4.

SULFATE PROCESS

Table of content

PRINCIPLE OF THE SULFATE PROCESS....................................................................................................................... 1
KRAFT COOKING LIQUORS........................................................................................................................................ 1
Black liquor ........................................................................................................................................................ 3
Green liquor ....................................................................................................................................................... 3
White liquor........................................................................................................................................................ 3
KRAFT COOKING CHEMISTRY................................................................................................................................... 4
Sodium sulfide (Na
2
S)......................................................................................................................................... 4
Alkali .................................................................................................................................................................. 5
Polysulfide and anthraquinone........................................................................................................................... 7
COOKING PROCESS................................................................................................................................................... 8
H FACTOR ................................................................................................................................................................ 9
QUESTIONS ............................................................................................................................................................ 10




Kaj Henricson
Professor Pulping Technology
Lappeenranta University of Technology
August 2004




Educational course material and only for internal and personal use during
the course: An introduction to chemical pulping technology.

1
Principle of the sulfate process
Picture 1 shows the basics of a fiber line of the sulfate process also called the kraft process. The
fiber line is a fiber line for producing bleached hardwood or softwood pulp to be used for
instance in the manufacturing of writing paper. The objective of the kraft cooking process is to
separate the fibers in wood chemically and to dissolve most of the lignin contained in the fiber
walls as gently as possible. The key operating variables during kraft cooking are the charge of
cooking chemicals, time and temperature. After cooking, kraft pulp is washed to recover the
used cooking chemicals and dissolved organic material. The pulp is then screened to remove
debris and bleached to the target brightness. The resulting sulfate or kraft pulp is dried and baled
or taken directly to a paper mill.

COOKING WASHING SCREENING BLEACHING
SULPHATE
PULP
PAPER MILL
DRYING
TREE
CROSS
CUTTING
STORAGE CHIPPING BARKING SCREENING
COOKING WASHING SCREENING BLEACHING
SULPHATE
PULP
PAPER MILL
DRYING
COOKING WASHING SCREENING BLEACHING
SULPHATE
PULP
PAPER MILL
DRYING
TREE
CROSS
CUTTING
STORAGE CHIPPING BARKING SCREENING TREE
CROSS
CUTTING
STORAGE CHIPPING BARKING SCREENING


Picture 1. The fiber line operation of the sulfate process for producing bleached pulp
Picture 2 shows the cooking chemical
regeneration cycle of the sulfate process.
After cooking, the spent liquor is separated
from the fibers by washing. The resulting
weak black liquor is evaporated to remove
excess water, and the strong black liquor from
evaporation is taken to the recovery boiler.
The spent liquor is burned in the recovery
boiler to produce heat and a smelt consisting
of the inorganic sodium-containing cooking
chemicals. The smelt is dissolved in water to
produce green liquor that is recausticized to
form the white liquor that is the cooking
liquor needed in kraft cooking. In the
recausticizing process, lime is used to convert
sodium carbonate into sodium hydroxide.

Picture 2. Sulfate pulp mill, chemical
regeneration cycle
Kraft cooking liquors
The kraft cooking liquor is a mixture of white liquor, water in chips, condensed steam and weak
black liquor used to adjust the liquor-to-wood ratio. The white liquor is a strongly alkaline
solution (pH~14), in which the main active compounds are sodium hydroxide (NaOH) and
sodium sulfide (Na
2
S). White liquor also contains small amounts of sodium carbonate (Na
2
CO
3
),
sodium sulfate (Na
2
SO
4
), sodium thiosulfate (Na
2
S
2
O
3
), sodium chlorine (NaCl) and calsium
carbonate (CaCO
3
) plus other accumulated salts and non-process elements. These additional
compounds can be considered inert from a cooking point of view. They enter the white liquor
either as contaminants with the used raw materials or as a result of inefficiencies in the chemical
regeneration cycle.
PMS
Taskinen

2
Hydrolyzed NaOH and Na
2
S are the active species in kraft pulping, and Na
2
CO
3
is that to a
lesser extent. The main reaction variables in alkaline cooking are wood species (i.e. their main
chemical components), chip dimensions, temperature, time, and the concentration of cooking
chemicals (OH- and HS- ions).
O H OH Na O H NaOH
2 2
+ + +
+

