Recovery Boilers

Esa Vakkilainen
26 August, 2016
esa.vakkilainen@lut.fi
Recovery Boiler
Lecture 4: Fouling

Recovery Boiler
Esa Vakkilainen -2-
 Formation of deposits
 Black liquors contain inorganic chemicals
 During combustion and reduction reactions
significant amounts of alkali compounds
vaporize
 Small char fragments and liquor particles may
entrain to flue gas flow
 These cause deposits on surfaces.
 Deposit build up reduces heat flows

Recovery Boiler
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 Fouling is still a problem
 Fouling and fouling related phenomena have long been
of concern in recovery boiler design and operation.
 Even with improved air systems and advances in
recovery boiler design, fouling remains one of the big
operating problems.
 Like many industrial problems there are number of
different causes that cause fouling.
 For a modern recovery boiler the crucial piece of
equipment is often the boiler bank.

Recovery Boiler
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 Cause for fouling
 Finding the cause for recovery boiler fouling can
be started by examining fouling at that boiler
 How fast is the recovery boiler fouling
 What measurements indicate the progress of fouling
 Is the fouling continuous or are there equilibrium
stages
 Are there any upset or abnormal operation conditions
that correlate with times of fast fouling
 Does the furnace operate smoothly and well

Recovery Boiler
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Prediction of fouling

Visual Observation
Prediction from Operating Parameters
Change of Measured Parameter
Change of Calculated Value

Pressure loss measurements

Flue gas side temperature measurements

Steam/water side temperature measurements

Recovery Boiler
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Deposits on superheaters

Recovery Boiler
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 Superheater fouling
 Superheater deposits are formed mainly by two
mechanisms, inertial impaction and fume
deposition
 Composition can be explained by assuming
different mixing ratio of carryover and fume
 Flue gas velocities at superheater area are
rather low 3 – 5 m/s. This creates good
conditions for separation of large, over 10 μm
particles

Recovery Boiler
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Deposition in the middle of the boiler
bank

Recovery Boiler
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 Boiler bank fouling
 Boiler bank plugging has been the most
problematic fouling in modern recovery boilers
 There are several indicators for tendency of
boiler bank plugging
 low melting temperature of ash deposited
 increased black liquor chloride content
 high flue gas temperature into boiler bank
 fast sintering rate of deposits

Recovery Boiler
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 Economizer fouling
 Economizer fouling is by low ash pH
 High ds increases furnace temperature
 Increased lower furnace temperature increases
sodium and potassium release. Thencarbonate
in ash increases
 Ash with low pH is sticky and hard to remove
form surfaces
 In practice pH of 10 % of dust in water solution
should be at least 10

Recovery Boiler
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 Carbonate in ESP as vs BL dry
solids
18.0

16.0

14.0
CO3 in ESP dust, w-%

12.0

10.0

8.0

6.0

4.0

2.0

0.0
50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0
Black liquor dry solids, w-%
A B C D E F G H I J K L M N O P Q X Y Z W

Recovery Boiler
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Effect of dust carbonate to pH of
ESP ash
13

12

11
ESP dust pH

10

7
0 5 10 15 20 25 30 35
CO3 in ESP ash, w-%

Recovery Boiler
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 Prediction of fouling
Heat transfer
surface
Use of heat transfer coefficient

/
O Tw
h =
A ( Tg - Tw )
gas

Fouling decreases h
h doesn't change linearly with load Tg
Reliable flue gas measurement difficult

Recovery Boiler
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 Prediction of fouling
Heat transfer
surface
Use of pressure loss measurement po

2
Dp = p
i
- po ~ rv
gas

Fouling increases deposits

Deposits block the flow area
Increased velocity increases
pressure loss pi

Recovery Boiler
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 Typical pressure losses
800
superheaters
boiler bank

Pressure loss, [Pa]

eco2 600
eco1
400

200

1 3 5 7 9 11 13 60
Niemitalo and Vakkilainen, 1994 days after startup

Load change changes pressure loss by load squared

Pressure loss shows stable behaviour
Fouling of boiler bank and economizers stabilizes
after few days
Recovery Boiler
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Superheating temperatures
140.
superheater I 130.
120.

