Continuous Pulping Processes PDF

Continuous Pulping Processes
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Queensland University of Technology. Brisbane, Australia
TAPPI STAP SERIES

1 The Training of Supervisors in Corrugated Box Plants: Ten
Lesson Plans; Lesson 11: Time Study
Petroleum Waxes: Characterization, Performance, and Additives
3 *Preparation, Circulation, and Storage of Corrugating Adhesives
4 *Operations Research and the Design of Management Information Systems
5 Management Science in Planning and Control
6 Technical Evaluation of Petroleum Waxes
2
* Out of print. Photocopy may be obtained from University Microfilms,

Ann Arbor, Michigan 48106.
Johan Richter
Pioneer in Continuous Pulping Technology
Born in Lier, Norway, in 1901
12 Lectures
By Sven Rydholm
Director of Research
Billeruds AB
SPECIAL TECHNICAL ASSOCIATION

PUBLICATION
STAP N O . 7
Gardens Point
A22810250B
Continuous pulping
processes : 12 lectures
A22810250B
Copyright 1970 by
Technical Association of the Pulp and Paper Industry
360 Lexington Avenue, New York, N. Y. 10017
Library of Congress Catalog

Card Number: 74-140131
Printed in the United States of America

By Mack Printing Company, Easton, Pa.
Preface
This book is a compilation of lectures given at the TAPPI Pacific Section
Meeting in Seattle, Wash., in September 1968. They dealt with experiences
in continuous pulping obtained over more than one decade at Billeruds AB
in collaboration with AB Kamyr.
One reason for my choice of topic was that Kamyr digesters have dominated the most vital operation in our industry for more than ten years and
still do, although some signs of healthy competition have appeared. A
second reason was that the Kamyr digesters are now becoming quite diversified, and thus the lectures would have to cover all pulping processes
needing a pressure vessel. A third reason was that I have been involved in
developing many of these process variants during my past sixteen years in
Billerud research. A final reason was that it was then 30 years since Johan
Richter started the development of a continuous digester. Someone,
perhaps outside his company, should tell the story of the devoted efforts
from him and his associates to realize an idea, in which he firmly believed,
in spite of innumerable troubles and a general disbelief from most people
in this industry for a good many years. I am not able to do that initial
story justice, but shall instead cover some experiences of continuous
cooking gained during the last decade. In preparing the lectures, I have
endeavored to give a brief background of wood chemistry and pulping
chemistry, which simplifies the understanding of what goes on in the
digester and what comes out of it. The theory is treated more extensively
in my book "Pulping Processes" (Wiley, New York, 1965). The treatment
of the continuous cooking itself includes the results of work undertaken
by my company. I think I may make clear that continuous cooking is
now ready for all pulping processes and offers possibilities for carrying out
process modifications which only with difficulty are feasible in batch
cooking. It gives a system available for the largest mill units conceivable,
lends itself well to control and automation, offers advantages in combination with other mill operations, and yields pulps which meet the highest
quality standards. It is one. of the weapons needed in this industry to
meet the competition from other materials in serving the markets of today
and tomorrow.
vii
viii
Thanks are due to Billerud and Kamyr for allowing the comprehensive
publication of all results which were previously unpublished or published
only in scattered presentations at Scandinavian and American meetings
and magazines. Actively involved in the administration of the Jossefors
experimental pulp mill were G. Ojermark, S. Haglund, and W. Ameen of
Billerud, and in the administration of the research program T. Bergek, L.
JQrgensen, and myself from Billerud, K. Dahl, J. Richter, and T. Christenson from Kamyr. Actively involved in carrying out the experimental
work during different periods over the 16 years were, from Billerud, myself, G. Arnborger, S. Boren, T. Krantz, J. Grundstrom, U. Mohlin, E.
Nilsson, G. Annergren, A. Haglund, K. Mattsson, S. Lokrantz, S. Wenneras,
B. Dillner, and an experienced crew of 10-20 men. From Kamyr, particularly, the following were involved in the experiments at varying periods: H.
Ortqvist, L. Jansson, A. Backlund, S. Jungeblad, and L. Westerlurtd. The
sparks necessary to carry the work over the critical periods and to yield
the successful redesigns of the machinery were supplied by Johan Richter. With Knut Dahl, the managing director of Kamyr, and Ake Pihlgren
and Gunnar Hindemark, former and present managing directors of Billerud, the financing of the program has rested. This has required from
them substantial courage and belief in the soundness of research and development efforts in machine and process design, perhaps rewarded in the
continued success of digester sales of Kamyr and in the successful operation of continuous pulping processes at Billerud. Part of the work has
also received substantial financial support from the Swedish development
fund Malmfonden.
Sven Rydholm
Billeruds AB
Saffie, Sweden
Lectures
1 Historical Development of Continuous Kraft Cooking...
2 Sulfite Cooking Process Theory
1
11
3 Continuous Acid Sulfite Cooking
33
51
Continuous Bisulfite Cooking
5 Continuous Neutral Sulfite Cooking
63
6 Kraft Cooking Process Theory
75
7 Continuous Conventional Kraft Cooking
97
Continuous Prehydrolysis-kraft Cooking
105
Continuous Modified Kraft Cooking
121
10 Washing Process Theory
159
11 Continuous Digester Washing
173
12 Technical and Economic Aspects of Present and Future

Developments of Continuous Pulping
Tndev
179
193
Lecture
Historical Development of
Continuous Kraft Cooking
The detailed story of the development of the continuous kraft digester
began with a 5 ton/day pilot plant at Karlsborg in northernmost Sweden in
1938 and continued, (after an interlude during the war) in 1948 at
Fengersfors, a small kraft mill in Central Sweden. During the period
1948-52, Fengersfors took the brave stride to continuous cooking from its
19th-century technique of stationary batch digesters, which opened at side
lids near the bottom and were emptied manually into wheelbarrows to
carry the pulp to the washing and screening departments.
In this mill, the Kamyr enthusiasts introduced their first commercial
unit, for 50 tons/day. The basic principle of a downflow digester with a
balanced high-pressure pocket feeder (Fig. 1.1) was already established,
but they had a long way to go.
The high-pressure feeder is still the key feature of the Kamyr system. It
solves the problem of introducing the wood chips into the high-pressure
system without mechanical compression damage, without excessive wear
on the feeder, and without losses of steam from the pressure room. The
chips fall from the steaming vessel into the pocket of the feeder when the
pocket is in vertical position, and are packed by a liquor circulation. The
revolving plug of the feeder contains 2-4 such pockets at varying angles, so
that always at least one pocket will receive chips. The plug, which is
slightly conical, is a precision work of stainless steel in an iron housing
with a monel sleeve. In turning, the plug delivers the pockets successively
into a horizontal position, in contact with the high-pressure feeding
line. By a circulation pump, the chips are then conveyed into the digester. The pocket is thus emptied of chips but full of liquor when it arrives
again at a vertical position. A liquor volume corresponding to the volume
of the new chip charge must thus leave the system at an overflow in the
chip chute and has to be pumped into the system again by a high-pressure
pump, together with the small leakage volume from between plug and
housing, and with the cooking liquor charge.
The first commercial continuous kraft digester is outlined in Fig.
1.2. Its basic design is similar to that of the present digesters, but many
improvements have been made. The chips are charged from a hopper
1
Lecture 1
Fig. 1.1. Principle of the balanced high-pressure pocket feeder.

over a measuring wheel into a low-pressure feeder, which introduces the
chips into the horizontal steaming vessel. After 3-5 min steaming, the
chips fall into the high-pressure feeder and are pumped into the digester. A top screw or separator keeps a strainer clean, through which the
feeding hquor returns to the circulation pump. A torsional indicator at
the end of the screw feels the chip level in the digester and gives an
impulse to the discharge system for balancing the charge and discharge
flows. Cooking liquor is fed into the digester top over the chip feeding
circulation, and is heated in a new circulation somewhat further down the
Historical Development of Continuous Kraft Cooking
BLOW STEAM RECOVERED FOR PRESTEAMING
Fig, 1.2. First commercial Kamyr kraft cooking system.

digester.
The circulation strainer is kept clean by the moving chip
column, but there was the problem of distributing the heated liquor over
the digester cross section. The initial arrangement was improved in cooperation with the Fengersfors mill staff, of which the contributions of
Ragnar Jonsson particularly should be mentioned. He also cooperated in
the improvement of the bottom scraper and discharge problems, which
were connected with the pulp quality. The distribution of the cooking
liquor was solved by the introduction of the central pipe, ending just
above the level of the circular strainer. The final solution of the discharge was yet to come.
In 1952, the Kamyr men thought they were ready for a larger unit in
Sweden (100 tons/day), which was sold to Wifstavarf. However, in spite
of their own efforts, and some very energetic ones from the mill personnel,
this digester did not turn out to be a success, and it was finally closed
down. This was watched by the entire Swedish forest industry, and many
wise and experienced men had their doubts confirmed. The system was
not ready for production, and what was, after all, the purpose and advantage of continuous cooking? Johan Richter at that time had only one
answer, which kept him going: "People used to ask the same question
when we started to make bleaching continuous, and look what they are
buying now, all of them."
However, there were still people in industry fascinated with the idea of
Table 1.1. Pioneering Mills in Kamyr Continuous Digester Systems

Year
Mill
1948 Fengersfors Bruks AB,

Fengersfors
1949 Cartiera Vita Mayer,
Cairate
Cartiera Burgo, Ferrara
1951 Ste". An. Progile, Condatle-Lardin
Ohji Seishi KK, Kasugai
Associated Pulp and Paper
Mills Ltd, Bumie
Tasmania
1952 Wifstavarfs AB,
Vifstavarv
Joutseno Pulp OY,
Joutseno
1954 Joutseno Pulp OY,
Joutseno
Cellulose du Rhdne,
Tarascon
N Z Forest Products,
Tokoroa
Billeruds AB, Saffle
Billeruds AB, Gruvon
1955 Billeruds AB, Jossefors
Backhammars Bruk AB,
Bjorneborg
North Western Pulp & Power
Co., Ltd., Hinton, Alberta
North Western Pulp & Power
Co., Ltd., Hinton, Alberta
International Paper Co.,
Camden, Arkansas
V Rosenlew & Cp. AB,
Bjorneborg
Sudbrook Pulp Mill Ltd.,
Sudbrook
Cellulose du Rh6ne,
Tarascon
Ohji Seishi KK, Kasugai
Gulf States Paper Co.,
Demopolis, Ala.
Weyerhaeuser Timber Co.,
Longview, Wash.
Country
Capacity,
tons/day
Sweden
50
Process:
Kraft
Wood
Softwood
Italy
90
Kraft
Softwood
Italy
France
25
40
NSSC
Kraft
Straw
Chestnut
Japan
Australia
90
60
Kraft
Soda
Softwood
Eucalypt
Sweden
100
Kraft
Softwood
Finland
120
Kraft
Softwood
Finland
120
Kraft
Softwood
France
60
Soda
Esparto
60
Kraft
Softwood
Sweden
Sweden
Sweden
Sweden
New Zealand
60
150
10
150
NSSC
Kraft
Pilot
Kraft
Hardwood
Softwood
Softwood
Canada
250
Kraft
Softwood
Canada
250
Kraft
Softwood
USA
150
Kraft
Softwood
Finland
200
Kraft
Softwood
England
60
NSSC
Hardwood
France
150
Kraft
Softwood
Japan
90
Kraft
USA
350
Kraft
Softwood,
hardwood
Softwood
USA
150
Kraft
Softwood
Table 1.1. Pioneering Mills in Kamyr Continuous Digester Systems

Mill
Nippcm Pulp Kogyo KK,
Yonago
Jujyo Seshi KK,
Yataushiro
Sanyo Pulp KK,
Iwakuni
Eastern Corp., Lincoln, Me.
Skogsagarnas Cellulosa AB,
Monsteras
Skogsagarnas Cellulosa AB,
Monsteras
Kokusaku Pulp KK,
Asahigawa
Dai Showa Seishi,
Fuji
La Cellulose du Pin,
Facture
La Cellulose du Pin,
Facture
Continental Can Co.,
Nixon Station, Ga.
Celulosa Argentina
Belisce Kombinat
Celgar Ltd., Castlegar, B. C.
Celgar Ltd., Castlegar, B. C.
Fibreboard Paper Prod. Inc.
Antioch, Calif.
Oxford Paper Co.,
Rumford, Me.
Associated Pulp and Paper
Mills Ltd., Burnie
Usutu Pulp Co. Ltd.
AB Statens Skogsindustrier,
Lovholmen
AB Statens Skogsindustrier,
Lovholmen
Tokai Pulp KK,
Shimada
Techmashimport
Techmashimport
St. Regis Paper Co.,
Tacoma, Wash.
Canadian International Paper
Country
Japan
tons/day
120
Process
Wood
Kraft
Softwood
Japan
120
Kraft
Softwood
Japan
120
Kraft
Softwood
USA
Sweden
150
120
Kraft
Kraft
Hardwood
Softwood
Sweden
120
Kraft
Softwood
Japan
150
Kraft
Japan
150
Kraft
Softwood,
hardwood
Softwood
France
150
Kraft
Softwood
France
150
Kraft
Softwood
USA
350
Kraft
Softwood
Argentina
100
Eucalypt
Yugoslavia
Canada
Canada
USA
50
250
250
250
Cold
Caustic
NSSC
Kraft
Kraft
Kraft
Hardwood
Softwood
Softwood
Softwood
USA
225
Kraft
Softwood
Australia
100
Soda
Eucalypt
Swaziland
Sweden
300
150
Kraft
Kraft
Softwood
Softwood
Sweden
300
Kraft
Softwood
Japan
150
Kraft
Hardwood
USSR
USSR
USA
420
420
300
Kraft
Kraft
Kraft
Softwood
Softwood
Softwood
Canada
300
Kraft
Softwood
Lecture 1
Fig. 1.3. Kamyr kraft cooking system after the

introduction of the cold blow.
continuous cooking. The next two units, sold to Finland, to Joutseno,
handled 120 tons/day each. There, much important work was done to
improve the reliability of the system, and although there were still disturbances, production went on smoothly enough to let a very serious problem
become evident: The pulp quality was not satisfactory. As seen from
the list of early buyers (Table 1.1), there was no general breakthrough;
only a few brave companies in various parts of the world were curious
enough to test the idea of continuous cooking. The essential reasons for
Historical Development of Continuous Kraft Cooking
this hesitation were the problems of production reliability and of pulp

quality.
Billerud belonged to the fairly early believers, and in 1954 we ordered
three units simultaneously, one 150 tons/day kraft unit for Gruvon, one
75 tons/day unit to Saffle for the production of neutral sulfite birch pulp
to bleached glassine, and one 10 tons/day pilot unit for all conceivable
process variants, to be placed at an experimental pulp mill within the
Jossefors sulfite pulp mill.
This decision was taken after thorough consideration and several visits to
kraft mills with existing Kamyr digesters. We also had had some direct
experience, since we had carried out, jointly with Kamyr and Mo &
Domsjo, the first effort in continuous sulfite cooking in a small, 1 ton/day
unit, located at Domsjo, during 1950-53. My first job in Billerud was to
attend to those trials, which were quite informative, but also quite unsuccessful.
With the kraft digester at Gruvon, we had a fair startup, and although
there were many teething troubles, we became eventually very satisfied
with the production reliability. The pulp quality was, however, unsatisfactory, and we were glad to have a fairly large batch digester room besides
the continuous unit. At that time, however, the solution to the quality
problem was underway, thanks to Kamyr, particularly Lennart Jansson, in
collaboration with the Finns at Joutseno, headed by Hannes Jansson. Some contributions were also made by the Central Laboratory of
the Cellulose Industry in Stockholm with Lennart Stockman, and some by
us at Gruvon, Saffle, and Jossefors.
Like Joutseno, we found that the kraft pulp became degraded by the
action of the discharge devices, when blown at full temperature, and that this
also applied to the neutral sulfite and particularly to the acid sulfite process.
Then the cold blow was introduced, first as a cooling of the bottom circulation liquor, and later on, with the introduction of cool wash liquor to the
bottom zone (Fig. 1.3). This again necessitated a change in the discharge
system. Up to now, the discharge was done through an Asplund sluice,
developed for the Defibrator process and consisting of a pressure room
with two alternating valves. The pulp was sluiced into that small chamber and then blown by its own thermal expansion when the second valve
opened toward the blow tank. With the cold blow, no such expansion
was possible. Instead, a blow-valve was developed which directly reduced
the digester pressure. Contributing here were the French Progile mill at
Condat, International Paper in Camden, and Billerud's mill at Saffle.
The cold blow improved the quality by 10-20% on most paper strength
properties, and the industrial progress of the continuous kraft digester
Lecture 1
1950
1955
I960
YEAR
1965
1970
Fig. 1.4. Development of Kamyr kraft cooking installations

during the first 20 years of commercial production,
million tons annual capacity.
could proceed. As seen in Fig. 1.4, the system had now its first major
breakthrough. This also meant that there was experience accumulating in
all parts of the world, not the least in North America. One of the most
valuable ideas emerged from a stubborn Australian, who was ahead of even
the Kamyr personnel in some thinking around the continuous digester. Ray Sloman, who had ordered his first Kamyr digester for APPM,
Burnie, Tasmania, as early as 1951, wanted to run his digester counter-
Fig. 1.5. Kamyr continuous kraft cooking system with digester washing
followed by filter washing. (1) Chip measuring wheel; (2) steaming vessel;
(3) high-pressure feeder; (4) white liquor pump; (5) impregnation zone; (6)
heating circulation; (7) cooking zone; (8) black liquor withdrawal; (9)
flashing system; (10) "Hi-heat" washing zone; (11) washing liquor circulation; (12) blow tank; (13) knotter; (14) washing filter.
10
Lecture 1
currently, succeeded, and has done so ever since. There may still be different opinions about the virtue of cooking countercurrently, but the mere
proof that it was possible to let the liquor flow upwards and the pulp
downwards gave rise to the second breakthrough, the high-heat countercurrent wash in the lower part of the digester (Fig. 1.5). This eliminated
quite a few problems in the filter wash after the digester, where Kamyr
had been temporarily less successful with its constructions, and which at
one period had caused more production disturbances than the digester
itself.
With both those features, the cold blow and the digester wash, the
system was quite competitive, technically and economically, and thereafter increasingly dominated the new capacity of the kraft pulp industry,
in increasingly large units. The largest one on order at the moment
is for 1150 metric tons/day, and this feature alone, the size, is
proof enough of the foresight and soundness of Johan Richter's basic idea.
Other advantages, such as heat economy and labor economy through facilitated combination of cooking with subsequent operations, will be further
discussed in the last lecture. It is no overstatement to say that the
continuous digester introduced on a massive scale the concepts of instrumentation and automatic control to the pulp industry, now being completed by digital control from computers.
The happy situation of Kamyr, with a practical monopoly in the field of
continuous kraft cooking, would have made many firms self-assured and
lazy. It is commendable that the company continued the development
efforts and extended them to adjacent fields, mainly sulfite pulping in
1957-64, prehydrolysis-kraft pulping in 1964-65, neutral sulfite pulping in
1965-66 and modified kraft pulping in 1965-68. Since that development
has been performed mainly in collaboration with Billerud, at times even by
Billerud alone or in collaboration with Swedish Cellulose Co., it is on this
topic that I should be able to speak with some experience. However, I
felt it was only fair to enlarge somewhat on the development of the kraft
digester, thus paying my respects not only to the Kamyr men but to all
pioneers of continuous cooking working in the industry, who have carried
the double burden of technical difficulties of development and the responsibility of the current production.
Lecture 2
Sulfite Cooking Process Theory

The wine dealers of France have for a long time disinfected their barrels
with sulfur dioxide. It is told that an observant American, Benjamin
Tilghman, made his invention of the sulfite process by reflecting about the
cause of wine barrels' becoming fiberized on the inside after repeated use
and disinfections. Tilghman got his patents in the 1860's, but he did not
succeed in making much money out of them, since he tried to carry out
his sulfite cooking continuously and it took a decade to make the sulfite
process work even on a batch system. This was done by a Swede, C. D.
Ekman, who started the Bergvik sulfite mill in 1874. A few years later, in
1883, the first Billerud sulfite mill started production at Saffle.
I must confess that the foresight and failure of Benjamin Tilghman was
often in my mind when we started, almost a century later, to make the
sulfite process continuous. Sometimes we thought we should go down in
history with the same rather dubious fame-foresight and failure. And if
you fail, somebody else has to prove whether you were really foresightedor just on the wrong track. The basic reaction of the sulfite
process is the introduction of hydrophilic sulfonate groups into a virtually
hydrophobic substance, the lignin (Fig. 2.1). This is done by reacting the
wood with bisulfite solutions, normally calcium bisulfite, but more recently ammonium, sodium, or magnesium bisulfite. The pioneers soon found
that calcium required an excess of sulfurous acid, in order to prevent the
precipitation of calcium sulfite at elevated temperature.
This immediately introduces us to the concepts of cooking acid composition and to the peculiar behavior of sulfurous acid at elevated temperature
(Fig. 2.2). Since the early days of the sulfite industry, the cooking acid
has been visualized as a mixture of sulfite and sulfurous acid, the former
named combined, the latter free S0 2 . Chemically we know now that in
these acidic solutions there is practically no sulfite, and instead twice as
much bisulfite as the combined S0 2 , and in addition S 0 2 , which is generally called excess S0 2 . The excess S0 2 stands in equilibrium with water
to form sulfurous acid, which is ionized into hydrogen ions and bisulfite
ions. The hydration equilibrium is much influenced by temperature, as
experienced by an increasing S0 2 pressure of the cooking acid with increasing temperature.
11
12
Lecture 2
Fig. 2.1. Mechanism of delignification according to two concepts:

sulfonation followed either by sulfitolysis or by hydrolysis with subsequent further sulfonation in solution.
Fig. 2.2.
Sulfite cooking acid concepts and composition.

Temperature, C
Ka
pKa
25
70
100
110
120
130
140
150
0.0172
0.0046
0.0024
0.0016
0.0011
0.0008
0.0005
0.0003
1.8
2.3
2.6
2.8
3.0
3.1
3.3
3.5
13
Fig. 2.3 Temperature dependence of the apparent ionization constant of

sulfurous acid.
Evidently, the dissociation constant of sulfurous acid decreases rapidly
with temperature. The constant is defined by the equation
Fig. 2.3 Temperature dependence of the apparent ionization constant of

sulfurous acid.
Evidently, the dissociation constant of sulfurous acid decreases rapidly
with temperature. The constant is defined by the equation
k=
[H + ] [HSOj ] =
[H + ] [HSO3 ]
[H 2 S0 3 ] + [S0 2 ] [total S0 2 ] - [HSO3 1
Measured in terms of hydrogen ion concentration, these changes are

apparently reflected as changes in the ionization equilibrium (Fig. 2.3),
though there is reason to believe that most of the sulfurous acid is ionized
at all temperatures. Including all excess S0 2 in the denominator of the
ionization equilibrium equation, sulfurous acid has a pK a of 1.8 at room
temperature and 3.0-3.5 at cooking temperature. This means a pH of this
order of magnitude for a normal cooking acid, containing after some gas
relief about 4% total and 1% combined S0 2 , i.e., equal parts, 2%, of excess
S0 2 and bisulfite S0 2 . When bisulfite ions are consumed during the cook
(Fig. 2.4), more excess S0 2 becomes hydrated and then more hydrogen
ions formed. There is thus an increase in acidity during the cook, after an
initial decrease due to excess S0 2 disappearing by gas relief, and because
of the temperature rise. The increase in acidity is pronounced only
toward the end of certain cooks, where more bisulfite ions have been
consumed than corresponding to the metal ions, or the "base." Such
cooks are avoided in most cases with paper pulps, and only with rayon
pulp is this acidity peak desired to speed up the hydrolytic degradation of
the pulp to a controlled viscosity level.
The cooking acid composition is with calcium base limited to such really
acid cooks. The solubility of magnesium sulfite is higher than that of
calcium sulfite, which means that a higher pH can be allowed for magnesium base cooking liquors, up to pH 5. A straight bisulfite solution, of
4% total and 2% combined S0 2 , for example, has a pH at room temperature of slightly above 4, and contains equal and small amounts of sulfite
and sulfurous acid (Fig. 2.5). Cooks at pH 4 were investigated during the
1930's and introduced to industry during the 1950's with the introduction
14
Lecture 2
15

15
Figure 2.4
Curves 1, 5.12% S02, k = 0.020 (20C)
2,5.12%
0.005 (70 C)
3,5.12%
0.002 (105C)
4,5.12%
0.001 (125 C)
5,2.56%
0.001 (125C)
6, 2.56%S02,fc =0.0005 (140 C) .
7,1.28%
0.0005 (140C)
8,0.64%
0.0005 (140C)
9,
0
Dotted curves: technical sulfite cook conditions.
Fig. 2.4. The relations of hydrogen and bisulfite ion concentrations to
combined S0 2 (or to strong acid anions formed) at constant levels of total
S0 2 and temperature.
of soluble bases. Such cooks are called bisulfite cooks, whereas the traditional sulfite cooks should now be called acid sulfite cooks. To increase
the pH still more requires ammonium or sodium base, which have easily
soluble sulfites. The so-called mixed sulfite-bisulfite cooks of pH 6-7,
with a cooking liquor composition of 4% total and 3% combined S0 2 ,
contain about equal parts, 2% S0 2 of bisulfite and sulfite. They are also
used industrially for very high-yield cooks.
When the cooking liquor contains only sulfite, e.g., with 4% total and 4%
combined S0 2 , it becomes alkaline, with a pH of about 10.5. Such
cooks are sometimes called monosulfite cooks. In order to save some
chemicals, cooks of this type are more often carried out with a deficit of
total S0 2 , e.g., 3% total and 4% combined, the rest being a sodium carbonate or rather bicarbonate buffer. They have a pH initially of 8.5-9.0 and
end at pH 6-7. They are usually called neutral sulfite cooks and are, of
course, widely used for hardwood semichemical pulps. Still more alkaline
sulfite cooks have also been tried in the laboratory. The function of the
sulfite in such cooks is not quite clear. In order to have them proceed
with any rapidity, a considerable excess of alkali must be present, and the
delignification is also speeded up by the presence of sulfide. This indicates that the delignification in such cooks involves the alkaline hydrolysis
of lignin bonds just as in ordinary kraft cooking. A decrease in the sulfite
content likewise retards the delignification, however, and shows that also
sulfonation plays a part.
Other variants of the sulfite cook are the multistage processes, whereby
attempts are made for effects not possible in one-stage cooks. These
cooks are generally combinations of the cook types .previously mentioned,
such as neutral sulfite-bisulfite or neutral sulfiteacid sulfite. I shall
come back to those processes later on.
<
16
Lecture 2
Fig. 2.5. Bjerrum diagram showing pH and ion concentrations of various

types of sulfite cooking liquors, assuming pKfl of sulfurous acid to be 1.75
at room temperature and 3.1 at 130C, and pKfl of the bisulfite ion to be
7.0.
Before doing so, I shall finish off the inorganic chemistry of the sulfite
cook by mentioning the decomposition reactions of the cooking
acid. Some discouraging experiences of the early sulfite process pioneers
with so-called burnt or black cooks have their cause in the catalytic
decomposition of bisulfite ions into sulfate and thiosulfate (Fig.
2.6). That reaction is among other things catalyzed by thiosulfate, and
will thus, once started, accelerate unless thiosulfate is removed. All sulfite
cooks at a pH below neutrality form thiosulfate, and hence it is not
possible to mix cooking acid with waste liquor to the same extent as has
been done in the kraft industry to increase the solids content of the waste
liquor for evaporation. If that is done with sulfite cooking acid and waste
liquor, the initial thiosulfate content will be excessive and cause an accelerated decomposition of the fresh bisulfite.
The reactions forming thiosulfate during the cook are not only the previously mentioned inorganic reaction, but also reactions of bisulfite with
sugars, as well as with terpenes, etc. (Fig. 2.7). In a normal acid sulfite
cook, these amounts of thiosulfate are consumed in a reaction with lignin
(Fig. 2.8), and the detrimental cooking acid decomposition is thus
checked. When cooking at a higher pH, such as in the bisulfite cook, it
appears that this reaction between lignin and thiosulfate does not occur to
any extent. Then the sensitivity to thiosulfate contamination becomes
accentuated, especially since the higher content of bisulfite ions tends to
give increasing amounts of thiosulfate in reaction with the carbohy-
17
Fig. 2.7. Decomposition of sulfite cooking acid in absence of organic

matter, as well as interaction of cooking liquor components and wood
components in forming and consuming decomposition catalyst, thiosulfate.
18
Lecture 2
drates. This prevents the cooking down to pulps with lignin contents
below 4% with the bisulfite process, as compared to less than 1% as the
minimum in the acid sulfite cook. It also became evident in our trials
with continuous bisulfite cooking that the decomposition reactions can
create real technical problems, which I shall refer to later. On the alkaline
side there is no similar spontaneous decomposition, and considerable
amounts of thiosulfate can be tolerated in the neutral sulfite cook, for
example.
The lignin reactions of the sulfite cook, disregarding that often neglected
one with thiosulfate, are predominantly sulfonation, hydrolysis, and
condensation (Fig. 2.9). In all cases, the initial reaction is probably a
protolysis of the dialkyl ether bonds of lignin, or protolysis at the benzyl
alcohol groups. Various model reactions have illustrated the various
reactivities of the possible configurations. Here it is sufficient to state
that, in the course of delignification, lignin is at first sulfonated to an
extent corresponding to one sulfonate group for every three monomers
without dissolving. Continued acidic treatment without bisulfite ions
will remove some of the lignin so sulfonated, but a continued sulfonation
will introduce more sulfonate groups, to at least one on every two
monomers, and results in a more complete delignification.
If the sulfonation is interrupted at too early a stage, e.g., by the decomposition of bisulfite ions to sulfate and thiosulfate, the reactive groups of
the lignin not only can be hydrolyzed, but to a considerable extent, also
condense with other reactive centers in the lignin molecule, particularly in
the 5-position of the aromatic ring. This is called the self-condensation of
lignin and leads to discoloration, screenings, and in bad cases to "burnt
cooks." A similar cause of the same phenomena is where the heating of
the cook has proceeded too rapidly in relation to the penetration of the
cooking liquor. Then condensation can occur within the lignin before
sulfonation has a chance to take place, and the end result will be nonuniform cooks, with "burnt centers" of the chips, where impregnation has
been incomplete. A large amount of research work has been devoted to
these phenomena, such as pretreatment in various buffer solutions. Part
of the problems has also been ascribed to physical phenomena, such as
"coalescence" of the lignin during the pretreatment, which should have
the same consequences as condensation. There is also direct chemical
evidence of condensation during such pretreatment, and it is likely that
both condensation and coalescence play a role in the deactivation of the
lignin.
Another condensation of a similar type occurs betwen lignin and
phenolic extractives, such as the pinosylvin compounds of pine heartwood,
19
Fig. 2.9. Mechanism of lignin sulfonation, etc., assuming proton activation: (1) hydrolysis (R' ,alkyl) or status quo (R'H); (2) sulfitolysis
(R alkyl) or sulfonation (R H); (3) condensation.
or the tannins of bark-damaged spruce surface wood (Fig. 2.10). This
prevents the cooking of such wood by the original acid sulfite process and
has led to the development of two-stage processes, such as the Stora process for pine or the Kramfors process for tannin-damaged spruce (Fig.
2.11). If namely the initial treatment is carried out in a less acid medium,
pH 4-10, sulfonation is favored and condensation suppressed sufficiently
to allow complete delignification.
In the neutral sulfite cook, carried out at higher temperatures than the
acid sulfite and bisulfite versions, the predominant sulfonation reaction
20
Lecture 2
Fig. 2.11. Temperature schedules of some two-stage cooks with industrial

application (cooking curves could be adjusted according to quality and capacity demands).
21
appears to be a sulfitolysis of the alkylaryl ether bond under formation of

a styrene sulfonate which tends to polymerize (Fig. 2.12). Likewise,
some sulfitolysis of methoxyl groups occurs, under formation of methane
sulfonate (Fig. 2.13).
22
Lecture 2
The dominant carbohydrate reaction in acid sulfite cooking is hydrolysis

of the glycosidic bonds (Fig. 2.14). The susceptibility to hydrolysis
varies. The arabinose groups of the softwood xylan (Fig. 2.15), are the
most sensitive ones, followed by the galactose groups of the
galactoglucomannan (Fig. 2.16). Then follow the xylosidic bonds of the
xylan chains, and the mannosidic and glucosidic bonds of the
glucomannan chains. Also the glucosidic bonds of the cellulose chains
(Fig. 2.17), are attacked, but less easily. That is largely the result of lower
23
accessibility to hydrolysis. The hemicelluloses are less well ordered than

cellulose and are preferentially attacked. We found that the glucomannan
molecules of softwoods can change their accessibility to hydrolysis when
their acetyl groups are removed by a neutral or alkaline precook prior to
the sulfite cook (Fig. 2.18). This preservation is not desirable in a rayon
pulp cook, where it is endeavored to remove as much as possible of the
hemicelluloses (Fig. 2.19). In a paper pulp cook, however, it is generally
desired to preserve them, and a yield improvement of 4-7% is possible by
applying the two-stage technique. In order to illustrate the location of
the hemicelluloses around the elementary fibril of the cellulose in the
secondary waE of those different pulps, schematic representations can be
made (Figs. 2.20, 2.21).
The pulp yields obtained with these various types of sulfite pulps also
depend on the degree of delignification (Fig. 2.22). The more lignin left
in the pulp, the higher is also the carbohydrate yield, since the industrial
delignification is far from selective. The two-stage cook with initial
deacetylation preserves a higher yield level throughout, and one-stage
24
Lecture 2
Fig. 2.18. Pulp yield, mannose content and acetyl content of two-stage
sulfite pulps, cooked to constant ligniri content at varying pH and temperature conditions of stage I.
25
Fig. 2.19. Yield of wood components on sulfite pulping of spruce and

birch with or without a preceding neutral sulfite stage.
high-yield semichemical cooks with deacetylating action likewise give a

higher yield at equivalent lignin content than does the conventional bisulfite cook at pH 4. The yield effects with deacetylating cooks concern
only softwoods. The hardwoods are low in glucomannan content, and it
is not known whether that glucomannan is acetylated. The acetyl groups
of hardwoods mainly belong to the xylan, that also contains branches of
glucuronic acid (Fig. 2.23), which do not split off completely in any of the
two stages. The hardwood xylan therefore remains accessible to degradation in the acid cook, whether deacetylated or not, at least under the
27
PULP LIGNIN.% of
Fig. 2.22. Dissolution of sprucewood components on sulfite pulping.

