Recovery Boilers

Esa Vakkilainen
26 August, 2016
esa.vakkilainen@lut.fi
 Recovery Boiler
Lecture 2: Combustion of black liquor

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 Combustion of black liquor
 The black liquor is composed of a large number
of organic and inorganic compounds.
 The amount and the composition of the black
liquor depend on the wood species, the cooking
method and the pulping process.
 The organic matter of black liquor is combusted
 Part of the inorganic matter is recovered as
smelt.

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 Black liquor has

 one of the lowest heating values of industrial fuels

 large inorganic portion of the black liquor (ash
content)
 high water content

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 Combustion of black liquor
 Black liquor combustion occurs
 as a droplet sprayed to the furnace from a liquor gun
 in the char bed at the bottom of the recovery boiler
furnace
 Black liquor is not finely atomized
 Rather black liquor is sprayed as coarse
droplets
 The average droplet diameter is about 2 ... 3
mm, so that unburned material can reach char
bed.
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 Main stages in black liquor
combustion
Stage Characterized by Time scale
in furnace, s
Drying Water evaporation 0.1 … 0.2
Constant diameter after initial swelling

Devolatilizat Appearance of flame, ignition 0.2 … 0.3

ion Swelling of the droplet
Release of volatiles
Char Disappearance of flame 0.5 … 1
burning Decreasing diameter
Reduction reactions
Smelt Constant or increasing diameter Long
Reoxidation
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 Swelling during combustion
 During combustion black liquor swells
 No other industrial fuel swells as much as black
liquor during combustion.
 The swelling behavior is caused by high volatiles
yields and suitable surface properties
 While black liquor can already be dry and
undergoing volatiles release at surface, drying is
not complete at droplet centre

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Characteristic swelling behavior of
black liquor during combustion

(Åbo Akademi)

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 Drying
 Drying is characterized by evaporation of water
from the black liquor droplet
 It is often experimentally defined by absence of
combustion (visible flame)
 Evaporation of water requires heat
 Drying of black liquor droplet proceeds as fast as
the heat is transferred to the droplet
 Even in the furnace temperatures drying is
limited by the heat flux to the droplet

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Example of drying black liquor
droplet, laboratory conditions

(Åbo Akademi)
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 Drying – what we know
 Black liquor diameter increases 1.3 - 1.6 times
during the first couple of milliseconds
 As water is evaporated, the density decreases,
but the diameter stays constant.
 Swelling restarts with the onset of the volatiles
release
 Typically about five percent of moisture remains
at the onset of volatiles release
 The drying rate for pine, birch and sodium sulfite
liquors is constant for black liquor droplets with
various dry solids contents at 700 oC and 800 oC
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 Drying - modelling

mo = m p + mw
mp
xd =
m p + mw
2.74
Td = 100 + BPR max xd

  
Q = mp c p T d + l mw
t d t t

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 Drying – heat balance

Qd = Qc + Qr

Dd = 154
. * Do

 Qc
= hc Ad ( T g - T d )
t

 Qr
= Ad  ( g - T d 4 )
4
T
t

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 Devolatilization
 As black liquor dries and temperature increases
reactions with lowest activation energies start
taking place
 Release of low molecular weight component
gases such as methane, carbon dioxide,
hydrogen and hydrogen sulfide starts
 Hydrogen, carbon monoxide, carbon dioxide,
light hydrocarbons, tar and light sulfur-containing
gases have been reported to be main product
gases during devolatilization
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 Devolatilization of black liquor
 Devolatilization is characterized by
 the increase of black liquor droplet volume
 release of volatile gases from the black liquor droplet
 appearance of visible flame

 The last one is the most typical criteria for

determining the length of devolatilization time in
experimental droplet combustion studies.

