WATER CHEMISTRY

ASPECTS FOR
SUPERCRITICAL UNIT


V Chandrasekharan
Sr. Manager
NTPC SIPAT
DETAILS

WATER TREATMENT
OT INTRODUCTION
BOILER ACID CLEANING
BOILER WATER PARAMETERS
LP & OXYGEN DOSING SYSTEM
ON LINE MONITORING
CHANGE OVER FROM ALKALINE
TREATMENT TO OT
WATER TREATMENT -
EXTERNAL
Depending on the source of water
1. Clarification
2. Filtration
3. Demineralization
4. DM With RO
Make up water quality at DM Outlet
Conductivity of > 0. 1 ms/cm
Silica - <10 ppb

FEED WATER TREATMENT


Type - A: AVT(R) ;using Ammonia and a
Reducing Agent (such as Hydrazine)

Type B: AVT (O); Similar to Type A minus
reducing agent

Type C : (OT); Oxygenated Treatment using
only ammonia and oxygen

SUPERCRITICAL DRUMLESS (ONCE THROUGH)
BOILER WITH OXYGENATED TREATMENT


THE KEY WORDS ARE



SUPERCRITICAL+DRUMLESS BOILER +OXYGENATED
TREATMENT



OT AN ALTERNATIVE
PROVIDES LONG TERM PROTECTION OF PRE
BOILER SYSTEM BY FORMING HAMETITE LAYER.
CPU OPERATING PERIOD WILL BE MORE DUE
TO LOW CONDENSATE AMMONIA CONTENT
IRON TRANSPORT WILL BE REDUCED BY 90%
LESS GENERATION OF CRUD
REDUCTION IN CHEMICAL CLEANING
FREQUENCY
REDUCTION IN OUTAGE TIME AND FASTER
START UP
FAC WILL BE MINIMIZED
ALL THESE LEADS TO VERY LESS BTF
SCHEMATIC OF OXIDE GROWTH AND
MORPHOLOGY UNDER 0XIDISING AVT AND OT
2 Fe3O4 + 0.5 02 = 3 Fe2O3
CHEMICAL CLEANING OF SUPER
CRITICAL BOILER
BY FORMIC ACID
Economiser
Bottom ring Header
Vertical waterwall
Spiral Waterwall
Separaters
Separator storage tank
AREAS UNDER CLEANING
STEPWISE CHEMICAL CLEANING PROCESS
Inhibitor efficiency test
Hydro test of the system
SH filling & DM Water Flushing of Boiler
Chemical Cleaning Of Boiler
Rinsing
SH Back Flushing
Pre Neutralization
Neutralization
Passivation
preservation

Inhibitor efficiency test

Acceptable limits
corrosion rate should be less than 0.1 Mg/cm2/hr
Formic Acid 10.0 %
Inhibitor Coronil-
200 S
0.30 %
Sorbic Acid 0.15 %
Citric Acid 0.10 %
Wetting agent 0.05 %
Temperature 85
o
C
Duration 6 hrs.
Materials Used
SA-106 / SA-210C / SA213-
T-12 / SA213 T-22 /
SAT-23 / SA-335 P-
91.
Temporary arrangements for chemical cleaning of boiler
CHEMICAL CLEANING OF SIPAT
*Total volume of boiler including temporary pipelines-370 M3
No Chemical Purity
(%)
Working
Conc. (%)
Q'ty (Kg) Remarks
1 Hydrazine
50 0.001
Pre-cleaning,
Hydrotest
2

Sorbic Acid
98.0 0.15 540

Simultaneous
Degreasing and
Descaling
Formic Acid
85.0 10.0 36000
INHIBITOR
(CORRONIL 200S)
100.0 0.3% 1070
Citric Acid
98.0 0.1 360
Non Ionic Detergent
100 0.05
3 Hydrazine
50 0.001 750
Rinsing
4

Citric Acid
98.0 0.1 360
Pre-Neutralization
Neutralization
Passivation
Ammonia
25 0.075 1050
Hydrazine
50 0.050 350
Function of Chemicals

Sorbic Acid: acts as a reducing agent convert Fe3+ to Fe2+



Formic Acid: (HCOOH) Removes mill scale, weld slag

Citric Acid: which dissolves the rust. The pH is raised to an alkaline value
using ammonia, and the sequestered iron remains in solution

Function of Chemicals
Inhibitor: Makes a passivation layer to save
the parent metal
Detergent: Removes oil & grease

COMPLETION CRITERIA FOR ACID CLEANING

Check point: Fe++, Fe+++ ,pH, TOC
Requirements: Fe++, pH, TOC Should be stable



Coupons to be placed in supply & return line prior to chemical
addition to circulation tank made of exactly same composition as of
boiler tubes of different locations.

