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Puu-0.
4110: Conventional and Non-

Conventional Pulping as a Basis for
Biorefinery (7 cr)
Lecture 13:
Kraft pulping: Recovery of chemicals and energy I
Learning Objectives
After this lecture the student:

• understands, and is able to explain, the objectives of the
kraft pulp mill recovery cycle and its sub processes
• can define the most important monitoring parameters of
the recovery cycle (e.g. sulfidity, caustisation degree,
reduction degree, dry solids content) and understands
their importance
• recognises the chemical reactions taking place at
different stages of the recovery cycle
Puu-0.4110 13. Kraft recovery I Keijo Salmenoja
2
Introduction to
Chemical Recovery Processes
3
Introduction
• Explanation of what recovery department of a modern

Pulp Mill does
• Recovery process of a modern pulp mill is based on best
available techniques (BAT)
• Examples shown are typical equipment, but details are
often vendor specific
4
Introduction
Mills are planned to make production 30 – 40 Continuous digester
years and longer was developed in the
Some of the key machines in the mills have -50’s
been almost the same for 50 to 60 years
Many equipment in this process were developed in the -80’s and -90’s
Recovery boiler
was developed
in the -50’s
DD washers were invented in 70’s and developed in the -80’s
Rotary lime kiln was developed in the -50’s
5
Introduction
RAUMA MILL
6
Introduction
• Pulp mill products

– pulp
• softwood / hardwood
– energy
• steam and electricity
– crude tall oil Biorefinery
– turpentine
– biomass
• bark, wood residues
– lignin
– methanol
7
Pulp mill processes in a nutshell
Fiberline
Woodyard
Pulp Drying
Chemical
Recovery Systems
Boiler
Evaporation
Effluent
treatment
plant
8
Recovery cycle mission
• Recovery systems are the core component of a kraft pulp

mill
• The three purposes of recovery systems are:

– regeneration of chemicals used in cooking
– production of steam for turbine and process
– destruction of waste streams generated elsewhere in
the mill
9
Recovery cycle
• Evaporation
• Recovery boiler
• Causticizing
• Lime Kiln
** *
10
Recovery cycle
11
Terminology
• Weak black liquor is liquor from the brown stock washing,

usually 14-20% ds
• Strong black liquor is high concentration liquor from the
evaporation, usually > 50% ds
• Green liquor is solution from the recovery boiler
containing chemicals mixed with water
12
Terminology
• White liquor is solution containing regenerated chemicals

to be used in cooking
• Lime is a solid stream containing mainly CaO
• Lime mud is a solid stream containing mainly CaCO3
13
Terminology
• Active sodium chemicals in the cooking process are

referred to as alkali
• Total alkali represents all sodium compounds present in
the liquor
• Active alkali represents those sodium compounds that
are the main cooking agents
• Effective alkali is a term used to describe the relative
strengths of sodium compounds as cooking agents – e.g.
in the case of sodium sulfide it is only half the amount of
the substance that is effective in the cooking process
14
Terminology
Total alkali: NaOH+Na2CO3+Na2S+Na2SO4

or all Na-compounds
Active alkali: NaOH + Na2S
Effective alkali: NaOH + ½ Na 2S
Effect of K on these values?
15
Purpose of the recovery system
• The purpose of the recovery system is to return the

inactive sodium compounds at the end of the cooking
process into active compounds that can be reused at the
beginning of the cooking process
• The active sodium compounds are in white liquor that
comes from the causticizing plant
• The inactive sodium compounds are first introduced to
the recovery system as part of the weak black liquor that
is emitted from the cooking process
16
Black liquor
% by weight
Organics (including organic Na and S) 78
Degraded lignin 37.5
Isosaccharine acids 22.6
Aliphatic acids 14.4
Resin and fatty acids 0.5
Polysaccharides 3.0
Inorganics 22
NaOH 2.4
NaHS 3.6
Na2CO3 and K2CO3 9.6
Na2SO4 and K2SO4 5.2
Na2S2O3, Na2SO3 and Na2Sx 0.5
NaCl 0.5
Non process elements (Si, Al, Fe, Mn, Mg, etc.) 0.2 Alén, kraft pulping of birch
17
Strong black liquor
• Concentrated to strong black liquor leaves the evaporation

