4/11/2013

Chemical Cleaning of Boiler Objectives of Chemical Cleaning

A step to prepare the Boiler to generate steam
of required purity on sustainable basis
To make the internal surface of water/ steam
circuit free from all foreign materials such as
adventitious metal, oxides, grease, oil, dirt,
etc.
To remove debris & thick oxide accumulated
during operation of older plants
To establish a smooth protective MAGNETITE
layer on internal surfaces

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Purpose of different Steps of Chemical Cleaning

Principle of Chemical Cleaning Initial Flush: to remove loose corrosion products or
volatile preservatives
Initial Flushing Alkali Boil-out: to remove any grease and oil from
Alkali Flushing/Alkali Boil-out the surfaces and loosen the metal oxides for
removal during acid cleaning
Rinsing (Hot/Cold) Rinsing: to flush the system and remove traces of
Acid Cleaning chemicals used during Alkali Boil-out
Acid Cleaning: After completion of Alkali flushing
Passivation cleaning with EDTA / acid to remove the firmly
attached mill scales, adherent rust & other debris
which remain after Alkali Boil-out
Passivation: to produce a continuous coherent
corrosion resistant layer of magnetite over the
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Methods of Chemical Cleaning in NTPC SERVICES REQUIRED

Chemical Cleaning using EDTA : DM tanks with sufficient qty of DM water:
Approximately, 6000 m3 of DM water will be
(EDTA : Ethylene di-amine tetra acetic acid)
required for the entire process. At any time of
1. Easier
acid cleaning, a minimum of two boiler volumes
2. Eco-friendly (app. 1400 M3) of DM water should be available
3. Lesser process time in ready stock to facilitate rapid flushing of the
Chemical Cleaning using HCl: system in the event of chemistry upset.
1. Slightly cumbersome All the required quantities of chemicals should
2. Less eco friendly be made available prior to the commencement
3. Larger process time of the chemical cleaning process
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SERVICES REQUIRED CHEMICALS REQUIRED

NAME OF CHEMICALS Qty. Purpose
Tri Sodium Phosphate 400 kg for alkali flushing
Temporary Drum level indications (Purity, as P2O5 :17.5% Min)
Disodium Hydrogen Phosphate 200 kgs For alkali flushing
HT/LT power & control supplies (99 % purity)

Express/Chemical lab Ammoniated EDTA, 40% wt/wt as active

EDTA, ammoniated solution pH=9.0 to 9.8,
40 tons for acid cleaning

Communication & Lighting Density : 1.18

(EDTA : Ethylene diamine tetra acetic acid
Effluent treatment facility Ammonia solution (20% Min NH3 sp 1800 litres for treated DM water
gr:0.91) as per IS 799 / 1990 and rinsing & passivation
Hydrazine Hydrate (80% Min. conc) as per
IS 12086/1991 ).
Bhelmax 700 kg used as inhibitors
Bhelsol 700 litres used as inhibitors
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SAFETY & EMERGENCY PROVISIONS STATE OF THE PLANT

Availability of gum boots, hand gloves,
aprons, goggles, helmets, face masks etc.
Ample supplies of tepid flushing and washing
water supplies available at all possible points
of discharge, spillage or escape of chemicals
Provisions for emergency treatment of the
eyes, first aid room & ambulance
Safety shower
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Essential control and instruments viz. protections,
interlock, alarms, measurement, annunciation etc. for
safe light-up of boiler
All the related boiler auxiliaries viz chemical dozing
pumps, tanks, fans, oil pumps etc for boiler light up
Hydraulic test of boiler, Furnace air tightness test &
detergent flushing of pre-boiler system should be
complete.
O & M instructions for the boiler and other auxiliaries
should be available
Proper effluent treatment arrangement should be
available
Chemical cleaning system / equipment should be
ready
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MINIMUM OPERATIONAL REQUIREMENTS MINIMUM OPERATIONAL REQUIREMENTS