Temperature raise, [oC]

superheater II
110.
superheater
** III 100.
90.
80.
70.
60.
50.
40.
30.
20.
10.
0.
1 3 5 7 9 11 13 60
Niemitalo and Vakkilainen, 1994 days after startup

Temperature raises decreases at first

Load changes cause small changes in fouling
Superheater fouling stops after 10 - 20 days
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Attemperating temperature drop
100.
attemperating I 90.

Temperature drop, [oC]

attemperating II 80.
attemperating III 70.
60.
50.
40.
30.
20.
10.
0.
1 3 5 7 9 11 13 60
Niemitalo and Vakkilainen, 1994
days after startup

Load changes affect attemperating flow

Attemperating shows stable behavior after 10 - 20 days
Fouling of previous surfaces increases inlet gas temperatures
and attemperating
Recovery Boiler
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 Formation of ash particles in
recovery boiler
 Alkali metals in burning black liquor droplets vaporize.
They react with furnace gases and condense to small
particles. This process is called fume formation.
 Some of the black liquor gets caught with flue gas. This
forms carryover particles. Also material is physically
ejected from burning black liquor droplets
 During char combustion intermediate size particles are
formed in the char bed

Recovery Boiler
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 Recovery boiler ash formation
30
2000 2200
2400 2600
25 2800 3000
Dust flow g/m3n, dry 3% O2

BB ash ECO ash

20

15

10

0
65 70 75 80 85 90
Black liquor dry solids [%]

Recovery Boiler
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 Fume formation
 When flue gases are cooled the alkali vapors become
supersaturated.
 Supersaturated vapors form particles via
 In homogeneous nucleation two vapor molecules stick together to
form a small particle. Vapors then start to condense on these
particles.
 Small metal oxides and other impurities serve as starting nucleus for
the vapors. This process is called heterogeneous condensation.
 Formed very small particles grow by agglomeration
 Mass averaged fume particle average sizes are 0.5 … 1.3
μm

Recovery Boiler
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Fume size distribution from the
furnace

3500 tds/d
2400 tds/d

(Mikkanen et al., 1999)

Recovery Boiler
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 Mean particle size of fume
 Mean particle size constant from the furnace
outlet
 After flue gas temperature decreases below 550
oC fume particles that hit each other do not stick

 Particles deposited on surfaces that touch each

other can grow together through sintering
 These agglomerates can re-entrain
 They show as larger 20 … 30 μm particles at
electrostatic precipitator inlet
 Amount of re-entrained dust is 10 … 30 % of
total dust flow
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ESP dust size

(Janka et al., 2000)

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 Amount of fume
 Furnace temperature increases with increased
black liquor dry solids
 This increases sodium and potassium release
 Black liquor sodium and potassium release
depends also on the liquor i.e. wood species
and the pulping conditions
 The firing conditions affect the lower furnace
temperature
 The actual fume formation rate can vary a lot

Recovery Boiler
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 ESP dust increases with dry
solids
35

30

25
Dust, g/m3n, dry

20

15

10

0
60 65 70 75 80 85
Black liquor dry solids, %

Recovery Boiler
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ESP dust increases with firing
rate

(Tamminen et al., 2002)

Recovery Boiler
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 Carryover
 Carryover is burned and unburned particles that
get caught with the flue gases.
 For modern recovery boilers running close to
MCR the typical carryover rate is 2 – 4 g/m3n
 The amount of carryover depends on the air flow
settings and the chosen air model
 Typically carryover decreases for lower loads
 Newer boilers have down to 0,5 – 1,5 g/m3n
 Older boilers achieve 5 – 8 g/m3n

