SAFETY & HAZZARD

O.R.USRETE,
M.Sc.(che.),b.a.(eNg.LIT.),B.ED.
SR.CHE.MAHAJECO,KTPS,KORADI,
NAGPUR,MAHARASTRA,INDIA.
MOB: +91-9423628363
Email: o.r.usrete@gmail.com
 ACTIVITIES OF CHEMISTRY

CHEMISTRY

COAL & OIL MAIN PLANT WATER TREATMENT PURCHASE,STORE

CHEMISTRY PLANT ENVIRONMENT SPECIAL LAB,
LWTP OPERATION
 USE OF WATER

•AS COOLING WATER FOR CONDENSER (RAW WATER)

•AS COOLING WATER UNIT AUXILIARIES (CLF WATER)
•DM WATER AS MAKE UP WATER
•DRINKING WATER (FILTERED CLARIFIED WATER)
•LP/HP WATER
OBJECTIVES OF WATER CHEMISTRY CONTROL

Maintain the plant in a condition where it

can operate reliably and smoothly.
• Maintain the integrity of feed, boiler and steam
systems
•Maintain the effectiveness of heat transfer surface
•Maintain the high level of steam purity
•Reduction of forced outages ,Reduce BTF
Avoiding acid cleaning ,Overall cost savings
 RAW WATER IMPURITIES

SUSPENDED SOLIDS DISSOLVED SOLIDS

• MUDS • CALCIUM SALTS
• SILTS • MAGNESIUM SALT
• SAND • SODIUM SALTS
• ORGANICS • IRON,
MANGANESE,
FLUORIDE SALTS
• GASES
 CHEMICALS USED IN TREATMENT
SL.N CHEMICALS USE
O
1 ACTIVATED TASTE,ODOUR & DECHLORINATION
CARBON
2 ALUM, FeCl3 COAGULANT
3 LIME pH ADJUSTMENT, SOFTENING
4 Cl2, O3, Na(OCl)Cl DISINFECTION, TO CONTROL BACTERIA,
VIRUS & ORG. MAT
5 HYDRAZINE OXYGEN SCAVENGER, MAGENTITE
LAYER
6 AMMONIA pH ADJUSTMENT
7 TSP TO TREAT BOILER WATER
8 HCl ACID REGENERANT OF CATION RESIN
9 NaOH REGENERANT OF ANION RESIN
CLARIFIER -3000 M3/HR RAW WATER
INLET
Chemical Feeding

CLARIFIER
No.1

CLARIFIER
No.3
CLARIFIER
No.2 Chemical
Feeding

Gravity Filters
CLARIFIED
CLARIFIED WATER
WATER STORAGE
STORAGE TANKS
TANKS To DM Plants SATGE 2
STAGE 1
PRE-TREATMENT PLANT
STANDARD FOR CHEMICAL CONTROL

SL ITEM pH TURBI SILICA

NO DESCRIPTION DITY/ K

1 DRINKING 6.5-7.5 < 10NTU

WATER

2 CLARIFIED 6.5-7.5 < 20 NTU

WATER

3 FILTERD WATER 6.5-7.5 < 5 NTU

3 DEMINERALISED 6.5-7.0 K= 0.2-0.1 20-10 PPB

WATER
DEMINERALIZATION
 S.CATION TO DM TAN

ACF W.CATION W.ANION S.ANION MIXED BED

DEGESSER

D.M.STREAMS: D.M.PLANT STAGE II

NOS. OF STREAM: 2+1
CAPACITY : 135M3/HR
 FUNCTION OF VESSELS

ACF- Removes turbidity & Residual Chlorine

CATION – Removes cationic part e.g. Na+ ,Ca++
DEGASER - Removes CO2
ANION – Removes Anionic Part e.g. Cl-, SO4-
MIXED BED – Removes slip over cationic &
anionic part
Note:- From ACF outlet to DM Water Storage Tank is
MSRL. D.M. Storage tank is Araldite / Epoxy coated.
•Removal of Colloidal Silica is not
possible through Resin Beds. To be
controlled only during Clarification
Process.
If colloidal silica is more, Boiler
Water silica will increase even if
CBD is open.
 PARAMETERS OF WATERS

Parameters pH Conducti Turbidity Residual Silica

vity Chlorine

ACF 6.5 – -- <2.0 Nil --

7.5 NTU

Anion 6.5 – <10 Nil Nil <200

8.0 ppb

Mixed Bed 6.5-7.0 <0.2 Nil Nil < 20

ppb
COOLING WATER TREATMENT

*CW CHLORINATION
* CYCLE OF CONCENTRATION
(COC)
*OTHER CHEMICALS DOSING e.g.
LIME, SULPHURIC ACID etc.
*Cooling Tower Bleeding.
CHEMICAL CONTROL OF
STEAM WATER CYCLE
CYCLE CHEMISTRY CONTROL AND INSTRUMENTATION
 Why DM water can’t be used directly in
boiler?
- Principle says if water is acidic – Corrosive.