Ensure free expansion of the furnace and duct and
ONE ID FAN provision of expansion markers
ONE FD FAN Blow down system of boiler
ONE SEC. AIR PRE-HEATER & ITS SOOT BLOWER Proper drainage system of boiler area
ALL CC PUMPS Air in leak test of two passes of ESP
STEAM COIL AIR PRE-HEATER Mechanical readiness of two passes of ESP
LIGHT OIL FIRING SYSTEM/ HFO FIRING Temporary sampling system
FSSS Water and steam systems & Air and flue gas system
SADC Readiness of MDBFP and feed system
SCANNER AIR SYSTEM
Test coupons & their fixing arrangements.
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Provisions should be made at the following locations for the measurement
of temperature:
A) Two locations in the drum (left & right) for the measurement of boiler
Water temperature. Long thermocouples of around 400 mm length
shall be installed directly in the spare / unused stubs in the drum
B) Water wall metal temperature measurements as given below:
At AB elevation, 4 number thermocouples shall be installed on
corner water wall tubes (outside the furnace) and
At GH elevation 2 numbers thermocouples shall be installed in the
front and rear water wall (outside the furnace) at accessible
locations.
C) Two more thermocouples one at left and right side of ECO coil shall be
welded at suitable locations, inside the boiler (or penthouse) to
measure the metal temp in the gas side.
(Totally 06 nos. thermocouples will be used for measurement of water
wall tube metal temperature and 02 nos. for economizer tube temp.)
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HOT WATER RINSE
Once the draining after Alkali Flushing is completed, refill
the boiler with DM water and light up the boiler.
Gradually raise the boiler water temperature to 130-140C.
Trip the boiler and keep the fans running for cooling with CC
pumps ON
After 30 minutes stop the running CC pump and drain the
boiler in the hot condition to the plants water disposal
system by keeping open the drain valves fully (without
throttling).
The pH and PO4 will be measured in the drain water. The pH
and PO4 are to be reduced to a level below 7.5 and 10 ppm
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ACID CLEANING & PASSIVATION
Solution of EDTA(3 + 1% by weight), Hydrazine hydrate(1000ppm),
Ammonia (pH 9-9.8) and inhibitors (BHELMAX & BHELSOL) prepared in
mixing tank
Solution filled into the Boiler through LP drain header using temporary
chemical fill pump in batches.
Boiler lighted up with minimum firing rate (say 2 oil guns in AB elevation)
Temperature of boiler water raised to 140C.
Temperature maintained at 140 to 145C for a min period of 4 hours
The approx. quantities of various chemicals that are to be mixed per batch
of 40 m3 is given below:
1. EDTA ammoniated (40 % ) concentrate: 3 to 4 m3
2. BHELMAX : 60 kgs
3. BHELSOL : 60 lit
4. N2H4.H2O (80%) : 60 litres
Ammonia will be added if required to adjust the pH between 9.0 to 9.8.
DM water will be used to make up to 40 m3.
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ALKALI FLUSHING
TSP (Tri-sodium Phosphate ) & DSP (Di Sodium Hydrogen Phosphate)
solution is prepared in a mixing tank with DM Water
Above solution will be thoroughly mixed by recirculation so that final
solution in the Boiler contains 0.1 % TSP and 0.05 % DSP
The solution will be injected into the boiler through the bottom ring
header drains and economizer drain by operating the chemical filling
pump.
Further DM water will be taken in the boiler up to normal level.
Light up the boiler & gradually raise the boiler water temperature to
130140 C
Trip the boiler and keep the fans running for cooling. Keep one CC pump
running.
After 30 minutes, stop the running CC pump. Drain the boiler at 950 C to
the plant water disposal system, by keeping open the drain valves fully
(without any throttling).
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COLD WATER RINSES
Cold water rinses will be done by fill and dump
method
During these steps, draining will be done to the
plants water disposal system.
pH will be monitored during draining of each
cold water rinse stage.
The rinsing operation will be continued until the
pH of the drain water is almost equal to pH of
inlet water used for rinsing.
Flush all sampling and blow down lines
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ACID CLEANING & PASSIVATION
Control the firing rate in such a way that the boiler water temperature is
maintained at 140 to 145 0C, for a min period of 4 hours. Then trip the
boiler but continue running of CC pump.
Continue running the ID / FD fans to bring down the boiler water
temperature.
Boiler water temp is allowed to come down. Minimum EDTA contact period
of 6 hours with temp above 110C
Samples have to be taken every 30 minutes from the sampling points and
analyzed for pH, EDTA concentration, and Iron content.
Cleaning process is to be continued till iron concentration in three
consecutive samples show equilibrium status.
EDTA contact period kept less than 8 hrs & more than 6 hrs with temp>
110C
When the temperature comes down to 950C, stop the running CC pump
and the system shall be drained completely in hot condition to the effluent
pit by opening all the drain valves.
Process is complete if iron concentration in 3 consecutive samples remains
same
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ACID CLEANING & PASSIVATION Acid cleaning by circulation method

PROCESS COMPLETION CRITERIA

When the iron concentration in the cleaning solution is
constant, it indicates that all the oxides have been
dissolved. However, a minimum EDTA contact period of 6
hours from the time of attaining the required
temperature (110 C) shall be allowed
If the iron concentration values do not level out and
attain equilibrium status, regardless of analytical results,
the EDTA contact period with temperature exceeding
110C shall not be allowed for more than 8 hours
(approx).
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Treated DM water rinsing INSPECTION CRITERIA