process at 85% dry solids
• Black liquor contains:
– water
– organic residue from pulping (that part of wood that does
not end up as pulp)
– inorganic cooking chemicals (mostly spent)
18
Strong black liquor
Na % 19
K % 1.6
Stot % 4.5
Cltot % 0.4
S2- % 1.93
CO3 % 6.2
SO3 % 0.1
S2O3 % 2.13
SO4 % 1.23
C % 34.5
H % 3.3
N % 0.1
HHV MJ/kgds 14.0
Figures are given to show indicative magnitude of the various chemical compounds.
19
From black to green liquor
• Strong black liquor that comes from

the evaporator fuels the recovery
boiler
• Recovery boiler is also fuelled by a
number of other sources (e.g. NCG,
methanol, natural gas, heavy oil)
• Inorganics in black liquor form the
smelt
• The smelt is dissolved into weak white
liquor from the causticizing plant to
produce green liquor
20
Recovery boiler smelt
• Carbonate melt (~70% Na2CO3)

– dissolves all known materials when hot
• Ionic liquid
– low vapor pressure
– no viscosity
– no surface tension
– all components in ionic form
21
From green to white liquor
• The green liquor reacts with lime in the slaker to

produce:
– lime mud
– white liquor
• The lime mud goes to the lime kiln where it is returned

to lime
• The white liquor goes to the digester at the beginning
of the cooking process – completing the regeneration
of the alkali compounds
22
Green liquor
Raw Green Liquor (RGL) Definitions
Raw material for white liquor
• “Product” of recovery boiler dissolving tank • Total Titratable Alkali (TTA)
• Composition: – Na2CO3, Na2S and NaOH
– smelt from the boiler – concentration typically 130-170 g/l
– water (weak wash) • Dregs
• Concentration is given g as Na2O/l or g as – insoluble compounds in GL
NaOH/l – inorganics salts and unburnt black
liquor
• Main compounds as NaOH are:
– Na2S 40 g/l
– Na2CO3 110 g/l
• Sulfidity
– NaOH 10 g/l – Na2S/(NaOH + Na2S)
– Na2SO4 10 g/l
– Dregs 1500 mg/l
• Density 1.17 kg/l
23
Terminology
• The efficiency of the process of regenerating black liquor
(post cooking) to reusable white liquor (at the start of the
cooking process) is measured by the ratio of active sodium
cooking agents produced from the total amount of sodium
compounds arriving into the recovery system
• This ratio can be monitored at various stages in the

recovery process (some continuously and others by
sample)
24
Terminology
Causticizing efficiency: NaOH/(NaOH + Na2CO3)
Reduction efficiency: Na2S/(Na2S + Na2SO4)

or
Na2S/Stotal
Effect of K on these values?
25
Departments and streams
MAJOR MINOR MAJOR STREAMS
DEPARTMENTS DEPARTMENTS
• Evaporation • Cl-K removal • Weak black liquor
• Recovery boiler • Condensate stripping • Strong black liquor
• Lime kiln • Spill collection • Smelt
• Causticizing • Methanol liquefaction • Green liquor
• Turbogenerator • Soap removal (with • White liquor
• NCG collection softwood) • Lime mud
• Lime
• DNCG +CNCG
• Water +Steam
26
Evaporation
27
Black liquor evaporation
• Black liquor recovered from pulping contains 14-17%

dissolved solids
• These solids are composed of about 1/3 inorganic
chemicals that were in the white liquor added to the
digester
• The remaining 2/3 consist of the organic chemicals
extracted from the wood
• Black liquor must be concentrated to above 60% solids
so that it will burn without supplemental fuel
28
Basic process requirements
• Efficient use of energy

