BOILER WATER CHEMISTRY –

CASE STUDIES

Dr. Pradeep Jain,

GM (NETRA)

14th SEPT. 2013

 CORROSION MECHANISM
ANODIC REACTION
Fe = Fe+2 + 2e-
Fe+2 + 2OH- = Fe(OH)2
Fe(OH)2 + H2O + 1/2 O2 = Fe(OH)3
Fe(OH)3 = Fe2O3.H2O + 2H2O
CATHODIC REACTION
2 H+ + 2e- = H° + H° = H2
4 H+ + O2 + 4e- = 4 OH-
O2 + 2H2O + 4e- = 4 OH-
 FOUR POSSIBLE CHOICES FOR DRUM TYPE
BOILER WATER TREATMENT
TREATMENT OT AVT PC CT
PC (L) PC (H)
PARAMETER
Feed water & steam cation - 0.15 0.2 0.2 0.3 0.3
conductivity, uS/cm

Steam, Na, Cl,SO4 ppb 2 2 2 3 2

Boiler water , Cation 1.5 1.5 10 25 9

175 Kg/cm2 Conductivity
0.18% uS/cm
mechanical Cl, ppb 50 50 150 600 300
carryover
SO4 ppb 100 100 300 1200 600
SiO2 ppb 180 180 180 180 180
S.N PARAMETER AVT(R) AVT (R) All AVT (O) OT ( All
(Mixed Ferrous) (All Ferrous)
Met) Ferrous)
1 pH at Eco Inlet 9.0-9.3 9.2-9.6 9.2-9.6 9.0-9.4
(drum)
8.0-8.5 (once
through)
2 Cation Conductivity <0.2 <0.2 <0.2 <0.15
(uS/cm) at Eco inlet
3 O2 (ppb) at Eco inlet <5 (<2) <5 (<2) <10 30-50 (drum)
30-150 (once
through)
4 O2 (ppb) at CEP <10 <10 <10 <10
Discharge
5 ORP a Deaerator inlet, -300 to -300 to Oxidizing +100 to + 150
mV -350 -350
6 Fe (ppb) at Eco inlet <5 <2 <2 (<1) <2 (<0.5)
7 Cu (ppb) at Eco inlet <2 --- ---- ---

•The Figures in ( ) indicate achievable values

•For units smaller than 200 MW, the limit for cation conductivity will be
<0.3 uS/cm
•The limit of cation conductivity will also depend on type of boiler water
treatment i.e. PC(L), PC(H) or CT ( Refer EPRI)
Core Monitoring Parameters for All Units Operating
on Phosphate Treatments for AVT (O) Feed water
(Drum units without a reducing agent and with an all-ferrous feed
water system)

Cation conductivity- CEP-Discharge, CP O/L or ECO I/L,

RH (or MS), Blow down

Specific conductivity- Make up, Blowdown

pH-Boiler Blow down

Dissolved oxygen- CEP-Discharge, ECO I/L

Sodium- CEP-Discharge, CP O/L or ECO I/L, RH (or MS), Blow down

Phosphate - Blow down

Refer EPRI Technical report: 1004188, Cycle chemistry guidelines for fossil
plants- Phosphate Continuum and Caustic Treatment, Jan-2004.
Core Monitoring Parameters for All Units Operating
on Phosphate Treatments in AVT (R) feed water
(Drum units with a reducing agent and with mixed
metallurgy in feed water system)

