemical which otherwise could delignify
or bleach the pulp. Because this carryover
Pulp suspension
Measurement
cell
Measurement
electrode
Current electrode
Light
source
Kappa
number
633
A pH measurement must be temperaturecompensated for two reasons: First, the instrument is temperature-dependent.
This
effect is pre-determined
by the manufacturer and is programmed into the sensor's
electronics. Second, the process pH is temperature-dependent
as well. For instance,
preceding an E+O tower, a WOC increase
in process temperature causes a downward
shift in pH of about 0.2 unit. An uncompensated control algorithm would incorrectly add more alkali, wasting valuable
chemical. Controls therefore should have
the capability of temperature compensation
(6).
2.4 pH measurement
pH is an electrochemical
measurement
of acidity or alkalinity. There are many instances in a bleach plant where pH-related
disturbances can be created by inadequate
or unstable pulp washing or by poor regulation of dilution filtrates of differing pH
added to the pulp stream entering a bleaching stage. pH is a logarithmic measurement;
therefore, a pulp slurry at pH 3.0 has ten
times less acidity than one at pH 2.0. Because DC or D stages are operated at a
higher pH than are traditional chlorination
stages, the pH level is more susceptible to
instabilities caused by variations in dilution
water flow. In extraction stages, pH is a
function of alkali charge. Some mills may
operate
at a high pl:I to maximize
delignification but at the risk of wasting
chemical if the pH is not well regulated.
Figure 6 shows the measuring elements
of a pH probe. pH probes can be mounted
in the process stream or used to measure a
fiber-free solution sample supplied by an
automated sampling device. Newer installations favor a ball valve installation which
allows for periodic flushing or maintenance
of the sensor. This flushing sequence can
be automated.
Light source
Optical
windows
634
C102
solution
flow
Transmitted
Fig. 7. Sebemttlk of" cblorltfe dioxUle COtfUtIlrtltkm $-'
light to detector
are now extremely rare. In many cases, however, the proven control strategies developed for the chlorination process can be
successfully implemented in modernized
stages, where chlorine dioxide has partially
replaced chlorine, by using different tun-
Potting Epoxy
AgJAgCI
Reference
Element
Dowel (4)
Wooden
Plug (3-4)
KCIS8turated
Autornlltlc
Temperature
Compensator
pH
Me8surament
Electrode
Epoxy
Berrlers
18rge
Wood or
Teflon
Junction
635
Chemical
Pulp
.....
suspension
In-line
mixer
sl..
111I4ralilul
Bleaching
tower
dlMlleIIl Sf!IIIIorSIllflSlJYlU.g tlul__
amtroll.
C or DC
"
Over-chlorination
II!
Q)
Target brightness
'C
II)
Under-chlorination
Iii
::>
"C
'0Q)
Target
residual a:
Time
Incoming
kappa number
- - - -Low
. ----- -- High
CfI1'fIfISP"c orDCs..
between over-chlorination
and under.{:hlorination. By mathematically combining and
weighting the measurements
from each
sensor, the control operates to a single tar-
636
3.3 Oxygen-stage
control
Oxidized
white liquor
f (kappa. temp)
I
637
638
S02
water
C102
Solution
Pulp
f (alkali, pH)
If (stockflow,Cs)~
Fig.11.SdImuIIkof ..,._
70
II)
:3
c:
60
..c:
C)
'C
.D
~
50
c:
Q)
en
40
Kappa
analyzer
10.2
10.4
10.6
10.8
11.2
11.0
pH
Fig. 10. ScbemtJtk
st"ge.
sbowI"g
luI/JJNI
"""'per
StJmpll"gpoi"ts
"rut amtrol
deslp
dellpljictJlImI
belwJenl brigbblns
develOJImMI
"rut pH I"
peroxide
"
sltlge.
11.4
639
3.5 Peroxide-stage
control
Hydrogen peroxide is used to bleach
(chemi)mechanical
pulps. The dual-sensor
control used in chemical pulp bleaching has
been used in hydrogen peroxide bleaching
stages. Under alkaline bleaching conditions,
peroxide dissociates into water and the
perhydroxyl anion (HOO-).To measure reaction progress the residual chemical sensor must be designed to measure this ion
which is an active bleaching species. Be-
640
Pulp Bleaching
-Principles
and Practice
against time, shows this effect. The other
quadrants illustrate the power spectrum
analysis, the cumulative spectrum analysis,
and the auto-correlation analysis of the flow
measurement. These analyses indicate the
dominant frequencies of the variation, the
contribution of various frequencies to the
overall variation and the degree of data randomness. The mechanical problem illustrated here must be corrected to achieve
better control of chlorine dioxide flow and
pulp quality. Many problems with instrument location, process measurement, control strategy design, and control tuning can
be determined using PC-based diagnostic
tools (12).
For optimum control loop tuning which
leads to minimum process variability, the
process dynamics must be assessed using
open-loop bump tests. A bump test is conducted by making a small change in the
setpoint of the controlled variable and observing the corresponding
change of the
controlled variable to the new setpoint over
a period of time. Several bump tests, evaluated under different process conditions,
should be performed. By fitting one of sev-
Time Series
Sodium
silicate, on pulp
15
14
13
c
12
"cu
OJ 11
en 10
en
Q)
9
c
..c
8
C> 7
";;::
CD 6
Power Spectrum
48.14
2.601
46.73
1.9SO
~
45.33
CJ
43.92
1.300
0.6SO
0.000
42.52
o
256
512
768
1024
1024
769
Cumulative Spectrum
0.5
75
::;:
Q. 0.0
CJ
Consistency:
;J.
slilute
tUltIltIon on brllbtness
In tbe pet'fdde
bleacblng
50
25
-0.5
-to
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
% NaOH
0.0
10.0
20.0
30.0
40.0
SO.O
S
ofmecbanlul
pulp.
256
100
1.0
3%
Peroxide:
Time:
Temp:
513
S/cycle
of cblurl_
769
513
S/cycle
258
641
642
T
.C.
TOWER
Brown stock
3000 USGPM
25 K.NO
MIXER
Ie
130"F
OPEN
LOOP BUMP
FC1 SP
200---+1
350
TEST
5%
II.BRT=6%
--
FC2 SP
or
FC3 SP
II.CT=4%
II.BRT=6%
II.CT= 4%
30
60
90
120
150
180
TIME,s
Fig.15. IIlllSlrtJtUmoftbe flU of open-loop Inmtptnts to n,"""e
control.
tbe dyrumtks of ~H
brlgbtuss
Fiber production line processes are often complex and many interdependent variables influence the outcome. Responses are
usually non-linear and may depend on operating points such as production rate. Many
different "rules-of-thumb" and operating
experience are incorporated into the "art"
of producing high-quality pulp, and some
uncertainties are associated with how the
end result varies with different input conditions.
The decrease in kappa number accompanying chemical pulping and the development of brightness
and delignification
during bleaching are two notable examples
of processes which are good candidates for
fuzzy logic control. Fuzzy logic control incorporates "rules of thumb" and the longterm practical experience of operators and
process engineers
into the controller
design.
Fuzzy logic does not override basic dosage control but modifies it by introducing a
- Production
6. Shive analysis
Dtptnding on 'hip 5ize uniformity and
pulping conditions, the bleach plant may
receive pulp containing a variable fraction
of "shives; which are visible, dark fiber
643
644
Fuzzy
feedback
Fuzzy
kappa brightness
control
Iprocesslstatus
Pulp
sample
Rotating
screen
-, -
,~_,
\
-'
-.
Fibers
out
Unbleached
pulp
Residual
sensor
Brightness sensor
6
Softwood Mill Experience
5
4
:::e
0
'>
0
I-en
I!I
Incoming
kappa STDV
Suspension
Flow
EOK
STDV
~D2 brightness
STDV
2
Laser
Diode
Linear
camera
o
Compensated
brightness
Fig. 17. ComptIrlMm of ~
bletU:b/I"'"t.
3.2mm
Fuzzy
logic
645
References
I. Reeve, D.W. and Weishar, K.M., TapptJ.74
(6):164 (1991).
2. Farrand,N.A.,"Bleach
Plant Sensors;
1990
TAPPI Bleach Plant Operations,
Short
Course Notes,TAPPl PRESS,Atlanta, p.205.
3. Hansson, A. and Kubelnieks
E., "The STFl
OPTIKappa - new tool fur On-Line Measurements
of Dissolved
Lignin:
STFI,
Stockholm,
1990.
4. VaimetAutomation
ture and personal
Inc., unpublished
communications.
literature
literaand per-
literature
and
Inc., unpublished
litera-
1989.
648
SECTIONVI:
Bleach Plant Operations,
Equipment and Engineering
CHAFfER VI:
Section 6: Water Reuse and Recycle
(Continued)
Chapter 6:
Water Reuse and Recycle
Jack Histed
Jack Histed Consulting Ltd.
L'Orignai Ontario, Canada
6. Countercurrent
6.1
Nell McCubbin
N. McCubbin Consultants Inc.
Foster, Quebec, Canada
Peter L Gleadow
systems.
6.2
Split-flow
6.3
Jump-stage
6.4
Process
6.5
1bree-washer
washing.
countercurrent
washing.
countercurrent
1. Introduction.
. . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
1.1 Historical review. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Typical water usage for various washing sequences. . . . . . . . . . . . . . . . . . . . .
1.3 Effect of discharge volume on pollution load. . . . . . . . . . . . . . . . . . . . . . . . . .
1.4 Effect of discharge volume on effluent treatment facilities . . . . . . . . . . . . . . .
649
650
650
651
651
.
.
.
.
651
652
653
653
654
654
3. Engineering approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
3.1 Need for rigorous mass balances
3.2 Tools available for calculating mass balances. . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Design of bleach plant towers
3.4 Control of washer showers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5 Effect of washer discharge consistency on wash ratio
654
654
655
656
657
657
4. Princlplesofcountercurrentsystems
657
4.1 Wash ratio. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
4.2 Countercurrent flow component. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 657
5. Faaors affecting water reuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
5.1 Washer design and loadings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.2 Seal tank design. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.3 Most critical washers in the system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.4 Number of washers in the system
5.5 Effects of residual chemicals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . , . . . . . . . .
658
658
658
659
659
660
5.6 Temperature limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
(continued next page)
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
washing.
660
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 660
plant
bleach
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 662
plant
662
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
7. Filtrate reuse
647
wasbing
Direct countercurrent
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
Chlorine/chlorine
dioxide
7.2
Extraction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
7.3
Peroxide
or (EP) stages.
7.4
Chlorine
dioxide
7.5
Bleach screen
7.6
Wire-cleaning
showers.
7.7
stages.
delignification
stage
666
7.1
. 666
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
bleaching
stages.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 666
mill filtrates.
. . . . . . . . . . . . . . . . . . . . . . . . . . 666
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 668
9. Water
9.1
9.2
9.3
9.4
670
670
670
670
671
Chapter VI 6:
Water Reuse
and Recycle
1. Introduction
:Ygr
1959
1969
1975
1979
1985
1988
m3/adt of pulJ)
240
156
III
96
79
72
proximately
649
75 m' of water/adt
of f)ulf), of
which about 20 m3/adt may bypass the effluent treatment system as clean water. The
most recent mill designs call for anticipated
Newer
Mi
Bleach plant
-Acid sewer
-Alkaline sewer
Total mill
~
21.1
10.0
72.0
(m'/1IlltojpalP) (2).
Current
D.Qign
Possible
~
10.5
10.6
35.5
10.5
0.1
14.8
650
Pulp Bleaching
-Principles
and Practice
washing sequences
The effluent discharge from a modern,
filter-type bleach plant in the 1990s is about
25-40 rn-'/t of pulp. The decrease has been
achieved primarily by water recirculation
together with some form of countercurrent
washing.
There are many approaches to the countercurrent use of water in today's bleach
plants, but most can be described by one,
or a combination of, the following terms:
1. ~,
where water is used once only and
all water applied to each stage is discharged
to sewer except for the relatively small volume carried forward with the pulp
2. Internal circulation, which makes use of
filtrate for tower and vat dilution and perhaps for wire cleaning and doctor showers
3. Jump-sta~e countercurrent
in which filtrate from later stages is used as wash water in two or more previous stages in the
bleach plant
4. Split-flow countercurrent, where filtrate is
used for some showers in previous stages
5. Direct countercurrent,in which the whole
shower water flow for each washer is
taken from the filtrate of the succeeding
washer.
These water usage schemes are discussed
in detail below. Typical water usage and
hence effluent discharge for the foregoing
processes applied to a typical (DC)(EO)DED
bleach plant is as follows:
Effluent Dischartle
(rn3/adt of pulp)
Theoretical
M:1Yi!
Filtrate System
Open
450
450
Internal circulation
within stages
Jump-stage
countercurrent
Split-flow
countercurrent
Split-flow-jump-stage
countercurrent
Direct countercurrent
55
55
23-25
30-40
23-25
30-40
11-15
13-15
12-25
15-25
651
652
Pulp Bleaching
and Practice
INTAKES
Water In pulp
Ctean-up
Pulpwashing._
Wlre-cleanlng showars
Watar with chamicaJs
Dilution!of (Me) pumps
CondonsaI8 from dInIcI~
Injection
Laa"-Ihrough
nonnaJIyclosed _
_
Hydraulic and steam
on washafs
Hose water to lower washer vat conslstancy
Water Inlata!of wash-up or start-up IeIIopen
Diluttonwater to faciNtata_1pmonI ~
ExcaaaIva maka-up to .eal tanks to avoid ..,,-
hoses
Outft0W8
. WIth bleached
pulp
washers,
Fig.1.
W.m''''''"
on bearings
BLEACH
PLANT
-Principles
DfII.fI-,..6lMcb pltllll.
-- - ------
1,100
1,050
c..
1,000
:;
c.. 950
:c
900
800
850
.::.:.
E
m
en
750
700
650
600
15
Fig. z. Effeet of eJJlrmu ml",,",
20
25
30
35
Effluent, m3/t unbl. pulp
011stell", COfISIImptimI.
653
40
45
654
Pulp Bleaching
Water treatment
-Principles
and Practice
cost (Can$)
[1]
0.63
= 200,OOOCflowrate, Us)
Effluent treatment
500,000
(flow
cost (Can$)
rate,
Us)
[2]
0.63
[3]
[4]
3. Engineering approach
3.1 Need for rigorous mass balances
Whether for designing a new bleach plant
or optimizing an operating system, a rigorous mass balance is an essential tool if the
best results are to be achieved. In the past,
it was common to rely simply on various
open-loop design calculations using numer-
--~--
655
656
time of their writing. More recent developments include Simon's IDEAS andWinGEMS
(the Window's version of PCGEMS) (14).
4. Principles of countercurrent
systems
4.1 Wash ratio
Laboratory work has shown that it is
important to maintain wash ratios above
1.15:1 at the chlorination and extraction
washers to prevent excessive chemical consumption in the stage following directly
thereafter.
Examples are presented
in
Table 3.
However, varying the wash ratio at the
H, D}, and E2 washers from 1.3:1 to 0.5:1
had only minor effects on the chemical consumption in the following stage. It is evident that, with respect
to chemical
consumption, the critical washers are those
for the chlorination
and first extraction
657
_",p-
tfmI mlbe
H SIiIgeS of II (CD)EHDED
E,"""
bIut:bI18g SNJIInIU (16-18)".
Washer
Chlorination
Wash
Ratio
1.25:1
3.0",1,NaOH on
pulp in E, stage
1.15:1
3.3
1.00:1
4.7
II
..
"
"
1.30: 1
1.15: 1
1.60
1.00:1
. Direct countercurrent
Chemical
Consumed
"
2.40 '
A wash ratio of 1.3:1 or higher is preferred at the E, stage washer. Low ratios
(e.g.,0.5:1) can be tolerated at the H,D"
and E2washers if water is added to the seal
tanks to ensure a countercurrent
flow and
provide sufficient wash water at the firstand second-stage
washers. Without this
countercurrent flow through the seal tanks,
the spent chemicals and reaction products
build up to very high levels until a steady
state is reached where impurities are removed from the system with the fully
bleached pulp.
658
Pulp Bleaching
-Principles
and Practice
its way forward in the system. This is analogous to a person moving forward by taking
13 steps forward and 10 steps backward.
The lower the countercurrent
component,
the longer it takes the wash water to move
forward in the system and the higher the
build-up of dissolved solids within a stage.
In the theoretical example, when the
wash ratio is less than 1.0:1 some ofthe E}
stage dissolved solids are transported from
the E} washer into the D I stage and consume additional chlorine dioxide.
The second way ffitrates can work forward in the washing system is through the
overflows of seal tanks. For example, when
the D I seal tank overflows
entering
required to achieve good washing) for various washer-types are shown in Table 4 for
comparison purposes. Values significantly
above these numbers may result in poor
washing efficiency.
Ttlble 4. TypktII
Washer1YPe
Loadin~ Factor
Wash press
< 27 adt/d/m'
21-27 adt/d/m'
Compaction-baffle
ffiter
on washers
is
659
This is also the optimum number for keeping the flows in balance. Washing is essential after the chlorination, extraction, and
final bleaching stages. Provided the kappa
number of the extraction-stage pulp is less
than 4.0 and the extraction-stage washer is
operating at 85% efficiency, there is no need
to wash after intermediate H,D" or Ez stages
(3,17,22,23),
When the kappa number after the El
stage is high or the Et washer is inefficient,
a wash after the third stage in the sequence
saves chemical in the final stage but is not
essential for pulp quality (21,23).
In five- or six-stage conventional bleach
plants, the prime use of the H,
Dl' or Ez
washers has been to convey the pulp to the
next bleaching stage (24).There is no need
for these washers when the stages are carried out in tubes instead
of towers
(16,17,23).
Elimination of a washer has the following benefits:
a) Decreased electrical and maintenance costs
b) Decreased water uSage due to seal leakage
and wire cleaning showers
c) Simplified seal tank connections
d) Simplified countercurrent washing system
e) Higher strength bleached pulp if there is
no wash preceding the ftnal chlorine dioxide stage (3)
85
0
80
~75
~0
iii
UJ
70
CD 65
t:
.s:::.
C)
(CD)(EO) bleached,
2.7 kappa number
softwood kraft pulp
60
-;::
II)
55
50
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
CI02 consumed in D stage, % on pulp
softrr004 mft
pulp.
660
6. Countercurrent washing
systems
Surveys (25,26) of NorthAmerican kraft
mill bleach plants in 1971 and 1976 showed
that there were three basic types of countercurrent washing systems operating in
conventional
bleach plants: direct, splitflow, and jump-stage countercurrent
as described below. The 1990s have produced
countercurrent
washing systems that combine features from the direct and split-flow
systems. The flowsheets for these systems
show the wash water flows to the showers
as well as the flows of excess water through
the seal tanks to the acid and alkaline sewers. Chlorination filtrate is also shown as
being added to the stock between the
decker and chlorination washer for highdensity dilution, consistency regulation,and
as injection water for cases where chlorine
gas is still in use. The flowsheets omit the
recirculation for tower and vat dilution. No
attempt has been made to distinguish between cold, warm, or hot fresh water and
machine white water used for the showers.
661
662
~~0._
C\I
(I)
~S
0
ai
(I)
.50
U1
~~~,!
'"
:::::
a"'"
co
~('I)
a
C\I
"":
~C\I
~(I)
a
0
~C\I
~a
C\I
~C\i
~C\I
(I)
II
00)
1
'1..
~~Qj
C\I
~~~~~~~,...
~IJ)
C\I
(I)
<
':'J
....
..;
II
...
~Q)
a"'"
iii
$
,...
Q)
"'"
~a
:2
,...
(I)
C\i
('I)
(I)
c:: C\I
~I
~:2Qj
o~
<(I)
IJ)
:eo
~1
:2 a
:i!
E
I~I
10
..:
(I)
II
iii
~0
~(5
.t::
0
E
:0
~,;
"5
()
0.
"3
Il.
C\I
cO
~"II
.!,
I
0""
C3
0
as
Z
t:
....
.fti
...
should
be D 1 to D. to (DC)
Jump-stage countercurrent
washing
A flowsheet for the jump-stage system is
shown in Fig. 6. As with split-flow, the
amount of fresh or white water used is the
equivalent of that of all the showers on two
washers. In its favor, jump-stage washing is
a much less complex system to operate than
the systems described above. However, it
consumes more acid or alkali for pH control because acid D2 illtrate is carried with
the pulp into the E2 stage and acid D, illtrate is carried into the (EO) stage. Similarly,
alkaline E2-stage illtrate is carried into the
D, stage where acid must be used for pH
control. Failure to do this leads to a high
pH in the D, stage and high residual chlorite levels in the D, illtrate being applied to
the (DC) washer. In the (DC) washer, the
chlorite can be converted to chlorine dioxide in an acid environment, causing severe
corrosion when the materials and construction of the washer and auxiliary equipment
are not suitable for such service. The high
pH also leads to low brightness and high
bleaching chemical cost.
6.4
(DC)
(EO)
(EO)
Fig.6.FIOflIsbeet for
JIImp-stage
cOIIntert:llmmt
white water
WtISbIng.
white water
Chapter
CD
iii
:=
'5
:x:
(I)
665
...
(I)
c:
:2 iii
u :=
IG
E $
.S;
D.....
,52
-..:
::::::
ci
....
'"
0
r-:
.....
ci
0
0
r-:
u'i
C\!
....
....
0
u'i
.....
ci
....
....
t\I
ci
C?
....
(')
0
r-:
~CL
0
"'"
ci
(I)...
.5 (I)
""
~~:I
..i
~en
m
<Ci
It)
(where
N represents
-Principles
and Practice
a neutralization
stage).
"'"
c::i
~C?
Pulp Bleaching
:2
:;a. 3:
666
0
r-:
IX!
....
....
0
u'i
decomposition
in the (EOP)
7. Filtrate reuse
~7.1 Chlorine/chlorine
i!
-cCD
'0 :=
(I)
en
0
r-:
:::
...
~IX!
~0
'" 0IG
U Z
stage.
delignification stage
dioxide-consuming
colored
dioxide
bleaching
filtrates
sta~es
contain
very
In low-consistency
chlorination
systems,
filtrate is usually recycled for dilution at the
reused in their
ways as shown
7.2 Extractionstages
Ie;;
chlorine
7.4
dioxide
]
t:
r(
more
...
~:=
0
:I:
667
Q)
Co
.~
'3
~c..
0
cD
0
,...:
"'"
~:::::
oq;:
....
....
0
-i
(\I
c::i
Q)...
Q)
.5:
~c::i
~II
ari
.!I
,...:
co
,...:
(\I
~l
I"--
M
....
).."
...
~Q)
~t
J
'0
en
ari
It
II:!
~0
,...:
cD
....
E-
r
i
:II
~]
N
and Practice
Fresh water, at about the operating temperature of the washer, is usually used for
wire-cleaning showers. To conserve water,
many mills use the wire-cleaning showers
on an intermittent basis. The need for wire
cleaning is decreased if an air doctor is used.
There is an increasing use of bleaching illtrates for wire-cleaning showers.
]!~
en
-Principles
~":
c::i
....
Pulp Bleaching
~~c:
:c
as
668
:I:
0
as
U z
j...
Examples of washer seal tank connections were cited above in Subsect. 6. Overflows from downstream bleaching stages
contain much cleaner water than do the seal
tanks to which they are connected. It is
desirable to use the cleanest water for vat
and tower dilution.To do this, the overflow
should be connected to the suction side of
a filtrate pump instead of flowing directly
into the seal tank.
..
~Oi;;
Im/Jnnie_In.,
8.2 Improvement
use systems
Plug flow bleach plants designed for on-line
process control
The advantages of bleach plants designed
for plug flow include having the same tonnage rate throughout the bleach plant and
a lower overall water consumption. However, to date they have suffered from designs which fail to take into consideration
the requirements for sensor location that
provide state-of-the"an feedback process
control. If there is a feed forward component to the process control system, an accurate measure of tonnage rate is essential.
Elimination of unneeded washers
Washing is not essential after H, D or E,
l'
stages as has been demonstrated in over 14
bleach plants using the (CD)(EOXHID)
sequence and two using the (DCXEOXD/
E;/D:Z>sequence (3,23,34). The bracketed
H, D., and E, stages may be carried out in
tIIUltIecretIM_ter ~
Action
Benefit
decking
Increased
consistency
Improved
Improved
vacuum
Decreased
effluent
Decreased
Decreased
water consumption
Improved
washing efficiency
b) Install improved
Replace
hot or fresh
shower
water
with
white
water
g) Replace constant
ratio control
flow showers
with wash
Decreased
Large decrease
consistency
chemical
consumption
in effluent volume
Decreased
effluent to sewer
Decreased
effluent volume
Improved
at higher-than-design
vat consistencies
669
drainage
Improve washing
and extraction
Higher discharge
consistency
670
Pulp Bleaching
-Principles
and Practice
shon-retention
bleach tubes (3,23). Another sequence that is becoming widely
used is (Dt/N)D, where sodium hydroxide
is added to the dilution
671
operation
10.1 Toward closed cycle operation
There is public demand to eliminate effluents and the U.S. Environmental ProtectionAgency is required by law to eliminate
effluent in any industry where it is technically and economically feasible. Although
the issue of closed-cycle
operation
of
bleached kraft mills is complex, there is little
doubt but that the bleached kraft mills of
the future will approach closed-<:ycle operation and that any action that decreases
effluent flow will assist in attaining this
objective. Whenever new equipment
is
purchased, the quantity of water required
to operate the system in which it is installed
should be carefully considered.
The dissolving-grade
sulfite mills at
Domsjo in Sweden and Lenzing in Austria
reportedly recycle all bleach plant effluent
to chemical recovery boilers, eliminating
discharges to sewer (43).
In the late 1970s, the first attempt at
closed-<:ycle operation of a (DC)EDED sequence bleached kraft mill was made at
Thunder Bay, Ontario, using the RapsonReeve process (27,44,45). Problems were
encountered with corrosion in the salt removal process equipment and in the superheaters in the recovery boiler.
Other problems contributed to high chlorine and chlorine dioxide consumption in
the bleach plant and to high chloride load
in the salt-removal process. These included
poor brown stock washing and consumption of chlorination chemicals by recycled
chlorination filtrate (27). Poor air removal
in the E, seal tank led to air in the E, washer
vat.This contributed to poor E,'stage washing and increased chlorine dioxide consumption
in the Dt-stage. The D,-stage
chlorine dioxide consumption was also adversely affected by the use of in-lIne mixers
in that stage (46).These were later shown
to be inefficient and were replaced by a
high-shear mixer (47).
At present another attempt at closedcycle operation is undergoing mill-scale
tests (28).This mill is using an OD(EOP)D
sequence to bleach southern pine pulp.
672
Pulp Bleaching
-Principles
and Practice
References
1. Miner,R. and Unwin,}., "Progress in reducing water use in waste water loads in the
U.S. paper industry;
National Council of
the Paper Industry for Air and Stream Improvement,
New York, Technical Bulletin
No.603, 1991.
2. Carter, D.N. and Gleadow, PL., Water Use
RedUdton
in tbe Pulp and Paper Industry 1994, Publications Dept. Canadian Pulp
and Paper Association,
Montreal
1994,
(Dee
Pap.
Ind.
51(9):43
WE.,
B.F., Eachus,
S.W.,
76(3): 115 (1993).
15. Towers, M. and Turner, P.A., To be presented at Pulp Washing '96, October 7-10,
1996, Vancouver.
16. Histed, }.A. and Andre, G., CPAR Project
Report 47-5, Environment
Canada library,
Place Vincent Massey, 351 St.Joseph Blvd.,
Hull, KIA OH3.
17. Histed,J.A.
(1976).
18. Histed,J.A.
78(3)TR23
59(3):75
ChapA.
3. Histed, J.A., U.S. Pat. NoA,238,281
9,1980).
PRESS,Atlanta,
private
file
courtesy
of
22. Histed, }.A. and Vega Canovas, R., "Decreasing the Usage of Chlorine and Caustic in Bleaching,"
1989 TAPPI Pulping
Conference
Proceedings,
TAPPI PRESS,
Atlanta, p. 85.
T.}.,
Tappt
673
Tappt j
J 78(3):55
40. Elliot, R.G. and Walley, C.A., "AOX and Dioxin Emissions Reduction
at Longview
Fiber Company,"
International
Pulp
Bleaching Conference
Proceedings,
SPCI,
Stockholm, p. 253.
24. Yankowski,A.A.,
Tappi 55(6):937
(1972).
71(2):47
(1988).
27. Pattyson,G.W.,
Rapson,w'H.,
(1981).
45. Reeve,D.W,
(1984).
Rae,R.G.,
Reeve,D.W.,
Pulp Pap. Can. 82(6):T212
28. Maples,
G., Ambady,
R., Caron, J.R.,
Stratton, S., Vega Canovas, R, Tappt j
77(11):71 (1994).
29. Nicolle, F.M.A. and Histed,].A.,Pulp
Can. 76(9):T253 (1975).
Pap.
30. HistedJ.A.
and Nicolle,F.M.A.,
CPAR
Project Report 47-4, Environment
Canada
library, Place Vmcent Massey, 351 St. Joseph Blvd.,Hull, KIA OH3.