• Efficient separation of water vapor from black liquor
• Proper separation of methanol, tall oil soap
• Concentration of black liquor to 75-85% dry solids
29
Objectives of evaporator
• Use of BAT equipment

• Final black liquor concentration high enough to minimize
SO2 and TRS emissions
• Capacity large enough to accommodate spills
• High number of effects for energy efficiency
30
Evaporation
Strengthening of black liquor
Handling of
Producing methanol fuel &
• Biosludge
CNCG & DNCG to incineration
• ClO2 plant waste
• CTMP filtrates
Producing Warm/District
Closing mill’s water
heating water
circulation with
secondary condensates
Cl/K purge
Treating cooking and bleaching effluents
31
Evaporation train
32
Evaporation
Mission:
• Evaporation of weak black liquor to separate water and
create a combustible product – strong black liquor
The three main processes that occur in the evaporator are:

Black liquor + Heat Strong Black liquor + Water + Steam
Condensate + Steam Clean + Dirty condensate + NCG
Black liquor Black liquor + Soap (only softwood)
33
Evaporation
34
Evaporation process in general
• Evaporation plant carries out a number of simultaneous

processes, which as well as producing strong black
liquor for the recovery system, include:
– separation from the black liquor of:
• turpentine
• methanol
• soap (softwood production)
– production of clean condensate for mill use e.g.
washing of lime mud
35
Evaporation capacity
• Typically expressed as ton H2O/h or kg H2O/s

• Evaporation capacity is determined by the heating
surface area, available temperature drop and overall heat
transfer coefficients
36
Basics of evaporation
Heat Transfer Area
• Increasing black liquor dry

solids with thermal energy Heat flow
kW
Heat
Transfer Temp.
coeff. diff.
Over
surface
37
Tube wall
Steam to Steam from
next previous
effect effect
Heat evaporates Steam

water (= steam) from condenses
black liquor releasing heat
Drier Condensates
black liquor are
is removed removed
38
• Multi effect evaporation (MEE), 6-7 effects

– 1 st effect uses primary LP & MP steam
– 2-7 effects use secondary vapor
– last effect vapor is condensed with cooling water in surface
condenser
– evaporation done mainly by secondary vapor
39
Minimization of steam
• Evaporator processes should be undertaken in a way that

maximizes the efficient use of energy e.g. as evaporation
is done in stages, which allows 1 kg of steam to
evaporate more than 7 kg of water
40
• The more effects the better is the steam economy

• But the higher is the equipment cost
41
Modern evaporator train
• Seven+ effects for good steam economy

• Weak BL dry solids design 14 – 15%
• Strong BL dry solids >85% (with ash)
• Integrated stripper
• Possibility to handle biosludge
• Possibility to separate soap during softwood operation
• 10% additional capacity reserve to process spills
• Enclosed methanol treatment to minimize odor
42
Evaporation
43
• WBL is flash cooled to effects 5, 6 & 7

• Sweetened to 20% ds (softwood)
• Evaporated in effects 7, 6, 5, 4 & 3 heating surfaces
• Heated up with stripper gases between 3 & 2 effects
• Mixed with ESP ash before effect 1
• Evaporated in effect 1
44
45
46
Condensates
• Condensates are liquids produced from vapor when they

are cooled by condensation
• They comprise mainly of water
– clean condensates are formed when pure steam
condenses
– foul condensates are formed when steam originating
from black liquor is cooled
47
Foul condensate formation
• Each time black liquor is evaporated it forms steam that

may be used at another stage
• When that steam is cooled it condenses to form a liquid
that contains mainly water with some other substances
that condense at the same temperature as water
• There are three main places in the pulp mill where foul
condensates are formed:
– evaporation plant
– NCG handling
– in cooking
48
Foul condensate formation
• In each of these three cases the condensate contains