Cation conductivity - CEP-Discharge, CP O/L or ECO I/L, RH

(or MS), Blow down
Specific conductivity- Make up, Blow down
pH-Boiler Blow down
Dissolved oxygen- CEP-Discharge, ECO I/L
Sodium- CEP-Discharge, CP O/L or ECO I/L, RH (or MS),
Blow down
Phosphate - Blow down
ORP - Deaerator I/L
Refer EPRI Technical report: 1004188, Cycle chemistry guidelines for fossil
plants- Phosphate Treatment, Jan-2004.
Potential - pH diagram for carbon
steel at 350°C and 165 kg/cm2
Black, thin internal magnetite protective layer
Internal deposit layer showing cracks
helps in wick boiling phenomena
 Factors influencing deposit in tubes
• Number of startups / shutdown
• Ingress of raw water from Condenser
leakages or seepages.
• Change in Feed / makeup water quality
• Crud formation due to corrosion at LP side
and transfer to the Boiler.
• Boiler water chemistry deviations
• Preservation of boilers during idle period
• Boiler cycle metallurgy
Values of Thermal Conductivities
Material W/m°C at Room temp.
Air 0.024
Carbon Steel 45
Boiler Scale 2.32
Cu-Ni 70:30 30
Cu-Ni 70:10 44
Copper 90
Titanium 16
Aluminium 0.04
Stainless steel 15
Steam 0.038
Red Brick 0.81-0.7
Water 0.55
Overheating of tube due to internal
oxide/deposition
 Increase in metal temperature due
to internal scale
T T
E H
M I
P C
E K
R N
A E
T S
U S
R
E

HEAT FLUX KW/m2

Mechanism of local concentration in Water wall
tubes due to under deposit corrosion and tube
thickness reduction by Wick Boiling
Pitting Corrosion in Water wall tubes
with deposition
 Porous and crack oxide layer on the
internal surface of tube with Cu particles
 Swelling in Water wall tubes due to under
deposit corrosion and tube thickness reduction
 Reasons of boiler tube failure
• Formation of internal oxides / deposits
in boiler tubes which is responsible for
• Overheating
• Localised formation of acidic / alkaline
condition due to ingress of raw water from
condenser. (Hydrogen damage / Caustic
gouging)
• Combined effect of both Overheating and
Corrosion
• Steam blanketing in upstream of welding
 Hydrogen Damage
• Bulk boiler water pH remains alkaline.
• Acidic condition generated on tube surface
beneath the deposits. Presence of chloride was
confirmed
• Acidic condition develops due to presence of
hydrolysable chloride concentrated by wick boiling
phenomena.
• Hydrogen generated due to localised corrosion
enters tube metal and forms methane with carbon.
• Fissures were generated in the tubes which
combines and failure due to hydrogen damage
takes place.
Hydrogen damage mechanism
H+ + Cl- = HCl
HCl + Fe2O3 = FeCl2 +
FeCl3
Fe + 2 HCl = FeCl2
H+ + e- = H°
(Atomic Hydrogen)

H° + Fe3C = Fe + CH4
Cementite (Methane gas)

Methane gas forms fissures on

grain boundary and form inter
granular cracks which when
joins, the tube fail.
 Cracks develop in water wall
tube due to hydrogen damage
 Vallur, Unit no.1
•#1 Synchronised on 09/03/12 and COD on
29/11/12
•Sea water use as cooling water for condenser.
Condenser tubes made of Titanium.
•Till date Unit does not have Express lab, SWAS , on
line analyzers and CPU which are critical
requirement especially for a unit using sea water as
coolant.
•Condenser tube leakages, Three times (1st
19/12/12, 2nd 23/01/13 and 3rd 01/08/13 ) and
due to non availability of CPU , in each leakage
with the unit on bar boiler Chloride varied from 565
to 1900 ppm, where as limit is 0.1 ppm
Vallur Unit#1 Date Received: 25‐04‐2013

S.no Site ref/R&D Sample details

1 4827 Water wall tube – Corner 3 CD elevation 30m

Microstructure and 
SEM micrograph 
showed micro 
fissures on the 
Micro fissures fracture surface 
(etched)

Water wall tube failure occurred due to hydrogen damage.
 Vallur, Unit no.1
•Repeat failure in water wall near CD elevation

•1st failure : March - 2013

•2nd failure : 24/08/13
•3rd failure : 01/09/13

•Representatives of OS-Boiler /Chemistry/ NETRA

and Site have jointly examined the matter in the
first week of September-2013 and the observation
are as follows :

•Frequent tripping and startup of the unit.

