Professional Documents
Culture Documents
By:Peter W. Hart
Alan W. Rudie
Copyright 2012 by
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ISBN: 978-1-59510-207-2
TAPPI PRESS Order Number: 0101R331
Printed in the United States of America
Table of Contents
i. Authors List
1. Introduction
1.1 Previous Pulp Bleaching Books
1.2. Current Pulp Bleaching Book
1.3. Organization of the Current Book
1.4. References Cited
2. Oxygen Delignification
2.1. Introduction
2.1.1. Comparison of Oxygen to Other Bleaching Agents
2.1.2. Advantages and Disadvantages of Oxygen Delignification
2.2. Chemistry of Oxygen Delignification
2.2.1. Lignin Reactions
2.2.2. Carbohydrate Reactions
2.3. Kinetics of Oxygen Delignification
2.3.1. Kinetic Rate Equations
2.3.1.1. Initial Kappa Number
2.3.1.2. Alkali Charge, Temperature and Oxygen Partial Pressure
2.3.1.3. Rate Equations
2.3.2. Carbohydrate Selectivity
2.4. Mass Transfer Effects
2.4.1. Oxygen Solubility
2.4.2. Liquid Phase Mass Transfer Coefficients for Mixers
2.4.3. Mass Transfer Coefficient in Retention Towers
2.5. Carry-over of Dissolved Solids
2.6. Control of Transition Metals
2.6.1. Addition of Magnesium Ion
2.6.2. Use of Chelating Agents
2.7. Commercial Medium Consistency Oxygen Delignification Systems
2.7.1. One-Stage Design
2.7.2. Two-Stage Designs
2.7.2.1. OxyTracTM Systems
2.7.2.2. GL&V System
2.7.3. Reductions in Kappa Number
2.8. Pulp Quality
2.9. Emission of Volatile Organic Compounds
2.10. Acknowledgments
2.11. References Cited
9. Ozone Delignification
9.1. Introduction
9.2. Fundamental Aspects of Ozone Bleaching
9.2.1 Ozone reactions with lignin and cellulose
9.2.2 Expression of ozone reactivity, effectiveness and selectivity
9.3. Process Conditions
9.3.1 Mass transfer of ozone to liquid phase
9.3.2 Pulp consistency
9.3.3 Ozone Charge
9.3.4 Effect of pH
9.3.5 Time
9.3.6 Temperature
9.3.7 Additives
9.3.8 Metal ions
9.3.9 Dissolved organic matter
9.3.10 Pulp processing before ozone stage.
9.3.11 Alkaline extraction after ozone stages
9.4. Role of Ozone in a Bleaching Sequence
9.4.1 Ozone delignification as a replacement for chlorination
9.4.2 Placement of ozone in a bleaching sequence
9.5. Process Equipment
9.5.1 High-Consistency Ozonation
9.5.2 Medium-Consistency Ozonation
9.5.3 Low-Consistency Ozonation
9.5.4 Materials of Construction
9.6. Environmental Considerations
9.7. References Cited
CHAPTER 1
Introduction
ALAN W. RUDIE and PETER W. HART
The current book has reverted to the style of the first three in the se-
ries. It aims to provide highly practical information on the current state
of industrially applicable pulp bleaching. This book includes direct in-
dustry input into 15 of the 20 chapters. In general, the chemistry associ-
ated with pulp bleaching has not changed much over the last 20 years
or so and therefore has been adequately covered in the fourth book in
this series. Notable exceptions to this statement are the impact and un-
derstanding of hexenuronic acid (covered in Chapter 5), the application
of enzymes, specifically xylanase (Chapter 6), and the impact of non-
process elements and scale formation on bleaching equipment, covered
in Chapter 7. Both hexenuronic acid and nonprocess elements are now
significantly better understood than in earlier years and are therefore
Current Pulp Bleaching Book
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FIGURE 1.1. Evolution of bleaching sequences over the last 40 years. Figure adapted
from Ref. [5].
chlorine dioxide at lower than natural pH in the first stage has been ex-
tensively studied, and typical application and troubleshooting methods
are discussed here.