Yield of components as a function of pulp yield or pulp lignin yield.
Broken lines indicate constant hemicellulose yield ("iso-hemi lines") as
suggested by Loschbrandt. GAX = glucuronoarabinoxylan; GGM = galactoglucomannan acetate.
28
Lecture 2
Fig. 2.24. Sulfonation and oxidative degradation of carbohydrates in

acid sulfite and bisulfite cook.
conditions of the two-stage cook that gives the yield effects with softwoods.
Another carbohydrate reaction in the sulfite cook is that of oxidation by
bisulfite ions under formation of aldonic acids and thiosulfate (Fig.
2.24). Its importance for the cooking acid stability has been commented
on already. It is also responsible for a yield decrease in the bisulfite
cook, to an extent which offsets the advantage of a lower hydrolytic
degrading action in that less acidic process variant. Bisulfite pulps are
therefore obtained in about the same yields as are acid sulfite pulps at
equivalent lignin content. Not only aldonic acids, but also sugarsulfonic
acids are formed, and this appears to be the case also with neutral sulfite
pulping, where, however, both hydrolytic and oxidative degradation are
quite limited (Fig. 2.25).
It is not necessary here to enlarge on the pulp properties obtained from
the various types of sulfite cooks. It suffices to say that the sulfite process generally gives a higher yield but a weaker paper pulp than the kraft
process, and that its sensitivity to the type of wood, to the state of wood
seasoning, to the extent of mechanical chip damageas well as the less
29
Fig. 2.25. Sulfonation and oxidative degradation of carbohydrates

in neutral sulfite cook.
highly perfected engineering of the sulfite processhave given it a poorer
competitive situation to-day. The efforts to improve this situation by
process variants have not given sufficient results. Exceptions are the semichemical pulps of neutral sulfite from hardwoods and bisulfite from softwoods, as well as the normal grades of viscose rayon pulp, particularly
from softwoods, where the acid sulfite process is still preferred.
A few words should be said also on the impregnation of wood chips
before concluding the lecture on the sulfite process. Impregnation problems were mentioned in connection with the acid self-condensation of
lignin, where sulfonation had not taken place. The occurrence of burnt
chip centers was often a problem to the sulfite industry before it learned
the influence of chip size and the impregnation variables. Wood consists
of a capillary system containing 50-75% of void spaces, filled with air or
water. These spaces are mainly the luminae of the fibers, tracheids, and
vessels. In softwoods, the luminae are interconnected over the pits, the
membranes of which are perforated with holes of 0.03-lju in size. The
pits are closed in pine heartwood, which is therefore difficult to penetrate. In hardwoods, the capillary system of the vessels is easily penetrated, unless blocked by so-called tylose formation, which sometimes
occurs in the heartwood of some species, such as white oak. Even in
those hardwoods which have easily penetrated vessels the fiber luminae
appear to be accessible only by diffusion through the fiber walls. Reasonable methods have been worked out to determine both the flow resistance of the capillary system of the various species and the diffusion
resistance of soaked wood. Both flow and diffusion are much more rapid
in the longitudinal than in the transverse directions, and hence a critical
factor for cooking acid penetration is the chip length. This is normally
30
Lecture 2
STEAMING, min
Fig. 2.26. Degree of penetration vs. time of steaming for spruce chips
treated at 75C with an acid containing 5% total S0 2 and applying a
pressure of 0.8, 5, and 9 atm (0.8 atm corresponding to the vapor pressure
of the acid). Penetration after 2 min , 5 min X, 10 min A, 15 min O, 30
min D, 45 min .
kept at about 20 mm, shorter chips leading to more mechanical damage
than can be usually tolerated.
A factor which complicates penetration is the air in the chips, which
becomes trapped in the capillaries and prevents complete penetration. In
the practical range of pulpwood moisture content, 30-50%, a combination
of air and water pockets fill the capillaries, the most difficult situation
from the standpoint of impregnation. Therefore, several methods of air
removal have been devised, the most efficient of which is steaming. Steaming causes the air pockets to expand thermally, and when
steaming to 100C at atmospheric pressure, the increased vapor pressure of
water will force the air to leave the system. Steam shooks have been
applied to increase this effect but have in general been found not to
31
improve the situation as compared to ordinary steaming of the same

endurance.
Provided most of the air has been expelled from the wood chips, impregnation is aided considerably by hydraulic pressure. Figure 2.26 shows
that penetration is rather incomplete even after considerable periods of
steaming and impregnation if the hydraulic pressure of the system does
not exceed the vapor pressure of the cooking acid. Increased hydraulic
pressure gives almost complete penetration even after 5-10 min each of
steaming and impregnation. I shall come back to this circumstance in
connection with rapid continuous cooking.
It was also mentioned that too short chips tend to give intolerable damage to the wood. That mechanical damage in combination with acid sulfite cooking will cause degradation has been manifested in many
ways. Sulfite cooking of mechanical pulp, either groundwood or the
more well-preserved Defibrator fibers, yields a very degraded sort of sulfite
pulp. It has been established that the mechanical damage of a longitudinal compression of the wood is sufficient to cause the sulfite pulp to
become degraded. Transversal compression is less harmful. It has also
been demonstrated that the morphological disturbance which leads to the
degradation is not cracks in the "lignin enamel," exposing cellulose to
hydrolysis, but rather disturbances in the cellulose fibrillar structure, socalled slip planes. The phenomenon not only leads to damage at the
bruised ends of the chips, and consequently efforts with new chipping
principles, it has also necessitated caution as regards movements in the
digester content during the sulfite cook or at the discharge. I shall later
demonstrate that this applies also to continuous sulfite cooking.
Lecture 3
Continuous Acid Sulfite Cooking

With the theoretical background just given for the sulfite process and its
variants, I shall now proceed to describe our efforts to make the process
continuous. Those efforts started contemporarily with the developments on soluble bases in the sulfite process and drew constantly from the
results of the laboratory work in progress.
The first approach was that of the 1 ton/day pilot unit at Domsjo in the
early 1950's. This was mainly a stainless steel version of the contemporary continuous kraft digester (Fig. 3.1). Thus, it contained equipment
for chip charging and steaming, to ensure efficient steaming there were
two steaming vessels. The system further contained a high-pressure
feeder with level tank, packing circulation, feeding circulation, and highpressure pump for charging of cooking acid and compensating liquor, top
screw, downflow digester body with strainers, circulations, and heat exchangers, and finally a discharge system with bottom scraper, Asplund
sluice, and discharge circulation.
Our first experience was that the size of 1 ton/day is too small for
practical development work of this type. The discharge of knots or uncooked chips caused excessive troubles, a leaking valve unproportionate
disturbances. The second experience was that calcium-based cooking acid
is not practical for development work. Any cooking acid decomposition
caused liming-up of the entire system and consequent cleaning of pipes
and heat exchangers, which consumed much trial time and patience. The
third and decisive experience was that the feeding system of a kraft digester is quite unsuitable for a straight acid sulfite cook. A proper hot acid
system gives a cooking acid of about 6% total S0 2 and an excess pressure
of at least 3 atm at the usual storage temperature, 60-70C. At
100-110C, the vapor pressure is still higher. However, in the feeding
system in question, the cooking liquor assumes the temperature of the
steaming vessel, 100-110C, whereas the pressure maintained by the lowpressure feeder is only 0.5-1.5 atm. It was therefore inevitable that the
excess S0 2 tended to leave the cooking liquor already in the feeding
circulation. This is undesirable from a process point of view, and also
caused hammering in the high-pressure feeder and liming-up of the feeding
circulation when using calcium-based acid.
33
34
Lecture 3
Fig. 3.1. First Kamyr pilot plant system for continuous sulfite cooking.
These experiences indicated a 10 ton/day pilot unit, a soluble base, and a
two-stage cook with no excess S0 2 in the initial stage. When the experimental pulp mill was created at Jossefors in 1956, it contained a digester
designed accordingly (Fig. 3.2). In order to separate the two stages completely, the digester consisted of two bodies, one upflow and one downflow. There were the usual arrangements for charging and steaming the
chips, the standard feeding circulation, and then the upflow digester,
equipped with two chip-lifting circulations, a top scraper for transferring
the chips to the second stage, with a transfer circulation as an additional
acid. The second body was equipped with a heating circulation and the
usual discharging system, with bottom scraper, discharge sluice, and bottom circulation. A blow tank with subsequent filter received the pulp for
further operations.
The machinery development work continued in that equipment for two
years, until it had been made to work properly, and then process studies
continued for some years. During this period, we had considerable mechanical experience, e.g., with the material of the high-pressure feeder,
corrosion in the digester top and behind blind strainer plates, where cooking acid decomposition took place and sulfuric acid corrosion was severe. We learned how to get the chip column moving upward in the first
stage, and how to discharge through a small blow valve instead of the
Fig. 3.2.
35
Two-body digester for acid sulfite pulping.
sluice. We learned how to construct a top scraper to transfer the chips

without damage, and reconstructed the bottom scraper to do the least
possible damage. We traced the flow of the chips with radioactive copper
wire bits, inserted in chips, and the flow of the liquid by injecting solutions of radioactive sodium carbonate. We put sight glasses on the digester tops to study the phenomena in the uppermost part of the digester and
tried various designs for chip level control. We learned how to charge
liquid S0 2 into the cooking acid circulation at a suitable rate, and how to
avoid the plugging of the high-pressure feeder with sawdust. In short, we
fought a great many troubles all around the clock, and at night we went up
to the roof of the digester house to derive inspiration from the Sputniks
and Explorers, which had just begun to encircle the planet. After all, our
problems ought to be the easier ones.
After a while, we got sulfite pulp on the subsequent filter. In the first
development phase, we wanted dissolving pulp from spruce. Our analyses
showed lower than normal Roe numbers and lower resin contents in the
pulp at a certain viscosity level. After preventing the cooking acid decomposition caused by back-water pockets in the digester, we succeeded in
getting a proper delignification and deresination; but how about the carbo-
36
Lecture 3
Fig. 3.3. Alkali non-solubility - viscosity relation, spruce sulfite

rayon pulps. Initial pH 7 in the continuous system.
hydrate reactions? The alpha-cellulose content, or rather the nonsolubilities in 18 and 10% NaOH, Rj 8 and Rj 0, showed a level about 3% too low
(Fig. 3.3). We eliminated a few obvious sources of mechanical damage to
the chips and had some improvements, but the larger part of the difference
remained. Could the very movement of the chips through the digester be
the cause of the damage? Then continuous sulfite cooking would be principally impossible.
At that time, the construction material of the high-pressure feeder had
now allowed us to run the feeding circulation on the acid side. Thus the
cooking liquor for the initial stage was kept at pH 7. We now began to
suspect that this deviation from normal cooking practice, 1.5 hr at 125C
and pH 7-6, though seemingly harmless, was the cause of our
troubles. This initiated a laboratory investigation, which led to the discovery that the glucomannan, for reasons then unknown, became resistant
to hydrolysis when we ran the upflow digester under neutral conditions. The desired improvement was obtained when pH was decreased to
37
VISCOSITY, cp(TAPPI)
Fig. 3.4. Alkali non-solubility - viscosity relation, spruce sulfite

rayon pulps. Initial pH 4 in the continuous system.
pH 4 in the precook (Fig. 3.4). After introduction of the complete cold
blow, we got a further improvement, which gave at last equivalent results
with batch cooking.
As" also shown in Fig. 3.4, an additional improvement in alpha-cellulose
content was obtained, after the reconstruction of the digester to the
"Mumin" version (Fig. 3.5) for other reasons, which I shall come back to.
In this system, the feeding remains the conventional one, and so does
the digester shell. What has been altered is the design of the digester
top. The internal top separator has been removed, and the new external
separator has been placed in an inverted and inclined position, with the
strainer at its lower end. The chips are moved upward by a screw and
discharged into the digester through an elbow. As the liquor level is
controlled at a point below the overflow, the chips are drained and do not
carry into the digester more liquor than that which has been absorbed by
the chips, unless the process requires more liquor to be introduced. In
that case there is also an overflow of liquor. Heating is conducted by
direct steam at the elbow. This means that the chips become uniformly
and almost individually heated. The chips are thus brought straight to
maximum temperature, and by introduction of liquid S0 2 at the digester
top, the desired acidity of the sulfite cook is also obtained, whereas the
38
Lecture 3
feed liquor contains the base and an amount of S0 2 corresponding to

bisulfite. The excess S0 2 is later recovered in the flash of the waste
liquor withdrawn from the digester and recirculated after liquification.
(I feel I must give a brief explanation of the nickname "Mumin." The
Kamyr men thus manifested the change of the profile of their digester
caused by the external top separator. A charming figure from a modern
Finnish fairy tale novel is a troll with a big nose, called Mumin. It is a
brief and practical name for the system, but unofficial, and will probably
disappear when the nose is eliminated. A somewhat less expensive construction can be expected if the inverted top separator is placed inside the
digester.)
The improvement in alpha-cellulose content achieved with this system
probably depends on the very short heating period (1.5 min) to maximum
temperature and full S0 2 concentration. This results in a rather rapid
hydrolytical degradation of the glucomannan before it becomes stabilized. The results are now somewhat better than can be obtained by
batch cooking with the heating periods of 3-5 hr necessary to get a uniform temperature distribution within the batch.
During the first stage of development, we also studied dissolving pulp
from birch in the continuous two-body digester. As in the case of spruce,
39
Fig. 3.6. Alkali non-solubilities and pentosan vs. viscosity for

birch sulfite rayon pulp cooked by batch, continuous two-body
and Mumin systems. AS-acid sulfite stage, BS-bisulfite, NS-neutral sulfite.
we got initially a much lower alpha-cellulose content than with batch

cooking (Fig. 3.6). As far as we knew then, this might have the same
cause as with spruce, since we ran the first stage at pH 7 and consequently
deacetylated the xylan, which could then have become less accessible to
hydrolysis. However, decrease in pH to 4 did not improve the results.
Some laboratory experiments indicated that the phenomenon instead had
something to do with the lifting circulation of the first stage. Some of the
xylan dissolved there could be adsorbed again when recirculating the liquor. This was confirmed by an increase in alpha-cellulose content when
decreasing the temperature of the precook to 110C and limiting the
lifting circulation to the bottom part of the upflow digester. Such measures were, however, limited by the demands of the upflow movement of
Table 3.1. Pulp Quality Obtained from Spru e, Birch, and Eucalypt Rayon Pulps by the Sulfite Process, Using Batch
and Continuous Cooking
the chips, which required a minimum length of the lifting zone and a
certain minimum temperature to make the chips soft enough to exert a
low friction against the digester walls. The final solution also here proved
to be the Mumin digester. Table 3.1 shows the results obtained by the
two-stage and the one-stage digester, as compared to batch mill scale and
laboratory scale cooks to the same viscosity, using spruce, birch, beech,
and eucalypt. It is quite evident that the final one-stage continuous cooking gave completely satisfactory results with all wood species, at least as
good as with batch cooking. It is also clearly demonstrated that experimenting with digester machinery often leads to theoretically unexpected
results because of deviations from batch cooking conditions. This, of
course, not only indicates troubles, but also possibilities.
Table 3.2 shows the cooking conditions. The most striking feature of
the successful one-stage cooking is the low liquor ratio, 2.2-2.5 (tons
liquor/tons o.d. wood). This includes chip moisture, steam condensate,
and seal water, as well as actual cooking liquor. Since the latter was only
about 1 ton/ton o.d. wood, and the charge of combined S0 2 about 40
kg/ton o.d. wood (or 4%), the concentration of the cooking liquor had to
be about 4% combined S0 2 . In a larger digester, the influence of seal
water from circulation pumps and other water-sealed shafts is less pronounced, and a somewhat larger volume of cooking liquor can be tolerated
yet to achieve such low liquor ratios. However, much higher concentrations of cooking liquor must be realized than the normal 1.2-1.3% combined S0 2 in batch cooking, where a large liquor volume is needed to
cover the chips. Soluble base is a prerequisite for a high concentration,
but then the concentration as such is no problem for either sodium or
magnesium base, as seen from the table. The design of the recovery system will, however, have to allow for this demand in order to realize the
possibilities of a better steam economy offered by continuous cooking.
42
Lecture 3
At this point we may enlarge on the differences between liquor-to-wood

ratio and degree of packing. I have found this a difficulty for most people
used to batch thinking. In a batch digester, the chips are packed with
suitable devices and then liquor is added into the digester to cover the
chips. Depending on the degree of packing, the wood density, etc., the
liquor ratio is about 4-5. In a continuous digester, there is about the same
degree of chip packing and consequently a similar liquor ratio when the
liquor has been introduced to cover the chips. However, in continuous
cooking this liquor ratio is not of the same interest as in batch cooking for
the steam consumption and waste liquor concentration. Instead, the liquor ratio of interest to continuous cooking is the flow ratio between
liquor and wood chips, and this is the ratio to be called liquor ratio in
continuous cooking. When this is 2.2, but the liquor ratio to cover the
chips in the digester is 4.4, this means that the linear flow of the chips
through the digester is about twice as fast as the linear flow of the liquor,
and that the retention time of the liquor is twice that of the chips.
The actual retention time and the actual degree of packing was determined by tracer experiments, as illustrated by Fig. 3.7. The two-body
digester thus gave a packing density of 0.18 tons o.d. wood/m3 digester
volume in the upflow and 0.19 in the downflow part, at spruce with a
wood density of 0.41. The downflow Mumin digester gave a slightly
higher degree of packing. From these direct determinations of retention
time at various zones of the digester, at a set chip flow, could be calculated
the approximate cooking time for other conditions. An indirect checkup could be made by determining the time required for chip filling of the
empty digester at an upstart. This time was invariably somewhat shorter
than the retention time for a chip at steady state, since the packing density
is always lower for uncooked chips than for semicooked ones. The difference is, however, usually surprisingly small, indicating that the wall
friction tends to prevent the additional packing made possible by the
softening of the chips. In a larger digester with a larger diameter, the
packing effect increases, but is still far from that corresponding to dissolution of wood substance.
Another striking feature is the very short impregnation periods, 1-2 min,
of the one-stage cooking, and yet the very satisfactory uniformity of the
pulp with low screenings and low lignin content at a certain viscosity
level. The impregnating liquor, at pH 5, penetrated the chips at a pressure
of about 7 atm, applied after 3 min of steaming. This is just the favorable
combination of steaming and pressure impregnation which has been found
particularly effective in the laboratory experiments previously
43
Fig. 3.7. Radioactive tracer experiment for the determination of

rentention time and packing density in the two-body digester system.
quoted. However, this is the first time that this impregnation system has
been proved in practical cooking and is now in production on a large mill
scale in Germany, using beech chips. After impregnation in the feeding
system, steam and S0 2 are directly introduced at the digester top. In
principle, this is the only heating necessary, but a circulation for an accurate adjustment of the cooking temperature is inserted a short distance
below the top. The accuracy of the cooking temperature should be better
than 0.5C. This demand was first scoffed at by our instrument people but
later on accepted. We could show, by means of accurate mercury thermometers inserted in specially devised pockets, that 0.2C can be felt and
correlated with small viscosity variations. Naturally, other variations also
occur, such as the base charge or the S0 2 charge, and these chemical flows
must be carefully controlled in relation to the chip flow. Measurement of
waste liquor color was also tried as an indication of the degree of cooking,
44
Lecture 3
Fig. 3.8. Viscosity variations during a 24-hour production of

rayon pulp from spruce, birch, and beech, Mumin system.
but with proper control of chip, steam, and chemicals flows, the frequency
of the viscosity variations was not higher than could be controlled by
direct viscosity analysis on the pulp. This is demonstrated in Fig. 3.8,
showing viscosity variations when cooking spruce, birch, and beech acid
sulfite rayon pulp in the Mumin digester system.
Of other quality data of Table 3.1, the favorably low contents of lignin
and extractives should be pointed out. Compared to the corresponding
batch pulps this means a decided saving in bleaching chemicals.
The efforts on the continuous cooking of acid sulfite paper pulp were
mainly concerned with the paper strength properties, after the initial cooking acid decomposition problems had been solved and the delignification
controlled by the same means as described for rayon pulp. The initial
trials showed a paper strength which was only half that of batch
pulps. This was a much more severe degradation than that experienced
for kraft pulp during the hot blow period. Considerable efforts were
made to locate the source of the damage by sampling from various levels
of the two-body digester and continuing the cook- on the laboratory scale,
followed by paper testing. This showed several degrading influences, commencing at the bottom screw of the upflow digester, when that ran heavily
loaded, continuing with a slight influence of the top scraper, and finally
severe,degradation by the discharge devices. Table 3.3 shows the paper
properties of pulps cooked to Roe No. 5 (lignin content 4-5%), using
bisulfite precook at 130C, followed by acid sulfite cooking at 135-140C
in the downflow digester body. The charge of combined S0 2 was 40-50
kg/ton o.d. wood (4-5%) and the excess S0 2 concentration in the cooking
liquor of the second stage 2.5-3.0%. It can be seen that by unloading the
bottom screw in the upflow digester through better lifting circulation and
introducing the cold blow (this was done at the same time as in the kraft
45
Table 3.3. Paper Properties of Spruce Acid Sulfite Pulp, Two-body Pilot Digester
Process: Bisulfite-acid sulfite, combined SO 2 charge 4.5%
of o.d. wood, pulp Roe No. 5.0.
industry) most of the degradation was eliminated and a pulp of decent

strength obtained. In fact, the pulp was somewhat better than the corresponding mill scale batch pulp, but not quite up to laboratory standard. It was concluded that the two-body digester contained too many
dangers to the acid sulfite paper pulp quality to be a safe unit for production.
After the reconstruction of the digester to the Mumin downflow system,
interest was focused on straight bisulfite cooking for paper pulp, as will be
described in the following lecture. However, two processes with an acid
cooking stage were tried, namely, neutral sulfiteacid sulfite and alkaliacid
sulfite cooking. Both two-stage cooking processes can be used for obtaining an increased carbohydrate yield through deacetylation and stabilization of the glucomannan prior to the acid sulfite cook. Figs. 3.9 and 3.10
show the systems used to produce this effect. In the first case, the chips
were introduced with neutral sulfite cooking liquor of pH 7, and steam
added at the digester top to give 155C for 2 hr precook, followed by
acidification withjiquid S0 2 for an acid sulfite cook at 142C for 1.5
hr. This two-stage cook was tried with both spruce and pine, yielding
acceptably low rejects, high brightness, and the desired glucomannan stabilization (Table 3.4). These trials are also interesting from the standpoint that there was no problem in maintaining the two cooking stages
sufficiently well-defined in the downflow one-body digester, provided the
temperature of the upper zone was kept higher than that of the acid
Fig. 3.9.
Kamyr digester with inclined top separator used for

two-stage neutral sulfite - acid sulfite pulping.
Fig. 3.10. Kamyr digester with inclined top separator used for two-stage
alkali - acid sulfite cooking.
Lecture 3
Table. 3.4. Two-stage Neutral Sulfite-Acid Sulfite Pulping
of Spruce and Pine in Mumin Pilot Digester
Digester Pressure: 10 atm.
cooking. If a considerable temperature gradient was attempted, with

10-20C lower temperature in the top, a gradual transition of the hotter
zone toward the top was experienced through convection along the walls
and a consequent acidulation of the top zone.
The second system made use of our observation on the laboratory scale
that deacetylation of the glucomannan can be achieved rapidly and at
fairly low temperature, provided that the pH is high enough. This makes
it possible to use sodium hydroxide or sodium carbonate as the feed
liquor, in an amount corresponding to the normal quantity of base, 40-50
kg/ton o.d. wood (4-5%), calculated as combined S0 2 . In one case only
sodium hydroxide was introduced, in the other sodium hydroxide in mixture with sodium sulfite. In equilibrium with S0 2 absorbed from the
digester top to the feeding circulation, this gave liquors containing, respectively, 20 and 70 molar percent of sodium sulfite and a pH greater than
13. After impregnation in this liquor for 1.5 min, the chips arrived at the
digester top to meet steam and S0 2 to full cooking conditions directly.
These are described in Table 3.5 together with the results of the pulp-
Table 3.5. Two-stage Alkali-Acid Sulfite Pulping of Spruce in Mumin Pilot Digester
Digester Pressure: 9 atm. Estimated yield improvement
over acid sulfite 4%, wood basis.
ing. It is seen that also in this case the screenings were very low and the
major part of the glucomannan stabilization obtained. This elegant process requires a recovery system that yields carbonate with some sulfite, but
simplifies the cooking liquor preparation very much.
From an operational point of view, both these two-stage cooks were thus
successful. The quality obtained was also entirely satisfactory, equal to
that of laboratory pulps, as shown in Table 3.6. There is every reason to
believe that a straight acid sulfite cooking without glucomannan stabilization would lead to laboratory quality also, although this was not
tried. Thus, the Mumin version of the continuous digester appears to have
eliminated the remaining slight disadvantages of the two-body digester as
regards acid sulfite paper pulp quality, which rounds off our development
work on continuous acid sulfite pulping very nicely. The system is good
for both rayon and paper grades, for both straight one-stage and two-stage
pulping.
Lecture 4

If the sulfite process is to have a future, three major improvements must
be accomplished: all species must be pulpable, the yield must be improved,
and the strength properties must be improved. Two-stage pulping with a
neutral or alkaline precook may be the answer to the first two demands,
but certainly not to the demand for strength, which is rather decreased
than improved. The bisulfite process allows the pulping of all wood
species and gives a definite strength improvement over acid sulfite pulping. It does not improve the carbohydrate yield, but the higher strength
at equal lignin content can be utilized for pulping to higher lignin contents. Then the strength improvement disappears, but instead a substantial yield improvement is achieved. Two bisulfite pulp types are therefore
of interest, namely a chemical bisulfite pulp for bleaching, of normal yield
and higher strength, and a semichemical bisulfite pulp of 65-75% yield,
with the strength of a chemical acid sulfite pulp. The semichemical bisulfite pulp cannot be economically bleached to high brightness because of its
high lignin content, but it is important to obtain the highest possible
brightness of the unbleached pulp, and it might also in some cases be of
interest to brighten the pulp with dithionite or similar brightening
agents. This pulp type is increasingly used as the long-fibered component
in newsprint and some magazine grades, and holds good possibilities for
use in various types of board.
The efforts to produce these pulps by continuous cooking started in the
two-body digester. From several aspects, bisulfite cooking is a very simple
and straightforward process, which ought to be quite suitable for the
trimming of a new digester system. That is at least what we thought when
starting the trials in 1956-57. There is little or no excess S0 2 and hence
no charging problems with liquid S0 2 and little gas problems. There is
just one charge of chemicals, and heating to maximum temperature can be
made as fast as desired.
Yet we learned very quickly that the process was not a very easy one.
The dominant problem was that of cooking acid stability. A disturbance in
the process, such as a temporary stop for clearing a discharge problem, and
51
52
Lecture 4
soon the liquor color started to darken, thiosulfate concentration to rise,

and the pulp to become discolored and shivy. The disease always spread
from the bottom of the downflow digester, where the thiosulfate content
is always the highest, but soon reached the cooking zone. Then the
situation was normally out of hand, the chips became umpulpable even
with fresh cooking acid,, and the digester content had to be dumped for a
fresh start after thorough cleaning.
This was the typical result of the autocatalytic decomposition of bisulfite ions to thiosulfate and sulfate, which was mentioned previously in the
lecture on sulfite process theory. The thiosulfate always formed in side
reactions is not sufficiently reactive with the lignin at pH 4-5 to become
"neutralized," but takes instead full part in the further decomposition of
bisulfite ions at an ever-increasing rate. The question was only: why does
it seem to be impossible to run a continuous digester on bisulfite, when it
is quite feasible to do it batch-wise? Batch bisulfite cooking is capable of
yielding chemical bisulfite pulps down to a lignin content of 4-5%; if
continued further, the decomposition reaction takes over and will cause
discoloration also of the batch pulp. Thus, thiosulfate does form also in
the batch bisulfite cook, but the difference is that batch pulping does not
allow the spreading of the cooking liquor disease backward in time; continuous pulping allows this phenomenon to spread to the simultaneously
present initial phase of the cooking. In a batch cook, the thiosulfate concentration is 0.5 grams/liter in the beginning of the cook at maximum
temperature and 2.5 grams/liter toward the end. We had 1.5 and 4
grams/liter, respectively, at the corresponding places of the digester before
complete collapse occurred.
At that point we could not be certain that continuous bisulfite pulping
was even principally possible, but we at least knew what to look out for:
places and opportunities for thiosulfate to form unnecessarily. We found
several such places-partially blindfolded strainers, behind which the cooking liquor had access, could decompose without contact with the chips and
ooze out thiosulfate to poison the cook. Furthermore, since we ran the
digester at hydraulic pressure, the volumes of cooking liquor were too
large at the top of the two-body digester, which did not contain any chips
and thus only served to prolong the retention of the liquor at full temperature. Finally, there were the cooking liquor circulations, which at least in
the pilot digester tended to give excessive mixing of cooking liquor in
various parts of the digester, as we could verify not only by thiosulfate
analyses but also with injections of radioactive sodium carbonate solutions
in the various circulations.
With the two-body digester, it was therefore found almost impossible to
Fig. 4.1. One-body pilot plant digester for bisulfite cooking,

produce the bleachable bisulfite grade of pulp at a steady state. Increasing the liquor ratio helped to keep the system clean for short periods of
time, during which pulp sampling for quality control was possible. Limiting the delignification to high yield pulps of a lignin content of 10-13%,
yields around 60%, or to semichemical pulp in the 65-90% yield range,
gave production at steady-state conditions.
This allowed us to study the quality of the various bisulfite pulps (Tables
4.1 and 4.2). We found, as expected, that the cold blow is important also
for bisulfite pulp quality, although perhaps not to the same extent as with
acid sulfite pulp. With the cold blow, some pulps, especially at the intermediate or highest yields, were almost up to the standard of laboratory
pulps. With that background two mills chose continuous digesters for
their bisulfite pulping, one in Switzerland and one in Canada, yet of the
standard, downflow type.
We felt, however, that this result of the development work was not
entirely satisfactory. The pilot digester was reconstructed to a long,
downflow digester, equipped for both concurrent and countercurrent
cooking, in which the bisulfite cooking experiments continued (Fig. 4.1).
In this system, the mixing action of the lifting circulation in the former
digester was eliminated. Unfortunately, the troubles of cooking acid
decomposition continued, when cooking down to yields of bleachable
bisulfite pulp. The digester was then run like a kraft digester, with a
Lecture 4
54
Table 4.1. Spruce Bisulfite Pulps of the Two-body Pilot Digester