•Avg. DM Consumption is 2.5 % against design

value of 0.5%. Major cause of high Dissolved
Oxygen
 Vallur, Unit no.1

•#1 Synchronised on 09/03/12 and COD on

29/11/12
•Sea water use as cooling water for condenser.
Condenser tubes made of Titanium.
•Till date Unit does not have Express lab, SWAS , on
line analyzers and CPU which are critical
requirement especially for a unit using sea water as
coolant.
•Condenser tube leakages, Three times (1st
19/12/12, 2nd 23/01/13 and 3rd 01/08/13 ) and
due to non availability of CPU , in each leakage
with the unit on bar boiler Chloride varied from 565
to 1900 ppm, where as limit is 0.1 ppm
 Vallur, Unit no.1, Recommendations

• Reason of failure of Condenser tube of this unit

needs to be established.
• Operational guidelines on handling of units during
condenser tube leakage for sea water cooled units
issued by COS shall be followed.
• SWAS and CPU commissioning is to be expedite.
• Steam-water Chemical parameters as per OEM
recommendation needs to be maintained
• In- situ Hydrogen embrittlement and thickness
survey and internal deposits of water walls of #1 to
be carried out to decide further course of action.
 APCPL – Jhajjar- #1
Sl Sample Date of Photograph of the samples
N description failure
1 WW tube LHS, tube 7.5.12
no 108 – failed tube
(elevation-26M)
2 WW tube LHS, tube 11.11.12
no 108 – failed tube
(elevation-28M)
3 WW tube LHS, tube 11.11.12
no 109 – failed tube
(elevation-28M)

4 Front WW, Tube-131 15.11.12

(Elevation 35m)

5 Front WW, Tube-148 15.11.12

(Elevation 35m)

6 Rear WW, Tube-84 17.11.12 NOT RECEIVED

(Elevation 41m)
 Visual Observations
S. Sample Dimension Observations
description
1 WW tube LHS, Nominal 51X6mm Longitudinal ruptured opening (~130mm)
tube no 108 – At rupture Bulging ~ 25%
failed tube thk:3.62mm Internal corrosion at failure edge
(elevation-26M)
2 WW tube LHS, Nominal, 51X6mm Longitudinal ruptured opening (~126mm)
tube no 108 – At rupture Bulging ~ 14%
failed tube thk:3.84mm Internal corrosion at failure edge
(elevation-28M)
3 WW tube LHS, Nominal, 51X6mm External denting marks
tube no 109 – No Bulging
Unfailed tube
(elevation-28M)
4 Front WW, Tube Nominal, 51X6mm Longitudinal ruptured opening (~121mm)
no-131 (Elevation At rupture thk:4.3mm Bulging ~ 5%
35m) Internal corrosion at failure edge

5 Front WW, Tube Nominal, 51X6mm Longitudinal ruptured opening (~117mm)

no-148 (Elevation At rupture Bulging ~ 8%
35m) thk:3.68mm Internal corrosion at failure edge
 APCPL – Jhajjar- #1
WW tube LHS, tube no 108 – failed tube
(elevation-28M)

Date of Failure: 11.11.2012

 4722
Observation failed sample (T-no:108)
Ruptured Internal Corrosion
tube

MICRO-FISSURES
due to hydrogen
damage
SEM & EDAX Analysis of tube no:108 4722

(28m elevation)
Element Weight
%
C 23.97
O 27.44
Na 1.81
Al 1.66
Si 3.42
S 1.41
Cl 2.43
K 1.99
Ca 2.45
Cr 5.58
Fe 22.68
 4722
Internal deposit study

Internal deposit
Hot side Cold side
133.8 16.64
mg/cm2 mg/cm2

Before & after cleaning

 4724
Crack origin from internal to external surface

Corrosion pits

Crack direction
Micro-fissures due
to hydrogen
damage

Magnification : 200X
 Macro & micro level features (Tube-148)
Ruptured
tube

Corrosion pits on
internal surface

Corrosion pits
on internal Micro-fissures due to
surface Hydrogen damage
 4722
Wet chemical analysis of Water Wall
tube deposit
 Investigations Summary
) Tubes failed with ruptured opening
) Micro-fissures were observed at failure edge.
) Gouging and internal corrosion was observed in
localized conditions.
) Deposit was showed presence of chloride and other
elements such as sodium, calcium etc. which show
propensity for corrosion pitting and cooling water ingress.