Recovery Boiler
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 Carryover
 Carryover can be broadly classified into two
distinct groups
 Still burning droplets can be seen as light streaks
against darker background.
 Carryover that has combusted totally has high
reduction and contains sodium sulfide. This can be
seen as pink or red color at superheater sootblower
lances
 In modern high dry solids boilers carryover
carbon content is very low
 Carryover particles are depleted of potassium
and chlorine
Recovery Boiler
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 Intermediate size particles types
 Large agglomerates of 0.3 … 0.7 µm diameter
primary particles. These are fume deposited
onto surfaces, sintered and re-entrained.
 Extensively sintered irregular particles 30 … 250
µm in diameter. They were formed by sintering.
 Spherical highly porous particles 5 … 100 µm in
diameter. Residue of burning black liquor.
 Dense spherical particles 5 … 250 µm.
 Irregular, rough particles 3 … 40 µm in diameter.
They originate from the mineral impurities in the
black liquor.
Recovery Boiler
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 Type four intermediate particles
 Small particles can be physically ejected during
black liquor droplet combustion
 During char combustion release of 10 … 100 μm
char fragments happens in laboratory
experiments and pilot plant tests
 In mill trials this size particles have been found
 In field studies 1 … 2 g/m3n have been found
 In another set of field studies 20 to 40 % of large
material at superheater inlet was ISP. The
measured ISP amount equaled 1 … 3 g/sm2.
Recovery Boiler
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Intermediate size particles

Kochesfahani and Tran, 2000

Recovery Boiler
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 Deposition of particles and
vapors
 Deposition of particles and vapors on surfaces
can occur through multiple pathways
 Thermophoresis or temperature gradient
transfers small particles to surface
 Larger particles are deposited by inertial or
turbulent impaction
 Vapor or gaseous species can condense on the
surface and react with deposits on the surface
 For very small particles (<0.1 μm) molecular
diffusion and Brownian motion can play a role
Recovery Boiler
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 Thermophoresis
 Thermophoresis plays
significant role in
DT  KBd d p Tg  Ts  Tl capturing the small
0.2 … 1 μm fume
particles suspended in
the flue gas
 Thermophoretic
deposition rate is
proportional to the
temperature gradient,
particle diameter and
particle concentration

Recovery Boiler
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 Inertial impaction
 For particle sizes larger
lp than about 20 µm the
Stk 
Rc main deposition
mechanism is the inertial
l p  U p ,0 impaction
 The capture efficiency of
mp r pbd p 2 a collector in a cross flow
  of combustion gases is
3 d p  18
mainly determined by
inertia, which can be
characterized with the
Stokes number

Recovery Boiler
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 Turbulent eddy impaction
 Important deposition
mechanism for large
particles, when boundary
layer between surface
18 l
 u 
1
l
2 2
  and host flow is turbulent
 r pb d p 2  Inside the turbulent
boundary layer turbulent
eddies have velocity
components, which are
normal to the main flow

Recovery Boiler
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 Vapor deposition
 Vapors may condense by
direct condensation on
heat transfer surfaces or
on the particles inside the
boundary layer
 Condensing vapor may
also react with surfaces

 D T  D T   
1/ 2
 pv Tg pv ,s Tw  
Iv  Sh(T )
v g v w
  
g  T Tw 
dc Rg  g

Recovery Boiler
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Fume deposition on heat transfer
surfaces

Recovery Boiler
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Dust composition in recovery
boilers

Precipitator dust Boiler bank dust

(small spheres) (mixture of different sizes)

Recovery Boiler
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 Liquid content
 When recovery boiler dust is heated it at first
behaves like solid
 At first melting temperature liquid appears
 Above that temperature there exists a state
where the deposit is partially molten and partially
solid
 Depending on the type of system after small or
larger temperature difference the whole system
is molten

Recovery Boiler
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Effect of carbonate content to first
melting temperature