TRS and volatile carbohydrates (e.g. methanol) and as a
result the condensate has a level of odor depending the
composition
• Cleaner condensate fractions are reused in parts of the
mill processes that are not sensitive to slight
contamination (e.g. pulp washing)
• All other foul condensate (smelly) streams are fed to the
stripper where they are cleaned
49
Treatment of foul condensates
• Foul condensates contain

– methanol
– malodorous sulfur compounds
– turpentine
– red oil (eucalyptus only)
– water
• Steam is used in the stripper to remove
contaminants
• Evaporator and stripper are integrated to get
better heat economy
– located between effects 1 and 2
50
Treatment of foul condensates
• The higher is the condensate quality demand

– the more foul condensate is segregated
– the more stripping vapor is used
– the more stripper losses are generated
• foul condensate heating
• vapor losses to stripper of gas & trim condenser
• stripped condensate taken out hot
• The more expensive equipment
51
Effect of dry solids to NHV
15.0
NET HEATING VALUE, MJ/kg dry solids
10.0
5.0
0.0
0 10 20 30 40 50 60 70 80 90
-5.0
-10.0
BLACK LIQUOR DRY SOLIDS, %
52
How to reach 80-85% dry solids?
• Due to the high viscosity

– MP-steam as heating medium
– liquor temperature 175 °C in final
concentrator
• Liquor retention time
– evaporator acts also as a LHT-reactor
• Duplex construction material
– high alkali content may cause Stress
Corrosion Cracking (SCC)
53
BPR – Boiling Point Rise
Ref: Principles of black

liquor evaporation, W J
Frederik.
54
Liquor Heat Treatment (LHT)
• Liquor is heated to 175 – 200 ˚C

• Polysaccharide molecules are splitted
• Liquor viscosity degreases permanently
• Sulfur compounds & MeOH are generated
• Results depend on liquor type and effective alkali level
55
Evaporator types
• Thermal evaporation
– rising film evaporator
– falling film evaporator
– film inside the heating surface
– film outside the heating surface
• Forced circulation
• Direct contact evaporation
• Mechanical vapor recompression evaporation
56
Falling film evaporator
film inside tubes
• Gravity pulls liquor downwards
(window during rain principle)
• Liquor inside the tubes
• Steam outside the tubes
• Fouls with high solids liquor
• Sold as 3 – 7 effect
57
Falling film evaporator
film outside tubes
• Gravity pulls liquor downwards
(window during rain principle)
• Liquor outside the tubes
• Steam inside the tubes
• Used with high solids liquor
• Sold as 1 - 3 effect and as
concentrator
58
Forced circulation evaporator
• Pump forces liquor through heat

exchanger
• Liquor inside the tubes
• Steam outside the tubes
• Used with high solids liquor
• Sold as 1 - 3 effect and as
concentrator
59
Lamella type evaporator
Liquor film
Steam flowing
flow downwards
Heat surface
60
Evaporator scaling
• Soap and tall oil scaling

– soap sticks to the surface
– soap carries fibre and calcium
– most of tall oil soap separates at 25-30%ds
• Lignin scaling
– precipitation at pH < 11
61
Evaporator scaling
Falling film lamella Tube evaporator
Resistant to scaling Plugging under

“Self-cleaning” severe scaling
Tolerates even non- conditions
soluble scaling Non-soluble
scaling requires
mechanical or
chemical
cleaning
62
Typical process challenges
PROBLEM SOLUTION
HEAT TRANSFER SURFACE SCALING

• Ash mixing
Low alkali (lignin precipitation) • Wash sequences
High soap & fiber content • Soap skimming
High Ca, Si, Al concentrations • Calcium deactivation reactor
• Liquor heat treatment (LHT)
FOAMING IN BACK END EFFECTS
Sweetening of WBL to over 20 %
• Low ds-%
POOR CONDENSATE QUALITY • Low secondary vapor velocities in shell