Since the initiation of the cluster rule, the use of oxygen delignifica-
tion and oxygen bleaching has expanded significantly as well. Better
FIGURE 1.2. Bleach plant washer developments from the early 1970s to date. Figure
adapted from Ref. [5].
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Current Pulp Bleaching Book 5
In general, the current book has been laid out to be user-friendly and
practical. Each chapter has been written in several well-documented
subsections to provide immediate access to subject content. Chapters 2,
3, and 4 deal with delignification of chemical pulps. Chapters 5, 6, and
7 cover modifications to traditional bleaching stages and include the
use of hot acid treatment, enzymes, and metals management. The next
four chapters deal with brightening stages and the removal of dirt and
shives. Chapters 12 through 18 cover bleach plant design and control.
Chapter 19 reviews the environmental impact of bleaching effluents,
and Chapter 20 covers bleach plant safety.
the chapters. The contributions of each and every chapter author to this
book are greatly appreciated.
The first book in the series required six years from initiation to pub-
lication. The fourth in the series required four years. This reality is re-
sponsible for one other change in the format of the book. The major
equipment suppliers have each been given one chapter to present the
equipment line that they supply for new bleach plants. Where this bor-
ders on advertising, it is honest advertising. For the editors, it gave us
the leverage of publishing without a supplier chapter. Thankfully, it did
not come to that. However, five authors complied with the initial target
deadline, and another five chapters were received before we had com-
pleted the editing on the first five. Not to force the remaining authors
to complete their chapters in a timely manner would have devalued the
efforts of those who had. Having watched Doug Reeve struggle with
this issue for years to complete the 1996 version, and knowing some of
the chapter authors who had to revise substantial portions of their text to
catch up with changes that had occurred in the two-year-plus delay, we
were determined to complete this version in a single year. With the help
of all our chapter authors and considerable work on the part of TAPPI,
we have achieved this goal. We hope that you, too, appreciate the effort
and most importantly, find the book useful for operating and optimizing
your bleach plants.
CHAPTER 2
Oxygen Delignification
JOSEPH M. GENCO, ADRIAAN R. P. van HEININGEN and
WILLIAM MILLER
2.1. INTRODUCTION
Joseph M. Genco, Calder Professor of Pulp and Paper Science and Engineering,
University of Maine, Orono, ME 04469
Adriaan R. P. van Heiningen, J. Larcom Ober Professor of Chemical Engineering,
University of Maine, Orono, ME 04469
William Miller, Operations and Maintenance Coordinator, Evergreen Packaging,
Canton, NC 28716
9
10 OXYGEN DELIGNIFICATIONCopyrighted Material
With the exception of caustic, all chemicals used in kraft pulp bleach-
ing are oxidizing agents that break down lignin macromolecules into
fragments small and hydrophilic enough to dissolve in water and alkali.
McDonough [6] compared various bleaching agents and distinguished
them on reactivity, selectivity, efficiency, the ability to bleach particles
or shives, and environmental effects (Table 2.2). Chemical reactivity
pertains to the rate and extent of reaction of the bleaching agent with
lignin. Selectivity refers to the rate of reaction of the oxidizing agent
with lignin relative to the rate of reaction with carbohydrates. Selectiv-
ity is often measured as the ratio of the reduction in kappa number to the
drop in pulp viscosity. Efficiency relates to the ability of the bleaching
12 OXYGEN DELIGNIFICATIONCopyrighted Material
the pulp are recycled back to the recovery system, there is an increase
in the solids loading of the recovery boiler, but not particularly in the
total heat input or in the resulting steam generation rate of the boiler [9].
RO + O2 RO + O2 (1)
RH + O2 R + HO2 (2)
moval of approximately half the lignin in the pulp entering the oxygen
stage. With some of the newer processes for softwood delignification,
the reduction in kappa number can be greater than 60% while still pre-
serving the viscosity of the pulp [28,29].