31. Wartiovaara,
T167 (1980).
I., Pulp
(1993).
B.I.,jPulp
Pap.
46. Steven,
(1976).
Pulp
F., Pulp
}.c.,
28
T.L., Tappi j
SEcnON VB:
The Properties of Bleached Pulp
Chapter 1:
Bleached Pulp Composition
and Its Determination
Jaana SjOstrom and
Anders Brolin
Stora Corporate Research
Satfle, Sweden
1. Introduction
677
683
683
684
684
685
4.
686
ExtraneousmaterlaJs...'
4.1
4.2
4.3
4.4
'
'
'
"
Organic extractives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Dirt specks, pitch deposits, and stickies
Chlorinated compounds. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Spectrometric
data analysis
675
686
689
689
689
. . . . . . . . . . . . . . . . . . . . 690
Chapter VII 1:
Bleached Pulp
Composition and Its
Determination
1. Introduction
Bleaching gives rise to changes in the
pa~~pro~~androemic~ro~
position of fibers. Although the influence
of chemic~ composition on the physic~
pro~rties of pulp fibers cannot,in all cases,
be fully explained, it is recognized that
measurement of manges in the roemic~
composition
of pulps occurring during
bleaming is useful in process control and
necessary in development
work. For instance, the major concern in running and
developing modem bleaming sequences is
to maintain pulp viscosity, that is, to avoid
reduction of cellulose molecular weight
and fiber strength (Table 1). Low fiber
strength limits the maximum attainable
pulp strength, but an increase in pulp hemicellulose content lowers the beating requirement
for a specific
pulp/paper
strength (1).
To minimize the use of expensive bleaching roemicals and reduce blearo plant emissions, pulping is extended to remove as
much lignin as possible before bleaming.
Because bleaching may only chemically
modify the lignin without removing it, as is
especi~ly the case when bleaching meroanic~ pulps, lignin reactions induced by
light and heat may affect paper quality
(Table 1). A high lignin content provid~
fiber stiffness which in some applications
is as important as high brightness. IT the
brightness stability ofblearoed fibers is critic~,information about example phenolic hydroxyl groups in lignin, whiro are largely
responsible for yellowing, can be ~uable.
A roemic~ change caused by bleaching
and which accounts for sevem effects on
papermaking properties can be measured
:IS ch:mges in the amount and distribution
of acidic groups on fibers (fable 1). The
mainly positive effects on papermaking of
these groups arise from their cation ex-
mange
capacity
677
678
2. Carbohydrate characteristics
and their measurement
The fiber strength of undegraded lignocellulosic mate~ is genemly proportio~
to the a-cellulose content; that is, the tensile load on the fiber is borne by the cellulose fraction, but hemicelluloses and lignin
are to distribute the load among the fibrils.
Pulp fiber strength is affected by the molecular weight of the cellulose roains comprising the fibers (24). The sites of native
irregularities or mechanical damage, e.g.,
chipping, hot blow disroarge from digesters, and high-shear mixing. are more acces-
e'" eu
~... -5.
.~ e
<i:I
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o~
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0-
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e
0
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ve 00.3
e
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v e..
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e a'"
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-"Q
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ff .~
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..-~~.2 e~c.",
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e
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t
~~. .~03''''~I:!
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e U
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os: e
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'"
t::
ti:i
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t
{
"Q
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'" .~
~~~~.~
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~:I::
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::!
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0
::! e
!~
'C >
c:Q
~e
- S .~0
_l:~..c
e~U
fc
.C
~c:Q
e .S
~-
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.;::
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I
~~~=
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= (j
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""";:1
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If&!
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15~
ft~
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~_.;::
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8.
~..sa
v v
.~ .2
8.~
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..:
'"
~'"
. ~~.~]
U .~'E:a
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~0..5
~~~1!!00
...
~~'"
_ e
15
.s~
..:
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.;::
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0.] ;g
~~;fu uU
-3
~~"Q
:=
~=-'"
1;j58.
.s = E .~
~88 ;::3
-0
;...0.
'"
.c '"
,g~
'"
'
g~ :gv
]e
~<I)
e
.s
'3
~U
~::>1
II>
g~
U 'C
&j E
[1'\J = Km
MQ
679
[1J
where
M is the number average (M.), length average ~,or
weight average (M~ molecular
weight or the corresponding average degree
of polymerization (DPn' DP, or DP~.
'
Km is the S<Kalled Staudinger constant and
a is a variable which decreases with increasing molecular weight.
Kmand a vary according to the method used
and the measurement performed and are
dependent on the structure of the polymer.
This effect becomes evident at DP > 1000,
that is for high molecular weight cellulose
(10).
As a general rule-of-thumb, low viscosity
implies low pulp strength but high viscosity does not necessarily indicate a high pulp
strength. The fiber strength represented by
the rewetted zero-span tensile index (Fig I
a) has been shown to decrease almost linearly with the viscosity of the pulp. The
strength is reduced to the same extent
irrespective of whether the viscosity loss
occurred during kraft pulping, oxygen delignification, or bleaching with different chemicals. Tear index at constant tensile index
drops rapidly at intrinsic viscosities below
approximately 750 drn31kg (Fig 1 b).
Ozone-bleached
pulps tend to have
higher strength than is suggested by their
viscosity.This may be explained by the carbonyl groups introduced in the cellulose
chain during bleaching and which distort
the viscosity value. During viscosity measurement in, for example, cupriethylenediarnine (CED) under the prevailing strongly
alkaline conditions, degradation of the cellulose chains by (klirnination may occur.
To avoid this problem it has been recommended
that
carbonyl
groups
be
removed by reduction with sodium borohydride prior to making viscosity measurements (11).
The viscosity of a polydisperse polymer
generally is affected mainly by the high
molecular weight fraction of the sample
which implies that viscosity measurements
are especially useful for samples having a
680
~140
Z
~'"130
~
'iij
c:
S 120
c:
IIIe8chIng 88qU8llce
o OC(EP)D(EP)D
. OQ(Z,O)(OP)
. OQ(Paa,O)(OP)
~
e
110
'"
500
600
700
800
900
1000
Viscosity, dm3/kg
15
0
.!2'
'"ZE 14
E
x 13
'0
'"
.5
; 12
Bl88chlng MqU8I1C8
o OC(EP)D(EP)D
. OQ(Z,O)(OP)
~. OQ(Paa,O)(OP)
b
11
500
800
700
800
900
1000
Viscosity, dm3/kg
Sample Type:
I""- (5).
IlIstmIIy
Sample Prqmation
and Derivatization
Sample Work-up
Swelling in water
Solvent exchange
DMAC + DMACI
UCI
narrow molecular weight distribution. Because the low molecular weight tail fractions significantly affect fiber strength,
information obtained from viscosity measurements becomes less relevant as the
polydispersity increases (2). It is therefore
imperative to have information on the molecular weight distribution to complement
the average molecular weight data provided
by the viscosity measurement. Application
of size exclusion chromatography (SEC) to
the analysis of underivatized cellulose therefore is valuable, and much effort has been
devoted to devise methods suitable for
pulps (Table 2).
Size exclusion chromatography
The main reasons for the slow development of SEC methods for the characterization of chemical pulps include, on one
hand, the problems involved in dissolving
cellulose samples and, on the other hand,
the lack of column packing materials
compatible with cellulose solvents (12, 13).
The most extensively studied cellulose
solvent for SEC is N,N-dirnethylacetarnidelithium chloride (DMAC-UCl). The main
Separation and
Chromatographic
Detection
and
Reference
Calibration
Conditions
Spruce sulfite
pulp, bin:h
kraft pulp
SEC, StyragelTTol
columns,
0.5%
RI (refractive
index) detector
(2)
ua in N,Ndimethylacetamide as eluent
Beech cfis.
solving pulp
Dissolution in cadoxen
(300 g ethylenediamine,
L water; 5.5 % Cd; 0.2
(15)
HEMA gels:
Exclusion limits
2'1()6,S'10'
and 3'10' Dalton.
cadoxen:water
M NaOH)
(1:1) as eluent.
Bleached
pine bisulfite,
dissolving pulp,
Swelling in pyridine
or DMSO, carbaniIation
with pheny\isocyanate
Precipitation of
cellulose tricarbaniIatesin
Polystyrene-i>ased
SEC packings,
tetrahydrofuran
uv, RI or low
angle laser light
prehydro\ysis
in pyridine
MeOH (pyridine)
or EtOH (DMSO),
washing, and
as eluent
(LALLS)
kraft pulp
or DMSO
drying
scattering
detector
(12, 16 - 18)
requirement
in viscosity
and SEC
measurements
Because viscosity measurements and SEC
combined with IN or RI detection are secondary methods, they need to be calibrated
to obtain absolute DP or MW values. Calibration is accomplished by the use of welldefined standards whose molecular weight
681
2.2 Determination
of cellulose
and
hemicellulose
content
Cellulose is the main pulp constituent
and, because of its chemical and physical
properties and its supramolecular structure,
the principal contributor to pulp strength
and other properties. Hemicelluloses affect
pulp strength properties by contributing to
bond strength and bonded area (19). In
general wood analysis, also applicable to
pulp, lignin is removed by treatment with
elemental chlorine or sodium chlorite under conditions that minimize chemical attack on the polysaccarides. The product
obtained after removal of lignin is extracted
with aqueous alkaline solutions to separate
the insoluble cellulose from the soluble
hemicelluloses. Hemicelluloses are precipitated from the alkaline solutions by acidification and by addition of organic solvents
(20). The cellulose fraction obtained by
such procedures is often contaminated by
residual lignin and polyoses while the hemicellulose fraction may contain low molecular weight cellulose.
Another approach used for measuring the
cellulose and hemicellulose content of pulp,
as well as the molecular composition, is to
determine the monomeric sugar units ari1r
ing from degradation of the polysaccharides.
Traditionally,
degradation
is
accomplished by acid hydrolysis, that is, by
682
Pulp Bleaching
-Principles
and Practice
is obof hex-
Separation
Technique
Pretreatment
Derivatization
of Hydrolysate
Procedure
Column
Detection
GC
Neutra1ization,
drying
Fuse<kilica
capillary with
nonpolar
liquid phase
FID
(25,26)
GC
Neutralization,
drying, reduction
to alditols with
KBH, or NaBH,
Acetylate with
acetic anhydride/
catalyst, extract
the alditol acetates
into organic solvent
Fused-silica
capillary column
with polar
liquid phase
FID
(22)
HPLC
Neutra1ization,
concentration,
clean-up
Polymer-based
cation exhange
column at
75-85 C
RI
(refreactive
index)
(27)
Ion
chromatography
pH adjustment
with NaOH
solution
Dionex HPIC-AS6
PAD(pulsed
amperometric)
(28)
IN of borate
complex,
(29, 30)
anion exchange
column
Capillary
electro-
No derivatization
phoresis
pyridine to form
N-2-pyridyl-
or add amino-
gIycamines
Silica capillary
column
indirect lN,
lNof
derivative
Reference
1736
co
'iij
In
'E
In
c:
~
I-
4000
2000
Wavelength, cm-1
683
"rJbleacHtl TMP.
450
684
Pulp
No.
Pulp;
Bleaching
Sequence
Brightness
(% ISO)
la'
Softwood
Ib'
Softwood kraft,
C/O Ell DED
2a
Softwood
2b
Softwood
Weak
Acids',
(mmol/kg)
0.190
18
80
0.190
17
28
96
0.172
35
88
kraft";
90.6
kraft";
TCF
3a
Softwood kraft";
D(EOP)DED
3b
Softwood
SO.l
5.0
97
0.176
10
64
88.3
0.5
94
0.171
31
84.4
1.7
95
0.172
45
96
0.263
12
65
94
0.238
13
104
0.260
10
76
88
0.183
13
81
kraft";
A(ZQ)(EOP)
Birch kraft";
D(EP)(D,E+P)D
88.9
4b
Birch
81.8
6.8
Birch kraft;TCF
(ozone)
89.2
2.8
6a
Eucalyptus
kraft";TCF
kraft";
ECF
6b
Strong
Acids',
(mmol/kg)
Total
HemicelV
Total
Carbohydrates, % Carbohydrates
32
kraft
D(EOP)D(EP)D
4a
Kappa
Number
685
Eucalyptus
90.7
kraft";
TCF
6
Softwood sulfite; P
Softwood sulfite;
OQP
85.8
86.4
5.1
90
0.181
11
114
15.0
90
0.164
36
82
87.4
4.8
94
0.126
17
52
rapid methods to pulps bleached with modem oxidative sequences needs to be evaluated to exclude
interferences
from
compounds having decarboxylation
rates
similar to those of uronic acids or from compounds forming colored reaction products
with the colorimetric reagents. A more reliable, but much more tedious, approach for
quantifying the carboxyl groups in uronic
acids is to analyze entire uronic acid residues as such. Individual uronic acid units
and carbohydrate composition usually cannot be determined simultaneously because
the glycosidic bond between a uronic acid
residue and a neutral sugar unit is resistant
to acid hydrolysis. Also, uronic acids are
probably degraded to a large extent during
hydrolysis with concentrated
acids. Re-
686
Pulp Bleaching
-Principles
and Practice
4. Extraneous
materials
Extraneous
materials are usually extracted from pulp with an organic solvent,
for example, acetone, ethanol, benzene, or
dichloromethane
in a Soxhlet apparatus or
a Soxtec apparatus (55). In the future, acetone will probably be the most common
solvent for extractions because the use of
aromatic and chlorinated solvents will be
restricted for health and environmental reasons. The weight of the acetone extract is
usually higher than that of a dichloromethane extract of the same pulp (56, 57).
For efficient extraction of fatty and resin
acids with acetone, it is important to acidify
the pulp to pH below 3 before the extraction to convert the acids from an insoluble
metal soap form to a soluble, free-acid form
(57).
The use of organic solvents can be minimized by supercritical fluid extraction.The
most commonly used solvent is supercritical
carbon dioxide. Only minor amounts of
687
molecular size and detected with the universal refractive index detector. The SEC
chromatograms in Fig. 4 reveal that the composition of cWorine dioxide-bleached pulp
extractives is different from that of unbleached pulp extractives. The upper chromatogram in Fig. 4 shows the presence of
the three groups of components
usually
present in unbleached sulfate pulp: steryl
esters, sterols and fatty acids, and resin acids. The lower chromatogram of cWorine
dioxide-bleached
pulp suggests that the
molecular volume of the extractives increases during bleaching, possibly because
of polymerization and oxidation. The chromatogram further shows that only a part of
the extract can be related to the groups
present in unbleached pulp and wood.
Chromatographic separation techniques
The group separation obtained by SEC
can be complemented
by other methods.
Thin layer chromatography on silica gel has
been used for analytical and preparative
fractionation of wood extractives in spruce,
pine, and birch (58; 59). Universal detection by spraying with aqueous sulfuric acid
and heating can be combined with densitometric scanning to obtain setniquantitative results. Specific detection with a UV
scanner affords chromatograms similar to
688
)(
en
1: Steryl esters
2: Fatty acids and sterols
3: Resin acids
."5
en
>
13
-a:~en
~
intemal
standard
20
22
24 Time, m-..
Increasing molecular volume
of tbe extrtlets
of ..bletlt:11M
tm4 ECF-bktu:11M
I.a
18:1
Q)
CJ)
~c:
0
a.
CJ)
l.a.-amide
I.a
16:0
u:
f.a 22:0
l.a24:0
~f.a
8:0
I.a
26:0
15
25
20
Retention
time,
<f.
Co
'iij
UJ
'E
UJ
c:
~
I-
3009
1153
1742
4000
Fig. 3. FI1R spec"."", of tbe _toree
2000
Wavelength,
450
cm-1
multaneous quantitative analysis of all major wood extractive groups in silylated extracts (51). The technique has been applied
to the analysis of white water from unbleached and peroxide-bleached
TMP suspensions.Analysis oflow concentrations of
specific low molecular weight compounds,
such as individual fatty acids, resin acids,
or defoaming agents is usually done by capillary gas chromatography using conditions
optimized for the specific compounds of
interest (Fig. 5).
689
characterization
of these sub-fractions is
difficult because the chlorinated
compounds are not readily distinguishable by
the techniques commonly used for characterization of pulps and extracts as a whole
(66).
Identification of cWorinated compounds
in extracts requires the use of special mass
spectroscopic
techniques. McKague and
Reeve were able to identify cWorinated linoleic acid derivatives and cWorination
products of prenols by negative ion methane desorption chemical ionization mass
spectrometry
of the extracts
of fully
bleached pulps but were unable to quantify the identified
compounds
(67).
Quantitative analysis of targeted trace compounds, for example, chlorinated phenolics, is feasible by selected ion monitoring
mass spectrometry (68).
4.4 Metals
Oxygen, hydrogen peroxide, and especially ozone bleaching are sensitive to transition metals. TWs is because of the ability
of these metals to induce the homolytic
cleavage of hydrogen peroxide and organic
hydroperoxides formed during bleaching to
yield hydroxyl radicals that in turn are capable of oxidizing and cleaving polysaccharide chains (see other chapters of this
book).To maintain pulp viscosity It is therefore vital to measure and control the metal
profile of a pulp during bleaching.
The metal profile (in the form of counter
ions attached to acidic groups) also influences papermaking
properties
as mentioned above in Subsect. 3.3. Variations in
papermaking properties therefore may be
attributable to variations in the composition
of the mill's water supply or to the retention of sodium ions by the pulp during the
pulping process (38).
Analysis of metals in pulp consists of destruction of organic material to dissolve the
metals and instrumental analysis of the resulting metal ions in aqueous solution. The
organic materials are usually destroyed by
incineration followed by dissolution of the
residue in hydrocWoric acid or by wet digestion with nitric acid in an autoclave or a
690
in solid state,for example,UV (75, 76),midand near-IR (77), NMR (78, 79), and Raman
(80, 81) spectrometry. Recently, multidimensional fluorescence
(MDF) has been
suggested as a potential tool in the quantitative determination of low concentrations
of lignin in pulp (82). Vibrational modes
which are weakly active in one technique
are generally detected as strong bands in
another technique with the result that techniques such as Raman and IR spectrometry
(or NMR and ESR) provide complementary
information.
Signals from these spectrometric
methods have been widely used in research to
qualitatively demonstrate structural changes
occurring during various types of pulp treatment. However, it is difficult to extract
quantitative information from specific wavelength bands without considering matrix
effects leading to overlapping bands. Furthermore, the signal at one frequency seldom originates from one specific chemical
constituent, that is, it is more common that
information from several components overlap making peak assignment impossible.To
interprete data correctly and to facilitate
quantification, special methods are required
to handle co-variation.
Methods that apply to restrictions caused
by co-variation are generally termed multivariate data analysis (MVDA) methods and
have been discussed by Martens and Naess
(83). In these methods, a factor extraction
procedure is applied to reduce the number
of variables and to render the variables orthogonal, that is, to fulfill the requirements
for a subsequent regression calculation to
relate the signals to the analytical information sought. The use of techniques such as
PCA (principal component analysis) and PU;
(partial
least squares
projection
to latent
References
1. Voelker,
of
13. Westermark,
Holzforscbung
(1994).
U. and Gustafsson,
48 (Supplement):
14. Kvemheim,A.L.and
Scand. 43(2):209
Lystad,E.,Acta
(1989).
691
692
K.,
146
33. Dence, C. in Metbods in Lignin Cbemistry (S.Y Lin and C.W. Dence,
Eds.),
Springer, Heidelberg,
1992, Chap 2.
Chem.
16. Lauriol,J-M.,
Froment, P., Pia, F., Robert,
A., Holzforscbung
41(2):109(1987).
36. Lai,Y-Z.,Guo,X.P.,Situ,W.J.Wood
Thcbnol. 10(3):365 (1990).
37. Francis,
R.C., Lai, Y-Z., Dence,
c.w.,
AJexander,TC., Tappij. 74 (9),219 (1991).
L., Pap.
Puu
20. Fengel,
D. and Wegener,
Chemistry,
mtrastructure,
Gruyter, Berlin, 1984.
71(4):356
G., Wood ReacUons, de
3. Kettuncn,].,
Laine, J.E., Yrjala, I. Virkola,
N.-E., Pap. Puu 64(4):205 (1982).
24. Churms,
(1990).
S.H.,)
Cbromatogr.
7. Lindgren,
B.O and Sundin, S., Svensk.
PappersUdn.
81(15):485 (1987).
28. Penersen,R.C.andSchwandt,Y.H.J,Wood
Cbem. Technol. 11(4):495 (1991).
9. Basch,
Polym.
A., Wasserman,
Sd. 12(6):1143
T., Lewin,
(1979).
Sd.
M:,)
10. Schurz,
I., in Die
Cbemie
der
Pflanzenzellwand
(E. Treiber,
Ed.),
Springer, Heidelberg,
1957, p 360.
11. Hartler,
N., Lindstrom,
E.-B., Tubek-
lindblom,
A., Cellul. Chern. Techno/.
387 (1987).
12. Rantanen, T, Farm, P., Sundquist,}.,
Puu 68(9):634 (1986).
21:
Pap.
500:555
M.M.,
11(4):
29. Hoffstener-Kuhn,
S., Pailus,A., Gassmann,
E.Widmer, H.M.,Anal. Chem. 63(15): 1541
(1991).
30. Honda, S., lwase, S., Makino, A. Fujiwara,
S.,Anal. Biocbem.
176(1):72 (1989).
31. Kleen, M. and Gellerstedt,
Pyrolysis 19:139 (1991).
32. Holmbom,
Eckerman,
(10A):VI6
G.JAnaI.ApPI.
51. Holmbom,
B. and Orsa, E,"Methods
for
Analysis of Dissolved and Colloidal Wood
Components
in Papermaking
Process Waters and Effluents; International
Symposium on Wood and Pulping Chemistry Pr0ceedings, CTAP!. Beijing, 1993, Vol II. p.
810.
35. Mimsson,
(1983).
34. Tschirner,U.
and Dence,
70(4):338 (1988).
4. Gumagul,N.,Page,D.H.,Paice,M.G.,Nord.
Pulp Paper Res.) 7(3):152(1992).
P., Holzforscbung
37:143
52. Belitz, H.-D. and Grosch, W:, Food Cbemistry, Springer, Heidelberg,1987,
pp. 164167.
Cbem.
Svensk
40. Lindstrom,
T. and Carlsson,
G., Svensk
PappersUdn.
85(15):RI4
(1982).
41. Lindstrom,
T and Kolman, M., Svensk
PappersUdn.
85(3):RI40
(1982).
42. Lindstrom,
T. and Carlsson,
G., Svensk
PappersUdn.
85(15):RI46
(1982b).
43. Katz, S., Beatson,
Svensk PappersUdn.
L.H..]
55. Halvarsson,
H. and Hult, 0., Tappi)
(10):105 (1983).
66
56. Bjorklund
Jansson.
M., Alvarado,
E,
Bergqvist,A.-K.,
Dahlman, 0., "Analysis of
Pulp Extractives with Off-line Supercritical
Fluid Extraction
(SFE) and Supercritical
Fluid Chromatography
(SFC); International Symposium on Wood and Pulping
Chemistry
Proceedings,
CTAPI, Beijing,
1993, Vol. II, p.795.
57. SCAN-cM 49:93 "Pulps-Determination
of
acetone-soluble
matter," Scandinavian
Pulp, Paper and Board Testing Committee,
Stockholm,
1993.
58. Holmbom,B.andAvela,E.,ActaAcadAbo,
Ser. B. 31(16) (1971).
59. Ekman,
(1979).
Ser B 39(4)
61. Sjostrom,}.
and Holmbom,
70(2):151 (1988).
49. Maekawa,
E. and Koshijima,
T, Mokuzat
53. Karlberg,
A.T.:Contact
Allergy
to
Colophony.
Chemical
Identifications
of
Allergens, SensiUzaUon
Experiments
and
Clinical
Experiences,
Doctoral Thesis,
Karolinska Institutet, Stockholm, Sweden,
1988.
62. Dunlop-jones,
N. and Allen, L.H., Tappi]
71(2):109 (1988).
K.M.J.Pulp
Pap.
Pulp
and Taylor,
L.T.,
29(8):351 (1991).
Nord.
Pulp
693
Tappt]
74(5):218
SECTION VB:
1. Introduction
697
697
698
699
701
702
703
704
704
3. Brightness measurement
3.1 Brightnesswavelength
3.2 Instrument geometries.
705
705
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 707
4. Sample preparation
712
695
Chapter VB 2:
Brightness: Basic
Principles and
Measurement
1. Introduction
Brightness indicates the level of success
in a bleaching operation. Bleaching chemically reduces the concentration of lightabsorbing
constituents
so that paper
reflects more light. Improved reflectance
is both the purpose of bleaching and the
means of monitoring its progress. Brightness, as a particular kind of reflectance,
belongs to a family of measurements based
on the interaction of light with paper.
Light interacts with paper or pulp sheets
in various ways: it may pass through, be absorbed and converted into heat, be absorbed and released again as lower energy
fluorescent light, reflect from the first surface encountered
as in gloss, or diffuse
through the paper to exit eventually from
one side or the other. Only light that actually penetrates the sheet can experience
absorption and influence the paper's color
in general and brightness
in particular.
Gloss, a mirror-like first-surface reflectance,
provides the papermaker with a valuable
index of surface roughness but complicates
brightness measurement.
Another optical
interaction
that complicates
brightness
measurement is fluorescence. Fluorescent
additives in paper absorb invisible ultraviolet light and replace it with visible blue light
that enhances brightness. Once light penetrates the paper sheet, it has the opportunity to reflect from fiber surfaces, scatter
from fines or filler, or be absorbed by fiber
wall constituents. If the likelihood of scattering is much greater than the likelihood
of absorption, most of the light will eventually exit from the illuminated side of the
sheet. Light that diffuses out from the illuminated side of the paper is designated dif.
fusely reflected light. The term "diffuse
reflectance" is used because the direction
of the exiting light beam has become more
697
698
Diffuse surface
reflectance
Gloss
------
~L
I
(a)
(b)
Diffuse internal
reflectance
Diffuse internal
transmittance
~ \~
,1/
(c)
"brightness." Over the next decade, brightness began to be specified in contracts and
regulations. By 1950, brightness measurement had become commonplace for paper
as well as pulp and remains so to this day.
It is still the only reflectance measurement
performed at some mills. Because brightness had been designed only as a tool to
monitor bleaching, its broader use as an
index of paper whiteness has led to some
inevitable confusion and controversy.
illumination
~ted
~I
Diffuse illumination
~/~
I
collimated
and
699
Ro
700
70
iii
(/)
60
-~
50
40
"5
d5
Black backing
30
20
10
White backing
o
Opaque pad of
the same paper
Fig. J. SebetMtk
~
iii
(/)
Q)
c:
II4grtIm
of
1I.Il-'
sbed
INdh8gs
Fig. 5. ReWlmlslnp
betrl1eer8 brlgbmess
100
90
80
90
60
30
0.4
0.6
of chromophores
IIIUI cbromopbore
0.8
removed
remoIIIIl.
80
70
C>
.;::
tbe e.llt
0.2
Fraction
100
50
.s::.
sIItnring
(/)
(/)
-~
40
"5
d5
70
60
50
40
30
20
20
10
o
10
o
o
0.2
0.4
0.6
0.8
1.0
1.2
k/s (Proportional to chromophore concentration)
Fig.4. RelMlmrsbipbetrl1eer8
brlgbmess au ebromojJboreetnU:MtrYItimte~
~ (ItIs).
0.5
-log(Fraction
1.5
chromophore
remaining)
of ebromopbore
removal.
(k\=(1-[B/l00])2
sl
2(B/1 (0)
[1]
and
[2]
where B is the brightness in percent. The
absorption coefficient, k, is proportional to
the chromophore concentration (~13) aJ:.ld
the scattering coefficient, s, is determined
by the fiber dimensions and the degree of
interfiber bonding. Because bleaching has
relatively little influence on the scattering
coefficient, k/s can be expressed as follows:
step. For example, if the ratio of (kIs) values before and after bleaching is 0.4, then
60% of the chromophores
entering that
bleaching step have been removed.
When reflectance at other wavelengths
is substituted for brightness, k and s are
functions of the wavelength. When more
than one chromophore
contributes to the
brightness, the absorption coefficient is the
average of the constituent absorption coefficients weighted by the respective chromophore concentrations. Recent work (14)
suggests an alteration of the Kubelka-Munk
equations that merely reduces the k value
by half, but this has no effect on the interpretation used here.
[3]
where c is the chromophore concentration
and q is a proportionality constant. IT the
brightness is measured before and after a
bleaching step and the corresponding
(kIs) values are calculated, the ratio of these
(kIs) values is equal to the fraction of the
chromophores
surviving that bleaching
~?-/p,\"
diagtYlm
illustrating
in
When a board is sawn, the sawdust appears whiter than the board. Similarly, the
more wood meal is ground, the lighter it
appears or, if colored glass is powdered, the
powder appears much whiter than the glass
because finer powder offers more opportunity for light to scatter. Chemically, the
sawdust is the same as the board, but the
ground material is brighter.
Because the brightness or intrinsic reflectance factor at another wavelength is only
a function of the ratio (kIs), a pulp with
20"10more scattering can also contain a 20%
higher chromophore
concentration
and
Fig. 7. Sebemstic
701
702
(2<onap~ -RBA)
s <X fiber thickness
[4]
SI
~icmn."