• Too much MeOH in WBL • Droplet separators
• If color in condensate, caused by too high evaporation rate & carry over • Proper segregation in lamellas
• If just smell & high COD, improper segregation of VOC’s • Dedicated condensation packages
• Liquor or fibers in fiber line foul condensate • Duct stripper
HIGH DRY SOLIDS

• High 1’st effect temp (MP-steam)
ds%, should be as high as possible, however this causes some special arrangements
• High circulation rate in 1’st effect
• High viscosity • Liquor heat treatment (LHT)
• Fouling • Ash mixing
• Poor heat transfer • Wash sequences
• Corrosion (high Effective Alkali) • Duplex in HD-concentrator
63
CNCG & DNCG sources and destinations
CNCG
DNCG
& Power boiler
64
64
Recovery Boiler
65
Purpose of the recovery boiler
• Recovery of Chemicals = Chemical Reactor

– recovery of chemicals from the
black liquor through combustion
(reduction) to be used for cooking
chemical preparation
• Recovery of Energy = Steam Boiler

– burn the organic materials in the
black liquor and produce energy
(steam, electricity)
66
Modern recovery boiler
• Steam pressure > 100 bar

• Steam temperature > 500 °C
• Capacity > 5 000 tds/d
• Dry solids content > 80 %
• Combustion air from several levels
• DNCG combustion (Diluted gases)
• Additional fuels
– CNCG (strong gases)
– methanol
– turpentine
– biosludge
– soap
67
Natural circulation
Steam
Drum
Driving force is static pressure difference
between water in downcomers and water-
Downcomer steam mixture (emulsion) in furnace
Furnace tubes tubes
Heat
Steam bubbles
∆Plosses = (ρwater - ρmixture)×g×h
Pressure increase reduces driving force

Heat to tubes by radiation and convection
68
Natural circulation
3
3
1
2
1 Water flows downwards to furnace

bottom and boiler bank
2 Water–steam mixture rises up in furnace
wall tubes and in boiler bank panels
2 2
3 Water–steam mixture flows to the drum
where water and steam are separated
69
Recovery boiler main parts
5. Steam drum
5. 6. Boiler generating bank

7. Economizers 1 and 2
6. 8. Rearwall screen
1. Superheaters (1B, 2, 3, 4, 1A) 9. Furnace screen

1. 8.
2. Bullnose/nose arch
7. 10. Ash hoppers (3 pcs.)
3. Black liquor nozzle openings 11. Feedwater tank

12. Ash conveyors
4. Start-up burners 9. 2.
13. (*) 13. Downcomers
10. 14. NCG ducts
15. 11. 15. Tertiary air ducts
12. 16. Secondary air ducts

14. 17. Primary air ducts
3. 18. Smelt spouts
16. 4. 19. Dissolving tank
18. 20. 20. Mixing tank
17.
19. (*) Electrostatic precipitator
70
Furnace process
• Black liquor is injected into the recovery
boiler from a height of 5…8 meters
• Combustion air is injected at three different
zones in the boiler Tertiary air
• Burning black liquor forms the char bed at Black liquor

nozzles
the bottom of the boiler, where
Upper
complicated reactions occur secondary air
• Smelt is drained from the boiler and is Lower

secondary air
dissolved with weak white liquor to form

green liquor, which contains the recovered Primary
air
cooking chemicals
Smelt
• High pressure steam is generated from
feed water by heat releasing from
combustion reactions
71
XT Training 8.2.2013
Chemical reactions in furnace
• Drying
– water is evaporated
• Devolatilization
– droplet size increases
– gases are released
• Char burning
– carbon is burned off
– inorganic salts melt, reactions
• Upper furnace reactions
– volatiles combustion
– formation of sodium sulphate
and sodium carbonate
72
Black liquor droplet burning
73
Liquor spraying
Tertiary air
• Target
– spray the liquor evenly on the Firing liquor
charbed
Secondary air
– optimize the droplet size
• Liquor gun openings on all walls
• Locations adjusted to the air system
between secondary and tertiary air ports
74
Smelt and green liquor
• Smelt is molten inorganic chemicals produced in the reducing zone of

