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SAFETY &

HAZZARD
O.R.USRETE,
M.Sc.(che.),b.a.(eNg.LIT.),B.ED.
SR.CHE.MAHAJECO,KTPS,KORA
DI,
NAGPUR,MAHARASTRA,INDIA.
MOB: +91-9423628363

ACTIVITIES OF CHEMISTRY

C H E M IS T R Y
C O A L & O IL

M A IN P L A N T
C H E M IS T R Y

W ATER TREATM ENT


PLANT

P U R C H A S E ,S T O R E
E N V IR O N M E N T S P E C IA L L A B ,
L W T P O P E R A T IO N

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
MUDS
SILTS
SAND
ORGANICS

DISSOLVED SOLIDS
CALCIUM SALTS
MAGNESIUM SALT
SODIUM SALTS
IRON,
MANGANESE,
FLUORIDE SALTS
GASES

CHEMICALS USED IN TREATMENT


SL.N
O

CHEMICALS

USE

ACTIVATED
CARBON

TASTE,ODOUR & DECHLORINATION

ALUM, FeCl3

COAGULANT

LIME

pH ADJUSTMENT, SOFTENING

Cl2, O3, Na(OCl)Cl

DISINFECTION, TO CONTROL BACTERIA,


VIRUS & ORG. MAT

HYDRAZINE

OXYGEN SCAVENGER, MAGENTITE


LAYER

AMMONIA

pH ADJUSTMENT

TSP

TO TREAT BOILER WATER

HCl ACID

REGENERANT OF CATION RESIN

NaOH

REGENERANT OF ANION RESIN

CLARIFIER -3000 M3/HR

RAW WATER
INLET
Chemical Feeding

CLARIFIER
No.1

CLARIFIER
No.2

CLARIFIER
No.3
Chemical
Feeding
Gravity Filters

CLARIFIED
WATER
STORAGE
TANKS
STAGE 1

To DM Plants

CLARIFIED
WATER
STORAGE
TANKS
SATGE 2

PRE-TREATMENT PLANT

STANDARD FOR CHEMICAL CONTROL


SL ITEM
NO DESCRIPTION

pH

TURBI
DITY/ K

DRINKING
WATER

6.5-7.5

< 10NTU

CLARIFIED
WATER

6.5-7.5

< 20 NTU

FILTERD WATER

6.5-7.5

< 5 NTU

DEMINERALISED
WATER

6.5-7.0

K= 0.2-0.1

SILICA

20-10 PPB

DEMINERALIZATION

S.CATION
ACF

TO DM TAN
W.ANION S.ANION

W.CATION

DEGESSER

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


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

MIXED BED

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-, SO4MIXED 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


vity
Chlorine

Silica

ACF

6.5
7.5

--

<2.0
NTU

Nil

--

Anion

6.5
8.0

<10

Nil

Nil

<200
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 cant 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 ( precommissioning ) 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
80
100
120
130
140
145

8.2
3.8
1.9
0.9
0.7
0.52
0.48

150
155
160
165
170
175
180

0.4
0.37
0.30
0.27 (200MW)
0.25
0.22
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

Cation Conductivity

Polisher Outlet & Economizer Inlet On-line

Cation Conductivity

Hot Reheat Steam or Main Steam

On-line

Cation Conductivity

Blowdown or Downcomer

On-line

pH (Drum Boilers)

Blowdown or Downcomer

On-line

Dissolved Oxygen

CP Discharge & Economizer Inlet

On-line

Sodium

CP Discharge

On-line

Sodium

Hot Reheat Steam or Main Steam

On-line

CHEMICAL CONTROL REGIME


PARAME
TERS

COND

FEED

BOILER

STEAM

COND

FEED

BOILER

STEAM

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

N2H4 ppm
NH3 ppm

0.01-0.02
0.5

<0.02

<0.02

Fe ppm

0.01

Cu ppm

0.005

Na ppb

1.0(Max)
1-2

<0.02

<0.01

<0.01

0.01

0.01

0.01

0.01

0.01

0.005

0.005

0.005

0.005

0.005

Cl ppb

TDS
(mg/l)

1.0 (Max)

2-4

Silica ppm

D.O. ppb

0.01-0.02

0.5

PO4 ppm

0.3

1000
40

<0.2

0.1

<0.01

500

40
15

5
10

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

S,H.

PO4,SiO2,K

HP/IP

DRUM

L.P.

Turbine
SiO2,K,NH3

R.H.

PO4
K,KH,N2H4,SiO2,D.O.

Condensor
K,KH,SiO2,NH3

D.A.

CEP

BFP

H.P.H.
DEPOSITS

L.P.H.
N2H4

CPU

NH3

CORROSION

NH3,K,KH,SiO2,N

IMPURITY INGRESS

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,KORA
DI,
NAGPUR,MAHARASTRA,INDIA.
MOB: +91-9423628363

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)

2)

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.
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
P
A
S
S

SG

SG

CPU-A

CPU-B

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.

Heater

Drain

REGERATION SYSTEM

Drain
Booster pump

Acid
Met.
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

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

12

16

17

18

19

CPU RUN DAYS

20

21

22