[5]
where t is the fiber wall thickness in microns. At small values of (k!s), the equation for reflectance as a function of (k!s)
can be approximated as follows:
B = 100"10(I-V 2~jn)
[6]
[7]
where k_ is the minimum k value of 0.15
m2 /kg. This equation reduces approximately to
Bow<= 100% - (8%) V t.mcro..
[8]
703
demoted by a fluorescent process and exits the paper as visible blue light, it passes
through the brightness filter and is detected
as bonus brightness.
Fluorescence
may
come from at least four sources: I)An optical brightening agent may be deliberately
added to the paper to enhance the brightness reading and to make the paper appear
whiter; 2) Inclusion of fluorescent paper
in the furnish of recycled pulp may transfer
an unplanned fluorescence to recycled paper; 3) In some cases, the bleaching of
nonfluorescent recycled paper can produce
fluorescent entities (26, 27); 4) A very low
level of fluorescence is naturally present in
paper (28,29).
TAPPI's official brightness test method
(2) defines a fluorescence factor and describes its measurement. The International
Standards Organization (ISO) and the Technieal Section of the Canadian Pulp and Paper Association have written standards for
brightness measurement that exclude fluorescent papers from the scope of the standard (30, 31) The ISO reintroduces
fluorescence in a standard for whiteness
instead of brightness (32). Both theTAPPI
and ISO methods rely on a filter to absorb
nearly all incident illumination having a
wavelength
lower than 420 nm. TAPPI
brightness or ISO whiteness is measured
first with the shott wavelengths included
and then with them excluded.
Care is
needed in calibration because light with
wavelengths between 390 nm and 420 nm
is detected in the brightness measurement
and insertion of a 420 nm high-pass filter
removes that light. Separate calibrations are
needed in which ultraviolet light is included
and excluded. Use of a 390-nm high-pass
filter might be preferred except that the
fluorescent whitening agents used in paper
are also excited by some blue light as well
as ultraviolet light.
Fluorescence often increases the brightness or whiteness by 10% or more with the
result that the apparent brightness may
exceed 100%. The fluorescent "bonus" to
the reflectance increases in proportion to
the amount of ultraviolet light in the illumination. The TAPPI Official Brightness Test
704
Pulp Bleaching
-Principles
and Practice
= 116
yl/3
16
[9]
3. Brightness measurement
3.1 Brightnesswaveiength
TAPPI and 150 brightness
The wavelength distribution was originally defined by a commercially avaIlable
Wratten filter. The central wavelength is
457 nm and the filter transmittance
is
greater than 50% from 440 nm to 480 nm
as shown inTable 1. Because a fluorescence
measurement is included in the same test
method, the relative intensity of incident
light in the ultraviolet spectrum is also specified. Table 1 can be taken as a specification
to be matched by a gelatin filter or it can be
used directly as a weighting function to calculate brightness from a reflectance spectrum. The 5-nm interval is sufficient
resolution for most paper spectra, but it suffers in comparison to the CIE colorimetric
functions (35). In common colorimetric
practice, reflectance is measured at 2-nm
intervals, multiplied by tabulated weighting
functions at the same wavelength intervals,
and integrated by simple summation. If the
reflectometer
records data at 10-nm or
larger intervals, then implicit interpolation
is used for the integration (44,45). Unfortunately, the choice of integration algorithm
705
706
Brightness
%
0
0
0
1
2.9
6.7
12.1
18.2
25.8
34.5
44.9
57.6
70
82.5
94.1
100
99.9
88.7
72.5
53.1
34
20.3
11.1
11.1
5.6
2.2
0.3
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
Tristimulus
Z
2.03
3.81
6.18
11.64
20.83
36.22
58.30
77.74
91.05
98.02
100.01
99.42
97.85
93.65
85.73
72.24
58.45
45.61
34.57
26.10
19.82
15.26
11.91
8.88
6.27
4.39
3.21
2.37
1.67
1.14
0.75
0.49
0.32
0.22
0.15
0.12
0.10
0.10
0.08
0.06
0.06
0.04
O.Oj
0.02
0.01
0.01
100
90
80
EC!
70
60
-0-0-
'ii)
3: 50
Brightness
Tristimulus z
.~ 40
Cij 30
CD
a:
20
10
o
o
0.1
0.2
0.3
0.4
0.5
Wavelength, 11Mmeters
can make a meaningful systematic difference and has been discussed within the ISO
with respect to ISO brightness.
The first instrument used for ISO brightness measurement was the Zeiss Elrepho,
and the combined effect of its detector, integrating sphere, lamp, and filter was a
weighting function having a central wavelength of 457 nm but which did not match
the details of the function in Table 1. The
SCAN brightness standard (46, 47) used the
Elrepho distribution as the new norm, but
the Technical Section of the CPPA, and later
the ISO,accepted the Elrepho as an approximation to the norm defined byTable 1. This
created some confusion as newer filter-type
colorimeters and abridged spectrophotometers having a choice of norms came into
use. All ofthis led to a call by some to abandon the brightness function and substitute
the better-defined CIE tristimulus Z measurement (48,49).
Brightness and the tristimulus Z value
Brightness is specific to the paper industry, but tristimulus colorimetry is applied
more widely. Brightness and the blue (Z)
colorimetric value sense the same part of
the spectrum as shown in Fig. 8. The Z function is better-defined
and better-studied
because of its nearly universal application
in colorimetry. At one point a decade ago,
it was proposed within the ISO to generate
0.6
0.7
1 do
R(I..)
n. WI.
'''''n
an is given by
[11]
= fdA.F(I..)R(I..)
[12]
=L a" JdA.F(A.)RQ.-457Y'
[13]
Z =L a"M~
[14]
and
B=Z+Ln=o a,,(M: -M~
[15]
Table 2 shows the first few terms of the difference in moments. In practice, the fiist
few terms can be written
B
Z + bl x slope + bl x curvature
[16]
'"
where the b coefficients are constants.
When the brightness and Z values are compared for newsprints (50), where the slopes
and curvatures of the R(l) curves are nearly
identical, the two color indices are highly
correlated. In a bleaching sequence, however reflectance increases with the extent
of bleaching and the slope of the reflectance curve becomes progressively less
steep. Therefore, the relationship between
brightness and Z varies with bleaching level.
la ..o..eats
bdftleea tbe
jrutdImts.
Difference
Brightness
x 100
x 100
x 100
First
0.01605
.{).34118
0.35723
Second
0.om4
0.06933
.0.03398
Third
.{).00015
0.00041
.{).00056
Fourth
0.00005
0.00015
.{).00010
.M2mm1
707
the specimen surface and views at 0" (norma! or perpendicular to the surface). The
second instrument type diffuses the light
around the white inner surface of a spherical cavity and allows this diffuse light to fall
at all angles onto a specimen placed at an
aperture in the sphere. The light is detected
normal to the surface (0") or nearly normal
(8") to the surface. ISO brightness uses only
the integrating sphere geometry in Standard
2470. Although TAPPI has official test methods using both geometries (T 525 uses an
integrating sphere and T 452 uses directional illumination), the term "TAPPI brightness" usually refers to the directional
brightness.
Description of the geometry
As shown in Fig. 9, the light from an incandescent bulb is directed onto the paper
at 45 to the surface with a cone of illumination having a half angle 11.5 and viewing is within one-half a degree of the
perpendicular
direction with a half angle
of 22.5. The dimensions are such that light
from the rim of the 9.53 mm diameter
specimen aperture Is not viewed by the
detector. The dimensions, and particularly
the haIf.angie defined inTest MethodT 452
for brightness,
are specified much more
precisely than in the corresponding method
T 524 for colorimetry.
Brightness scale and calibration
It is important to distinguish between
relative rejlectam:e, absolute dtffuse reflectance, and absolute directional reflectance.
Barium sulfate powder may reflect about
99% of all the diffuse visible light falling on
it. This number corresponds to absolute
dtffuse reflectam:e and can be compared
with the reflectance of a fictitious "perfectly
reflecting diffuser" that reflects all diffuse
light. The perfect diffuser is also said to be
"Lambertian" in that it reflects light at all
angles with equal likelihood. Barium sulfate is not perfectly Lambertian and reflects
about 2% more light at mid-angles around
45 than it does for glancing angles or even
angles near normal (51). The reflectance
of the material for 45 illumination compared with the reflectance of a perfect dif-
708
Detector
Filters
Paper
Fig.'. SckmMie tlMgtwmillllStrtltillgtbe ill_IutUm
_.
system fIHtl to __
"'m:HOIu" (TAPl'1)bright-
The geometry of TAPPI brightness corresponds to reading paper with a lamp behind the the shoulder, but the geometry of
ISO brightness corresponds to reading with
709
indirect lighting in a white room. As illustrated in Fig. 10, light is forced to diffuse
about inside a spherical white cavity before
it impinges on the paper specimen. light
fal1son the paper from nearly all angles. ISO
brightness is the standard form of brightness measurement in Europe and Canada
and much of the world.
Description of the geometry
The ISO brightness geometry is specified
in ISO Standards 2469 and 2470 and is more
restrictive than the CIE requirements for
reflectometers
employing
integrating
spheres. The diameter of the measuring
aperture is 30 mm to allow adequate sampling of the paper surface; the sphere diameter is 150 mm, but the total area of all
apertures must cover less than 10"16of the
sphere surface. The paper is viewed normal (perpendicular)
to its surface. Presently, colorimeters having smaller spheres,
or those viewing 8 from the normal are excluded from the standard.
The detector aperture is surrounded by
a black portion of the sphere surface that
subtends a half angle of 15.5 as measured
from the specimen surface. This region is
called a "gloss trap" and is either painted
matte black or can be an aperture in the
sphere opening to the black interior of the
instrument. The aperture form of gloss trap
is more popular in instruments excluded
from the ISO brightness standard because
they view 8 from the normal (47). The
purpose of the gloss trap is to exclude
specular (mirror-like) gloss reflectance from
the measurement.
When the gloss trap is
working well, the colorimeter
registers
nearly zero reflectance when a good mirror is placed at the specimen position. In
practice, 2% to 4% reflectance has been
observed (58) indicating that gloss exclusion is good but far from perfect. Agreement among colorimeters from different
manufacturers would improve if gloss traps
were absent or were identical (59), but
gloss exclusion is needed for several reasons: Creation of a glossier surface in a
brightness pad should not be a substitute
for more effective bleaching. Under usual
viewing conditions, specularly reflected
710
Pulp Bleaching
-Principles
and Practice
system used to __
Q(t..)= P(t..)
I-p(/..)
P(t..)
Q(A.) =
I-p(t..)
[17]
[18]
71 I
tetrafluoroethylene)
maintain stable high
reflectance from visible wavelengths well
into the ultraviolet region. The more common barium sulfate paint, however, has a
reflectance that smoothly drops from about
0.99 for green light to about 0.80 well into
the ultraviolet region depending upon its
age. If the sphere yellows with age, the
effective wavelength of the spectrum-exciting fluorescence
is substantially altered.
Reflectometers
using integrating spheres
can correct for this sphere error by measuring the light intensity on the sphere wall
with one detector and dividing this into the
intensity registered from the specimen. The
correction is more complete if done wavelength by wavelength instead of with the
intensities
transmitted
by broad filters
where major sphere yellowing can bias the
effective filter function. The integral of a
ratio is not the same as the ratio of integrals
is shown below:
rdA.
Q(t..)F(t..)R(t..)
Q(t..)
'*
JdA. Q(t..)F(t..)R(t..)
Jdt.. Q(t..)F(t..)
[19]
712
(d/O)
4. Sample preparation
Machine-made paper needs no special
sample preparation for brightness measurement except to ensure that the paper stack
is sufficiently thick to be opaque. The concern in preparing pulp for brightness measurement is to form a sheet in a way that
does not introduce measurement complications.
Some sample preparation steps complicate the measurement (67). The measurement is more representative of the pulp if
the sheet is uniform from top to bottom and
across the top. Slowly draining pulps can
form density gradients in fines or residual
ink from top to bottom. Swirling of the
slurry during drainage often results in nonuniform brightness across the sheet surface.
Drying without restraint permits shrinkage
together with crinkling of the sheet surface.
When the crinkled pad does not lie flush
against the aperture
of an integrating
sphere, it cannot be properly measured. If
the pH of the slurry is not appropriate for
the pulp components or the product enduse, the pulp may discolor. or filler may
coagulate and become less effective. Mechanical pulps or unbleached kraft pulp can
lighten by one or two brightness units per
pH unit change produced by souring. Souring is appropriate if the paper is manufactured under acidic conditions. Otherwise,
souring increases the discrepancy between
the brightness of the pulp pad and the
brightness of machine-made paper.
Standard practice in Canada calls for making a 4-g pad in the stainless steel deckle of
a standard sheet mold followed by restrained drying. The relatively fast drainage
lessens the sidedness of the sheet, but whatever sidedness is present is measured and
noted. The pulp is diluted in the sheet mold
713
International
Commission
on mumination (the initials come from Commission
International
de L' Eclairage), an international group of optical experts.
Color (colour)
A sensation
associated with
the sight of light in particular wavelength
ranges.
Colorimetrv
A process of objective measurement that corresponds
to the sensation of
color under
specified
viewing
conditions.
in the
llluminant
An officially tabulated spectrum
of energy emitted from a physical source
like the diffuse light from the north sky or
the light from an incandescent
lamp. The
illuminant function is used for colorimetric calibrations.
Chromo!,hore
A chemical entity that absorbs
light at a specific frequency.
714
Specular
reflectance
Index of refraction
The ratio of the speed of
light in a vacuum to the speed of light in
the material.
When light encounters
an
interface between
regions with different
indices of refraction, the light may scatter
or refract.
Infrared lilZht Light with slightly too little
energy to be visible; light with a wavelength greater than 770 om.
Int~tinsz
s!,here Light reflecting repeatedly
from a white coating inside a hollow sphere
illuminates
paper situated at an aperture
of the sphere with light impinging equally
from all directions.
Lambertion illumination
Incident light from
all directions above the sheet with equal
likelihood.
Luminous reflectance
factor The intrinsic reflectance factor of light with a spectral distribution corresponding
to the sensitivity
of the eye. Tristimulus Y reflectance.
light.
Transmittance
The fraction of incident light
intensity that diffuses all the way through
a sheet.
Tristimulus functions The eye processes
red,
green, and blue light in separate sensory
channels, so the perception
of any color
can be factored into a combination
of these
three basic "stimuli." The average detection
efficiency of each channel per wavelength
is called its tristimulus function x(A.), Y(A.),
or zQ..).
Tristimulus
values The reflectances
of red
light 00, green light 00, or blue light (Z)
with the spectral distributions
of the corresponding
tristimulus functions.
Ultraviolet light Higher-energy
light with a
wavelength somewhat shorter than 400 om
that is invisible.
Wavelen~
The distance light travels during
one full oscillation
of its electric vector.
Light scatters
strongly
from structural
discontinuities
that are one-quarter
wavelength wide. Wavelength
is inversely proportional to the light energy.
Whiteness A colorimetric index that takes into
account the human bias for blue-whites
over pink-whites.
It applies only at very
high reflectance.
References
Relative reflectance
A reflectance
scale in
which 100% corresponds
to the reflectance
of a reference material such as barium sul-
fate.
Specular reflectance Mirror-like reflectance.
If the incident light is collimated, the reflected light will be equally collimated.
(1994).
3. Barkas, WW, Proc. Pbys. Soc. 51(2):274
(1939).
A., Svensk.
Papperstidn.
56: 607
Trade]
10. Steele,
(1937).
F.A., Paper
Trade]
54:663
104: TSI57
w: D., Paper
Trade]
Cbem-
105:TS39
(1937).
13. Nolan, P.,Paper Trade]
105:TS42 (1937).
E.E, Tappi
Tappi
55(4):
(1988).
72(7):
159 (1989).
11(3):223
S., Dessureault,
30. Technical
Section, CPPA Standard
E-l,
"Brightness
of pulp, paper and paperboard; CPPA, Montreal.
l00(37):TSI51
715
31. International
Standards Organization Standard 2470, "Pulp and paper: Diffuse blue
reflectance
factor (ISO Brightness);
ISO
Control Secretariat, Geneva.
32. International
Standards
Organization
Document
ISO. CD 11475, ISO Control
Secretariat, Geneva.
33. Jordan, B.D. and O'Neill,
74(5): 93 (1991).
38. Stenius,A.S.,j
Res. Appl.
Color Appear.
Griesser,
1:8 (1972).
(1976).
R., Appl.
72(9):95
Opt.
(1989).
42. Malthouse,
D.D. and Popson,
48(1):95(1995).
43. Doshi, M. R.,Progress
107 (May 1995)
E.7P."LuCPPA,
19(6):475
S.].,Apptta
in Paper Recycling:
44. American Society for the Testing of Materials Standard ASTM E308-95 , ASTM Standards on Color and Appearance
Measurement,4th
edn.,ASTM,
1916 Race Street,
Philadelphia,
1995.
45. Bristow,].
S., Dubreuil,
M.A., Tappi
A., Tappi]
78(12):45
P3, "Pulps,
(1995).
paper
and
716
Pulp Bleaching
-Principles
and Practice
Tappi]
59. Budde,W:,Color
77(5):174
(1994).
49. Technical
Section CPPA Standard EP.6,
"Blue reflectance
(Rz) of pulp, paper, and
paperboard;
CPPA, Montreal.
50. Weiss, G. and Bruce, A., Pulp Pap. Can.
83(2):T50 (1982).
51. Eagan, W:G. and Hilgeman,
15(7): 1845 (1976).
A.R., Appl.
Res.
Opt. 11(9):1936
of OpUcal
New York,
M.A., Sommerville,
Pulp
Pap. Set.
Res.Appl.
5(2):73 (1980).
60. Budde, w: and Chapman, S. M., "Measurement of brightness and opacity according
to ISO standards,"
Transactions
2: 61
(1975).
Farbe 19:94
(1970).
62. Budde, W. and Chapman, S. M., Pulp Pap.
Mag. Can. 69(7):T206
(1968).
63. Commission Internationale
de I'Eclairage:
Technical report No. 44, "Absolute methods for reflection
measurements"
1979.
Bureau Central de 1a CIE, P.O. Box 169,A1033 Vienna, Austria, 1979.
64. Erb, w: and Budde,
4(3):113 (1979).
W:, Color
M.,j
Res. Appl.
Pulp Pap.
Standard
3688,
"Pulps
- Preparation
of laboratory
sheets for the measurement
of diffuse blue reflectance
factor (ISO
Brightness);
ISO Control
Secretariat,
Geneva.
SECTIONVB:
The Properties of Bleached Pulp
Chapter 3:
Strength Properties and
Characteristics of Bleached Chemical
and (Chemi}mechanical Pulps
G.E. Annergren
SCA ResearchAB
Sundsvall, Sweden
1. Introduction
1.1 General considerations.
. . . . . . .. .. . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Principles underlying strength teSt measurements. . . . . . . . . . . . . . . . . . . . . .
1.3 General effect of bleaching on papennakiog properties. . . . . . . . . . . . . . . . . .
2. Factors affecting the mechaoical properties of chemical pulp fibers . . . . . . . .
2.1 Fiber dimensions
2.2 Fiber damage. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Cellulose content. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Degradation of cellulose and hemicelluloses
2.5 Drying . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Factors affecting the mechanical
properties
4. Factors
properties
of (chemi) mechanical
719
719
722
723
723
725
725
726
726
727
4.1 Principles
730
4.2 Test methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 730
4.3 Interpretation oftest results
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 732
5. Mechaoical properties ofb1eached
pulps in standard paper networks
6. Relevance of a standard
(chemi)mechaoical
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 735
papennakiog
736
kraft pulps . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
sulfite pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
(chemi)mechanical pulps. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
in pulp strength testing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
717
738
743
744
745
Chapter
Chapter VB 3:
Strength Properties
and Characteristics of
Bleached Chemical and
(Chemi)mechanical
Pulps
1. Introduction
1.1 General considerations
Bleached chemical pulps are used for different types of products, but mainly for paper products (fable 1). The most important
product, particularly for hardwood pulp, is
so called wood-free printing and writi(1g
paper (paper with less than 10% mechanical pulp) often tenned fine paper (1). Softwood pulps are also used for reinforcement
in wood-containing
printing paper (mechanical pulp-containing paper),newsprint,
and magazine papers. Board and tissue are
other important products made from both
softwood and hardwood pulps. Their use
in markedly strong paper products, such as
higb-quality sack, is limited. The requlre-
Paper or Board
Printing and writing paper
Wood-free
Wood- containing
Newsprint
Tissue
719
Pulp Type
Contribution
Softwood kraft
Hardwood kraft
Softwood sulfite
Hardwood sulfite
Reinforcement
Opacity, formation
Reinforcement Opacity'
Filler pulp
Softwood kraft
Mechanicalb
Reinforcement
Opacity, printability
Softwood kraft
Mechanical pulp
Various chemical
pulps
CfMp<
Reinforcement
Bleaching in case of dark wood
Softness, absorption
Absorption,
to Paper Furnish
r,,6k
paper
Softwood kraft
Strength
Container
boxboard
Chemical pulps
COIIlrlbatN
by tlI./fnnt
Softwood Pulp
Hardwood Pulp
Strength
Runnability
Formation
Opacity
Mechanical Pulp
Opacity
Forming Section
pulp
,
Chemithermomechanical
pulp.
Press
Section
1
"Free. Vacuum
Drainage Drainage
Dominating component.
Fig.1. ~
Chemicals
Retention
Hydrophobicity
Strength
Brightness
smoothness, although strength is also desirable. Long fibers, on the other hand, often have a purely strength-contributing
function which is also associated with the
diffuse concept of runnability (i.e., the ability to run the paper machine or printing
press smoothly, without breaks). In this
case, good strength is often used to minimize the long-fiber content of the furnish
to decrease costs or to improve other papennaking properties of the furnish. These
concepts also apply to the production of
wood-containing printing papers.
Mechanical pulps consist of a mixture of
long fibers and fiber fragments (2). Fiber
fragments (i.e. ,fines) play an important role
in bonding, light scattering, and surface
smoothness. The more or less undamaged
fibers help to form the backbone of the
paper sheet. The bleached mechanical
pulps are used together with reinforcing
softwood chemical pulps in printing paper
where the ability to interact and create the
required bonding in the fiber network is of
major importance.
The runnability of a pulp in a paper mill
has become increasingly important as the
demands for productivity and efficiency
have increased in paper mills. Improvements in paper machine technology have
eliminated some problems but, at the same
Headbox
Fillers
Opacity
Bulk
Surface and pore
structure for
printability
Surface
smoothness
bulk
Packaging
CTMP'; mechanical
720
Dryer
1
Paper
3.
FIIdors
tlffeclitlg
I'IIIUIIIIJI1Uy.
Beating (refining)
objectives:
Development
of fiber flexibility
and tensile strength
Reasonably
Minimum
Retention
Impurity
721
low energy
requirement
fiber damage
and formation
deposition
Drainage on the
paper machine:
(e.g., pitch)
Free drainage
Vacuum drainage
Drainage in presses
release of paper
strength
web
722
eommercItIl~.g.
"""
Commercial Papermaking
Multkomponent
Poorer retention
Extremely
formation
of fines
good random
sheet
paper furnish
machine
Large variation
Mild pressing
and drying
in grammage
Chapter
properties
723
724
wood assortment.
Mill processes
may
contribute to fiber heterogeneity through
nonuniform operating conditions.
Fiber
heterogeneity is sometimes considered to
have an adverse effect on papermaking
properties. This view is probably correct
when an unintended
heterogeneity
becomes too large. However, the fact that
paper mills successfully mix different kinds
of pulps to create the required paper properties demonstrates that fiber homogeneity
is not necessarily disadvantageous.
Because of the inherent heterogeneity of
pulp, mean values, confidence intervals,
distribution curves, and extreme values are
required for a comprehensive characterization of fiber properties. In general, mechanical properties can be related to mean
values. Flocculation and poor formation are
caused primarily by extremely long fibers.
Extremely coarse fibers contribute to an uneven paper surface with poor printing properties and unsatisfactory softness. Several
of the factors affecting the strength properties of bleached chemical pulps are listed
in Table S.
Factor
Effect on Mechanical
To some extent observable under the microscope; a quantitative determination of their effect
011papennaking strength properties requires an
imitating papennaking test
Cellulose content
Cellulose fibrils are the main load-bearing components: the relationship between ordered (crystalline) and less ordered cellulose determines stiffness
and elasticity of the fibrils
Hemicellulose
content
2. Mechanical properties of
chemical pulp fibers
Degradation
of load-bearing carbohydrates
Properties
fibers
by viscosity measuresolvents
Usually very small effect, except possibly properties related to fiber surface. At higher concentration, some influence on beating response.
Chapter
725
Fibers are damaged mechanically in different ways in the pulp manufacturing processes with the result that pulp mill fibers
contain more kinks and cell wall dislocations than do fibers in corresponding laboratory pulps (22, 82). Fibrous material is
obviously quite sensitive to mechanical
loads, both high-shear forces, for instance
in medium-consistency
high-shear mixers,
which give a kind of beating effect (83, 84)
and loads on fibers whose motion is restricted, as, for example, in soft chips during pulping or free fibers present at such a
high consistency that a rigid network is
formed, as is the case in medium- or highconsistency operations.
Severe damage, sometimes visible as
kinked fibers with sharply acute bends, as
cell wall fractures and, in more severe cases,
as cut fibers, irreversibly affects papermaking strength.
Strength effects are often
measured as so-called "strength delivery" in
the form of tear strength at a reasonably
high tensile index after standard laboratory
beating in comparison with the corresponding values for an undamaged pulp obtained
from the same kind of process (i.e., a mild
laboratory process) (26, 85). Less pronounced damage, conspicuous as curl, less
severe kinks, or micro-compressions
in the
fibers, is reversible and can be restored by
homogeneous, mild laboratory beating but
not under less ideal mill beating conditions
where strength development
is retarded
(27, 28).
Mechanical damage leading to dislocations in the fiber wall exposes cell wall
material to intensified chemical attack. This
may lead to strong localized weakening of
the fiber wall. A typical example is the
mechanical damage occurring during chipping which greatly impairs the strength of
acid sulfite pulps. Kraft pulping, on the
other hand, is affected only to a small extent by fiber damage during chipping (29,
30). This difference in the effects of acid
and alkaline conditions in pulping suggests
that the risk of harmful combinations of
mechanical damage and chemical attack is
726
_ E15
Jfz
C\i'014
EO
~ -;
CI)13
xCI) -g
12
I- ~ 10
1ii
9
40
42
44
46
Total yield % of wood
of to,," yield
48
50
Degradation
of cellulose
and hem i- .
celluloses
Degradation of cellulose and hemicellulose chains to fragments is an important
consequence of both pulping and bleaching. Degradation is determined by measurement of the viscosity of a solution of the
pulp, usually in a cupriethylenediamine
(CED) solution (37). The method is based
on the fact that the viscosity of a solution
containing linear polymers depends on the
chain length, that is the degree of polymerization (DP). Cuprammonium
hydroxide
and cadoxen (a cadmium complex) have
also been used as pulp solvents (37). In all
cases, dissolution of the pulp takes place in
an alkaline medium. Viscosity testing is of
great importance in process and quality
control, particularly in the bleach plant,
Chapter
Density
(kgIm3)
Wet pulp
Dried pulp
PFt beating,
640
42.5
592
30.8
handsheet
made
Unbeaten Pulp
Tensile
index
(kNm/kg)
727
Tensile
Tear
light
Air
Beater
index
index
scattering resistance,
R'volu- Density
ions
(kgIm3) (kNm/kg) (Nm2/kg) (m2/kg) (log Gurley)
8390
8825
according
838
106
7.9
13.2
2.57
813
98.5
8.4
14.9
2.16
to SCAN-C 26:76.
2.5 Drying
Drying has a strong influence on fiber
properties (32, 41-43) ,as illustrated inTable
6; it decreases swelling ability and makes
fiber conformability
more difficult to
achieve. In principle, mild beating should
offset adverse drying effects. However, in
practice, refining is not mild enough to allow the strength development to occur in
the same manner as that for never-dried
pulp. Thus, never-dried pulp is preferred
when strong papers are required. Fine paper is an exception because,in this instance,
the required balance berween strength and
opacity (light scattering of the fibrous material) can more easily be attained with previously dried pulp.
Recycled fibers are conventional fibers
which have been refined and dried in one
or more cycles. Contamination
with, for
728
Pulp Bleaching
1::
Q)
Q.
:
0
C
0
+:
::]
.c
.;::
20
.~
Q)
0
0>
c:
as -10
.c
()
0:
geneity of the fibrous material makes it difficult to distinctly characterize this material.
A Bauer-McNett fractionation using for instance 16-,30-.50-, and 200-mesh screens
can give a general view of the characteristics of different mechanical pulps as illustrated in Fig. 4 where the distribution
berween >30 mesh, 30- 200 mesh, and >200
mesh fractions are shown (45). The +16,
+30, +50, +200, and the -200 fractions correspond, respectively, to shives, coarse fibers, finer fibrous material having good
papermaking potential, and shives.
