What is our
objective?
10-10-2015
3 + 2OH
10Ca2+ + 6PO
$
+
4
[Ca3(PO4)2]3Ca(OH)2
10-10-2015
Attemperator
Economizer
RH
SH-1
SH-2
L P Heater
Condenser
H P Heater
Riser
Down comer
Riser
Deaerator
CEP
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Natural Circulation:
Nucleate Boiling :
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Film Boiling
Increase in concentration of
contaminants
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Natural Circulation
P =
H d g -
Downcomer
Riser
H r g = H g (d r)
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Natural Circulation
Down comer
Riser
Drum Level
P = H g (d r)
17
10-10-2015
10
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c = (P x D ) / 2 t
When c exceeds Allowable..Tube fails in the
longitudinal direction
11
10-10-2015
Water Analysis:
What do we check in the Feed Water, Boiler Water & Steam?
Analysis
Feed Water
Boiler Water
Steam
Cond.
pH
Conductivity
Silica
Residual
Hydrazine
Residual
Phosphate
P Alkalinity
M Alkalinity
Chloride
Residual
Ammonia
12
10-10-2015
Scale
Corrosion
Carry Over
13
10-10-2015
Carry Over :
14
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Carry Over :
Impurities in Water
15
10-10-2015
called
IMPURITIES
from
the
earthen
layer
in
dissolved
as
well
as
in
16
10-10-2015
SOLID IMPURITIES:
Dissolved Solids:
Na+ + Cl-
17
10-10-2015
Non Reactive
Reactive
Non Reactive
HCO3
(Bicarbonate)
Mg++ (Magnesium)
CO3
(Carbonate)
Na+
SO4
(Sulphate)
Cl
(Chloride)
(Sodium)
NO3
(Nitrate)
PO4 (Phosphate)
HSiO3 (Bisilicate)
18
10-10-2015
Scale Formation
t2 = t4 + (1/ + D/ k2) x Q
Where,
t2 = inner skin temperature of tube (C)
t4 = boiler water temperature (bulk) (C)
= heat transfer coefficient of boiling surface
(kcal/ m2hC)
D = scale thickness (m)
k2 = thermal conductivity of scale (kcal/ mhC)
Q = heat flux (kcal/m2h)
Substance
Thermal conductivity
(kcal/m2hC)
Silica scale
0.20.4
0.40.6
0.52.0
0.50.7
35
Carbon steel
4060
19
10-10-2015
Magnesium,
Iron
and
bicarbonate
and
20
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21
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22
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reactive
silica
at
high
23
10-10-2015
MS
Economizer
BW
FW
ms
mw
24
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25
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Managing Silica
ms
mw
MS
FW
Managing Silica
SiO22 in steam in ppm
Pressure in bar
26
10-10-2015
Managing Silica
EPRI recommended Guideline for Boiler Water
Managing Silica
EPRI recommended Guideline for steam
27
10-10-2015
Managing Silica
ms
mw
MS
FW
Managing Silica
GEN
HP
IP
LP
APH
HRH
SH1
SH2
Down comer
Condenser
Economizer
HP Heater
Deaerator
LP Heater
CRH
28
10-10-2015
Managing Silica
Silica Control:
Clariflocculator
Strong Based Anion
Mix Bed
Ultra Filtration
Reverse Osmosis
Drum Separator
Unwanted intrusion
Managing Silica
Membrane treatment can remove virtually all
colloidal silica. Both reverse osmosis and ultrafiltration are effective in this respect. Reverse
osmosis offers the additional advantage of
significant reduction (98%+) of reactive silica as
well.
29
10-10-2015
Managing Silica
Checking of Drum
mechanical carry over
Separators
to
avoid
Managing Silica
Unwanted intrusion
GEN
CR
H
HR
H
SH1
IP
LP
AP
H
SH2
Down
comer
Condens
er
Economi
zer
HP
Heater
Deaerator
LP
Heater
H
P
Boiler Feed
Pump
Cond. Extraction
Pump
30
10-10-2015
Managing Silica
150 MW unit, silica went sky high during
commissioning
Date : 03.8.11 To 19.08.11 (Day Average data)
Boiler Feed water
Boiler Drum
Main Steam
Condensate Water
Date
pH
Silica
Iron
pH
Control Limits
8.8-9.5
Unit
< 0.02
0.01
9.4-9.7
ppm
ppm
03.08.11
9.43
0.21
0.16
05.08.11
9.43
0.24
07.08.11
9.39
08.08.11
Cond
Silica
< 80
Iron
Po4
pH
Silica
Iron
pH
Silica
Iron
Boiler Pr.
