2022-06-20

Pulp production
Harald Brelid
Content
• General background
‒ What is pulping?
‒ Mechanical and chemical pulping

• The Kraft pulping process

‒ Fibre line
‒ Energy and chemical recovery
Pulping
• Pulping represents the process by which wood or other lignocellulosic material
is transformed to a fibrous mass, denoted as pulp

e.g. kraft pulping

Wood is a bio-composite material composed of different
types of fibres

TRANSVERSAL SURFACE

RADIAL SURFACE
TANGENTIAL SURFACE
Liberation of fibres from the wood matrix

Wood Fibre liberation Pulp

Mechanical pulping: The fibres are
liberated from each other by shear forces

Chemical pulping: Dissolution of the

material that ‘glues’ the fibres together
Pulp production – methods
Mechanical
Stone ground wood (SGW)
Thermo-mechanical (TMP)
Chemi-thermo-mechanical (CTMP)

Chemical
Sulfite (active chemicals: SO32- and/or HSO3-)
Soda process (active chemical: OH-)
Kraft process (active chemicals: OH- and HS-)

Semi-chemical
Mechanical pulp fibres
• Relatively stiff fibres

• Many damaged fibres

• A lot of fines
Chemical pulp fibres
• Fibres are easily separated after the
chemical treatment

• Less damaged fibres

• More flexible fibres

Chemical composition

MECHANICAL PULP

CHEMICAL PULP
Different mechanical pulp qualities
Ground wood processes Refiner pulp processes
Wood Chips

Wood storage
Rotating refiner segment
Rotating grinding stone

➢ SGW (Stone Ground wood) ➢ RMP (Refiner Mechanical pulp)

➢ PGW (Pressurized Ground Wood) ➢ TMP (Thermo-Mechanical Pulp)
➢ CTMP (Chemi-Termo-Mechanical Pulp)
Liberation of fibres in mechanical pulping

Stone Ground wood TMP/CTMP

• Softening of the wood material when the • Initial softening by steam (and chemical
wood is pressed against the rotating treatment in the case of CTMP)
grinding stone • In the refiner: softening/cracking due to
• Release of softened fibres in a layer compressions/expansions
closest to the stone • Shear forces => liberation of fibres
• After-treatment of the released fibres as • Subsequent fibrillation in the refiner gives
they are removed from the grinding zone fibre flexibility
Sulfite cooking
Chemistry Processes
• Lignin solubilization: • May be performed at different pH-levels (from acid to
‒ Depends mainly on sulfonation of certain lignin alkaline conditions)
structures
• Neutral and Alkaline conditions used for Semi-
chemical pulps (only limited degree of delignification)
• Carbohydrate degradation
‒ Mainly due to acid hydrolysis • In the fibre line, essentially the same process steps
as in the case of kraft pulping

The first sulfite pulp mill

Bergvik mill (1000 ton/year) Nymölla mill (300 000 ton/year)
 Production of different types of pulps

• Sulfite pulping was the dominating chemical

pulping method until the 1950s Kraft
pulp
• Increased use of kraft pulp
‒ Better strength properties of kraft pulp
‒ Development of kraft pulp bleaching

Sulfite
pulp
Layout of a kraft pulp mill
Fibre line and chemical recovery
CHIPS PULP BLEACHED PULP
Oxygen- Bleaching
Digester
delignification
Effluent to waste
water treatment
Fibre line
BLACK LIQUOR Chemical recovery
Recovery
WHITE LIQUOR Evaporation
boiler SMELT

GREEN LIQUOR
Causticizing Slaking Dissolver

CaCO3 CaO

Reburning
Fibre line: From wood to bleached pulp fibres

Wood chips Cooking with OH- + HS- Pulp after cooking

at 150-170°C

Bleached pulp Washed pulp

Bleaching with oxidizing chemicals
e.g. O2, ClO2 and H2O2
From log to chips
Kraft cooking
• Digester dimensions (examples)
‒ Batch: 4-10 à 250-400 m3
‒ Continuous: 1-2 à 1600 m3 (height 55 m, width 6.5 m)

• Process conditions
‒ SW: 155-170ºC
‒ HW: 140-160ºC

• Cooking chemicals
‒ hydrogen sulfide ion [HS-] and
‒ hydroxide ions [OH-]
‒ additives to improve carbohydrate yield (polysulfide and/or anthraquinone, AQ)
Digestion in continuous or batch processes
Continuous digester Displacement batch digester
Kraft pulping chemistry

Wood material in the

form of chips is treated

Chemical treatment in large- Chemical reactions induce

scale reactors changes in chemical composition
and porosity of the fibres
Distribution of lignin over a double fiber wall in spruce
Lignin content

S: Secondary wall
ML: Middle lamella
CC: Cell corner
Cell wall of a single fibre
Solubilization of lignin
• Lignin is made soluble in the cooking by the action of OH- and HS-, which
cause chemical fragmentation and introduce charged groups in the lignin

STRUCTURAL ELEMENTS IN LIGNIN PART OF THE S2-LAYER LIGNIN REMOVAL

Favis (1981)
Brunow et al. (1998)
Carbohydrate degradation during kraft pulping

- Highly alkaline cooking liquor Fragmentation and

dissolution of
- High temperature carbohydrates

Approx. 40% of the carbohydrates is dissolved during pulping

(mainly hemicelluloses, cellulose is much more stable)
Yield loss of lignin and hemicellulose during kraft pulping

Lignin Temperature 160

25
Glucomannan
20 (conventional 120
kraft pulping)
Glucomannan
15 (kraft with 80
polysulfide)
10

40
5 Xylan

0 100 200 300

Time (minutes)
Question
• A higher yield of glucomannan (achieved by e.g. polysulfide)
5
enhances the tensile strength properties of the pulp
• Tear strength may be negatively affected (less fibres per gram)

• Which strength property is the most important for you?