Analytical data. Cooking conditions: 160-165 C, 4 hr, 8-10% combined S 0 2 ,
wood basis, initial pH 4.5.
Table 4.2. Spruce Bisulfite Pulps of the Two-body Pilot Digester

Paper properties. Cooking conditions of Table 4.1.
Discharge temperature, C
Roe chlorine No.
Paper properties at 45 SR
Beating time, min
Tensile strength, km
Tear factor
125
50
10
22
10.1
64
25
8.8
62
11
24
10.4
65
7
28
9.0
73
moderate-temperature zone followed by a heating circulation to give the

maximum temperature, 160-170C, of the cooking zone, prior to a
countercurrent washing. The decomposition tendencies were probablyconnected with excessive mixing of the liquor from various parts of the
digester. This was partly caused by the circulations and partly by migration of hot liquor from the cooking zone along the walls to the upper,
low-temperature part of the digester. The mixing and migration was also
directly demonstrated by injection of radioactive bromide to the circulations. The effect is probably less pronounced in the large mill-scale digesters, but the development work on continuous bisulfite cooking could not
be regarded as finished to satisfaction.
A fresh approach was possible after the development of the Mumin
digester system (Figs. 4.2 and 4.3). With that system, the temperature
gradient at the upper part of the digester was eliminated, and likewise the
mixing action of the heating circulation, provided the chip impregnation in
the feeding system could be regarded as satisfactory. To eliminate any
55
possibility of liquor mixing, we started the cooking trials with a vapor

phase down to the washing zone. This immediately gave what we wanted,
a steady-state production of bleachable bisulfite pulp. However, at least
on the pilot digester scale, the packing of the semicooked chips and the
pulp became excessive in the vapor phase and tended to give hangings of
the chip column in the digester, a phenomenon normally only encountered
in exceptional cases of overcooking, etc. Therefore, the liquor level was
raised to that of the chips, which resulted in a steady movement of the
chip column and maintained steady cooking conditions without decomposition tendencies of the cooking liquor. This allowed the production of
bleachable bisulfite pulp down to lignin contents of 4-5%, at liquor ratios
similar to those of batch cooking, or lower, 3.5-4.5. That the liquor ratio
is important even in the Mumin system, when cooking bleachable bisulfite
pulp, was shown by decreasing the liquor ratio down to 2.5, at which the
decomposition reactions tended to get out of hand. With high-yield
chemical and with semichemical pulping, there were no such trends even at
the lowest liquor ratio.
The most sensitive indication of the absence or presence of undesirable
liquor decomposition is given by the pulp color. Figure 4.4 shows the
brightness of unbleached bisulfite pulp at various yields. The batch curve
shows a rise in brightness when cooking to increasingly lower yield, until
at around Roe No. 5-6 the brightness starts to drop sharply. The brightness of the pulp from the conventional downflow digester was better than
batch in the higher-yield region, but tended to get lower as the cooking
approached the chemical pulp yields. With the Mumin digester system, a
stable pulp color was maintained down to the bleachable yields. The
brightness level was high throughout the yield region and exceptionally
high for green sprucewood, where it reached the 70-75% brightness level.
The unorthodox system of instant heating of the bisulfite cook to maximum temperature had been tried already in the two-body digester, without excessive screenings as a result.
The question of whether the impregnation of the chips in the Mumin
feeding system would be adequate or not is best answered by giving the
screenings for chemical grade bisulfite pulp from spruce, pine, and
birch. Table 4.3 shows those figures, together with the cooking conditions and other pulp data. The uniformity of cooking is obviously entirely satisfactory for spruce, and as good for pine and birch as is normally
achieved in batch pulping of those species. The screenings did not contain
uncooked or burned chips but mainly easily fiberized fiber bundles. The
unusual brightness has already been commented on, and the remaining
pulp data are quite normal.
Fig. 4.3.
Schematic comparison between the feeding principles of

conventional and Mumin feeding systems.
58
Lecture 4
10
15
ROE NUMBER
20
25
Fig. 4.4. Brightness of spruce bisulfite pulps from various

types of cooking.
The difficulties of obtaining a bisulfite pulp with strength properties
comparable to those of laboratory cooking were mentioned in connection
with the pulps from the two-body digester. It was suspected, that part of
those difficulties were connected with the tendencies for cooking liquor
decomposition. Table 4.4 shows the strength properties of chemical bisulfite pulp cooked from spruce in the Mumin system at varying liquor
ratios. It appears that a decrease in the liquor ratio will lower the pulp
quality, as it tended to decrease the pulp brightness. Table 4.5 shows the
strength properties of spruce bisulfite pulps cooked to three yield levels in
the Mumin digester system, as compared to laboratory pulps. The laboratory pulps are a shade stronger throughout, but it can be said with some
conviction that the bisulfite pulps from the Mumin digester are at least as
good as any batch bisulfite pulp produced on the mill scale.
The above results were obtained with sodium bisulfite. Magnesium bi-

Table 4.3. Bisulfite Pulping in the Mumin Pilot Digester
Conditions and results. Digester pressure 10 atm.

Paper properties of chemical bisulfite pulps from spruce at varying liquor
ratio. Roe chlorine No. 6.5.
60
Lecture 4
Paper properties at three yield levels as compared to laboratory pulps.
Pulp
yield,
%
53
58
75
Scale
Beating
time,
min
Lab.
Pilot
Lab.
Pilot
Lab.
Pilot
13
14
15
16
33
19
Lab.
Pilot
Lab.
Pilot
Lab.
Pilot
26
27
27
29
49
28
Tensile
strength,
km
Tear
factor
8.7
109
8.5
100
9.8
100
8.9
103
8.8
80
8.8
73
Sheet
density
0.67
0.68
0.66
0.66
0.64
0.61
53
58
75
9.8
9.4
10.5
9.8
10.0
9.9
98
88
86
85
66
62
0.74
0.76
0.75
0.74
0.64
0.68
sulfite was also tried at the intermediate yield level and found to perform
equally good as sodium bisulfite.
The one-body downflow digester allowed countercurrent cooking operation. However, with bisulfite it is not surprising to find that countercurrent operation resulted in rapid cooking liquor decomposition. More
interesting results with countercurrent operation were obtained with
prehydrolysis-kraft and kraft pulping, which will be described later on.
In order to achieve additional brightness with a chemical bisulfite pulp
of 70% brightness, dithionite was added to the washing zone and the pulp
thus subjected to a brightening action at 130C. The result was disappointing, since the brightness improvement was less than with dithionite
at a subsequent conventional brightening stage. The idea of using the
washing zone for brightening is, however, tempting, and might work out
better after a more systematic effort made on a laboratory scale prior to
mill scale trials.
One remaining doubt regarding the sufficiency of the short impregnation
period, when using sprucewood with excessive heartwood content, initiated further trials. It was found that such wood from northern Sweden
gave on cooking somewhat discolored centers in about 2% of the chips, as
compared to none with spruce from central Sweden. The brightness of
61
Table 4.6. Cooking Conditions, Analytical Data and Paper Properties of Spruce
Bisulfite Semichemical Pulps for Newsprint, Produced in the Mumin Pilot
Digester, Without and With Pressure Preimpregnation at HO^C. Sodium Base
Mumin system
High-pressure
preimpr.
Mumin system
Mumin impregnation
Retention time, hr
Impregnation
Cooking
Temperature, C
Pressure, atm
Liquor ratio, m /ton
o.d.wood
Total S 0 2 , % on wood
Combined S0 2 ,% on wood
Initial pH
Roe chlorine No.
Brightness, % SCAN'
Resin content, %
Carbohydrate analysis, %
Galactose
Glucose
Mannose
Arabinose
Xylose
Cellulose content, % on
carbohydr.
Estimated pulp yield,
% on wood
Beating time, min
Tear factor
Sheet density, g/cm3
Beating time, min
Tear factor
0.02
0.83
169
9.2
0.02
2.00
160
9.2
0.02
3.50
152
7.4
0.02
4.85
145
8.0
1.40
2.00
156
8.9
3.0
17.0
8.5
4.4
24.2
64.4
1.1
3.0
16.6
8.3
4.4
23.6
62.4
1.0
3.5
16.4
8.2
4.5
24.3
60.9
...
3.4
17.0
8.5
4.6
23.5
62.1
...
3.0
16.0
8.0
4.3
22.7
65.7
1.2
1.4
76.2
14.8
...
7.6
1.2
77.6
14.0
...
7.2
1.1
81.0
11.9
...
6.2
1.0
79.0
12.7
...
7.4
1.0
78.4
13.2
...
7.4
71
73
77
74
72
77
75
72
74
76
24
8.6
73
0.57
16
8.6
76
0.59
21
8.9
74
0.63
21
8.3
72
0.56
32 1
9.1
70
0.63
35
9.5
62
0.66
23
9.4
64
0.68
30
9.7
67
0.70
33
9.4
60
0.65
47 1
10.2
59
0.74
Testing at a different laboratory, giving denser sheets. Same tensile-tear relation.
62
Lecture 4
the refined pulp was virtually unaffected by this phenomenon, and the
only conceivable disadvantage would show up in a slightly higher shive
content. Some trials with a preimpregnation vessel for high-pressure
impregnation {cf. Lecture 9) prior to cooking (Table 4.6), indicated
possibly an improvement, although the differences were fairly hard to
detect, and a comparison with batch pulp of the same type gave better
brightness and uniformity for the continuously cooked pulp. The table is
of interest mainly to show that the cooking time and temperature can be
varied considerably without quality problems. This indicates the
flexibility in capacity of a system chosen initially for a retention time, for
example, of 2 hi.
To sum up the development efforts on continuous bisulfite pulping, it
might be said that the Mumin digester system appears to allow bisulfite
pulping at all yield levels with satisfactory result from both an operational
and a quality standpoint.
Lecture 5
Continuous Neutral Sulfite Cooking

When discussing the previous cooking processes, acid sulfite, two-stage
sulfite, and bisulfite cooking, as well as the subsequent ones, prehydrolysis-kraft, kraft, and modified kraft cooking, there is no need to compare
the Kamyr digester system with other designs, since attempts to present
similar machinery by others have been few or none at all. With neutral
sulfite cooking, the situation is rather the reverse. In particular Pandia,
Defibrator, and M & D units have given satisfactory production of neutral
sulfite pulp for many years. Of Kamyr units, only two were in operation
in earlier years (on hardwoods), namely ours at Saffle and another unit in
Great Britain. These two units have, furthermore, produced a somewhat
different pulp, neutral sulfite for full bleaching to be used in white papers,
whereas most of the others produced unbleached neutral sulfite pulp for
corrugating medium. An Impco digester in the United States has also
been used for neutral sulfite pulp for bleaching. Later on, a few NSSC
digesters for corrugating medium were delivered by Kamyr to Yugoslavia,
Australia, and Poland. They were all of the conventional design.
I do not intend to compare the virtues of the various types of neutral
sulfite digesters, since my experience with the other designs is limited to
mill visits. I shall only describe our reasoning when choosing the Kamyr
version for Saffle and our purpose for the development work on the new
type of Kamyr neutral sulfite digester for corrugating medium at Gruvon.
The neutral sulfite pulps are mainly produced from hardwoods, and are
all semichemical. By using the mild chemical conditions of the neutral
sulfite process and by limiting the delignification, the xylan of the hardwoods is quite well preserved in the pulps. This gives the corresponding
corrugating medium board the desired stiff structure, and the bleached
neutral sulfite pulp grade becomes very easy-beating and suitable for dense
papers, such as greaseproof and glassine.
The cooking liquor is generally prepared from sodium carbonate, which
is then reacted with S0 2 to give sodium sulfite with an excess of buffer in
bicarbonate form. This gives a pH of about 8.5, and the function of the
cooking liquor is partly to maintain pH above 6, and partly to sulfonate
63
Fig. 5.1. Schematic diagram of the first NSSC continuous cooking system
at Billerud: (1) digester; (2) discharge pipe; (3) Asplund Defibrator; (3a)
blow valve; (4) blow tank; (5) Davenport press; (6) Sprout-Waldron refiner; (7) to screening.
the lignin. The buffer, 25-33% of the original carbonate, has mainly to
take care of the uronic acid and acetyl groups of the xylan to give uronic
acid sodium salt and sodium acetate, under formation of carbon dioxide. The total quantity of sodium carbonate charged is about 160 kg/ton
o.d. wood (16%) when cooking to bleachable grades of 70-75% yield, and
110 kg/ton (11%) when cooking to corrugating medium grade of 77-83%
yield. The cooking temperatures used vary between 160 and 190C and
the cooking time is adjusted according to the temperature used and the
yield desired. It thus varies between 15 min and several hours.
Our reason for choosing the Kamyr system for Saffle was that we desired
maximum uniformity of cooking for the bleachable pulp grade. We did
not feel convinced that the other systems would give an acceptable impregnation because of short heating periods to maximum temperature and
sometimes rather primitive methods of adding the liquor to the chips. Today, we know we were wrong about the heating period required for uniform cooking, but we might still have made the best choice from an
impregnation point of view.
The system chosen was the standard kraft digester, although with a shell
lined with stainless steel and some auxiliary machinery attached (Fig.
5.1). Thus, before the blow valve and the disk strainer of the bottom
circulation, a Defibrator was inserted, to fiberize the semicooked chips
65
Fig._5.2. The effect of temperature on the tensile strength of (7) waterswollen sprucewood, (2) birchwood, and (.?) neutralisulfite-cooked birchwood, 75% yield.
before blowing. The blow tank did not contain the conventional impeller
at the bottom, but instead a low-pressure feeder to handle even very coarse
material. The pulp was then to be discharged to a Davenport press prior
to refining in a Sprout-Waldron 36-2 precision refiner. The intention with
the Defibrator was partly to facilitate the blowing and subsequent handling of the semicooked material, partly to save refining energy, and possibly to improve quality. Refining at high temperature of uncooked
chips, as practiced in the Defibrator process, gives a less damaged fiber
than groundwood and at a much lower power consumption, since the
fiberizing is done above 170C, in the temperature of plastic flow of the
lignin (Fig. 5.2).
One immediate experience with the system was that the bicarbonate
buffer had to be abandoned and substituted with the more expensive
66
Lecture 5
sodium hydroxide. The carbon dioxide evolved from the bicarbonate

gave rise to troubles in the upper part of the hydraulic digester and in the
high-pressure feeder. The migration of gas bubbles to the top accentuated
the thermal flow, which gave excessive temperatures in the feeding circulation and steam hammering in the feeder. The hammering was accentuated
by the presence of carbon dioxide gas bubbles.
With sodium hydroxide buffer, the system worked quite well mechanically, but gave a pulp quality much lower than that of the previous laboratory cooks. The pulp quality was then measured both on the unbleached
pulp and after a standard bleaching procedure. This quality experience
came in 1957, contemporaneously with the experience on kraft pulp quality in Gruvon and just prior to the quality efforts on acid sulfite pulp in.
Jossefors. Thus, it was natural to look for degradation in combination
with mechanical action, particularly from the digester arrangement.
Perhaps the high-temperature fiberizing, in spite of giving a seemingly
undamaged fiber in the Defibrator process, led to a quality degradation in
combination with a chemical cooking, even the very mild one of the
neutral sulfite process. The first attempt was therefore to make the fiberizing coarser. Table 5.1 shows that increasing plate setting of the Defibrator from 0.3 to 2.0 or 5.0 mm only slightly improved the quality of the
bleached pulp. Then, with the Defibrator maintained open, the effect of
the temperature was investigated by charging varying amounts of cold
water to the bottom circulation (Table 5.2). Cooling down to 110C gave
the desired considerable quality improvement on bleached pulp, as also
shown in Fig. 5.3. In order to show whether that improvement corresponded to undamaged pulp, a new series of runs were made, with sampling both at the digester bottom and after the fiberizing and discharge.
The plate setting of the Defibrator was varied at the extreme temperature
levels. The results are shown in Table 5.3, with the strength properties of
bleached pulps. The strength of unbleached pulps gave analogous results,
showing that the quality decrease of fiberizing and discharge was substantial at 160C, more with a tight plate setting, but intolerable with an
open Defibrator. At 110C the quality damage was eliminated whether
the Defibrator was open or tightly set. Table 5.4 shows the analytical
composition of the unbleached and bleached pulps. No differences in the
composition of these pulps with such widely differing strength properties
could be detected; hence it must be concluded that the damage of the hot
blow is not connected with a dissolution of material, but rather with a
local damage of the cellulose in the fiber wall. This may well be a combination of mechanical and chemical degradation, but with the chemical
action not detectable by carbohydrate analysis.

Table 5.1. Effect of Refiner Plate Setting on Quality of Bleached Neutral Sulfite
Semichemical Pulp from the Saffle Digester. Refining Temperature 167C
Paper properties at "greaseproof density'
Refiner
plate setting,
mm
Beating
time,
mm
Tensile
strength,
km
Tear
factor
Sheet
density
Slowness,
SR
0.3
2.0
5.0
Batch cooked and
refined at low
temperature
19
21
15
7.9
8.2
8.2
48
46
48
0.98
0.98
0.99
73
69
74
15
10.0
60
62
Table 5.2. Effect of Refining Temperature on Quality of Bleached Neutral Sulfite

Semichemical Pulp from the Saffle Digester.
Refiner Plate Setting 5.0 mm (wide open)
Paper properties at "greaseproof density"
Refining
temperature,
C
162
130
120
110
Batch cooked and
refined at low
temperature
Beating
time,
mm
Tensile
strength,
km
Tear
factor
15
15
23
13
8.2
8.8
9.2
10.0
48
51
55
61
15
10.0
60
Sheet
Slowdensity ness, SR
0.99
0.99
0.97
74
68
61
61
62
Table 5.3 also contains information on the CMT value of the unbleached
pulps. This value indicates the corrugating medium properties. The results are somewhat bewildering, since they indicate more damage at 110C
than at 160C. The average indicates some 10% quality decrease from the
fiberizing and discharge equipment, as compared to fiberizing at low temperature in the laboratory of samples removed from the digester bottom.
After these experiences it could be concluded that continuous cooking
of bleachable neutral sulfite pulp from birch is feasible in the normal
Kamyr kraft system, and that a good quality can be obtained if the discharge is made at 110C or lower. The Defibrator was removed from the
pressure system and the fiberizing done entirely with the Sprout-Waldron
refiner at 60-80C. Following this experience the British digester was
68
Lecture 5
VALLEY BEATING TO
45 SR SLOWNESS
10 cm 3 /sec POROSITY
DEFIBRATOR PLATE SETTING, mm
Fig. 5.3. Effect of refining temperature on quality of bleached pulp.

Refiner plate setting 5.0 mm.
also designed and started. The disadvantage of omitting the bicarbonate
as buffer remained for this hydraulic digester system, but was accepted at
Saffie and presented no problem with the British mill, where the cooking
liquor was made up from byproduct sodium sulfite entirely.
The problem of cooking corrugating medium grade pulp could be solved
with the same system. However, with that grade, bicarbonate-buffered
cooking must be feasible to get maximal economy, and further, it was an
open question whether the Kamyr system was competitive with the other
continuous digesters, with regard to investment costs. However, just as
with kraft cooking, it is desirable to develop machinery for the very large
production units. Until recently, the largest unit for the production of
corrugating medium board pulp was about 150-200 tons/day, either limiting the board production correspondingly, or necessitating 2 to 3 pulping
lines for one fairly large board machine. We regarded the Kamyr digester
to hold the "best possibilities for large-scale production, provided the sys-
69
Table 5.3. Effect of Refining Temperature and Plate Setting on Quality of Neutral
Sulfite Semichemical Pulp from the Saffle Digester
Paper properties at
"greaseproof density," bl.
Refining
temp.,
C
110
Refiner
plate setting, mm
0.3
5.0
130
160
5.0
5.0
0.3
SamCMT of Beating
pling at unbl. pulp, time,
discharge
lb
min
Before
After
Before
After
Before
After
Before
After
After
65
60
63
(54)
68
64
59
58
...
9
9
11
12
9
9
9
10
19
Tensile
strength,
km
Tear
factor
9.5
9.7
9.7
9.7
9.2
9.3
9.3
8.6
7.9
62
60
60
62
64
58
59
53
48
tem could be adapted to the demands of the bicarbonate-buffered neutral

sulfite process. The possibilities of digester washing were a further plus
for the system, with the increasing demands to minimize stream pollution. There was, however, no experience on whether digester washing
could be applied with any material effect on semicooked chips in this
high-yield range.
The development work on corrugating medium grade of birch neutral
sulfite pulp started after the reconstruction of the pilot digester to the
Mumin system, with all the experience of the prehydrolysis-kraft, bisulfite,
and acid sulfite cooking behind. We therefore knew that the system
would be able to run continuously with a suitable C0 2 relief and had
every chance to run well on bicarbonate-buffered neutral sulfite. It was
thus rather quick development work. We tried vapor phase as well as
liquor phase and found no particular advantage of running a vapor-phase
cook, but possibly somewhat less, uniform pulp. All further development
work thus concentrated on liquor-phase cooking. Sodium-based cooking
as well as ammonia-buffered ammonium sulfite was tried, with practically
the same results. Laboratory trials in connection with bleachable grades
had already shown that ammonia base was quite feasible, though yielding a
darker pulp with very slightly inferior yield and strength properties. Three different yield levels were chosen for the sodium-based cooking, which were, as nearly as could be determined, 78, 80, and 82%. The
cooking conditions and the analytical data of the corresponding pulps are
Table 5.4. Analytical Composition of Neutral Sulfite Semichemical Pulp from the Saffle Digester;
Varied Refining Temperature and Plate Setting
Refining
temp.,
C
130
160
Pentosan Anatytical composition of

content,
pulp carbohydrates, %
Refiner Sampling
plate setat disting, mm charge
Before
After
Before
After
Before
After
Before
After
%
85.4
82.5
85.8
85.9
84.8
85.2
84.7
85.7
79.2
74.4
80.6
79.7
79.4
79.2
78.2
80.5
24.4
23.6
23.1
24.8
23.8
24.4
23.4
22.6
Glucose
68.5
66.4
71.0
69.8
70.8
69.9
69.2
69.4
Mannose Xylose
28.0
30.3
27.5
28.4
25.7
27.5
28.4
28.0
Analytical composition
of fraction soluble
in 10% NaOH, %
Glucose
Mannose Xylose
90.6
89.0
71
Table 5.5. Cooking Conditions, Analytical Data and Paper Properties of NSSC Birch
Pulps for Corrugating Medium Board, Produced in the Mumin Pilot Digester and in
the Laboratory
Laboratory pulps
Yield level, % on wood
Retention time, hr
Impregnation
Cooking
Temperature, C
Liquor ratio, m /ton wood
Cooking chemicals charged
Na 2 C0 3 , % on wood
S02,%onwood
Final pH
Roe chlorine No.
Brightness, % SCAN
Resin content, %
Galactose
Glucose
Mannose
Arabinose
Xylose
Beating time, min
Tear factor
CMT at 127 g/m 2 , lb
Beating time, min
Tear factor
CMT at 127 g/m 2 , lb
Pilot plant pulps

78 1
82
78
72
2.0
1.5
153
4
2.0
3.7
153
4
2.0
4.0
160
4
0.02 0.02 0.02 0.02

1.75 1.75 1.75 1.75
155 160 160 165
1.7
1.8 2.0 1.8
120
48
6.5
19.3
48.1
0.64
120
48
6.1
18.9
47.1
0.81
120
48
6.4
16.9
46.4
0.94
110 103 103 116

44
46
40
40
6.6
6.3 6.6 6.5
19.9 19.6 19.0 18.6
53.5 50.2 49.0 46.6
0.76 0.81 0.90 1.00
67.8
2.2
68.7
3.2
71.1
1.9
30.1
28.1
27.1
0.6
69.4 69.2 68.8 70.3
3.6 5.2 2.2
3.2
0.4
27.5 27.3 25.4 27.5
15
4.4
61
0.51
37
8
4.9
65
0.56
38
12
6.2
70
0.63
39
6
1
4
7
4.9
5.4 5.3 6.0
73
77
80
70
0.52. 0.58 0.54 0.61
38
36
40
42
27
6.0
54
0.62
47
14
6.4
57
0.65
48
20
7.8
62
0.73
49
12
6
9
12
6.9
7.4 7.3 7.6
60
66
71
69
0.62 0.66 0.64 0.70
48
46
48 48
82
80
76
Vapor phase cooking.

shown in Table 5.5. They show that the pulps obtained corresponded to
laboratory quahty in every respect, and that they were obtained with a
minimum of cooking chemicals and a favorable liquor ratio.
The recovery of the waste liquor will be described in a subsequent lecture on washing. The pulp produced in the pilot digester was taken to
two paper-machine trials. One was with the experimental wet end of
Fig. 5.4.
NSSC pulping at Billeruds fluting mill of Gruvon.
Table 5.6. Corrugating Medium Board, Produced out of NSSC Birch Pulp from the
Mumin Pilot Digester, as Well as from a Full-Scale Mumin Digester and from a
Conventional Multiscrew NSSC Digester.
Pine Kraft Addition to the Furnish 15% or Less
Pilot
Mumin
Pulp yield level, %
Slowness of furnish at
headbox, SR
Basis weight, g/m2
MD
CD
Elongation to break, %
MD
CD
CMT, kp
MD
CD
82
Commercial
Mumin
84
Commercial
multiscrew
83
38
126
0.69
35
127
0.59
127
0.57
7.7
4.2
8.8
3.8
7.9
4.0
1.8
4.6
2.1
2.6
2.2
2.7
28
17
31
15
25
73
KMW, where it was run at the maximal speed of 600 m/min without
wet-web breaks, with 15% pine kraft, and at 550 m/min with no addition
of long-fibered pulp. The other trial was at the experimental paper machine of PCL (Central Laboratory of the Swedish Paper Industry) at
Stockholm, where the pulp was run at moderate speed, but instead a
finished corrugating medium was produced. The test results of this board
are shown in Table 5.6 together with an average of mill-scale produced
Scandinavian corrugating medium boards. The board was further run on
the experimental corrugator of CL (Central Laboratory of the Finnish
Pulp and Paper Industry) at Helsinki. There it showed no breaks up to
the maximal speed of the corrugator, 300 m/min, and goQd glueability
over the entire practical speed range.
To judge from the experimental pulping, papermaking, and converting
data, the Mumin digester system produced an excellent corrugating medium board grade. This, together with the satisfactory washing results, contributed to our decision to order a digester for Gruvon, for a corrugating
medium board line which is the largest in the world so far. The design of
the system, which will have an ultimate capacity of about 600 tons/day, is
shown in Fig. 5.4. The Mumin digester is attached to a blow tank in the
form of a live-bottom bin to allow a reliable feeding of the refiners and
some drainage after the digester washing. This will, so far, at 300-400
tons/day, be the entire washing system, with high-density pumps after the
refiners directly feeding the thick stock buffer tower with no intermediate
washing or screening. Ultimately, with the increased cooking capacity, a
pressing stage can be included prior to the refiners to complete the washing. We also considered omitting the live-bottom bin and feeding the
refiners directly from the digester blow cyclones, then passing the stock
through a continuous diffuser prior to the buffer storage towers. This
may be the most elegant solution but it was not sufficiently developed at
the stage of decision for us. As shown by Table 5.6, the quality experience of the pilot digester and experimental paper machine has been verified on the large scale.
It remains to be added that an equally large digester has been ordered for
Japan for the same purpose, and a smaller one for Sweden. It should also
be added, that there is now also one large Defibrator digester unit coming
into operation in Finland for the production of 300-400 tons/day which
was considered by us but finally decided against because of limitations of
expansion and absence of digester washing. Another NSSC digester of
similar capacity, Esco, has been recently installed in North America.
Lecture 6
Kraft Cooking Process Theory

Many of you will now think that I have spent more than enough time on
processes other than kraft. I agree that the paper pulps of tomorrow are
kraft and mechanical pulp, with some semichemical neutral sulfite and
bisulfite for special purposes. However, I am convinced that the men of
the kraft and groundwood pulping industries will have to draw from the
entire pulping knowledge in order to introduce some new approaches to
these two well-developed and standardized industries.
The simplicity of the kraft process is of course a great asset. It used to
be still more simple, before the discovery of the advantage of sulfide. The
original process of Watt and Burgess, patented in 1853, concerned the
cooking of wood with sodium hydroxide under pressure. With a sufficient charge of alkali, free fibers were obtained from hardwoods. With
softwoods, alkaline cooking with pure sodium hydroxide did not yield a
chemical pulp very easily, and prolonged cooking to achieve fiber liberation resulted in a weak and brittle pulp. Accidentally, it was discovered
that sodium sulfide accelerated the cooking process. This was in 1879,
when Dahl in Danzig tried to add sodium sulfate instead of carbonate as
make-up chemical in the recovery process. The soda pulping became
sulfate pulping, and eventually the high strength of that pulp motivated
the name of kraft pulping. The new process had two snags: the pulp was
brown and difficult to bleach. It could not be used in printing papers in
unbleached form like sulfite pulp, and it could not be used in very white
papers as bleached. The development of the packaging papers and boards
created, however, a large market for unbleached kraft. Multistage
bleaching in the beginning of the 1930's, complemented by chlorine
dioxide bleaching 20 years later, solved the problem of kraft pulps for
white papers and boards. The development of bleached hardwood kraft
in the 1950's invaded the fine paper field, where bleached sulfite had one
of its last strongholds, and the development of prehydrolysis-kraft rayon
pulp during and after the last world war invaded another protected sulfite
area. Today, the kraft process, together with groundwood, could cover
the markets for wood pulp and paper almost entirely, and because of its
75
76
Lecture 6
well-developed technology, its quality and economy, it is gradually taking

over the markets.
The competition is, however, not confined to sulfite versus kraft, but
also kraft versus kraft, and paper versus other materials. Therefore development must continue to improve the economy and quality of the kraft
process. The improvement of economy must come largely in three areas:
decreased wood raw material costs, decreased other operating costs, and
decreased investment costs. The ways to achieve this must be increased
pulp yields and increased size of one-line units. As to quality improvements, it can be stated that there is fairly little to achieve in cooking and
bleaching today, when comparing with a well-run uniform cooking and a
six-stage bleach plant including two chlorine dioxide stages. I know of
only one process modification which gives a stronger pulp than chemical
kraft, and then at the expense of pulp yield. With new raw materials
coming in, such as certain eucalypts for hardwoods, radiata pine, and the
light-weight softwoods of British Columbia, there are, of course, substantial quality effects to be achieved, but these are somewhat outside the
scope of what can be achieved by process modifications.
The quality aspect rather enters in a negative way with the process
modifications: how much quality can be sacrificed in order to gain economy? This question must be interpreted not to imply that a real quality
should be sacrificed, but rather what we have erroneously believed to be a
quality factor without really knowing, and perhaps by overestimating its
importance. Everybody will agree, for instance, that a double fold of
4000 is not a quality criterion to keep up for a liner board or sack paper
pulp, if it costs money, as long as the scoring and creasing resistance of the
products remains adequate. More discussion will arise if, instead of
double folds, I mention burst, tensile, or tear strength, and yet none of the
qualities have any direct bearing on the service strength of a box or a
sack. We have to look for the directly relevant quality criteria, and to
relate them back to the pulping process, and that is now increasingly being
done.
The principal lignin reaction- of the soda cook is the hydrolysis of the
alkyl-aryl ether bond between the monomers, proceeding via epoxide formation (Fig. 6.1). This ether bond is very difficult to split in the acid
processes, and also with pure sodium hydroxide the reaction is not fast
enough to prevent excessive carbohydrate degradation, particularly with
softwoods. In the presence of sodium sulfide, the reaction is accelerated
without much sulfide being really consumed. From many years' study of
kraft pulping, lignin reactions, and reactions of model compounds, it appears likely that not sulfide, but rather the hydrosulfide ion reacts with
Fig. 6 . 1 .
Alkaline hydrolysis of lignin.
the vanillyl alcohol groups of lignin to form mercapto groups, which then
give episulfide under splitting of the bond between two monomers (Fig.
6.2). The episulfide is subsequently hydrolyzed to alcohol groups in the
lignin under reformation of hydrosulfide, whereas the sodium hydroxide is
consumed by the lignin in the principal splitting reaction of the alkyl-aryl
ether bond. That reaction not only decreases the molecular size of the
lignin but also makes it water-soluble as a phenolate and thus brings it into
solution. Only 0.1 -0.2 S/monomer remains in that lignin.
Unfortunately, there are also other lignin reactions. There is condensation to larger molecules, which partly counteracts the degradation just
mentioned. To some extent the condensation is favored by the formaldeh y d e formation occurring from the aliphatic part of t h e lignin monomer in
the absence of sulfide (see Fig. 6.1). In the kraft cook, lignin condensation is not a factor to watch out for as in sulfite cooking, in the sense that
it should prevent delignification if conditions are not chosen correctly. There is merely one phenomenon of importance, which is likely to
OCH3
Fig. 6.2. Sulfide-induced alkaline hydrolysis of lignin.
have connection with condensation, and that is color formation of the
pulp lignin. It has had to be accepted that kraft pulp and papers are
brown, but there are different shades, brighter or darker, reddish, yellowish, or blueish. In the first approximation, a kraft pulp can be said to
be the darker the more lignin it contains, as illustrated by Fig. 6.3. Then
there is an influence from other colored compounds present, such as
extractives, or the blue color from iron and bark tannins when pulping
spruce containing substantial amounts of bark. Such influences may
necessitate a more complete color measurement than brightness, such as
with the tristimulus filters of the Elrepho meter.
Unbleached kraft pulp brightness and color shades are of increasing
importance, not only for kraft paper to envelopes, etc., but also to sacks
and for liner board to boxes, which are increasingly being printed. The
increase in pulp color with an increase in yield is therefore a serious
limiting factor in our efforts to save wood. The cause of the discoloration
of lignin in kraft pulping is therefore an urgent subject of research, since
we know too little today to describe the reaction and define its variables. We can only suspect that it has to do with the formation of
quinoid or semiquinoid structures. Demethylation of guaiacyl propane
monomers leads to pyrocatechol structures, which in order to yield
o-quinone structures must find a ready hydrogen acceptor. This may be
dioxocyclohexene, likewise formed from pyrocatechol structures, which
after hydrogenation and rearrangement ends up as hydroxycyclopentanecarboxylate, a proved reaction.
This demethylation has been studied quite closely for a different
reason: odor abatement. Softwood lignin contains a methoxyl group on
almost every monomer, and hardwood lignin in addition has a second
40
50
60
70
80
YIELD, %
90
79
100
Fig. 6.3. Brightness of unbleached spruce pulps.