Load
< 0.5
5 to 10
8.8-9.5
< 0.02
< 0.02
8.8-9.5
< 0.02
mS/cm
ppm
ppm
ppm
ppm
ppm
ppm
ppm
Kg/Cm2
MW
9.68
31
3.44
0.03
2.6
9.52
0.08
0.02
9.44
0.10
0.14
0.13
9.55
32
4.41
0.05
2.1
9.44
0.07
0.01
9.50
0.13
0.08
0.18
0.11
9.51
32
2.96
0.04
3.3
9.33
0.06
0.02
9.38
0.13
0.09
9.45
0.19
0.09
9.69
31
2.88
0.07
3.1
9.46
0.04
0.02
9.39
0.11
0.09
10.08.11
9.46
0.17
0.09
9.62
34
2.08
0.07
4.6
9.39
0.06
0.03
9.38
0.10
0.13
15.08.11
9.40
0.12
0.10
9.66
34
1.89
0.09
5.4
9.45
0.06
0.05
9.39
0.08
0.09
16.08.11
9.44
0.09
0.07
9.68
40
1.83
0.03
5.7
9.46
0.04
0.02
9.48
0.05
0.05
17.08.11
9.54
0.08
0.04
9.70
42
1.45
0.03
4.4
9.53
0.04
0.02
9.54
0.04
0.04
112
107
18.08.11
9.43
0.08
0.07
9.62
38
1.97
0.04
5.0
9.45
0.05
0.01
9.49
0.05
0.05
109
75
19.08.11
9.41
0.06
0.03
9.64
34
0.95
0.02
6.0
9.42
0.03
0.01
9.43
0.03
0.02
139
97
Average
9.44
0.14
0.09
9.64
35
2.39
0.05
4.2
9.44
0.05
0.02
9.44
0.08
0.08
120
93
Managing Silica
Mine water was being used
Treatment :
RO
DM
MB
DM water analysis
S.No
Description
Unit
Design value
Actual value
RO water
ppm
<3
< 0.4
MB outlet
ppm
< 0.02
< 0.02
Condensate
ppm
< 0.02
0.04
31
10-10-2015
Managing Silica
strongly advise against operating with lower drum level
as mechanical Silica carry over is not indicative. It also
doesn't appear to be Colloidal Silica Problem, but rather
physical Silica intrusion from some point, so don't go for
that test immediately. First rule out silica intrusion from LP
dozing / HP dozing, Deaerator and CST. better clean all of
them. Covering the area is a good idea
C
R
H
H
R
H
S
H1
I
P
GE
N
L
P
AP
H
S
H2
Down
comer
Econ
omiz
er
HP
Heate
r
Deaerato
r
LP
Heat
Cond
er
ense
r
H
P
Boiler Feed
Pump
Cond.
