Professional Documents
Culture Documents
Table of content
Kaj Henricson
Professor Pulping Technology
Lappeenranta University of Technology
August 2005
Educational course material and only for internal and personal use during
the course: An introduction to chemical pulping technology.
Chemical recovery cycle
One of the main advantages of the kraft process is the efficient recovery of chemicals as
compared to, for instance, sulfite pulp production. Picture 1 shows the principal unit operations
of the kraft recovery process: evaporation of weak black liquor; combustion of thick black liquor
in a recovery furnace to form a smelt, which is dissolved in water forming green liquor;
causticizing sodium carbonate (Na2CO3) in green liquor to form white liquor containing sodium
hydroxide (NaOH) and sodium sulfide (Na2S); and regeneration of lime mud in a limekiln.
Black liquor is recovered with a high recovery rate after cooking and the black liquor is
combusted in the recovery boiler to produce heat and power in amounts that exceed their
consumption at the kraft pulp mill. There is no need for external heat or power in the production
of kraft pulp. The only exception is the limekiln, where usually oil or natural gas is used. In the
lime kiln, the use of fossil fuels can be replaced with for instance combustion gases produced by
gasifying bark. The water evaporated in the evaporation plan can be reused in white liquor
preparation and in the fiber line as purified condensates.
BAT
Picture 1. Recovery cycles of chemicals for a kraft mill
1
The amount of water that normally has to be evaporated from the weak black liquor after
cooking and brown stock washing in order to produce thick black liquor for combustion in the
recovery boiler is in the range of 7-9 m3/ton of pulp.
Black liquor properties
Black liquor is composed of the organic material dissolved from the wood in the digester and at
the oxygen delignification plant and of the chemicals used in cooking and oxygen bleaching. In
the case of re-circulation of bleach plant effluents from final bleaching, also the dissolved
material from bleaching and used chemicals in bleaching will be found in black liquor. In
addition, non-process elements circulating with the active cooking chemical have accumulated
in the chemical recovery cycle.
Black liquor contains extractives originating from the wood raw material. Extractives are
removed from black liquor in the form of soap. The volatile components are removed from the
condensates by stripping. Soap separation is important in order to avoid scaling of heat transfer
surfaces during evaporation and to avoid foaming. Black liquor has a strong tendency to foam at
low dry solids concentrations and the soap content contributes to the foaming tendency. The dry
solids content of black liquor from the cooking and washing plant can be increased by adding to
it some intermediate liquor from the evaporation plant before entering the evaporation plant in
order to avoid foaming.
The scaling of heat transfer surfaces occurs in particular at high dry solids concentrations. The
scaling tendency of black liquor depends for instance on the content of calcium soap in the black
liquor. The contents of inert components like sodium sulfate and sodium carbonate also affect
the scaling behavior of black liquors.
Table 1 shows the composition of a hardwood kraft black liquor. Table 2 shows the elementary
composition of a softwood kraft black liquor. The composition of black liquor always depends
on the used raw material and process conditions at the mill.
Table 1. Composition of black liquor dry solids from the kraft pulping of birch
Organics, % by weight 78
Degraded lignin, including Na and S, % 37.5
Isosaccharinic acids, including Na, % 22.6
Aliphatic acids, including Na, % 14.4
Resins and fatty acids, including Na, % 0.5
Polysaccharides, % 3.0
Inorganics, % by weight 22
NaOH, % 2.4
NaHS, % 3.6
Na2CO3 and K2CO3, % 9.2
Na2SO4, % 4.8
Na2S2O3, Na2SO3 and Na2Sx, % 0.5
NaCl, % 0.5
Non-process elements (Si, Ca, Fe, Mn, Mg, etc), % 0.2
Fapet 6B: p.B13
2
Table 2. Typical composition of black liquor from Scandinavian wood
Softwood (pine) Hardwood (birch)
Typical Range Typical Range
Carbon, % 35.0 32-37 32.5 31-35
Hydrogen, % 3.6 3.2-3.7 3.3 3.2-3.5
Nitrogen, % 0.1 0.06-0.12 0.2 0.14-0.2
Oxygen, % 33.9 33-36 35.5 33-37
Sodium, % 19.0 18-22 19.8 18-22
Potassium, % 2.2 1.5-2.5 2.0 1.5-2.5
Sulfur, % 5.5 4-7 6.0 4-7
Chlorine, % 0.5 0.1-0.8 0.5 0.1-0.8
Inert, % 0.2 0.1-0.3 0.2 0.1-0.3
Total, % 100.0 - 100.0 -
Fapet 6B: p.B15
Heating value
The heating value of black liquor expresses the amount of heat that is released when combusting
a specified amount of black liquor dry solids. The types of organic compounds present in black
liquor and inorganic material in black liquor influence the heating value of black liquor. For
instance, the type of lignin and the ratio between lignin and carbohydrates affect the heating
value of black liquor as shown in Table 3. The reactions of inorganic material during
combustion influence the heating value, and for instance the reduction of sulfate to sulfide in the
recovery boiler consumes energy. All black liquors have to be tested separately to know the
heating value and combustion properties in a recovery boiler.