30
0
~Q. 10
and Practice
example, dyes and inks and mixtures of different types of fibers and fillers also characterizes this material. The dominating
changes in the fibers are caused by degradation during refining and decreased swelling capacity of the fibers caused by drying.
The effect on papermaking properties of
repeated drying cycles is illustrated in Fig.
3 (44).
100
II)
Q)
-Principles
50
I.. mN"",,Il
Shives
Fiber bundles
Fiber fraction
Fines
Mesh
<200
30-200
II)
is
>30
-20
0
-30
2
98.5
97.5
97.0
95.0
56.5
46.5
Yield,%
Fig. 4. 1yp1al11l1strllnltttm of ftImnIs ",.,erltIlIlSeIiI..
leI!eu (1IIUIerMcNettclllSslj'laltWrl) (45).
_spri..t
)'lelll
.
c:m. be use d to exp Iam differences between
similar types of pulps. However, differ-
.
.
. between
ences In mec h ~c al properties
pulps made by different processes have yet
729
Method
Measurement
TAPPI
Scan
CPPA
T2050m-88
T 205 om-88
T 200 om -89
T 248 cm -85
C 18:65
C 18:65
C 25:76
C 24:67
ClOP
Drainage properties
Handsheet formation for physical
testing of pulps
Strength properties
T 221 om -93
C 19:65
CI
C2
C7
730
4. Mechanical properties of
bleached chemical pulp fibers
in standard paper networks
4.1 Principles
The papermaking properties of a pulp
depend on how pulp fibers behave in the
papermaking process and how they influence mechanical and other paper properties. To a considerable extent, the answer
to this question can be predicted from measurable fiber properties; however, the quantitative effect of such important phenomena
as mechanical
damage and structural
changes in the fiber wall on the papermaking properties carmot be easily determined
by direct measurements on the fibers. Furthermore, there is a difference between the
general behavior of fibers and their behavior in a dense network such as is present in
paper.
In the laboratory testing of papermaking
properties, the procedures that are used
attempt to imitate industrial papermaking
which consists of several different unit operations (Table 8). In any test method, the
procedure has to be carefully standardized.
Because papermaking practice varies considerably among paper mills, the test
method must involve a compromise
in
which the goal is to obtain internally repeatable and, if possible also, externally reproducible results. This means that laboratory
tests do not closely mimic common industrial operations and that they should be
considered only as an indicator of fiber behavior in a standardized network of a type
which can be found in paper, but not necessarily in a particular paper. In such instance, results are relevant for papermaking
but need to be translated to become directly
applicable to a particular paper mill situation.
4.2 Test methods
Sheet formation procedures that mimic
the formation of paper in the papermaking
process involve the following steps:
I) Disintegration of the sample;
T 205 om-88
T 220 om-88
C 26:76
C 28:76
C4
DI2
Chapter
loss of some fines in the sheet-forming process should be noted. Despite differences
in the standard methods, pulps are usually
ranked in a similar order. Some pulps need
more beating to develop optimal sheet
strength; sheet-forming methods which produce denser sheets for a given degree of
beating tend to favor these pulps, but the
deviation in ranking seems to be small.
Handsheet tests usually consist of density, tensile index (and/or burst index which
usually is correlated to tensile index), tear
index, and light-scattering coefficient measurements. Characteristic
values are obtained for the pulp tested.
Other tests
731
which are more sensitive to the fine structure of the sheets, for example porosity and
surface structure, require a more sophisticated sheet-forming procedure to give reliable results.
Examples of beater curves are shown in
Fig. 5 for a normal Scandinavian softwood
kraft pulp and a eucalypt kraft pulp of medium strength.
Over the years, different "standard" methods have been used, making it difficult to
compare test results from diverse pulp
sources unless results from well-characterized pulps are included. Strength test results have also been reported differently:
60
Property
Pair
Tensile index
Effect Measured
Tensile strength
beating time!beater
40
30
o Drainage resistance, SA
. s, light-scattering
/;. CSF x 0.05
o Density x 0.05
20
10
coati.
0
0
2000
4000
6000
Possible variations
Light-scattering
SA
Tensile index
Density
s
40
30
o Drainage resistance, SA
Tear index
20
o Density x 0.05
. Tensile index x 0.5
[J Tear index x 3
10
. s, light-scattering
0
0
2000
4000
6000
8000
coati.
10000 12000
Baater revolutions
Fig. 5. &!ater
CflMJeSfor
ty/IkIIl
COIIIIIIeI'ritIlly
bte.ebetl
ScIIIuUtUlvIsn
sojlwJood
IHIrtlwootl
"""
(elWidypt)
during
beating
coefficient
in beating
behavior,
paper bulk
tensile index
tensile strength as breaking length or tensile index (about ten times the breaking
length) and tear strength as tear factor or
tear index (about one-tenth of the tear factor).
development
revolutions
50
60
732
development
Chapter
....
as
Q)
I-
30
25
20
15
10
5
733
Batch,
indirect,
Douglas Fir
Batch,
direct steaming,
Black Spruce
Continuous,
Jack Pine
...~
",
-25% '........
10
12
14
Breaking
Fig. 6. CtmIptIrlsoII of ItHIr-tnslle
relilttmublp
lIIOOIlirflft rmbIetu:bed pulps (58).
14
10
12
14
km
(sollilll_)
soft-
60
~A...
-N
E 50
......
....................
A 66
:s::
Q)
0(.) 40
CI
c:
.;::
Q) 30
:t:
<tI
(.)
I1J 20
----
Hardwood
Softwood
1500
B1
xQ)
"C
.S:
~I1J 1000
c:
Q)
-x
x
73
78
"'-n.
100"...102
500
00
o
500
700
Intrinisic
~158
A Conventional
bleaching of
unbleached pulp
10
~
ization (DP). When the cellulose OP becomes too low, paper strength is affected.
However, the effect of cellulose OP is superimposed on the effects of other variables
such as fiber type, mechanical fiber damage, and cellulose content which may give
rise to uncertainty.
Viscosity measurements are affected by
carbonyl groups in the pulp which contribute to falsely low-viscosity results. Reduction of the pulp with borohydride prior to
the test eliminates this problem which, in
most cases, is too small to justify taking this
step. An exception may be ozonated pulp
although, even in this situation the problem is usually eliminated when the ozone
treatment is followed by an alkaline (e.g.,
peroxide) stage.
With the introduction of major changes
in bleaching technology, different relationships between strength and pulp viscosity
may be expected. By analogy with the effect of pulping pH on damaged chips having obvious fiber wall dislocations, chlorine
dioxide bleaching at low pH and high tem-
....
<tI
Q)
+----. 215
~
sents the specific surface area of dried fibers (62, 88). An unfavorable development
of tensile strength during beating can, how.
ever, produce a deviation from the normal
relationship. It should also be noted that,
in the competition for fiber surface, differences in the increase of bonding surface
area and loss of light-scattering surface area
may appear when the sheet is formed differently. This is particularly obvious for mill
sheets.
Laboratory tests for evaluating papermaking properties
are time-consuming
and
unsuitable for direct process and quality
control in the pulp mill. Several investigations (38, 63-66) have shown that there is
a strong correlation between the mechanical properties of bleached pulp and pulp
viscosity in conventional bleaching. In mills
that maintain good control of the wood raw
material and pulping conditions, viscosity
variations reflect most pulp quality variations (66).
Pulp viscosity is an indirect measure of
cellulose chain length or degree of polymer-
I"'"
b:".:-"
CI
~
.S:
..,
100"-_
::i
12
10
length,
734
100
1~
900
viscosity,
o Conventional
bleaching of
oxygen-delignified
pulp
1100
dm3/kg
0 Acid hydrolysis
of bleached pulp.
OfJet'tIllstrMgtb (teMltUlu x tnslle Index) tIfIIl httrlask IIiseosUy for softFig. 8. Relilttmublp be'IIIOOIlInwft pulps flfter tlIfferetll trefltmmts (64). BetltlflgllltlS cmulrIeted lICCM'diflgto SCAN-C 18:65;
sbHt-furmirlg,
cbenrktIl c~).
tIS Jtreserlbed,.
SGtN-C 25:76(64).
(B1-B7 deJwtes
dtjJeretlt
bletlCbt"g
sequnlees
find
5. Mechanical properties of
bleached (chemi)mechanical
pulps in standard paper
networks
The
papermaking
properties
of
(chemi)mechanical
pulps are determined
through use of the same standards for sheet
making and testing as for chemical pulps.
However, the wood bolts or chips, with or
without pretreatment,
have already been
ground or refined to the target freeness in
the pulp mill, thereby eliminating the need
for additional laboratory beating. On the
other hand, for the purpose of studying the
characteristics of the pulp mill equipment
or a special type of process, it may be desirable to vary the mechanical energy input
in the mill to obtain pulp at different freeness levels.
The presence of fines in mechanical
pulps is a significant issue in pulp testing
because fines retention in normal sheetmaking is not particularly high, at least not
in cases where standard tests specify a low
basis weight. White water recirculation has
been used to increase the fines retention to
a high level, an important goal, for instance,
in bonding studies (67). Otherwise, white
water recirculation is a complication and
usually is avoided when only a relative scale
is required for comparing pulps.
Control of the fines content is also essential in the sampling of mechanical pulps
735
736
80
~70
60
==
CD 50
0
0
01 40
c:
'C
CD 30
0
I/J
.,!.
.s=
01
::i
~20
10
0
0
10
20 30 40 50 60 70
Tensile index (kNm/kg)
80
90
20
01
~C\I 15
E
Z
CD 10
".5
lIS
"CD
~Arrowindicating
effect of refining
0
0
10
20
30
Tensile
40
index
50
60
70
80
90
(kNm/kg)
Fig..9A(UPJWr):
blllliolublp be'lIgbt-sadtm.g coejJfdnlt tmtl telUile ilUlD:for diffet'ftlt ebemiCIIl
tmtl (,.",,~
JIII".,.fttrM 10tUlf-'j'twtIa&l_ls
(45).
,..,. tmtl telUile ilUlD:fordiff-'
ebemiCIIltmtl (ebemi)mlHuliCIIl
Fig. (w-r): blllliolublp be''B
JIII/JIs,.fttrM 10 tUjfnnI
Jr-leffls
",."ft
TMP.."---_#all""',
,."" SBK
_ibletlcbed
JnIl"
CI'MP
=cbemU~iCIIl
JIIII,.
=,.ftMr mecbaiCIIl
JIIII"UBS=afli1ktlcbetlsalftte
Chapter
illustrated in Fig. 10, printing paper furnishes consist of three types of components: a dominating, more or less shortfibered pulp ( a mechanical pulp or a chemical hardwood pulp), filler, and a reinforcing long-fibered
softwood
pulp. The
amount of reinforcement pulp, usually the
most expensive component, depends on
how well it fulfills its reinforcing role.
The reinforcing effect is determined by
the manner in which the different fibers
long, more or less flexible softwood chemical pulp fibers and less flexible mechanical
pulp fibers of different length or short, flexible hardwood chemical fibers
and the
filler interact synergistically (70). Fiber
length plays an important role in the reinforcing effect, at least within the reasonable
limits determined by the ability of the lopg
fibers to provide good formation.
Fiber
length is particularly important for imparting strength to the wet web in the paper
machine and to dry paper sheets having a
low degree of bonding. Fiber strength is
important in the dry paper, particularly for
sheets having a high degree of bonding.
Good fiber strength is also required when
contending with harsh beating conditions.
The development of tear strength during
bleaching illustrates what may happed to
fiber strength when it is measured on a wellbonded sheet. However, tear index as such
is not a completely reliable measure of the
reinforcing potential of a pulp because it
tends to favor pulps with coarse fibers, at
least at a low- or medium-tensile index level.
737
Filler
Reinforcement
pulp
Mechanical
short-fiber
pulp or
chemical pulp
738
kraft pulps
TAPPI
Viscosity"
cps.
Beater
revolutions
Density
(kg/m3)
Tensile
Index
(kNm/kg)
105
Tear
Index
(Nm2/kg)
739
25) ",
lightscattering
Coeff.
(m2/kg)
25.5
17.4
9000
7800
825
830
700
11.7
6500
820
99
9.3
8.7
13.5
14.5
89
7.7
16.6
15.2
11.7
7125
6200
835
830
99.5
92
Pulp Bleaching
8.9
8.2
14.6
15.9
-Principles
and Practice
Drainage
Resistance,
SR
Beating
Time,
min.
Density
(kgIm3)
Tensile
Index
(kNm/kg)
Tear
Index
(Nm'/kg)
Lightscattering
coeff.
(m'/kg)
Fiber
Coarseness
(mg/km)
Strong"
birch kraft
25
45
21
44
687
780
65.0
82.0
8.2
7.5
31.2
26.2
102
Soft<
birch kraft
25
45
13
33
645
28
53.3
70.0
7.3
7.1
34.0
29.3
100
Strong
25
45
23
50
601
711
52.8
76.1
7.3
7.6
38.6
31.8
78
25
45
24.5
55
576
647
45.9
71.3
7.3
8.1
41.0
34.7
73
25
45
15
41
576
647
32.1
52.6
55.0
46. 5
66
25
45
16
40
565
660
28.3
43.8
4.3
'U
4.1
4.3
40.5
35.0
98
Soft U.S.
25
southern
45
hardwood kraft
23
44
556
630
43.0
61.0
7.8
8.1
37.0
34.0
100
Scandinavian
25
softwood kraft 45
39.5
70
685
754
91.6
101
11.0
9.9
23.3
20.7
158
eucalypt kraft
bTAPPI methodT-230
740
Strong
eucalypt kraft
Filler
eucalypt kraft
om-89.
Beech sulfite
producing
pulps having a carbohydrate
composition which varies only slightly with
the bleach sequence and the applied chemical (elemental chlorine, hypochlorite, and
chlorine dioxide) under reasonably wellcontrolled
conditions.
Provided
the
pulping process is not extended too long
(kappa number~ 25), its effect on the carbohydrate composition is small enough to
make variations in pulping conditions of
minor importance. Therefore, conventionally bleached softwood kraft pulps are primarily characterized
by their intrinsic
viscosity (13, 66). Introduction of an alkaline oxygen delignification stage and a corresponding
reduction
of the chemical
charge in the following bleaching stages do
not significantly change the relationship
between
strength properties
and pulp
viscosity.
Table 10 shows the difference in properties of a softwood kraft pulp bleached to
different viscosity levels after PFl beating
to a drainage resistance of 45 Schopper
Riegler (about 260 mL CSF) when a pulp
has been bleached to different viscosity levels by different bleaching sequences (conventional
5- to 7-stage sequences
with
elemental chlorine or chlorine dioxide as a
prebleaching chemical and one sequence
consisting
of an introductory
oxygen
delignification
stage).
lead to low pulp viscosity levels and a correspondingly low pulp strength.
Pulps bleached in TeF Sequences
The commercialization of extended kraft
pulping leading to low kappa number softwood pulps, and totally chlorine-free (fCF)
bleaching for the production
of semibleached or fully bleached pulp types have
made the evaluation of strength properties
more complicated. Substantial increases in
residual lignin content and in the amount
of charged groups, which promote swelling, increased cellulose content,particularly
in the case where wood is pulped to very
low kappa numbers, and low pulp viscosity are among the present-day factors affecting pulp quality. Decreased carbohydrate
yield and hemicellulose content, brought
Chapter
alkaline peroxide stages, the pulp has moderately high residual lignin content and an
increased concentration of charged groups
which can be expected to promote swelling and offset the negative effect of the residuallignin on beating. As shown in Table
12, more rapid strength development can
then be obtained during the beating operation.
TCF bleaching to high brightness is also
based primarily on the use of alkaline peroxide following an oxygen stage. Because
of the limited de1ignifying ability of peroxide, however, it is necessary to delignify the
pulp to a low residual lignin level before
the final peroxide
stage. This can be
achieved through 1) modified pulping to a
low kappa number and yield and a high
cellulose content arising from a severe oxygen delignification or 2) modified pulping
to an intermediate kappa number, oxygen
delignification, and a multi-stage bleaching
process in which peroxide (with or without additives), ozone (or organic and inorganic peracids), and possibly oxygen have
a role. Other chemicals currently being
studied in the laboratory and/or in mill trials such as peracids, polyoxometalates,
laccase5 combined with mediators, and dimethyl dioxirane eventua11y may be used
commercia11y to enhance pulp strength.
lIIbu 12. ~
(13).
741
("Upox. JIt'OCeSS)
Drainage resistance 45 SR
Pulp
Description
Beater
Revolutions
Density
(kgIm3)
Tensile
Index
(kNm/kg)
Tear
Light-scattering
Index
Coefficient
(Nm2Jkg)
(m2Jkg)
Tear Index
at Tensile
Index 100
D(EOP)D(E+P)Dbrightness -90,
kappa number 0.5.
intrinsic viscosity
870 dm3!kg
8000
828
102
9.1
13.7
9.3
OQP-brightness -SO.
kappa number 6.5.
intrinsic viscosity
855 dm3!kg
6550
818
101
9.1
13.3
9.2
OQf-brighmc5S ~60,
)no
7.9)
13.8
7.9
kappa number 5,
intrinsic viscosity
730 dm3!kg
742
Pulp Bleaching
-Principles
and Practice
Brightness
(%)
Coarseness
(mg/m)
Beater
Revolutions
Tear
Index
(mNm'/g)
Density
(g/cm')
Ughtscattering
Coefficient
(m'fkg)
88.3
0.217
1469
13.7
0.71
20.2
79.6
88.7
0.219
0.208
1271
1208
13.9
14.2
0.71
0.69
20.6
21.8
89.1
79.4
0.220
0.220
1093
1152
13.4
13.3
0.73
0.73
19.7
19.7
89.4
0.214
939
15.1
0.71
20.7
Oxygen-delignified
Softwood pulp A
Multi-stage
TCF"
Peroxide-bleached
TCF
ECF
Oxygen-delignified
Softwood pulp B
TCF"
TCF
ECF
Chapter
743
10
C)
~
C\f
E
z
X
Q)
"tJ
.!:
....
as
Q)
I7
90
Tensile
80
index,
erties of the pulp, however, is smaIl compared to the effects of other variables, particularly those affecting pulping.
Pulp
Yield % of Wood
Unb!.
Bleached
110
100
kNmlkg
Beating
TIlDe
(min)
Breaking
Length
(kID')
Tear
Factor
"
Density
(g/cm')
Inwft JIIIIp
Opacity
25
52.4
48.9
50
7.3
89
0.74
0.745
Two-stage acid
sulfite, moderate
hemicellulose
stabilization,
extended delig.
10
52.7
50.8
45
6.9
77
0.74
0.72
Bisulfite
25
40
52.3
54.9
48.8
49.4
60
55
7.5
8.6
90
87
0.74
0.74
0.75
0.725
32
49.2
46.0
88
11.0
115
0.74
0.71
Beaten
in a Valley
and Practice
r"",.u.
I!./ft of~
blHebl", ore.
beater.
treatment)
(Amount
groups)
of charged
% ISO
Tensile stiffness
p/IyskIIIproperHa of N~
59.4
28.8
3.4
105
351
index
Unbleached
TMP
CEDEDsequence.
Old SCA standard.
-Principles
Brightness,
Kraft
Pulp Bleaching
Property
Acid sulfite
744
scattering
absorption
coefficient,
index,J!kg
m'!kg
8.2
385
45.3
SJWIIUTMP(69, 81).
Peroxide
Low
Low
71.5
- bleached
TMP
High
High
31.3
3.6
115
382
71.3
34.6
3.8
139
452
8.2
415
45.0
8.0
510
40.1
Chapter
745
746
References
17. Clark,].
2. Forgacs,
(1 %3).
O.L., Pulp
19. Paavilainen,
(1990).
20. Paavilainen,
(1993).
L., Pap.
Puu
(1973).
72(5):
Tech.
S 16
21. Heikkurinen,A.,
Levlin,J.-E., Paulapuro,
Pap. Puu 73(5):411 (1991).
22. Paavilainen,
(1993).
L., Pap.
Puu
H.,
75(5):343
D., Sav(1987).
24. Parham, R.A., in Pulp and Paper Manufacture, Volume 1, Properties of Fibrous
Raw Materials and Theft' Preparation for
Pulping, 3rd edn., Joint Textbook
Committee of the Paper Industry, Atlanta,
Montreal, 1983, p. 60.
25. Colley,].,
Cross,
39(1):260986).
Tappt
64(3):81
12. Annergren, G., Backlund, S., Hagglund, T.A., lindblad, P., "Optimizing
and control
of pulp bleaching plants," 1971 TAPPI Alkaline Pulping
Conference
Preprints,
p.133.
13. Annergren,
G.E., unpublished
results.
14. Backstrom,
M, "Nagra synpunkter
pa
modifierad sulfatkokning," licentiate Thesis, Royal Institute
of Technology,
Stockholm, 1993 (in Swedish).
15. Clark,]. d -A, Pulp Technology and Treatment for Paper, Miller Freeman,
San
Fransisco, 1985, pp. 184-%.
16. Fahey, M.D., "How bleaching can change
pulp strength," 1992 TAPPI Bleach Plant
Operations
Short Course Notes, TAPPI
PRESS, Atlanta, p. 55.
26. Macleod,
(1986).
P., Tabert,
J.M., Pulp
J., Apptta
L., Svensk
Pr0Pub-
Chapter
lication,
131.
STAP No.7,
35. Annergren,
G., "Modifierad
kontinuerlig
suIfatkokning;
2a nordiska
sulfatkollokviet,
Meddelande
fran Cellulosaindustriens
Centrallaboratorium
SerieA8
No. 56, 1%7 (in Swedish).
36. Dillner, B., Svensk Pappersttdn.
(1993) (in Swedish).
37. Henley, D., Svensk
(1960).
%(2):22
63(5): 143
38. Rydholm,
S.A., Pulping
Processes,
Interscience
Publishers, New York, 1%5,
pp. 970-971.
39. Lennholm, H., "Investigations
of Cellulose
PoIymorphs
by 13C-CP/MAS-NMR Spectroscopy
and Chemometrics;
Ph.D. Thesis, Royal
Institute
of Technology,
Stockholm,I994.
40. Rydholm,
S.A., Pulping
Processes,
Interscience
Publishers, New York, 1%5,
pp. 1155 - 1163.
41. McKee, R.C., Paper Trade],
155(21):34
(1971).
42. Nordman,
L., Hirvonen,
P., Levlin, J.-E.,
Ebeling, K., Papter 34(6):219 (1980).
43. Karenlampi,
(1992).
P., Pap.
Puu
74(8):650
48. Mannstrom,
49. Franzen,
(1986).
Papperstidn.
(1972).
Pap. Res.]
1(3):4
Pap.
747
77:10(1994)
748
1.E., Tappt]
54. Kibblewhite,
(1972).
54(11):709
55. Kibblewhite,
(1972).
R.P., Appita
26(3):196
82. Hartler,
N., Nord.
10(1):4 (1995).
83. Bennington,
c.P.J. and Seth, R.S., in Fundamentals
of Papermaktng:Transactions
of the Ntnth Fundamental
Researcb Sympostum held at Cambridge (C.E Baker and
V.W Punton, Eds.) Mechanical
Engineering Publiehations
Ltd., London, 1989, p.
87.
56. Malmberg,B.,Svensk
Papperstidn.65:911
(1%2); 67:69 (1%4).
57. Dasgupta,
S., Tappt]
77(6):158
(1994).
1.J., Tappt]
60. Clark,J.d' A,Pulp Technology and Treatment for Paper, Miller Freeman, San Francisco, 1985, pp. 518-535.
(1989).
62. CIark,J. d' A, Pulp Tecbnology and Treatmevt for Paper, Miller Freeman,
San
Fransisco, 1985, pp. 720-721.
63. Croon, I. and Dillen, S., Tappi
(1%8).
51(5):97A
1. and
(1975).
Levlin,
J.-E., Papter
V.,]
Pulp
Shridharan,
R.,
Kovasin, K.K.,
S.,
Pulp
Paper.
Res. J
(1995).
86. McKenzie,A.W,Appita
87. Page, D.H., Tappt]
42(3):215
77(3):201
(1989).
(1994).
88. Middleton,
S.R. and Scallan, A.M., Nord.
Pulp Pap. Res.] 7(1):22 (1992).
SECTION vm:
Pulp Bleaching and The Environment
Chapter 1:
Emuent Characteristics
and Composition
A. B. McKague
Pulp & Paper Centre
University of Toronto
Toronto, Canada
G. Carlberg
The Norwegian Pulp and Paper
Research Institute
Oslo, Norway
1. Introduction
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 751
751
751
752
752
752
753
754
754
Chaptervm
1:
Emuent characteristics
and composition
1. Introduction
Describing the characteristics and composition of bleach plant effluent is like trying to hit a moving target whose speed is
increasing exponentially. Five to ten years
ago it was possible to categorize bleaching
as conventional or modified in the sense
that "modified" meant some chlorine dioxide substitution was employed or that oxygen delignification
preceded what was
essentially conventional bleaching. Reflecting the environmental and matket pressures
to eliminate cWorine from the bleaching
process, bleaching is now classified according to the use of cWorine-containing bleaching agents. Thus, processes that do not use
molecular cWorine are referred to as elemental chlorine-free (ECF), and those that
do not use any chlorine-containing
bleaching agents are referred to as totally chlorinefree (fCF). The rapid changes which have
recently occurred have led to the appearance of a large number of publications in
which the general effluent characteristics
are reported, particularly the amount of adsorbable organic halogen (AOX), but little
is known about effluent composition in
terms of individual compounds.
In this
chapter, an attempt is made to provide a
description of bleachery effluents, recognizing that in focusing our sights on this
target, it is moving rapidly.
2. General characteristics of
bleach plant effluent
To describe bleach plant effluent in a
systematic manner, a classification system
is needed for the different types of bleaching processes. In view of the current emphasis on decreasing
the quantities of
cWorinated organic compounds
formed
during bleaching
and the anticipated
growth of TCF bleaching, effluents have
been classified as conventional (up to IO"/"
cWorine dioxide substitution), ECF,andTCE
75 I
2.1 BOD
BOD (Biochemical Oxygen Demand) is
a measure of the oxygen required for the
biochemical degradation of organic material in water or effluent, The BOD of bleach
plant effluent depends on the kappa number and extent of washing of the unbleached pulp because both the residual
752
Pulp Bleaching
-Principles
and Practice
2.3 COD
COD (Chemical Oxygen Demand) is a
measure of the oxygen consumed in the
chemical oxidation of organic material in
water or effluent, by a strong chemical oxidant. As with BOD, the COD of bleach plant
effluent depends on the kappa number of
the unbleached pulp.Typicallevels of COD
for conventional
bleaching of softwood
kraft pulp are shown in Table 3. COD levels of hardwood pulp effluent are substantially lower. As discussed in a previous
review (1), COD decreases with increasing
cWorine dioxide substitution as would be
expected since the products of chlorine dioxide bleaching are at a higher oxidation
level than those from chlorine bleaching.
A decrease in 20-25% of the COD occurs
at 100% chlorine dioxide substitution
(1,13,16,22). Oxygen delignification lowers COD values in proportion to the reduction in kappa number (typically 40-50%).
The COD of effluent from TCF pulp is 662951b (30-134 kg)/t (8, 12,23).
2.4 Color
Effluent from the first two stages of conventional bleaching of softwoods and hard-
Type of bleaching
C(D) stage
IbIt (kg/t)
E stage
Iblt (kg/t)
Total bleach
Iblt (kg/t)
Conventional
9-22(4-10)
4 - 18 (2 - 8)
ECF
14 (6.5)
11 (4.8)
18.35 (8 - 16)
26 - 86 (12 - 39)
TCF
'Kappa number: 30 . 35
753
754
T4ble 5. '/'yJIIaIlAOX
MlfleSjor
lnwft pulp'
bletlebi"g
Type of bleaching
C(D) stage
Ibit (kglt)
E stage
Ibit (kgIt)
Total bleach
Ibit (kglt)
Type of bleaching
Cb(D) stage
Ibit (kgIt)
Conventional
7-29(3-13)
70 - 75 (32 - 34)
44 - 53 (20 - 24)
ECF
9- 48 (4 - 22)
36 - 37 (16 - I7)
Conventional
ECF
'Kappa number: 26 - 38
Tule
lnwft}nlll'
bluebhJgejJllIeIII
C(D) stage
Ibit (kglt)
Type of bleaching
(6,9,13,Z8,3Z
- 34).
E stage
Ib/t (kglt)
Total bleach
Ibit (kglt)
8.1-15
(3.7 - 6.8)
- 1.7)
2.0 - 3.7(0.9
TCF
effl_t
- 57(21
Conventional
46
ECF
48 (22)
- 17,n - Z5).
(8,9,tZ,13,15
E stage
Ibit (kglt)
- 26)
68
- 119
(31-
54)
Cb(D) stage
effl_t
(Z9,30,3Z,38
E stage
ECF
'Kappa number:
- 41).
Total bleach
Ib/t (kg/t)
0.018 - 0.15 (0.008 - 0.07)
Conventional'
TCF
softwood
Type of bleaching
Total bleach
Ibit (kglt)
117 (53)
6. EOX IJtdfleSfor
- 0.01)
- 26
'Kappa number: 30 - 37
Tule 4. Color of softwood lnwft pull' bleaebi"g effl_t
(8,9,13
- 16,ZZ
- Z4).