Extraction
Pump
Managing Silica
A gunny bag was found in Deaerator storage tank
CONCLUSION:
Mass can not be created, neither can it be destroyed
32
10-10-2015
Corrosion
Mainly due to Dissolved Oxygen
Corrosion
Oxidation of Fe in Boiler water:
Fe + O2 + H2O Fe(OH)2
4Fe2 + 3O2 + 6H2O 2Fe2O3 6H2O
3Fe + 4H2O = Fe3O4 + 4H2
Magnetite
33
10-10-2015
Corrosion
Formation of Magnetite:
N2H4 + 6Fe2O3 4Fe3O4 + N2 + 2H2O
When carbon steel is exposed to oxygen-free
water, the following reaction occurs:
Fe + 2H2O Fe2+ + 2OH- +H2 Fe(OH)2 + H2 (1)
This reaction is then followed by the Schikorr
reaction where precipitated ferrous hydroxide
is converted into magnetite:
3Fe(OH)2 Fe3O4 + 2H2O + H2 (2)
34
10-10-2015
Galvanic Corrosion:
Anode:
Fe Fe2+ + 2e
Cathode:
O2 + H2O + 2e 2OH
Overall:
Fe + O2 + H2O Fe(OH)2
35
10-10-2015
Galvanic Corrosion:
It occurs when a metal or alloy is
electrically coupled to a different metal or
alloy while being immersed in an
electrolyte
Anything that results in a difference in
electrical potential at discrete surface
locations can cause a galvanic reaction,
such as:
scratches in a metal surface
differential stresses in a metal
differences in temperature
conductive deposits
Effect of Temperature:
Influence of temperature on carbon steel
corrosion in water including dissolved oxygen
36
10-10-2015
Effect of pH:
Anode:
2Fe (solid) 2Fe2+ (aq) + 4e-
Cathode:
O2 (gas) + 4H+ (aq) + 4e- 2H2O
(liquid)
Further oxidation of
Fe2+(aq) ions at Anode:
4Fe2+(aq) + 3O2 (gas) + 6H2O
(liquid) 2Fe2O3 .6H2O (solid)
pH
The pH indicates the concentration of hydrogen ion in an
aqueous solution and is used as an index showing the
acidity or alkalinity of water.
Water only slightly dissociates into hydrogen ion (H+) and
hydroxide ion (OH); H2O H+ + OH
The ion product of water is a constant and it is 1 X 1014 at
25C; [H+] x [OH] = 1 X 1014
The pH is calculated from the H+ concentration by using the
equation; pH = log 1/[H+] = - log [H+]
In case of pH 7, [H+] and [OH] are equal at 1 X 107 and
this water is said to be neutral.
37
10-10-2015
Effect of pH:
The corrosion rate of carbon steel at high
temperature is minimized in the pH range of 11
to 12 as shown in Figure below.
Effect of pH:
The corrosion rate of copper is low in the
condensate of the pH 6 to 9 as shown in Figure
below.
38
10-10-2015
Alkalinity
The three basic sources of alkalinity in water are: alkalinity
resulting from
the bicarbonate ion (HCO3-),
the carbonate ion (CO32-), and
the hydroxyl ion (OH-).
HCO3-
Heat
Alkalinity
"P" alkalinity: It is the measure half of the carbonate ion (CO32-)
and Hydroxyl ion content and is expressed in ppm of calcium
carbonate.
M" alkalinity: It is the measure of carbonate ion content,
bicarbonate ion (HCO3-) and hydroxide content.
1. At the P endpoint, all OH and 1/2CO3
would be reacted.
2. At the M endpoint, all OH and all CO3
would be reacted, or,
P = 1/2CO3 + OH; 2P = CO3 + 2OH
M = CO3 + OH + HCO3
When HCO3 is absent;
Subtracting, 2P M = OH
and
CO3 = (M OH) = [M (2P M)]
= 2 (M P)
Neutralization of alkaline water with H2SO4
(assume 50 ppm M alkalinity)
39
10-10-2015
Alkalinity
EXAMPLE :
If P = 86 ppm as CaCO3, and if M = 118 ppm as CaCO3
Then, situation 2 exists (P > M)
Hydroxyl = 2P - M = (2 x 86) - 118 = 54 ppm as CaCO3
Carbonate = 2(M - P) = 2 x (118 - 86) = 64 ppm as CaCO3
Bicarbonate = 118 54 64 = 0 ppm as CaCO3
40
10-10-2015
Porous Oxide
Protective
Protective
Oxide Oxide
Fe3O4
41
10-10-2015
Case study:
30 MW BFB Boiler
Location: Bed Coil Tubes
Size & Spec : 51 x 6.35 mm & SA 210
Gr.A1
Bed Temperature: 905C
Service: less than 1 year
84
42
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Tube Location
BFB Boiler
85
Failed Tube
43
10-10-2015
Failed Tube
Failed Tube
44
10-10-2015
89
Acid Attack:
45
10-10-2015
FeCl2 + H2
Embrittlement
92
46
10-10-2015
47
10-10-2015
Case Study:
120 MW Oil Fired Boiler
Location: Goose Neck Rear Water Wall
Size : 76.1 x 5.5 mm
Specification: SA210 GR A1
Working Temp. & Pressure: 350C & 90
kg/cm
Service: 250000 Hrs
96
48
10-10-2015
Outside Diameter
0-180 90-270
78.73
0
4.08
3.97
Thickness
90 180
6.12
5.60 5.78
270
5.67
49
10-10-2015
99
Opposite
the failed
region, the
On a ring to
section
a littleaway
from the failed
microstructure
of is
polygonal
grains
region,
a similarconsists
structure
observed
of ferrite and pearlite
100
50
10-10-2015
Conclusion:
Several oxide filled discontinuous cracks are
observed on the ID surface of the tube. The
flattening test result indicates hydrogen
embrittlement.