Table 3. Heating values of black liquor components
Component MJ/kg Btu/lb m
Softwood lignin 26.9 11.57
Hardwood lignin 25.11 10.8
Carbohydrates 13.555 5.83
Resins, fatty acids 37.71 16.22
Sodium sulfide 12.9 5.55
Sodium thiosulfate 5.79 2.49
Fapet 6B: p.B18
Boiling point rise and viscosity
When dimensioning an evaporation plant, one needs to know the boiling point rise and the
viscosity of the liquor to be evaporated at the dry solids contents and the process conditions,
such as temperature, prevailing during evaporation.
The temperature where black liquor boils is higher than the boiling temperature of water at the
same pressure. The temperature difference is called the boiling point rise. As the dry solids
content of black liquor increases, the boiling point increases as shown in Picture 2 for some
black liquors.
3
Fapet 6B: p.B21
Picture 2. Black liquor boiling point rise vs. dry solids concentration
The viscosity of black liquor depends on the temperature and dry solids content. The viscosity
increases at higher dry solids contents, and a temperature increase decreases the viscosity as
shown in Picture 3 for one black liquor after evaporation to a high dry solids content. The
viscosity behavior varies from one black liquor to another. The evaporation of black liquors to
high dry solids concentrations above 75% to 80% usually requires that these black liquors are
heat treated at higher temperatures to reduce the viscosity of these liquors.
Modified by KH;
Fapet 6B: p.B23
Picture 3. Effects of temperature and dry solids on the viscosity of one high dry solids black liquor
Terminology used in the evaporation of black liquors
The evaporation stage or effect is one evaporator, or possibly several parallel evaporators
operating at the same steam pressure level. The effects are numbered in the direction of the
steam flow with the first effect operating at the highest steam pressure. Multiple-stage
evaporation means evaporation in a plant consisting of a number of evaporator effects connected
4
in series. An evaporation plant normally consists of 5-7 stages in series. Picture 4 shows a
typical configuration. The condensate streams are segregated into fractions A, B and C
according to their content of methanol and COD.
CONDENSERS
FRESH
STEAM
CONCENTRATED
BLACK LIQUOR BLACK LIQUOR
FROM COOK
KAM: p.28
Picture 4. Typical configuration of a black liquor evaporation plant
The evaporator body or the evaporator itself is a heat exchanger unit used in the evaporation
stages. One stage or effect might have several bodies in parallel. Picture 5 shows some
commonly used evaporator designs in the evaporation of black liquors.
A
C
B
Modified by KH;
Fapet 6B: p.B46, 47, 51
Picture 5. Evaporators; A: rising film, B: falling film, C: forced circulation (or crystallizer)
The rising film evaporators [also called long-tube-vertical (LTV) or Kestner evaporator] were
widely used for the evaporation of black liquor in the pulp industry until the mid-1980s. In a
rising film evaporator, the forming steam causes the liquor to rise in the evaporation tubes. In
later installations, the falling film evaporator and forced circulation evaporator are more
common. In the falling film evaporator, the liquor is fed to the bottom of the evaporator from
where it is pumped to the top of the heating element by a circulating pump and flows
downwards on the heating surface by gravity. In the forced circulation evaporator, the black
liquor is pumped through the tube heat exchanger to a separate chamber where the vapor is
5
released. The power needed in black liquor evaporation and the dimensioning of the heat
transfer surfaces is dependent on the viscosity of the black liquor.