methoxyl on every two monomers (Fig. 6.4). Just as the main interconnecting bond between the monomers is an alkylaryl ether bond, the
methyl is attached to the benzene nucleus, and tends to split off on
cooking in alkali, particularly if the adjacent position contains a free
phenolic group (Fig. 6.5). We have also learned that the hydrosulfide ion
is a more powerful demethylating agent than the hydroxide ion, whereby
the reaction product is no longer methanol but the foul-smelling methyl
mercaptan (Fig. 6.6). We have learned that methyl mercaptan is
ionized during kraft cooking conditions, and that also the mercaptide ion
is a more powerful demethylator than is the hydrosulfide ion, and yields
dimethyl sulfide, which unfortunately smells almost as bad as mercaptan.
The carbohydrate reactions of the kraft cook are partly similar to the
lignin reactions. The demethylation of the methylglucurono groups of
the xylan (Fig. 6.7) proceeds in parallel with the lignin demethyla-
81
tion. The splitting of the alkyl-aryl ether bond of lignin has its counterpart in the scission of the glycosidic bonds of the carbohydrate chains,
which appears to proceed over an epoxide (Fig. 6.8). It is thus understandable that the conditions of the delignification in the soda cook had to
cause carbohydrate degradation, until a reaction was found to speed up
the lignin degradation. As far as is known, it is not possible to accelerate
the carbohydrate degradation with hydrolsulfide, and thus episulfide formation is not an intermediate reaction in this case.
The chain splitting reaction of the carbohydrates proceeds mainly at
maximum temperature of the kraft cook, 160-180C. At lower temperature, 60-160C, an important carbohydrate reaction takes place, called the
peeling reaction (Fig. 6.9). This starts at the aldehyde end groups of the
chains, and after certain internal rearrangement reactions leads to the removal of the terminating monomer in the form of the sodium salt of a
saccharinic acid. The nature of this acid varies with the carbohydrate
attacked, but it is usually a C6- or C5-isosaccharinic acid. In addition,
some fragmentation of the end monomer occurs, to give acids of lower
molecular weight, formic and lactic acid, also consuming alkali. After
peeling of the end monomer, a new terminating unit appears, likewise
H OH
Fig. 6.7. Demethylation of glucuronoxylan in .the kraft cook.
ending with an aldehyde group and capable of the same reaction. In this
way, monomer after monomer is peeled off under consumption of alkali,
and the entire carbohydrate wouid be destroyed if there were not a
stopping mechanism. There are several types, having in common the elimination of the aldehyde group, which is the weak point of the molecule
(Fig. 6.10).
One stopping reaction would be a fragmentation of the end monomer,
yielding a terminating unit of 3-5 carbon atoms and ending with an acidic
or alcoholic group. This type has not been definitely proved but is rather
likely. Another stopping reaction is an intermolecular rearrangement of
Fig. 6.8. Alkaline hydrolysis of glycosidic bonds.

the full terminating monomer, to give a metasaccharinic acid end monomer. This rearrangement may be facilitated by a suitable substitution of
the molecule, and it has been indicated that the arabinose units in the
3-position on the xylose monomers has such an influence. The glucuronoarabinoxylan of softwoods thus tends to stabilize toward alkali more
easily than the glucomannan. Also the cellulose is subjected to peeling
but is less accessible because of its ordered superstructure.
These two types of stopping reactions occur spontaneously and decide
the yield of the normal kraft cook. Attempts to bring about additional stopping of the alkaline peeling, in order to improve the carbohydrate yield, have led to modified kraft cooking methods. These employ
either reduction or oxidation of the aldehyde end groups to alcohol or
carboxyl groups (Fig. 6.11). The most well-known agents are borohydride (sodium tetrahydridoborate) and polysulfide, which, applied in suitable amounts, lead to 3-7% yield increases (Fig. 6.12). The changes in
carbohydrate composition shows that the main preservation occurs with
softwood glucomannan and hardwood xylan but with polysulfide also
some cellulose yield improvement is indicated (Figs. 6.13 and 6.14). Also
other redox agents have been tried with some success, such as chlorite,
hydroxylamine, hydrazine, and hydrogen sulfide. The last is the only one
with some commercial possibilities, together with polysulfide, and both
present complications in the cooking chemicals recovery which have not
been completely solved yet. The reason for these complications, and also
the cause of the economical unfeasibility of the other redox additions, is
the low degree of utilization of the redox agents, because of their contemporary decomposition in side reactions. It is the object of the
development work of the' cooking process variants to choose the conditions so that these side reactions are limited.
Fig. 6.9. Alkaline peeling and stopping reactions of carbohydrates.
CH2OH
H^ ^CHOH OH
c
\ ~ / \ O H ACOOH
H H
Fig. 6.11. End group stabilization by redox reactions.
In connection with the methods of increasing the carbohydrate yield
should also be mentioned the method for diminishing it by prehydrolysis. By subjecting the wood to an acid hydrolysis, either with mineral
acids at moderate temperature or with a steam or water treatment at
160-180C, the carbohydrates are degraded to shorter molecules, which to
a certain extent dissolve during the prehydrolysis but predominantly remain in the chips. Because of their shorter chains, they contain more
aldehyde groups and therefore degrade more easily by alkaline peeling. Since the cellulose is more protected against the prehydrolysis than
are the hemicelluloses, because of its more well-ordered superstructure, the
prehydrolysis-kraft cook yields a rather pure cellulose, suitable for the
viscose process (Fig. 6.15). In order to illustrate how the main part of the
fiber wall is influenced by these process modifications, Figs. 6.16-6.18
show the schematical carbohydrate distribution around the secondary wall
elementary fibril, analogous to Figs. 2.20-2.21 for wood and sulfite pulps.
Changes not only in the chemical reactivity but also in physical accessibility to peeling may influence the carbohydrate yield of kraft pulping. The reprecipitatfon of xylan onto the fiber has been indicated to be
of this kind. Anyway, it has been proved that some carbohydrates dissolve in the beginning of the kraft cook, reach a maximum concentration
at the end of the impregnation period, and then eventually disappear again
from the solution (Fig. 6.19). Some of them probably degrade in solu-
2.0
2.5
SULFUR, % on wood
Fig. 6.12. Increase in unbleached kraft pulp yield, given in percent based
on the wood, in relation to the amount of sodium borohydride (above),
and polysulfide sulfur (below) added to the cooking liquor, given in percent based on the wood.
tion, but it has also been demonstrated that part is capable of becoming
adsorbed to cellulose. This phenomenon is dependent on the alkali concentration of the liquor (Fig. 6.20), and therefore on the alkali charge. It
is mainly xylan that is capable of readsorption, probably because it is more
easily stabilized chemically than the glucomannan, which degrades rather
quickly in solution. When the alkali charge of the cook is increased, the
xylan content in the pulp decreases, the glucomannan content increases,
and the pulp yield goes down for a constant degree of delignification. For
the same reason, a decrease in pulp yield and xylan content must be
expected of a countercurrent kraft cook, since that will leave the highest
alkali concentration to the end of the cook.
There are two more carbohydrate reactions of importance to the alkali
consumption, namely, the direct neutralization of the glucuronic acid
Fig. 6.13. Yield of wood components on pulping to Roe number 4-5,

using the kraft process without additions (KR), polysulfide (PO) or tetrahydridoborate (BO) additions. Spruce, pine, birch.
groups of the xylan, and the deacetylation of the glucomannan of softwoods, and of the xylan of hardwoods (Fig. 6.21). Those two reactions
occur instantaneously as soon as the wood comes into contact with the
white liquor. Some of the peeling of the easily accessible hemicelluloses
also occurs fairly quickly, whereas most of the peeling proceeds during the
heating period and some also at full cooking temperature. The chain
splitting mainly occurs at maximum temperature.
With this background of lignin and carbohydrate reactions, I should like
to comment on the alkali consumption of the kraft cook and the concepts
of active and effective alkali (Fig. 6.22). A normal white liquor has a
sulfidity of 30%, that is, the molar fraction of sulfide as related to the sum
of hydroxide and sulfide. A normal charge of white liquor in Scandinavia
is 200 kg/ton o.d. wood, or 20%, expressed as NaOH and active
alkali. Expressed as Na 2 0, this would mean 15.5%. Of these 200 kg, 60
kg would be sulfide and 140 kg hydroxide. The term "active alkali"
includes the entire sulfide together with the hydroxide, and this assumes
that all sulfide gives an equivalent amount of hydroxide in the cook. With
POLYSULFIDE SULFUR, %
Fig. 6.14. The effect of polysulfide on yield and composition of

bleached loblolly pine pulps.
the knowledge that the pH of the black liquor is about 12, or seldom,
slightly lower, it is quite obvious from a Bjerrum diagram (Fig. 6.23), that
only one of the two stages of hydrolysis of the sulfide is utilized, and that
in principle only half of the sulfide should be regarded as effective
alkali. In the given example, with 200 kg active alkali of 30% sulfidity,
thus 140 + 0.5 x 60 = 170 kg are effective alkali. Normally, about 90% of
the alkali charge is consumed, and in this example, thus, about 150 kg
NaOH/ton o.d. wood.
This cook gives an unbleached chemical kraft pulp at a yield of 47%,
meaning that 3% extractives, 25% lignin, and 25% carbohydrates were
dissolved. With about 0.8 phenolic groups per lignin monomer to be
neutralized in the dissolved lignin, this means a consumption of about 40
kg NaOH/ton o.d. wood in lignin reactions, or roughly one fourth of the
alkali. The acetyl groups will consume about 15 kg NaOH/ton o.d. wood,
the uronic acids about 10 kg; the remaining 90 kg NaOH/ton o.d. wood
have thus been consumed in peeling, which means about 1.6 moles of acid
Fig. 6.16. Schematic representation of cross section of cellulose

elementary fibril, surrounded by hemicelluloses, in main secondary
wall of kraft pulp.
Fig. 6.17.
Schematic representation of cross section of cellulose elementary fibril surrounded by hemicelluloses, in main secondary wall of j>olysulfide or borohydride kraft pulp.
Fig. 6.18. Schematic representation of cross section of cellulose

elementary fibril, surrounded by hemicelluloses, in the main secondary wall, prehydrolysis-kraft pulp.
Fig. 6.20. Dissolution of lignin and carbohydrate components during the

kraft cooking of pine; upper curves 0 g/liter NaOH, 20 g/liter Na2S; lower
curves 35 g/liter NaOH, 10 g/liter Na2 S.
CH3COONa
Fig. 6.21. Instantaneous carbohydrate reactions of the kraft cook.
produced per hexose unit. This is what is found by direct reaction of
carbohydrates with alkali.
Thus the predominant part of the alkali is consumed by carbohydrates. The amount consumed at immediate contact between wood and
cooking liquor at 100-110C is about 70 kg NaOH/ton o.d. wood, 7 or 8%
92
Lecture 6
active alkali, expressed as NaOH, or almost half of the alkali consumption,

consisting of about 25 kg with acetyl and uronic acid, 15 kg with native
phenolic hydroxyls of lignin, and about 30 kg in rapid peeling of easily
accessible carbohydrates, constituting about 8% of the wood. The yield
at this stage is about 90%.
It should be observed that the cooking-rate-controlling part of the alkali
is that consumed toward the end of the cook by the lignin-degrading
reaction and the unavoidable accompanying carbohydrate reactions. The
alkali concentration at cooking temperature and time at temperature, and
the cooking temperature itself, are thus the reaction variables of interest. Of course, the alkali concentration at temperature is related to the
liquor ratio and to the total alkali charge.
The sulfide concentration does not materially influence the rate of cooking, as long as it is kept above a certain minimum. The amount of sulfur
involved in the lignin reactions would be about 40 kg/ton o.d. wood (4%),
if the sulfur were consumed in the main reaction, the episulfide formation. However, since it is only some sulfur consumed in side reactions,
Composition, g/liter Na 2 0:
NaOH
76
lg5
)
|
Na 2 C0 3 19
)
M28
[13()
Na 2 S
33
J
Na 2 S0 4
2
'
Concepts, g/liter Na 2 0: Total alkali NaOH + Na 2 C0 3 + Na2S + Na 2 S0 4
Total titrable alkali NaOH + Na 2 C0 3 + Na2 S
Total active alkali NaOH + Na2 S
Total effective alkali NaOH + Vi Na2 S
%:
Sulfldity Na 2 S/(Na 2 S + NaOH)
Causticity NaOH/(NaOH + Na 2 C0 3 + Na2S)
Causticizing efficiency NaOH/(NaOH + Na 2 C0 3 )
Fig. 6.22.
Fig. 6.23.
White liquor composition and concepts.
Electrolyte systems of kraft cooking liquors.
130
128
109
93
30
60
80'
93
which really becomes fixed to the lignin, the amounts of organically combined lignin toward the end of the cook is only 5-10 kg S/ton o.d. wood
(0.5-1%). With an effective alkali charge of 170 kg NaOH/ton o.d. wood,
10 kg S only means 25 kg Na2S, or a sulfidity of about 13%. The normal
sulfidity of 30% means 24 kg S, which thus leaves a considerable surplus
above the sulfur consumed in side reactions. Extensive investigations on
the role of the sulfidity in kraft pulping indicate a critical level of 15-20%
and no major improvement in the rate of pulping above 25%.
Although the above considerations are principally correctthat alkali
concentration, temperature, and time are the major variables controlling
the rate of pulping, provided that the sulfidity is high enoughit would be
wrong to treat the kraft pulping as a homogeneous-phase system. Since a
large part of the alkali is consumed immediately or almost immediately, it
is an obvious possibility that some of the alkali has been consumed before
impregnation is complete and that there exists an alkali concentration
gradient in the chips. This means a danger of non-uniform cooking from
different parts of the chips and different chip thicknesses. A dependence
of the rate of cooking from the chip thickness has been well established
(Fig. 6.24). Assuming that the chips can absorb 2 m3 of liquor per ton
o.d. wood and have a moisture content of 50%, this means that 1 m3 of
chip moisture and 1 m3 of white liquor can be absorbed, disregarding
steaming condensate. That volume of white liquor of normal strength will
contain 110-120 kg active alkali, of which about 80 kg will be consumed
directly and 40 kg will be left over for the genuine cooking. Another
60-80 kg active alkali/ton o.d. wood will have to diffuse into the chips,
and run the risk of being consumed on the way in, thus overcooking the
exterior and undercooking the interior of the chips. Since the diffusion
paths are normally only 1-2 mm to the interior from the outside, the
effects are not catastrophic at normal chip thickness and normal chemical
pulp grades. With nonuniform chips or with semichemical kraft pulp for
liner board, the heterogeneity becomes quite noticeable and may limit the
maximum yield level. This makes various systems for impregnation
pretreatment of interest, in addition to the steaming and pressure-impregnation treatments already described in connection with the sulfite process. The figures quoted are valid for Scandinavian softwoods. The
heavier southern pines absorb less liquor, and the diffusion of alkali into
the wood becomes more important, whereas some of the lightweight soft.woods of Canada may be able to absorb the entire alkali demand by good
impregnation with white liquor of normal concentration.
The properties of spruce kraft pulps at varying yield and process modifications are shown in Fig. 6.25, together with the properties of sulfite
94
Lecture 6
Fig. 6.24. The charge of effective alkali required to reach

Roe number 6 using different chip thicknesses and cooking temperatures.
process variants and groundwood. It is seen that kraft pulp gives the
strongest combination of the controversial tensile and tear strength properties. A strength maximum occurs at around 50% yield. Further cooking reduces tensile and improves tear strength, largely along the beating
curve, meaning that the additional lignin and hemicellulose removal made
the pulp less easily beaten and less easy to give paper bonding at a certain
drainage and porosity level. The same effect, though still more pronounced, is obtained by additional hemicellulose removal with the prehydrolysis-kraft process. Increasing the yield by limiting the delignification will cause a decrease in strength, finally approaching the groundwood
region. It is rather striking that kraft pulp at 75% yield has lost half its
tensile strength but comparatively little tear, whereas a bisulfite pulp at
75% yield has lost only somewhat more than 10% of each property, as
compared to the maximum strength yield level. Increasing the carbo-
100
120
140
160
180
200 220 240
TEAR FACTOR
Fig. 6.25. Tensile-tear strength relation in the 25-45SR region for spruce
pulps of various degrees of delignification from various processes. Numbers
indicate pulp yield.
hydrate yield of the kraft process by polysulfide or borohydride additions
keeps up the tensile fairly well, but at the expense of tear strength.
All those changes reflect the influence of the hemicelluloses to improve
the paper bonding characteristics, at the same time tending to make the
paper more sensitive to locally applied stresses, such as in the tear
test. The figure also illustrates the strength advantage of kraft pulps as
compared to acid sulfite, and the insufficiency of the sulfite process
modifications to meet the strength demands that the market is used to put
up because of kraft pulp.
This picture would not be complete without showing the influence of
wood species on kraft paper pulp strength (Fig. 6.26). Two main conclusions can be drawn from that figure and comparisons with the previous
one. One is that hardwood kraft represents a widely varying quality concept, with the poor members being filler pulps of little strength and the
better ones approaching or surpassing spruce sulfite in strength. The same
picture is obtained when bleached grades are compared and also when
opacity is introduced as one of the quality criteria. The other main conclusion from the figure is the influence of softwood density, i.e., fiber wall
thickness or summerwood content, on kraft pulp strength. A lightweight
softwood, as grown in Scandinavia or Canada, gives a better paper bond-
96
Lecture 6
Fig. 6.26. Tensile-tear strength relation in the 25-45SR region for kraft
pulps of various wood species. Numbers at each curve indicate basic density/average fiber length for the respective wood species.
ing, with a higher tensile and lower tear, than a heavier softwood such as
slash pine. In general, these differences move along the general beating
curve for softwood kraft, meaning that a southern pine kraft, beaten to
the extreme, reaches similar paper characteristics, aside from porosity, as a
light-beaten Scandinavian or Canadian softwood kraft.
This terminates the process background for kraft pulping. As in the
case of sulfite, it has had to be a rather sketchy one, serving as an introduction to the presentation of efforts on continuous cooking rather than to
give a complete coverage of what is known today on the subject.
Lecture 7
Continuous Conventional Kraft Cooking

This is a field where some of you may have considerably more experience than I have. I shall limit my presentation here to the quality experience we have had in our 150 tons/day digester at Gruvon, recently expanded to 250 tons/day, and some experience from Jossefors, where the
pilot digester was run on a few wood species, mainly as control runs when
trying process modifications. I shall also add some information given to
me by Kamyr, regarding the quality investigations made at other mills and
laboratories, as well as some statistical information on digester performance etc.
In conventional kraft cooking there is now 20 years of mill experience
with continuous cooking. We thus ought to know the quality we get and
the reliability of the system. Yet it is not very easy to get objective
comparisons. Not often has the pulp from a local digester been compared
either to mill batch or laboratory batch pulp on identical raw material and
comparable conditions. Gruvon is one of the places where this has been
done. The objection against those data is, however, that Gruvon has one
of the early digesters, which in spite of improvements lacks some features
of a modern digester, especially the countercurrent digester wash, which
ensures the best and most uniform cold blow. The Gruvon system is
shown in Fig. 7.1, as it was originally and as it has been modifiedexcepting the last reconstruction, which was mainly an elongation of the digester
body to allow a larger capacity. Instead, the final development of the
cold blow, the countercurrent washing, is shown. This system is now
standard and will be installed in the next 1000 tons/day digester at
Gruvon.
The Gruvon digester was designed in 1956 and started in spring
1957. It had a volume at the delivery of 145 m3 and is now 177 m3 by
means of increased height from 20 to 24.5 m. The nominal capacity at
delivery was 150 tons/day, it was run at 120 tons/day during the first few
years and is now making up to 250 tons/day. The digester was run with a
hot blow for one year. Limited bottom cooling was introduced in January 1958, with black liquor charged at the bottom connections. This
97
99
brought the blow temperature down from 170 to 145C. In August

1958, the bottom connections were prolonged inwardly to facilitate the
cooling. Also there were some adjustments on the bottom scraper blades
and reductions in the scraper speed from 3 to 2 rpm, then to 1 rpm, which
was found to give discharging difficulties and again increased to 1.6
rpm. In Spring 1959, a screw press was installed between digester and
blow tank to improve the black liquor recovery, and in February 1960, the
cold blow system of strainers and flash tanks was introduced, allowing
blow temperatures of about 100C.
With suitable intervals during the first five years, pulp samples were
analyzed and tested for paper properties, whereby these changes in the
system were reflected. Contemporary sampling of the pulp from the
batch digesters, run on the same raw material, was done for similar testing. The batch digesters have a volume of 85 m3 and run a straightforward kraft cook at 170C and are blown at 5.5 atm. To complete the.
Table 7.1. Survey of Kraft Pulp Quality of Continuous and
Batch Cooking Systems in Gruvon, 1957-68
Year and cooking system
1958
1957
Batch
Speed of bottom scraper, rpm
Screw pressing
Number of tests per average
Beating time, min
Tear factor
Cont.
Cont.
1959
Batch
Cont.
2
145
20
20
59
59
33
1.6
145
+
33
59
10.3
114
62
9.9
101
60
10.5
114
60
10.4
102
55
10.1
111
58
9.9
97
3
170
1960-61
Batch Cont.
Speed of bottom scraper, rpm
Screw pressing
Number of tests per average
Paper properties at 45SR
Beating time, min
Tear factor
Batch
1967
Batch Cont.
34
1.6
100
+
34
40
1.6
100
+
39
61
10.5
112
66
10.6
113
57
10.0
124
69
10.0
122
1968
Batch Cont.
. 18
48
10.2
121
1.6
100
+
19
57
10.2
125
Table 7.2. Kraft Pulp Quality at Various Stages of

Processing, Hot or Cold Blow
Discharge
temp.,
C
145
100
Sampling
station
Beating
time,
mm
Tensile
strength,
km
Tear
factor
Sheet
density,
g/cm3
Above scraper
After discharge
Batch pulp
Above scraper
After discharge
Batch pulp
39
39
39
42
47
39
9.5
9.4
9.5
10.2
9.6
9.6
131
114
125
144
134
132
0.67
0.65
0.67
Beating
time,
min
Above scraper
After discharge
Batch pulp
Above scraper
After discharge
Batch pulp
Tensile
strength,
km
Tear
factor
Sheet
density,
g/cm
10.4
10.2
10.3
11.3
10.8
10.6
119
102
113
129
119
119
0.71
0.70
0.73
information, some laboratory cooks on the same chips were performed,

and further sampling was done at several places in the digester discharge
system, namely above the bottom scraper, in the discharge line prior to the
disk strainer, and before and after the screw press.
Table 7.1 summarizes the results of the comparative testing of batch and
continuously cooked pulp over the period. At a discharge temperature of
170C there was a considerable strength loss as compared to batch. Almost the same loss was experienced at 145C. At 100C blow temperature, the quality appears to be well up to that of batch pulp. Table 7.2
shows the results of testing samples taken in the discharge system at blow
temperatures of 145 and 100C. Again, the strength loss in discharging is
considerable at 145 and less severe at 100C. The pulp above the bottom
scraper appears to be a shade stronger than the batch pulp, enough to
cover the slight strength loss in the discharge. A more extensive paper
testing on the various pulp samples and also on laboratory pulp is shown in
Table 7.3.
101
Table. 7.3. Kraft Pulp Quality at Various Stages of Processing; Extended Testing
Discharge Temperature, 100C
Sampling
station
Beating
time,
nun
Tensile
strength,
km
Stretch
at break,
Above scraper
After discharge
After screw press
Batch pulp
Laboratory pulp
38
41
42
35
31
9.9
9.9
9.5
9.5
9.6
4.7
4.7
4.9
4.8
4.5
Tear
factor
Sheet
density,
g/cm3
Air
resist.,
sec/100 ml
139
136
134
138
146
0.67
0.67
0.65
0.66
0.67
29
31
26
34
31
Beating
time,
min
Above sciaper
After discharge
After screw press
Batch pulp
Laboratory pulp
58
64
65
58
54
Tensile
Sheet
Stretch
strength, at break, Tear density,
factor g/cm3
km
11.3
11.1
10.8
11.0
10.9
4.9
5.0
5.1
5.1
4.9
124
123
119
121
130
0.72
0.72
0.71
0.72
0.73
Air
resist.,
sec/100 ml
335
300
270
390
400
These trials clearly demonstrated the necessity of the cold blow and
showed that the continuously cooked pulp was up to mill batch pulp
standard. They also indicated the possibility of surpassing it and reaching
the laboratory pulp standard, and this has been realized elsewhere in connection with the countercurrent washing, where the cooling of the pulp to
blow temperature is more uniform than it can be in the rather primitive
cooling system of Gruvon.
We also sought to find out the reasons why the hot blow gave an inferior
pulp quality. Table 7.4 shows the results of paper testing, fiber length
measurements, chemical analysis, and DP determination of pulp and
hemicellulose fractions, of the samples taken before discharge, after hot
and semi-hot blows, and from batch cooking. No evidence whatsoever
can be seen on any measurable property of those usually having an influence
on paper strength. It is therefore concluded that the damage done by the
hot blow is restricted to very limited regions of the fibers, such as the
so-called slip planes of the fiber wall in the superstructure of cellulose. The agreement with the previously reported experience on the hot
blow of other pulp types is striking, as compiled in Table 7.5.
Table 7.4. Effects of Hot Blow on the Pulp Carbohydrates in

Continuous Kraft Pulping
Beating time, min
Tear factor
Fiber length, length average, mm
Analysis
Viscosity, cp TAPPI
Alpha-cellulose content, %
Rio, % (nonsolubles, 10% NaOH)
ft o, % (precipitable solubles)
7io, % (nonprecipitable solubles)
DP of fro
DPof710
Pulp composition, %
Cellulose
Glucomannan
Glucuronoarabinoxylan
0io composition, %
Cellulose
Glucomannan
7i o composition, %
Cellulose
Galactoglucomannan
20
57
10.5
117
1.8
77
87.3
87.1
5.7
8.6
182
145
60
10.2
170
Batch
2.0
54
9.8
91
1.9
61
10.3
119
1-9
83
86.8
86.6
2.7
10.2
141
115
75
86.7
86.3
3.8
9.9
180
108
81
86.7
86.5
2.7
10.0
142
113
103
78
7
15
78
8
14
78
8
14
4
9
81
4
7
79
4
7
81
0
30
70
0
31
69
0
31
69
The Jossefors experience of normal kraft is confined to a few runs on

pine, birch, and eucalypt, which are of interest only so far as they have
been performed with countercurrent washing and have been compared to
laboratory cooks. Table 7.6 shows that in these cases, laboratory standard has been reached for all wood species. This confirms the conclusion that the standard system for continuous kraft cooking gives a
satisfactory performance and quality. All experience on modified kraft
cooking, whether modified in the cooking process or in the impregnation,
will be dealt with in the two subsequent lectures.
The digester performance is of great importance for the production efficiency in a pulp and paper mill. Many claims have been made over the
years that the continuous digesters endanger the reliability of the production. Such claims were indisputable in the early days, before the machine
elements had been sufficiently developed and enough running experience
gathered. Likewise, every new mill with a new crew has to learn to run
103
Table 7.5. Development of Paper Pulp Quality in Continuous Cooking

Using Various Processes
Pulping process
Digester
Neutral sulfite, birch

(bleached grade)
Cont., 1-body
Cont., 1-body
Cont., 1-body
Batch, mill
Cont., 1-body
Cont., 1-body
Cont., 1-body
Batch, mill
Cont., 2-body
Cont., 2-body
Batch, mill
Batch, lab.
Cont., 2-body
Cont., 2-body
Cont., Mumin
Batch, mill
Batch, lab,
Cont., 2-body
Cont, 2-body
Cont., Mumin
Batch, mill
Batch, lab.
Kraft, pine
Bisulfite-acid sulfite,
spruce
Neutral sulfite-acid
sulfite, spruce
Bisulfite, spruce
Discharge
temp., C
160
130
110
170
145
100
120
50
120
50
50
120
50
50
Paper properties, 45SR

Beating
Tensile
time,
strength,
Tear
min
km
factor
7
9
9
6
62
60
66
61
20
22
20
23
16
17
19
21
14
25
24
29
28
27
8.0
8.6
9.6
9.4
9.9
10.4
10.9
10.5
7.5
9.0
8.7
9.5
8.1
8.3
8.4
9.3
8.6
8.8
10.4
9.8
10.3
10.5
57
62
68
70
101
102
117
114
59
68
66
75
49
55
66
53
64
62
65
85
75
86
their digester, as well as their paper machines. Many problems have also
come up because the continuous one-line production requires a different
approach to maintenance than a batch system with several digesters and
chests. Systematic preventive maintenance is vital to the success of a
continuous digester. By experience and skill, several mills have achieved
a digester performance of 99%. In Gruvon, with the pulp mill attached
to a paper mill, the average downtime of the continuous kraft digester
during recent years has been about 5%, of which 3% occurred because of
the paper mill, power failures, or steam shortage, 0.5-1% because of miscellaneous disturbances, and 1-1.5% because of actual digester
troubles. No major changes have been made in the machine parts. Lowpressure and high-pressure feeders are worn out in about two years, which
appears to be general experience.
Table 7.6. Kraft Pulp Quality from Pine, Birch, and Eucalypt in the Jossefors Pilot Digester, as Compared to Laboratory Pulping
Wood species
Pine
Pinus silvestris
Pulping operation
Roe chlorine No.
Brightness, % SCAN
Resin content, %
Glucose
Mannose
Xylose
Beating time, min
Tear factor
Beating time, min
Tear factor
Birch
Betula verrucosa
Laboratory
Pilot
hydraulic
Pilot
Mumin
Laboratory
5.2
24.3
0.34
5.4
27.1
0.18
5.1
30.6
0.19
3.0
32
0.9
84.4
6.2
8.7
84.2
7.5
8.3
82.9
9.1
7.6
41
9.5
156
53
9.9
143
66
10.8
130
82
11.0
129
Pilot
hydraulic
Eucalypt
Eucalyptus globulus
Pilot
Mumin
Laboratory
Pilot
hydraulic
2.2
35.9
0.51
3.0
34.8
0.51
2.2
35.3
0.27
2.2
42.3
0.40
2.6
37.8
0.25
73.7
0.5
25.8
73.1
0.0
26.9
73.2
1.7
25.2
81.2
18.8
80.1
0.3
19.6
80.9
0.3
18.8
43
9.4
149
16
7.0
88
14
6.6
90
17
7.1
103
18
5.7
95
14
5.5
93
17
5.4
100
67
10.8
128
25
8.6
73
26
8.9
81
31
9.5
87
37
8.6
105
28
8.1
106
33
7.9
103
Pilot
Mumin
Lecture 8