furnace
– Sodium carbonate Na2CO3 (65 … 75 %)
– Sodium sulfide Na2S (20 … 25 %)
– Sodium sulfate Na2SO4 (2 … 3 %)
• Green liquor is a mixture of smelt from RB and Weak White Liquor
from Causticizing Plant
– temperature at dissolving tank outlet 95 … 98 °C
– dregs content (unburned carbon) 500 … 1000 mg/l
– reduction efficiency (in smelt): 93 … 97 %
• Na2S/(Na2S + Na2SO4)
• increasing reduction efficiency decreases steam production
75
Smelt-water explosion
• Even a small amount of water mixed with

molten smelt at high temperature can cause
it
– purely physical phenomenon
• Water turns into steam in few ms
– sudden evaporation causes increase of
volume and a pressure wave of
10 -100 000 Pa
– sufficient to cause furnace walls to bend
• Furnace equipped with a weak corner to
control the direction of explosion
76
Recovery boiler process
77
Useful numbers
• ADt (bleached) 1.3 - 2.0 tds

• Dry solids (virgin) 65 - 83 %
• Density 1.35 - 1.43 kg/l
• HHV 13.0 - 15.0 MJ/kgds
• Furnace bottom loading 18 - 25 tds/d/m2

3.0 - 4.0 MW/m2
• Steam production 3.0 - 4.5 kg/kgds
78
Effects of dry solids
140
+ Steam generation increases
Steam flow / kg / s
135
(less water to the furnace)
+ Less flue gases 130
+ Lower SO2 emissions
125
60 70 80 90
- Less desuperheating more Dry Solids / %
heating surface
- Viscosity increases black liquor
flashing, fouling
79
White Liquor Plant
80
Modern white liquor plant
Lime Cooling Burnt Lime Bin
Lime Flash Dryer Green Liquor
Make-up
Storage Tank
Limestone Silo White liquor
Lime Kiln preparation
Raw Green
Liquor Storage
Lime Dryer Tank
™ Green Liquor
Cooler
Lime Slaker Green liquor

filtration
White liquor filtration
White Liquor Lime Free

Storage Tank dregs handling
Weak White
Liquor Storage Tank
Electrostatic
Precipitator Lime Mud Storage Tank
81
Recausticizing
Lime
Smelt
Mission:
• Production of white
liquor for cooking by
converting sodium
carbonate to
Grits
hydroxide with lime
and removal of non
Dregs
process elements
This image is indicative only and does not purport to show all features of AMT technology.
82
Terminology
• Green liquor dregs are solids separated from green liquor

by filtration
• Slaker grits are solids separated during lime addition
• Burnt lime is a solid stream from lime kiln containing
mainly CaO
• Make-up lime is an incoming solid stream containing
mainly CaO
83
Recausticizing
• The three main processes that

occur in recausticizing are:
CaO + H 2O Ca(OH)2
Na2CO3 + Ca(OH)2 2NaOH + CaCO3
solids in liquor solids + liquor
84
Recausticizing
• There are three processes undertaken in the

recausticizing stage:
– cooking liquor is produced from green liquor by adding
slaked lime which produces white liquor and lime mud
(calcium carbonate)
– lime mud (calcium carbonate) is fed into lime kiln to
produce lime
– process residue is purged as dregs and grits
85
Recausticizing unit operations
• Smelt dissolving tank (in RB area)

