OXYGENATED BOILER WATER CHEMISTRY
FOR SUPER CRITICAL BOILERS
Dr. Pradeep Jain,
GM (NETRA), NTPC Ltd.
pkjain@ntpc.co.in
15th June 2016
Boiler Water treatment
Drum Units Once through units
Phosphate treatment Oxygenated treatment
All volatile Treatment All volatile treatment
Caustic treatment
Oxygenated treatment
Boiler Water treatment
FAC PROBLEMS
All Ferrous systems: Boiler pressure drop due to WW
deposits of ripple magnetite deposits of once through
boiler units
Mixed metallurgy system: Copper deposits in HP turbines,
primary super heaters & HP heaters
All feed water systems: Boiler deposit, increased boiler
pressure drop, frequent need to chemical clean, Boiler
feed pump fouling and orifice fouling
Steam Water Analysis System
System Type of Measurement
ACC ACC, SP.COND,HYDRAZINE,
SILICA
MAIN STEAM pH, ACC, Na, SILICA,
SP.COND.
WATER SEPERATION
STORAGE TANK OF BOILER ACC
REHEATED STEAM ACC
CONDENSER COOLING pH, SP.COND.
WATER
Steam Water Analysis System
System Type of Measurement
MAKE UP DM WATER SP.COND, ACC
CEP DISCHARGE pH, ACC, Na, DO, SP.COND.
Condensate Polisher O/L pH, ACC, Na, Silica, Sp.Cond.
Deaerator Outlet DO
Feed Water at pH, ACC, COND, SP.COND.
Economiser Inlet HYDRAZINE,SILICA,
TURBIDITY
Water Analysis System
AVT OT
Treatment Chemical cost Treatment Chemicals cost
is high is low
Passivation of Ferrous Passivation of Ferrous
material over narrow pH materials over broad pH
range range
CPU efficiency is low CPU can operate in
higher efficiency
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
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 conductivity
(S/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
Metal A 1 Fe = Fe2+ + 2e-
2H2O + 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
B: Formed via transformation of individual Ferrite grains to magnetite
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 + 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 S/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 CP CEP Condenser
Boiler BFP DA
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 S/cm
pH 8.0-8.5
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 S/cm IN
CONDENSATE, FEEDWATER AND STEAM
3. HYDRAZINE AND OTHER OXYGEN
SCAVANGERS ARE NOT USED
4. CONDENSATE POLISHING UNITS
Black colour magnetite inside boiler drum
Brown colour Hematite inside boiler drum
LP Heater
Hot Well
Feed Water Tank
HP Heater
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 IN BOTTOM RING HEADER,
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