O H S Na O H S Na
2
2
2 2
2 + + +
+


+ + OH HS O H S
2
2

During kraft cooking, about 45% to 65% of the wood material will result in pulp and the rest of
the wood is dissolved to form the organic material in the black liquor. The pulp yield varies
depending on the pulp type produced. The yield is lower in pulp to be bleached for white board
and paper grades and higher in pulp for brown board and paper grades.
CELLULOSE
830 596
HEMICELLULOSE
596
LIGNIN
106
EXTRACTIVES ECT
222
42
5
LIGNIN
HEMICELLULOSE
730
CELLULOSE
WOOD
PULP 1000
DISSOLVED WOOD
0,53*2128 = 1128
TURPENTINE,
METHANOL,
NON-
CONDENSABLE
25
ORGANIC DRY SOLIDS
IN BLACK LIQUOR
1103
1000
0.47
=2128
CELLULOSE
830 596
HEMICELLULOSE
596
LIGNIN
106
EXTRACTIVES ECT
222
42
5
LIGNIN
HEMICELLULOSE
730
CELLULOSE
WOOD
PULP 1000
DISSOLVED WOOD
0,53*2128 = 1128
TURPENTINE,
METHANOL,
NON-
CONDENSABLE
25
ORGANIC DRY SOLIDS
IN BLACK LIQUOR
1103
1000
0.47
=2128

Picture 3. Wood material during kraft cooking

Picture 4. Schematic diagram relating to the terminology used in describing the composition of kraft
cooking liquors
In Scandinavia, the chemical properties and composition of kraft cooking liquors are usually
defined as:
Total alkali, g/l = all Na- compounds (NaOH, Na
2
S, Na
2
CO
3
, Na
2
SO
4
, Na
2
S
2
O
3
,
Na
2
SO
3
)
Active alkali, g/l = NaOH + Na
2
S
Fapet: p. A43
PV, Modified by KH

3
Effective alkali, g/l = S Na NaOH
2
2
1
+
Sulfidity, % = 100
2

+ S Na NaOH
S Na
s

Causticity, % = 100
3 2

+ CO Na NaOH
NaOH

Reduction, % = 100
4 2 2
2

+ SO Na S Na
S Na

The amounts of the compounds are calculated as equivalents of NaOH or Na
2
O and can be
converted to other equivalents based on their sodium contents as expressed in Table 1. The
conversion of the compounds into other sodium compounds present in white liquor takes place
by means of equivalent molecular weights. B
A
= M
A
/M
B
, where B
A
is a coefficient through
which compound B can be converted into A, M
A
is the equivalent molecular weight of
compound A, M
B
is the equivalent molecular weight of compound B.
Table 1. Conversion factors for kraft cooking chemicals
Compound
as is
Multiply to get
Na
2
O
From Na
2
O
to compound
Multiply to get
NaOH
From NaOH
to compound
NaOH 0.775 1.290 1.000 1.000
Na
2
O 1.000 1.000 1.290 0.775
Na
2
S 0.795 1.258 1.025 0.975
NaHS 0.554 1.807 0.714 1.400
Na
2
CO
3
0.585 1.710 0.775 1.325
Na
2
SO
4
0.437 2.290 0.563 1.775

Black liquor
Black liquor is formed during cooking, and it contains the used cooking chemicals and the
dissolved organic material. The water content in weak black liquor is high and the liquor
contains only 15%-20% of dry solids, the rest being water. Weak black liquor is evaporated to
form strong black liquor having a dry solids content of 65%-85%.
Green liquor
Green liquor is formed when the smelt from the recovery boiler is dissolved in water. The main
components of green liquor are Na
2
CO
3
and Na
2
S. Green liquor also contains inactive sodium
compounds, accumulated salts and non-process elements. Non-process particles include
unburned carbon, solids from the furnace construction and some calcium compounds. Green
liquor needs to be clarified or filtered before used for cooking chemical production.
White liquor
White liquor contains the active cooking chemicals. It is an aqueous solution where the active
chemicals are NaOH and Na
2
S. Mill white liquor also contains some inactive dead-load
chemicals. The primary one is Na
2
CO
3
. White liquor is formed when green liquor is treated with
lime in order to form NaOH from Na
2
CO
3
.