Our interest in rayon pulp has resulted in development work not only in
continuous acid sulfite cooking but also in continuous prehydrolysis-kraft
cooking. The advantages of the latter process are little sensitivity to wood
species, better economy in producing the highly purified grades, quality
advantages in the DP distribution of rayon cord pulp, and finally, the
possibility of producing kraft pulp as the paper grade alternative of the
mill.
The principles of the prehydrolysis-kraft process were developed around
1930 in America, carried to mill production in Germany during the war,
and resulted in large-scale production after the war in Sweden, USA,
Russia, Japan and India. The theory behind the process was presented
previously. The purpose of the acid prehydrolysis is to degrade the hemicelluloses with the least possible damage to the cellulose. The degradation
partially dissolves the he mi celluloses in the prehydrolyzate, but also leaves
shortchain molecules, which are efficiently degraded by peeling in the
kraft cook. Whereas a straight kraft cook results in a final bleached pulp
yield of 43-53%, depending on wood species, prehydrolysis-kraft yields
35-40%. Our experience on continuous prehydrolysis-kraft is limited to
water and steam hydrolysis. Steam hydrolysis gives essentially the same
effect as hydrolysis in liquid water, but there exists a series of practical
differences which shall be commented on subsequently. The prehydrolysis used to be performed with dilute mineral acid in the first mills,
but subsequent mills have favored water hydrolysis, i.e., hydrolysis at
160-180C in water, whereby an acidity of pH 3-4 is developed by the
wood constituents, particularly by acetic acid from the acetyl groups.
The first company to study continuous prehydrolysis-kraft cooking with
a Kamyr digester was the Italian SAICI. In the early 1950's, it initiated
experiments with a small two-body unit in its Torviscosa dissolving pulp
mill. This unit had a capacity of 1 ton/day and consisted of one upflow
and one downflow tower of different pressures, separated by a rotary
pocket feeder. As with the first continuous acid sulfite digester at
Domsjo, this one also proved to be too small to give reliable experimental
conditions. The initial Jossefors two-body digester was a simplified ver105
106
Lecture 8
Fig. 8.1. Two-body continuous digester for prehydrolysis-kraft cooking.

sion of this unit, with both digester bodies operated at the same pressure
(Fig. 8.1). The reason for having two digester bodies was to facilitate the
operation of a two-stage process by maintaining well-defined, separate
cooking stages.
After presteaming, the chips were fed, together with water, by the conventional feeding system into the upflow digester. Liquor withdrawn
from the upper part of the digester and recycled just above the bottom
screw helped to move the chip column upward, thereby reducing the load
on the screw. This circulation was also heated to the desired temperature
for prehydrolysis. The prehydrolyzed chips with their hydrolyzate were
transferred over to the downflow digester by the top scraper, and then
mixed with white liquor. The chips were then digested by the kraft
process and the pulp was discharged according to the cold blow method.
The movement of the chips in the upflow vessel was problematic. It
was quickly discovered that prehydrolysis of wood species such as pine
and birch resulted in pitch deposits on the strainers of the lifting circulation, which plugged after 3-6 days of continuous operation. This proved
to be crucial for the whole systemalthough an alkaline wash would remove the pitch deposits, a safe continuous operation was obviously prevented. Experience accumulated from other cooking processes indicated
107
H.P. STEAM
Fig. 8.2. Downflow, liquor-phase continuous digester for prehydrolysiskraft cooking.

that there were other disadvantages with the upflow digester, as already
described. Therefore, the system was redesigned.
Experience with the two-body digester had proved that it was easier than
anticipated to keep two different stages apart. Therefore the digester was
reconstructed to the conventional downflow Kamyr system. The new
digester (Fig. 8.2) was higher than the two-body system and was equipped
with more strainers and central pipes than a standard kraft digester. The
strainers and central pipes were arranged to allow cooking in two stages,
followed by countercurrent washing. The digester volume was 27 m3 and
had a capacity of 8 tons/day of airdry prehydrolysis-kraft pulp. This
volume gave a total retention time of 5.5 hr, of which 1 hr was for heating
to prehydrolysis temperature, 1 hr prehydrolysis at maximum temperature, 2 hr kraft cooking and 1.5 hr washing.
The new system was similar in principle to a conventional kraft digester
with a downward chip flow, and no trouble was expected with the chip
movement. The main concern was whether the prehydrolysis and kraft
cooking stages could be effectively separated and if deposits of pitch
would occur. The system was tried separately on pine and eucalyptus
using essentially the same prehydrolysis and kraft cooking conditions. Chips and water for prehydrolysis were fed into the top of the
108
Lecture 8
digester, using the conventional Kamyr feeding equipment. After a period

of gradual temperature rise, the digester was heated to full prehydrolysis
temperature by indirect heating in the upper circulation zone. This
temperature was maintained until the chips reached the second circulation
zone, where the acid prehydrolysis liquor was neutralized by alkaline
liquor for the kraft stage.
The kraft cook was carried out either concurrently or countercurrently. In the concurrent cooks all the white liquor was added to the
second circulation zone that formed the transition point between the prehydrolysis and kraft stages. This circulation zone was also used for heating to cooking temperature. When cooking countercurrently, the white
liquor was not introduced until the third circulation zone. Later, a modification was incorporated, wherein the white liquor was divided into two
parts, with one part added at the second circulation zone and one part at
the third zone. The total liquor flow, including dilution from the washing
stage, was extracted at the second circulation zone and thus the liquor and
chips moved countercurrently against each other below that zone. The
concurrent as well as the countercurrent kraft cooking stages were followed by a countercurrent high-heat wash and the prewashed pulp discharged according to the cold blow method.
The separation of the prehydrolysis and kraft cooking stages proved to
be quite effective as long as there was a certain flow of free liquor from
the prehydrolysis into the kraft cooking stage. The most favorable
liquor-to-wood ratios achieved in the prehydrolysis were 3.0 for pine and
3.5 for eucalyptus. The reason for the higher liquor ratio in the latter
case was an increased tendency for carbon dioxide evolution in the prehydrolysis stage. This caused a flow of hot liquor to the top of the
digester and resulted in disturbances in the feeding circulation. By introducing more water, these disturbances were avoided. An attempt was
made to extract the prehydrolyzate before mixing with alkaline liquor, but
when doing so the flow of free liquor into the kraft stage was reduced and
the black liquor level raised. This caused precipitation of alkali lignin on
the extraction strainer and in the pipelines, clogging the system.
Deposition of pitch on strainers and in the heat exchanger of the prehydrolysis stage proved to be about as extensive for the new system as for
the two-body digester. Though in the downflow system the chip movement was not disturbed, the pitch deposits reduced the liquor flow in the
heating circulation and impeded the rate of heat transfer. Difficulty was
thus encountered in maintaining the desired prehydrolysis temperature.
The pitch problem was partially solved by using wider strainer slots and
by direct steam heating in the prehydrolysis circulation. These innova-
109
tions permitted sufficiently long operation to allow considerable studies of

the process and pulp quality, but presented no final solution. Another
complication was pitch migrating into the feeding circulation, particularly
with hardwoods. This necessitated the addition of considerable amounts
of alkali to that circulation in order to prevent pitch deposition in the
high-pressure feeder. The alkali added affected the pH of the prehydrolysis and thus the pulp quality.
Considerable interest centered on the possible advantages of countercurrent cooking versus concurrent cooking. According to earlier experiences,
countercurrent kraft cooking seemed to give a somewhat higher dissolution of xylans which might prove to be an advantage for dissolving
grades. Also, in concurrent cooking a great deal of the active alkali was
found to be consumed directly in the heating zone, where the white liquor
was added. This gave a low concentration of chemicals which most likely
caused deficiencies in the chemical distribution, particularly to the interior
of the thicker chips. As a consequence, high percentages of screen rejects
were obtained even though the pulp was of a low lignin content. In
contrast, countercurrent operation resulted in a pulp with low screenings.
These results are most likely explained by the difference in active alkali
concentration gradients in concurrent and countercurrent cooking. Figure 8.3 shows the concentration of active alkali in the liquor
measured at different points in the cooking and washing zones. The curve
for countercurrent cooking goes from a low concentration at the transition
point between the prehydrolysis and kraft stages to a very high concentration at the end of the cooking zone. The corresponding curve for concurrent cooking starts at a medium concentration at the transition point
and goes down to a low residual active alkali content at the end of the
cooking stage. It is obvious that these differences must have a certain
effect on the distribution of active alkali in the inner parts of the chips and
also influence the rate of delignification. The latter is well illustrated by
the cooking temperatures that were necessary. At the same production, a
higher alkali charge and the same final pulp viscosity, concurrent cooking
demanded 170C in contrast to only 155C for countercurrent cooking.
Under certain conditions of countercurrent cooking there was a tendency of too low an alkalinity at the transition point between the prehydrolysis and kraft cooking stages. This resulted in the precipitation of
alkali lignin, which clogged the strainer plates and pipelines. To maintain
control of the alkalinity it was found suitable to split the white liquor
charge into two flows, one part added to the transition circulation and one
part to the lower cooking circulation. This gave good control of the pH
110
Lecture 8
Fig. 8.3. Concentration of active alkali in liquor vs. digester height:

,
concurrent kraft stage, 25% active alkali (NaOH) on moisture-free wood
added at A; O countercurrent kraft stage, 22% active alkali (NaOH) on
moisture-free wood added at B; - A -, countercurrent kraft stage, 15%
active alkali (NaOH) on moisture-free wood added at B, 7% active alkali
(NaOH) on moisture-free wood added at A.
of the extracted liquor and prevented any tendency to clogging, and yet
the advantages of countercurrent cooking were preserved.
Although operation of the downflow, liquor-phase system was managed
under comparatively steady conditions, the result was not satisfactory. Deposition of pitch, flow disturbances by gas evolution, and the
relatively large amounts of water required to ensure good separation between the two stages, were all disadvantages which could render a full-scale
operation difficult, uneconomical and not completely satisfactory from a
quality standpoint.
During the experiments with the two-body digester, it had been visualized that prehydrolysis-kraft cooking could be carried out in a downflow
digester, where the prehydrolysis was to be performed in the vapor phase
and the kraft cook in the liquor pnase. Such a cooking method would
give an efficient separation of the two stages and result in a simple opera-
111
Fig. 8.4. Downflow, vapor-liquor-phase digester for

prehydrolysis-kraft cooking.
tion. The great problem was how to feed the chips into the digester. Although there were several vapor-phase feeders, none was very satisfactory
from all aspects such as operation, maintenance, and steam economy. The balanced liquor-phase feeder used in conventional kraft cooking is superior in most respects. Furthermore, any prehydrolysis-kraft
digester should preferably also be suitable for the production of high
quality kraft pulp for paper grades, for which the standard high-pressure
feeder is desirable.
The final answer to these demands proved to be an inverted top separator placed outside the digester shell. Figure 8.4 shows this digester
version, the "Mumin" system, arranged for prehydrolysis-kraft cooking. The feeding system remains the conventional one, and so does the
digester shell, although a separate circulation for heating the prehydrolysis
is no longer needed. What has been altered is the design of the digester
top, as described earlier. As the liquor level is controlled at a point below
the overflow, from the external, inclined top separator, the chips are
drained and do not carry into the digester more water than that which has
been absorbed by the chips.
The direct steam meeting the chips heats them very uniformly and al-
112
Lecture 8
most individually, in contrast to the danger of local overheating in batch

vapor-phase cookingone of the major reasons why the existing mills run
batch liquor-phase cooking. The steam flow is controlled by the temperature in the prehydrolysis stage. Since the need of a prehydrolysis heating
circulation is thus eliminated, so is the danger of resin problems there.
The instant heating to maximum prehydrolysis temperature results in a
digester volume not appreciably larger than that of a conventional kraft
digester, since the prehydrolysis zone corresponds to the zone of gradual
temperature rise in the conventional digester. Therefore the system has a
great versatility and can be used for either rayon grade pulp or kraft paper
pulp, with slight alterations.
The liquor level can be kept at an arbitrary height in the prehydrolysis
stage; but preferably it should be slightly above the transition circulation
to ensure an efficient separation of the two stages. The cooking can be
performed either concurrently or countercurrently and be followed by
countercurrent washing.
The main interest when starting the cooking trials after the last reconstruction was to study the behavior of the inverted top separator and the
combined vapor-liquor phase operation. After a slight adjustment of the
top separator screw, this arrangement worked satisfactorily, with little or
no heat flow from the vapor phase back to the feeding circulation. The
liquor level in the top separator could be easily controlled, and no more
liquor was carried over to the digester than what had been absorbed by the
chips. Since the feeding liquor was not in contact with the hydrolyzate,
there were no significant pitch troubles in the high-pressure feeder, in
contrast to the previous systems.
The heating with direct steam went smoothly and the carbon dioxide
evolved caused no trouble, since it occurred in vapor phase. In fact, the
C0 2 gas served as a pressure controller, since pressure in excess of the
steam pressure is desirable for undisturbed liquor circulation in the kraft
cooking zone. Thus there is no need for maintaining the same or higher
temperature in the prehydrolysis than in the kraft stage, leaving the choice
of temperature above a minimum level entirely to quality considerations. The desired digester pressure is maintained by relief of excess gas
through a control valve.
The chip flow through the vapor phase zone presented no problems, and
the pitch deposits on the digester walls in the prehydrolysis zone were
inconsequential in the absence of liquor circulation. The transition from
prehydrolysis to kraft cooking caused no particular problems. With
countercurrent cooking, the addition of white liquor was done, as before,
in two parts with about half added at the transition circulation and half at
113
the lower cooking circulation. By this method the pH of the extracted

mixture of prehydrolyzate and black liquor could be carefully controlled
and any precipitation of alkali lignin on the strainers avoided.
The filtrate from a subsequent washer was introduced into the digester
bottom as a wash liquor for the countercurrent wash. The disadvantage
of having to heat this wash liquor to the full temperature of the countercurrent cook is partially offset by the increase in flash steam from the
extracted black liquor. This steam can be used for presteaming and hot
water preparation, the same as in conventional kraft cooking. A further
compensation is the lower maximum temperature required with countercurrent cooking.
The black liquor volume extracted should correspond to the sum of
water in the chips, direct-steam condensate, white liquor addition, and
dilution in the washing. Because of the small quantity of liquor used in
the prehydrolysis stage, the extracted liquor has a comparatively high
concentration of dissolved solids. When cooking eucalyptus, the liquor to
the evaporators will have a solids content of 17-19%, depending on the
white liquor strength, dilution of washing, etc.
Heat economy is good with the downflow vapor-liquor phase system,
and under normal conditions there will be no need for live low-pressure
steam to the steaming vessel, since the flash steam from the extracted
black liquor will be sufficient for the presteaming. The total high-pressure
steam consumption for eucalypt prehydrolysis-kraft pulp will be about 1.4
ton/ton airdry pulp. About 40% of this quantity will be available as
flash steam for hot water preparation. The consumption of high-pressure
steam can be reduced further by preheating the white liquor with flash
steam or with the extracted black liquor.
The flow of the chips through the digester was studied by the conventional radioactive tracer technique in order to determine the uniformity
and retention in the various zones (Fig. 8.5). At a feeding rate of 25 tons
of moisture-free wood per day, corresponding to a production of 11 tons
a.d. pulp, the retention times were 2.5 hr in the prehydrolysis zone, 3.0 hr
in the kraft cooking zone, and 2.5 hr in the washing zone. A 50% increase
in the rate of feeding with a corresponding change in cooking conditions
gave a reduction in retention to about 1.5 hr prehydrolysis, 2 hr kraft
cooking and 1.5 hr washing. The continuous digester purchased by Billerud for the Leirosa rayon pulp mill in Portugal has been designed for
approximately the same retention times as those last mentioned, in order
to obtain reasonable temperatures in the process.
During the initial trials with the vapor-liquor phase system the digester
was started up by carrying out a batch kraft cook without preceding
114
Lecture 8
Fig. 8.5. Radioactive tracer experiments to determine retention time and

packing density in the one-body prehydrolysis-kraft pilot digester.
'hydrolysis. The startup pulp became mixed in the pulp storage chest with
the subsequent prehydrolysis-kraft pulp. Such a method, however, is not
acceptable, since for quality reasons, "no admixture of paper pulp in the
rayon grades can be allowed. To avoid any mixing of kraft pulp and
prehydrolysis-kraft, it is desirable to start up the digester with prehy-
115
Table 8.1. Cooking Conditions and Quality Data for Eucalypt

Prehydrolysis-kraft Pulp, Mumin Pilot Digester
Prehydrolysis
Kraft cooking
Washing
Prehydrolysis
Kraft cooking
Washing
To transition circulation
To cooking circulation
Total
White liquor sulfidity, %
Roe No.
Screenings, % on pulp
Viscosity, cp TAPPI
Rl8.%
R10,%
R, % (= alpha-cellulose)
Brightness, unbleached, % SCAN
Retention time, hr
2.5
1.5
3.0
2.0
2.5 '
15
Temperature, C
166
170
155
158
135
135
Active alkali charge,
% Na2O on wood
8.6
8.5
9.4
9.8
18.0
18.3
30
0.7
0.9
65
97.8
96.4
97.2
48
30
0.6
0.9
56
97.5
96.4
97.0
49
drolysis. This was achieved by feeding the first chips into the empty
digester at full vapor-phase prehydrolysis conditions. After reaching a
certain chip level, white liquor which was preheated to cooking temperature was introduced to the digester bottom and the liquor level successively raised. The discharge was started at the moment the chip level
reached the digester top. This startup method gave a rayon grade pulp
from the very beginning, and any contamination by paper grade kraft pulp
was avoided.
After the initial adjustments in equipment and operation, and a limited
trial period with three wood species, a reUability test was performed to
investigate the operation efficiency. During a test period of one month,
the digester was in operation more than 99% of the time, disregarding a
short stop because of a pipe welding failure. The remaining 0.8% downtime was caused by tramp iron. Considering that this reliability test was
carried out with a new system, the results must be regarded as quite
satisfactory. Subsequent operation of the pilot digester for over half a
year to produce trial quantities for customers fully confirmed these conclusions, and this can also on the whole be said about the commercial
operation of the 300 ton/day digester in Portugal, after some necessary
116
Lecture 8
Table 8.2. Cooking Conditions and Quality Data for Prehydrolysis-kraft
Pulps from Pine, Birch, and Eucalypt, Mumin Pilot Digester and Laboratory
Cooking. Retention Times Not Identical
Prehydrolyzate withdrawn before charging white liquor.
adjustments caused by scaling-up factors. Digesters have also been ordered for USA and Russia with identical design but twice the size.
Table 8.1 shows digester conditions and quality data for eucalypt prehydrolysis-kraft pulp produced at two different rates of production. The
retention times were fairly long, though not excessive. The comparatively
low temperatures in the kraft cooking stage indicate that the volume of
this zone can be reduced. The necessary charge of active alkali, 230
kg/ton o.d. wood, as NaOH (18% Na 2 0), is rather high owing to the fact
that the prehydrolyzate is not extracted separately. In many cases, however, it is an advantage to include the solids dissolved by the prehydrolysis
stage in the black liquor. This will give more heat from the recovery
furnace and also minimize the water pollution problem.
The pulp quality was uniform and on a high level. The high alpha-cellulose content of 97% obtained was partly due to severe hydrolysis conditions and partly to the fact that eucalyptus is a wood species well suited
for high-grade rayon pulp. The effect of different wood species on final
pulp quality is illustrated in Table 8.2, which shows the result of similar
trials on pine, birch, and eucalyptus. The quality data obtained are
satisfactory and quite comparable to those of laboratory-cooked batch
pulp. Possibly the countercurrent principle in the kraft cook gave a shade
higher purity than the corresponding batch cook, though the main reason
for maintaining it is the greater uniformity obtained from the kraft cook.
One can therefore conclude that the new continuous cooking system
Table 8.3. Quality Data for Eucalypt Prehydrolysis-kraft Pulp, Produced

in Mumin Pilot Digester, Without and With Cold Alkali Purification
Incorporated in the System
developed produces a prehydrolysis-kraft pulp of good uniformity and

high quality. One further possibility of increasing the pulp purity exists,
which is unique to the system. The highest grades of cord pulps are sold
at an alpha-cellulose content of above 98%. They are produced by more
or less complicated methods of cold alkali purification. The alkali consumption is generally economically prohibitive, or anyway a severe economic burden. It is therefore sometimes attempted to use white liquor
for the cold alkali purification and then to use the waste liquor from the
purification in the cooking. Normally, however, elaborate machinery
would be necessary to realize this idea at a reasonable heat economy. Continuous cooking, particularly countercurrently, in combination
with countercurrent digester washing, is ideal to accomplish cold alkali
purification in a simple and economical way. As already shown in Fig.
8.3, the alkali concentration realized in pure countercurrent cooking at the
end of the cooking zone is above 60 grams/liter even with washing liquor
introduced into the digester bottom. For an efficient cold alkali purification, 80 grams/liter NaOH and 30C are required. If the white liquor
required for cooking is introduced into the blow line (Fig. 8.6), the blow
tank becomes the logical purification tower and the washing of the pulp
from white liquor can be performed on the normal filter wash. The
white water from the filters is carried countercurrently to the digester
bottom and is used in the washing and cooking zones for the kraft
119
cook. That white water has to be cooled before the introduction to the
digester base, to ensure proper cold alkali purification temperature, and
then subsequently heated in the digester as usual between the washing and
cooking zones. Likewise the fresh white liquor should be cooled to
ensure 30C in the purification. A less good heat economy and a slightly
reduced pulp yield are the limited disadvantages to obtain the increased
cellulose purity shown in Table 8.3. The system has thus been tested on
the pilot scale and will soon be tried on the large scale. It constitutes an
elegant example of how the continuous cooking system can be advantageously utilized in combination with a subsequent operation.
I have described the development of prehydrolysis-kraft cooking fairly
elaborately, in spite of its specificity, partly because that was the process
which initiated the development of the flexible Mumin digester system,
and partly because several of its elements may become useful in other
process applications. The reliable performance of the system further
shows that once a continuous system has been worked out, one should not
fear to run a series of seemingly complicated operations, such as steaming,
liquor impregnation, vapor-phase cooking, countercurrent liquor-phase
cooking, and countercurrent washing, or even cold alkali purification.
Complexity is not a virtue in itself, but in order to achieve the goals of
quality and economy it may sometimes be necessary to accept it, and to
make it work.
Lecture 9

The targets for the development work on modified kraft cooking have
been, to carry out some chemical process modifications in the continuous
pilot digester, and also to investigate how the ideal impregnation system of
a kraft digester should be designed. The work has concerned both chemical kraft pulping to a lignin content of about 4% and semichemical kraft
pulping to a lignin content of 10-15%. The corresponding pulp yield
ranges would thus be about 47 and 53-58%, respectively, for normal pine
kraft and 3-5% higher in some of the modified processes. Pine was predominantly used for the trials, but some runs were also made on birch and
eucalyptus. As always, these trials were preceded by careful laboratory
investigations, but some of the process modifications, particularly those of
rapid heating and of countercurrent cooking, are not easily simulated in
the laboratory.
The development work on prehydrolysis-kraft pulping just described had
led to a digester essentially the same as the standard kraft cooking system,
with a few extra features. The major deviation in the machinery was in
the digester top, which gave instant heating to maximum temperature
instead of the usual 0.5-1.5 hr of gradual temperature rise in the upper
part of the digester. The question now was whether this digester would
allow satisfactory production of kraft paper pulp, which is the desired
second grade in a prehydrolysis-kraft pulp mill, and sometimes growing to
be the primary grade. There was always the possibility of purchasing a
second top separator and changing separators when changing pulp grades,
but this solution was regarded as too complicated for current production. The Mumin digester had also proved to be admirably easy to operate, and it was thus desired to maintain this system if acceptable from a
quality standpoint. We therefore launched a program to investigate the
kraft pulping of eucalypt with instant heating in the Mumin system, and
extended that later to the pulping of birch and pine.
Figure 9.1 shows the system arranged for kraft pulping. The chips and
white liquor are thus charged to the feeding system, and only 1-2 min are
allowed for impregnation before live steam is added at the digester top.
121
122
Lecture 9
Fig. 9.1. Concurrent cooking of kraft by the Mumin system.

Impregnation pressure is digester pressure, 8-9 atm. After cooking, the
black liquor is withdrawn and washing countercurrently performed in the
lower part of the digester. The pressure is controlled by the top relief
valve and an air compressor, and the liquor level by balancing the waste
liquor withdrawal and the wash liquor introduced into the digester bottom.
From the previously related success with this impregnation system on
acid sulfite, bisulfite, and neutral sulfite pulping, it would seem fairly sure
that it would work also on kraft. The impregnation problems have always
been more accentuated in sulfite than in kraft pulping. However, for
reasons discussed in Lecture 6, the impregnation problems are somewhat
different in kraft cooking, since so large a quantity of the chemicals are
rapidly consumed, and since normal concentration of cooking liquor does
not allow the introduction of all chemicals needed for the cook, even with
complete penetration of the chips with liquor. This means that with
normal white liquor concentrations some liquor has to flow over to the
digester with the soaked chips from the top separator, and that the chemicals of the liquor must diffuse into the chips during the retention of the
chips in the cooking zone. If that diffusion is too slow in relation to the
reactions at maximum temperature, cooking with instant heating may lead
to nonuniform pulp.
123
Table 9.1. Cooking Conditions and Analytical Data for Chemical Kraft Pulps
Produced with the Normal Hydraulic System and the System with Instant
Heating (Mumin). Pine, Birch, Eucalypt
Hydraulic system
Pine
Birch
Eucalypt
Mumin system
Pine
Birch
Eucalypt
The results of the kraft paper pulp cooking in the Mumin digester system
with instant heating are shown in Tables 9.1 and 9.2 ( cf. also Table 9.4),
in comparison with normal hydraulic cooking with a heating period. In
the case of eucalypt and birch, only chemical kraft pulps were produced,
and the composition, strength, and screen rejects with the Mumin system
were found to be entirely equivalent to normal hydraulic cooking. This
conclusion has been further corraborated by the preparation of several
hundred tons of trial quantities of bleached eucalypt paper pulp in
sefors and by the 500 ton/day operation at Leirosa, Portugal.
In the case of pine, some differences could be detected, seemingly insignificant, perhaps, but important enough in view of the size of the pine
kraft pulping of the world. The carbohydrate composition of the pulps
from the cooking with instant heating appears to be slightly different, with
somewhat less xylan and somewhat more glucomannan, indicating about
124
Lecture 9
Table 9.2. Paper Properties of Chemical Kraft Pulps Produced with Normal Hydraulic System and System with Instant Heating (Mumin). Pine, Birch, Eucalypt
Hydraulic system
Pine
Birch
Eucalypt
Mumin system
Pine
Birch
Eucalypt
2% lower cellulose content and 1% higher yield. As shown in the tables,

there is hardly any significant difference in paper strength for chemical
grades, but the few results from the semichemical pulp testing appear to
indicate a shade lower strength with instant heating "Mumin cooking."
The screenings of the chemical grade pulps at a Roe No. level of 5, or
about 4% lignin content, appears to be about 2% for hydraulic cooking
and about 3% for Mumin cooking. No additional shiviness could be detected in the latter pulp type. Some trials in more rapid Mumin cooking,
to utilize the extended cooking zone for a higher capacity, increased the
screenings to 5%. These cooks, however, had to be performed not at a
higher capacity, because of the limitations in receiving capacity of the pulp
plant, but at a lower chip level in the digester, which may have influenced
the results. At Roe No. 6, hydraulic cooking gave 2% screenings at a
certain white liquor charge, Mumin cooking 6% screenings on pulp. A
10% increase in the white liquor charge compensated for this disadvantage. For kraft pulps of somewhat higher lignin content, somewhat larger
differences in screenings appeared. The refining energy of the semichemical pulps was also quite similar, within the considerable experimental
error, with possibly a shade higher consumption in the cooks with instant
heating. One interesting aspect is the unusually high brightness of the
Mumin pulps, particularly the chemical grade.
Taken together, the results on pine cannot be said to have indicated any
important advantages for Mumin cooking, other than a higher brightness
and a slightly higher yield, but neither were there any great disadvantages. The extra white liquor needed for equal screenings level must,
however, be considered as a drawback. The subsequent results on coun-
125
Fig. 9.2. Countercurrent cooking of kraft by the Mumin system.

tercurrent cooking, polysulfide cooking, and preimpregnation cooking give
some additional aspects on these problems.
Countercurrent soda cooking has been practiced for several years in Australia on eucalypt. It works well mechanically and is claimed to give no
disadvantages in quality. It was also tried with kraft cooking on radiata
pine in New Zealand, and the investigation carried out by us for Kamyr on
those pulps indicated a certain decrease in yield, beatability, tensile and
bursting strength, and an increase in tearing strength. This could be expected from a loss in xylan due to the higher alkalinity toward the end of
the cook. The brightness of the pulp was improved, however, which was
also to be expected from the elimination of any lignin reprecipitation toward the end of the cook, through the higher alkalinity.
In connection with the radiata pine pulp characterization, we also carried out a few trials with countercurrent cooking in the two-body digester. This was not very well equipped for the purpose, and the project had
to await the two reconstructions of the digester system. Trials were then
run with countercurrent cooking both hydraulically and in the Mumin
digester system. Both the pure countercurrent version and the modified,
partial countercurrent process were tried (Fig. 9.2). In the latter process,
the white liquor charge is split between the top and bottom, but the black
liquor is always withdrawn at the top, thus maintaining a proper counter-
126
Lecture 9
Fig. 9.3. Countercurrent cooking of kraft by the conventional system.

current flow principle in the digester. The white liquor charge at the top
has the function of preventing the pH from becoming too low from wood
acids, which leads to blockage of the black liquor extraction strainer.
This was the experience with prehydrolysis-kraft, and it was again confirmed with countercurrent normal kraft.
With pure countercurrent kraft cooking, the chips are charged to the
impregnation system together with black liquor only. In the conventional, hydraulic digester, the chips will then move in black liquor during the
entire zone of impregnation, which can hardly be an advantage (Fig.
9.3). A system without that zone, i.e., the Mumin digester system, would
in this case be a particular advantage.
As shown in Table 9.3, pure countercurrent kraft cooking on pine gave a
chemical pulp with normal screenings, relatively high brightness, and low
content of hemicelluloses, particularly of xylan. This corresponds to
3-4% lower yield, based on the wood. With partial countercurrent cooking the screenings, hemicellulose content, and pulp yield were intermediate, whereas the brightness decreased considerably.
The paper properties of the pulps were changed by countercurrent
cooking toward decreased beatability, lower tensile and burst, and higher
tear and folding endurance, just as expected from the lower hemicellulose
content. The partial countercurrent cooking gave intermediate results.
127
Table 9.3. Cooking Conditions, Analytical Data, and Paper Properties for Pine
Chemical Kraft Pulps, Produced Concurrently and Countercurrently. In all cases
instant heating in the Mumin system.
The countercurrent cooking trials with semichemical pine kraft pulp

(Table 9.4), showed essentially the same results, i.e., 2-3% lower yield at
equal lignin content, mainly through a loss of xylan, and a certain increase
in tear strength. The decrease in tensile and burst strength was not
observed here, however; but neither was there a significant brightness
improvement. An advantage appeared to be an observed decrease in fiberizing energy with countercurrent cooking. Since the corresponding
laboratory refining on washed semicooked chip samples gave no differences, the result is interpreted so that the semicooked chips after digester
wash have a higher pH with countercurrent cooking than with concurrent
128
Lecture 9
Table 9.4. Cooking Conditions, Analytical Data and Paper Properties of Semichemical Kraft Pulps, Produced Concurrently and Countercurrently. Hydraulic
cooking as well as Mumin cooking
Hydraulic cooking
Concurrent
Partial
countercurrent
Countercurrent
Mumin cooking
Concurrent
Partial
countercurrent
Retention time, hr
cooking, and that this facilitates the fiberizing. Partial countercurrent

cooking gave an intermediate and rather insignificant yield decrease.
Partial countercurrent cooking of birch to chemical kraft pulp gave a
pulp with similar screening rejects and not noticeably lower in hemicelluloses than concurrent cooking, but with slightly less good paper strength.
129
Fig. 9.4. Polysulfide cooking by the Mumin system.