- Principle say if water is alkaline – Scale

forming.

As DM water (also called as hungry water) is

having no salt, when it comes in contact with
metal surface attacks the metal.
 AMMONIA DOSING
1. By dosing ammonia solution (Alkaline) pH of steam
water circuit is maintained around 9.0 pH , so that
corrosion is minimum .
2. During acid cleaning alkali boil out ( pre-
commissioning ) of water circuit ( upto drum) ; a
protective magnetite layer is formed which protects the
parent metal from further attack . This magnetite layer
is only stable at pH 8.0 – 10.0. Hence, we have to
maintain pH  9.0.

Ammonia is dosed to maintain steam water circuit pH 9.0

 HYDRAZINE DOSING
Dissolved Oxygen (D.O) is very detrimental to
steam water circuit.
-D.O also causes electrolytic corrosion by facilitating
electrolytic action between dissimilar metals.
Hence, D.O is to be removed completely before the
water is allowed to boiler circuit. Hydrazine is added
to remove D.O
N2H4 + O2  2H2O + N2 
Some excess hydrazine (called as Residual Hydrazine) is
maintained at feed sample (ECO –Inlet) 10-20ppb.
This excess hydrazine is converted to ammonia at boiler
drum pressure and temperature. 3N2H4  4NH3 + N2
 PHOSPHATE DOSING
HP DOSING SYSTEM : TRI SODIUM PHOSPHATE /
DISODIUM PHOSPHATE /

Na3PO4 + H2O <=> NaOH +Na2HPO4

Na2HPO4 + H2O <=> NaOH +NaH2PO4
SLUDGE REMOVAL

2 Na3PO4 + 3CaSO4  3Na2SO4 + Ca3(PO4)2

2Na3PO4 + 3MgSO4  3Na2SO4 + Mg3(PO4)2
PHOSHPHATE SLUDGE REMOVED BY CBD
 PHOSPHATE HIDEOUT
Solubility of phosphate increases with temperature
but after 1200C to 2200C, this solubility decreases
and after 2200C solubility decrease is very rapid. So
at boiler drum temp  3500C, the solubility of
phosphate becomes very low. It hides out in the form
of a complex salt and leaves free NaOH. This hidden
out phosphate is not alkaline rather slight acidic. So
when this hidden out phosphate comes, pH of boiler
water goes down and PO4 concentration goes up.
Which is very much detrimental to boiler water circuit.
 SILICA:

As long as silica is in the boiler water, it

creates no problem (of course very high silica
concentration in boiler water will lead to tube
scaling). However, when it goes along with
steam, it is deposited at the low-pressure area
of turbine (HP/LP/IP), which will create
vibration problem – Pressure restriction inside
the turbine.
CONTROL OF SILICA IN STEAM
Distribution Coefficient of silica = Silica in
steam / Silica in boiler water
This distribution coefficient depends on :-
1. pH of boiler water .
2. Pressure of boiler Drum
3. Temp. of boiler drum(  Constant )

To restrict 20 / 10 ppb silica in steam, drum pressure

is to be reduced .
Pressure  Silica in steam
pH of boiler water  1/ silica steam
RECOMMENDED LIMIT OF SILICA IN BOILER
WATER AT PH 9.5 AT DIFF OPERATING PRESSURE TO
LIMIT SILICA IN STEAM

DRUM PR BLR SILICA DRUM PR BLR SILICA

60 8.2 150 0.4

80 3.8 155 0.37
100 1.9 160 0.30
120 0.9 165 0.27 (200MW)
130 0.7 170 0.25
140 0.52 175 0.22
145 0.48 180 0.18(500MW)
 ACTION – ORIENTED PROCEDURES
pH (BOILER WATER) ACTION REQUIRED
>10.0 Inform Chemist, Shutdown unit and drain boiler
9.6 to 10 Open blowdown. Check condensate storage tanks for
contamination. Increase boiler monitoring to hourly.
Feed DSP if PO4 is low. Inform Chemist
9.0 to 9.6 Normal Operating range
8.5 to 9.0 Calibrate pH meter, Resample & verify pH if PO4 is less.
Increase TSP Feed. If PO4 is normal, Feed Caustic.
7.0 to 8.5 Check for signs of a condenser leak. Check condensate
storage tanks for contamination. Increase boiler
monitoring to hourly. Feed TSP if PO4 is low. Open
blowdown.
>7.0 Shut down unit and drain boiler.
 CHLORIDE
Monitoring of chloride is necessary because chloride
contributes to the following:
- Corrosion fatigue, stress corrosion cracking, and pitting
in LP turbines,
- Corrosion, hydrogen damage, and pitting in boilers, and
- The synergistic effect on corrosion in the presence of
oxygen and copper oxide, i.e. the total effect of all three
is greater than would be expected by simply adding the
effects together.
 SODIUM
•SODIUM IS MONITORED BECAUSE:

•- Sodium is present in the steam in corrosive forms of NaCl and

NaOH and are two major corrodents of the turbine,

•- Can lead to stress corrosion cracking of turbine blades and

stainless steel superheater tubes, and

•- Sodium hydroxide has in the past caused gouging-type failures

of boiler tubes.
 BOILER WATER TREATMENT
•PHOSPHATE TREATMENT
-Co-ordinated Phosphate Treatment (1:3)
-Congruent Phosphate Treatment (1:2.6)
- Equilibrium Phosphate Treatment (1: 1-3)
•CAUSTIC TREATMENT
•ALL-VOLATILE TREATMENT

FEED WATER TREATMENT

•ALL VOLATILE TREATMENT
a) AVT(O) b)AVT ( R )
•OXYGENATED TREATMENT
 CORE MONITORING PARAMETERS
Parameter Measurement Locations Usage Frequency

Cation Conductivity CP Discharge On-line C

Cation Conductivity Polisher Outlet & Economizer Inlet On-line C
Cation Conductivity Hot Reheat Steam or Main Steam On-line C

Cation Conductivity Blowdown or Downcomer On-line C

pH (Drum Boilers) Blowdown or Downcomer On-line C

Dissolved Oxygen CP Discharge & Economizer Inlet On-line C

Sodium CP Discharge On-line C

Sodium Hot Reheat Steam or Main Steam On-line C
 CHEMICAL CONTROL REGIME
PARAME COND FEED BOILER STEAM COND FEED BOILER STEAM
TERS
pH 8.8-9.0 8.8-9.0 9.2-9.4 8.8-9.0 9.0-9.2 9.0-9.2 9.1-9.4 9.0-9.2

KH us/cm ,0.3 <0.3 <0.3 <0.2 <0.2 <0.2

N2H4 ppm 0.01-0.02 0.01-0.02

NH3 ppm 0.5 0.5 1.0 (Max) 1.0(Max)

PO4 ppm 2-4 1-2

Silica ppm <0.02 <0.02 0.3 <0.02 <0.01 <0.01 0.1 <0.01

Fe ppm 0.01 0.01 0.01 0.01 0.01 0.01

Cu ppm 0.005 0.005 0.005 0.005 0.005 0.005

Cl ppb 1000 500

D.O. ppb 40 5 40 5

TDS 15 10
(mg/l)
Na ppb 5 5
 OPERATOR CONTRIBUTIONS TO CYCLE
CHEMISTRY CONTROL
-Blowing down boiler during start ups and when periods of high
suspended and dissolved solids occur
-Clean up of the heater drains during start up to reduce inventory of
corrosion products
-Re-circulation to the condenser and clean up system on start up
-Turbine washing on start ups or shutdowns to remove deposits
-Minimum use of de-superheating sprays
-Delayed cut-in of feed water heaters during start up
-Detection and reporting of increased air in-leakage
-Detection, reporting and isolation of contaminated make-up
-Maintaining proper drum level
- Detection and reporting of main steam contamination
DEPOSITS IMPURITY INGRESS
CORROSION
 BOILER LAY UP CONSIDERATIONS
-BTF mechanisms directly affected by improper lay up include pitting
in water touched and SH/RH tubing
-Pitting can also be a precursor to corrosion fatigue.
-A host of other BTF mechanisms can be activated during start up as a
result of improper lay up which can generate an excessive amount of
preboiler corrosion products.
-Utility should have written procedures to cover unit layups of less
than 72 hours, 7 days and long term storage.
-Alternatives for boiler lay up include:
*Wet layup, pH of 10 using ammonia, 200 ppm of hydrazine,
condensate quality water, and a pressurised nitrogen blanket.
*Wet layup, good quality treated water used during operation without
any additional additives.
*Dry layup, hot boiler is drained and purged with nitrogen or dry
dehumidified air.
PRIMARY WATER
CONDENSOR LEAKAGE