Fapet 6A: p.A43

4
Table 2. Typical white liquor composition
Concentration, g/l Compound Molar
weight /m
NaOH Na
2
O Actual compound
NaOH 40 95 73.6 95
Na
2
S 78 40 31.8 39
Na
2
CO
3
106 23 17.8 30.5
Na
2
SO
4
142 4 3.1 7.1
Na
2
S
2
O
3
158 2 1.6 4.0
Na
2
SO
3
126 0.5 0.4 0.8
Other - - - 3.0
Na
2
O 62 - - -
Effective alkali 135 105.4
Active alkali 115 89.5
Total alkali 164.5 128.3 179.4
Sulfidity 29.6%
Causticity 80.5%
Reduction rate 80.0% (all S-compounds are taken account in calculations)

Kraft cooking chemistry
Sodium sulfide (Na
2
S)
Sulfide increases the selectivity of the sulfate cooking process and increases the rate of
delignification. There is a catalytic effect caused by the hydrosulfide ion on the cooking process.
The sulfide ion is only, to some extent, bound to the organic material dissolved during cooking.
The sulfide ion leads to the formation of odorous gases that cause the characteristic smell at
sulfate pulp mills.
Increasing sulfidity up to 30% has a strong impact on the cooking process. Further increase in
sulfidity improves the process only marginally. Sulfidity is 35%-45% in most Scandinavian
mills and in North American mills 25%-35%. Generally, sulfidity tends to increase when the
losses of mill liquor decrease.
When sulfidity increases from 0% to 31% as shown in Picture 5, the time needed to delignify the
pulp is reduced in the temperature interval 150C to 170C. When cooking time can be reduced
the yield will increase and the pulp strength will improve as the fibers as subjected to strong
alkaline conditions a shorter time.
At the same degree of delignification, yield will increase when sulfidity is increased as shown in
Picture 6. For hardwood the effect can be seen up to a sulfidity of 20-30 % after which the effect
is small. For softwood the benefits of a higher sulfidity continues up to a sulfidity over 50%.
Modified by KH;
PV: p.383

5

Picture 5. Effect of cooking time, temperature and sulfidity on the kraft cooking of spruce
Picture 5 shows how the lignin content of wood decreases during cooking as a function of time,
temperature and sulfidity. The cooking has been done using the same charge of effective
chemical to the cooks.
SULFIDITY
T
O
T
A
L

Y
I
E
L
D
%

(
O
F

W
O
O
D
)
YIELD PINE,
KAPPA 55
YIELD BIRCH,
KAPPA 55
SULFIDITY
T
O
T
A
L

Y
I
E
L
D
%

(
O
F

W
O
O
D
)
YIELD PINE,
KAPPA 55
YIELD BIRCH,
KAPPA 55

Picture 6. Effect of sulfidity on the total yield in
the kraft cooking of spruce and birch

Picture 7. Effect of white liquor sulfidity on the
fiber length distribution of beaten
pulp

The pulp properties improve when sulfidity increases. This is illustrated in Picture 7, which
shows fiber length distribution for softwood fibers after refining as a function of sulfidity. The
fiber length as such is not influenced by sulfidity but the fibers become stronger and are more
resistant to being cut during refining.
Alkali
A major portion (30%-40%) of the total alkali charged will be consumed during the
impregnation phase or the extraction phase although lignin dissolution is slight. The alkali goes
Modified by KH
Fapet 6A: p.A59
Fapet 6A: p.A49
Modified by KH;
PV: p.322

6
to the neutralization of the acid groups formed, the end-wise degradation of polysaccharides and
the splitting of acetyl groups from the hemicellulose chains. Sulfide takes part only in minor
amount in the dissolution of the polysaccharides.
Most of the alkali consumption takes place during the extraction stage also called impregnation
and initial cooking. Only a limited amount of alkali is consumed during the bulk delignification
phase, but the consumption increases again during residual delignification. Delignification itself
does not require much alkali, but the conditions need to be strongly alkaline for lignin to
dissolve. There needs to be a certain amount of alkali left at the end of the cook to maintain a pH
high enough also at the end of the cook.
Sulfide and hydrosulfide ions are not consumed or transformed much during cooking. The
balance between hydroxyl ions and hydrosulfide ions changes during cooking due to the
consumption of alkali.