The reactions involved can be divided into two categories: one is
random chain cleavage by radical species, and the other is carbohydrate
peeling reactions. Random chain cleavage occurs at any glycosidic
linkage along the chainlike molecule, while in carbohydrate peeling re-
actions, individual sugar units on the end of the chain are attacked and
successively removed one unit at a time [30]. Both types of reactions
may occur during oxygen delignification, but random chain cleavage is
thought to be the most significant. The radical species responsible for
random chain cleavage originate mostly from the peroxyl radicals and
hydroxyl radicals generated by lignin oxidation reactions (see Figures
2.3 and 2.4). However, metals such as iron and copper are also capable
of creating hydroxyl radicals from generated hydrogen peroxide. The
random attacks on the cellulose chain decrease the average length of the
cellulose, as indicated by a decrease in pulp viscosity, which if exces-
sive, leads to the loss of pulp strength. Guay and coworkers used com-
putational methods on the cellulose model compound methyl cellobiose
to determine that the step involving the elimination of the superoxide is
lysis. This will then lead to a significant yield loss, as quantified by Ji,
who also showed that the carbohydrate yield loss is linearly correlated
with the cellulose chain cleavages [33].
Kinetic data that represent the decrease in kappa number with time
during oxygen delignification exhibit two distinct stages or periods at
a fixed initial alkali concentration and temperature. This is illustrated
in Figure 2.9 for Scandinavian softwood, for which the oxygen del-
ignification experiments were carried out at 110C temperature, 0.02
FIGURE 2.9. Kappa No. After Oxygen Delignification for Scandinavian Softwood.
moles NaOH/liter concentration, and 0.98 MPa (142 psi) oxygen pres-
sure [35]. Olm and Teder described the kinetics for the lignin remaining
in the pulp using two pseudo-first-order reactions: a rapid initial delig-
nification followed by a slow final delignification. K02 in Figure 2.9 is
the amount of slowly eliminated lignin, and the value K1 = K0 K02
is the amount of easily eliminated lignin, where both are expressed in
terms of kappa number.
Lignin removal in the initial rapid stage is thought to involve lignin
moieties that react readily with the oxygen free-radical species present
in the cell wall. In the second, slower delignification stage, it is thought
that the moieties in the lignin react very slowly with the free radicals
being generated by the caustic and oxygen. The moieties in the lignin
that are difficult to remove may originate in the pulp from the digestion
process or may result from the condensation reactions shown in Figure
5. The two delignification stages are directly paralleled by two corre-
sponding cellulose reaction phases [35].
It is easier to delignify pulps with high rather than low initial kappa
numbers. It has been reported that southern hardwood kraft pulps with
high initial kappa number have lower resistance to oxygen delignifi-
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Kinetics of Oxygen Delignification 21
cation and a higher reaction rate compared to pulps with low initial
kappa number [36]. The reason for this observation is that the kappa
number represents a combination of different oxidizable components:
lignin, nonlignin oxidizable structures, and hexenuronic acids (HexA)
[37], and the relative contribution of HexA, which are unreactive under
standard oxygen delignification conditions, decreases with increasing
kappa number. This same effect of kappa number has been observed for
southern softwood by Tao [38]. However, when the kappa numbers are
corrected for HexA content, the delignification rate is shown to be pro-
portional to the amount of residual lignin in loblolly pine kraft pulps,
irrespective of their initial kappa numbers of 23, 26, and 34 [32]. Other
studies have shown that stopping the cooking process at a high kappa
number, at 40 for example, instead of the conventional kappa number of
30, and then using an oxygen delignification stage leads to an increase
in pulp yield of approximately 2% [39].
FIGURE 2.10. Effect of Caustic Addition on Reduction in Kappa No. for Southern Soft-
wood (90C and 100 psig pressure).
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FIGURE 2.11. Effect of Temperature on Reduction in Kappa No. For Southern Softwood
(2.5% NaOH and 100 psig pressure).
FIGURE 2.12. Effect of Oxygen Pressure on Reduction in Kappa No. for Southern Hard-
wood (100C and 2.5% NaOH).