The failure of the tube is attributed to
hydrogen embritlement.
101
Case 1:
120 MW Oil Fired Boiler
Location: LHS Water Wall
Size : 76.1 x 5.5 mm
Specification: SA210 GR A1
Working Temp. & Pressure: 350C & 90
kg/cm
Service: 254378 Hrs
102
51
10-10-2015
103
104
52
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105
106
53
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107
108
54
10-10-2015
109
Conclusion:
Micro examination reveals presence of
copper coloured copper rich phase on the ID
surface and blister edges of the tube. Also
damage due to Hydrogen embrittlement is
observed in the PM, weld and HAZ regions of
the weld joint.
The blisters observed on the OD surface is
attributed to waterside corrosion may be
due to condenser leakage.
The circumferential crack observed near the
fusion line of the butt joint is attributed
Hydrogen embrittlement caused by
waterside corrosion.
Swab analysis shows presence of some
chloride and sulphur with a pH value of 7.8.
110
55
10-10-2015
CAUSTIC EMBRITTLEMENT
REASON
For caustic embrittlement to occur, three
conditions must exist:
The boiler metal must have a high level of
stress
A mechanism for the concentration of
boiler water must be present
The boiler water must have embrittlementproducing characteristics
CAUSTIC EMBRITTLEMENT
Fine cracks adjacent
and parallel to the weld
joint can be seen on a
Super heater tube.
Surface branching of
the crack is apparent
56
10-10-2015
CAUSTIC EMBRITTLEMENT
Micro-structural examinations
revealed branched cracks running
across the grains (trans-granular)
and originating on the internal
surface. The cracks are located in
the heat-affected zone immediately
adjacent to the weld.
CAUSTIC EMBRITTLEMENT
REMEDIAL ACTION
Proper stress relieving of all welded or
rolled section
Application of a coordinated pH/phosphate
control
57
10-10-2015
Carry Over
58
10-10-2015
Water treatment
59
10-10-2015
Water treatment
Pre treatment
Demineralization
Deaeration
Chemical conditioning
Pre-treatment:
Effective Biocide
60
10-10-2015
Pre-treatment
Clariflocculator:
Clarification
Coagulating agent added
Alum [Al2(SO4)3] and Hydrated Lime [Ca(OH)2]
solutions
Polyelectrolyte solutions (PAC)
Lime precipitates and forms sludge:
Ca ( OH )2 + Ca ( HCO3 )2 2CaCO3 + 2H2O
Ca ( OH )2 + MgCO3 Mg( OH )2 + 2CaCO3
61
10-10-2015
Polyelectrolyte
These are polymers with ionizable groups that can
dissociate in solution, leaving ions of one sign bound
to the chain and counter-ions in solution. They are
soluble in water and help to coagulate.