Picture 8. Consumption of effective alkali as a
function of lignin yield in the kraft
cooking of pine and birch
H FACTOR
PINE BIRCH
EFFECTIVE ALKALI = 24%
SULFIDITY = 25%
R
E
S
I
D
U
A
L

L
I
G
N
I
N
,

%

(
O
F

W
O
O
D
)
BULK DELIGNIFICATION
RESIDUAL
DELIGNIFICATION
EXTRACTION PHASE
H FACTOR
PINE BIRCH
EFFECTIVE ALKALI = 24%
SULFIDITY = 25%
R
E
S
I
D
U
A
L

L
I
G
N
I
N
,

%

(
O
F

W
O
O
D
)
BULK DELIGNIFICATION
RESIDUAL
DELIGNIFICATION
EXTRACTION PHASE

Picture 9. Rate of dissolution of pine and birch
lignin as a function of H factor
EA in chips EA in chips

Picture 10. Effective alkali in the liquid phase and inside the chips during kraft cooking. The time it
takes for the alkali to impregnate the chips at the beginning of the cook is about 30
minutes. Much of the alkali is consumed before actual delignification starts.

Fapet 6A: p.A47
AP: p.215
Modified by KH;
PV: p.304

7
Polysulfide and anthraquinone
Polysulfide stabilizes hemicelluloses during cooking and reduces carbohydrate dissolution in
cooking of hardwoods and softwoods. Proper application of polysulfide will lead to substantial yield
improvements as shown in the picture. These yield increases in pulping sustain in bleaching.
Polysulfide is used at many mills as a way to increase the yield during kraft pulping. There will be a
slight change in pulp properties when polysulfide is used.

Picture 11. Yield increase for spruce as a function of polysulfide sulfur addition
Unmodified anthraquinone can stabilize carbohydrates against alkaline degradation by slowing
down peeling reactions on hardwoods and softwoods. The way anthraquinone functions in kraft
pulping can be explained as shown in Picture 12. Anthraquinone (AQ) reacts with reducing end
groups of carbohydrates, stabilizing them against alkaline peeling and producing reduced
anthrahydroquinone (AHQ) which is alkali soluble. AHQ reduces lignin, which becomes more
reactive; AQ is formed again and reacts with carbohydrates. This semi-catalytic redox
mechanism explains why very small additions of anthraquinone are effective.
Anthraquinone is used as an additive at many kraft mill to increase pulp yield. The cost of the
amount of anthraquinone used must be balanced against the savings in wood costs.
Anthraquinone is also used in sulfur-free cooking to speed up delignification and increase yield.
Especially on hardwood, soda-anthraquinone cooking can be used and the results are almost
similar to kraft cooking. There are a few mills using soda-anthraquinone cooking.

Picture 12. The oxidation and reduction cycle in anthraquinone-enhanced kraft pulping
Fapet 6A: p.A52
Fapet 6A: p.A53