Cause of failure
Tube failed due to hydrogen damage. Under deposit
acidic conditions and high heat flux is responsible for
this type of failure.
 Remedial measures Suggested
1. Water wall tubes should be inspected
thoroughly for tube thickness reduction &
corrosion mapping at high heat flux area.
2. Severely damaged tubing must be replaced.
3. Internal deposit buildup must be removed by
chemical cleaning to prevent further
pitting/corrosion.
4. Meantime, operate the boiler at low pressure
5. Maintain the boiler water chemistry
parameters to reduce further corrosion.
 Waterwall tubes deposit quantitative 
analysis ‐ December‐2012
Sl.N Sample  Hot side  cold side Description
o No (mg/cm2) (mg/cm2)
1 4764 19.0 15.2 Front wall corner 1 side – F1
2 4765 17.0 13.8 Front wall center ‐ FC
3 4766 20.7 10.8 Front wall corner 4 side – F4
4 4767 19.6 14.4 Left wall corner 1 side – L1
5 4768 24.2 15.5 Left wall center ‐ LC
6 4769 24.2 17.4 Left wall corner 2 side – L2
7 4770 26.2 16.0 Rear wall corner 2 side – B2
8 4771 39.5 11.9 Rear wall center ‐ BC
9 4772 17.9 13.4 Rear wall corner 3 side – B3
10 4773 16.6 15.0 Right wall corner 3 side – R3
11 4774 22.1 18.7 Right wall center ‐ RC
12 4775 20.85 13.5 Right wall corner 4 side ‐ R4
200X
 APCPL – Jhajjar- #1

• On the basis of results of internal deposits,

Post operational chemical cleaning of boiler is
carried out in the month of May-2013

• Corrosion mapping is performed after

chemical cleaning and approx. 78 numbers of
waterwall tubes removed which are having the
thickness reduction more than 20% level.
 Ramagundam Unit#3 Date Received: 26‐04‐2013
S.no Site ref/R&D Sample details
1 4829 (16 tubes) Water wall tubes above burner location

Microstructure showed degraded
Structure (Hardness: 122‐124 HV)

Water wall tubes showed tube 
failure due to prolonged over 
heating.
This boiler was chemically cleaned in 
Microstructure showed thick  July‐2000 and August‐2008
internal oxide
Analysed in Nov. 2012, Deposit Qty. is >40mg/cm2 in 8 tubes out of 15
tubes. Post operational chemical cleaning carried out in last in Aug-
2008. Suggested chemical cleaning of boiler.
 Ramagundam # 3 
TUBE  1
COLD SIDE 13.5

TUBE 
HOT SIDE 52.7

ddj
ffff
7d
77

11
01
11.6

12.1
79.2
72.8

4
3

71.9 HOT SIDE
TUBE

18.7 COLD SIDE

TUBE
2

Analyzed in June 2013, Deposit Qty. > 40mg/cm2 as per BIS

10391. Recommend Single stage chemical cleaning . This boiler
was Chemically Cleaned in August 2008.
 Kahalgaon Unit#3 Date Received: 14‐03‐2013
S.no Ref/R&D Sample details Dimensions
1 4798/ Water wall tube no: T-47 60 X 6 mm
U#3Khs-09 from rear (35mtr, elevation, (Mat.-SA 210 Gr A1)
15mtr above burner, RHS)

Cross section
Thickness of the deposit 
was ~6.25mm at one end.

Requsted site to send 
atleast 12 numbers of tubes 
for deposit Qty. analysis.