The term concentrator refers to the first effect where the liquor is evaporated to its final
concentration. Earlier, the final concentrators were clearly separated from the multiple effect
evaporation train and had a different design. In a modern evaporation plant, this difference does
not exist but the terminology is still in use. The concentrators have to be cleaned regularly to
remove scaling on the heat transfer surfaces, and evaporation plants usually have at least two
concentrators in parallel so that one concentrator can be cleaned without influencing the
operation of the whole evaporation plant.
Live steam, primary steam, or fresh steam is the clean steam from the boilers at the mill. Live
steam is mainly only used in the first effect in the evaporation plant. The steam must be at
saturation temperature or only slightly superheated. Primary condensate is the clean condensate
from the live steam. Secondary steam or vapor is the steam evaporated from the black liquor.
Vapor from the first effect is used as a heating medium in the second effect. Vapor from the
second effect is then used in the third effect etc. The surface condenser is a water-cooled heat
exchanger that condenses the vapor from the last evaporation effect.
The vapor always contains some organic materials evaporated from the liquor or even liquor
droplets entrained in the steam flow. Secondary condensate is condensate derived from the
vapor. It contains various levels of organic contaminants. It is therefore not as clean as primary
condensate. Foul condensate is the most contaminated secondary condensate and has to be
purified by stripping. The amount of organic material carried over into the condensates in the
form of droplets is reduced by installing droplet separators in the steam phase of the evaporators.
The condensates can on the side of the condensing steam of the heat transfer surface be
segregated into a foul and clean condensate fraction.
Vapor out
A
Vent
Flow 1%
MeO H 10%
Vapor in Foul
condensate
Flow 10%
MeO H 80%
Liquor out
Clean
condensate
Flow 89%
MeO H 10%
MPS, Andritz
Liquor in
Picture 6. Falling film evaporator A with condensate segregation and droplet separator B at the top of
the evaporator
Vapor condensate, which has some degree of contamination mainly consisting of methanol, is
one of four fractions determined by the degree of contamination indicated in Table 4. Often,
fractions 2 and 3 are combined. Vapor condensate fraction 1 and some fraction 2 can be used in
bleaching and brown stock washing. Fraction 3 is used in the causticizing plant. Fraction 4 is
treated in the stripper and is comparable to fraction 2 after stripping.
6
Table 4. Vapor condensate fractions from a modern 7-stage multiple falling film evaporation
Vapor Vapor condensate Flow, MeOH MeOH Remarks
condensate drawn m3/adt content, amount,
fraction mg/l g/adt
Fraction 1 From effects 2, 3 and 3.4 30 100 -
4
Fraction 2 From effects 5 and 6 2.5 300 700 -
Fraction 3 From effect 7 and 2.0 600 1,200 Slightly odorous
surface condensate
Fraction 4 Foul condensate 1.0 6,000 6,000 Malodorous
from evaporator
Total - 8.9 - 8,000 -
Stripped From evaporation 1.6 300 500 Stripper MeOH
condensate and cooking foul purification
condensate stripping efficiency=95%
Fapet 6B: p.B71
The stripping column purifies the foul or contaminated condensate from the evaporation and
cooking plants. Stripping is a mass transfer process where volatile gas components such as
methanol and reduced organic sulfur compounds transfer from the liquid phase into the gas
phase. Picture 7 shows a typical stripping column.
Modified by KH;
Fapet 6B: p.B41
Picture 8. Principle of multiple evaporation
Picture 9 shows a perspective of a multistage falling film evaporation plant. The steam or heat
balance of the evaporation plant is dependent on the number of effects as shown in Table 5. The
number of effects chosen is a balance between the investment costs of additional effects, the
investment cost and amount of heat transfer surfaces in the individual effects and the savings in
steam due to additional effects.