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Example of start of devolatilization,
laboratory conditions

(Åbo Akademi)
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 Devolatilization - process
 During devolatilization the gas release is large
so no oxygen can contact the droplet surface
 Therefore the conditions at droplet resemble
those of pyrolysis = heating in inert athmosphere
 Devolatilization of black liquor tends to be a fast
process and depends essentially on the heat
transfer to the liquor
 Devolatilization occurs in an outer shell of
expanding thickness, while a core of colder,
unpyrolyzed material remains within
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Example of end of swelling,
laboratory conditions

(Åbo Akademi)
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Example of change during
devolatilization, laboratory

start end
(Åbo Akademi)
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 Swelling
 The black liquor droplets swell considerably
 Swelling is continuous from the onset of ignition
until the devolatilization is complete
 Swollen particles exhibit macroporosity and
often a hollow central core is found.
 The maximum swelling can change from one
type of liquor to another
 The maximum swollen volume for black liquors
can change from less than 10 to 50 cm3/g.

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 Swelling characteristics
 Swelling both for softwood and hardwood is
proportional to the ratio of lignin to aliphatic
acids.
 Typically a longer cooking time increases
swelling
 Liquor from soda cooks and NSSC cooks seem
generally to swell less than Kraft liquors
 Adding of sodiumsulfate or sodiumcarbonate to
virgin black liquor decreases swelling

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What affects black liquor
combustion

(Alén, 2000)

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Swelling versus organic combustion
time for single droplet at 800 oC
80

70
Swelling, cm3/g dry solids

60

50

40

30

20

10

0
4,0 6,0 8,0 10,0 12,0 14,0 16,0 18,0
Organic combustion time, s
organic combustion time = sum of devolatilization and char burning times

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Reactions during devolatilization
 Many reactions occur during black liquor
devolatilization
 The main processes are
 Sulfur release
 Sodium release
 Carbon conversion

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 Sulfur release during
devolatilization
 During devolatilization a large amount of sulfur
release reactions take place
 The main forms of sulfur release are
 dimethyl sulphide
 methyl mercaptane
 Hydrogen sulfide, H2S is formed rapidly with
decomposition reactions after gases are
released from the droplet
 Formation of dimethyl disulfide is small

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Sulfur species released

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 Sodium release during
devolatilization
 There is some experimental evidence that
during devolatilization fragmentation though
ejection of small particles occurs
 This process is partly responsible for sodium
loss from combusting black liquor droplets
 In addition sodium associated with activated
carboxylate and phenolate sites can volatilize

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 Carbon during devolatilization
 Devolatilization occurs very rapidly when black
liquor solids are heated to temperatures
substantially above 200°C
 During devolatilization a significant portion of
carbon in char is consumed
 Increasing temperature results in higher
pyrolysis yield
 Volatiles release seems to decrease when
swelling increases

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Effect of temperature on char
conversion
50
Conversion after devolatilization, %

40

30

20

Char, red=0
10 Char, red=0.95
total on ds., red=0
total on ds., red=0.95
0
600 700 800 900 1000 1100 1200 1300
Temperature, °C

(Järvinen et al., 2000)

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 Devolatilization - modelling
 m 0.001634 pO 2
= + 0.0034 - 0.54 pO 2 - 0.316
t m0d d 0d d 0d

xo
Q p = mo [ c p ( T d - T o ) + l(1 - )] + Qp
xd

Nv
Q p (t)
D(t) = Dd +( D p - Dd ) ( )
Qp

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 Char combustion
 Char combustion of black liquor starts as the
volatiles release is finished
 Often the combustible material remaining after
volatiles release is termed fixed carbon
 Fixed carbon does not include inorganic ash
 In laboratory tests char combustion starts when
the visible flame is extinguished
 In practice char combustion and devolatilization
overlap considerably.