Type of bleaching
C(D) stage
Ibit (kgIt)
Estage
Ibit (kgIt)
Conventional
ECF
TCF
Total bleach
Ibit (kglt)
486
- 939
(221
- 427)
'Kappa number: 25 45
determination of chlorinated organic material in effluent. Thus, TOCl, AOX, and results from other combustion methods are
all considered equivalent.
Typical AOX levels in bleach plant effluent are shown in Table 5. Chlorine dioxide
substitution results in a virtual linear decrease in AOX in both conventionally
bleached and oxygen prebleached
pulps
(6,9,13,28,29).A
small amount of AOX is
present in effluents from 100% substitution
because, during the reaction of chlorine
dioxide with pulp lignin, a small amount of
hypochlorous acid is generated which reacts with lignin to fonn chlorinated material. The fonnation of AOX is complicated
and dependent on the chlorine multiple
(30) and mode of addition of chlorine and
chlorine dioxide (31).A low chlorine multiple and split addition give effluent containing less AOX. As expected, effluents
from TCF bleaching contain negligible
amounts of AOX. Enzyme pretreatment is
reported (7) to decrease the amount of
bleaching agent required, and to reduce
AOX accordingly.
2.6 EOX
EOX is the tenn used for Extractable Organic Halogen. Since the very non-polar
solvents used for extraction, namely, hex:me, heptane, and cyclohexane, extract only
a small portion of the extractable material,
the tenn is used here to mean that portion
of extractable organic halogen which has a
potential to bioaccumulate. A compound
755
756
55%
50%
"--Chlorination stage
CJ
CJ
~
Extraction
stage
MW<1000
1000< MW<10,000
1000<MW<25,000
MW> 25,000
three kraft softwood pulp prebleaching sequences: CE, OCE, and DE. In the acidic
effluents, about 65-70",,(,of the organochlorine material (as TOCl) was found in the
high molecular weight fraction (M>I000)
of the C and OC liquors. When chlorine
dioxide (0) was used in the first stage, only
45% ofthe organically bound chlorine was
found in the high molecular weight fraction.
In the alkaline extraction liquors, 90-95%
of the organically bound chlorine was found
in the high molecular weight fraction for
all three bleaching sequences. In the alkaline extraction liquors of the CE and OCE
sequences, 5~5% of the organically bound
chlorine was found in the highest molecular weight fraction (M>25000). The alkaline extraction liquor from the DE sequence
was only ultrafiltered at a relative molecular weight limit of M>I000. Pfister and
Sjostrom (59,60) and Hardell and de Sousa
(61,62) had previously found a lower proponion of high molecular weight material
using similar experimental
conditions.
Pfister and Sjostrom (59,60) and O'Connor
et al. (32) found that oxygen prebleaching
increased the proponion of material in the
M<I000 fraction ofthe alkaline extraction
liquor and combined chlorination and extraction effluents.
Combining
samples from different
bleaching stages or upward adjustment of
the pH leads to mineralization and dechlorination which may change the molecular
weight distribution
(63,64).
Recently,
McKague and Reeve (65-67) have provided
some clarification of the reactions taking
place during the alkaline treatment. They
reacted lignin model compounds sequentially with chlorine or chlorine dioxide and
sodium hydroxide.
After the oxidation
stage, muconic acid esters, lactones, and
quinones were formed (see also Brage et
al. Holzforschung
45:23(1991);
ibid.
45:147(1991);
Ni et al. J. Wood Chem.
Technol. 14:243(1994)).
During the alkaline treatment, the quinone rings were
opened and some organically bound chlorine was displaced. Similarly, the lactones
were convened
to muconic acids. These
reactions increase the polarity of the material and, with it, its ability to associate.
Sameshima et al. (56) used cellophane
membranes for dialysis of bleachery effluents. The nominal molecular weight cutoff
was not stated. In the chlorination liquor,
nearly all (95%) of the organic matter (TOC)
was found in the low molecular weight fraction. Two experiments were performed on
the alkaline extraction stage effluent. After
a single 24-hr dialysis, 65% of the TOC was
found in the high molecular weight fraction.
After excessive and repetitive dialysis, only
32% of the TOC remained in the high mo-
757
758
Pulp Bleaching
-Principles
mg61
tllstrl1nU#oll
eJP8MI.
Kraftmill effluents
Softwood
_ _ _ Hardwood
and Practice
of orgawally
Type of Bleaching
CID Stage
E Stage
Total Bleach
% of Effluent Solids Having a MW > 1000 daltons
Conventional
65-70
35-40
20
ECF
45
45
90-95
85-90
Fig. 2. Apparettl
molecular
10'
10'
Molecular weight (polystrene sulphonate)
weig61 distrlbullott
of orga,,'c
rtUIIerltIl
I"
bleached
(71).
TCF
I"
blHCbittg
Ref.
57,58
59
68
65-75
70
32
45
54
57,58
90-95
80
40-50
10'
mtIIter
59
40
55
32
40-45
75
30-40
75
Bleaching
Sequence
C/Cl
C/O
Functional
Methoxyl
Acidic liquor
CE
1.2
0.22
OCE
8.5
1.1
DE
45
1.2
CE
14
OCE
20
DE
118
759
3.5
5.2
0.35
4.9
4.7
0.74
8.7
2.9
1.3
0.58
1.2
0.39
1.7
0.94
3.4
4.2 - 4.5
3.4
4.2
5.8
0.8
Alkaline liQ.uor
Kraft li2llin
,
Determined
molecular
effluent.
by potentiometric
weight
3.7
7.5
titration
material
in bleaching
3. Chemical characteristics of
effluent components
Bleach plant effluent contains an extremely complex mixture of chemical components. Because most of the material has
a molecular weight> 1000, its exact chemical structure is unknown. General structural
features are known, however, and are described in the following section. An enormous amount of work has been done on
material having a molecular weight < 1000
as this is the molecular weight range which
causes most biological effects and is more
amenable to analysis. Over 400 individual
compounds have now been reported, but
it is interesting that this list does not contain any compounds in the 500-1000 molecular weight range. This is the range
where dimeric-to-tetrameric 1ignin degradation products or lignin-carbohydrate
compounds should be found.The identification
of compounds
in this molecular weight
range could provide extremely valuable information about the types of chemicalIinkages present in the high molecular weight
material.
l1
5.
4.3
760
Pulp Bleaching
-Principles
and Practice
effluent
(80,81).
Re-
Pulping
Process
Bleaching
Process
AOX
(kg ptp)
Conventional
OD(EOP)OOP)D
0.53
1.4
94
1.7
2.8
40
Extended
OD(EO)D(EP)D
0.]9
0.51
260
1.2
2.3
40
n.d.
<0.] >]200
1.2
3.6
7'5
OQP
Cl
%
C/Cl
Functional Groups
(mmoU)
Methoxyl Carboxyl
Ref.
Because of the large number of compounds reported, it is not possible to provide a list complete with structures and
quantities. However,ofthe 456 compounds
now reported, 330 are chlorinated and 126
unchlorinated. The different types of chlorinated compounds reported are summarized in Table 10. Important examples of
each group are shown in Fig. 3.
Most of the chlorinated compounds reported were identified in effluents from
conventional chlorine bleaching. Levels of
chlorinated compounds drop by a factor of
about lOin ECF bleaching, and there is a
change in the relative proportions of some
types of compounds. For example, the total amount of chlorophenols decreases from
> 100 g/t of pulp in conventional bleaching effluent to 1-10 g/t in ECF effluent, and
the wide spectrum of chlorophenols found
in conventional chlorine bleaching effluent
changes to one dominated by 6-chlorovanillin in ECF effluent (6, 13, 28, 103). A
acid
~.~
a
3.4.5- Tnchloroguaiacol
;Yro>
222- Trichloroethanol
6-Chlorovanillin
"
1.1.Dichlorodimethyt
Chloroform
xx
oyya
al#o~a
sulfone
Type of Chlorinated
eomptnmdsformed
in bleaebtng.
Number Reported
Compound
furanones,
2.3.7.8- Telrachlorodibenzo-p.dioxin
Aldehydes
and ketones
75
25
20
Hydrocarbons
Alcohols
Dioxins and furans
Miscellaneous
Total
few compounds, for example, 1, l-dichlorodimethyl sulfone, do not appear to be markedly affected
by the change
from
conventional
to ECF bleaching (32,89).
Only trace quantities of a few polychlorinated (> 2 chlorine atoms) compounds are
found in ECF effluent. The level of chloroform drops from > 300 g/t of pulp in conventional bleaching effluent to < 10 g/t in
ECF effluent (104). As stated in the introduction, individual compounds have not
been identified in TCF effluent.
Process
for
4. Cook, R.A., "A Bleaching
Mlnimising AOX Discharges," 1992 TAPPI
Environmental
Conference
Proceedings,
TAPPI PRESS, Atlanta, p.l 055.
5. Hise, R.G., Streisel, R.C., Bills, A.M., "The
Effect of Brownstock Washing, Split Addition of Chlorine, and pH Control in the CStage on Formation
of AOX and Chlorophenols
during Bleaching,"
1992 TAPPI
Environmental
Conference
Proceedings,
of various
types of eblorluted
eom}HnInds formed
in bleael1tng.
77
52
66
pyrones
.y CHO
3-ChI0r0-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone
II
~CHSC~
c,~k
CI3CCOOH
762
References
.yZ.
Tnchloroacetic
761
6. Liebergott,
N., van Lierop, B., Kovacs, 1.,
Nolin,A., TappiJ 73 (10):207 (1990).
15
330
E, Svensk
E., Svensk
15. Liebergott,
N., and van Lierop,
Pap. Can. 87(8):T3oo
(1986).
B., Pulp
Graves,lw.,Joyce,T.W,Jameel,
) 76(7):153 (1993).
20.
Schwantes,
T.A. and McDonough,
T.A.,
"CharacteriZation
of Effluent Fractions
From ClO, and CI, Bleaching
of Unbleached and 0, Bleached Softwood Kraft
Pulps; 1993 TAPPI Pulping Conference
Proceedings,TAPPI
PRESS,Atlanta,p.17.
21.
du Manoir,
J.R.,
83(2):T58 (1982).
22.
23.
24.
Pulp
H., Tappi
Pap.
38.
73.
ES., Wat.
56.
Stuthridge,T.R.,
Campin, D.N., Langdon,
A.G., Mackie,
K.L., McFarlane,
P.N.,
Wilkins, A.L., Wat. Set. Teebnol.
24(3/
4):309 (1991).
74. Jokela,lK.,
Laine, M., Ek. M., SalkinojaSalonen,
M., Environ.
Set. Tecbnol.
27:547 (1993).
75.
58.
Osterberg,
Holzforscbung
59.
76.
60.
77.
61.
62.
78.
63.
Dorica,lJ.PuIpPap.Set.18:J231
79.
64.
65.
Gelierstedt,G.and
Lindfors,E.-L.,"On
the
Structure and Reactivity of Residual lignin in Kraft Pulp Fibres; 1991 international Pulp Bleaching Conference,
SPCI,
Stockholm, p. 73.
42.
Connors,WJ.,
Holzforschung
66.
80.
43.
67.
44.
Lundquist,
K. and Wesslen,
Cbem. Scand. 25:1921 (1971).
68.
Sagfors,
Tecbnol.
45.
Kristersson,
P., Lundquist, R. Simonson,
R., Tingsvik, K., Holzforscbung
37:51
(1981).
69.
81.
46.
Stenlund,
(1976).
70.
82.
Cbemo-
47.
Sarkanen,
McCarthy,
(1981).
83.
Rantio,T.,
(1992).
84.
Hall,
E.R.,
Cornacchio,
9O(11):T421
Fraser,
J., Garden,
S.,
L-A., Pulp
Pap. Can.
(1989).
48.
Lindberg,J.J.,
49.
85.
50.
Lindstrom,
T., Colloid.
257:277 (1979).
86.
51.
E.B.,
Rosenberg,
C., Aalto, T., Tornaeus,
J..
Hesso, A., Jappinen,
P., Vainio, H.,)
Cbromatog.
552:265 (1991).
87.
PeIIinen,l
and Salkinoja - Salonen,
Cbromatogr.
328:299 (1985).
M.,]
Petersen-Bjergaard,
S., Asp, T.N., Vedde.
l, Carlberg, G.E., Greibrook,T.,
Cbromatograpbia
35:193 (1993).
EH.,
Tappi
28.
Axegard,
(1986).
29.
Axegird,
(1989).
30.
Axegird,
P., Tappi)
31.
Marwah,
N., Joyce, T.W., Chen, c.-L.,
Gratzl, J.S., Tappi)
75(7):167
(1992)
and references therein.
P.,)
presentation
35.
Tappi)
53.
Lindstrom,
K. and
Osterberg,
HolzjOrsebung
38:201 (1984).
34.
D.W.,
764
57.
26.
33.
D.,
32.
37.
Can.
25.
27.
36.
763
Pulp
Pap.
69(10):54
Sci.
39.
40.
41.
12:J67
(1986).
No. 14.
Mackay,D.,Environ.Set.Technol.16:274
(1982).
52.
Brunsvik,ll,
Grundelius, R., Kordes, R.,
Swan, B., "Environmental
Compatible
Bleaching of Chemical Pulp; 1989TAPPI
Pulping Conference
Proceedings, TAPPI
PRESS, Atlanta, p. 411.
DahIman,O.,
Haglind, I., Morek, R., de
Sousa, E, Stromberg, L., "Chemical Composition of Effluents from Chlorine Di.
oxide-Bleaching
of Kraft Pulps before and
after Secondary
Effluent Treatment;
1993 EUCEPA International
Environmental Symposium,
Centre Technique
du
Papier, Paris, p.193.
B., Advan.
E., Bobleter,
(1980).
B., Acta
Cbromatgr.
S., Teller,
D.C.,
lL, Macromolecules
Pap. Puu
0..)
14:37
Hall, J.,
14:426
71.
37:1 (1955).
Polym.
c.,
Set.
E and
Lindstrom,
39:149 (1985).
Dence,
K.,
(1992).
C.W., Tappi
Environmental
ProtectionAgency,Report
4031, Stockholm,
72.
F.,
p.155.
Cbemospbere
25:505
D.,
G.E..
Remberger,
M., Hynning,
A.H., Environ.
p-A., Neilson,
90.
Koistinen,].,
Nevalainen, T., Tarhanen,].,
Environ. Sei. Teehnol. 26:2499 (1992).
91.
92.
96.
97.
98.
99.
(1991).
89.
B., Tikkanen,
5:142 (1990).
1.,
94.
Kronberg,
L. and Franzen, R., Environ.
Sd. Teehnol. 27:1811 (1993).
95.
G.R.,
Can.
100. Sinkkonen,
S., Kolehmainen,
E.,
Paasivirta, J., Koistinen, J., Lahtiperii, M.,
Lammi,
R., Chemosphere
28:2049
(1994).
101. Koistinen,J., Paasivirta,J., Nevaiainen,T.,
Lahtipera,
M., Chemosphere
28:2139
(1994).
102. ViIen, E., Reeve, D.W., McKague,
HolzJorsehung
in press.
93.
765
A.B.,
104. Crawford,
R.J., Dallons, VJ., Jain, A.K.,
Jett, S.w., Tappi] 74:159 (1991).
SECTIONvm:
Pulp Bleaching and The Environment
Chapter 2:
Assessing the Potential Impacts
of Pulping and Bleaching Operations
on the Aquatic Environment
J. william Owens
The Procter & Gamble Company
Cincinnati, Ohio
Karl-Johan
Lehtinen
Finnish Environmental Research Group
EspOO, Finland
1. Introduction
.......................................... 3
of
4
3. Biological
characterization
of effluents
and receiving environments
4
3.1 Single-species acute and short-term
toxicity tests. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
3.2
needs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
767
Chapter
VITI 2: Assessing
the Potential
Chapter vm 2:
Assessing the potential
impacts of pulping and
bleaching operations
on the aquatic
environment
1. Introduction
In recent years, the discharge of bleaching effluents into aquatic receiving environments has been the focus of intense
scientific and regulatory scrutiny. Observations prompting this scrutiny include the
long-range dispersal of bleach plant compounds in Canadian rivers (1) and in the
Gulf of Bothnia (2), the mutagenic activity
of untreated effluents from bleach plants
using elemental chlorine (3,4), the detection of 2,3,7 ,8-tetrachlorodibenzo-p-dioxin
(rCDD) in effluents from bleach plants using chlorine gas (5,6), and the adverse environmental effects of bleached kraft mill
effluent (BKME) discharges lacking biological treatment (7,8). In reaction to such observations, environmental
concerns have
been focused almost exclusively on chlorinated organics, often measured as absorbable organic halogen (AOX) (9). As a result,
the paper industry has sharply reducedAOX
emissions and has eliminated persistent,
polychlorinated materials through chlorine
dioxide (CIO) substitution for elemental
chlorine (10). Simultaneously, the industry has begun to develop bleaching sequences whose stages employ no chlorine
compounds, that is, sequences that are totaIly chlorine-free (rCF).
The aquatic environmental
impacts of
pulp and paper effluents have been the subject of previous reviews by McLeay (11) and
Owens (12). In the 1950-60s, pulp mills
were associated with sometimes devastating effects on receiving waters caused by
the discharge of excessive amounts of suspended solids and organic matter. Historically, the observed adverse impacts have
been attributed to three possible causes: (a)
gross habitat alteration, (b) organic enrich-
Impacts
on the Aquatic
Environment
769
770
2. Chemical
and physical characterization
of effluents and
receiving environments
3. Biological characterizationof
effluents and receiving environments
Chapter
VIII 2: Assessing
Tllbk 1. CIHmtktU ~
Measurement
the Potential
of bktwW..,
orTest (units)
Inorganic Parameters
pH, Color/Turbidity (Pt units), Nitrogen and
Total Phosphorus (g/ton and kg/day) Transition metals (grams or mil1igrams per day),
Chlorate (g/ton and kg/day)
Organtc Cbaracterlsttcs
Extractable Organic Chlorine (EOX)
(g/ton and kg/day)
(g/ton
tI.ffIrIMIs 11II4rwm"""
Environment
771
fINIIers.
(fest)
The BOD reflects the combination of process and effluent treatment efficiency (kg/ton) and the overall size of the point source
(tons/day); TSS reflects the suspended solids load in the effluent; AOX reflects the organic material removed in the bleach
plant, the substitution of chlorine gas with chlorine dioxide or
other bleaching agents, and the treatment efficiency.
Aquatic communities are affected by pH; light transmission affects photosynthesis; nitrogen and particularly phosphorus determine enrichment and algal growth; transition metals can be
highly toxic; chlorate can be toxic to certain highly sensitive
algae.
Bioaccumulation is based on the partitioning of a material from
water into lipid. Lipophilic components win be contained within
EOX.There are no standard, established protocols for EOX measurements.
Wetgbt Organtcs
on the Aquatic
Sum Parameters
Biochemical Oxygen Demand (BOD), Total
Suspended Solids (I'SS),Absorbable Organic
Chlorine (AOX) (kg/ton and tons/day)
Low Molecular
Impacts
and kg/day),
Chlorophenolics
- mono-
These materials reflect the tree species pulped (resin and fatty
acids), the chlorine multiple or indicated by the degree of chlorine substitUtion by chlorophenols with di-, trio,and tetra-substitUtion, and the efficiency of effluent treatment.
High molecular weight oxidized Ugnin fragments isolated using
membrane filtration analysis compose the bulk of material discharged after biological treatment of effluent. The elemental
ratio relates to the rate of chlorine used in the bleach plant.
Receivtng Waters
BOD,COD,andAOX (jJg/L) pH, Dissolved Oxygen, Color and Twbidity (Pt units) and Secchi
disk (em), Nitrogen and Phosphorus (mg/L),
chlorate (JJg/L), Resin Acids and Chlorinated
Resin Acids, and Chlorinated Phenolics (jJg/L)
772
Pulp Bleaching
-Principles
and Practice
EPA Studies at
HeavIly Improved Industrial
Effluent SItea
North Carolina
Study of Industrial
and Municipal Discharges
Sedtments
Loss on Ignition (%)
Sediment Oxygen Demand
Transition Metals (ppm or ppb)
Extractable Organic Chlorine (EOX) (ppm)
Resin Acids, Chlorinated Resin Acids and
Chlorinated Phenolics (Ppb)
TCDD andTCDF (ppt)
Btota
Resin Acids, Chlorophenolics, and EOX
(ppb in bile)
TCDD and TCDF (ppt in lipid or fillet)
.
D
o
~
(false negative)
(false positive)
Chapter
vrn 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
773
the
hydrophobic
or fatty
portion
of AOX)
774
Pulp Bleaching
-Principles
and Practice
4>
~~
. Unbleached
pulp
. Bleached pulp
iE.!!!
~o
m_
4> c:
~ 5E
III
0.1
.
. .
.
~ 20
...J
us-
... -.
~100
~~
80
=m
.,~
!j
exposures
:6.2
c: c:
.2 c: 60
e'E
c~
g.2! 40
00;
Uu.
E-
Extended laboratory
ing single species
1
10
EffluentAOX,mg/L
mill e./ll_ts
1mffltbetUI mi_
100
larva hi sirtgle-spedes
Chapter
VITI 2: Assessing
58
Impacts
on the Aquatic
Environment
775
10.0
u';;
the Potential
5.0
-60
eu
g-J!!
... c: 1.0
as 0
'2"0; 0.5
~.~
as
<D
.
o to.,. ...
.
~~
~.~g 0.1
o
.
.
. .
1
2
3
AOX, kg/metric
KraitMiHEffluent
o Unbleached and treated
. Bleached and treated
to Unbleached and untreated
Bleachedand untreated
4
5
ton of pulp
been measured in several extended exposures. In Sweden, morphology and cartilage chemistry have been examined in
fourhom sculpin (Myoxocephalus quadrlcomts), bleak (Albumus
albumus),
and
perch (Perea fluvtattlts)
(42). Minor
changes occurred in several of the 13 bone,
cartilage, and other parameters studied in
all the kraft mill effluents tested. The number of parameters that significantly changed
in these experiments are enclosed in parentheses for each effluent tested with sculpin
and bleak, respectively:
untreated,
unbleached kraft hardwood (8 and 4), untreated, CI/CI02 (52/48) bleached kraft
softwood (9 and 7), untreated chlorine dioxide-bleached kraft hardwood (6 and 3),
and elemental chlorine-bleached kraft softwood with biological treatment (2 and 1).
Thus, the effects of exposure to unbleached
effluent were similar to those observed in
bleaching effluents and the severity of the
effect tended to decrease following biological treatment and chlorine dioxide substitution
(42).
In North America,
no
morphological effects were noted in full lifecycle studies with fathead minnows (41)
or extended exposures in chinook salmon
fry (Oncorhynchus
tshawytscha) (43).
Histopathology provides a means to determine structural changes and lesions in
body tissues, such as liver and kidney, under microscopic examination.
Exposures
776
Chapter
VIII 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
777
778
Pulp Bleaching
-Principles
and Practice
months.
Measurements
included
the
growth, biomass, and organism number of
the bladder wrack, the invertebrates associated with the bladder wrack, invertebrates
found in the sediments, growth of sticklebacks in the original mesocosms and, in
adjacent pools, rainbow trout biomarkers.
The BKME having the greatest impact was
that from a pre-I 980 conventional mill characterized by high washing carryover, high
elemental chlorine
application, and no
biological effluent treatment.
The other
tested effluents included those from mills
with a wide range of characteristics including both unbleached and bleached softwood and hardwood
kraft furnishes.
However, most mills used little or no biological treatment (49-52). The processes
and the wide range of corresponding
biological results are summarized in Table 3.
Fish mortality was observed with threespined stickleback (Gasterosteus
aculeatus) exposed to untreated, conventional
BKME. Growth, parasite frequency, and
histopathological
endpoints (particularly
liver vacuolization) in sticklebacks were affected by several effluents even at doses of
less than 0.1 %, including the unbleached
effluent. Several biomarkers in rainbow
trout exposed to the softwood BKME were
changed to a statistically significant degree,
including up to six-fold EROD induction.
The effluent displaying the fewest and least
severe effects was that from a mill using an
oxygen delignification stage and lOO"A,chlorine dioxide substitution in the bleach plant
but lacking biological effluent treatment.
Effluent AOX levels in mesocosms did
not consistently correlate with environmental impacts. Unbleached effluent effects
were similar to those of BKME at AOX levels below 2 kg/metric ton (see Fig. 4), and
low AOX hardwood effluents were more
toxic than softwood effluents having higher
AOX levels (51,52). The biological results
were, in several instances, related to high
chlorate levels in the effluent. In other
Ca5CS, organisms living on and in the sediments were affected. The results suggest
that multiple differences in mill operations,
furnish, and process equipment
make
Chapter
VIII 2: Assessing
the Potential
Impacts
on the Aquatic
I'-
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0
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....
&."B-"=
i!
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Environment
e./f:l& ", -_
direct mill-to-mill process comparisons difficult. Most of the mesocosm studies involved single experiments.
Because
year-to-year variability in the control data
has been observed to be almost as large as
differences between within-year control
and exposed mesocosms (51), the use of
replicate systems would have been beneficial to improve the resolution between
effluents.
The experimental
stream studies performed in the United States used two conventional softwood BKMEs
32 kappa
brownstock, extensive biological effluent
treatment). The streams modelled freshwater situations using rainbow trout in cold
water streams
and largemouth
bass
(Micropterous salmotdes), bluegi1i sunfish
(Lepomts macrocbtrus), and golden shiners (Notemtgonus
crysoleucus) in warm
water streams. Experiments have been continued for over a decade with exposures
ranging from 9 months up to 3.5 years
(48,53-57). AOX concentrations were approximately 2 kg/metric ton of pulp during the original experiments
conducted
before 1989. Tests involving .experimental
stre:l11l systems were conducted with du-
(-
ton of pulp
wttbAOX 1erJe1&
I. bIMeW tlflillIIIble4eW
1nwft mI"
Chaptervm
Biomarker experiments
performed on
fish in experimental streams show that both
EROD and P450lA induction occurred at
high (70%) chlorine dioxide substitution in
largemouth
bass and channel
catfish
(Ictalurus punctatus) (these tests were not
run on chlorination-stage
effluents). The
fish were exposed to 4 and 8% effluent concentrations continuously for 260 days followed by 30 days of depuration in streams
without effluent (58). Induction rapidly
declined during the depuration phase, suggesting that compounds with extended haIflives such asTCDD are not the only inducers
in these effluents. No significant induction
of EROD activity was observed in preliminary experiments in streams containing up
to 12% effluent from a process further modified by oxygen delignification and 100%
chlorine dioxide substitution. The results
of other biomarker measurements, such as
hematocrit, leucocrit, and liver somatic index, were not significantly different for
control fish and fish exposed to chlorination-stage effluents (53).
The controlled
exposure
of fish in
mesocosms and experimental streams deals
largely with BKME and data relating to mechanical pulp, CTMp, or bleached sulfite
pulp effluents are limited. Single-species
toxicity tests performed simultaneously indicated that the experimental stream effluents were not toxic under acute and
subchronic conditions. The experimental
stream exposures using biologically treated
effluents had little or no effect on most
freshwater species at effluent concentrations in the 4-6% range (53,55,57). In contrast, the mesocosm
data indicate that
effluents from some mills may alter community and population structures even at
0.1% concentrations.
These extended exposure results reinforce the need for sitespecific limits on total organic discharges
by in-process and effluent treatment steps
and good process control and indicate the
potential usefulness of chlorine dioxide
substitution
and, possibly, oxygen delignification in reducing toxicity. However,
as in all biological tests, the toxicity of nonchlorinated and chlorinated materials is integrated and the effects attributable
to
781
782
Pulp Bleaching
and Practice
,-,
"0
...