Recovery Boiler
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Basic phase diagrams for binary
systems

eutectic minimum melting

Recovery Boiler
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 Liquid content
 The temperatures where 15 w-% of the deposit
is at molten state and 85 w-% is at solid state is
called T15 or sticky temperature
 The temperatures where 70 w-% of the deposit
is at molten state and 30 w-% is at solid state is
called T70 or flow temperature
 Recovery boiler dusts tend to stick to the heat
transfer surfaces and form hard deposits when
they are between T15 and T70

Recovery Boiler
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Amout of melt in a dust
100

90 Before the superheaters, windward

Before the superheaters, leeward
After the superheaters, windward
80
Precipitator dust

70 T 70

60
% melt

50

40

30

20
T 15
10

0
500 550 600 650 700 750 800 850 900
t (°C)

Recovery Boiler
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 Sticky temperature of deposits

- + 600 o C preferred
for deposit T15
- Cl/(Na+K) > 5
requires lower
superheating K in BL~

1.0
2.0
3.0
- K not so important

Cl in BL~ 0.5 1.0 1.5 2.0

Backman, et al., 1995

Recovery Boiler
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 Sintering
 Sintering is a process where dust particles that
have stuck to a heat transfer surface gradually
densify and harden
 Originally loose and porous material becomes
solid almost crystal like
 As deposits densify, their strength increases
exponentially, and they become more difficult to
remove by sootblowing
 Because of the end product the process is often
called deposit hardening
Recovery Boiler
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Progression of neck development
during sintering of ash

450 oC for
Original three minutes

450 oC for 450 oC for

fifteen min sixty minutes

Recovery Boiler
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Real deposits have both small
and large particles

Recovery Boiler
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 Sintering rate

DL ksin t  t 1/ 3 po1/ 3 
 2/3  0.5 
L r  T 

Recovery Boiler
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 Strength of deposits

σ = 42800 e6.64 P

Recovery Boiler
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 Enrichment of potassium
 Potassium enrichment
factors range from 1 to 2.5
K sample  Weight fraction of
potassium is 2.5±0.5 times
( Nasample  K sample) the potassium in virgin BL
EK 
K BL  Mole ratio of potassium to
( NaBL  K BL ) the sum of sodium and
potassium in ESP dust is
4.6±0.9 times the mass
weight percent of
potassium in virgin BL

Recovery Boiler
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Potassium enrichment versus
carbonate in ESP ash

Recovery Boiler
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 Enrichment of chlorine
 Chloride enrichment from 0.3
to 6
Clsample  Average is 2.9
( Na2 sample  K 2 sample)  Mole ratio of chloride to the
ECl  sum of sodium and potassium
ClBL
in ESP dust is 8±1 times the
( Na2 BL  K 2 BL ) mass weight percent of
cloride in virgin BL
 Weight fraction of chloride in
ESP dust is about 4±2 times
the chloride in virgin BL

Recovery Boiler
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Chloride enrichment versus
carbonate in ESP ash

Recovery Boiler
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Effect of SO2 on chloride
enrichment
600
Mill S/Na2
A 45
500
B 43
SO2, ppm (@ 3% O2)

B 37
400 C 35
D 36
300 D 49

200

100

0
900 950 1000 1050 1100 1150

Lower furnace temperature, oC Frederick, et. al., 1998

Recovery Boiler
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Enrichment of chlorine to dust
(reverse N – curve)

Recovery Boiler
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Potassium and chlorine
enrichment

Recovery Boiler
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Potassium and chlorine
enrichment

Recovery Boiler
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Effect of dry solids to BB dust
BB ash flows (0.7)
900 BB ash sticks (0.15) 4000
Aerosols stick
850 SO2 3500
HCl
800 3000
C
o
Deposit temperature,

Emission, ppm
750 2500

700 2000

650 1500

600 1000

550 500

500 0
60 65 70 75 80 85 90
Black liquor dry solids, weight-%

Recovery Boiler
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Effect of sulfidity to BB dust
900 BB ash flows (0.7) 1000
BB ash sticks (0.15) 900
850
Aerosols stick
SO2 800
800
Deposit temperature, oC