8
Table 5. Steam economy and specific heat consumption in multiple evaporation including an
integrated stripper column
Number of Steam economy, Specific heat consumption,
stages ton H2O/ton steam MJ/ton H2O
4 3.7-3.6 630-650
5 4.3-4.1 550-570
6 5.1-4.9 460-480
7 6.2-5.9 390-400
Fapet 6B: p.B42
The mixed liquor sequence in the five-stage evaporation plant shown in Picture 10 is a favorable
sequence commonly used in the evaporation of black liquors. The mixed liquor flow pattern
gives the following advantages:
Soap separation from the intermediate liquor is optimum due to the concentration of 27%-
30% dry solids and the low temperature of approximately 60C.
Liquor feed to effects 3 and 4 in parallel allows balancing the feed according to the feed
liquor temperature and operating temperature in the effects.
Release of non-condensable gases that enter with the feed liquor is evened between the
effects. The gases vent from effects 4 and 5.
10
Fapet 6B: p.B42
Picture 13. Principle of vapor compression evaporator (VCE)
Recovery boiler
The recovery boiler is a chemical reactor for the recovery of the cooking chemicals used and for
the generation of heat from dissolved inorganic and organic material in the black liquor. The
recovery of cooking chemicals in a recovery boiler includes several steps:
combustion of the organic material in black liquor to generate heat
production of sodium fume to capture sulfur-containing combustion residues
reduction of the inorganic sulfur compounds to Na2S
production of a smelt of molten Na2CO3 and Na2S
recovery of inorganic dust from the flue gas
recovery of the heat formed during combustion
Picture 14 is a schematic diagram of a two-drum recovery boiler and Picture 15 shows some of
the chemical reactions taking place inside the recovery boiler. The components of the recovery
boilers in Picture 14 are: furnace, where the combustion of black liquor takes place, superheaters
for heating the steam with hot combustion gases, boiler generating bank where water boils, and
economizers that recover residual heat in the flue gases and cool the flue gases. In the steam
drum, water and steam are segregated. The air enters through primary and secondary air ports and
tertiary air ports. The black liquor enters through liquor guns in the lower part of the furnace. The
smelt exits through smelt spouts to the dissolving tank. The heat transfer surfaces are cleaned by
soot blowing steam. The flue gas is cleaned in an electrostatic precipitator.
11
KRB: p.5
Picture 14. Schematic diagram of a two-drum recovery boiler
The recovery boiler consists of heat transfer surfaces made of steel tubing. The tubes contain
steam or water, and the heat generated inside the recovery boiler is recovered into the water and
steam inside the tubes as in normal power boilers. Recovery boilers have a lower power-to-heat
ratio compared to normal power boilers mainly due to limitations coming from the sodium and
sulfur content in the black liquor.
Recovery boilers produce steam with lower heat and pressure than normal power boilers. Some
of the limiting issues concerning recovery boilers are: corrosion and cracking risks, fouling of
heat transfer surfaces, air emission requirements, today almost zero SO2 is possible, very low
NOx emissions, no or low odor from the boiler, safety, and smelt-water explosion risk.
12
BAT
13
Liquor Guns pyrolysis gases
drying
small
devolatilization
droplets
3rd Secondary Air
char
combustion
2nd Secondary Air in flight
KRB: p.8
The recovery boiler has a risk of smelt and water explosion due to the presence of the porous hot
char bed containing molten sodium salts. The water and smelt can come into direct contact due to a
recovery boiler tube failure causing a smelt and water explosion in a recovery boiler. An emergency
rapid drain system minimizes potential damage. Water remains at the lowest part of the furnace to
provide cooling for the floor tubes. If all water drains from the floor tubes, the heat from the hot char
bed will damage the boiler tubes.