– molten smelt from recovery boiler and weak white
liquor are mixed to produce green liquor
• Raw green liquor stabilization tank
– variations in green liquor composition are reduced by
sufficient retention time
• Green liquor filtration
– particles in green liquor removed by filtration
86
Recausticizing unit operations
• Slaker
– lime and green liquor are mixed to produce white
liquor
• Causticizers
– three or more agitated tanks in series are used to
ensure as complete a reaction as possible
• White liquor filtration
– lime mud is separated from white liquor by filtration
87
Recausticizing Process
LimeMilk
LimeFree
88
88
Green liquor handling
Filtrated green liquor
Raw green liquor
Dregs
89
Green liquor
Na g/kgds 90.8
K g/kgds 14.5
Stot g/kgds 24.1
Cltot g/kgds 1.9
S2- g/kgds 19.1
NaOH g/kgds 18.8
Na2S g/kgds 42.7
Na2CO3 g/kgds 134.9
Na2SO3 g/kgds 1.41
Na2S2O3 g/kgds 7.08
Na2SO4 g/kgds 8.7
Total alkali g NaOH/l 165.2
Active alkali g NaOH/l 62.7
Effective alkali g NaOH/l 40.7
Figures are given to show indicative magnitude of the various chemical compounds.
90
White liquor definitions and reactions
White Liquor (WL) Definitions Reactions
• Containing small amount • Active Alkali (AA) • Lime slaking
Suspended Solids (SS) < – NaOH + Na2S – CaO + H2O
20 mg/l • WSA (Water Soluble Alkali) Ca(OH)2 + 1130 kJ/kg
• Concentration is given g – Soluble Na as Na2O CaO
as Na2O/liter or g as
NaOH/liter • Causticizing Degree (CE)
– NaOH/(NaOH + Na2CO3) • Causticizing reaction
• Main compounds as – Ca(OH)2 + Na2CO3
NaOH are: • Suspended Solids (SS)
2 NaOH + CaCO3
– Na2S 40 g/l – Compound insoluble in WL
– Na2CO3 20 g/l – Typically measured after
White Liquor filter
– NaOH 100 g/l
– Concentration < 20 mg/l,
– Na2SO4 10 g/l mainly CaCO3
– Suspended Solids < 20 – Lime
mg/l
• Lime Kiln product or make-up
lime
• Mainly CaO > 90%
– Lime Milk
• GL + Lime
91
91
Green liquor filtration
• Green liquor contains 800-1 200 ppm of impurities

called dregs
• Impurities originate from raw material sources, primarily
wood chips
• Dregs contain almost all the minerals in the wood
92
Green liquor filtration
• Dregs only place where these minerals are removed

• Often separate stabilization tank to minimize variations
in
– density
– temperature
– flow
• Storage after filtration
93
Process steps
• Once green liquor is produced to a stabilized

concentration it is mixed with lime and the slaking
process commences
• The lime reacts with the water in the green liquor
producing slaked lime
• Slaking occurs in a short time
• Slaked lime then reacts with sodium carbonate in the
green liquor to lime mud and sodium hydroxide (white
liquor)
94
Process steps
• This second reaction is called causticizing and occurs in

the causticizing tanks, long residence time needed to
complete reactions
• The lime mud goes to the lime kiln to produce lime
• The white liquor is then used in the digester
95
Slaking chemistry
96
Causticizing chemistry
• Slaking +1130 kJ/kg CaO
CaO (s) + H2O (aq) ↔ Ca(OH)2 (s)
• Causticizing -560 kJ/kg CaO
Ca(OH)2(s) + Na2CO3 (aq) ↔ 2NaOH (aq) + CaCO3(s)
97
Dregs washing
• 3-8 % of suspended solids in green liquor

• Sodium recovery
• Drum filter with precoat
– coating with lime mud of 50-10 mm thick
– dry solids 40 – 50 %
98
White liquor
• Final product from causticizing system

• Cooking chemical to the digester
• Active ingredients NaOH and Na2S
99
White liquor analysis
Na g/kgds 78.0
K g/kgds 14.1
Stot g/kgds 22.4
Cltot g/kgds 1.7
S2- g/kgds 18.0
NaOH g/kgds 88.2
Na2S g/kgds 41.8
Na2CO3 g/kgds 40.3
Na2SO3 g/kgds 0.1
Na2S2O3 g/kgds 8.99
Na2SO4 g/kgds 0.5
Total alkali gNaOH/l 161.6
Active alkali gNaOH/l 131.2
Effective alkali gNaOH/l 109.8
Analysis is given to show indicative magnitude of various chemical compounds
100
Objective of causticizing
• High active alkali concentration