• A) High tensile strength at a low input of refining energy

• B) High tear strength at a certain input of refining energy

• C) High tear strength at a certain level of tensile strength (e.g. tear

@ 85 Nm/g)
Bleaching
A chemical process aimed at the removal of color and impurities from the pulp
• Residual lignin
• Extractives (resin compounds)
• ‘Dirt’ (e.g. bark, fibre bundles, shives)

Bleaching
Oxygen delignification
• Further removal of lignin without losing too much
of the carbohydrates

• Oxygen and sodium hydroxide generate active

chemicals

• One or two stages

• 90-110ºC, 30-90 min/stage, final pH 11

Bleaching – chemicals
Bleaching agent Designation Function End-pH in bleaching stage
Chlorine C Oxidizes and chlorinates lignin 2

Hypochlorite H Oxidizes and removes chromophores 9-11

Chlorine dioxide D Oxidizes and removes chromophores 3-4

Oxygen O Oxidizes lignin 10-12

Hydrogen peroxide P Oxidizes and removes chromophores 10-12

Peracetic acid Paa (T) Oxidizes lignin 5-6

Ozone Z Oxidizes and removes chromophores 2-4

Sodium hydroxide E Hydrolyses chlorinated lignin and ionizes acid 10-12

groups in the lignin
Chelating agent Q Removes transition metal ions 5-7
from the pulp (e.g. Mn)
Bleaching – different approaches
• TCF (Totally Chlorine Free) or ECF (Elementary Chlorine Free)

• Active bleaching agents

‒ TCF: hydrogen peroxide, peracetic acid, ozone
‒ ECF: chlorine dioxide (in combination with oxygen based chemicals)

• Several stages (3-5), examples Q(OP)Q(PO) or D(EP)Q(PO)

Question
• The environmental impact of modern ECF- and TCF-bleaching is nowadays
considered to be at the same level (BAT, Best Available Technique)
6
• The choice of bleaching method may influence pulp properties to some extent
• Company policies may result in preference for one of the two

• Which type of pulp do you prefer in your paper production?

1. TCF-bleached pulp

2. ECF-bleached pulp

3. The bleaching method does not matter

From chips to bleached softwood pulps

BRIGHTNESS (% ISO)

~50 ~30 ~45 ~70 ~90

Cooking

Oxygen bleaching
Bleaching
Pulp dryer with airborne web
Flash dryer
Fibre line and chemical recovery
CHIPS PULP BLEACHED PULP
Oxygen- Bleaching
Digester
delignification
Effluent to waste
water treatment
Fibre line
BLACK LIQUOR Chemical recovery
Recovery
WHITE LIQUOR Evaporation
boiler SMELT

GREEN LIQUOR
Causticizing Slaking Dissolver

CaCO3 CaO

Reburning
Energy and chemical recovery
• About half of the wood material is burnt in the recovery boiler

• The energy content is transformed to steam, electricity and district heating

• The cooking chemicals are recovered and brought back to the process
Black liquor composition
Element Amount (wt%)

C 34-39

H 3-5

O 33-38

Na 17-25

S 3-7

K 0.1-2

Cl 0.2-2

N 0.05-0.2

~2/3 is organic material

~1/3 is inorganic material
 MIXED-FLOW
S S S S S Steam to surface
Evaporation plant Live
condenser

steam 1 2 3 4 5 6
C
• Black liquor (spent cooking liquor) is C C C C C

evaporated in several steps

• The dry content is increased from ca Strong black Weak black
liquor liquor

15% to 70-85%
• Designed for high energy efficiency and
high dry contents COUNTER-FLOW
S S S S S Steam to surface
condenser
Live
steam 1 2 3 4 5 6
C C C C C
C

Strong black
liquor Weak black
liquor
The recovery boiler

Black liquor is sprayed into the recovery boiler using spray nozzles
The recovery boiler
• Recovery of sodium and sulfur

• Generation of steam and electricity

White liquor preparation
CaCO3 CaO+CO2

Water condensate
Smelt Weak white Lime mud
wash wash
Lime kiln

CaO
Weak white
wash

Cauticization
White liquor
vessels
NaOH

Filter

Filter

Na2CO3 Slaker
Ca(OH)2 Na2S in the green liquor
Ca(OH)2 + CO32-
CaO+H2O  Ca(OH)2 CaCO3 goes through the process
 CaCO3 + 2OH-
and ends up in the white
Green liquor dregs
liquor
The Kraft process– Principal overview
COOKING OXYGEN DELIGNIFICATION BLEACHING DRYING

CHIPS PULP

EVAPORATION
Thin liquor
White liquor Thick liquor

CAUSTICIZING DEPARTMENT RECOVERY BOILER

Green liquor Electricity and steam

Lime mud LIME KILN Quick lime

sodra.com
 2022-06-20

Södra Cell Värö

 2022-06-20

Södra Cell Värö

Södra Cell
• One of the world’s largest
manufacturers of softwood pulp
• Three pulp mills: Värö, Mörrum
and Mönsterås
• 90% of production is softwood pulp,
the remainder is hardwood pulp
• The pulp is mainly sold to European
manufacturers of tissue, speciality paper,
packaging and publishing paper.
• Dissolving pulp is made at Mörrum
• Major supplier of biofuel,
green electricity and district heating
Södrakoncernen

Södra Cell
Mönsterås

Södra Cell
Värö
Södra Cell
Mörrum
48

Södra Cell Värö

Starting year 1972
Employees 375
Capacty 780 000 tonnes/yr
The kraft process
Mill Tour
sodra.com