8

Picture 13. Effect of anthraquinone on mixed southern hardwood soda pulping
Cooking process
Before the chips are impregnated with the cooking liquor, they are usually presteamed. There
are two reasons for presteaming chips: (1) to drive off the air inside the chips and replace it with
steam; and (2) to heat the chips. Air inside the chips prevents the cooking liquor from
penetrating and diffusing into the chips. Steam can, contrary to air, condensate, and steam makes
it possible for the cooking liquor to penetrate and diffuse into the chips.
After presteaming, the cooking liquor is added to the chips, the suspension is pressurized and
impregnation begins. The objective of impregnation is to distribute the cooking liquor uniformly
into the chips. Impregnation consists of two different processes: penetration of void parts of the
chip and diffusion. As early as during impregnation, the chemical reactions start, the wood
material is dissolved and alkali is consumed.
After or during impregnation, the temperature is raised, and as the temperature rises,
delignification starts. Most of the delignification takes place after reaching a temperature above
140C. Normal final cooking temperatures are in the range of 150C-170C. Most new digesters
have been designed for rather low cooking temperatures. During cooking, the alkalinity of the
cooking liquor can be controlled by adding alkali and by exchanging cooking liquids during
cooking.
The chips retain their structure during cooking and are about the same size after cooking as
before cooking. After cooking, the chips are soft and can be disintegrated into fibers by light
agitation if the kappa number has been lowered sufficiently. Some high-yield pulp grades
require that the chips are disintegrated by refining after cooking in order to produce a pulp
suspension consisting of individual fibers.
The variables affecting the cooking process can be divided into three categories: chip quality,
white liquor properties and cooking control variables. The mixture of chip grades, available at
the chip storage, determines chip quality. Mill chemical balances and the operation of the
chemical recycling process determine the white liquor properties. Cooking control variables are
controlled during cooking. The main cooking control variables are time and temperature (H
factor), alkali charge and liquor-to-wood ratio.
Fapet 6A: p.A54

9
The charge of alkali is dependent of type of wood used. Usually softwoods require a larger
charge of alkali as percentage on wood than hardwoods. Too small a charge of alkali will lead to
high amounts of reject after cooking due to uncooked parts of chips remaining after cooking.
Too large a charge will lead to increased operational costs, lower yield and corrosion problems
especially in the black liquor recovery cycle.
The goal of the kraft cook is to get a high yield of cellulose with a high degree of polymerization
and a low yield of lignin. The cooking conditions are chosen to make the cook as selective as
possible.
A high yield of hemicelluloses increases the yield on wood but also influences the fiber
properties. To some extent, the hemicellulose yield can be influenced by controlling the cooking
conditions.
Extractives cause problems during pulp washing, bleaching and papermaking. The extractives
are removed as thoroughly as possible during cooking together with the black liquor and by
degassing during cooking. Hardwood extractives are especially harmful and the amount of
hardwood extractives can be reduced by adding black liquor or tall oil from softwood cooking to
the hardwood cooking process. Some additive chemicals to cooking can also be used to lower
the amount of extractives in the pulp after cooking.
H factor
As mentioned earlier, time and temperature are very important factors in cooking. They can be
represented by a single numerical value, the H factor. As long as the H factor is constant, the yield
and lignin content of cooking will be the same if the other conditions like raw material and alkali
concentration are the same.
The contribution of the heating time to the H factor is very small compared to the contribution of the
cooking time at higher temperatures (Picture 14). Modern digester control systems automatically
compute and accumulate the H factor during the cook to compensate for deviations from the
intended cooking cycle.

Picture 14. Temperature, reaction rate and accumulated H factor during kraft cooking. The H factor is
represented by the integral of reaction rate and cooking time. The reaction rate is strongly
dependent on temperature.
AP: p.54

10
Questions
1. Factors influencing yield during normal kraft cooking. / Massasaantoon vaikuttavat tekijt
tavanomaisessa sulfaattikeitossa.
2. Polysulfide and anthraquinone in alkaline cooking. / Polysulfidin ja antrakinonin kytt
alkalisessa keitossa.
3. The stages of delignification and the consumption of alkali during kraft cooking. / Ligniinin
liukenemisen eri vaiheet sulfaattikeitossa ja alkalin kulutus keiton aikana.
4. The effect of sulfide on delignification and the consumption of sulfide during cooking. /
Sulfidin vaikutus keittoon ja sulfidin kulutus keiton aikana.
5. The use of the H factor in controlling cooking. / H-tekij keiton ohjauksessa.
6. Main cooking control variables. / Keiton ohjauksen trkeimmt parametrit.
7. Give the definition for the following pulping terms: a)total alkali, b)active alkali, c)effective
alkali, d)sulfidity, e)causticity, f)reduction. / Mrittele seuraavat termit: a)kokonaisalkali,
b)aktiivialkali, c)tehollinen alkali, d)sulfiditeetti, e)kaustisointiaste, f)reduktioaste.