In general, it can be concluded that countercurrent kraft cooking of pine
and birch offers little advantage over concurrent operation, and that a
decrease in yield and sometimes in paper strength occurs. Partial countercurrent cooking gives intermediate results. The possibility cannot be
excluded, however, that further trials, particularly with decreased charge
of white liquor, might eliminate at least part of the yield loss.
Polysulfide cooking appears at first sight be a straightforward kraft process, with sulfur added to the white liquor to give polysulfide and thus the
desired end group oxidation of the carbohydrates and an increased
yield. That is the way it has been practiced so far in the few mill scale
runs with batch digesters. In principle, therefore, the normal Kamyr
system should be applicable to polysulfide cooking, and this was also our
first approach at Jossefors. Polysulfide cooking with rapid heating was
another obvious variant, and both were tried with chemical as well as
semichemical pine kraft (Fig. 9.4).
In order to economize with the sulfur addition while maintaining the
yield improvement, laboratory trials have been made with two-stage polysulfide cooking, essentially employing a polysulfide cooking stage at lower
Table 9.5. Cooking Conditions, Analytical Data, and Paper Properties of Chemical and Semichemical Kraft and
Polysulfide Pulps, Produced by the Hydraulic or Mumin Systems
Mumin cooking
Hydraulic cooking
Chemical
Retention time, hr
Impregnation
Cooking
Temperature, C
Impregnation
Cooking
Pressure, atm
Active alkali charge, %Na 2 0 on wood
Sulfur charge, % S on wood
Roe chlorine No.
Screenings, % on pulp
Brightness, % SCAN
Resin content, %
Galactose
Glucose
Mannose
Arabinose
Xylose
Chemical
Semichemical
Kraft
Polysulfide
Kraft
Polysulfide
2.5
2.0
2.5
2.0
2.5
2.0
125
168
10
14.5
0
5.4
2
27.1
0.18
125
171
10
18.0
4.4
5.2
4
21.9
0.18
...
84.2
7.5
...
8.3
...
83.2
8.7
0.9
7.2
Polysulfide
Semichemical
Kraft
1-stage
1-stage
2-stage
Kraft
Polysulfide
2.5
2.0
0.02
2.2
0.02
2.2
0.02
2.2
2.0
2.4
0.02
2.0'
0.02
2.0
125
155
10
13.5
0
14.5
125
150
10
15.0
3.8
14.5
105
156
9
18.5
4.3
5.2
4
26.7
0.20
122
151
9
18.5
4.0
5.5
1
26.5
0.27
105
147
9
14.0
3.2
14.5
15.7
0.38
105
158
9
17.0
1.0
4.4
4
29.6
0.15
105
152
9
14.0
0
14.5
17.9
0.38
105
165
9
16.0
0
5.1
3
30.6
0.19
19.2
0.37
18.0
0.35
1.1
79.9
8.5
1.7
8.8
1.2
78.1
11.0
1.7
8.0
0.2
82.9
9.1
0.2
7.6
0.6
83.1
10.3
0.6
5.4
0.6
"81.3
11.4
1.0
5.7
0.8
79.9
12.7
0.7
5.9
1.2
79.4
10.5
1.5
7.4
1.6
76.0
13.7
1.7
7.0
Table 9.5 Cont'd. Cooking Conditions, Analytical Data, and Paper Properties of Chemical and Semichemical Kraft and
Polysulfide Pulps, Produced by the Hydraulic or Mumin Systems
Mumin cooking
Hydraulic cooking
Chemical
Cellulose content, % on carbohydrate

Estimated pulp yield, % on wood
Beating time, min
Tear factor
Sheet density, g/cm3o
Beating time, min
Tear factor
CeEulose, % on wood
Galactoglucomannan
Lignin
Total
Kraft
Polysulfide
81.7
47.3
Chemical
Semichemical
Polysulfide
Semichemical
Kraft
Polysulfide
Kraft
1-stage
1-stage
2-stage
Kraft
Polysulfide
80.3
48.1
77.1
55.0
74.4
57.5
79.9
48.5
79.7
49.0
77.5
51.5
75.7
53.5
75.9
56.0
71.4
61.2
53
9.9
143
0.70
39
9.6
146
0.67
37
7.6
148
0.57
35
7.6
129
0.56
43
9.4
149
0.68
42
9.2
129
0.66
35
9.0
131
0.65
44
8.8
124
0.66
34
7.4
135
0.55
34
7.2
116
0.55
82
11.0
129
0.76
65
11.2
126
0.75
58
9.0
130
0.63
51
9.0
113
0.64
67
10.8
134
0.74
62
10.4
116
0.72
53
10.4
116
0.72
63
10.1
110
0.69
51
8.7
117
0.64
48
8.4
100
0.62
132
Lecture 9
temperature to stabilize the carbohydrates, followed by a normal kraft

cook for delignification.
Table 9.5 shows the results of all polysulfide cooking variants. In comparison with the results shown for normal kraft with the hydraulic and the
Mumin systems, the carbohydrate analyses prove a yield increase due to
better preservation of glucomannan. Hydraulic cooking, however, gave
with 4% S on wood only rather insignificant yield increases, 1-2%; whereas
with instant heating, better results were achieved, about 3% for chemical
and 5% for semichemical pulps, in addition to the extra 1% obtained by
the instant heating without sulfur. This is at least as good as can be
expected from laboratory trials, which gave about 4% yield increase for 4%
polysulfide sulfur added, both on wood basis. It is somewhat difficult to
calculate the yield increases from carbohydrate composition figures. The
yield increase due to glucomannan stabilization can always be calculated,
but in addition there is normally by the same end group mechanism also
an increased cellulose yield, 1-2%, wood basis, at normal polysulfide cooking conditions.
It can thus be stated that normal hydraulic kraft cooking will not be an
ideal procedure to give the expected yield improvement on sulfur addition
to polysulfide cooking, whereas cooking with instant heating in the Mumin
system is. The cause of this difference is probably differences in the
cooking liquor concentrations. Figure 9.5 shows the concentrations of
alkali and polysulfide sulfur found in the hydraulic and the Mumin systems. The cause of the low concentrations in the top of the hydraulic
digester is probably the thermal convection flow from the hotter cooking
zone. This phenomenon is likely to be less pronounced in the large digesters.
One very encouraging observation is that the pulp brightness, which
with polysulfide cooking normally suffers by as great a percentage as the
yield is improvedprobably because of carbonyl group formation in the
ligninis not lower with the Mumin polysulfide pulps than for normal
kraft pulps cooked hydraulically. Thus, one of the objections to polysulfide cooking is eliminated by continuous cooking with instant heating.
Another serious objection to polysulfide cooking is the decrease in
strength properties, as shown previously for laboratory cooks. That decrease was also observed in these continuous cooking trials, where a yield
improvement was achieved. However, this general strength decrease is no
more serious than that, for each pulp application, it must be considered
whether this change in paper properties is acceptable or not. As seen by
the tables, the screenings also increase, as does the consumption of active
alkali, when changing to polysulfide cooking; but these disadvantages can
133
Fig. 9.5. Concentration of active alkali and polysulfide

sulfur vs. digester height, hydraulic and Mumin systems.
be met. More serious, perhaps, is the fact that the refining energy of
semichemical polysulfide may be 200 kW-hr/ton in excess of that of kraft
at equal lignin content, with some reservation for the accuracy of that
determination.
The third objection to polysulfide cooking is that the addition of sulfur in quantities of about 4% on wood tends to increase the sulfidity of the
white liquor stock from 30 to 60%. This is undesirable from an economical standpoint, and although there are methods devised for the recovery
of elemental sulfur from the reclaimed chemicals, such methods are costly
in both investment and operation. It is therefore very desirable to perform the cooking in a way which achieves maximum yield improvement at
a minimum sulfur addition. With the Mumin system a yield increase was
obtained of about 2% above normal kraft, wood basis, at a polysulfide
sulfur charge as low as 1% (Table 9.5). Such a low charge is feasible
without any special recovery arrangements other than using carbonate
instead of sulfate for makeup chemical. A still greater efficiency in the
polysulfide utilization is desirable, however. One of the few possibilities
of improving it would be to react wood with a polysulfide solution prior
to the kraft cooking. To design a corresponding cooking system, the
Mumin digester was used in the manner described below (see Fig. 9.6).
134
Lecture 9
Fig. 9.6. Polysulfide-kraft two-stage cooking by the Mumin system.

The feeding circulation was charged with a limited quantity of white
liquor, corresponding to less than half of the total charge, or about 80
kg/ton o.d. wood active alkali, expressed as NaOH (6.2% Na2 0). That is a
quantity corresponding to the amount normally consumed by the chips at
feeding conditions, 100-110C for 1-2 min, and leaves a feeding circulation liquor essentially consisting of sulfide-hydrosulfide. This solution is
ideal for dissolving sulfur to polysulfide, and it can be bled off to a sulfur
dissolving tank at the same rate as polysulfide solution is fed to the system. It is also possible, however, to dissolve the sulfur in the white liquor
with rather small sulfur losses, provided correct conditions are
chosen. The chips, thus impregnated, will fall into the digester, and can
be allowed to react with the polysulfide a suitable time at a suitable
temperature, before white liquor is added to the digester to accomplish the
kraft cook. To ensure that the stages are well separated, the liquor level is
kept just above the white liquor addition, and the polysulfide stage carried
out in vapor phase.
The choice of the temperature in the first stage is not optional, unless
special precautions are taken. If the temperature should be kept lower
than that of the kraft cook, addition of a gas is necessary to keep the
digester pressure above the vapor pressure of the kraft cooking
liquor. Such pressure control with a compressed air cushion has been
135
Table 9.6. Cooking Conditions, Analytical Data and Paper Properties of One-stage
and Two-stage Kiaft and Polysulfide Pulps, Mumin System
Kraft
1-stage
2-stage1
Polysulfide
1-stage 2-stage2 2-stage1
Impregnation followed by vapor-phase treatment about 125C prior to cooking. All

chemicals charged at impregnation.
Impregnation in a limited amount of white liquor plus all polysulfide sulfur, followed by instant heating to maximum temperature. The remaining white liquor
charged to the second half of the cooking zone.
2
136
Lecture 9
tried in the two-body digester and found to work well. In the two-stage
polysulfide cookings, both 130 and 170C were tried for the initial cooking stage, the latter temperature being equal to that of the subsequent
kraft cook. The results are shown in Table 9.6, indicating that the yield
improvement of polysulfide cooking disappeared with two-stage cooking
using two white liquor charge points. This rather astonishing result indicates that the polysulfide oxidation of carbohydrate end groups requires a
fairly high-alkalinity. As shown in the table, a straight polysulfide cook in
the Mumin system, with all white liquor charged to the feeding circulation
but a lower temperature, 122C, kept in the upper part of the digester for
the polysulfide reaction, gave an unusually high yield. The system must
be arranged for vapor phase in the polysulfide reaction zone to prevent or
limit thermal flow from the kraft cooking zone. The combined high alkalinity and polysulfide concentration of the Mumin feeding system and the
favorable temperature conditions of the vapor-liquor phase cooking explain the good polysulfide efficiency. This is in accordance with laboratory results. It should therefore be possible to limit the sulfur addition to
reasonable amounts, 2% or less, to achieve a desired yield improvement of
4%, but regrettably, lower sulfur additions were not tried with the vaporliquor phase system. Another favorable observation with the vapor-liquor
phase system is the low screenings obtained with both kraft and polysulfide cooking.
The trials with polysulfide cooking have thus shown that continuous
cooking systems can be designed to fit advanced process requirements for
optimal economy and quality.
Before continuing with the presentation of additional process variants, I
should like to sum up the experience on carbohydrate composition of pine
pulps, cooked by the normal kraft process and the variants of instant
heating, countercurrent cooking, and polysulfide cooking, for both chemical and semichemical pulps (Tables 9.3-9.5). The sugar analyses have
been recalculated to cellulose, galactoglucomannan, and glucuronoarabinoxylan (Fig. 9.7). Countercurrent cooking decreases primarily the xylan
yield, whereas instant heating, as well as polysulfide, increases the glucomannan yield and causes a certain loss in xylan. Limiting the degree of
cooking causes a gain not only in lignin yield, but also in xylan and
particularly in glucomannan yield.
A process variant of kraft which has attracted considerable attention
recently is the so-called "Alkafide" process, which is essentially a hydrosulfide-sulfide cook. It is unique so far as it has been developed directly
for continuous cooking by the M & D "piggyback" system, that is, a
two-body digester for a two-stage cook. The essential virtue of the pro-
138
Lecture 9
cess is that it can utilize uncausticized liquor and that therefore the calcium cycle of the recovery system can be eliminated. The snag isso far
-that the recovery furnace cannot be run to give 100% sulfidity in the
green liquor, but that the carbonate must be separated from the sulfide, a
process which has always been within reach of the kraft industry but not
been regarded as a very attractive unit operation. Leaving the recovery
aspects aside, the cooking process consists of a pretreatment at a somewhat lower temperature, where a limited amount of sodium sulfide is
allowed to react with the wood chips to form at steady state a mixture of
hydrosulfide and sulfide. In the second digester body, run at a higher
temperature, the semicooked chips are allowed to react with more sulfide
to give a pulp of essentially kraft pulp yield and strength.
In order to run this process in a really large-scale new mill, or in those
mills already having a Kamyr digester, it could be of interest to apply the
Kamyr system to the Alkafide process. This could be accomplished in a
similar manner as the two-stage polysulfide cooking just described, i.e.,
with a limited charge of sodium sulfide to the feeding circulation, to an
extent corresponding to the first stage of the Alkafide cook. The alkali
consumption in the feeding circulation will convert most of the sulfide to
hydrosulfide and the chips will become impregnated with hydrosulfide,
which may then react with the chips in the precook in the vapor phase,
down to the liquor level, where more sulfide is added. There is also the
obvious possibility of adding sulfur to the feeding liquor for polysulfide
effect.
In the first approximation it was tried to run a straight sodium sulfide
cook, with all cooking liquor added to the chips, and in the second approximation, liquor from the middle of the digester was recycled back to
the top, which also ought to give the desired hydrosulfide cooking medium. The cooking temperature was in both cases constant throughout the
digester, 168 resp. 174C, and the sulfide charged 260 kg/ton o.d. wood,
26%, expressed as NaOH or Na2S. The liquor ratio was kept as low as
possible, about 2.5, which gave a reasonably fast reaction. The chemical
pulp obtained contained more screenings than previous pulps, but was in
most other respects equivalent to kraft pulp (Table 9.7). The carbohydrate composition indicates a fairly normal yield, the strength was on the
kraft pulp level, the brightness somewhat lower, and resin content somewhat higher, without extremes. Considering these trials to have been
rather short and exploratory, the process can be said to have definite
possibilities without having shown any advantages over kraft pulp, as also
indicated by laboratory trials. The interest in the process thus appears to
lie mainly on the recovery side. If the advantages there are found large
139
enough to validate a development, the cooking process is likely to give no

particular obstacles. The addition of sulfur to give a polysulfide yield
increase was, however, not successful, as shown also in Table 9.7. This is
another indication that a high alkalinity in the initial polysulfide treatment
is essential to get the yield improvement.
A process of both theoretical and possibly practical interest is the alkaline sulfite cooking method. This has been tried in many variants since
the original work on the Keebra process variants in the 1920's. The most
interesting version is that containing sodium sulfite, sodium sulfide, and
small quantities of sodium hydroxide or carbonate as the active cooking
chemicals. Laboratory work by us and in other laboratories has shown
that both the sulfite and the sulfide have a function to fulfill, since the
cook is retarded when the charge of any of them is decreased. Substituting thiosulfate for them does not give the same result, although it seems
unavoidable that thiosulfate is formed during a cook containing both sulfite and sulfide. As far as can be understood, both sulfonation and sulfidation reactions with the lignin occurs, but the reactions of the cook
have not been more closely studied. With the pH considerably lower than
for the kraft cooking varieties, the carbohydrate degradation appears to be
less rapid, with almost no cellulose degradation occuring until the chemical
pulp region is approached.
The drawback with the process is the large amount of chemicals needed
to accomplish pulping. The total charge of chemicals necessary to get a
reasonable cook is about 30% Na 2 0, wood basis, or almost twice that of
kraft cooking, at a liquor ratio of 4.0. However, much of those chemicals
appear to be unconsumed after the cook, indicating that concentrations of
the cooking chemicals rather than absolute charges are important. A
lower liquor ratio therefore ought to give considerable savings in chemicals, such as the 2.7 reached in continuous cooking. It was therefore
attempted to try alkaline sulfite pulping at low liquor ratios in the Mumin
digester system, without as well as with pressure preimpregnation (for
details, see below). The main reason for the interest in alkaline sulfite
pulping is that it represents the only pulping process known which gives a
significantly better strength than kraft cooking, or possibly higher yield at
equivalent strength. The results of the trials in the pilot digester are
shown in Table 9.8. On the whole, the laboratory results were confirmed,
whereby it is possible to produce either the same Roe No. as kraft at a
slightly higher yield and strength, but using large amounts of chemicals, or
to produce a pulp of equal strength as semichemical kraft at a higher Roe
No. and about 5% higher yield, using reasonable amounts of chemicals.
The work presented so far gives the results of process modifications of
Table 9.7. Cooking Conditions, Anayltical Data, and Paper Properties of Chemical
Sodium Sulfide, Hydrosulfide, and Polysulfide Pulps (Mumin System)
Retention time, hr
Impregnation
Cooking
Temperature, C
Impregnation
Cooking
Pressure, atm
%Na20 on wood
Sulfidity,
% on total alkali
Sulfur charge,
% S on wood
Roe chlorine No.
Screenings,
% on pulp
Brightness, % SCAN
Resin content, %
1-stage
polysulfide
Normal
High
sulfidity
sulfidity
2-stage
polysulfide
Normal
High
sulfidity
sulfidity
Kraft
Sodium
sulfide
0.02
2.2
0.02
2.2
0.02
4.2
0.02
4.4
2.0
2.4
2.0
2.4
105
165
9
105
172
8
105
156
9
105
177
9
122
151
9
130
168
8
16.0
20.0
18.5
5.5/15.51
18.5
5.0/17.01
30
90
30
100
30
125
0
5.1
0
5.3
4.3
5.2
4.0
5.8
4.0
5.5
4.0
5.0
3
30.6
0.19
8
23.2
0.35
4
26.7
0.20
2
20
...
0.7
26.5
0.27
5
22
Table 9.7 Cont'd. Cooking Conditions, Analytical Data, and Paper Properties of Chemical
Sodium Sulfide, Hydrosulfide, and Polysulfide Pulps (Mumin System)
1-stage
polysulfide
Galactose
Glucose
Mannose
Arabinose
Xylose
Cellulose content,
% on carbohydrate
% on wood
Beating time, min
Tear factor
Sheet density,
g/cm3
Beating time, min
Tensile strength,
km
Tear factor
Sheet density,
g/cm3
1
Charged after 2 hi cooking.
Kraft
Sodium
sulfide
Normal
sulfidity
0.2
89.9
9.1
0.2
7.6
...
85.4
6.9
1.6
6.1
0.6
81.3
11.4
1.0
5.7
2-stage
polysulfide
High
sulfidity
...
83.4
8.6
0.9
7.2
Normal
sulfidity
High
suffidity
0.8
79.9
12.7
0.7
5.9
83.5
7.3
1.0
8.2
79.9
83.1
77.5
80.6
75.7
81.1
48.5
46.5
51.5
48.0
53.5
47.5
43
9.4
149
41
9.5
145
35
9.0
131
39
10.0
155
44
8.8
124
41
10.1
152
0.68
0.66
0.65
0.70
0.66
0.68
67
66
53
65
63
64
10.8
134
10.9
129
10.4
116
11.0
136
10d
110
11.2
137
0.74
0.73
0.72
0.77
0.69
0.74
Table 9.8. Cooking Conditions, Analytical Data, and Paper Properties of Semichemical Kraft and
Alkaline Sulfite Pulps (Mumin System)
Kraft
Mumin
only
Retention time, hr
Impregnation
Cooking
Temperature, C
Impregnation
Cooking
Pressure, atm
% Na20 on wood
Roe chlorine No.
Brightness, % SCAN
Resin content, %
Galactose
Glucose
Mannose
Arabinose
Xylose
Cellulose content,
% on carbohydrate
0.02
2.0
Mumin with
no extra preimpr.
0.02
2.0
0.02
2.0
Alkaline sulfite
Mumin with
pressure preimpr.
1.25
2.0
Laboratory
1.25
2.0
0.2
2.0
0.2
2.0
105
152
9
14.0
105
170
9
29.0
105
175
9
19.8
105
170
9
27.0
105
175
9
19.8
105
170
9
27.0
105
175
9
19.8
14.5
19.2
0.4
14.5
20.0
0.5
18.0
14.5
1.2
14.5
18.9
0.9
18.0
14.9
1.2
14.5
17.0
0.5
18.0
14.0
0.6
0.92
82.8
8.0
1.4
7.0
1.2
84.2
6.9
1.3
6.4
1.3
83.5
7.5
1.3
6.4
1.0
85.2
5.5
1.3
6.9
1.0
84.6
5.8
1.3
7.3
80.1
81.9
81.0
83.4
82.7
1.2
79.4
10.5
1.5
7.4
75.9
0.8
83.2
7.6
1.4
7.3
80.7
Table 9.8 Cont'd. Cooking Conditions, Analytical Data, and Paper Properties of Semichemical Kraft and
Alkaline Sulfite Pulps (Mumin System)
Kraft
Mumin
only
% on wood
Beating time, min
Tear factor
Sheet density, g/cm
Beating time, min
Tear factor
preimpr. = preimpregnation.
Alkaline sulfite
Mumin with
Mumin with
no extra preimpr.
pressure preimpr.
56.0
58.5
61.5
57.5
61.0
34
7.4
135
0.55
42
8.5
132
0.60
33
7.5
121
0.58
33
8.1
140
0.56
35
7.7
140
0.56
51
8.7
117
0.64
59
9.5
116
0.67
45
8.5
109
0.64
47
9.6
123
0.64
48
9.0
124
0.63
Laboratory
60.5
57
45
8.6
150
0.61
67
10.0
135
0.67
39
7.6
142
0.57
57
9.2
125
0.63
144
Lecture 9
Fig. 9.8. Low-pressure preimpregnation system for Mumin kraft cooking.

more or less radical chemical deviations from the kraft process. The work
on instant heating has been included in that series of presentations, since
so many of the real process modifications employed that system. I shall
now describe the work done to investigate whether the impregnation of
the kraft pulping can be improved or needs any improvements. In addition to normal hydraulic cooking and that of instant heating in the Mumin
system, the following versions have been tried: Mumin system but with
the vapor-liquor phase arrangement (see Fig. 9.6), to allow some time at
lower temperature, preimpregnation in a vertical steaming vessel, the lower
part of which is kept under liquor level at steaming pressure, followed by
the Mumin digester system (Fig. 9.8), and finally preimpregnation in a
hydraulic pressure vessel after a normal horizontal steaming vessel, followed by the Mumin digester system (Fig. 9.9).
The impregnation vessel in the latter two systems was originally designed
by Kamyr and delivered for steaming at a bisulfite digester in Switzerland. It consists of a vertical cylinder, equipped with two alternative
circulation strainers and a discharge table for the impregnated chips. For
low-pressure impregnation, the upper part is used as a steaming vessel,
attached to a low-pressure feeder, with the liquor level kept somewhat
below the chip level in the vessel, and the discharge of chips and liquor
attached to the packing circulation of the high-pressure feeder to the
145
146
Lecture 9
147
148
Lecture 9
Fig. 9.10. Pulp screenings vs. white liquor charge at

various kraft cooking systems.
Mumin system. For high-pressure impregnation, the vessel is simply attached under hydraulic pressure in the Mumin system between the high
pressure feeder and the inclined top separator. The impregnation vessel
will then need a conventional top separator. The virtue of the latter
system as compared to the normal hydraulic system is that the temperature conditions of the impregnation can be well defined and thermal flow
disturbances in the digester avoided, thus combining the advantages of the
hydraulic and the Mumin systems at an extra investment cost.
The results of the preimpregnation studies on pine (Table 9.9) are best
illustrated in a series of curves for screen rejects of kraft pulp as a function
of the white liquor charge at two lignin content levels (Fig.
9.10). Hydraulic cooking gave a uniformity equivalent to laboratory
batch cooking with 2.5 hr heating time. Instant heating with the Mumin
system gave, as previously mentioned, a clearly higher screenings content
at equal white liquor charge, although the differences would be eliminated
by increasing the white liquor charge. Preimpregnation in the low-pressure system prior to Mumin cooking compensated for the difference to
hydraulic cooking even at equal white liquor charge, and high-pressure
preimpregnation for 2 hr at 105C actually gave lower screenings than the
hydraulic system. Such a system, however, adds considerably to the investment costs, and it is therefore interesting to find the same effect
achieved by simply using the Mumin system but allowing the impregnated
149
chips to prevail at 120-130C for an hour in the vapor phase in the digester
top before increasing the temperature to cooking in the liquor phase.
Analogous results were obtained on polysulfide cooking with these various
systems, i.e., less screenings through preimpregnation or prevailing in vapor
phase at lower temperature before cooking. The results are summarized
in Table 9.10, together with those of other modifications of chemical kraft
cooking. Similarly, preimpregnation treatment prior to Mumin cooking
of semichemical kraft pulp variants appeared to decrease the fiberizing
energy, indicating better homogeneity of cooking (Table 9.11).
Obviously, differences in the penetrability of the wood may influence
the choice of the kraft pulping system (see experience on semichemical
bisulfite pulping quoted in Lecture 4). For chemical kraft pulps from
hardwoods, such as eucalypt and birch, there appears to be no reason for
choosing elaborate impregnation equipment, and indeed the Mumin digester system is the simplest, fully adequate equipment to choose. For
chemical kraft pulps from pine, the choice is more open to question. The
ordinary hydraulic system appears to come fairly close to ideal uniformity,
and gives somewhat better uniformity than instant heating. If the instant
heating system is preferred for other reasons, and yet absolute unchanged
uniformity desired, the steaming vessel should preferably be designed as
the vertical impregnation chamber. With demands on improved uniformity, the pressure impregnation vessel could be chosen. This is possibly
the case with chemical pulping to higher lignin content than normal. A
possible alternative is the simple Mumin system for vapor-liquor phase
cooking. For semichemical pulping, the impregnation effects should be
reflected in the fiberizing energy consumption and in the paper properties. As indicated in the previous tables, this is the case to only a very
limited extent as far as paper properties are concerned, and the measurement of fiberizing energy did not allow any fine gradation, although preimpregnation did seem to decrease the energy demand. The impregnation
in the simple Mumin system with a white liquor of high concentration may
in many cases yield equivalent results, and could motivate the choice of a
simple digester system. However, the first steaming-impregnation vessels
for the large-scale production of kraft pulps have already been delivered,
to Italy, Japan, and Sweden, and further experience may bring out their
possible advantages more clearly.
The uniformity of impregnation and cooking of semichemical kraft must
be important not only for the energy consumption of the fiberizing, but
also for the shiviness and runnability of the stock on the paper machine. Particularly at the highest yields, this influence of pulp uniformity
ought to be pronounced and a limiting factor in the efforts to decrease
150
Lecture 9
151
152
Lecture 9
153
154
Lecture 9
Fig. 9.11. Uniformity of semichemical kraft pulp, low-pressure preim

pregnation.
155
Fig. 9.12. Uniformity of semichemical kraft pulp, high-pressure preim

pregnation.
156
Lecture 9
Fig. 9.13. Paper strength between 25 and 45SR for pulps cooked continuously in the experimental pulp plant, as compared to kraft pulps cooked
by the batch and continuous systems on the full mill scale.
wood consumption and cost. A new technique for study of the uniformity of semicooked kraft chips has been applied on four pulps from the
trials with low-pressure and high-pressure preimpregnation. Step-wise
laboratory turrnix treatment of the chips followed by lignin content determinations on the pulp fractions liberated indicated (Figs. 9.11 and 9.12),
considerably better uniformity by the high-pressure preimpregnation. Further studies along these lines appear motivated, and the results
suggest that a perfect impregnation prior to cooking may make higher
yields possible. Several large-scale installations are under way.
To sum up the results of the kraft pulping development work, it is fair to
say that both the process and the machinery may deserve to be less standardized than they used to be. Systems have been designed for simpler
operation, for higher process flexibility, and for improved uniformity. The
process modifications indicated so far by research have all been realized
with fair success in continuous cooking. Their large-scale realization will
now depend on how the recovery problems can be solved, and whether the
quality of the process variants can be accepted. My personal opinion is
that the conventional kraft process will remain dominant for considerable
time, and that the inroads of the process modifications will first come on
special applications. The urge for less wood costs will, however, move the
yields upward by limiting the delignification and by stabilizing the
157
Fig. 9.14. Tear factor at equal tensile strength vs. pulp yield
for the pulps produced in the experimental pulp plant by
various processes and process variants.
carbohydrates. Yields of 60% and above will then be realized. Figure 9.13
compiles the paper strength of the pulps produced in the experimental
pulp plant by various processes and process variants in a diagram plotting
tensile strength against tear strength. The large variety in strength
properties makes those pulps useful in different areas. As shown in Fig.
9.14, the strength variation is largely a function of pulp yield, with the
exception of acid sulfite pulping, where the acidity combined with the
mechanical chip damage results in lower strength at equal yield. It is not
irrelevant, however, how a certain pulp yield was obtained, since the
drainage properties at a certain tensile strength will be quite different for
example, for a semichemical kraft pulp and a chemical polysulfide pulp of
equal yield. A combination of less delignification and less carbohydrate
degradation may therefore prove to be the best alternative in some cases.
Since it is now fairly well known how the process conditions should be
chosen to obtain a certain yield and a certain combination of properties, I
am personally convinced that the most important task for future research
is not to improve the pulping processes as such (aside of their recovery
systems), but to find out what properties are important for each essential
application and then to apply existing knowledge to select the process and
its conditions.
Lecture 10
Washing Process Theory

The primary reason for washing is to obtain a pulp free of soluble
impurities. Yet, as long as subsequent operations were run with an abundance of water, the pulp was automatically cleaned from the soluble impurities by the repeated dilution and thickening operations. The solubles
then went down the drain, and they still do in many places. This, however, is becoming unacceptable for two reasons: stream pollution and
economics. The so-called waste liquor has a value because of its chemicals
and combustible organic matter. The second reason for washing is thus to
recover the waste liquor as completely as is economically possible. The
costs of recovery are investment in equipment and current steam costs for
the evaporation of the wash water added, or rather for that portion of the
wash water which did not remain in the washed pulp but found its way to
the recovered waste liquor and thereby diluted it.
The interest of the washing operation and washing system design thus
centers around the problem of how to recover a maximum of waste liquor
at a minimum dilution and a minimum investment.
The kraft industry was the first of the pulping industries to devote
attention to the problem in this sense, and it introduced in the 1880's the
diffuser, a construction originally designed for the sugar industry. The
sulfite industry used less valuable chemicals and concentrated on the primary task, to rid the pulp of the waste liquor sufficiently to allow screening to take place without foaming. Blow pit wash or batch digester wash
were the systems used.
Filters were first introduced to the pulp industry as washers in the
bleachery, but in the 1930's, the kraft industry began to use filter washers
instead of diffusers. It was then found necessary to apply a series of 3-4
filters and the countercurrent washing principle, i.e., to introduce the wash
water on the last filter and to pass the filtrate therefrom onto the previous
filter as wash liquor, etc., until the filtrate from the first filter could be
recovered in concentrated form and passed to the evaporators. The
countercurrent principle as such had been applied already in the diffuser
washing, but met with greater practical difficulties in the filter systems,
159
160
Lecture 10
because these allowed air to mix with liquor and to cause immense foaming problems. These were only eventually solved by improving the filter
design, adding large seal tanks with foam tanks and foam
breakers. Thereby filter washing became an efficient operation but also
required expensive equipment. With the increasing capacities of the kraft
mills, the filter sizes have grown immensely (now approaching 15 m in
width), until it has become evident that a different design principle is
needed.
The filter washing has contributed to the pulp washing technique in
many ways. It introduced continuous operation and instrumentation to
pulp washing, with an easy control and adjustment of the dilution water. However, its design principle has many fundamental drawbacks. It
involves too much of a complicated pulp transport and web-forming operation before it arrives at the proper washing phase; it allows fairly little
time for diffusion during that phase; it introduces the entrainment of air
to the pulp and liquor; it leaves to the atmosphere malodor and steam,
necessitating ventilation hoods and odor abatement systems, it introduces
an operation which requires attention by the operator to prevent overflowing of pulp slurry; and it requires indoor operation.
Presses were more lately introduced to the washing operation. They do
not allow diffusion nor displacement, but are quite efficient by also
squeezing out liquor from the fiber lumen. In combination with filters or
with several presses in series and intermediate dilution, satisfactory washing is obtained. However, a press stage does not give better results than a
filter stage, requires a similar high investment, introduces air, and has
similar operation problems. With the ever-increasing capacities of the
pulp lines, press constructions have had still more difficulties than have
filters in keeping pace with the development.
The diffuser really represented a much sounder approach to washing
than the filter or the press, because it involved fewer moving parts, gave a
closed operation without air entrainment and ventilation, and allowed
both liquor displacement and time for diffusion. Its essential drawback
was the batch operation.
For that reason, the continuous diffuser has been subject of many efforts. However, it was only recently that a successful construction could
be presented. The principal difficulty has been to ensure that the necessary strainer is kept clean of the pulp mat which tends to form at the
withdrawal of liquor from a pulp slurry. At fairly high consistency, this is
not a problem, but then the resistance to liquor flow within the pulp is
excessive instead. A fairly dilute pulp suspension, 5-10% consistency,
must be used, and the strainers must be kept clean by movement. One
161
162
Lecture 10
construction tried rotating strainers in the bottom of an upflow tower,

with wash water applied to the top. The final successful construction by
Kamyr, (Fig. 10.1) makes use of concentric strainer rings, moving slowly
upward with the pulp in an upflow tower, and then rapidly dropping back
to move up again with another part of the pulp column. The wash water
is applied in ring shape between the strainers. This construction is now
being applied for both black liquor recovery and bleach tower washing. It
is too early to judge whether it represents the final solution to the problem
of the continuous diffuser and the end of the filter era, but there are
considerable possibilities.
A variant of the continuous diffuser was realized some years earlier,
namely the continuous digester washing. The main problem of the continuous diffuser, the clogging of the strainers, is thereby avoided, since the
fibers are not completely liberated and the pulp is still in the form of soft
chips with a comparatively loose degree of packing, about 100-110 kg/m3
digester volume or 10-11% "consistency." In the lower part of all continuous Kamyr digesters delivered after 1961, there is provision for
countercurrent washing, normally with wash liquor derived from a filter
washer after the blow tank, but in some cases with hot water directly (Fig.
10.2). The washing zone is of varying length, corresponding to a retention of 1-4 hr. This, of course, corresponds to a digester volume as large
as, or often larger than, that used for cooking. Therefore, and also because of the necessary additional strainer and circulation, continuous digester washing involves considerable investment costs, and some steam is
required to heat the wash liquor to the desired temperature, about
130C. Yet it represents a very satisfactory technology for performing
the washing, and is one of the keys to the success of the entire digester
system. I shall come back to discussion of its efficiency after describing
some of the underlying principles of washing.
The washing process has been visualized in many different ways, and
several concepts have been introduced to describe the phenomena in
quantitative terms. It is quite easy to conceive that part of the waste
liquor is more available to displacement by the washing liquor than the
rest, which is entrained within the fibers or the chips. The solubles of
that portion can join the recovered solution only by diffusion into the
moving liquor, and that diffusion can take place only where there is a
concentration gradient, i.e., after some displacement has taken
place. Furthermore, when the waste liquor is displaced by the washing
liquor, some mixing is unavoidable, which causes the recovery even of the
displaceable waste liquor to be incomplete in undiluted form. One theory
has treated the mathematics of partial volumes in displacement recovery,
163
Fig. 10.2. Kamyr continuous digester washing.

assuming complete mixing between waste liquor and washing liquor within
each one of them.
Some concepts are commonly accepted, others are more dependent
upon the manner of conceiving the washing process. The substance yield
factor or degree of recovery is simply the percentage of solubles recovered
in the washing. The concentration quotient is simply the ratio between
the concentrations of the recovered liquor and of the original liquor. The
relative liquor volume is the ratio between the recovered liquor volume
and the original one. The dilution factor is the volume of wash water
which found its way to the recovered liquor, expressed per weight of
airdry pulp. Losses of solubles, generally sodium, and expressed as salt
164
Lecture 10
Fig. 10.3. U-f diagram for waste liquor recover in practice.