15
The risk of a recovery boiler tube failure is
decreased and the use of corrosion resistant
materials in the recovery boiler has increased
the lifetime of a boiler. The materials vary in
different parts of the boiler according to the
conditions prevailing in the different parts of
the boiler. For instance, the lower portion of
the recovery boiler is often made of composite
tube material as shown in Picture 20. The
outer surface of the boiler tube is covered by
corrosion-resistant stainless steel. Also,
keeping the amounts of certain corrosive
chemicals, like chlorine and potassium, below
critical levels in the chemical recovery cycle
reduces corrosion. KRB: p.12
Picture 20. Lower furnace arrangement with
composite tube wall construction
16
Fapet 6B: p.B206 Fapet 6B: p.B207
Picture 21. Material flows in a steam boiler Picture 22. Flow diagram of a cogeneration
steam cycle
The black liquor is combusted in the furnace of the recovery boiler. About 70%-75% of the heat
value of the black liquor will convert into superheated steam when the dry solids content of the
black liquor is 72%-85%. The smelt consumes heat due to the heat of the smelt and the chemical
reactions to form the reduced sulfur in the smelt. About 15% of the heat will go to the smelt.
The rest of the heat is lost with the flue gases. Picture 23 shows how the combustion heat is
divided between recovered heat, heat to smelt and heat losses in the flue gases as the flue gas
temperature and the dry solids content of the black liquor vary.
12
11
Modified by KH;
Fapet 6B: p.B205
Picture 24. Principle of a water tube boiler
The hot flue gases carrying the heat from combustion meet the heat surfaces in the following
order: superheater boiler bank economizer. The hottest gas heats the steam in the superheater
and the coldest gas heats the feed water interring the boiler. The boiling water cools the walls of
the boiler.
The feed water system of the recovery boiler
consists of the feed water tank (1), deaerator,
boiler feed water pump (2), control valve, and
feed water piping (3). The water from the
economizer generates clean attemperating
water (5) from steam in a sweet water
condenser (4). The attemperating water is
used to control the temperature of the steam in
the superheaters and thus to control the
surface temperature of the tubes in the
superheaters. Picture 26 shows some typical
superheater platens. The main steam valves
control steam flow (9). The steam from
superheaters flows through the main steam
line (10) to the turbine.
Fapet 6B: p.B122
Picture 25. Water circulation system
18
KRB: p.13
Fapet 6B: p.B121
Picture 26. Arrangement of two superheater
platens Picture 27. Air system for a recovery boiler
The air is typically delivered at several horizontal elevations to ensure complete combustion and to
minimize emissions. In boilers built after the year 2000, air is often introduced over almost the
whole height of the furnace section of the recovery boiler. Picture 27 shows a boiler air system. It
has an inlet duct with silencer (1), venturi for airflow measurement (2), air blower (3), air heater (4),
distribution ducts (5), and air ducts (6 and 7). Pressure and temperature measuring devices are also
necessary at proper locations. Air intake is typically high inside the boiler house to ensure an even
vertical temperature profile and to recover heat losses through boiler walls and openings.
Recovery boiler operation
Spent kraft pulping liquors contain inorganic salts. During the combustion reactions, the
temperatures increase to levels where significant amounts of inorganic chemicals vaporize.
Small char fragments and black liquor particles also entrain into the flue gas flow. Combustion
and chemical reactions take place in the hot gas phase and cause deposits that collect on heat
transfer surfaces and foul them.
The deposits formed on the heat transfer surfaces consist mainly of Na2CO3, Na2SO4, Na2S and
small amounts of NaCl and potassium salts. The composition of the deposits varies according to
the mechanics of deposit formation, type of black liquor and combustion conditions. Deposits in
the lower part of the furnace generally contain more Na2CO3 and Na2S and less Na2SO4, NaCl
and potassium salts that deposits in the upper furnace. Picture 28 shows typical compositions of
deposits in a recovery boiler.
19
KRB: p.296
Picture 28. Composition of fireside deposits
The fouling of individual heat transfer surfaces is removed and controlled by soot blowing. Soot
blowing is done with steam and is directed to the critical heat transfer surfaces. Soot blowers are
usually in pairs on the left and right side of the boiler as shown in Picture 29. Picture 30 shows a
soot blower cleaning a tube bank.
Potassium and chloride in the black liquor influence the fouling of heat transfer surfaces and the
corrosion of recovery boilers. Even small amounts of potassium and chloride influence the sticky
temperature of dust. The sticky temperature is the temperature above which dust contains sufficient
amounts of sodium in molten state to stick to the heat transfer surfaces and form deposits as shown
in Picture 31. The deposits of chemicals on the heat transfer surfaces become an effective barrier to
heat transfer from the flue gas to the tube wall. From the wall, the heat is transferred to the steam or
water inside the tube.