=
'S
c::
o
.~
may not
-Principles
='"
~o
U
Chapter
VITI 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
783
784
Pulp Bleaching
-Principles
and Practice
of ",iIls
",'-e -lor
Description of Operation
f"U
785
Norrsundet (Sweden)
50% unbleached softwood kraft and 50% bleached softwood kraft until 1983; after
1983 l00"Aibleached production; conventional pulping; oxygen delignification beginning in 1983; chlorine dioxide substitution rising to 100% in the late 19805; no
biological treatment until 1994; discharge into very shallow estuary of Bothnian
Bay,dilution provided by pumping into effluent mixing basin
Softwood kraft furnish; conventional pulping and bleaching technology; no biological treatment until 1990; discharge into small creek flowing into isolated bay on
northern shore of Uke Superior
Monsteras (Sweden)
Softwood kraft furnish; conventional pulping and bleaching until 1990 when chlorine dioxide substitution was raised to 100%; hypochlorite stage also removed in
this period; efficient biological treatment in aerated stabilization basin; discharge
into Wapiti River with low dilution during winter ice cover
Softwood kraft furnish; conventional pulping and oxygen delignification since start
up; 70% chlorine dioxide substitution during study and now l00"Aisubstitution;
and efficient biological treatment in aerated stabiIization basin. There is a 9O-day
holding capacity to control in-stream effluent concentration during low flows. The
discharge is via a submerged diffuser into a warm-water stream
LaThque (Canada)
Espanola (Canada)
Mixed softwood and hardwood kraft furnish; conventional pulping and oxygen
delignification; 50% CIOz substitution; and efficient biological treatment with AOX
levels < 1 kg/ton; discharge into Spanish River
expenditure of energy, especially for reproduction. Condition factors were higher for
fish at bleached kraft mill sites, including
perch at Norrsundet (70), white suckers at
LaThque (76),andjackfish
Bay (75,77),and
longnose suckers at Grande Prairie at the
site nearest the mill (71,72). Some associations have been found between condition
factor and food supply (72), lower growth
rates at jackfish Bay were associated with
empty stomachs and stomachs containing
less nourishing prey (77). At Norrsundet,
fin erosion in perch and ruffe and bone
deformities in pike (Esox lucius) were observed in 1984-85 (69,79). Changes in external pathology have not been observed
at other sites, including the untreated, high
AOX effluent at the LaThque site (65,72,
78). A possible exception for this generalization were gashes observed on the sides
of lake whitefish (Coregonus clupeafonnis)
at jackfish Bay (80). Fish parasite infestation rates were not elevated at BKME field
sites (65,72,75,76)
except at Norrsundet
where perch and ruffe parasite frequencies
were normal, but roach gill parasite numbers were increased (81).
Wrthin-organism parameters
Within-organism parameters include various biomarkers: histopathology of body tissues, liver size, hematology
and serum
chemistry, and reproductive
parameters
such as gonad size. Care is needed when
using this diverse array of measurements to
select those measures that represent important evidence of fish health. In this chapter, the histopathology
of tissues and
especially the measurement of fish reproductive parameters are emphasized. Other
biomarker endpoints may be of questionable value unless care has been taken to
786
confirm the association between these observations and the presence of chemical
contaminants or more meaningful biological measurements. Many of these measurements vary significantly
depending
on
habitat, food supply, and other field conditions so careful selection of reference sites
is necessary and the data should be compared with results of other studies before
the implications of adverse effects are deduced .
Histopathology
of liver, gill, kidney,
spleen, heart, muscle, and gonad from
white sucker captured near the Espanola
mill and of liver, gill, kidney, spleen, and
gonad of longnose sucker, and mountain
whitefish at Grande Prairie indicated that
effiuent-exposed fish were normal (78,82).
Detailed histopathology has not been conducted at other sites although ateric ovaries (where eggs were not released and
resorption of the eggs was underway) were
noted in limited
samples
taken at
Norrsundet (70).
Liver size or liver somatic index (LSI) was
reported in several studies. The liver is a
central organ for metabolism, detoxification, and energy maintenance. Changes in
ISI are usually non-specific because changes
in lipid or glycogen levels, water content
of liver cells, and other parameters may affect liver size, casting doubt about the significance of any such change. Some studies
have led to speculation that an increase in
the quantity of detoxification enzymes may
cause increased liver size. However, it is
unlikely that P4501A induction is related to
liver size because the quantity of this protein system is very small in the liver. Increased LSI values were observed in perch
at Norrsundet
(8), in several species at
jackfish Bay (77), in white sucker at
LaThque (76) and Espanola (78), and in
longnose sucker at Grande Prairie (82).
Few efforts were made to determine the
possible cause of any LSI increase. Near
the Grande Prairie mill, longnose suckers
having higher LSI had a parallel increase in
liver lipid content which was associated
with increased somatic condition factor and
more abundant food supplies (72,82).
787
788
Chapter
VIII 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
789
790
4. Expected
~... ~
...
e e
trends
and future
research
needs
The available data on pulp and paper mill
effluents indicate that environmental protection first requires the limiting of organic,
nutrient, and suspended solids loadings.
These loadings can be controlled using both
in-plant controls and efficient effluent treatment. Secondly, production of persistent
and bioaccumulative cWorinated materials
in the bleach plant can be addressed by replacement of elemental cWorine with cWorine dioxide.
In the future, continued
technical improvements in delignification
such as extended kraft pulping, ozone
delignification, and associated processes
will allow further reduction in mill loads
per ton of pulp. Unfavorable economics
may prevent older, established mills from
retrofitting extensively with newer technology. This problem may be compounded
by limits to mill expansion caused by limitations in the available wood supply. Increasing mill closure by recovery and
evaporation/incineration
of waste streams
may be practiced with decreasing water
used per ton of pulp. This may ultimately
be limited to mills that can afford to retrofit
with these technologies and whose customers are willing to pay the added capital and
production costs.
Environmental assessment of pulping and
bleaching effluents will continue and will
remain a multi-discipiinary effort. Several
measurement systems ranging from laboratory single-species tests to complex, multiyear field :itudie:i can be employed with
increasing confidence. The inherent complexity and expense of environmental testing and monitoring suggest the need for a
Chapter
vm 2: Assessing
the Potential
Impacts
on the Aquatic
Environment
791
792
References
1. Carey,}.H. and Hart,}.H.,
] Can. 23:55 (1988).
2. Jonsson,
P., Jonsson,
B., Hakanson,
L.,
Martinsen,
K., Statens Naturvardsverket
Rapport 3228, Swedish National Environmental Protection
Board, Soma, Sweden,
1988.
3. Nazar, M. and Rapson.
81(8):75 (1980).
H., Pulp
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4. Stockman,
L., Stromberg,
L., DeSousa,
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5. DeSousa,
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72(4):
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Kringstad,
Glas,
F.
K.P.,
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6. Kringstad, K.P.,Johansson,
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DeSousa, F., Swanson, S.E., Glas, B., Rappe,
C, Tappt] 72(6):163 (1989).
7. Larsson, A.,Andersson, T.. Fortin. 1., Hardig,
J., Water Set. Tech. 20:67 (1988).
8. Andersson, T., Fortin, L., Hardig,}., Larsson,
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J.H.,Donnini,G.P.,
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10. Berry, R.M., Luthe, CE., Voss, R.H., Wrist.
P.E.,Axeg:int,P., GeUerstedt, G., lindblad,
P.-o., Popke, I., Pulp Pap. Can. 92(6):43
(1991).
11. McLeay, DJ, Aquatic
toxicology
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P.F/l, Environment
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12. Owens, }.Wm., Envtron.
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16. Gertngard,
71:255
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VllI 2: Assessing
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mentals
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18. Bruce, R.D. and Versteeg, D.)., Environ.
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19. United States Environmental
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organtsms, 2nd ed., EPN600/4-89/001,
Cincinnati,OH,1989.
20. Mount, D.1., Thomas, N.A., Norberg, T.).,
Barbour, M.T., Roush, T.H., Brandes, WP.,
Effluent and ambient toxtctty testing and
instream
community
response
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Ottawa River, Ltma, Ohio, EPA 660/3-84080, Environmental
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21. Eagleson, K.W, Lenat, D.L., Ausley, L.W,
Wmborne,
P.B., Environ. Taxicol. Chem.
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22. Cherr, G.N., Shenker, J.M., Lundmark, e.,
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46. Kloepper-Sams,
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47. Andersson,T.,
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48. Hamig, J., Andersson, T., Bengtsson, B.-E.,
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49. Lehtinen, K.-J., Kierkegaard,A.,Jakobsson,
E., Wandell, A., Ecotox. Environ.
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50. Lehtinen,
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24. Scroggins,
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26. Hall,T.J.and
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40. Burton, D.T., Klauda, R.J., Hall, L.W, Margay, S.L., Water Res. 18: 1365 (1984).
du-
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biologically
treated bleacbed kraft mill
effluent on tbe peripbyton
community
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experimental
streams for
1976 and 1977, National Council for the
Paper Industry for Air and Stream Improvement, New York, 1984.
60. NCASI Technical Bull. No. 423, Effects of
biologically
treated bleached kraft mill
effluent on the peripbyton
community
in Southern
experimental
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1979 and 1981, National Council for the
Paper Industry for Air and Stream Improvement, New York, 1984.
61. Landner, L., Nilsson,
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R.,
S.,
21:308
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in the aqUlltic
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the Potential
R.,
0., Can.
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80. Munkittrick,
K.R., McMaster, M.E., Portt,
C.B., Van Der Kraak, G.]., Smith, I.R.,
Dixon,
D.G., Can.]
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49:1560 (1992).
81. Thulin,].,
Hoglund, J., Lindesjoo,
ter. Set. Teebnol., 20:179 (1988).
on the Aquatic
fIuents Proceedings,
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Environment
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795
oIToronto,
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E., Wa-
82. Kloepper-Sams,
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96. Landner,
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99. Sandstrom, 0., Coastal Research laboratory, Swedish Fisheries Board, Oregrund,
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796
mill environcommunica-
C.A.,
(1994).
pulp
at the
SOdra
Cell AB mill
Varo
Contamin.
D.M.,
K.R.,
Chapter
VIII 2: Assessing
the Potential
Glossary
Impacts
on the Aquatic
Environment
797
Anoxic - Characterized
by the absence of oxygen, a condition
which is lethal to most
organisms except for certain bacteria. Sediments become anoxic when the bacterial
degradation
of organic matter, such as a
deposited mat of cellulose fiber, consumes
the available oxygen.
Ateric - A histological
condition where eggs
in the ovary have not been released under
spawning conditions
and the eggs are being metabolized
(resorbed).
Benthic - Indicating the bottom or sediments
of aquatic environments
such as those organisms which inhabit the surface of the
sediments or dwell within the sediments.
Biomarker - A within-organism
physiological
and biochemical measurement
which theoretically provides a sensitive warning !lignal of external stressors (chemical or other
changes in the environment).
Presumably
biomarkers
provide quantifiable
measures
in the early phase of an organism's response
to natural or anthropogenic
stressors. That
is, biomarker changes occur and provide a
signal before irreversible
adverse changes
occur.
Condition Factor - The ratio of the weight of
fish to its length. The ratio is greater for
heavier individuals which have more lipid
(fat) or more muscle content.
There is a
presumption
that this indicates excess energy which can be stored as fat either because of increased food supplies, alteration
in energy expenditure
for growth, or alternation in energy expenditure
for reproduction.
Eutrophication - The excessive growth of algae and plants caused by an excess of nutrients, usually phosphorus. This classically
leads to an excess of organic matter which
decreases the oxygen levels of lakes because oxygen-consuming microbcs con-
matter.
(continued)
798
Glossary
(continued)
Osmoregulation
- Regulation of osmotic pressure in the body of a living organism. Fish
in freshwater environments
must maintain
a higher concentration
of vital ions, such
as potassium, sodium, and chloride, inside
their bodies than exists in an aquatic environment. They must maintain this concentration gradient of ions across their gills
while preventing
an influx of water to dilute the ions (an osmotic gradient).
This
regulation of water and ions across the gills
(osmoregulation)
is achieved by chemical
pumps in the gill membranes.
Tubercle - A visible external growth of the
skin. Often, these growths are found in
one sex at a certain stage of the reproductive cycle, such as the male sucker, and are
used to estimate the reproductive
status or
strength ofthe reproductive
response.
Under microscopic
Vacuolization
of liver
examination
(histology), the liver cells appear to have smaIl voids in the cell structure or a spongy appearance
(vacuoles).
This observation may be due to several reasons ranging from deposition of starch granules for energy storage to oxidation stress
damage from peroxisomal
proUferation.
SECTIONvm:
Pulp Bleaching and the Environment
Chapter 3:
Dioxins and Furans in Effiuents,
Pulp, and Solid Waste
Richard Berry
Pulp and Paper Research Institute of Canada
Pointe Claire, Quebec
1. Introduction.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 801
. . . . . . . . . . . . . . . . . . . . . . . . . . 804
807
807
2.1 History
807
808
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 808
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 809
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 810
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 811
dioxin formation
812
812
815
standards
816
. . . . . . . . . . . . . . . . . . . . . . . . . . 816
.........................................
8] 7
817
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 817
799
Chapter VIll 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
Chapter vm 3:
Dioxins and Furans
in Effiuent, Pulp, and
Solid Waste
1. Introduction
1.1 Definition of terms, nomenclature
conventions, and physical properties
Dioxin is properly the shortened name
for dibenzo-p-dioxin. However dioxin is also
the common name given to the members
of a family of tricyclic chiorinated aromatic
compounds (Fig. 1) which comprises 75
polychiorinated dibenzo-p-dioxins (PCDDs)
and generally includes 135 polychiorinated
dibenzofurans (PCDFs). Each member (CORgener) of the family belongs to a homologue
group which is defmed by the degree of
chiorination.
Tule 1. Pbyskal properties of2,3,7,S-TaJD
(1).
802
TCDD
TCDD
PeCDD
PeCDD
HxCDD
HxCDD
HxCDD
HxCDD
HpCDD
HpCDD
OCDD
2,3,7,8Other
1,2,3,7,8Other
1,2,3,4,7,81,2,3,6,7,81,2,3,7,8,9Other
1,2,3,4,6,7,8-
Other
Tule
3. ~
Atoms of Chlorine
1
2
3
4
5
6
7
8
Total
Fig. 1. Strwetures of Ml1M%o-p.~,.
lUlled molllk tIIUltile ~
polyeblorltulted dlbnzofu,.",.
6
Dioxin Isomers
2
10
14
22
14
10
2
1
75
0.1
0
0.5
0.05
0
0.1
0.1
0.1
0.1
0
0.01
0.01
0
0.001
Species
~me
IDw~~)
Oral
Oral
Oral
Dermal
Intraperitoneal
Oral
Oral
Oral
Oral
Intraperitoneal
Oral
Oral
Oral
Oral
Intraperitoneal
0.6
2.1
115
275
152-500
<70
22
45-500
<150
120
30-300
>100
1,000
1,157
3,000
Dlbenzofuran
Dlbenzo-p-dloxln
I-TEF
TCDF
TCDF
PeCDF
PeCDF
PeCDF
HxCDF
HXCDF
HxCDF
HxCDF
HxCDF
HpCDF
HpCDF
HpCDF
OCDF
7~~3
run
1,2,3,4,6,7,81,2,3,4,7.8,9-
7~~3
0.2:t 0.2
570
7.2 x 10.10
6.8
310
2,3,7,8Other
1,2,3,7,82,3,4,7,8Other
1,2,3,4,7,81,2,3,6,7,82,3,4,6,7,81,2,3,7,8,9Other
1
0
0.5
0
0.1
0.1
0.1
0
0.01
0
0.001
Other
8~2
Solubility
In Water, ppb
In Benzene, ppb
Vapor Pressure, torr
Log Kow
Furan
Congeners
I-TEF
8~O~2
322
303-305
(3).
Dioxin
Congeners
Mol.Wt.
M.P., C
A maximum,
801
4
Furan laomers
4
16
28
38
28
16
4
1
135
Chapter VIII 3: Dioxins and Furans in Eftluents, Pulp, and Solid Waste
803
804
3,500
COMBUSTION
3,000
0..
':
c
Carbon
+ Hydrogen
+ Oxygen
+ Chlorine
Heet..
CI <y0Y'lr
hO~
2,500
0 2,000
CI
CONDENSATION
~...
-c
1,500
:i~(6~
CD
0
c 1,000
0
U
500
CI N80
P5 H6 H7 08
T4
Remarks
Workers
Exposed
Location
of Accident
1949
250
Monsanto plant
in Nitro,WV
1953
75
BASF plant
in Ludwigshafen
1956
Rhone-Poulenc
plant in Grenoble
1963
106
NV Philips
plant inAmsterdam
1964
61
1965-1969
78
Continuing leaks
in Spolana plant
near Prague
Rh6ne-Poulenc
plant in Grenoble
21 chloracne
cases
79 chloracne
thrombosis
1966
1968
90
1976
156b
'v
verified.
= total
lcmesa plant
in Seveso, Italy
exposure
of 37,000
residents
communities
O=
~
CI
t)
~
CI
CI
1,2,3,6,8,9-HexBChlorodlbenzo..p-dloxln
CHLORINATION
o=:t)
"-~II86IIe.
CI
P5 H6 H7 08
PCDFs
PCDDs
FI,. 2.lHM1I~"
CI
Hepl8chlorlnllted Predloxln
T4
C~
C1
DBD
FI,. 3. G-.l
O= t)
C1
CI
CI
~1C1
2,3,7,8-
TCDD
of PCDDtIItiIPCDF
j'ormtIIIqt8.
The dioxins from these sources can be considered as arising by three main mechanisms: combination
of chlorine radicals
with hydrocarbon structures at high temperature (11), condensation of chlorinated
sodium phenolate structures (12), and electrophilic substitution
by chlorine of an
unchlorinated
precursor compound (13,
14) (Fig. 3).
Chlorinated
dioxins can also be destroyed during combustion. The conditions
in combustion, in particular, are critical in
determining the amount and type of each
dioxin congener that is emitted into the environment (15).
Because dioxin fonnation is very depen.
dent upon the conditions that exist in the
particular dioxin-forming process, it is difficult to obtain an accurate evaluation of the
relative amounts produced by each source.
Several attempts have been made to produce a ranking, and one example is given
in Table 6 (16). Some of the most revealing
data in determining the general contribution from major sources are the results from
a comfY.lrison of industrial, suburban, and
rural sites (Fig. 4) (17).
These results show that dioxins are
largely a result of human and particularly
805
806
Source
Sielkin
CDC
EPA
FDA
FRG
LMS
M-K-V
MLE
NRC
CANADA
pg
PCIJF-..Is
Forest fires
Municipal waste incineration
Sewage sludge incineration
Firewood combustion
Wood preserving waste water
Chlorophenol prod., air emissions'
Wood preserving waste disposal
Residential heating
Coal-fired utility boilers
1,000
o
T4
Motor vehicles
Cigarette smoke
IlI./fere81 _IUS
c:
o
:;:;
.1
c:
Q)
P5 H6 H7 08
PCDDs
of tIM PCDIJs ..
PCDFs fourut
1400-3300
1800
1500-6500
3
4
1000
600
600
>300
700
5
6
7
8
9
ZOO
10
11
T4
P5
H6
H7 08
PCDFs
In soils at frulllstrltll,
suburbtln,
100
80
()
60
o
c:
'xo 40
is
~
:;:;
20
Soil - SE England
Sediment
- Lake
Huron
0
1800
1850
1900
1950
2000
Year
1
550-21700
(16).
FI,. 4. ComptIrlstm
a:I
Q)
a:
250-13700
900
>500
900
300
Industrial
2,000
Rank
58700
Urban
f:SJ
()
PCDF
g/year
'E
Q)
PCDD
=picograrn.
o Rural
c:
.2
0.006
0.007
0.03
0.06
0.07
0.6
1.0
2.4
4.0
10.0
26.0
(MLE)
: 3,000
pg'/kg/day
EPA(LMS)
California
CDC
FDA
NRC Canada
M-K-VModel
FRG
NY State
Netherlands
Canada
4,000
UJIosItImt lit
"'U-t
loetItIorIs.
industria1 activity. Contributions from natural sources, however, cannot be ruled out.
Although attempts have been made to make
correlations (18), it is difficult to specify a
particular human activity beyond increased
combustion-related
activities. Also rural
contamination, if consistent, represents a
very large accumulation because the total
is the product of the concentration found
and the area contaminated. Historical data
on the concentrations
of dioxins in soil
samples also help to identify the contribu-
of increasing
public aware-
ness
Table 4 (9) shows that there has been a
recognition of human health effects from
industrial exposure to dioxins since 1949,
when it was first understood that chloracne
was specifically associated with exposure
to the chemical. General public awareness
of concerns over dioxin exposure was awakened by the industrial accident at the
Icmesa-Givaudian plant near Seveso, Italy,
in 1976 (20). It was further heightened by
the evacuation of the contaminated areaS
atTunes Beach, Missouri, in 1983 where oil
mixed with sludge waste contaminated
with 2,3,7,8- TCDD from a hexachlorophene
plant was used for dust control on local
roads and recreational areas in 1971 (21).
These events led to concern by Vietnam
veterans about the effects of their exposure
to the defo1iantAgent Orange which possibly contained 2,3,7,8-TCDD (22).The concerns arising from these events led to an
evaluation by the U.S. Environmental ProtectionAgency (EPA) of the degree of dioxins exposure
at sites where it might
reasonably be considered that higher than
background
levels of dioxins would be
found. In 1985, a seven-tier study, known
as the National Dioxin Study, was initiated
to evaluate locations having different levels of contamination; the seventh tier of the
study involved an examination of the background level of contamination (23).
product
807
808
120
100
a.
80
c
0
-a.
~60
-c
CD
(,)
c
0
40
U 20
0
T4 P5 H6 H7 08
T4 P5 H6 H7 08
PCDDs
Fig. 6. 1h
typWl
SjIIrrIm
IIuIIaIH",
PCDFs
blMeb p",,,,-genertIIetI
1,2,7,8-TCDF
congeners
were always
present (Fig. 6). Of the bleaching filtrates,
the E-stage filtrate was found to have the
highest concentration of dioxins.This rmding led to speculation
that chlorinated
phenols generated in the chlorination stage
but carried over into the extraction stage,
had condensed to form dioxins by the same
mechanism as that occurring in trichlorophenol production (34). However, the particular chlorinated phenols generated in the
C stage, when condensed,
should have
given a very different congener distribution
than the one observed; the actual profile
was the same as that found in the C-stage
pulp. It was therefore concluded that the C
stage was the point of formation and that
the elevated level of dioxins in the E-stage
filtrate was a consequence of their removal
from the pulp in soap micelles or on fines
(35).The dioxins associated with the fines
accumulate in the sludge from both the primary and secondary treatment (36).
The very distinct pattern of formation,
together with the observed approximate 3
to 2 ratio of 2,3,7,8-TCDF to 1,2,7,8-TCDF,
provided a clue to the mechanism of generation because the congeners found were
also those which were predominantly
formed when unchlorinated aromatic precursors, with the basic dibenzo-p-dioxin
(OBD) and dibenzofuran (OBF) structure,
were chlorinated (37). The understanding
2,3,7,8-TCDF
tUoxhts.
Chapter VIII 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
the concentrations
of 2,3,7,8-TCDD and
2,3,7,8-TCDF under the bleaching conditions that cause dioxin fonnation are often
only one order of magnitude different. The
reason for this discrepancy is that DBD reacts faster than DBF with chlorine (37).
Dioxins can also be fonned from alkylated precursors which are present in the
environment
at higher levels than the
unalkylated precursors. The alkyl group,
however, does not undergo electrophilic
substitution very easily therefore; the formation of unalkylated chlorinated dioxins
from alkylated precursors during bleaching
occurs only slowly (43).
2.5 Wood
Another source of dioxin precursors is
the wood itself. In particular, compression
wood contains higher concentrations
of
precursors than normal growth wood. Compression wood also contains higher levels
of coumaryl-type
lignin which may be a
source of these DBD- and DBF-Iike precursors. The concentrations of dioxins fonned
in laboratory pulping and bleaching of compression wood in the furnish has been
found to be greater than from similar treatment of nonnal wood (44,45).
Debate has continued on the predominant mechanism of fonnation of chlorinated
dioxins in bleaching. Some authors have
809
810
Pulp Bleaching
1.2
a.
Co
c:
.Q
i
....
0.8
-cQ):
0.6
c:
()0
0.4
(.)
0.2
0
Fig. 8. Possible
spectrum
of PCDDs
g 2,000
o
1,000
T4 P5 H6 H7 08
PCDDs
spectrum
a""
PCDFs lukati"g
Q)
'"
C.
E
<tI 0.8
'"
.5
c
0
~0.6
Q)
'E
0
c 0.4
0
0
'0Q)
.!!1
10
E
0
effluent
contamination
of PCDDs
a""
PCDFs i""kllli"g
T4 P5 H6 H7 08
PCDFs
PolyCP-contaminateti
chips.
from fly-ash.
0.2
T4
P5
H6
P5 H6 H7 08
H7
IUstrlInItion
fmuul
for samples
:0:;
n!
.::. 3,000
cQ)
Fig. 7. Possible
PCDFs
PCDDs
4,000
T4 P5 H6 H7 08
PCDFs
PCDDs
: 5,000
()
H6 H7 08
P5
T4
6,000
and Practice
1.4
-Principles
contamitltltetl
by tbe everydlly
environment.
Chapter VDI 3: Dioxins and Furans in Eftluents, Pulp, and Solid Waste
Bleached Kraft
Unbleached Kraft
811
812
ND
0.02
Newsprint
Deinked Pulp
0.19
0.35
Recycled Linerboard
2.5
o
0.5
1
Toxic Equivalents,
FIg. 10. CmrtptJrlsmI of PCDDIFcmtItm8l_ts,
prot/Ircts.
_millS
1.5
2
2.5
pg 2378-TCDD/g
toxk eq.dvtllnlts,
3
of dlff-t
j"dp IIIIIl}ItIJIn'
Plastic Packaging
Clothes Dryer Lint
Vacuum Cleaner Dust
Room Air Filter
83.7
167.4
o
50
100
150
200
Toxic Equivalents, pg 2378-TCDD/g
Fig. 11. CmrtptJrlsmIof PCDDIFcmtItm8luats, _millS
f1fInydtrynmrormumt.
these boilers, the scrubbing water becomes
contaminated with dioxins and these dioxins can be partially transferred to the mill
effluent (52).
has recently been shown that exposed materials can become contaminated with dioxin through the entrapment of dust, which
contains high concentrations
of dioxins
35
0.
a.
Kappa
37.7
30
ci 25
33.1
a.
.~
0
0
U
I-,
28.1
.
25.9
"'5
20
15
10
~.....0
5
~C\I
0
0
0.1
Active
0.2
Chlorine
wltb cblorine
0.3
0.4
Multiple
m"lHpll!
IIIf/I1M .."mber.
Chapter VIII 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
813
100
o.
c:
0
+:: 80
::J
Non-measurable
dioxin
40
15
20
0
0
0.05
0.1
0.15
Active chlorine
Pig.13. CtnI4ItknIsollldlve cblorllw _ltiple
(FilIM _rUts, 2,3,7,S-TCDD-mle,
mill
11411I; elrr:les,
lllbortItory
0.25
0.2
0.3
TCDPlomI4Ho1t
(38).
C-stage: 0.21 x kappa number (% CI, on o.d. pulp); 50C for 30 min; 3.5% consistency.
,
ND = not detected, detection limit given in brackets.
multiple
II1Iilcblorlu ~
SllbslUrlHoIttlMtform 2,3,7,S-TCDD
8".ftIW 1IIiI1'Urs.2,3,7,S-TCDD__tYlble;
If'U'"'s,
11411I).
8
C+D
-a.a.
011 TCDD _
::J 60
en
(I)
and Practice
Consistency, %
~..c
c:
'1::
.Q
.c
0
-Principles
Pulp Bleaching
:::.!!
(I)
"'C
'x
0
814
C/D
ci
0
0 4
lcb
r-:
D/C
.
.
M 2
N
.
10
60
%
70
Is 11II-
WOC!- + W + C!-
35
30
2,3,7,8 25
TCDD, 20
ppt
15
10
5
35
30
2s2,3,7,S TCDD,
20
ppt
15
02040-
Chlorine 60Dioxide
80Substitution.
%
100-
[1]
20
30
40
50
Chlorine Dioxide Substitution,
CI+CI-+ HP
3.2
0
o
ion (CI+) with dioxin precursors. The concentration of this ion for a given charge of
chlorine is dependent upon elemental chlorine, chloride and hydrogen ion (pH) concentrations,and temperature because of the
chemical equilibrium
formed by dissolution of chlorine in water:
10
5
.....
0.16
0.12
0.2
'0.24
....
0.28
Active Chlorine
Multiple
and cblorine dioxide substitution
level 011
Chapter VIII 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
TtIbk 8. hlcrNrill/f"
pH '-ers
bkllebed}1roMcl (38).
NaOH
Applied,%
on o.d. pulp
0.0
0.1
0.5
1.0
2.0
3.5
5.0
7.0
10.0
tbe _",
C-stage pH
Initial
8.2
8.5
8.3
8.9
11.0
11.1
11.5
Final
1.5
1.6
1.6
1.6
2.3
2.0
2.3
6.3
11.3
815
CE
Kappa
No.
3.5
3.2
3.1
3.0
2.9
2.9
3.1
4.5
8.1
Cuene
Vise.,
mPd.s
15.6
12.3
12.1
11.3
10.2
11.2
8.5
10.1
14.5
Cone. in C-stage
pulp, ppt
2378-TCDD
2376-TCDF
15
15
15
12
11
6
2
ND(1)'
ND(1)'
456
482
461
383
347
165
23
10
5
.NO=
DBD and DBF was to ensure that any defoamer used in the brown stock or bleach
plant areas was produced with an oil base
that was first treated to remove dioxin precursors or with a water base (42). Because
water-based defoamers do not work as well
as oil-based defoamers in brown stock applications, the simple expedient of substituting one product with another was found
not to be the solution. Instead, using a
hydrorefined oil base proved to be necessary. Oil-derived contamination
was also
found to occur, for example, from kerosene
(used to prevent chips freezing in chip
trucks), lubricating
oils and creosotetreated, wood-lined channels. It has been
determined that the dioxin formed by the
Canadian pulp and paper industry was decreased by approximately half through using purified defoamers (48).