22
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Kinetics of Oxygen Delignification 23
ure 2.11), and oxygen pressure (Figure 2.12) accelerates both deligni-
fication and cellulose degradation reactions [36]. In laboratory studies
where the pressure is kept constant, beyond a minimum value of ap-
proximately 4 atmospheres, the effect of oxygen pressure is generally
small in comparison to the effects of alkali charge (Figure 2.10) and
temperature (Figure 2.11). Increases in oxygen pressure in laboratory
studies have relatively little effect in the absence of an excess of alkali
or an increase in temperature. In commercial installations, because the
pressure decreases as the pulp proceeds upward through the delignifica-
tion tower, the pressure in the second stage is sometimes increased, as
for example in the OxytracTM process [28].
dK (3)
rL = = k[OH ]m [ PO2 ]n K q
dt
where (K) is the kappa number; [OH] is the sodium hydroxide concen-
tration, and (PO2) represents the oxygen pressure [43]. The empirical
constants m, n, and q in Equation (3) are determined from experimen-
tal data. The reaction rate coefficient k depends on temperature and is
given by the Arrhenius equation:
E (4)
k = A exp A
RT
where (EA) is the activation energy, (R) is the gas constant, and (T) is
the absolute temperature. Two-region models are also widely used. Olm
24 OXYGEN DELIGNIFICATIONCopyrighted Material
and Teder summarized the drop in lignin content (L) expressed as kappa
number for Scandinavian softwood by a two-region model assuming
first-order kinetics for the kappa number (q = 1) [35]. The empirical
constants for the exponents on the hydroxyl ion and the oxygen pres-
sure were determined from experimental data:
dL
rL = = k1[OH ]0.1 Pox0.1K 01 + k2 [OH ]0.3 Pox0.2 K 02 (5)
dt
Some studies have found that the exponent on the kappa number for
one-region models is greater than one [36,38,4042]. One explanation
given for these high reaction orders is that the delignification reaction is
the sum of a great number of parallel first-order reactions taking place
simultaneously and corresponding to the different lignin moieties in the
pulp [46].
Ji and coworkers were able to express the delignification rate as a
first-order reaction with respect to lignin content calculated from kappa
number corrected for the presence of nonreactive HexA [32]. The effect
of alkali concentration was accounted for by fitting the pKa value (11.5
at 90C) of the rate-limiting active lignin site. This site was identified
as the cyclohexadienone hydroperoxide anion formed by superoxide
reacting with the phenolate radical located at the carbon-3 position. The
effect of oxygen pressure was modeled by Langmuir-type adsorption
of oxygen on the active lignin site. The final rate equation at 90C is:
FIGURE 2.13. Intrinsic Viscosity versus Time (minutes) for Southern Hardwood.
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FIGURE 2.14. Selectivity for Southern Hardwood (100C and 100 psig pressure).
FIGURE 2.15. Intrinsic Viscosity [] versus Kappa Number for Southern Softwood Pulps
in Single-Stage Oxygen Delignification (100C, 75 psig and 3% NaOH).
26
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Kinetics of Oxygen Delignification 27
dM
rC = = k[OH]m [ PO2 ]n M q (8)
dt
FIGURE 2.16. Effect of Initial Kappa No. on the Number of Moles of Cellulose per Tonne
of Pulp Formed During Oxygen Delignification at 100C, 75 psig (517 kPa), and 3%
NaOH.
28 OXYGEN DELIGNIFICATIONCopyrighted Material
The rate of oxygen transport can limit the rate of the overall pro-
cess [34,4852]. Transport effects on the overall reaction rate can be
divided into interphase and intraphase factors (Figure 2.8). The mass
transfer resistance of oxygen in the gas phase is insignificant compared
to the resistance in the liquid phase [53]. There was no improvement in
the oxygen delignification rate after southern hardwood kraft pulp was
heavily refined. This suggests that intrafiber mass transfer effects also
do not greatly influence the delignification rate [36].