20
T0 T70 100
Tgas
80
Tube wall .
Q Tflow
Tsteam
20
KRB, MPS Tsticky
Deposit
Picture 31. Deposit on superheater
0
500 600 700 800 900 1000
Temperature [C] KRB, MPS
Picture 32. Different compositions give different
melting behavior
The chloride and potassium levels influence the melting behavior of dust in recovery boilers and
decrease the melting point of dust as shown in Picture 32. The graphs in the picture show the
melting behavior of some typical recovery boiler dusts with varying potassium and chlorine
content. Chloride levels at Scandinavian and North American mills are typically 0.2%-0.8% of
mass. Potassium levels at Scandinavian and North American mills can vary widely: 1%-4% of
mass. Chloride and potassium enter the chemical recovery cycle mainly with the wood and
enrich into the recovery cycle. The level of chloride and potassium must be kept sufficiently low.
The levels are controlled by purging dust from the recovery boiler as dust tends to enrich more in
chlorine and potassium compared to the rest of the recovery cycle.
Increasing chloride and potassium contents reduces the melting point of sodium-containing dust.
Only a few percentages on molten metals make the metals sticky. Tsticky is the temperature when
enough sodium is in molten state and makes a dust particle stick to surfaces of the recovery boiler.
Tsticky is usually in recovery boiler defined to the temperature when 15% of the metals are in molten
state. Tflow is the temperature when enough sodium is in molten state to make the metal a flowing
smelt. Metals start to flow when over 70% is in molten form but usually in connection with recovery
boilers Tflow is defined as the temperature when 85% of the metals are in molten state.
Picture 33 shows the material balance of a recovery boiler and how the generated steam is used
inside the boiler and as steam being fed to the turbine at the mill. Dust from the heating surfaces is
mixed with the black liquor and fed back into the boiler. Some of the dust may be purged from the
recovery cycle to control the content of non-process elements, in particular chloride and potassium.
21
KRB: p.19
22
Dregs removal from green liquor
Green liquor results when the smelt from the recovery boiler is dissolved in weak white liquor or
water in the dissolving tank. Green liquor is an aqueous solution mainly consisting of sodium
sulfides, sulfates and carbonates. It contains some unburned char and some non-process elements
that have a low solubility in the green liquor and that can be removed by sedimentation or filtration.
Most impurities in the lime cycle come from green liquor. Solid particles in green liquor mix with
the lime and accumulate in the lime cycle. Many of these impurities can be removed as dregs from
the green liquor. Without dregs separation, the need for lime makeup may be 30% of the lime
circulation. With good purification of green liquor, the lime makeup required can decrease to 3%-
5%. The separation of the solids, called dregs, from green liquor normally uses sedimentation or
filtration methods. Green liquor purification concepts in industrial use include:
Clarification
Sedimentation
Sludge blanket clarification
Filtration
Cake filtration with or without precoat
Cross flow filtration
The closing of the process cycles has led to an increased need to control the amount of non-process
elements in the recovery cycle by separating dregs in causticizing. The non-process elements enter
with wood and with chemicals used in the process as for instance magnesium used in oxygen
delignification. Table 7 shows an example of green liquor prior to and after filtration. The green
liquor treatment process in Picture 35 includes the following main process stages:
Separation of solid impurities and dregs from green liquor
Cooling of green liquor for causticizing
Treating the dregs for proper disposal
23
Table 7. Removal of various elements from green liquor
Raw green liquor Filtered liquor
Dregs, mg/l 310 7
Potassium (K), mg/l 5.3 5.3
Magnesium (Mg), mg/l 53 1.1
Aluminum (Al), mg/l 60 40
Iron (Fe), mg/l 17 8.2
Manganese (Mn), mg/l 16 2.2
Copper (Cu), mg/l 1.3 0.88
Phosphorus (P), mg/l 43.8 41.2
Fapet 6B: p.B146
Green liquor can be clarified by sedimentation. In sedimentation, the density difference between the
solid material and the liquid in green liquor separates the solid material by allowing it to settle. A
clarifier is normally an open cylindrical tank as Picture 36 shows. The solid material that is heavier
than the liquid settles to the bottom of the clarifier to form sludge. The clear liquor in the upper part
of the clarifier is removed as an overflow.