O.R.USRETE,
M.Sc.(che.),b.a.(eNg.LIT.),B.ED.
SR.CHE.MAHAJECO,KTPS,KORADI,
NAGPUR,MAHARASTRA,INDIA.
MOB: +91-9423628363
Email: o.r.usrete@gmail.com
 CONDENSOR LEAKAGE
DETECTION ,ITS EFFECT ON
UNIT OPERATION & CPU
 SOURCES OF CONTAMINATION
1. CONTAMINATION FROM WATER TREATMENT
PLANT
2. USE OF IMPURE WATER FOR DOSING SYSTEM
3. USE OF IMPURE DOSING CHEMICALS
4. PRESENCE OF PLASTIC POLYMERS or,
HALOGENETED SOLVENTS
5. RESIDUES FROM CHEMICAL CLEANING
OPERATION
6. CONDENSOR TUBE LEAKAGE / SWEATING.
 DETECTION OF CONDENSOR
LEAKAGE
IF LEAKGE IS MINOR
1. ON-LINE SODIUM ANALYSER
2. AFTER CATION CONDUCTIVITY
3. TOTAL HARDNESS OF CONDENSATE
SAMPLE
4. HIGH BOILER SILICA & CONDENSATE
SILCA
5. SILICA WILL BE IN INCREASING TREND
FROM CONDENSATE – LPHS-FEED.
IF LEAKAGE IS MORE
1. CONDUCTIVITY OF CONDENSATE /
FEED WILL BE VERY HIGH BUT pH
WILL BE LOW.
2) DO OF CONDENSER WILL BE VERY
HIGH
3) HOT WELL MAKE WILL BE LOW AS
WELL AS LEVEL WILL BE HIGH
4) DEAERATOR LEVEL WILL GO HIGH
5) BOILER WATER WILL pH BE LOW
BUT CONDUCTIVITY IS HIGH.
PREVENTIVE / REMEDICAL ACTION
1) INCREASE BOILER BLOW DOWN
(BUT IF THE SOURCE OF IMPURITY IS WTP,
INCREASE MAKE UP WILL INTRODUCE
MORE IMPURITIES TO THE SYSTEM)
2) INCREASE THE CONCENTRATION OF
PHOSPHATE AND FREE ALKALINITY IN
BOILER
3) MONITORING: INCREASE THE MONITORING
FREQUENCY OF BOILER WATER
CONDENSATE, FEED AND SATUARATED
STEAM SAMPLE
 EFFECTS OF CONDENSER LEAKAGE
ON UNIT OPERATION
1) IF LEAKAGE IS HIGH : DIFFICULT TO MAINTAIN HOT
WELL LEVEL, DEAERATOR LEVEL AND ALSO BOILER
AND STEAM WATER QUALITY. HENCE UNIT IS TO BE
TAKEN OUT OF SERVICE.
2) IF THE LEAKAGE IS MINOR:
- REDUCE DRUM PRESSURE TO RESTRICT ENTRY OF
SILICA INTO THE STEAM
- MONITOR CHLORIDE LEVEL IN BOILER WATER SO
THAT ENTRY OF CHLORIDE IN STEAM IS RESTRICTED
- DO NOT USE ATTEMPERATION SPRAY
- OPERATE CBD TO CONTROL BOILER WATER SILICA
AND CHLORIDE LEVEL.
 CONDENSER LEAK IDENTIFICATION

1) FIRST PATH DETECTION

2) FLOOD TEST
3) CANDLE TEST
4) DYE TEST
5) FOAM TEST
6) BUBBLER METHOD
ATTENDING THE TUBE LEAKAGE:
i) Once the leaking tube is identified, this should be plugged
with a suitable plug, which is made up of SS/Cu / Plastic
Teflon.
Stage I Cu } Teflon can be used in both the stages
Stage II SS}
In general, condensers are having 25% excess condenser
tubes. So, if more plugging is required, then the bundle of
tubes are to be changed, which is a major job.
ii)Suppose the leakage is from the expanded joints (minor
leakage or sweating), then the end of the tube is expanded to
arrest the leakage.
 NORMALIZATION OF THE UNIT
I) UNIT NOT UNDER S/D
After the leakage has been attended, the leaky half
is thoroughly flushed and taken into service. Go for
CBD for some time till the chemical parameters are
achieved.
II) Unit under S/D
Flush pre-boiler, boiler and condenser thoroughly
with DM Water (And if possible with N2H4 &
NH3)and then take into service. Go for CBD for
some time till the chemical parameters are achieved.
 CONDENSATE POLISHING UNIT