816
Pulp Bleaching
-Principles
and Practice
Chapter VIll 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
monthly until compliance is shown and
thereafter monitored at progressively longer
intervals.
The results of annual mill testing surveys
(48, 71) shows that dioxin levels have decreased by 98% since 1988 when the first
survey was made and will decrease still further as all mills complete the modifications
required to achieve full compliance. Even
with these efforts, a small residual dioxin
level will persist because of contamination
from the ambient environment which affects all materials, not just bleached chemical pulps.
Canada is the only country which presently has a national standard for dioxin discharges from the pulp and paper industry,
but there are several states in the United
States that have also required mills, by regulation, to ensure that dioxins are not discharged. Recently proposed EPAregulations
may provide an equivalent national standard
for dioxin discharges for the U.S. pulp and
paper industry (71). (See Chap.VIII 5.)
817
818
concentrations
of ItCDD and HxCDD in
water decrease (half lives of 0.94 and 2.5
days respectively) through environmental
photolysis and that TCDD photo-decomposes in the vapor phase. However, it is
necessary for the molecule to be exposed
to light which is unlikely to occur in all circumstances.
Several artificial methods of eliminating
dioxins have been studied particularly in relation to the cleanup efforts made at Seveso
(74). To date, thermal destruction is the
most effective method of eliminating dioxins. The extent of destruction is a function
of time, temperature, and oxygen concentration.Temperatures
in excess of715"C for
1 second can eliminate 99",.(,of the dioxins
(75).
Photolysis by UV light can be accelerated
by the addition of chemicals, for example,
ethyl oleate/xylene, and high energy radiation such as gamma rays can be used with
solvents, for example, ethanol, to cause
dechlorination of dioxin molecules (76).
Another method consists of the direct
application
of a highly active oxidant.
Ozone can destroy dioxins after they are
extracted into an inert solvent. For example,
dioxins are degraded after being extracted
into carbon tetrachloride and then exposed
to a high concentration of ozone (77).
Another active oxidant is a mixture of
peroxide and polyethylene glycol (PEG).
Using a mixture of PEG 6000, K,CO} and
Nap, at 85C, 99.9% ofTCDD dissolved in
n-decane is destroyed in 3h.At 500C, using
the same mixture, all theTCDD is destroyed
in 3 h (75).
References
1. Crummet, W, 1988 CPPA Bleaching
mitteeTechnical
Session Proceedings,
Tech. Sect., Montreal, Chap.1.
2. Milby,
TH.,
Miller,
TL.,
Forrester,
ComCPPA
TL.,
iegiotW Office
for EUf01)e
IPCICHE
SO 11
m 05, 1985.
4. Kociba, R.]. and Cabey, 0., Cbemospbere
14(617):649 (1985).
5. Poland,A. and Kende,A., in Origins of Human Cancer (H.H. Hiatt, ].D. Watson, ].A.
Winston, Eds.) Cold Spring Harbor, New
York, 1977, p. 847.
6. Poland, A. and Knutson,].,
Pharmacol.
Toxicol. 22:516
Annu.
(1982).
Rev.
7. Kociba,
R.]., Keyes, D.G., Beyer, J.E.,
Carreon, R.M., Wade, e.E., Dittenber,
D.,
Kalnins, R., Frauson, L., Park, e.N., Bernard,
S., Hummel, R., Humiston,
e.G., Tuxicol.
Appl. Pharmacol.
46:279 (1978).
8. Schecter, A., Ryan, J.]., Girtitz, G., in Chlorinated Dioxins
and Dibenzofurans
in
l'Prspective (e. Rappe, G. Choudhary,
L.H.
Keith, Eds.) Lewis Publishers,
Chelsea,
Michigan, 1986, Chap. 4.
9. Tschirley,
254(2):29
F.H.,
(1986).
Scientific
American
1.]., J
B., Chemosphere
in tbe Environment
20(7in Dioxins
(Kamrin, M.A.,
Chapter VIII 3: Dioxins and Furans in Effluents, Pulp, and Solid Waste
25(9):1619
(1991).
(19S8).
32. De Sousa, F., Kolar, M-C., Kringstad, K.P.,
Swanson, S.E., Rappe, c., Glas, B., Tappi
72(4):147
819
(1989).
P., Pulp
(1991).
-Principles
and Practice
R.H.,
R.M.,
51. Someshwar,A.
V, Jain,A. K., Whittemore,
R. c., lafleur, L. E., Gillespie, w,J., Chemosphere 20(10-12):1715
(1990).
52. Luthe, C.E. and Prahacs, S.,Pulp Pap. Can.
94(8):T227 (1993).
53. Rappe, C., Glas, B., Kjeller, L.-o., Kulp,
S.E., deWit, c., Melin, A., Chemosphere
20:1701 (1990).
54. Rappe,C.,Glas,B.,Wiberg,K.,"Solved
and
remaining PCDD and PCDF problems in
the pulp and paper industry," Short Papers
from the Tenth International
Symposium
on CWorinated Dioxins and Related Compounds,
Eco-Informa
Press, Bayreuth,
Germany, 1990, Vol. 3, p. 287.
55. Shariff, A. and Nguyen,
Can. 93(9):29 (1992).
X.T., Pulp
Pap.
L., Chemosphere
Pulp Bleaching
820
Hintz,H.L.,
43(6):421
TappiJ
(1990).
73(1):185
C. J.
Pap.
Pulp
75(2):
Apptta
57 (1992).
T.,
E..
69. McKee,
P., Burt, A., McCurvin,
D.,
Hollinger, D., Ciement, R., Sutherland, D.,
Neaves, W, Cbemosphere
20(10-12): 1679
(1990).
70. CEPA Pulp and Paper Mill Effluent CWorinated Dioxins and Furans Regulations.
Canada Gazette Part II, Vol. 126, No. 11,
1992, P 1940.
71. United States Environmental
Protection
Agency, 40 CFR Partrs 63 and 430, "Effluent Limits Guidelines, Pretreatment
Standards, and New Source Performance
Standards: Pulp, Paper and Paperboard
Category; National Emission Standards
for
Hazardous Air Pollutants for Soource Category: Pulp and Paper Production;
Proposed Rule," Federal Register, Vol. 58, No.
241, P 66078,1993.
72. "Reference Method for the Determination
of Polychlorinated
Dibenzo-p-dioxins
(PCDDs) and Polychlorinated
Dibenzofurans (PCDFs) in pulp and paper mill effluents," EPS Report 1/RM/19, Environment Canada, Ottawa, Ontario, 1992.
73. Kieatiwong, S., Nguyen, L.V, Hebert, VR.,
Hackett,
M., Miller, G.C., Miille, M.J.,
Mitzel,
R., Environ.
Sci. Technol.
24(10):1575
(1990).
74. Friesen, K.J., Muir, D.C.G.,Webster, G.R.8.,
Environ. Set. Technol. 24(11): 1739 (1990).
75. Fortunati, G.U., in Chlorinated
Dioxins
and Dibenzofurans
in Perspective
(C.
Rappe, G. Choudhary,
L.H. Keith, Eds.)
Lewis Publishers,
Chelsea,
Michigan,
1986, Chap. 37.
76. Miller, H., Marklund, S., Bjerle, I., Rappe,
c., Chemosphere
18(7-8):1485 (1989).
77. Liberti,
A., Brocco,
D., Allegrini,
I.,
Cecinato,
A., Possanzini,
M., Sci. Total
Environ.
10:97 (1978).
SECTIONvm:
Pulp Bleaching and The Environment
Chapter 4:
Bleach Plant Air Emissions
A.K.Jain
National Council for
Air & Stream Improvement,
(NCASI)
Gainesville, FL
Inc.
1. Introduction
823
chemicals
823
of organic compounds
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 824
824
. . . . . . . . . . . . . . . . . . . . . . . . 829
. . . . . . . . . . . . . . . . . . . . . . . . 830
830
821
. . . . . . . . 830
. . . . . . . . . . . . . . . . . . 833
Chapter
Chapter vm 4:
823
Bleach Plant
Air Emissions
1. Introduction
CWorine and cWorine dioxide are gases
used in significant quantities in bleach
plants and, as a result, bleach plants contain several vents which have the potential
for releasing gaseous cWorine and cWorine
dioxide. If oxygen or ozone is used in the
bleach plant, it would also be expected to
be present in the vent gases. Of these, only
cWorine, cWorine dioxide, and ozone emissions are of environmental significance. In
addition to the gases employed for pulp
bleaching, a number of volatile organic compounds such as cWoroform, methanol, acetaldehyde, and methyl ethyl ketone are
either produced during pulp bleaching or
are present in the liquid streams which are
introduced into the bleach plant and so are
also likely to be present in bleach plant vent
gases.
824
Pulp Bleaching
- Principles
and Practice
_1ssIorIs
fram
blelleb Pi"",
fJMts prior
to sawbber.
Process
Furnish
C(EO)HP
(C+D)(EO)D(EP)D
CEHD
(CD)(EO)HHD
C(EO)H
CEH
CHDED
(C+D)(EO)D
(DC)(EO)DED
(C+D)OD
K-Kraft
S - Sulfite
HW - Hardwood
SW - Softwood
Minimum
Maximum
Average
HW
0.00
0.23
0.07
SW/HW
0.02
0.14
0.08
SW/HW
0.38
5.21
2.56
SW/HW
0.01
1.71
0.41
S
S
K
K
K
K
SW/HW
SW/HW
SW/HW
SW
SW
HW
0.00
0.24
0.13
0.01
0.04
0.17
0.004
1.06
0.72
0.04
0.06
5.13
0.003
0.63
0.33
0.02
0.05
2.00
with alkaline
chlorine
(t.e., hy-
Sequence
Furnish
Minimum
Maximum
Average
SW/HW
SW/HW
0.32
0.61
0.50
0.03
0.09
C(EO)HHD
0.05
SW/HW
0.04
0.98
0.32
CHDED
(C+D)(EO)D
SW/HW
0.02
0.09
0.05
SW
0.08
0.29
0.19
(DC)(EO)DED
SW
0.64
1.21
0.86
(DCXm)D
HW
0.61
12.75
2.65
(C+D)(EO)D(EP)D
CEHD
K-Kraft
HW - Hardwood
SW - Softwood
Process
E- 0.4
::>
c..
.;:
Ii
...
t:.
100%
o
0.3
1]
.1
0.1
.. ..
~t
t:.
t:.
...
..
0
0
~8
~]
...
...
41
......
.2:0
o
o
E~
42-5 0.2
e i8
E
-c
CO;
Cot:
..
o..~
826
15%
D
825
L>.
g...
.. u
... ..
~.!!
. ... .
...
1~::I
E
1
...
"
0.2
0.1
Chlorine
CHCI3,
kg/admt
of pulp
0.4
40
60
80
Chlorine
dioxide
substitution.
100
factor
0.3
20
SIIffIJIles_/dyzell
", pH
Fig. 2. Melllmwi
OOfI/ml of ftllrtlles
from
C lI"tI E slllges
I"
IIIe bleaelll"g
of pine
llraft pulp.
827
828
~~Q.
"S
Q.
0
~O'"
or-.
tit .0
o
c:: V)
Q.
"5
Q.
oS: 5
t!
.J<I.
U
01!
c:~
~.2~
~"
6-
'"
.
'"
..
g
'"
.5
1,
.J<I.
"0
0
80
100
0\ 00 r<;
~~0
N
unbleached
pulp, shower
water
S<>-
of pulp can
from bleach plants is that the methanol content of the effluents increases with chlorine
dioxide substitution up to 70% and then
decreases slightly for 100% substitution
(Figs. 2 and 3 (15)).
Methanol has a high solubility in water,
and the vapor pressure of methanol in
methanol-water
solutions is low. Conse~~~~quently,
most of the methanol in bleach
plants remains in the effluent. The results
of methanol
tests on various process
streams and vent gases carried out at 13
bleach plants are summarized in Table 3
(16). The data show that methanol emis~sions increased with increasing amounts of
total methanol in the bleach plant and were
higher from bleach plants which utilized
"'.~E.c
u ""
. ~'"
c:: '" 0
aJ"'.!j
",CQ
.5
\()
chlorine dioxide absorption tower. Methanol concentrations up to 1.1 g/L have been
measured in the chlorine dioxide solutions
showers.Table
net effect
3 shows
\()
-~1t
~CQ
~I'- r<;
N
r<;
r<;
N
r<; r<;
~~N
N .,;
~~~~"".
~N
~or-.
or-.
~~or-.or-. or-.
N N
N 0
0
tJ
.c
'"
~~~I'0
00
00
~~~0
Q.
..
0
~N
~0\
~~N
C
0
~~"O
c
.2
ON$
_.~?f.
U!i;
.c::0
V)
~0
or-.
or-.
0 or-.
~~
or-. r<;
or-.
~or-.
00
Q.
'3 'in "S
-e J '0Q.
<5
0
'O~
g ;
~0
0\
or-. or-.
o 0 0
~r<; r<;
f.~'8
00
~;:::
0 0
~~8 0
0
ji"'8"O
o
~~8
C::"'"O~
~-:;
3~=7~
or-.
'""
'-'
~r<;
N I'0
N
r<;
<5 0 .g
~.sCrl
CQ'" 0
~;;
!1
!s
!s !s
..:,
~'St '"
]u -~ti~E
~'"
~~~~~-g~.~"O
_",B.c
!s !s !s !s X ~!s
B~2S~a
z~~~!:
EEEC::ji
.@sggo
. ...
1
!
'"
t'~
0
..
0
.~Hi
~'s
~-"I
.!
(16).The
0\
'0c
~.c
ti'"
~::!1
011Hlr4lDoo4",.ft pip.
"O. Q.,
~..c_
~~'5
~;
~plant with
"<1' '::S
...
0
6-
~\0
""
'1'
"S
Q.
60
'b.
40
or-. !::;
"
E
20
00
N
r-. r<; 'D
""
ti C
7!rJ.!! ":
~=Q., -
~~o><ySen-delignifoed
~~~
':!:
6-
""
~&a'8
..
'"
C!~e
0\
~0
:oot'~ '"
.c
.:!3
...
U
U
~'-'
-<
Z'-'
ob
I:i:j
~~~~~~~'
~~~~~~~~~~~~~"'C::C::0:E
~"
8(g!s
[2J
ClO2
Substitution,
%
C Stage
om
10
829
E Stage
. D Stage
E Stage
D Stage
Total
0.07
0.24
0.0
0.04
0.36
0.02
0.07
0.20
0.0
0.05
0.34
30
0.04
0.09
0.18
0.0
0.03
0.34
50
0.10
0.07
0.19
0.0
0.02
0.38
70
0.18'
0.25
0.09
0.18
0.0
0.04
0.49
0.08'
0.20"
0.0
0.04
0.57
100
0.2
.' -
, ",,(SW)
. ',
N(SW)
..l~
:KfHW)
/IiI(I'IW)
",...
rom/JOfUUlnttissImufrom
g/odmt of
Unbleached Kraft Pulp
Compound
Softwood
Hardwood
Acetaldehyde
4.2
1.4
Acetone
3.7
1.8
Acrolein'
0.2
0.038
Benzene
0.11
0.05
1.0
<0.85
0.11
0.03
46
65
1,2-Dichloroethane
0.28
<0.19
1,2-Dichloroethylene
0.17
0.11
Dimethyl disulfide
3.8
<1.4
2.4
0.60
Carbon tetrachloride
Chlorobenzene
Chloroform
Dimethyl sulfide'
Formaldehyde
<5.5
0.43
n-Hexane
0.06
0.01
Methanol
130
47
0.11
0.06
0.46
0.27
Methyl mercaptan'
6.0
0.50
Methylene chloride
0.80
0.21
Styrene
0.14
0.07
Terpenes
12
2.3
0.90
0.13
.
j(Sw)
1,2,4-Trichlorobenzene
C(l~W)
0.1
Actual methanol emissions
(kglodmt unbleached kraft pulp)
Toluene
C(SW)
0.05
Tetrachloroethylene
A~H,W) E(~W)
.
A(~W)
830
0.15
0.2
75
34
0.11
0.03
2.0
0.65
1,1, I-Trichloroethane
0.22
<0.15
1,1,2-Trichloroethane
0.21
<0.19
Trichloroethylene
0.40
0.18
m,p-Xylene
0.12
0.02
o-Xylrnc
0.10
0.03
'Unexpected
bReference
and unconfirmed
(19)
by GC/MSD.
Chapter
Chlorine
55-76
28- 52
78-87
30-66
44-72
9-59
20-65
160 - 540
35-87
90-640
78-94
43 - 120
67-95
110 - 220
>99
1- 310
>99
250 440
840 - 1600
290 - 670
4
5
Chilled water
CWorine dioxide is very soluble in chillc;d
water. Consequently, a number of cWorine/
cWorine dioxide scrubbing systems utilize
a cold water scrubbing stage to recover
cWorine dioxide from the vent gases. Although the solubility of cWorine in chilled
water is not as high as that of cWorine dioxide, chilled water scrubbers are also capable of removing some vent gas cWorine.
A packed scrubber facility using chilled
water reportedly (1) removed over 97% of
the bleach plant vent gas cWorine dioxide
which was present in the inlet gas in the
concentration
range of 6,000 to 24,000
parts per million (ppm). The liquid-to-gas
mole ratio in this scrubber was, however,
well over 50. This scrubber also removed
63-93% of the cWorine from the vent gas.
The concentrations
of cWorine in the inlet
gas ranged from 1700 to 6000 ppm. The
spent scrubbing solution was used in the
cWorine dioxide bleaching stage.
Sodium hydroxide solution
Sodium hydroxide reacts rapidly with
chlorine
to form sodium hypochlorite
which is an effective scrubbing agent for
cWorine. CWorine dioxide is hydrolyzed in
alkaline solutions to cWorite (CI02-) and
cWorate (CI03-) according to the following
rtictiuo;
2 CI02 + 2 NaOH -> NaCI02 + NaCIOJ
+ H,o
Inlet Chlorine
Concentration
Chlorine Removal
Efficiency Range, %
Range, ppm
Dioxide Removal
Efficiency Range, %
831
Range, ppm
Mill
[3]
832
Pulp Bleaching
-Principles
and Practice
tests ...,
"'"""""
Inlet Chlorine
Dioxide
__
Chlorine
Dioxide
Removal
Inlet Chlorine
Concentration
Range, ppm
Efficiency Range, %
Chlorine
Removal
Mill
Scrubbing
Fluid
Range, ppm
Efficiency Range, %
Weak wash
96-150
87-93
2-15
>80->97
Weak wash
25-120
>99
260-810
>99
Weak wash
330-610
>99
28-540
>99
White liquor
130-1400
>99
9-130
>89->99
White liquor
80-480
>99
67-520
>99
White liquor
440-820
62->99
<0.5-24
>96->98
Concentration
833
Pulp Bleaching
-Principles
and Practice
References
834
R.,JArn.
TapptJ
73
C.W, Tappi 53
K.Y.,
Part 6O,Appendix
A Reference
Method
25A "Determination
of
SECI10N vm:
Pulp Bleaching and The Environment
Chapter ;:
Environmental Regulations
Douglas c. Pryke
Erin, Ontario
Reid A. Miner
National Council for Air and Stream Improvement
New York, NY
John Pinkerton
National Council for Air and Stream Improvement
New York, NY
1. Introduction
2. Canadian
reguJations
837
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 837
837
(CEPA) . . . . . . . . . . .. . . . . . . . . . . . . 838
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 839
840
842
842
. . . . . . . . . . . . . . . . . . . . . . 843
844
4.1 Sweden
844
4.2 Finland
845
ChapterVllI
Chapter vm 5:
Environmental
Regulations
1. Introduction
Since 1985, new environmental regulations for bleached chemical pulp, paper, and
paperboard mills, particularly those employing the kraft pulping process, have been developed and implemented in most of the
major pulp and paper producing regions of
the world. Historically, environmental regulations limited the discharge of the group
parameters, biochemical oxygen demand
(BOD) and total suspended solids (TSS), and
required fmal effluent to pass acute and
chronic toxicity tests. The newer reguI:itions, while providing more stringent limitations on these traditional parameters, also
limit the discharge of a new set of parameters such as 2,3,7,8-tetrachlorodibenzo-pdioxin (2,3,7,8- TCDD), 2,3, 7,8-tetrachlorodibenzofuran (2,3,7,8- TCDF), chlorinated
organic compounds
as measured by the
group parameter adsorbable organic halogen (AOX), polychlorinated
phenols, chloroform, chemical oxygen demand (COD),
and effluent color.
The incentive for the development
of
these regulations can be traced to two important events. The first was the discovery,
in 1985, that dioxin (2,3,7,8-TCDD
and
2,3,7,8- TCDF)was an inadvertent by-product of the bleaching processes used at the
time (1,2). The second was the release of
studies, known as the Environment/Cellulose I Project (3,4). and SSVL 85 (6), of the
ecological consequences
of the discharge
of waste water from kraft pulp mills to the
Baltic Sea. These studies were interpreted
as suggesting a link between chlorinated
organic matter and environmental effects.
As the results of these studies became
widely known, two parallel initiatives arose.
One was the response of the international
pulp and paper industry which began an
unprecedented
research and development
effort to create processes to eliminate the
formation and discharge of dioxin. The
other was the dramatic increase in pressure
5: Environmental Regulations
837
from non-governmental
environmental organizations and an increasingly concerned
public on government to enact regulations
and on industry to change their bleaching
technology. In response to such pressure,
governments in most of the major pulp producing regions of the world began to develop regulatory
policies to limit the
discharge of chlorinated
organic compounds from bleached chemical pulp, paper, and paperboard mills.
In some jurisdictions, reports assessing
the magnitude and impact of discharges of
chlorinated organic compounds were prepared and effluent limitations were developed. Because most regulatory policies and
effluent limitations are based on the concepts of "Best Available Technology (BAT)"
and "Economic Achievability," additional
studies were undertaken to assess technology options and the economic consequences
of national or regional implementation
of
effluent limitations. From 1987 through
1993 a large number of environmental, tech-
nology, and economic studies were undertaken. Regulatory policies for today and the
near future are based on such studies
(5-28).
2. Canadian regulations
Regulations affecting the pulp and paper
industry in Canada are promulgated under
two acts of the national parliament: 1) The
Fisheries Act, and 2)The Canadian Environmental Protection Act (CEPA).
2.1 Fisheries act
Revisions to the Pulp and Paper Effluent
Regulations under the Fisheries Act were
issued in May 1992 and require compliance
by December 31, 1995 (29).These regulations authorize the discharge of limited
quantities of deleterious substances: acutely
lethal effluent, BOD, and TSS.
The limitations for BOD and TSS are daily
maxima and monthly averages per unit of
pulp and or paper production using a 90th
percentile
reference
discharge rate as
shown in Table 1. The limitations for acutely
lethal effluent require the final mill effluent at 100% concentration to pass a 96-hour
LC 50 static bioassay using rainbow trout
838
as the test species. In addition, for monitoring purposes only, a similar bioassay is
required for Daphnia magna. These tests
must be run monthly.
Table 1. CtnuulUm pulp arut paper elfllletll
films for trellled flrud elfl_t.
Parameter
BOD', kg/air-dried
TSS', kg/air-dried
Acute
tonne
tonne
regula-
Monthly
limit
Daily
Maximum
7.5
12.5
11.25
18.75
lethality
Rainbow
trout
Daphnia
magna
LC 50 ~100%
Monitor
monthly
Compound
limit
2,3,7,8-TCDD
< 15 parts/quadrillion
2,3,7,8-TCDF
< 50 parts/quadrillion
839
mills
1.5
1.5
1.0
1.5
1.0
0.8
1, 1994
I, 1995
1,2001
2.5
2.0
0.8
New millb
0.30
0.25
0.25
'Adsorbable organic halogen
"New mill is one whose construction was completed on or after October 22,1992.
(34). In addition, the government of Ontario
has a goal of "zero AOX" by 2002 and requires each mill to periodically submit "AOX
Elitnination Reports"(34).The
province of
Alberta has site-specific regulations for each
mill that are embodied in a five-year operating license.AOX limitations are included'
and range from 0.5 to 1.5 kg/air-dried ton
of pulp.
1'tIbk 4. OJrliIrlopIllp"rut /MJH!rmlllllmltsfor AOX
e.8l_t.
"IUt chloroform /" fl""'lrMtM
Parameter
limit (Average)
Monthly
Daily
0.002
0.004
1.5
0.8
2.0
1.0
tonne
2.5
2.5
1.0
0.30
840
centrations in the recehing water. A variety of criteria are derived to protect aquatic
organisms, consumers of aquatic organisms,
and drinkers of surface water from both
acute and chronic health effects. States may
adopt the EPA's criteria or develop criteria
that are tailored to the conditions in the
state. State-developed criteria may be more
or less restrictive than the EPA's, provided
the latter accepts the rationale behind their
development.
The EPA has developed criteria or water
quality guidance for approximately
190
chetnicals or classes of chetnicals (36).The
criteria that have had the greatest impact
on U.S. pulp and paper mills are those for
dissolved oxygen. Water quality-based permit litnits on nutrients are also relatively
common. There are also, however, national
criteria for a number of chlorinated chetnicals of special interest at facilities where
pulp is bleached with chlorine-based
bleaching agents. Table 5 contains some of
the national water quality criteria (or updated guidelines) for those chlorinated
chetnica1s named in bleached chetnical pulp
mill discharge pertnits reviewed by the National Council for Air and Stream Improvement (NCASl).
The EPA also works with state agencies
to add water quality-based bioassay provisions to discharge permits. It is common
rtlbk 5. SelectM tHter qrutllty crlterlIIfor chlorl""ted cbemkals specified I" U. S. blucbed pilip mill dIscNrge permits.
Fresh Water
Chronic
Toxicity
Criteria
Q1g/L)
Chemical
1.240'
Chloroform
2-Chlorophenol
Human Health
Criteria
- Based
Upon
Consumption of
Fish and Water
Q1g/L)
0.19/5.7b
180"
2,4-Dichlorophenol
365'
3090 / 93"
<0.00001'
0.000000013
Hexachlorobenzene
3.68'
0.00072
2,4,6- Trichlorophenol
970'
1.2
2,3,7,8-TCDD
Chaptervm
guidelines for existing sources represent the
outcome of the EPA's mid- to Iate-1970s
assessment of the capabilities of the Best
Practicable
Technology
(BPT). In most
cases, these limits were derived from the
performance of mills utilizing efficient biological wastewater treatment.
The law allows the EPAto establish guidelines for BOD and TSS that are more restrictive than BPT guidelines if the Agency can
demonstrate that the cost of the changes is
reasonab1e.These more restrictive BOD and
TSS guidelines are termed Best Conventional Technology (BCT) guidelines. The
pulp and paper industry's BCT guidelines
are currently identical to BPT guidelines.
The BPT/BCT guidelines
for bleached
chemical pulp mills are listed in Table 6.The
limits are given in kg per kkg (metric ton)'
of product (usually air-dried). The national
guidelines for new sources (New Source
Performance Standards or NSPS) are lower.
T4ble6. CfIfTMIpltlelilrn for IIOIJIIIUlTSS Msebargedfrum ~
bietreW Inwft}nIlp
",Ills.
Mnimnm
Category
Market
kraft
8.05
Kraft
paperboard
7.1
Kraft fine
paper
5.5
.
b
Modest
Averal!e k~
BOD"
Monthly Dally
additional
15.45
13.65
10.6
allowance
TSSb
Monthly Dally
16.4
12.9
11.9
available
30.4
24.0
22.15
for mi1Is
5: Environmental Regulations
841
2,4,5-trichlorophenol
and pentachlorophenol. Companies can comply with the guidelines by monitoring effluent quality or by
certifying that these chemicals are not
present in the biocides used in the mill.Virtually all companies have complied by certification.
842
Proposed
regulations
for emissions
843
844
Pulp Bleaching
-Principles
and Practice
from
U"tled
Slales
bleaebetl
}nIlp mills.
Chemical
and Year
kgx
1<J6
Average
Emission Rate
Median
Emission Rate
(kg! ADTBP')
(kg! ADTBP' )
Number
of Mills
Reporting
0.335
0.175
104
Chlorine
1987
9.4
1988
8.9
0.32
0.15
103
1989
4.9
0.175
0.075
105
1990
3.0
0.105
0.05
106
1991
2.0
0.07
0.03
108
1992
1.5
0.05
0.02
107
1993
0.6
0.02
0.004
107
Chlorine dioxide
1987
5.9
0.23
0.15
82
1988
6.0
0.235
0.15
84
85
1989
3.3
0.135
0.075
1990
2.5
0.09
0.05
88
1991
1.8
0.065
0.04
92
1992
1.4
0.05
0.G3
92
1993
0.7
0.025
0.015
88
1987
9.5
0.4
0.35
83
1988
9.1
0.35
0.3
92
1989
9.5
0.35
0.3
101
1990
8.8
0.3
0.25
103
1991
7.4
0.25
0.225
102
1992
6.9
0.25
0.175
98
1993
5.4
0.22
0.135
90
Chloroform
pulp
by'. StHMsbErm-
rtJIf1IIeIII4lProIllo8~,
Year
'--
1Ig/1IIr-tlrletl
o/j1IIlp,--.l
tlvertIp.