HCl 700

Emission, ppm
750
600

700 500

400
650
300
600
200
550
100

500 0
10 15 20 25 30 35 40 45 50 55 60
Sulfidity S/(Na2+K2), mol-%

Recovery Boiler
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Sintering index versus dry solids

Recovery Boiler
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Decline of exit velocity of
sootblower jet

Recovery Boiler
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 How to decrease fouling rate
 Fouling rate is a combination of three
parameters; amount of incoming particles, their
ability to stick to the surface and the removal
rate by sootblowing
 There are several measures that can be used to
decrease fouling in a recovery boiler
 affect the liquor properties
 decrease flue gas temperatures
 decrease carryover rate
 improve surface cleanability

Recovery Boiler
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Potassium and chlorine levels in
a Scandinavian mill

Recovery Boiler
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Change black liquor composition
Boiler bank fouling, ds = 80 %

900 BB ash flows (0.7) 6

BB ash sticks (0.15)
850 Aerosols stick
5
SO2
Deposit temperature, oC

800
HCl
4

Emission, ppm
750

700 3

650
2
600
1
550

500 0
10 15 20 25 30 35 40 45 50 55 60
Sulfidity S/(Na2+K2), mol-%

Recovery Boiler
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Types of recovery boilers fouling
 combustible carryover
 small still burning black liquor droplets
 inorganic carryover
 residue from black liquor droplets
 carryover from char bed
 low pH in dust
 SO2 in FG
 sticky ash
 K, Cl, sulfide

Recovery Boiler
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 Dust accumulation in ESP
caused by low pH conditions

Photo by Alstom Power

Recovery Boiler
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Chlorine concentration in ash
Ash sampled 1.8

from conveyors 1.6

Cl/(Na+K) in dusts, mole %

1.4

Higher chlorine 1.2

concentration 1.0

in colder 0.8
0.6*Cl/(Na+K) in BL

surfaces 0.6

0.4

0.2
Negative 0.8 1.0 1.2 1.4 1.6
enrichment in Cl/(Na+K) in black liquor, mole %

Boiler bank ash BB ECO1 ECO2 ESP

Niemitalo and Vakkilainen, 1994

Recovery Boiler
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Potassium concentration in ash
Ash sampled 2.0

from conveyors
1.8

Higher K K
Na + K 1.6
concentration
K
in colder Na + K BLS1.4

surfaces
1.2

Enrichment
always over unity 1.0
7.7 7.8 7.9 8.0 8.0 8.1 8.2 8.3 8.4
Molar ratio K/(Na+K) in virgin black liquor

Niemitalo and Vakkilainen, 1994

Recovery Boiler
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 Chlorine and potassium in
typical black liquors

typically Cl < 1 % 4
3.5
3
typically 1 < K < 3 %

Chlorine, w-%
2.5
2
maximum Cl ~ 4 % 1.5
1

maximum K ~ 8 % 0.5
0
0 1 2 3 4 5 6 7 8
Potassium, w-%

Recovery Boiler
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Effect of dry solids on ESP dust
35
y = 0.3533x - 7.3903
30 R2 = 0.2338

25
Dust, g/m3n, dry

20

15

10

0
64 67 70 73 76 79 82 85 88
Black liquor dry solids, %

Recovery Boiler
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 Carbonate in ESP ash

18.0

16.0

14.0
CO3 in ESP dust, w-%

12.0

10.0

8.0

6.0

4.0

2.0

0.0
50.0 55.0 60.0 65.0 70.0 75.0 80.0 85.0 90.0
Black liquor dry solids, w-%
A B C D E F G H I J K L M N O P Q X Y Z W

Recovery Boiler
Esa Vakkilainen -72-
 Estimation of fouling and
corrosion propensities of fuels

Fouling
Materials

Fly ash
formation

Corrosion
Furnace
Fuel reactions

Recovery Boiler
Esa Vakkilainen -73-