• CONDENSATE POLISHING UNIT IS BASICALLY MIXED BED

OF CATION EXCHANGER AND ANION EXCHANGER
 A FILTER TO REMOVE ALL TYPES OF SUSPENDED SOLIDS
FROM THE CONDENSATE
 IT PRESERVES THE QUALITY OF CONDENSATE BY
REMOVAL OF THE DISSOLVED SOLIDS THROUGH ION
EXCHANGE REACTION
 IT MAINTAINS THE QUALITY EVEN DURING THE
INGRESS OF COOLING WATER IN STEAM WATER CYCLE
THROUGH CONDENSER
 CPU DESCRIPTION

•KORBA 500MW CPU HAVING PROVISION TO

UTILIZE 100% FOR CONDENSATE
TREATMENT

•AUTO BYPASS ALLOW BYPASSING OF CPU

AT SET PRESSURE

•THE RATIO OF CATION TO ANION IS 1.5 : 1.0

•CONCEP PROCESS FOR RESIN SEPERATION

 From CEP

B
Y SG
SG

P
A CPU-A CPU-B
S
S

To deareator
CPU SERVICE VESSELS
From CEP CPU SERVICE
FT

bypass
valve DPT SG
Service Vessel

CE
To dereator RT

BY PASS VALVE & OTHER INSTRUMENTS

 ARU CRU

Alkali Met.

Drain Drain
Heater Acid
Met.
Booster pump
REGERATION SYSTEM
From DMW Tank
A) DESIGN DATA & SPECIFICATION

NOs OF VESSELS 02
SIZE OF VESSEL 2850 MM(dia) x 2185 MM
DESIGN FLOW/VESSEL 675 M3/HR

B) RESIN DETAILS CATION ANION

TYPE OF RESINS IR-252 IRA-900

QUANTITY 4.25 M3 2.8 M3
DEPTH 0.72 mts 0.475 mts
REGENERANT 408 kgs 358.4 kgs
REGEN.CONCENTRATION 4% 4%
TEMP.LIMIT 120 oC 60 oC
 PROCESS

A) SERVICE
•SERVICE MODE INITIATED FROM LOCAL CONTROL PANEL
IN SEMIAUTO MODE
•THE EXHAUTION OF BED IS INDICATED BY HIGH
COND. ALARM

B)REGENERATION
•THE EXHAUSTED RESIN IS TRANSFERRED HYDRAULICALLY
TO REGENERATION SYSTEM
•REGENERATION INVOLVE 49 STEPS FOR CLEANING,
SEPARATION AND RGENERATION
•THE SEPERATION UTILIZES “CONCEP PROCESS”-
-TO ENSURE COMPLETE SEPERATION
-INCLUSION OF RIU DURING TRANSFER OF RESIN
DESIGN PERFORMANCE (under normal operating condition

PARAMETERS INLET OUTLET

_____________________________________________________
•TDS (AS CaCO3) 100 25
•TOTAL CRUD, ppb 50 10
•SILICA as SiO2, ppb 20 05
•IRON as Fe,ppb 50 05
•COPPER as Cu,ppb 10 02
•SODIUM as Na,ppb 10 02
•CHLORIDE as Cl,ppb 10 02
•CONDUCTIVITY(KH),us/cm 0.2 0.1
_____________________________________________________
 PERFORMANCE OF CPU

THE CHEMICAL CONTROL DURING THE STARUP IS

VERY EFFECTIVE

•REDUCTION IN CBD HOURS BY 50%

•CONTROL IN DRUM PRESSURE RESTRICTION

•VERY EFFECTIVE IN CONDENSOR TUBE LEAKAGE

CONDITION
 PERFORMANCE OF CPU UNDER NORMAL
OPERATING CONDITIONS

PARAMETER CPU (IN) CPU (OUT) H+ CPU

(OUT) NH4+
________________________________________________________
______
SILICA,PPB 05 -10 02 - 05 05 -10
COPPER,PPB 02 - 03 01 - 02 02 - 04
IRON,PPB 03 - 05 02 - 05 02 - 05
SODIUM,PPB 01 - 03 01 - 03 01 - 03
CHLORIDE,PPB 02 - 05 <2 >5
CRUD,PPB 20 - 40 01 - 05 01 - 05
COND.,kH,us/cm 0.1 - 0.2 0.05 -0.07 0.1 - 0.15
________________________________________________________
______
 BOILER WATER SILICA vs RUN TIME
0.8
0.7
0.6
0.5
BOILER 0.4
SiO2
0.3
PPM
0.2
0.1
0
0 2 4 6 8 10 12 14 16 18 20

RUN TIME
 BOILER WATER CHLORIDE VS CPU RUN

1400

1200

1000

800
Cl , PPB
600

400

200

0
4 8 12 16 17 18 19 20 21 22

CPU RUN DAYS