(A) Sulfite industry, Ca base, digester washing; (B) kraft industry, diffuser
washing.
cake per ton of airdry pulp, are the part remaining in the washed
pulp. Sulfite waste liquor recovery has generaUy been expressed as substance yield factor at a defined concentration quotient (Fig. 10.3), whereas kraft black liquor recovery is defined by the dilution curve, i.e., salt
cake loss at varying dilution factor (Fig. 10.4).
These two pairs of figures mainly describe the net result of the washing,
not the contributions to the washing from the various submechanics assumed. Sulfite pulp washing in digester or blow pit generaUy results in a
liquor volume about as large as the original liquor, and thus has about
equal numerical values for substance yield factor and concentration quotient, between 0.8 and 0.9. With kraft pulp washing, with its more expensive cooking chemicals, it pays to recover a larger black liquor volume
of 1.2-1.4, which gives a concentration quotient of 0.7-0.8 and a substance
yield factor of 0.95-0.99, as indicated by the shadowed area in Fig.
10.3. This means something like a loss of 10-30 kg of salt cake per ton of
airdry pulp and a dilution factor of 2-3 tons of water per ton of airdry
pulp. To accomplish this, normally 3-4 filter washers in series are re-
165
1 = One-drum two-stage, spruce-balsam fir, permanganate no. 16

2 = Two-drum three-stage, hemlock-Douglas-fir, permanganate no. 22
3 = Three-drum five-stage, southern pine, permanganate no. 28
4 = Three-drum five-stage, southern pine, permanganate no. 34
5 = One-drum four-stage, southern pine
6 = One-drum three-stage, southern pine
Fig. 10.4. Dilution curves at brown stock filter washing, with various
numbers of drums and stages, and with pulps of various types.
quired. Of the sodium loss, about 2-5 kg salt cake per ton of pulp is
chemically combined with the pulp and cannot be recovered by washing
unless the pulp is acidulated.
Filter washing is often visualized as predominantly a displacement operation, since the retention timesonly a few secondsare considered too
short to allow much diffusion.* In countercurrent continuous digester
washing, on the other hand, with 1-4 hr, considerable diffusion must be
expected, despite the considerable diffusion distances from the chip centers. Also, the slower the flow rates, the more efficient must the displacement process be, and hence the less the turbulence and mixing between waste liquor and washing liquor. In crude terms, old-fashioned
batch diffuser wash involved linear flow rates of about 1 m/hr, continuous
*Assuming accessibility of the individual fibers, however, diffusion will take place
because of the short diffusion distances.
166
Lecture 10
digester wash a relative linear flow rate of about 10 m/hr, and filter wash
about 100 m/hr through the pulp pad. In all cases, channeling is obviously detrimental to the result.
A concept widely used in filter washing is the displacement ratio, DR,
which is defined as the ratio between the recovered solids in a volume
corresponding to the liquor volume of the pulp leaving the washing operation, and the solids in a corresponding volume of liquor entering the
washing stage. Assuming the same pulp consistency in and out of the
washing, the DR becomes equal to U, the substance yield factor, but if
there is an increase in consistency, the substance yield factor will be higher
than the DR as a result of a thickening preceding the displacement. The
DR is simply measured by the ratio of concentrations as follows:
where Cin and c o u t are the concentration of solubles in the liquor of the
pulp entering and leaving the washing, and c w a s h , the solubles concentration of the wash liquor. This is a convenient way of measuring the washing result but tells nothing about the quality of the operation unless related to the dilution factor, since the DR must necessarily increase by an
increasing volume of wash liquor. A related concept to the displacement
ratio is the entrainment, E, or the amount of solids entrained by the pulp
leaving the washing stage with a weight of W ton of liquor per ton of
pulp. Obviously, E = W( 1 - DR).
The continuous digester washing must obviously involve some diffusion
from the interior of the chips to their surface, as long as the chip structure
is preserved. There will always be a larger resistance to flow within the
wood structure than between the chips, until complete fiber liberation has
taken place. It can be assumed that all solutes are in equilibrium between
the liquors inside and outside the chips, when these enter into the coun
tercurrent washing zone, and that the solutes in the outside liquor are
withdrawn by displacement in the very beginning. The solutes in the
interior of the chips, on the other hand, diffuse to the chip surface and
into the outside liquor during the further course of the washing in the
lower part of the digester, where a liquor of increasingly lower solute
concentration passes the chips on the way upward through the washing
zone.
The diffusion of solutes through the chips occurs at a rate varying with
the nature of the solute. The inorganics and low-molecular organics diffuse faster than the carbohydrate and lignin polymers. The diffusion is
slower in wood than in water, and slower in tangential-radial direction
than in longitudinal direction of the wood. Particularly in the former
Fig. 1 0 . 5 .
Table 10.1.
167
Effect of pH on the effective capillary cross-sectional

area of aspen.
Experimental Diffusion Coefficients for Kraft Cooked Pine Chips
directions, the diffusion rate is also dependent on the pH of the liquor and
the yield of cooking. One way of expressing the diffusion rate in wood
relative to water is the so-called effective capillary cross-sectional area,
ECCSA, which is the fractional area of the wood considered open for
diffusion at the rate of diffusion in water. As shown in Figs. 10.5-10.7,
this is about 50% in longitudinal direction and 5-10% in the tangential-radial direction for uncooked wood at all but alkaline solutions, where the
diffusion in the latter two directions increases to 20 (pine)-40 (aspen)
%. At a pH slightly higher than that of black liquor, the tangential-radial
diffusion in pine increases from about 20% to 30-40% as the pulp yield
drops from 100 to 65%, whereas the longitudinal diffusion remains at
50-60%.
168
Lecture 10
Fig. 10.6. Effective capillary cross-sectional area (ECCSA) vs. pH

for the diffusion into softwood blocks.
In crude terms, then, diffusion at kraft pulp washing conditions in the
continuous digester proceeds at a rate half of that in water for the longitudinal direction of the chips, and one quarter to one third in the transversal directions. Since the chips are about 20 mm long and 3 mm thick
on average, the predominant part of the solutes will diffuse out across the
chips to the flat sides. The thickness distribution will thus be important
for the result.
It is an old experience that the washing result is improved by the use of
hot water. Direct determination of the rate of sodium chloride diffusion
in uncooked pine chips gave a diffusion constant of 0.5 x 10-5 cm2/sec at
20C and 1.1 x 10-5 at 50C for the longitudinal direction. Another
investigation on the rate of sodium ion diffusion out of pine chips, cooked
to normal-yield chemical kraft pulp, gave the diffusion constants shown in
Table 10.1. The diffusion rate is thus doubled at a temperature increase
of 30 C. The temperature dependence of the diffusion constant,
calculated according to the formula
D = AT0.5e-E/RT
with the experimentally determined activation energy (5000 cal/mol for
transversal diffusion), allows us to compute the effect of increasing the
temperature from that of hot water in filter washing (D = 0.7 x 10-5 at
65C) to that of the cold blow (D = 1.4 x 10-5 at 100C) and that of the
countercurrent "high-heat" diffusion washing (D = 2.4 x 10-5 at
130C). It is thus an advantage to increase the temperature of the kraft
pulp washing to that of a pressure operation such as in the digester.
169
Fig. 10.7. ECCSA vs. pulp yield for blocks of partially digested softwood
at a pH of 13.2.
A mathematical model has been developed by McKibbins et al* to
describe the diffusion subprocess in the countercurrent diffusion washing
in the digester, based on the following simplifying assumptions:
Subsequent to an initial displacement of the external black liquor, it is
considered that the washing mechanism consists of diffusion from the chip
interior to the chip surface, followed by local mixing with the outside
liquor. The chips have all the same thickness, sufficiently low as compared to the length to consider the diffusion as occurring exclusively across
the thickness. The degree of packing is assumed to be no greater than
that all chip surfaces are available to the wash liquor. The diffusion is
slow compared to the local mixing of liquor outside the chips. The wash
water-chip flow is countercurrent and uniform over the digester cross section.
Applying Fick's second law of diffusion,
where c(x,t) is solute concentration in chip liquor at the time t after the
start of washing and at distance x from the midplane of the chip in the
direction of diffusion, an equation is finally derived for the system, which
*McKibbins, S. W., Tappi 43: 801 (1960); Williams, D. A., McKibbins, S. W.,and
Riese, J. W., Tappi 48: 481 (1965).
170
Lecture 10
Fig. 10.8. Gross washing efficiency as a function of reduced time

(Dtr/L2) and wash liquor to chip liquor flow rate ratio (F) for counter
current washing.
is only graphically illustrated here in Fig. 10.8. It employs on the abscissa
the concept "reduced time," Dt/L2, which refers the retention time in the
washing zone to a certain diffusion constant D and chip thickness L. On
the ordinate, the gross diffusion washing efficiency G is employed, defined
as G = 100E/[l (c w a s h /c i n )], where E is the diffusion-recovered solutes
divided by initial solutes in the chip interior. The parameter F of the
figure is the important flow ratio of wash liquor to liquor moving with the
chips in their interior.
From the figure, the following implications can be derived. Chip
thickness is important, and a reduction to half the thickness should give
the same washing result at a retention time just one-fourth of the previous
one. An increase in temperature from 100 to 130C, which nearly
171
doubles the diffusion constant, should reduce the required retention time
by half. A flow ratio F much lower than 1 will cause the washing efficiency to level off at a value corresponding to F even at rather long
retention times, whereas a ratio much above 2 will not appreciably improve the result, unless the retention times are very short. In the units of
the figure, 1 hr retention at 130C and a chip thickness of 3 mm should
correspond to a reduced time of about 1.0. The least defined function is
that of F. The upward flow of wash liquor ought to equal the dilution
factor times the pulp capacity, but the downward flow of liquor inside the
chips should be dependent on the extent of fiber swelling and chip swelling, and thus to the species and to the degree of cooking, but possibly also
to the degree of packing of the soft chips. It can be anything from 1 to 4
ton/ton of pulp and F thus anything from 0.2 to 2, as indicated in the
figure, with a normal value of about 1.0. With both F and "reduced
time" being about unity, the expected digester washing efficiencies ought
to be considerable, about 90%, or even above, particularly if a prolonged
washing zone of 3-4 hr is used. Lecture 11 will present some evidence
from mill scale and the Jossefors pilot digester experience.
Comparisons between the various types of washing equipment is desired
for obvious reasons. A recent attempt has been made by Kommonen,
based upon theoretical work by Norden. The latter introduced the concept of efficiency factor, defined as the number of ideal mixing stages
required to get the washing effect of the washing equipment in question. Kommonens data indicate an efficiency factor of about 2.5 for a
kraft brown stock filter washer and 7-9 for a complete multistage kraft
filter washing station. The continuous diffuser has an efficiency factor of
about 5, and the continuous high-heat diffusion wash in the digester gives
an efficiency factor of 5-10, depending on washing zone retention time,
1-3 hr. A comparison has to take also into consideration the pulp consistency from the washing stage, and ends with the result that the continuous
diffuser is worth about 1.5 filters, continuous digester wash 2-3 filters,
depending on retention time, 1.5 resp. 3 hr. The results are in agreement
with the general opinion, that a 3 hr digester wash needs no additional
filter, but that 1 hr digester wash will require at least one filter washer.
Lecture 11
Continuous Digester Washing

In the previous lecture, the fundamentals of washing were outlined, and
the present washing principles and equipment described. It was found
that the washing technology is still under development, and that continuous digester washing is likely to remain an important part of that technology. In some cases it might constitute the sole washing operation; in
others it will be complemented with filters, presses, or a continuous dif
fuser. The development of large one-line production units favors continuous digester washing alone or complemented by a continuous diffuser.
In this lecture, the experiences of continuous digester washing will be
surveyed, not only that in the Jossefors pilot digester, but also some of the
Kamyr experience on the mill scale.
Figure 11.1 illustrates the principles of continuous digester washing.
The cooked chips, still essentially retaining their original shape, enter the
washing zone at full cooking temperature. To avoid continued reactions
in the washing zone, some of which may be less desirable for the pulp
quality, the pulp is cooled to washing temperature by a radial displacement circulation. This circulation not only cools the entire cross section
of the digester content but also accomplishes a washing by displacement of
the original black liquor. This black liquor, in mixture with the excess
wash liquor, is extracted at a strainer immediately above the displacement
circulation strainer. The wash liquor is injected into the bottom of the
digester and flows upward countercurrently to the chip flow. Slightly
above the digester bottom the wash liquor is heated to 130C in a circulation. This improves the rate of diffusion in the washing zone and yet
allows a discharge from the digester at below 100C to avoid mechano
chemical damage to the pulp. The wash liquor introduced to the digester
bottom usually comes from a filtrate tank at 70-80C and the pulp leaves
the digester at about 5C higher temperature.
The balance of the liquor introduced into the digester bottom less that
leaving again with the pulp is the wash liquor passing countercurrently to
the chip plug upward through the digester washing zone. Expressed on
the basis of pulp weight, it corresponds to the dilution factor concept of
Lecture 10.
173
174
Lecture 11
Fig. 11.1. Principal zones of a Kamyr kraft digester with countercurrent

washing.
The efficiency of the washing is a function of the dilution factor, the
washing temperature, the chip retention time, the chip thickness distribution, and the liquor-to-wood ratio above the washing zone.
The normal way of studying the digester washing efficiency experimentally is to measure flows and concentrations of sodium and of total
175
solids in black liquor to flash respectively with the discharged pulp. In

addition, the flow and concentration of the sodium and total solids entering the washing zone is calculated from the knowledge of charged chips
and cooking liquor flows and the approximate pulp yield. Then the wash
liquor concentration entering at the digester bottom must be determined,
unless it is hot water only. If the digester wash is combined with a filter
wash, finally the sodium and solids losses after the filter or filters are also
measured.
From these measurements, the displacement ratio DR, as defined in
Lecture 10, and the wash efficiency or substance yield factor U are
calculated. The experience from careful measurements on the mill scale
production of pine kraft pulp is exemplified in Fig. 11.2 and Table 11.1.
Those results are among the best obtained and should represent the best
washing technology of today, for Scandinavia and America. Earlier installations appear to require two filter stages for equivalent results. There are
several possible reasons for this difference: one is improvements in mechanical design, another the decreased or eliminated black liquor charge to
the feeding circulation of the digester, which means less sodium to recover. The flow conditions of the chip and liquor columns are also important. There is likely to be a wall effect, where wash liquor may flow
upward without receiving solutes by diffusion, and that effect should be
proportionally more important in digesters with a smaller cross section and
lower capacity.
Some of those reasons, and particularly the wall effect, will apply to the
Jossefors pilot digester and decrease its washing efficiency. Yet it was
considered of interest to compare the influence of pulp yield and pulping
process on the efficiency of continuous digester washing. Table 11.2
shows that the results were obtained at different liquor ratios and dilution
factors and are thus not entirely comparable, but they correspond on the
other hand to liquor ratios realistic for each process. Figure 11.3 shows
that the washing efficiency on kraft pulp was less good than in the commercial digesters quoted earlier, whereby it should be observed, however,
that the retention time was considerably lower in the pilot digester washing. Another observation is that the digester washing of semichemical
kraft or polysulfide pulp is almost as efficient as with chemical kraft
pulp. As evident from Table 11.1, that is true also on the large scale,
although the difference is quite noticeable, expressed in salt cake
losses. Even bisulfite and neutral sulfite semichemical pulp in the yield
range of 75-80% appears to be quite washable in the digester. An interesting feature appears to be that it is easier to recover sodium than total
solids for all pulps, but particularly so with the semichemical bisulfite and
176
Lecture 11
DILUTION FACTOR, / 9 0 p u l p
Fig. 11.2.
Results of continuous digester washing of chemical pine kraft

pulp on the mill scale (Kamyr).
Digester washing only

47
47
47
47
47
4
4
4
3
3-4
1.7
2.6
3.0
3.0
2.0
47
47
54
2
2
1.5
2.5
1.8
2
54
1.5
24
30
17
14
11
15
14
17
25
Digester plus onefilter stage
11 (69 1 )
13
30
5 (62 1 )
8
20
96.9
98.6
98.8
98.4
97
96.1
97.5
97.8
97.4
99.5
98.8
96.8
99.0
98
95.9
97.9
97.2
Digester plus two filter stages

23
17
Salt cake losses with pulp discharged from digester.
Neutral
sulfite
(birch)
Bisulfite
(spruce)
Kraft
(pine)
Poly sulfide
(pine)
80
80
80
75
58
55
47
59
51
1.8
1.8
1.8
5.0
5.0
2.8
2.8
2.8
2.8
0.45
0.82
1.50
3.0
3.0
2.7
2.7
2.7
2.7
177
70
84
91
87
87
88
88
87
87
70
75
83
79
86
86
86
82
83
178
Lecture 11
neutral sulfite pulps. This may reflect both the diffusion hindrance of the
chip structure and the fairly high-molecular structure of the organic
solutes of those processes as compared to kraft.
The conclusions of those trials are mainly that the continuous digester
washing is called for at all yield levels and pulping processes, and since
then commercial digesters with a countercurrent washing zone have started
operation at all yield levels between 40 and 85%, including kraft, prehydrolysis-kraft, acid sulfite, bisulfite, and neutral sulfite pulping. The following design philosophy appears to be gaining ground: The digester volume is dimensioned according to a future capacity demand, with a large
washing zone and no subsequent filter. When the mill is expanded, a filter
or a continuous diffuser is added, and if necessary the cooking zone of
the digester is extended downward at the expense of the washing
zone. Thereby, the one-line operation economy can be maintained with
only marginal investments.
One advantage with digester washing is the minimization of foaming
troubles. With a complete digester wash, no foaming is experienced,
since there is no introduction of air to the system. Even with a combined
system of digester and filter, the foaming troubles around the filter are
considerably decreased because the dominant part of the tall soaps have
been removed in the high-temperature digester wash. Particularly for the
introduction of open precision refiners for semichemicaJ pulps, it is vital to
have removed the waste liquor.
Lecture 12
Technical and Economic Aspects of

Present and Future
Developments of Continuous Pulping
Continuous Pulping Processes Realized
Now it is time to sum up what has been accomplished during the development of continuous pulping and what remains to be done in the future.
Continuous digester systems have been developed for most of the existing variants of chemical and semichemical pulping, namely:
Kraft*
Acid sulfite dissolving pulp*
Acid sulfite paper pulp, one-stage*
Acid sulfite paper pulp, two-stage
Bisulfite chemical*
Bisulfite semichemical*
Neutral sulfite semichemical*
Prehydrolysis-kraft dissolving pulp*
Polysulfide one-stage
Polysulfide two-stage
Hydrosulfide-sulfide
Alkaline sulfite
Kraft, instant heating*
Kraft, preimpregnation, low pressure*
Kraft, preimpregnation, high pressure*
Kraft, countercurrent*
Advantages of Continuous Pulping Systems
With the modifications of the original kraft digester it has become possible for the industry to make use of the possibilities offered by modern
pulping chemistry. With the exception of countercurrent cooking, however, the same variants can be carried out in batch digesters. Has therefore the development work only brought continuous cooking to the level
* Units in operation or under installation.
179
180
Lecture 12
of batch cooking? To some extent, the choice between batch and continuous remains a matter of philosophy. Yet, there are some good reasons
why those in the pulping industry with few exceptions now choose continuous cooking.
1. Large one-line units have been made possible.
2. Improved heat economy.
3. Ease of instrumentation, automation, and coordination with paper
mill.
4. Ease of attaching subsequent operations, such as washing, refining,
evaporation, odor abatement, etc.
5. Improved quality.
I shall comment on each of these items and also point out what remains
to be done to improve the systems.
Large One-line Units
One of the most spectacular trends of the pulp and paper industry in
recent years is the increased size of the mills. This increase has been
stimulated by the severe competition in most sectors of the industry, and
particularly those of market pulp, newsprint, liner board, corrugating
medium board, and other packaging grades. Not long ago, 50,000 tons/
year was the output of a sizable mill, and 100,000 tons/year a large
one. The units now constructed are for 200,000-500,000 tons/year. It is
also important to observe that good economy demands few lines, preferably one, in those units to achieve maximum benefit from the large size.
Machinery development in all sections of the pulp and paper mill has
been required to meet the demands of the large one-lined mill. The most
spectacular ones have been the digester, the recovery boiler, and the paper
machine, where now 1000 ton/day units are available. The largest digesters in operation or on order are as shown in Table 12.1.
No doubt there are mills of similar sizes in all those categories equipped
with batch digesters, but they tend to get fairly complicated and not very
labor-saving. That is particularly true for two-stage processes, semichemical pulping, and acid sulfite pulping. That the present size of digester varies
considerably with the process is more nearly ascribable to historical development than to real technical limitations. If somebody for some less
understandable reason would like to build an 800 ton/day acid sulfite
dissolving pulp mill today, it would be technically quite feasible, although
both seller and buyer of the digester would probably sleep better after
having seen not only the present 275 ton/day unit in operation but also
one or two of intermediate size. Kraft digesters have been through that
Present and Future Developments of Continuous Pulping
181
Table 12.1. Largest Size Units, Delivered or on Order, for Kamyr

Digesters on Various Pulping Processes
Capacity, metric tons/day
Kraft, bleached market pulp
Kraft, semichemical pulp for liner board
Prehydrolysis-kraft, bleached market pulp
Neutral sulfite, semichemical pulp for
corrugating medium
Bisufite, bleached market pulp
Bisulfite, semichemical pulp for newsprint
Acid sulfite, bleached market dissolving
pulp
850
1150
620
600
400
200
275
phase, and since the development work for the other processes has endeavored to make as much use as possible of the kraft digester details, it is
likely that these processes will catch up in size quite rapidly. In fact, it
took kraft 17 years and 17 units before reaching 300 tons/day, but prehydrolysis-kraft and neutral sulfite less than one year and one unit before
reaching the same size.
It may be fascinating but fairly useless to speculate on the ultimate
digester size. The present units are far from ultimate size, since the largest
chip feeder in operation is capable of feeding chips for 1150 tons/day of
liner board pulp and there is always the possibility of two feeding lines to
one digester if necessary. The ultimate digester size is therefore likely to
be decided by external factors, such as wood transportation costs or
economical size of other machinery used. It is a good testimonial to the
digester machinery development that it can be said that the pressure operation of pulp production will not become the bottleneck of the large mill
for the foreseeable future.
On the other hand, it must be admitted, that the large-capacity digesters
have become rather monstrous, and that efforts should be made to decrease their size and costs. It is debatable though, whether a temperature
increase alone will bring about an improvement, since the decrease in size
will be accompanied by an increase in shell thickness due to the increased
pressure. The elimination of the excess hydraulic pressure achieved
through, the inverted external top separator is one of the better means of
reducing shell costs and some circulations.
It is also conceivable that the really large digesters of the future may
have to minimize the volume spent on countercurrent washing. That a
considerable part should be devoted to the task is an obvious advantage
when considering the subsequent unit operations of liquor recovery and
182
Lecture 12
Fig. 12.1. Mass and heat balance for continuous cooking and washing plant.
odor abatement. The development of the continuous diffuser is likely to
offer an alternative to the extreme digester wash in cases where filters
should be few or entirely avoided.
Heat Economy of Cooking and Subsequent Operations
One of the original arguments in favor of continuous cooking, the superior heat economy, still holds and has become accentuated through
some refinements of the system. Figure 12.1 shows the heat flow to and
around the digester system. The blow steam used to be passed to the
steaming vessel for preheating the chips, which is a major improvement in
heat economy as compared to batch cooking. With the introduction of
the cold blow and countercurrent washing, an increased digester steam
consumption was experienced, since the wash liquor is heated to about
130C. A further increase in steam demand is experienced when cooking
countercurrently, since all liquor, including the wash liquor, is then heated
to cooking temperature, about 170C.
On the other hand, improvements in the liquor balance have contributed
to reduce the digester steam demand. In the original system, considerable
quantities of black liquor were added to the chip feeding system as socalled "compensating liquor." This served to keep up the hydraulic
pressure of the digester, compensating for the drainage of liquor from the
183
digester. When it was realized, that the compensating liquor could be

added to the bottom, this reduced the liquor to be heated to maximum
temperature to the actual cooking liquor plus the chip moisture. For a
liner base pulp from Scots pine in a mill with a decent white liquor concentration, this means about 1.3 m 3 /ton o.d. wood plus 1 m 3 /ton o.d.
wood for 50% chip moisture, or a total liquor-to-wood ratio of 2.3 as
compared to about 3.5 in a normal batch kraft operation. As mentioned
earlier, acid sulfite or bisulfite cooking has been carried out at similar low
liquor ratios, 2.3, when cooking continuously in Jossefors, whereas batch
operation for these processses require 4.0 or 4.5 in order to cover the chips
of the digester entirely with liquor.
When using the external inverted top separator, the liquor absorbed by
the chips in the top separator will decide the liquor ratio, since the chips
become completely immersed in the liquor of the feeding circulation but
can then be transferred by the screw to the digester body under drainage. For neutral sulfite pulping of birch, a liquor ratio of 1.2 to 1.8 is
thereby reached. In case the chips tend to absorb more liquor than required by the charge of cooking liquor at actual concentration, water or
waste liquor must be added to maintain a liquor level in the top separator. This appears only with dry chips of lightweight wood. With wood
of normal density and moisture, cooking liquor concentration is the factor
deciding the liquor ratio. It is suggested that there is more to be done to
improve the concentration of cooking liquor for several processes, and that
this is more motivated than it used to be when the liquor was charged to
batch digesters.
With the preimpregnation system at low pressure, there are additional
possibilities to utilize blow steam, since not only the wood, but also the
cooking liquor, is preheated to steaming temperature, 110C.
An interesting feature of the continuous cooking system with countercurrent washing in the digester is that the wash liquor is obtained
at almost full cooking temperature. This introduces two new possibilities. One is the treatment of waste liquors, particularly black liquor, at
high temperature without the use of much extra steam. This may become
of importance in kraft odor abatement and will be discussed further later
on. The other new possibility is to use the flash steam in the evaporation
system rather than for preheating of the chips. In any event, the hightemperature flash will increase the black liquor concentration and thus
improve the heat economy of evaporation. However, the flash can also be
limited to a smaller temperature drop, to allow the flash steam to be
utilized in pressure evaporation of subsequent evaporation stages (Fig.
12.2).
184
Lecture 12
Fig. 12.2. Evaporation system utilizing combination of flash heat evaporator

and live steam evaporators.
The effect of all those modifications of the system on the heat economy
of the various pulping processes, as compared to batch pulping, is not easy
to show here. It will suffice to exemplify with heat balances and steam
demands calculated for kraft, prehydrolysis-kraft, and neutral sulfite pulping, using the Kamyr system (Table 12.2).
Instrumentation and Automation
With some exaggeration it could be said that continuous cooking
brought a consistent instrumentation to the pulp and paper industry. Certainly there were instruments before, scattered all over the pulp
and paper mill, controlling a consistency here and a flow there. The
continuous digester presented us a system, which had been logically analyzed for control loops and instrumented accordingly (Fig. 12.3). The
early versions naturally contained less good solutions, and some of the
early machine elements introduced oscillations to the control loops. For
example, the high-pressure feeder, before it got large enough to have
pockets in contact with the feeding circulation in all positions, introduced
regular pressure variations, and so did the discharge sluice with its two
alternating valves, which preceded the present continuous blow
valve. The discharge conditions also created other disturbances. The
consistency of the discharge was difficult to control, and this caused variations in the "compensating liquor" to keep the hydraulic pressure constant. As long as the compensating liquor was added to the top, its variations then introduced temperature variations to be compensated by adjustment of the steam flow. The chip level control was not reliable in the
early stages and introduced additional variations, to be compensated either
Table 12.2. Heat Balances and Steam Consumption With