Under deposit corrosion lead to the rupture and failure of the tube. Adjacent 
tubes in this region may be inspected for internal deposits.
 NSPCL Rourkela Unit#2 Date Received: 27‐06‐2013
S.no Site ref/R&D Sample details Dimensions
1 4874 Water wall tube 57 X 5 mm (Mat.-SA 210 Gr A1)

Cross section
1.0‐1.5 mm thick deposit was 
observed on the internal surface 

Failure may be attributed to Prolonged Overheating
Failed waterwall tubes – S panel #7,
vindhyachal – March-2013
 Vindhyachal - #7
• Failure of WW takes place on 1st March 2013 in
Front waterwall tubes.
• All the waterwall tubes are having the orifices
fitted in the opening of W/W tubes from bottom
ring header
• Deposition in front side header orifices are more
compare to other sides tube orifices. Almost
30% tube orifices of front ring headers are
having deposition.
• Possible reason of water wall tubes failure may
be reduction of water flow due to partial
chocking of orifices.
 Vindhyachal - #7
• Thinning of stubs of economiser inlet header
and deposits on orifice of Bottom header
Boiler Unit No 7 of Vindhyachal.
• A team of OS-Boiler/Chemistry and NETRA
visited site in the month of Sept.-2013
• thinning of stubs of economiser inlet header
and deposits on orifice of Boiler Bottom
header.
• Replacement of 70 stubs of economiser inlet
header due to flow accelerated corrosion.
 Vindhyachal - #7
• UNIT -7 was declared commercial on Jan-2000.

• Chemical treatment used was as per OEM

guidelines in AVT ( R) in feed water with
phosphate dosing in Boiler drum.

• Problem of Phosphate hide out and carryover

was observed in unit-7 since very beginning
and therefore phosphate dosing stopped in the
year 2006.
 Vindhyachal - #7 parameters as per OEM
PARAMETER Feed Boiler Condensate Super Heated
Water Water Steam
pH at 25 oC 9.0- 9.2 9.1 – 9.7 9.0- 9.2 9.0 – 9.2
Cation conductivity 0.2 - 0.2 0.2
(µs/cm)
Specific conductivity 15
(µs/cm)
Dissolved Oxygen 5 40
(µg/l)
Silica (µg/l) 10 100 10 10
Phosphate (mg/l) 1-2
Chloride (mg/l) 500
Residual Hydrazine 10-20
(µg/l)
Total Iron Max(µg/l) 10 10 10
Ammonia (mg/l) 1.0 1.0
Sodium (µg/l) 5
 Vindhyachal - #7

•In the year 2004, after interaction with EPRI, all

units with all ferrous feed water metallurgy were
suggested to be converted to AVT (O) mode of
Cycle Chemistry regime from existing practice of
using hydrazine dosing at BFP suction as per OEM
guidelines

•The feed water treatment for Unit-7 of Vindhyachal

was changed to AVT (O)
i.e., no hydrazine dosing, in August-2006.
 Vindhyachal - #7 parameters as per EPRI
PARAMETER LIMIT
pH at Eco inlet at 25 oC 9.2- 9.6
Cation conductivity (µs/cm) < 0.2
at Eco inlet
Cation conductivity (µs/cm) < 1.5
Boiler drum sample
Dissolved Oxygen at Eco inlet < 10
(µg/l)
Dissolved Oxygen at CEP discharge (µg/l) <10
ORP at deaerator inlet (mV) Oxidising
Silica (µg/l) 10
Phosphate (mg/l) Nil
Chloride (mg/l) 50 at 175 kg/cm2 drum
pressure
Total Iron Max <2 (<1)
(µg/l)
Total Copper Max (µg/l) --
Sodium , Chloride & Sulphate (µg/l) Steam 2
 Vindhyachal - #7 - Observations

• Dissolved oxygen level in condensate is in the range of 12

ppb to 42 ppb (high) against the limit of 10 ppb.