62
10-10-2015
63
10-10-2015
Pressure Filters
Chlorination:
Cl2 + H20 HOCl + H+ + Cl-
Effective Biocide
De-Chlorination:
Na2S2O3 + Cl2 + H2O Na2S04 + S + 2HCl
Na2S2O3 + HCl NaCl + H2O + S + SO2
64
10-10-2015
Demineralization:
Ion exchange
Membrane desalination (RO)
Thermal desalination
65
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66
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R+OH-
67
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68
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69
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70
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71
10-10-2015
Membrane
Osmosis):
Desalination
Process
(Reverse
Membrane
Osmosis):
Desalination
Process
(Reverse
Membrane Material:
Cellulose Acetate
Polyamide
Nylon
72
10-10-2015
Membrane
Osmosis):
Desalination
Process
(Reverse
Example:Pressure:
Osmotic
-3;
A simple equation
Concentration
in solution
relates =
osmotic
100 kg.m
pressure
to
concentration:
T
= 300 K; for a
P compound
= C x R xwith
T A molecular weight
Where,
of
0.050 kg.mol-1
P is=osmotic
C
100/ 0.05
pressure
= 2000,
in Pa,
5 Pa =-350 bar
C=is2000
P
difference
x 8.3143
in concentration
x 300 = 50 x in
10mol.m
[mol.m-3 = concentration in kg.m-3/ mol. Weight in
kg.mol-3]
R is constant of an ideal gas = 8.314 (J/mol.K),
Membrane
Osmosis):
Desalination
Process
(Reverse
73
10-10-2015
Membrane
Osmosis):
Desalination
Process
(Reverse
74
10-10-2015
Deaeration:
at 10C, the solubility of principal gases under
a pressure of pure gas equal to 102 kPa
Gas
Solubility
mg.l-1
N2
23.2
O2
54.3
CO2
2318
CH4
32.5
75
10-10-2015
Deaeration:
Dissolved
oxygen
is
removed
by
thermomechanical action.
Temperature is raised with
steam
to
lower
the
solubility of gas and trays
are used to atomize the
water
Oxygen removal up to
0.007 ppm
Temperature
0 solubility at saturation temperature
Partial pressure of Oxygen on water surface
PT
LT
TE
152
76
10-10-2015
Chemical conditioning
Oxygen scavengers:
Sodium sulfite: It reacts readily with oxygen,
particularly at elevated pH and temperature, to
form sodium sulfate
2 Na2SO3 + O2 2 Na2SO4
The use of sodium sulfite should be avoided in
high pressure boilers because of its potential for
thermal decomposition
2 Na2SO3 + H2O + Heat 2NaOH + SO2
77
10-10-2015
Alternative of Hydrazine:
Carbohydrazide:
[1.4 : 1]
H6N4CO + 2O2 CO2 + 2N2 + 3H2O
Methylethylketoxime, or MEKO:
[11 : 1]
2 H3C(C=N-OH) CH2CH3 + O2 2 H3C (C=O) CH2 CH2 + N2O + H2O
Hydroquinone:
[6.9 : 1]
HO CH6 OH + O2 H2O + O=(double bond) CH6=O
Diethylhydroxylamine, or DEHA :
[1.3 - 3 : 1]
4 (CH3CH2)2 NOH + 9O2 8 CH3 COOH + 2 N2 + 14 H20
78
10-10-2015
pH correction
pH correction
Volatile pH booster chemicals:
79
10-10-2015
pH correction
When non-condensed gases, such as ammonia
and oxygen, are contained in the steam, they are
highly concentrated near the air ejector and copper is
attacked by the following reactions:
+ 2H2O
80
10-10-2015
HP Economizer drain
tube
Feed Pipe
Feed Pipe
162
81
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163
164
82
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165
83
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84
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85
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Formation of Magnetite:
When carbon steel is exposed to oxygen-free
water, the following reaction occurs:
Fe + 2H2O Fe2+ + 2OH- +H2 Fe(OH)2 + H2 (1)
This reaction is then followed by the Schikorr
reaction where precipitated ferrous hydroxide is
converted into magnetite:
3Fe(OH)2 Fe3O4 + 2H2O + H2 (2)
86
10-10-2015
Dissolution of Magnetite
87
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Effect of pH on FAC
88
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178
89
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179
90
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91
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92
10-10-2015
OT (Oxygenated Treatment)
The requirements for OT:
Cation conductivity of less than 0.15 S/cm
Addition of oxygen to the feed water
93
10-10-2015
187
Case 1:
120 MW Oil Fired Boiler
Location: Primary SH Coil
Size : 57.15 x 4.2 mm
Working Temp. & Pressure: 510C & 85
kg/cm
Service: 243000 Hrs
188
94
10-10-2015
Outside Diameter
0-180
90-270
Thickness
90
180
270
-59.21
-61.81
3.03
3.35
-3.68
4.27
-3.93 3.82
190
95
10-10-2015
191
192
96
10-10-2015
Conclusion:
Micro examination indicates several rounded
pits filled with oxides on the ID surface of
the tube.
The failure is attributed to waterside
corrosion.
193
97
10-10-2015
195
196
98
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197
99
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100