MPS
Picture 36. A clarifier
In green liquor cross flow filters a thin film of green liquor fall onto a vertical filter cloth. Some
falling liquor is forced through the vertical filter cloth while most of the liquor including the dregs
continues to fall to the bottom in the film. The liquor is recirculated to the top of the filter to
maintain the film by pumping. Filtration continues and the sludge thickens in the circulation until
reaching the desired sludge density. Thickened sludge is discarded from the filter by the pressure
inside the filter.
24
MPS
MPS
Picture 37. Cross-flow filter for green liquor
filtration Picture 38. Green liquor cooler
It is necessary to cool the green liquor and to control the temperature of the green liquor that enters
the slaker in recausticizing to prevent the liquor from boiling in the slaker. Boiling may occur due to
the heat generated as a result of the exothermic slaking reaction. Cooling of green liquor, and even
of weak liquor, is difficult with indirect heat exchangers because of the rapid scaling and plugging
due to reduced solubility at lower temperatures.
Lime slaking and causticizing
Green liquor is mixed with calcium oxide, CaO, and the calcium oxide slakes with water and forms
calcium hydroxide, Ca(OH)2. The calcium hydroxide reacts with the Na2CO3 in the green liquor to
produce NaOH and CaCO3. Picture 39 shows a slaker in which lime is slaked into green liquor.
MPS
MPS
26
Fapet 6B: p.B169
Picture 41. Water balance for causticizing with a pressurized disc filter for white liquor separation
Other commonly used machines for white liquor and lime mud separation and mud washing are
the candle filter shown in Picture 42 and the disc filter shown in Picture 43. The heat and water
balances when using these machines are somewhat different than the ones when using
pressurized disk filters.
MPS, Andritz
MPS
27
The white liquor produced and separated from the lime mud is taken to the digester for cooking.
Table 8 shows typical properties of white liquor.
Table 8. An example of white liquor composition
Compound Concentration, Concentration, As compound,
g NaOH/l g Na2O/l g/l
NaOH 95 73.6 95
Na2S 40 31.8 39
Na2CO3 23 17.8 30.5
Na2SO4 4 3.1 7.1
Na2S2O3 2 1.6 4.0
Na2SO3 0.5 0.4 0.8
Other compounds - - 3.0
Effective alkali 135 105.4 -
Active alkali 115 89.5 -
Total alkali 164.5 128.3 179.4
Sulfidity, % 29.6
S/Na equivalent ratio 0.58
Causticizing degree, % 80.5
Reduction degree, % 82.2
based on total S
Reduction degree, % 90.9
based on total SO4
Fapet 6B: p.B171
The target in lime mud dewatering is to complete lime mud washing and increase the dry solids so
that the lime mud can be dried thermally and fed to the lime kiln. The moisture in the lime mud has
a considerable effect on the energy consumption of the lime kiln. Dry solids contents of 80%-90%
are possible after mechanical dewatering. The water soluble alkali content in the lime mud after
mechanical filter dewatering is under 0.1% as Na2O on dry mud. A low content of sodium is
necessary for the trouble-free operation of the lime kiln.
MPS
28
Lime drying and reburning
The lime reburning process is shown in Picture 45 and consists of the following unit operations:
Pumping of lime mud, that is CaCO3, from lime mud storage
Mechanical dewatering of lime mud to a high dry solids content
Thermal dewatering in the kiln or in a separate cyclone
Heating and calcining
Cooling of the lime, that is calcium oxide, product
Screening and crushing of lime
Conveying of lime to storage
29
MPS, Andritz
Picture 47. A pneumatic dryer for lime mud
The traditional method for the drying of mud is the chain section of the rotary kiln. Picture 48 shows
a chain system. The length of the chain section of the limekiln is chosen so that the mud is
completely dry when leaving the chain section. The length of the chain section is usually about 20%
of the total kiln length.