• Chloride level in the drum water is in range of 60-70 ppb

(high). The boiler water chloride limit under AVT regime is
35 ppb at normal operating drum pressure.

• One CPU vessel is in service till Mar 2013 thereafter both

vessels are being operated. Average flow is 450 cubic meter
/ Hr per vessel with bypass valve open for remaining
condensate.
 Vindhyachal - #7
•Difference of pH values of Boiler Drum samples observed
in Laboratory and online instrument readings reflecting in
PI server reading.

• pH of whole system always maintained in lower band i.e.

9.2.

•Ammonia dosing is being done at BFP suction and CPU

outlet both valves found open leading to dosing at BFP
suction only.

•Calibration of SWAS instruments carried out as and when

required, no structured preventive schedule available.
 Vindhyachal - #7

•Feed water sample collected by team from units 8 ,9 and 10

are having very high Iron content 69 ppb, 52 ppb and 47 ppb
respectively against the prescribed limit of 2 ppb analysed in
NETRA

•On occasions Feed water flow has been maintained high to

an extent up to 110% of design flow of 1564 M3/hr. (Random
data enclosed from pi server).

• Present testing practices at station is incapable for

measurement of such low level of Iron in feed water.
 Vindhyachal - #7

CONCLUSION:
Pre Boiler Corrosion has led to high
Iron contents in feed water and
deposition of corrosion products on
orifices.

The pattern of thinning of stubs of

economizer inlet header has been
caused due to Flow Accelerated
Corrosion.
 Remedial Measures
• pH of whole system shall be maintained on upper side.

•Ammonia dosing shall be done at CPU discharge point only

and its quality shall be ensured.

•Dissolved Oxygen level in condensate shall be maintained

below the desired level of 10 ppb by improving Condenser
tightness.

•Chemical laboratory testing practices need to be

strengthened/ developed for measurement of low levels of
Iron in feed water.
 Remedial Measures
•Format of Daily report of Chemical Parameters (stage I, II &
III) shall be modified as per OD.

•Boiler Water Chloride level shall be brought down to levels

specified in OD.

•Feed Water flow should not exceed the design flow.

•Feed Water samples of Units 7, 8 ,9,& 10 shall be tested at

NETRA at monthly interval for one year.

•FAC prone areas to be examined in available opportunities.

 Vindhyachal - #7

Rely mostly on online SWAS parameters. Off line

parameters checked as and when required.

Calibration schedule of On line SWAS instruments shall be

maintained as per OS guidelines ( being sent in soft
copies).

Possibility to be explored for conversion to Oxygenated

Treatment.
 On-line thermal monitoring in waterwall tubes in
500 MW boiler Unit no.7, Vindhyachal
Hot side of furnace
T-1
Objectives:
1. Non-intrusive method Waterwall
2. Monitoring of Heat flux tubes
3. Monitoring of combustion T-5
4. Online internal scale T-2 T-3 Fins
deposit Monitoring Cold side of furnace
5. Reduction of tube failure
T-2, T-3, T-4, T-5,
6. Decision for post operational T-4
Thermocouples
chemical cleaning.

Heat Flux Heat

Status: Evaluation Flux
Lab. Scale studies. Programme
Waterwall tubes with deposit –Farakka
Time
Waterwall tubes without deposit -Dadri
Fabrication of test rig & experimentation

Principle:
Software develop on the basis of research
Work by scientist thro M.Tech. programme.
Validation in laboratory and at site
 Vindhyachal-Unit no.7
D e pos it Qty . m g/c m 2