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Example during char burning

(Åbo Akademi)
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 Composition of kraft char
Component moles/mole weight, %
Na2
Sodium Na2S 1/6 9.0
sulfide
Sodium Na2SO4 1/6 16.4
sulfate
Sodium Na2CO3 2/3 49.0
carbonate
Carbon C 3 24.9

Hydrogen H 1 0.7
(Grace, 1990)
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 Reduction reactions
Na2S + 2O2 -> Na2SO4

Na2SO4 + 2C -> Na2S + 2CO2

Na2SO4 + 4C -> Na2S + 2CO

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 Reduction rate

 [ SO4 ] [ SO4 ] Ea
= - K Red  C e RT
-
t B+ [ SO4 ]

 Constants measured for Kraft char

KRed = 1310+410, 1/s
B = 0.022+0.008, kmol/m3
Ea = 122, kJ/kmol

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 Char oxidation
 If there is oxygen the carbon in the char reacts
with the oxygen
 If there is a no oxygen the char is gasified with
carbon dioxide CO2 and water vapor H2O
 Both carbon dioxide and water vapor react with
char to form carbon monoxide CO.
Cchar + CO2 -> 2CO
Cchar + H2O -> CO + H2
 The CO is further oxidized to CO2 higher in the
furnace when it reacts with oxygen.
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 Smelt reactions
 As combustion is finished the inorganic residue
remains
 The black liquor droplet has shrunk to a liquid
droplet
 If oxygen contacts this smelt, the sulfide in smelt
is reoxidized to sodium sulfate Na2SO4
 In recovery boiler it is important to have enough
reacting material on top of smelt to avoid smelt
reoxidation

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Example during smelt reactions

(Åbo Akademi)
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 Experimental procedures to look
at black liquor combustion
 Laboratory-scale devices are used for studying
the combustion properties of the liquors
 Single-droplet muffle furnace is maybe the most
typical of these
 Another typical device is the single droplet tube
reactor

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 Single-droplet muffle furnace
 The duration of the
pyrolysis and char
burning times and
swelling during
combustion is recorded
with a video camera
 Experiments are
performed typically in air
at 700 and 800 oC
 The sample size is
usually of order of 10 mg
wet black liquor
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 Single droplet tube reactor
 The main benefit of the
tube furnace is that gas
N2
analysis of combustion
products can be made
 In the Åbo Akademi one N2/O2/CO2 pump pump
can follow the burning
SO2
process of individual Furnace
NO
droplets with on-line gas CO/CO2
analysis for CO2, CO,
SO2 and NO
 The experiments are
typically performed on 40
mg samples at 900°C in
different O2 compositions.
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 Combustion of black liquor
droplet in the furnace
 A typical lower part of recovery furnace consists
of
 Three air levels
 Primary
 Secondary
 tertiary levels
 The furnace bottom is covered with a char bed
 The black liquor is sprayed from black liquor guns

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Liquor spraying to lower furnace

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 Black liquor droplet flight path
 Black liquor drying occurs close to the liquor gun
 When volatiles release starts the droplets swell
 Increased drag then slows them down
 At the same time droplets curve upward
because of the drag from flue gases
 As char burning is completed the droplet density
increases
 It starts falling down until it hits the char bed.
 Drops with higher initial dry solids start swelling
faster and tend to burn higher in the furnace
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Effect of increased dry solids to
combustion

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 The combustion properties of high
dry solids black liquors
 The main interest has been the release of
sodium, sulphur and chloride and the
combustion properties of the high dry solids
droplet
 The black liquor droplet is a poor heat conductor
 The burning process is controlled by the slow
rise of the temperature inside the droplet
 The increase of the dry solids affects only
slightly the black liquor combustion when the dry
solids of black liquor is raised
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 Heat treatment of black liquor
 The heat treatment of black liquor can be
defined as a thermal treatment method where
residual alkali reacts with dissolved
polysaccharides and lignin
 These reactions are very slow in typical
evaporator temperatures
 The black liquor needs to be heated up to 180 ...
190 oC
 The effect is destruction of high molecular
weight compounds and reduction of black liquor
viscosity Recovery Boiler
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 Heat treatment = viscosity
reduction
 The main benefit of the liquor heat treatment
(LHT) is viscosity reduction which allows
 evaporation up to 90 % dry solids
 keeps the black liquor in a pumpable form even at
atmospheric pressure
 storage of the strong liquor in atmospheric tanks
 Viscosity reduction is especially beneficial, if the
raw material and cooking method at the mill is
such that the handling of strong liquor is a
problem.
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 LHT plant