Lime reburning
Heating or reburning of lime mud converts lime mud to lime according to the following reaction:
CaCO3 - CaO + CO2
Dissociation of CaCO3 to CaO and CO2 starts when the temperature is above 820C. Increasing the
temperature accelerates the reaction. Reburning is done at a temperature of about 1,100C in order
to obtain sufficiently fast reaction rates.
Lime mud entering the limekiln also contains some unreacted lime CaO, water, a small amount of
alkali, other impurities and non-process elements. The amount of impurities in the lime mud is
typically about 7%-10% and depends on the amount of impurities introduced into the lime cycle
with the green liquor and the makeup lime. Non-process elements normally present in the lime cycle
are magnesium (Mg), aluminum (Al), silica (Si), phosphorus (P), iron (Fe), manganese (Mn) and
sulfur (S). Silica is a major problem when pulping annual plants or tropical wood. Sulfur comes for
instance from the burning of non-condensable gases in the lime kiln. Table 9 provides an example of
different lime compositions in the case of a Scandinavian mill and a mill for mixed tropical
hardwood. The major difference between the mill limes is in the content of silica.
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Table 9. An example of different lime compositions
Component Makeup Scandinavian mill with Mill with mixed
(expressed as lime softwood or hardwood tropical hardwood
oxides) as raw material as raw material
CaO, wt. % 93 N/A N/A
Na2O, wt. % 0.06 N/A N/A
SiO2, wt. % 2.5 0.4 7.9
MgO, wt. % 1.3 1.3 1.2
Fe2O3, wt. % 0.5 0.06 0.4
MnO, wt. % 0.04 0.1 0.01
Fapet 6B: p.B147
Silica is a serious impurity in the lime cycle and causes problems especially when pulping annual
plants and tropical wood. The lime mud becomes difficult to handle and dewater with an increasing
silica content as shown in Picture 49.
31
Fapet 6B: p.B184
Picture 50. Burner
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Questions
1. The source of water, organic material and inorganic material in black liquor. / Mustalipen
sisltmn veden, orgaanisen aineen ja eporgaanisen aineen alkuper.
2. Properties of black liquor influencing the evaporation plant. / Mustalipen ominaisuudet
haihduttamon kannalta.
3. Multistage evaporation plant, number of stages and steam consumption, soap separation. /
Monivaihehaihduttamo, vaiheiden lukumr ja hyrynkulutus, suovan erotus.
4. The most common evaporator designs used in black liquor evaporation. / Yleisimmt
haihdutinkonstruktiot mustalipen haihdutuksessa.
5. Condensate handling and reuse at kraft pulp mills. / Lauhteiden ksittely ja uudelleenkytt
sulfaattisellutehtailla.
6. List the main steps of the kraft recovery process. / Luettele sulfaattiprosessin
talteenottopuolen trkeimmt vaiheet.
7. The smelt reactions in a recovery boiler. / Sulareaktiot soodakattilassa.
8. The combustion of black liquor in a recovery boiler; the black liquor droplet during
combustion, and the different stages of combustion. / Mustalipen poltto soodakattilassa;
mustalipepisaran kyttytyminen polton aikana ja palamisen eri vaiheet.
9. Recovery of heat in a recovery boiler. / Soodakattilan energian talteenottojrjestelm.
10. Scaling of heat transfer surfaces in the recovery boiler. / Soodakattilan lmmnsiirtopintojen
likaantuminen.
11. The main factors influencing the heating value of black liquors. / Polttoarvoon vaikuttavat
trkeimmt tekijt.
12. Influence of chlorine and potassium on recovery boiler operation; what can be done to
control chlorine and potassium levels? / Kloorin ja kaliumin vaikutus soodakattilan
toimintaan; mit voidaan tehd kloori- ja kaliumtasojen hallitsemiseksi.
13. Green liquor treatment, measures to reduce the need for makeup lime. / Viherlipen
ksittely, miten vhennetn korvauskalkin tarvetta.
14. Slaking of lime and causticizing reactions. / Kalkin sammutus ja kaustisointireaktiot.
15. The operation principle and construction of the lime kiln. / Meesauunin toimintaperiaate ja
rakenne.
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