50
40
30 Hot Side
20 Cold Side
10
0
UNIT-7, 10/06 UNIT-7, 07/09 UNIT-7, 03/11
Chemclean 08/09
Time - Month/Year
Thick and adherent deposit in water
wall tube and crack generated due
to hydrogen damage
Window opening due to Hydrogen
damage in Water wall tube
 Fissures and Cracks developed in
• the tube due to Hydrogen damage
 Fissures and Cracks developed in
the tube due to Hydrogen damage
•
 Fissures and Cracks developed in
the tube due to Hydrogen damage
•
 Fissures and Cracks developed in
the tube due to Hydrogen damage
•
 Remedial Measures
• Periodic Post operational acid cleaning of
boilers to remove the existing internal
oxide layer and formation of protective
magnetite layer.
• Control the ingress of impurities i.e.
cooling water through condenser, which
will reduce the phenomena of salt
concentration by “wick boiling”.
 Recommendations
• To control such failures, attempts have been
made in NTPC and worldwide to use condensate
polishing units (CPU)
• Maintain the boiler water chemistry parameters
suggested by manufacturers to reduce the internal
corrosion.
• Control of cooling water ingress from condenser.
• Follow the guidelines of Boiler preservation
during shutdown.
• Periodic chemical cleaning of water wall in
boilers.
• DM water washing of super heater tubes.
• maintain the parameters during startups and
shutdown of boiler.
THANK YOU
VERY MUCH
OXYGENATED BOILER WATER TERATMENT
– A CASE STUDY
ST-CMS ELECTRIC POWER COMPANY PVT. LTD –
NEYVELI
OEM – ABB – ALSTOM POWER
1X250 MW LFPP (LIGNITE FIRED),
ONCE THROUGH BOILER
PRESSURE - 170 BAR (SUB CRITICAL UNIT)
STEAM TEMP. – 536 °C
OXYGENATED BOILER WATER TREATMENT
OXYGENATED BOILER WATER TERATMENT
CONDENSER AND DEAERATOR ARE LIMITING THE
OXYGEN LEVELS IN CONDENSATE AND FEED
WATER
OXYGEN IS DOSED DOWNSTREAM CONDENSER
DURING COMBINED CONDITION OPERATION.
DEAERATOR VENT VALVE MUST BE CLOSED
DURING NORMAL OPERATION.
3X50% CONDENSATE POLISHING UNIT IS
INSTALLED FOR STARTUP CONDITION AND TIMES
OF INCREASED POLLUTION LEVEL.
 SHUTDOWN AS A RESULT OF SERIOUS CHEMISTRY
EXCURSION
In case of an increasing Cation conductivity due to
condenser tube leakage, makeup water
contamination etc. the following actions are to be
Cation cond.
(µS/cm) Action required
<0.15 Normal operating value
<0.2-<0.3 Increase system pH to AVT level (9.2-9.6)
>0.3 Stop oxygen feed, operate on AVT
without the use of N2H4
>2.0 for 5 minutes or
>5.0 for 2 minutes Stop firing
SCHEMATIC OF OXIDE GROWTH AND MORPHOLOGY
UNDER AVT IN REDUCING CONDITION

1 Fe = Fe2+ + 2e-
2H20 + 2 e- = 2 OH- + H2
2 Fe2+ + OH- = Fe(OH)+
2 Fe (OH)+ + 2H2O = 2 Fe(OH)2+ + H2
3 Fe(OH)+ + 2 Fe(OH)2+ + 3OH- = Fe3O4 + 4 H2O
 SCHEMATIC OF OXIDE GROWTH AND
MORPHOLOGY UNDER 0XIDISING AVT AND OT

Ferric iron species formation (example)

4 Fe 2+ + 02 + 2 H+ = 4 Fe3+ + 2 OH-
Fe (OH)+ + H2O = FeOOH + 2 H+ + e-
Fe3O4 + 2 H2 O = 3 FeOOH + H+ + e-
2 Fe2+ + 2 H2O + ½ O2 = Fe2O3 + 4 H+
2 Fe3O4 + H2O = 3 Fe2O3 + 2 H+ + 2e-
MAIN ADVANTAGES OF OXYGENATED BOILER
WATER TERATMENT
RELIABLE FORMATION OF PASSIVE LAYERS,
RESULTING IN A LOW PRESSURE DROPS
IRON CONTENT IN FEED WATER IS REDUCED
PRECIPITATION ON BOILER SURFACES IS KEPT
LOW
POST – OPERATIONAL ACID CLEANING IS
DRASTICALLY REDUCED
AMMONIA CONTENT IS LOW RESULTING IN
LONGER OPERATIONAL CYCLES FOR CPU & LOW
CHEMICAL CONSUMPTION
 SCHEMATIC COMPARISION AVT Vs OT IN
ONCE -THROUGH SYSYTEM
All Volatile Treatment (AVT)
• Ferrous or mixed feedwater train
• Cation conductivity 0.2-0.4 µS/cm
• pH 8.8-9.6 (Dependent on feedwater metallurgy