45 %
43 %

80 %

15 %

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 Viscosity of black liquors from
three mills using liquor heat
700

600
treatment
500
Viscosity [mPas]

400 Mill-A
Mill-B
300 Mill-C

200

100

0
50 55 60 65 70 75 80
Black liquor dry solids [%]
Mills A and B before heat treatment, Mill C after heat treatment

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 Release of NCG during LHT
 Simultaneously with the reaction of the
polysaccharides and alkali there happens also
another reaction
 The sulfide in the liquor reacts with the lignin
generating
 dimethylsulfide
 methyl mercaptans
 This NCG gas is released from the liquor when
the pressure is decreased after the treatment

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 LHT – effect on BL combustion
 LHT treatment splits long lignin chains
 Increasing the amount of shorter (Mw 1500 …
3000) lignin chains increases swelling
 Heat treatment of black liquor has also been
found to increase the swelling during combustion
 LHT can also affect beneficially to the NOx
emissions
 Released NO convertible nitrogen and nitrogen
remaining in the liquor is reduced with LHT

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 CO2 profiles at 80 % ds for
combustion at 3% O2 = burning rate
20000
18000 LHT
CO 2 formed (ppm)
16000
14000
12000
10000
8000
6000
4000
2000
0
0 50 100 150 200 250

20000
18000 Virgin
CO2 formed (ppm)

16000
14000
12000
10000
8000
6000
4000
2000

0 50 100 150 200 250

time (seconds)

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LHT – Effect on swelling
60,0

50,0
Swelling, cm3/g .

40,0

30,0

20,0

10,0

0,0

10
11
12
13

14
15
16

17
18
19
1
2

3
4
5
6

7
8
9

First line in each series is swelling of a liquor sample without liquor heat treatment
and subsequent 1 – 3 lines are for progressively more heat treatment.

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 LHT - process
 Increased burning rate is caused by increased swelling
 Increased swelling increases the effective external
surface area during the combustion process
 This gives higher heat transfer from the hot environment
to the droplet and a higher heating rate during pyrolysis
 Larger external surface increases the amount of oxygen
diffused for char burning.
 During LHT volatile organic gases are released
 The mass loss during LHT is from 1 to 5 percent
 LHT affects the polysaccharide content and so also the
surface properties of black liquor droplet
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Swelling versus polysaccharides
content

70,0

60,0
Swelling [cm3/g]

50,0

40,0

30,0

20,0

10,0

0,0
0,0 2,0 4,0 6,0 8,0 10,0
Polysaccharide [%]

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 Sulfur release
 The LHT seems to decrease the sulfur release
 Dimethyl sulphide, methyl mercaptane and
hydrogensulfide are the main species released
during heat treatment
 The concentrations of dimethyl sulphide and
methyl mercaptane decrease for LHT liquors
 At least part of the sulfur released during
pyrolysis comes from the lignin demethylation
reactions
 Changes in swelling do not wholly explain the
changes in sulfur release
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 SO2 profiles at about 80 % ds for
combustion at 3% O2 = burning rate
700

600
Virgin
SO formed (ppm)

500

400

300

200
2

100

0
0 50 100 150 200 250
700

600
LHT
SO 2formed (ppm)

500

400

300

200

100

0
0 50 100 150 200 250

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 Nitrogen release
 LHT treatment decreases NO formation
 Decrease in the NO formation is approximately
10 %

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LHT – Effect on nitrogen release
40

35
NO formation [mg N/100 gBLS]

30

25

20

15

10

0
1

10

11

13
First line in each series is swelling of a liquor sample without liquor heat treatment
and subsequent 1 – 2 lines are for progressively more heat treatment.

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