WATER CHEMISTRY FOR SUB /

SUPER CRITICAL BOILERS

Dr. Pradeep Jain,

GM (NETRA), NTPC Ltd
pkjain@ntpc.co.in

15th June 2016

 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-
 ADVANTAGES OF AUSC BOILERS

Plant Type Steam Steam Efficiency CO2 Coal

with power Pressure Temp. (0C) (%) Emissions Consumption
rating (Kg/Cm2) (Kg/hr/MW) (MT/hr/MW)
Sub Critical 170 540 38 900 0.6469
Super 247 565-593 About 40 830 0.6138
Critical
Ultra Super 270 600 About 41 784 0.5892
Critical 41.5
Advanced 310 710-720 46 740 0.5459
Ultra Super
Critical
 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, ACC, 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, ECO I/L, RH (or MS), Blow

down

Specific conductivity- Make up, Boiler Blowdown

pH-Boiler Blow down

Dissolved oxygen- CEP-Discharge, ECO I/L

Sodium- CEP-Discharge, 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, 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, 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 350C and 165 kg/cm2
 Boiler water treatment by Tri sodium
phosphate in 200 / 500 MW boilers
Addition of TSP either by itself or in conjunction with
NaOH provide the pH necessary to minimise the
corrosion of carbon steel tubes.
TSP also provide the sufficient chemical buffering
capacity to cope with small system upset e.g. a small
condenser leaks.
Phosphate also has the ability to significantly curtail the
incidents of caustic embrittlement.
It is economical and easy to handle.
It requires a need to get tighter control.
Black, thin internal magnetite protective layer
Internal deposit layer showing cracks
helps in wick boiling phenomena
Porous internal deposit layer in
water wall tube
Non uniform thick internal deposit
layer in water wall tube
Whitish, thick, adherent internal
deposit in water wall tube
 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/mC 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
 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
Pitting Corrosion in Water wall tubes
with deposition
 Porous and crack oxide layer on the
internal surface of tube with Cu particles
 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
 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
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