COUPON PLACEMENT
PASSIVATED COUPON
QUALITY OF
MAGNETITE LAYER
FORMATION AFTER
PASSIVATION AS
VISUAL INSPECTION.
FEED WATER SPECIFICATION
S.NO Parameter Units Normal Operation During
Start up
Alkaline water
Treatment
Combined
water
Treatment
1 pH Min 9.0 8-8.5 Min 9.0
2 Cation Conductivity,
ms/cm
ms/cm Max 0.2 <0.15 Max 0.5
3 Dissolved Oxygen ppb < 5 30-150 Max 100
4 Iron ppb < 2 < 2 < 20
5 Sodium ppb < 2 < 2 < 10
6 Silica ppb <10 < 10 < 30
7 Turbidity NTU <2 < 2 <5
FEED WATER RECIRCULATION VIA BOILER TO ACHIEVE FEED WATER
QUALITY.
LP DOSING AND OXYGENATED
TREATMENT SYSTEM AT SIPAT
AMMONIA DOSING
Cycle pH is controlled by feeding an ammonia
from a pump having a automatic stroke
adjustment.
The adjustment is automatically adjusted by
CEP outlet pH and Feed water flow.
The dosing system includes two positive
displacement pumps with auto stroke adjustment
Automatic switching of pumps upon pump
failure.

LP DOSING AND OXYGENATED
TREATMENT SYSTEM AT SIPAT
HYDRAZINE DOSING
Cycle oxygen is controlled by feeding an
hydrazine from a pump having a automatic
stroke adjustment.
The adjustment is automatically adjusted
by Deaerator outlet Dissolved Oxygen and
Feedwater flow.


LP DOSING AND OXYGENATED
TREATMENT SYSTEM AT SIPAT
OXYGEN DOSING
The cycle oxygen is controlled by flow
control valve having a automatic controller.
The injection control is automatically
adjusted by Feed water flow and
Condensate extraction pump outlet
dissolved oxygen / Deaerator outlet
dissolved oxygen.
The dosing system includes four(4) flow
control valves with auto controller.




STEAM WATER ANALYSIS SYSTEM (SWAS)
FOLLOWING IS THE PROCESS MONITORING FOR CHEMICAL
CONTROL OF STEAM AND WATER USED FOR BOILER AND STEAM
TURBINE
S.NO SYSTEM TYPE OF MEASUREMENT
1 MAKE UP DM WATER SP.COND., CATION CONDUCTIVITY
(ACC)
2 CEP DISCHARGE pH, ACC, Na, DO, SP.COND.,

3 CONDENSATE POLISHER O/L pH, ACC, Na, SILICA, SP.COND.,

4 DEAERATOR OUTLET DO

5 FEED WATER AT
ECONOMIZER INLET
pH, ACC, COND.,HYDRAZINE,SILICA,
TURBIDITY

STEAM WATER ANALYSIS SYSTEM (SWAS)
FOLLOWING IS THE PROCESS MONITORING FOR CHEMICAL
CONTROL OF STEAM AND WATER USED FOR BOILER AND STEAM
TURBINE
S.NO SYSTEM TYPE OF MEASUREMENT
6 VENT HEADER OF BOILER
(SEPARATOR OUTLET
STEAM)
ACC, SP.COND., HYDRAZINE, SILICA

7 MAIN STEAM pH, ACC, Na, SILICA, SP.COND.,

8 WATER SEPARATION
STORAGE TANK OF BOILER
CATION CONDUCTIVITY(ACC)

9 REHEATED STEAM CATION CONDUCTIVITY(ACC)

10 TG ECW COOLING WATER pH
PROCEDURE TO CHANGE OVER TO OXYGENATED
TREATMENT
CPU TO BE IN SERVICE WITH FULL
CONDENSATE FLOW.
UNIT IN FULL LOAD & STABLE CONDITION.
THERE SHALL BE 4 CPU VESSELS (3 IN
SERVICE OF 33% CAPACITY EACH)
REQUIRED WATER QUALITY:
FEED WATER CATION CONDUCTIVITY : < 0.15
us/cm
FEED pH value : 9 ~ 9.5
D/A O/LOxygen : 7 ppb





DURING 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