Continuous Cooking of Various Pulp Types. Units per Ton Aitdry Pulp
Pulp type
NSSC, hardwood (Mumin)
Kraft
Liner base, softwood
Chemical pulp, softwood
Chemical pulp, softwood1
Chemical pulp, hardwood (Mumin)
Prehydr.-kraft, hardwood (Mumin)
Black liquor to evaporation 128 C.
Demand
LPHPsteam, ton steam, ton
Production
secondary
steam, ton
Total
heat
demand,
Meal
Secondary
heat
produced,
Meal
0.14
0.48
0.25
395 x 1 0 6
155 x 10 6
0.06
0.01
0.36
0.09
0.00
0.79
0.90
0.91
0.60
1.33
0.36
0.38
0.22
0.31
0.73
485
465
755
365
755
230
240
140
200
460
Fig. 12.3.
Instrumentation of the Kamyr cooking system.
187
by the chip feed, which then required corresponding adjustments in the

flow of cooking chemicals, or by the pulp discharge, which again introduced the variations in pulp consistency, compensating liquor, and steam
flow.
These are only a few examples of the early instrumentation and control
problems. The system allowed, however, almost from the start, something new to this industry: one could observe what happened in quantitative terms and analyze what measures should be taken to eliminate the
problems. The continuous blow valve, the adjustable speed of the bottom
scraper, the compensating liquor to the bottom of the digester, the reliable
gamma ray chip level indicators, and many other adjustments have now led
to a fairly reliable and well-controlled system.
A few things are still desired to make it perfect. A reliable chip moisture meter would be advantageous to get the liquor balance completely
covered. Efforts are underway here. (With the Mumin system we have
found another way to observe the moisture variations, since they are reflected in the variations in liquor flow needed to keep the liquor level in
the top separator constant.) A reliable indication of the alkali concentration is needed to allow adjustments in the white liquor flow to the chip
feed, or perhaps directly to the cooking zone, to keep the degree of
cooking constant. An automatic reader of the degree of cooking would
naturally also be a good aid, but measurements on the final pulp leaving
the digester will not, however rapid, be an ideal guide to adjustments of
the cooking conditions, since the digester washing constitutes a considerable time lag. In general, therefore, material balances and feed-forward
principles are better suited to the control of continuous digesters than
feed-back principles. The indication of alkali concentration could be regarded as belonging to either control principle, but is a very direct and
essential measurement at the central zone of reaction. We have tried
conductivity measurements at Jossefors and installed a conductivity cell in
one of our digesters. With a suitable construction it gives reliable readings
but a higher sensitivity to alkali concentration would be desirable. An
automatic sampler and titration analyzer has also been tried by us and is
under further development elsewhere. This will give a higher sensitivity if
the snags of the complicated equipment can be overcome. For special
purposes, such as preventing the pH from dropping under a certain value in
the combined prehydrolyzate and black liquor from the prehydrolysiskraft digester, the conductivity cell is quite adequate.
Instrumentation has also been introduced to batch digesters, predominantly temperature and pressure control and eventually also control of the
charges of wood and chemicals. A few cases of rather elaborate automa-
188
Lecture 12
tion of batch digester rooms have also been seen, with remotely controlled
valves and automatic charging and discharging. For some processes, instrumentation of the end point control of the cook has been attempted.
In general, however, it can be said that batch cooking requires a more
elaborate instrumentation and control to be fully automated, and
particularly so with two-stage processes and other deviations from the
simple kraft process. The large number of digesters in the batch system
naturally increases the points of measurement, and the discontinuous operation complicates the control of the system to give a uniform quality.
The final stage of automation is to put the continuous digester on a
computer control. This has already been done at some places, but the
main development remains to be seen. For the running of a constant pulp
grade, the general instrumentation already in use today allows the continuous digester to be put on digital control, although the system analysis to
give the process equations will have to be done specifically for each process and digester type. We now attempt to do so for the simple case of
neutral sulfite semichemical pulping. The principles for digital control of
the digester switching from one grade to another have also been worked
out jointly by Kamyr, International Business Machines and International
Paper. It is to be expected that during the years to come, most new mills
will run their digesters on a computer basis, but with the same computer as
controls the other activities of the pulp and paper mill. We make efforts
in this direction with our NSSC digester, which is directed from the same
computer that controls the corrugating medium board machine and intermediate operations. This will also eliminate the traditional borderlines
between the pulp and the paper mill as far as supervision and personnel
organization is concerned. The continuous cooking principle has then
made pulping an operation too simple to validate its own organization, and
it will also have eliminated the pulp equalizing chests and minimized
buffer storage facilities. This development, of course, owes much to the
corresponding simplifications of the intermediate operations as well, but it
should be stressed that their progress could not be fully utilized without
the development of the continuous digester, as will be discussed now.
Combination of Continuous Cooking With
Subsequent Operations
The development of continuous pulp washing on filters preceded the
development of continuous cooking. Considerable problems were encountered, particularly with foaming, which made the filter constructions
sophisticated, instrumentation elaborate, and the liquor tanks voluminous. The expenses were multiplied through the considerable number of
189
stages necessary to make washing complete. With batch digesters, large

blow tanks were necessary as capacity buffers between the discontinuous
and continuous systems.
Sad to say, the large blow tanks have not been eliminated even after the
arrival of the continuous cooking principle, since they are considered necessary to meet shutdowns for minor repairs in the system before or after
the blow tank. The size of the blow tank can, however, now be kept
more reasonable, which is of some importance with the present large mill
units.
Also, the size of the filters for washing is becoming rather monstrous
with present-day capacities, as has been pointed out already, and a fourstage filter wash with adjacent tanks in a 300,000 tons/year mill is a massive
sight. Here continuous cooking has made one of its major contributions,
as elaborated in previous lectures. Countercurrent washing in the lower
part of the digester not only eliminates the need of a certain number of
filters, but also facilitates the operation of the remaining ones by removing
the tall soap.
At the expense of making the digester shell more than twice as big as is
needed for cooking, the entire filter wash can be eliminated. Some mills
consider this worthwhile, since the washing zone of the digester represents
a possibility of future capacity expansion, if only space is allowed for the
installation of a future outside washing. The development of the continuous diffuser here introduces new aspects. With the elimination of the
filters, the need of the blow tank is eliminated, since there will be only a
simple screening equipment between the digester and the thick stock storage for unbleached pulp.
Combination of cooking with refining of semichemical pulps is also considerably facilitated when cooking is done continuously. So far, a live
bottom bin is still the safest solution for the storage between cooking and
refining, but it can be kept fairly small after a continuous digester and
consequently offers few problems. For semichemical kraft pulps of liner
base type, the handling problems of the semicooked chips with the black
liquor have been limiting the yield in the batch system. The normal blow
tank has been equipped with fiberizing impeller, or with a breaker trap in
the pipe from blow tank to washer. Normally also the final fiberizing has
been carried out in closed pump-through refiners before the final washing. Continuous cooking here offers a possibility to apply a coarse fiberizing in the blow line prior to the blow tank, and this, in combination with
the digester wash, and possibly with the continuous diffuser, will allow the
final fiberizing in open precision refiners. Thereby, both handling and
fiberizing arrangements will be able to take care of really semichemical
190
Lecture 12
kraft pulps and not just high-yield chemical kraft for liner board and
similar purposes.
The combination of cooking with evaporation was touched upon earlier. Batch cooking delivers the black liquor to evaporation at a temperature of only 70-80C, which means that the enthalpy drop from cooking
temperature can be used only for hot water production. With continuous
cooking, including digester washing, the black liquor is delivered at almost
full cooking temperature, and the flash can be used in pressure evaporation
in a suitable countercurrent system. We shall see more developments in
that field. Closely connected with this train of thought is our idea of
treating the black liquor at high temperature for odor abatement. Batch
cooking delivers malodorous compounds in two ways: partly in the blow
gases, partly in the black liquor. The collection of the blow gases causes a
special problem, which has been solved at considerable expense in the
so-called "Vaporspheres," gas buffers to receive the batch flow of gases
and deliver a continuous flow of gases for treatment. Furthermore, the
blow gases unavoidably become admixed with the air of the blow system,
which also complicates their treatment. Here the first and fundamental
virtue of continuous cooking is obvious. The second source of malodorous compounds is the black liquor during evaporation, which delivers these
compounds to the condensates of all stages. It is not impossible that a
prolonged treatment of the black liquor at or above cooking temperature,
will create all obnoxious volatiles at once and eliminate their successive
formation during evaporation and combustion. Such a heat treatment,
possibly combined with a suitable stripping arrangement, might therefore
concentrate the odor problem to one convenient spot, where suitable
means of destruction or by-product recovery could be arranged. Continuous cooking is a prerequisite for doing this at a reasonable steam comsumption.
Quality Aspects of Batch and Continuous Cooking
The quality aspects have been commented on in connection with each
process. Therefore I just need to summarize that laboratory pulp quality
has been achieved when pulping continuously, with the possible exception
of acid sulfite paper pulp, where also batch pulping on the mill scale gives
a somewhat lower quality than in the laboratory. Whether with this general statement it can be maintained that continuous pulping yields a superior quality as compared to batch is thus mainly a question of batch
pulping standard. At some instances, mill scale batch pulping yields a
quality close to that of laboratory pulping, but in many cases, perhaps
normally, some quality is sacrificed to gain production or production
191
economy. This need more seldom be the case with continuous cooking,
which thus normally yields a somewhat better quality than batch cooking,
provided the modern modifications of cold blow and countercurrent washing are installed. The advanced process control likewise has generally resulted in a superior uniformity of the pulp as compared to batch.
Index
AB Statens Skogsindustrier 5
Accessibility 23, 39, 82, 85
Acetic acid 105
Acetyl groups 23-25, 28, 48, 64,
87-88, 92, 105
Acid sulfite cook 15-16, 33-50
second-stage 45-47,49,103,157
Acid sulfite pulp washing 178
Active alkali 87, 109-110, 116,123,
127, 130, 132-135, 140, 142
Air compressor 122
Air in chips 29-31
Aldehyde end groups 81-82, 85
Aldonic acids 28-29
Alkafide process 136,138
Alkali consumption 77, 80, 87-88,
91-92, 109,117,122,132, 138
Alkali lignin 108-109,113
Alkaline hydrolysis 77, 82-83
Alkaline peeling reaction 81, 88, 92,
105
Alkaline sulfite cook 15-16,139,
142-143, 152-153
acid sulfite second-stage 45, 47, 49
Alkalinity 109, 125, 136
Alkalirresistant cellulose 36, 40, 54,
70,102
Alpha-cellulose 36-40,61,102,
115-117,123-124,127-128,131,
135, 141-142, 147, 150
Ammonium bisulfite 11
Ammonium sulfite 69
Arabinose 22,61,71,82,123,
127-128, 130, 135, 141-142, 147
Arabinoxylan 22
Arabitol 84
Aspen 167
Asplund Defibrator 64-67
Asplund sluice 7
Associated Pulp & Paper Mills Ltd.
4-5,8
Automatic control 10, 180, 184,
187-188
Backhammars Bruk AB 4
Back-water pockets 35
Bark extractives 19,78
Batch cooking 40,99,187-188,
190-191
Batch diffuser 165
Batch digester wash 159
Beating time, see Paper pulp quality
Beech 43-44
Belisce Kombinat 5
Benzyl alcohol 18
Bergvik mill 11
Beta-cellulose 102
BillerudsAB 4,7,10-11,64,113
Birch 7,38,40-41,44,55,59,65,
67, 69, 71, 72-73, 87, 89-90,
102-104,106, 116, 121,

123-124,128-129,156-157,177
Bisulfite cook 15-16,51-62, 103
Bisulfite liquor 11-31,51-53,55,60
Bisulfite, pulp 103, 175,177-178
Bjerrum diagram 16, 88
Black cook 16
Black liquor 97, 108,113, 122,
125-126,164, 173, 175, 182-183,
190
Bleachable pulp {see also Brightness)
51,53,55,63-64,66-68, 103, 123
Blow gas 182-184,190
Blow pit wash 159,164
Blow tank 64-65,73, 99, 117, 189
Blow temperature (see also Cold blow;
Hot blow) 100
Blow valve 7,34,64,187
Board-grade pulp 51
Bonding strength 95
Borohydride 82, 85-87, 90
Bottom scraper 3, 35, 99
Bottom screw 37, 44, 99
Breaker trap 189
Brightness 40, 45, 48-49, 51, 54-55,
58-62,71,79,104,115,118,
123-126, 130,132, 135, 138,140,
142, 146, 150"
Bromide (radioactive) 54
Buffer liquor 15, 18, 63-65, 68, 69
Buffer storage 72,188
Burgess-Watt process 75
Burnt cook 16,18,29
By-product recovery 190
Calcium-base cooking acid 33
Calcium bisulfite 11
Calcium recovery cycle 138
Calcium sulfite 11,13
Canadian International Paper Co. 5
Capillarity of wood 29-31,167-169
Carbohydrates (see also Arabinose,
Galactose, Glucose, Mannose,
Xylose) 16-17, 22-29,40, 76,
79-92,102,104,129,132,
136-137,157
Carbohydrate sulfonic acids 28-29
Carbon dioxide 64,66, 69, 108, 112
Carbonyl groups 132
Cartiera Burgo 4
Cartiera Vita Meyer 4
Celgar Ltd. 5
Cellulose (see also Alpha-cellulose)
22-23,26,31,82,87-90,105
Cellulose du Pin, La 5
Cellulose du Rh&ne, La 4
Cell wall 23, 26, 29, 85, 89, 95, 101
Celulosa Argentina 5
Central Laboratory of the Cellulose
Industry 7
194
Central Laboratory of the Finnish Pulp

& Paper Industry [CL] 73
Central Laboratory of the Swedish
Paper Industry [PCL] 73
Channeling (in chips) 166
Chemical consumption (see also Alkali
consumption; Sodium sulfate; Sulfur
charge) 122, 139
Chemical recovery 41, 82, 133, 138, 181
Chip damage 1, 28, 30-31, 36, 44-45,
157
Chip dimensions 29-31, 168-170, 174
Chip feeding and flow 1-2, 106-108,
111-113, 187
Chip impregnation 18, 29-31, 42-43,
55,62,64, 121-157, 166-171,
182-183
Chlorine number, see Roe Number
Chlorite oxidation 82
Cold alkaline purification 117-119
Cold blow 6-7, 10, 37, 44, 53, 97-99,
101, 106, 108, 182, 191
Color (see also Brightness) 43, 52, 55,
60, 69, 78
Combined sulfur dioxide 11-12
Compensating liquor 182,187
Compressed air 134
Computer control 188
Concentration quotient 163-165
Concora Medium Test [CMT] 67, 69,
71-72
Concurrent cooking 53,108-109,
112, 127-129
Condensate odor 190
Conductivity cell 187
Consistency 160,162,171
Continental Can Co. 5
Continuous diffuser, see Diffuser
Continuous digesters, see Digester
Control loops 184,187
Convection 132
Cooking degree (see also Lignin; Roe
Number; Yield) 43, 187
Cooking liquor composition, see Sulfite
cooking acid; White liquor
Cooking liquor flow 1-3,35,43,52,
106-119
Corrosion 34
Corrugating medium 63-64, 68, 69,
71-72
Countercurrent cooking 86, 108-110,
112-113,117,119,124-129, 136,
150-153
Countercurrent-flow digester 8-9, 53,
60,182
Countercurrent washing 97, 101,
107-108, 112, 117, 119, 122, 165,
173-178, 181-182, 191
Dahl 75
Dai Showa Seishi 5
Davenport press 64-65
Deacetylation, see Acetyl groups

Deaeration, see Air in chips
Defibrator 64, 67
Defibrator digester 63, 72
Defibrator process 65-66
Defibrator pulp 31
Degree of polymerization 101
Delignification 11-31, 76-79
Demethylation, see Methoxyl groups
Diffuser 98, 159-162, 173, 189
Diffusion 29-31, 122, 165-169, 178
Digester capacity 97, 112, 178,
181-182
Digester design 1-2, 8, 10, 33-50,
63-73, 97-99
Digester wash 8, 10, 70, 162, 166,
173-178
Digital control 188
Dilution curve 164-165
Dilution factor 163-165, 173-177
Dimethyl sulfide 79, 81
Dicyclohexene 78
Direct steam heat 108,111-112
Discoloration, see Color
Displacement ratio 166,175
Displacement washing 162, 165, 173
Dissolving pulp 13, 23, 35-36, 38,
40-41,44, 75, 85, 105-119
Dissolving tank 134
Dithionite bleach 51,60
Down flow digester 42, 44-45, 53, 60,
105-108, 110-113
Downtime 103, 115
Eastern Corp. 5
Economics of continuous cooking
75-76, 105,133, 136, 179-191
Effective alkali 87, 94
Effective capillary cross-sectional area
167-169
Efficiency of washing factor 171,
174-177
Ekman, C. D. 11
Electrolyte system 92
Energy consumption, see Fiberizing:
Refining
Entrainment 166
Episulfide formation 77, 92
Epoxide formation 76
Erythritol 84
ESCO digester 73
Eucalyptus 40-41, 76, 89, 102, 104,
107-108, 115-117, 121,123-125
Evaporator system 159,183-184,190
Excess sulfur, see Sulfur charge
Excess sulfure dioxide 11-12, 33, 38,
51
Extractives 18-20, 78
Feed-forward control 187
Feed liquor 48,134
Feeder system 1-2, 33, 36, 57, 66,
103, 106, 108-109, 111-112
Index
Fengersfors Bruks AB 1,3,4
Fiber length 101-102
Fiber wall, see Cell wall
Fiberizing (see also Refining) 64-66,
127-128, 149, 189
Fibreboard Paper Products Inc. 5
Fick's diffusion law 169
Filter washing 117,159-160,165,
175,188
Fine papers 75
Flash steam 113,183-184
Flash tank 99
Flow ratio 42,171
Flow resistance 166
Foam problems 160,178,188
Formaldehyde 77
Formic acid 17, 81, 84
Free sulfur dioxide 11-12
Friction 41-42
Galactan 91
Galactoglucomannan 22, 102,131,
136-137
Galactoglucomannan acetate 27
Galactose 22, 61, 71, 123, 127-128,
130, 135,141-142, 147
Gamma-cellulose 102
Gas bubbles 66,110
Glassine/greaseproof pulp 7, 63, 67,
69
Gluability 73
Glucan 91
Glucomannan 22-23, 26, 36, 38, 45,
48, 50, 82-84, 86-89, 102, 123, 132
Glucometasaccharinic acid 84
Glucosaccharinic acid 83
Glucose 40-49,59,61,70-71,73
104, 123, 127-128, 130, 135,
141-142, 147, 150
Glucuronic acid 22, 25, 28, 86
Glucuronoarabinoxylan 27, 82, 88,
102,131, 136-137
Glucuronoxylan 26, 81, 87, 89
Glycolic acid 84
Glycoside hydrolysis 22-23, 81-92
Green liquor 138
Gross washing efficiency 170
Groundwood 31
Guaiacylpropane 78
Gulf States Paper Co. 4
Hardwood pulping 15, 25, 28-29,
63-73, 95-96,109
Heat balance 182,186
Heat economy 10, 43, 113, 119,
182-184
Heat exchangers 108
Heat recovery 116
Heat transfer 108
Heat-up time 18,37-38,51, 55, 64
107-108,112,121,132,135,148
Hemicellulose (see also Xylan, etc.)
22-29,70, 87, 89-90, 94-95, 101,
195
105,126,128
High-heat washing 10,108, 168, 171,
178
High-yield pulping 15, 25, 53
History of
acid sulfite cook 33
bisulfite cook 51
cold blow 7
countercurrent digester 8,10
Hi-Heat washing 10
Keebra process 139
kraft continuous cook 1-10
kraft process 75
multistage bleach 75
Mumin digester 37-38
neutral sulfite cook 10
prehydrolysis kraft cook 10
pulp washing 159
sulfite continuous cook 7, 10
sulfite process 11
Holocellulose 26
Hot blow 66,97-99, 101-102
Hydraulic pressure 31, 52, 144,148,
181
Hydrazine 82
Hydrogen sulfide 82
Hydrosulfide ion 76-77, 79
Hydrosulfide-sulfide cook 134, 136,
140-141
Hydroxycyclopentane carboxylate 78
Hydroxylamine 82
Hydroxypyruvic acid 84
IMPCO digester 63
Instrumentation 10, 43, 180, 184-186,
187-188
International Business Machines [IBM]
International Paper Co. 4, 7, 188
Iron in pulp 78,115
Iso-hemi lines 27
Isosaccharinic acid 81,83
Jansson, Hannes 7
Jansson, Lennart 7
Jonsson, Ragnar 3
Jossefors mill 7,34, 123, 173
Joutseno Pulp Oy. 4, 6, 7
Jujyo Seshi KK. 5
KamyrAB 3,97,188
Kamyr digester 1-10,46-47,63,67,
105-108,138,161,163,174,
180-181,184-188
Kamyr impregnating vessel 144
Kamyr washing system 161,163
Karlsborg pilot plant 1
Keebra process 139
KMW machine 73
Knots 33
Kokusaku Pulp KK. 5
Kommonen efficiency factor 171
Kraft cooking
continuous 97-104
196
historical development 1-10

"modified" processes 82, 121-157
prehydrolysis process 105-119
semichemical 127-157
theory of 75-96
Kraft digester 1-10
Kraft pulp 94-95,102-104,175-177
Kramfors process 19-20
Lanor economy 10
Lactic acid 81, 84
Leirosa (Portugal) pulp mill 113, 123
Level control 2,35,112,122
Lignin content, see Roe Number
Lignin enamel 31
Lignin reactions 11-12, 15-21, 29,
76-81, 87-91, 139
Lining-up of feeders 33
Liquor balance 182
Liquor ratio 41-42, 53, 55, 108,
138-139, 174-176
Loschbrandt 27
Luminae in wood elements 29
M&D digester 63, 136
McKibbins, S. W. 169
Magazine-grade paper pulp 51
Magnetite neutral process 20
Magnesium-base liquor 41
Magnesium bisulfite 11,58-59
Magnesium sulfite 13
Maintenance 103,111
Mannan 83, 91
Mannose 22-24, 40, 48-49, 59, 61,
70, 72, 104, 123, 127-128, 130,
135, 141-142, 147, 150
Mass balance 182,187
Mechanical pulp 31
Mercaptide ion 79
Mercapto groups 77
Metasaccharinic acid 82
Methane sulfonate 21
Methoxyl groups 21, 78, 80-81
Methylglucuronoxylan 79
Methyl glyoxal 84
Methyl mercaptan 79, 81
Modified kraft cooks 121-158
Moisture control 187
Moisture in wood 28, 30
Monel 1
Monosulfite cook 15
Mo och Domsjo AB 7
Multistage bleach 75
Multistage pulping, see Two-stage
Mumin digester 37-45, 54-61,
69-73, 111,119, 121-157
Natchez process 20
Neutral sulfite cook 7,10, 15-16,
19-21, 28-29, 63-73, 103
acid sulfite 2nd-stage 45-46, 103
Newsprint stock 51,61
New Zealand Forest Products 4
Nippon Pulp Kogyo KK. 5
Norden efficiency factor 171

North Western Pulp & Power Co. 4
NSSCpulp 63-73,175,177-178
Oak 29
Odor control 78, 180, 182, 190
Ohji-Seishi KK. 4
Opacity 95
Oxford Paper Co. 5
Packaging papers 75
Packing density 42-43, 55, 114, 169,
171
Pandia digester 63
Paper pulp quality 28, 44-45, 50-51,
54,59-61,63,67,69,71,94-95,
99-104, 121-157
Peeling reaction 81,88,92
Pentosans 54, 70 .
13,16,36-37,63,105,109,113,
PH
127, 167-168, 187
Phenolic extractives 18-20
Phenolic groups 77, 92
Piggyback digester 136
Pine 18-19,45,48,55,59,76,
87-91, 96, 102-104, 107-108, 116,
121, 123-127, 129, 136, 146-148,
156-157, 167,175-177
Pinosylvin 18
Pitch deposits 106-110,112
Pit membrane 29
Pocket feeder 1-2
Polysaccharide, see Carbohydrates
Polysulfide cook 82, 85-88, 90, 125,
129-136, 139-141, 146-147, 149-153
157, 175, 177
Power demand (see also Fiberizing; Refining) 65,124,127,133,149,152
Power failure 103
Prehydrolysis kraft cook 10, 85, 90,
94, 105-119, 126, 178
Preimpregnation of chips 62,139,
143-145,148,154-155, 183
Press washers 160
Pressure control 112, 122, 134
Pressure impregnation 139, 143-145
Production reliability 7, 102
Progil SA. 4, 7
Propanediol 84
Protolysis 18-19
Pulp chests 114,188
Pulp mill capacity 160, 180-181
Pulp quality (see also Paper pulp quality)
6-7, 40, 48-50, 62, 66, 96, 99-104,
115-117,137,190-191
Pumps 1, 72
Pyrocatechol 78
Quinones 78
Radioactive tracers 35,42-43, 52, 54,
113-114
Rayon pulp, see Dissolving pulp
Reactivity 85
Recovery system 41,116, 138, 181
Redox reactions 82, 85

Refining (see also Fiberizing) 65-69,
70,124,133,152,178,189
Relative liquor volume 163-164
Resin in pulps 27, 40, 48-49, 54, 59,
61, 71, 104, 117, 123, 127-ll8, 130,
135,138,140,142, 146
Retention time 43, 113-114, 116, 123,
127, 130, 140, 142, 146, 171, 174
Richter, Johan 3,10
Roe Number 40,48-50,54,59,61,71,
94,104,115-117,123, 127-128,
130, 135, 139-140, 142,146, 150,
154-155
Rosenlev, V., & Co. AB 4
Runnability 149
Saccharinic acids 81
SAICI (Italy) 105
St. Regis Paper Co. 5
Saltcake, see Sodium sulfate
Sanyo Pulp KK. 5
Sawdust 35
Screen rejects 18,40, 45, 48-50, 55,
59,109,115-116,123-124,126,
128, 130, 132,135-136, 138, 140,
146, 148, 150
Screw press 99-100
Secondary wall 23, 26, 85, 89-90
Semichemical pulp
bisulfite 51-62
kraft 127-157,175-176
neutral sulfite 63-73
poly sulfide 133
Separators 111-112,121, 148, 183
Shives 52, 62, 149
Skogsagarnas Cellulosa AB 5
Skutskar process 20
Slip planes 31,101
Sloman, Ray 8
Soda process 75,90,125
Sodium acetate 64
Sodium-base liquor 41,70
Sodium bicarbonate buffer 15, 63,
65-66,68,69
Sodium bisulfite 11, 16-17, 5 8
Sodium borohydride 82, 85-87, 90
Sodium carbonate 15, 35, 48, 52,
63-64, 138-139
Sodium hydrosulfide 138
Sodium hydroxide 48, 66, 75, 139
Sodium sulfate 16-17, 75,163-165,
174-176
Sodium sulfide 15, 75-76,138-141,
150-151
Sodium sulfite 63,68,139
Softwoods (see also Pine; Spruce) 29,
95-96,167-169
Spent pulping liquor 159,164, 178
Sprout-Waldron refiner 64-65, 67
Spruce 19, 25, 27, 30, 35,40-41,
44-45, 48-50, 54-55, 58-62, 65, 78,
87,95,103,156-157,177
Stainless steel 1, 33, 64
Startup 114-115
Steam economy 41, 111, 114,182-183,
188
Steam flow 112
Steam hammering 33, 66
Steam hydrolysis 105
Steam shock 30-31
Steaming 30-31,119
Steaming vessel 33, 144
Stiffness 63
Stockman, Lennart 7
Stora process 19
Strainers 52, 99, 106-109, 113, 144,
160, 162,173
Styrene sulfonate 21
Substance yield factor 163-165, 175
Sudbrook Pulp Mill Ltd. 4
Sugars, see Carbohydrates
Sulfate formation 16-17
Sulfidation of lignin 13 9
Sulfide cook 15,75,134
Sulfidity 87,93,115,133,138,
140-141
Sulfite-bisulfite mixed cook 15
Sulfite cook 7,10-31
Sulfite cooking acid 11-17, 33,41, 48,
63-65, 68, 69
Sulfite pulp 26, 164
Sulfitolysis 12, 19, 21, 29
Sulfonation 11-12,15, 18-19, 21,
28-29, 63-64, 139
Sulfur charge 129-130,135-136,
138-140, 146
Sulfur dioxide 11-31,51
Sulfuric acid 34
Sulfurous acid 11,14, 16
Summerwood (latewood) 95
Swedish Cellulose Co. 10
Swelling degree 171
Tall oil soap 178,189
Tannins 19,78
Techmashimport 5
Temperature schedules 11-12, 20, 43,
64, 66-69, 81, 91, 98-100, 108-109,
132, 134,136, 140, 142, 146,168,
171, 173-174
Terpenes 16
Thermometry 43
Thiosulfate 16-17, 28, 52, 139
Tilghman, Benjamin 11
Tokai Pulp KK. 5
Top scraper 2-3, 35, 106
Tramp iron 115
Two-body digester 34, 37-38, 43, 45,
51-52,105-107,110,125,136
Two-stage polysulfide 129,134-136,
138
Two-stage sulfite cook 15, 19-20, 23-24,
44-50, 103
198
Tyloses 29
Upflow digester 36, 39,44, 105-107
Uronic acids 64,88,92
Usutu Pulp Co. Ltd. 5
Vanillyl alcohol 77
Vapor-phase cooks 55, 110, 112, 119,
135-136,138, 144,146-149
Vapor pressure 31
Vaporspheres 190
Viscose pulp, see Dissolving pulp
Viscosity 40, 43-45, 54, 59, 102,
115-117
Wall effect 178
Washing 159-178,188-189
Wash liquor 117, 122,173, 175
Wash zone bleaching 60
Water hydrolysis 105
Water pollution 70, 116, 159
Watt-Burgess process 75
Weyerhaeuser Timber Co. 4
White Uquor 87, 92, 106-119, 121-122,

124-125, 129, 134-136, 148
Whitewater 117-118
Wifstavarfs AB 3-4
Xylan 22, 25-26, 28, 39, 63-64, 79, 82,
85-87,91,109, 123,125-127,136
Xylose 40, 48-49, 59, 61, 70, 71, 104,
123,127-128,130, 135, 141-i42,
147, 150
Yield of
acid sulfite pulp 49
alkaline sulfite pulp 143
bisulfite pulp 60-61
kraft pulp 78, 82, 86-87, 90
modified kraft cooks 121-158
NSSCpulp 69,71-73
prehydrolysis kraft cook 105,119
spruce pulp, strength affected by 95
sulfite pulps 23-25, 27-29
washing effect on 167,175-178

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Disclaimer: In some cases, the Million Book Project has been

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* Out of print. Photocopy may be obtained from University Microfilms,

Continuous Pulping Processes

SPECIAL TECHNICAL ASSOCIATION

Library of Congress Catalog

Printed in the United States of America

Continuous Pulping Processes

3 Continuous Acid Sulfite Cooking

Continuous Bisulfite Cooking

5 Continuous Neutral Sulfite Cooking

6 Kraft Cooking Process Theory

7 Continuous Conventional Kraft Cooking

Continuous Prehydrolysis-kraft Cooking

Continuous Modified Kraft Cooking

10 Washing Process Theory

11 Continuous Digester Washing

12 Technical and Economic Aspects of Present and Future

Fig. 1.1. Principle of the balanced high-pressure pocket feeder.

Historical Development of Continuous Kraft Cooking

BLOW STEAM RECOVERED FOR PRESTEAMING

Fig, 1.2. First commercial Kamyr kraft cooking system.

Table 1.1. Pioneering Mills in Kamyr Continuous Digester Systems

1948 Fengersfors Bruks AB,

Table 1.1. Pioneering Mills in Kamyr Continuous Digester Systems

Fig. 1.3. Kamyr kraft cooking system after the

Historical Development of Continuous Kraft Cooking

this hesitation were the problems of production reliability and of pulp

Fig. 1.4. Development of Kamyr kraft cooking installations

Sulfite Cooking Process Theory

Fig. 2.1. Mechanism of delignification according to two concepts:

Sulfite cooking acid concepts and composition.

Sulfite Cooking Process Theory

Fig. 2.3 Temperature dependence of the apparent ionization constant of

Fig. 2.3 Temperature dependence of the apparent ionization constant of

Measured in terms of hydrogen ion concentration, these changes are

Sulfite Cooking Process Theory

Sulfite Cooking Process Theory

Fig. 2.5. Bjerrum diagram showing pH and ion concentrations of various

Sulfite Cooking Process Theory

Fig. 2.7. Decomposition of sulfite cooking acid in absence of organic

Sulfite Cooking Process Theory

Fig. 2.11. Temperature schedules of some two-stage cooks with industrial

Sulfite Cooking Process Theory

appears to be a sulfitolysis of the alkylaryl ether bond under formation of

The dominant carbohydrate reaction in acid sulfite cooking is hydrolysis

Sulfite Cooking Process Theory

accessibility to hydrolysis. The hemicelluloses are less well ordered than

Sulfite Cooking Process Theory

Fig. 2.19. Yield of wood components on sulfite pulping of spruce and

high-yield semichemical cooks with deacetylating action likewise give a

Sulfite Cooking Process Theory

Fig. 2.22. Dissolution of sprucewood components on sulfite pulping.

Fig. 2.24. Sulfonation and oxidative degradation of carbohydrates in

Sulfite Cooking Process Theory

Fig. 2.25. Sulfonation and oxidative degradation of carbohydrates

Sulfite Cooking Process Theory

improve the situation as compared to ordinary steaming of the same

Continuous Acid Sulfite Cooking

Continuous Acid Sulfite Cooking

Two-body digester for acid sulfite pulping.

sluice. We learned how to construct a top scraper to transfer the chips