– high causticity
– high reduction
• Clean white liquor to minimize chemical consumption
• Efficient lime mud washing
101
Causticizing in modern mill
• White liquor active alkali (NaOH) g/l 136

• White liquor sulfidity % 32
• Causticity % 82
• Reduction efficiency % 95
• Green liquor filtration
• White liquor filtration
• Capacity m3WL/d >10 000
102
Lime kiln
• The two main processes that

occur in lime kiln are:
Lime mud + Heat CaCO3 + vapor
CaCO3 + Heat CaO + CO2
103
Lime kiln
Mission – Converting used lime mud into lime
104
Lime product quality
• Ideal reburnt lime forms soft pebbles of approx. 2 cm in
diameter pebbles
• Reburnt lime quality is judged in terms of:
– availability - refers to the fraction of lime (as CaO) in
the reburnt lime product
– residual calcium carbonate
– reactivity
– particle size
105
Lime product quality
Fresh lime Reburnt
Soft Hard
Density, kg/l 1.6 >2,2 1,7-2.1
Porosity, % 50 <34 44-67
Surface area, m2/g >1.0 <0,3 0,21-0,43
Reactivity, oC/min >10 <2 low

From Adams, 1997
106
Lime kiln fuels
• Natural gas
• Fuel oil
• Hydrogen (from chemical plant)
• Odorous gases (option)
• Methanol (option, methanol burning decreases CO2
from mill)
• Gasification gas
• Saw dust
• Lignin
107
Lime kiln
• Lime mud + heat → burned lime + carbon dioxide

• Adiabatic flame temperature 1750 °C
CO2 Fuel: Oil, Gas, CNCG’s

CaCO3
CaO
108
Energy balance
MJ/t CaO
Water heating & evaporation 2 090
Energy in kiln product and dust 140
Enthalpy of calcination 2 890
Enthalpy in CO2 from calcination 90
Enthalpy of combustion products 410
Radiation loss 820
Total input 6 440
109
Pulp mill processes in a nutshell
Fiberline
Woodyard
Pulp Drying
Chemical
Recovery Systems
Boiler
Evaporation
Effluent
treatment
plant
110

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Puu-0.

4110: Conventional and Non-

After this lecture the student:

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Explanation of what recovery department of a modern

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

DD washers were invented in 70’s and developed in the -80’s

Rotary lime kiln was developed in the -50’s

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Pulp mill products

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Recovery systems are the core component of a kraft pulp

• The three purposes of recovery systems are:

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Weak black liquor is liquor from the brown stock washing,

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• White liquor is solution containing regenerated chemicals

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Active sodium chemicals in the cooking process are

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Total alkali: NaOH+Na2CO3+Na2S+Na2SO4

Active alkali: NaOH + Na2S

Effective alkali: NaOH + ½ Na 2S

Effect of K on these values?

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• The purpose of the recovery system is to return the

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Concentrated to strong black liquor leaves the evaporation

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Strong black liquor that comes from

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Carbonate melt (~70% Na2CO3)

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• The green liquor reacts with lime in the slaker to

• The lime mud goes to the lime kiln where it is returned

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• This ratio can be monitored at various stages in the

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Causticizing efficiency: NaOH/(NaOH + Na2CO3)

Reduction efficiency: Na2S/(Na2S + Na2SO4)

Effect of K on these values?

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Black liquor recovered from pulping contains 14-17%

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Efficient use of energy

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

• Use of BAT equipment

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

The three main processes that occur in the evaporator are:

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja

Puu-0.4110 13. Kraft recovery I Keijo Salmenoja