N2H2 (>3XO2)
Fe < 10 ppb NH3 ( 0.15-2.3 ppm
O2 ( < 5 ppb)

HP LP Condenser
Boiler BFP DA CP CEP
Heater Heater

Fe < 2 ppb O2 ( >30 ppb) O2 ( >30 ppb)

NH3 ( 20-70 ppb)
Oxygenated Treatment (OT)
• All ferrous feedwater train
• Cation conductivity <0.15 µS/cm
• pH 8.0-8.5
Black colour magnetite inside boile drum
Brown colour Haematite inside boile drum
LP Heater
Hot Well
Feed Water Tank
HP Heater
STARTUP, SHUTDOWN AND OPERATION GUIDELINES
FOR OT FOR LONG-TERM SHUTDOWN

Stop oxygen feed at least one hour before shutdown

Increase ammonia feed rate to achieve a pH > 9.0
Open Deaerator vents
LP & HP heaters should be vented
STARTUP, SHUTDOWN AND OPERATION GUIDELINES
FOR OT FOR SHORT - TERM SHUTDOWN

Stop oxygen feed at least one hour before shutdown

Open Deaerator vents
LP & HP heaters should be vented
Stop ammonia addition with unit shutdown
FEED WATER TOTAL IRON AND COPPER
CONCENTRATIONS DURING STARTUP
FOUR PREERQUISITE CONDITION FOR OT IN
ONCE-THROUGH AND DRUM

1. ALL-FERROUS FEEDWATER HEATER

METALLURGY (COPPER ALLOYS MAY BE
USED ONLY IN CONDENSER TUBING)
2. CATION CONDUCTIVITY <0.15 µS/cm IN
CONDENSATE, FEEDWATER AND STEAM
3. HYDRAZINE AND OTHER OXYGEN
SCAVANGERS ARE NOT USED

4. CONDENSATE POLISHING UNITS

OT REDUCES OR ELIMINATES MOST OF THE
TYPICAL AVT PROBLEMS
1. FLOW ACCELERATED COROSION
2. DEPOSITION OF FEEDWATER CORROSION
PRODUCTS
3. CORROSION PORDUCT TRANSPORT INTO THE
BOILER RESULTING IN ORIFICE FOULING,
BOILER DEPOSITS, OVERHEATING AND
FREQUENT TUBE CLEANING
4. TURBINE FOULING
5. COPPER ALLOY CONDENSER TUBE FAILURES
(WHEN OPERATING WITH OT AT REDUCED
AMMONIA LEVEL)
THANK YOU
VERY MUCH
 Caustic Gouging
• High degree of localised concentration is necessary
for caustic corrosion.
• Caustic generated due to decomposition of TSP
dosing in the boiler.
• Caustic reacts with the magnetite and forms
sodium ferrite (NaFeO2) and sodium Ferroate
(Na2FeO2).
• Ferroate / ferrite changes to magnetite and caustic
in the boiler. Loose magnetite settles in drum or
down comers.
• Carbon steel shows the gouging where as stainless
steel shows inter-granular or trans-granular
corrosion.
Internal and whitish deposit
formation due to caustic attack
Gouging and thickness reduction in
w/w tube adjacent to weld zone
Gouging and thickness reduction in
w/w tube near the weld zone after
chemical cleaning in laboratory
 Caustic gouging due to salt
concentration in water wall tube