Softwood
Hardwood
1992
2.0
1.0
1995
0.5
2000
0.5
0.3
2010
0.1
0.1
'See
footnote
to Table 3.
1995
AOX'
COD"
0.1-0.2
10-15
4.2 Finland
In 1989 the Finnish government developed objectives for water protection to be
achieved by 1995. Specifically, the govern-
845
1995
'See
I!JJl-t~oItjeeHws~
by
the FI-ub Mirfistry 0/ the Erml'fMmerll,
IIg/tlir-tlrlft imine 0/ pilip.
AOX'
BOD7b
1.4
2-4
footnote
CODe Phosphorous
65
0.06
to Table 3.
References
1. The National Dioxin Study, Tiers 3, 5, 6,
and 7, U.S. Environmental
Protection
Agency, Office of Water Regulations and
Standards, U.S. Government Printing Office,Washington, D.C., USA,1987, EPA440/
4-87-003.
2. Amendola, G.A., Barna, D., Blosser, R.,
lafleur, L., McBride,A., Thomas, E,TIernan,
T.,Whitemore, R.,"The occurrence and fate
ofPCDDs and PCDFs in five bleached kraft
pulp and paper mills; Seventh International Symposium on Chlorinated Dioxins
and Related Compounds Proceedings,
1987.
3. Sodergren, A., Ed., Biological Effects of
Bleached Pulp Mill Effluents, National
Swedish Environmental Protection Board,
Report 3558, Solna, Sweden, 1989.
4. SOdergren, A., Ed., Bleached Pulp Mill Ef
fluents: CompostUon, Fate and Effects in
the BalUc Sea, National Swedish Environmental Protection Board Report 4047,
Solna, Sweden, 1992.
846
5. "Environmentally
Harmonized
Production
of Bleached Pulp; SSVL Project Final Report, Stockholm, Sweden, 1982.
6. "Production
of Bleached
Pulp," SSVL-85
Project Final Report, Stockholm, Sweden,
1986.
7. Janssson,
B., Alsberg, T., Bergman,
A.,
Renberg,
L., Reuterg:irdh,
L., "Persistent
organic compounds
in the marine environment: background document for the action
plan for marine pollution;
National Swedish Environmental
Protection Board Report
3395, Solna, Sweden, 1987.
8. "Environmental
Priorities for the Finnish
and Swedish Pulp and Paper Industri. ,"National Swedish Environmental
Protection
Board Report 3443, Solna, Sweden, 1988.
9. Sinclair, WF., Controlling
PolluUon from
Canadian Pulp and Paper Manufacturers:
A Federal
Perspective,
Environment
Canada, Conservation
and Protection,
Environmental
Protection,
Ottawa, Ontario,
Canada,1988.
10. Bonsor, N., McCubbin, N., Sprauge, J.B.,
Kraft Mill Effluents in Ontario, Environment Ontario, Toronto, Ontario, Canada,
1988.
11. Reduction
of Chlo7'O-Qrganic Discharge
in the Nordic Pulp Industry, Nordic Council of Ministers
Environment
Report
1989:6E, Copenhagen,
Denmark, 1989.
12. Fandry, C.B., Johannes, R.E., Nelson, P.J.,
"Pulp Mills: Modern Technology
and Environmental
Protection;
Report to Senator the Hon. John Button, Minister for
Industry, Technology
and Commerce,
Commonwealth
of Australia, 1989.
13. Controlling the Discharge of Chlorinated
Organic Substances from the Canadian
Pulp and Paper Industry,
Environment
Canada, Ottawa, Ontario, Canada, 1990.
14. "Summary ofTechnologies
for the Control
and Reduction
of Chlorinated
Organics
from the Bleached Chemical Pulping Subcategories
of the Pulp and Paper industry," U.S. Environmental
Protection
Agency, Office of Water Regulations
and
Starndards, Office of Water Enforcement
:md Permits,U
.S.
fice, Washington,
Government
D.C., 1990.
Printing Of-
Gazette,
Part l, December
14,
847
36. "Quality Criteria for Water, U.S. Environmental Protection Agency," Office ofWater, Washington,
D.C., 1992.
26. "Regulatory
Impact Assessment
of Pr0posed Effluent Guidelines and NESHAP fur
the Pulp," Paper, and Paperboard
Industry, Office of Science and Technology, U.S.
Environmental
Protection
Agency, U.S.
Government
Printing Office,Washington,
D.C., 1993.
27. "Development
Document
for Proposed
Effluent limitations,
Guidelines and Standards fur the Pulp, Paper and Paperboard
Point Source Category," U.S. Environmental Protection
Agency, Office of Water,
U.S. Government Printing Office,Washing.
ton, D.C., 1993.
28. "Seventh Biennial Report on Great Lakes
Water Quality," International
Joint Commission, Washington,
D.C., 1993.
29. Canada
Gazette
30. "Aquatic
Effects Monitoring
Requirements," Environment
Canada, EPS 1/RM/
18, Ottawa, Ontario, Canada, 1992.
31. "Reference Method fur the Determination
of Polychlorinated
Dibenzo-para-dioxins
(PCDDs) and Polychlorinated
Dibenzofurans (PCDFs) in Pulp and Paper Mill Effluents," Environment
Canada, EPS 1/RM/
19, Ottawa, Ontario, Canada, 1992.
32. Carey,].H.,Hodson,
p,y', Munkittrick, K.R.,
Servos,M.R.,Recent
Canadian Studies on
the Physiological
Effects of Pulp Mill Effluent
on Fish, Environment
Canada, Ottawa, Ontario, Canada, 1993.
33. Gazette Offidelle du Quebec,
Vol. 124, No. 43, 1992.
October
7,
- Pulp
Effluent
limits
Province
Canada,
of Ontario,
1993.
and
Paper
Toronto,
Sector,"
Ontario,
35. "Amendmentto
B.C. Reg.470/90, the Pulp
Mill and Pulp and Paper Mill liquid EffIuentControIReguiation,"ProvinceofBri~
ish Columbia, Ministry of Environment,
lmds,
1992.
B.C. Canada,
to Freshwater
Organisms
- 2nd
Subject Index
849
788,791,838,839,845
Aceta1c1ehyde 208, 823, 830, 843
Acetic add, chIoroacetic adds
41,147,257,325,330,366,713,824
ACETOCEU..Process 41
Acetylation, acylation 197,198,
202-203,209,682,755
Addie groups, structures (see also
under carboxylic, phenolic hydroxyl,
and sulfonic acid groups) 585, 677, 678
Determination in pulp 684-686
Add treatment 224,330,336,353,415,
424,425,426,427,428,515,517,519,
523
Activated sludge treatment (AST)
488,651,779,799
Activation energy 37-38, 266, 280,
312,383,401,416,417,450
Aerated stabllization
651,776, 779, 785
basin (ASB)
38, 40,
~66,'6?,'65, 3??,i07,i13,i17,i18,
423,427,430,611~12,
744, 759,824,829
Pulp Bleaching
-Principles
and Practice
SUBJECT INDEX
A
850
41,44
Ascorbic: add,
208,210
ascorbates
205-206, 207,
Autoxidation
105, 141, 143, 165, 166,
188,198,209,487
laboratory
streams
solids 58~584
(see under Unbleached
Bleached ~p
Chemical composition 10, 684, 685,
742
End uses 719
tight and heat stability 3, 53,188,189,
190, 191,237,278-279,298,316,
349,358,406,429,430,487,506,585
~uction
6,7,8,215,287
Strength properties 49, 150,216,237,
280,328,331,358,371,431,437,
584, 727,739, 740, 741, 742, 743,744
Strength testing principles
Bleaching
Chemicals M, 1+16
723
Critical parameters 4
Efficiency 12-13, 16,247,264,305,
356,389,419,479,544,602,650
Flowsheets 19-20,2-23
Gaseous chemicals 17-18
General description M
History of ~
Kinetically controlled reactions 326,
327,544,602,610,611,612,61~15
Objectives 4
Process conditions 17-18
Unit operations 20
Reaction rates, kinetics 54+545, 546,
600
Selectivity 13, 16, 17, 127, 152-153,
217,22+225,243,247,349-350,355,
357,385,415,436,738
Sequences 16-17
Trends 20-24
Bleaching eftluent (&trate)
19
Biological characterization 770-790
Biological treatment, treatment costs
19,53,257,359,434,65~54,
755,
758,769,773,77+775,777,778,
779,780,781,784,785,790,826,
842
Chemical characterization,
characteristics 759-762,770-771,775,
790,838
Chlorination stage 129,132,246,250,
251,252,255,256,257,285-286,
289,373,660,666,671,755,756,
807,826,824,827
CE 153, 759
Chlorine/chlorine
dioxide stage 278,
585,660,752,753,754,755,758
Chlorine dioxide stage 251,252,282285,314,600,662,666,669,756
Color 340, 752-753
Compounds detected in 760-762
DE 756, 759
Discharge volume 19,649,651,710,
773,781,784,786,837
Effect on aquatic organisms 770,775,
776, 780, 781, 779, 780, 781, 782783, 784, 785, 786, 787, 788, 789
Elemental chlorine-free
(ECF) 340341, 752, 753, 754, 758, 761, 762,
774, 790, 791
Extraction
stage (E, EO, EOp) 256,
278,296,302,317,305,315,391,
Subject Index
393,413,660,660,662,666,668,
826,
827,
831.s32
~Jdd~stagc
421,432,479,480,
614,616
Reuse (recycling) 226,250,251,255,
258,278,384,434,478.479,666,
670672
Screen room 236,666,668
Totally chlorine-free (1'CF) 340-341,
666, 752, 753, 774, 777, 790. 791
ToJddty 23, 129, 135, 153, 176,256,
285,340-341,~361,434,488,678,
769,770,772-778,781,782,784,
785,790,791,837,838,839
Bleach plant closure (see Closed cycle
bleaching)
B~ht__R towers (seeTowcrs)
BreakIng Icngth (see Tensile strength)
Brightness (cUffuse Intrinsic
ref1cctance factor) 3, 12, 107, 174,
186.26~271,272,281,311,312,313,
314.317,332.334.385,386,387,389,
390,392,406,418,420,421,422,423.
426.427,428,429,430,445,449,450,
451.453,462,464,465,466,468,469,
470,472,473,474,476.483,484,486,
501.508,509,627,629,630,635,636,
637,638,639.659,697-713,742
711,71Z
Fluorescence effect on 703-704
Gloss effect on 7~710
851
c
Calclum.compounds, ions
Carbohydrates
148.150,151,153,167,176,247,256,
257,263,381,493,585
Content
Conversion
In pulp 685
to aromatic
structures
37,40,
117,145,151,152.176,224,233,
234.298,325,329,330,353,366,
852
Pulp Bleaching
- Principles
and Practice
227,231,309,382,
679,681,735
Properties 9
Solvents 679,680,681
Structure 9, 117
Cell wall, fiber wall 11, 19, 27-28, 35,
37,42,48,50,93,226,294,296,477,
542,544,610.684,702,703,724,725,
728, 729, 733, 742
Chcladng agents, scquestrants 14, 46.
153,209,350,352,353,354,358.359,
373,415,425,426,428,434,453,464,
465,466,467,478,486,495,501,770
Chelation treatments 188,190,330,
334,352,353,354,355,357,358,359,
372,421,424,424,427.428,453,~
466,479,482,487
Chemical recovery 215, 216-217, 234,
237,352,353,356,671.672,833
(Chemi)m
h nl pulp, pulping 34,
43,163,167,174,177,188,206,425,
463,493,572.684,719,728,744
Composition 728-729
Chcmirc6ncr pulping 43
Chcmithcrmom
h tca1 pulp
(CI'MP), pulping 6, 34, 42-43, 49, 51,
52,97, 185, 188, 195, 196. 203, 205,
428,463.511,687,736,810
Physical properties
51-52,486
Chcmithcrmom~h
pulping 485-487
Chlorate
ion
L-aI alkaline
13,62.63,64,65,66,67,
133,137,264,265,271,272,273,277,
278,286,381,382,389,390,392,770,
771,778,782,783,785,831
130, 132,
245,253,256,264,265,268,272.277,
278,381,391,392,583.689,832
Chlorination,
chlorination
stage
234 ,
276,278,303,413,451-452,542,544,
563,604,606,610,635,769,775,777,
778,807,814.829,831
Chemistry
127-128,245-246,295
252.253,254,255
Effect
on
pulp
cleanliness
255
Environmental effects255-257
Subject Index
853
271,272,274,275,279,280,281,
282,283,284,285,286,287,297,
298,303,310,314,370,386,387,
413,452,542,591,636,751,752,
754, 758, 775, 778, 779, 781, 785,
788,825,827,828,829,842,843
Chlorine monoxide radical
(hypochlorite radical) 132,133,137,
151,407,408
Chlorine factor 280, 825
Chlorine multiple 249, 250, 264, 369,
754,812,813,814
Chlorodioxins
(see Dioxins)
Chlorodibenzofurans
(see Dioxins)
854
Pulp Bleaching
-Principles
and Practice
o
Dakin reaction, DaIdn-Uke reaction
168, 171, 173, 174
DeaIkyIation 52, 103, 118, 119, 1~132,
133,137,148,165,189,190,196,202,
257,356,683,686
Deckers 236, 357, 373, 478, 482, 590
Defoamers (see also underWasbing)
231,590,620,686,808,815,838
142,
Dioxiranes
(see Dimethyldioxirane)
Subject Index
Dyes, Inks 44, 53-54, 494, 509, 705, 728,
729
E
EDTA (ethyleu
i..rninetetraacetic
add) (see Chelating agents)
Eft1uents (see Bleaching eIDuents)
Electron spin resonance (ESR)
spectroscopy 198, 205, 207
Electrophiles,
e1ectropbllic reactions
118, 119,
855
Environmental
Mechanism
effects 371-372
Process flowsheets
372-373
856
Pulp Bleaching
-Principles
and Practice
supply
723,
337,554,555,562,609,600,604,613,
616,617,618
Fluorescence (see under Brightness)
Formaldehyde 37,95, 101, 102, 105,
174,830,843
Formamidine
G
Gel permeation
(GPC) 105
chromatography
H
Heat reversion (see under Yellowing)
Hemice1lulases (see Xylanascs)
Hemice1luloses (see also Carbohydrates)
3,9,12.29,39.40,44.45,48,106,107,
124,163,176,221,244,247,293,298,
365, 366, 367, 374, 375, 493, 677, 678,
683,684,726,727,744
Analysis 681-683
Content in wood and pulp 9,27,366,
374,375,723,724,739,740,741
Subject Index
Properties 9
Structure 374
IH NMR spectroscopy
132
203-204, 209
Hydroxonium
HydroperoxyI.
radicals 116,142,144,
145,146,151,197,200,205,209,210,
218,219,324,329
radicals
and Practice
219
ion 116
p-Hydroxybenzyl
alcohol
129, 171, 199, 200
p-Hydroxyphenacyl
200
Hypochlorite
Hydroquinone
structures,
hydroquinones
54,95,105,140,164,
171,174,208,209,436,487
4,
Hydrosu1fite
blrM'hing
185, 187, 188,
190,475,480,484,526,592,729,744,
745
Brightness response for dlffcrent pulps
510
Dcinked pulps 509-510
Effect on pulp properties 501
Factors influencing brightness
response 495-501
Future trends 511-512
Process control 505, 506
Process fIowshccts 505,506,507,508
Process variables 495499
Reactions with chromophores
177-178,
493494
Safety and environmental factors 510-
511
-Principles
Hydroxyl radica146,
116, 141, 142,144,
145, 146, 151, 153, 167, 168, 171, 173,
176, 219, 223, 225, 324, 329, 349, 350,
415,416,424,459,460,461,487,689
Hydroperoxide
(pcrhydroxyl)
anion
96,116, 141, 144, 152, 154, 166-167, 168,
171, 172, 176, 195, 218, 349, 351, 415,
416, 417, 421, 459, 460, 461, 469, 639,
640
Pulp Bleaching
Hydroxide
ion 96, 116, 142, 155, 160,
168, 171, 176,219,301-302,461
Hydrolysis
Acid-catalyzcd 9,40, 105, 109, 135,
150,151,393,679,682,686
Basc-catalyzcd 9,40,97,99,100,103,
105,106,121,139,150,295,296,
299,325,759,824,825
HydrosuIftte
(dithionite),
hydrosuIfite
b1PAtohing solutions
51,54,97,163,177,178,505,525,592
Active bleaching species 176-177,
494-495
Composition 494-495, 502-504
Handling and storage 502-503
Manufacture 15, 503-504
Properties 501-502
Stability 177,495,497,498,500,526
858
Hydrotrioxy
857
groups
groups
97,
171,197,
Hypochlorite
bleaching
151, 255, 257,
313,317,397-407,437,476,650,604,
824,825,843
Environmental effects 407
Economic factors 406-407
Process control 398,399,401,404-406
Processflowsheet402
Process variables 398-400
Reaction kinetics 400-401
Sequences 17,50, 397,403,406,407
Hypochlorite
Hypochlorous
add 127,128,130,132,
133,135,136,137,138,151,154,245,
257,264,271,381,408,410,754
Bleaching 407-410
Generation 410
I
Impellers (see Pumps and Mixing)
132,687,
K
Kappa factor 250, 264, 268, 270, 276,
283,285,369,826
Kappa number 10, 48, 50, 232, 233,
243,264,267,269,274,279,280,283,
307, 308, 311, 329, 333, 353, 354, 355,
359, 368, 386, 392, 398-399, 422-423,
629,635
C-stage 299
number
analyzer
197, 198,200,201,
(see
radica1132
Kappa
642
Subject Index
34,36,37,49,269,307,422,450,
627,632,677,724,741
Determination in wood and pulp 50
Determination in bleached pulp 683684
Effect of sulfidity on degradation 99
Hardwood 93,128
Interunit linkages 94, 106
~99,
100,102,103,105,
144, 148,
349, 758
IJnkage with carbohydrates 37,93,
103-105, 108, 223, 294,759
Milled wood lignin (MWL) 97,107,
109,165,196,198,203
Model compounds 122, 129, 130, 133,
135, 137, 138, 139, 145, 153, 166,
168,193,198,199,350,414
Modification of functional groups 93,
97, 102, 103, 106, 124, 165, 197-198,
200, 201, 202-204
Soflnwood 93, 128, 129, 165,246
Sttucture, functional groups 9,93-95,
96,422,~5
'ig1'inues
(see Enzymes)
Ugnosulfonates,
lign08u1fonic
97,106,132,193,684
Ugnox process 352,741
acids
Pe~xide
Mesoc:osms
stage 78,357,433,467
778-781, 791
ethyl ketone
Milox process
41,437
Minox
351-352
859
process
860
Pulp Bleaching
-PrInciples
and Practice
Mixing 251,253,304,336,454,525,
54+554, 600
Assessment 557-561
Efficiency 392, 454, 482, 499-500, 559
Energy (Power) consumption 543,544,
547, 550, 557, 561-562
Fluidization (see also Fluidization under
Ptmnp~327,338,542,548,550,563
Fluid shear in 541, 546, 547, 548, 549,
551, 554
Gas contacting 542-544,549,551,557,
601
General principles 539-544
Index 558, 564
Laboratory-scale 563
Power dissipation in 541-542,543,544,
545,547,548,550,561-562
Quality 544, 557, 561-562, 563, 564
Rate 5#545,
562-563
Scales of 539-540, 546, 547, 558-561
Thrbulence 541-542,543,545,546,
547,548,554,556,561,604
Molecular weight, molecular
weight
distribution
105, 148,256,301,591,
679-681,75+758
Monox-L
MOXY process
39
data analysis
Mutagens, mutagenk:ity
677, 690-691
129, 135, 285,
286, 769
N
Nitrilamine (Cf'ln..ftlid~) 357, 435
Nitrogen dioxide 225,306,357,842
Nonwood fiber 30-31, 39, 50
Nucleophiles, nucleophilk: reactions
116, 117,118, 120, 123, 124, 130, 138,
142, 144, 151, 165, 167, 168, 171, 176,
221,295,296,415,435,461
Nucleophilk: displacement 139-140,
142,296
o
Octanol-water
284, 754
partition
coefficient
pulping
(see Chelating
40-41
Oxidation,
O1l:,di7.Jng agents 3, 14, 100.
105,116,119,122,124,127,131,133,
134,137,141,145,146,150,165,217,
219,223,245,246,303,305,350,358,
382,408,413,414,416,417,423,429,
436,438,493,509,612,679,684,760,
818
Oxidation-reduction
53,254,436,630,833
potential
(ORP)
ofb
hi"'g
Subject Index
Medium-consistency
227-229
Oxygen and alka1i consumption 226-227
Processes and equipment 227-232
Process flowsheets 216, 228. 230
Process variables 232-234,417-428
Reaction kinetics 226, 232,600,612, 619
Reactors 227,228.229,230,231,237.
612-613,614-615
Relationship to other mill operations 234
Selectivity 219, 224-225, 227, 232, 233,
234,235,236,615
Typical operating data 227
p
p4S01 induction
786.787.791
861
366,375
of mechanical
Peroxide b~h'"'B
pulps 153.334,604,612,614,684,741
Chemistry 414
Economic factors 434
Effect on pulp quality 430-431
Environmental factors 434
Factors affecting brightness 417-428
Filtrate reuse in 666
Kinetics and stoichlometry 416-427
Process flowsheets 432-434
Typical bleaching sequences 428-430
Peroxide b
h'"'B (brightening) of
(chemi)mecbanica1 pulp 97, 153, 185,
187,414,45~54.50'-50Q,592,614,
639,683,684,687,688,690,744
Bleach plant configurations 484
862
Pulp Bleaching
-Principles
and Practice
~O~,~Oj,Z01,Z05,Z~.Zl~,j50.4B7
13pNMR spectroscopy 194,222
Polysulfide pulping 34, 38-39, 45, 670
11
Subject Index
Pumping and Hydraulics 38
Basic concepts 51~521
Cavitation 518,519,521,522,531
Degassing, deaeration 517,522,523,525,
526527,528,529,551,585,617,658
Flow metering,flow meters 403,533-534,
583,634
Flow velocity 515,516,517,521,525,
528,529
Fluidization of puip suspensions 517,
522,523
Frictional losses 516,517,526,527,
528,529
General design considerations 529-534
Low-conslstency puip 517,521-522,
544
Medium-conslstency systems 274,515,
517,520,554
Mixing during 525,554
Net positive inlet pressure (NPIP) 518,
521
Net positive inlet pressure requirement
(NPIPR) 519
863
Thick-stock 230,311,384,398.399,
400,402,482.515,526.611.613,614
Twin-screw 520, 526-527, 529, 530
864
Pulp Bleaching
-Principles
and Practice
Quinone methides
98, 100, 101, 103,
105, 116, 117. 123, 143, 164, 165. 171,
172,204,220,221,493
0- and p-quinonoid
units, quinones
54,96,97.99.105,116,118,119,120121, 130. 131, 132, 133, 134. 135, 137,
139,140,141,142,146,147,164,165,
168, 170, 171, 172, 173, 176, 177, 178,
188,189,193,194,197.202,206.208,
209,221.222,246,351,436,493,494,
684, 756, 759
R
Reactors (see Towers and Reactors)
Recycled (secondary) fiber, recyding
6,31,32.43-44,512,703,704,727-728,
811
BleachabiHty,brightness response 52-53,
474,475,476
Color stripping 54
Composition 52
Deinking 44
Dyes 53-54, 704
Hydrosulfite bleaching of deinked fiber
476,509-510
Peroxide bleaching of deinked fiber 474
Physical properties of 52
Pulping 43-44
Reduction, reducing agents 54,62,63,
64,67,75,97,102,116,119,134,141,
142,177,189,195,202,203-204,206,
209,298,484,493,494,502,504,509
Refiner bl(opching 497, 504-506, 507
Refiner mechanical pulp (aMP),
pulping 14, 34, 42, 49.177,187,194,
463,497,736
RefinIng, refiners 97, 166,237,407,
485,497,505,507,516,721,722,726,
728, 742
pulp 719,720,735,
Subject Index
Stilbenes 93-94, 97, 100, 103, 117, 120,
129, 137, 144, 146, 148, 149, 166, 174,
175,176,198,222,323
Stock chest bJ
hing 5()6.507
Stone cell aggregates 446-447
Stora process 34,40
Strength (mechanical) properties of
bleached pulps (see also Strength
properties under Bleached pulps) 16,
730-735
Chemical pulps 659, 679, 730-735
(Chemi)mechanical pulps 477,735-736
Effect of (Chemi)mechanical pulp
bleaching 744-745
Effect of kraft pulp bleaching 738-743
Effect of sulfite pulp bleaching 743-744
Factors affecting 186,723-728
Relationship to viscosity 734-735,739,
740, 742
Relevance of standard tests in
commercial papermakinq 736-738
Strength property pairs 732-735,736
Strength property measurements
Future trends 75
Interpretation ottest results 732-735,
736
Standard testing procedures, tests 729,
730-732
Under1ying principles 722-723
Sugars, sugar analysis 45,105,107,
368,682
Sulfamic add 128, 149, 247, 682
Sulfite pulp, sulfite pulping 6,10,34,
35,3941,49,50,97,132,154,187,188,
189,190,279,293,305,307,351,353,
357,422,428,430,719,726,736,740,
743-744, 812
Sulfonic add groups, sulfonation 43,
51,97,106,177,178,494,684,723,
729, 745, 813
Determination of in pulp 684
Sulfoxylate ion 177, 494
Sulfur 34, 832, 833
Sulfur dioxide, sulfur dioxide-water
39,62,63,65,116,176,177,353,373,
388,400,426,460,477,478,479,484,
865
494,503,506,509,606,637,638,639,
660,669,832,842
Sulfur dioxide anion radical 116, 176,
178,494
Sulfuric add (see also Sulfate ion) 63,
64,65,67,80,330,353,358,373,435,
477,484,504,511,525,682
Superoxide anion radica1116, 141,
142,145,167,171,176,205,218,219,
220,349,415,416,424,459,460
S~ts
474,475
Suspended solids (see Total suspended
solids,TSS) 651
Syringyl units 93, 128, 129, 130, 144,
166, 760
T
Tear strength (tear index, tear factor)
47,48,49,52,237,280,328,371,431,
477,486,487,551,679,720,727,731,
732,739,740,741,743
Tear-tensile relationship 49,328,431,
679, 732, 733, 736, 743
Tensile strength (tensile index,
breaking length) 47,49,52,205,206,
208,237,280,327,371,431,477,486,
487,551,679,720,727,731,732,733,
739,740,741,743
Thermomechanical
pulp (TMP) 34,
42,49,51,97,185,187,188,189,190,
195,462,463,511,736,744,810
Thk~.-ning, thickeners (see also
Presses) 593, 594
Thioethers
207-208
866
Pulp Bleaching
-Principles
and Practice
365,370,372,373,419,422,424,42~
430,431,432,437,510-511,584,585,
684,685,739,740-743,751,752,753,
754, 758, 760, 790, 792
U
Ultim-o process 649
Ultrafiltration 755, 757, 758
Unbleached chemical pulps 7
Bleachability 4~50
Chemical composition 10, 36, 38, 39,
40,~,50,244,255
Heterogeneity 48-49
lignin accessibility In 48
49,
29,
v
Vapor pressure
758
osmometry
755, 757,
830
W
216,229,244,477,659,668,
823
AIka1Ineextraction (including oxidantreinforced) 402,404,407,585,587,
588,590,662,666
Atmospheric diffusers 21,575,580581,584,609,650,671
Brown stock 228,359,586,627,632,
637,671
Chlorination-stage 254, 311, 660
Chlorine/chlorine dioxide-stage 587,
660, 662, 666
Chlorine dioxide-stage 660, 666
Discharge consistency 399,593,657,
668
1Vashers
Subject Index
Drum displacement 11,20,21,575,
576,579
Elimination of unneeded 659,669-670
Factors affecting selection of 575
H~orit~tage
398,402,588
Loading factors 576, 678
Manufacturing and design considerations
588-589
Material selections for different
bleaching stages 586-587
Oxygen-stage 587,590
Peroxide-stage 588
Pressure 23, 229, 572, 575, 578-579,
584,658,670
Pressure diffusion 433,572.581-582,
585,650,671,828
Three-washer bleach plant 666-667
Vacuum drum filter 216, 572, 575-578,
.
827,828
867
Supply 32, 33
868
Pulp Bleaching
-Principles
and Practice
x
Xy)an (see Hemicelluloses)
xy1anases 48, 365, 366, 367, 368, 369,
370, 371, 372, 3?3, 375
Y
Yellowing (reversion) 406,417,469,
500,506,509,575
Aging tests 186,430
Effect of bleaching on 188-189
Effect of metal ions 190
Effect of pulping 188
Effect of oxygen 19&197
Effect ofwood species 187
Inhibition of 202-209
Light-induced 186, 1~209, 475, 487,
683
Mechanism of 197-202
Optical measurement of 185-186, 190191
Post-<:olor (PC) number 185, 186, 188,
189, 190, 191
Relative reflectivity 191-192
Thermal (heat-induced) 153, 185, 186190,209,298,475,683
z
Zero-span tensile test 371,679,680,
733, 745