Done by a Blended solution of ammonia (pH 9.0 to 9.5 ) & The test coupons placed at identified
Hydrazine (hydrazine content 50 ppm ) and heat the solution
to 60 C & filled in boiler to normal level through low point locations will be taken out. All coupons shall
drains and economizer drain . be free of deposits and shall have uniform
Start the middle CC pump and light up the boiler coating of the protective layer.
Raise boiler water temperature up to 1200C and then shut
down the boiler. Allow the boiler to cool down naturally The drum surface shall be visually inspected
When the boiler water temperature comes down to 95 0C stop for uniform smooth coating of protective layer.
the CC pump and drain the boiler to the effluent pit and allow
the system for natural aeration. The low point headers will be inspected and
blr drum checked for smooth coating loose debris if any, will be removed.
Fit the bottom drum internals and restore the boiler and
prepare it for regular operation for steam blowing, safety valve
floating etc.
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Test Coupons before EDTA Chemical cleaning Test Coupons after EDTA Chemical cleaning

THANK YOU

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Effluent Treatment & disposal CHEMICAL CLEANING USING HCL

Hot DM water flushing drained to plant CHEMICALS REQUIRED
DSP & TSP- for alkali Boil-out
normal drain.
HCl(Conc-30% MIN ) & Ammonium bifluoride (97%),
The organic spent EDTA chemical solution - for acid cleaning
is drained into a pit & aerated for 10 days to Rodine : 213 SPECIAL- As inhibitor
break down before disposal Citric Acid & Ammonia(20% )-for rinsing
Hydrazine Hydrate(80%) & Ammonia- for passivation,
Nitrogen Cylinders- for N2 capping
Hydrated Lime , Bleaching Powder, Caustic Soda Lye
(50%) for effluent treatment

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Chemical Cleaning Method METHOD (contd/-)

ALKALI BOIL OUT DM WATER RINSE
Blr filled with homogeneous soln of DSP & TSP prepared Done by filling & dumping method
in hot water(DSP-500 ppm & TSP-1000ppm)
Blr lighted up & pressure raised to 40 ksc Temp of DM water is kept 80 C by heating
Pressure maintained at 40 ksc for 4 hrs S/H backflushed with treated DM Water (pH-
Sample analysis done for alkalinity, silica, pH & oil content
Firing killed & blow down carried for 1 min.
10 & hydrazene-200ppm)
Pressure again raised to 40 ksc & maintained for 02 hrs Flushing is complete if PO4 content in
Firing killed & blow down carried for 1 min sample< 2ppm
Phosphate conc maintained during the process Upper & lower drums inspected & manually
Boil-out is complete if oil content< 5ppm or 8 blow downs
are done cleaned

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Method (contd/-) Method (contd/-)

Acid Cleaning
Carried out using soaking method using hydrochloric acid of 5% + 1%,
0.2% V/V inhibitor Rodine 213 and 0.25% ammonium bi-fluoride DM Water Rinse
The boiler filling in 1 hour (approx.) and draining in 1 hour (approx). is
accomplished
All the draining operations is done under nitrogen capping (Nitrogen
Rinsing done throu DM water pump with DM
press~0.5 1.0 ksc)
Total acid contact period< 6 hrs (including filling & draining time)
water temp~60-70 C
Temp of DM water restricted to 60-70 C
01 no CC pp run intermittently for 5 min after every 30 min Back flushing of S/H done by treated water
S/H back flushed with treated DM water (Hydrazene 200ppm & pH
10) Rinsing done under Nitrogen capping
Blr lighted up & blr water temp raised to 80 C
Acid pickling / soaking process is continued till iron concentration in
three consecutive samples shows equilibrium status
CC pp run & sample analysed
pH of the DM rinse is not allowed to go above
4.0
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Method (contd/-) Method (contd/-)

AMMONIATED CITRIC ACID RINSE DEMINERALISED WATER RINSE
Done by a solution of ammoniated citric acid (0.2%
acid soln & pH- 3.5 to 4) Done by fillng & dumping method
DM water temperature restricted to 60 to 65 C DM water temp maintained around 60 C
CC pp run & sample analysed for Fe & acid conc.
If lron concentration attains a steady state value for 3 Draining done under Nitrogen capping
consecutive readings, citric acid rinsing is declared Rinsing is complete if iron content in the
complete
Duration of rinse >4hrs & <5hrs(including filling and
sample is less than 25 ppm.
draining time)

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Method (contd/-) Method (contd/-)

NEUTRALISATION:
Done to neutralise any acidic pocket remaining in the system
and also to mildly passivate the acid pickled surface.
Done by a homogeneous soln of DSP(0.1%) & TSP (0.2%) filled
under Nitrogen capping
Blr lighted up & pressure raised to 10 ksc
Pressure of 10 ksc maintained for 06 hrs
Firing killed & blr allowed to cool before draining at 90 C
All the instrument lines that might have come into contact
during acid pickling are blown off
PASSIVATION:
Done to form a protective magnetite coating on the steam generating and
water touched surfaces that were exposed to the pickling process.
A blended solution of hydrazine and ammonia containing 200ppm
hydrazene & pH 10 is used
Blr filled with the blended solution throu water wall and the economizer
drains
Blr lighted up & pressure raised to 40ksc
Press held at 40 ksc for 24 hrs maintaining pH & hydrazene content
After 24 hours, boiler is shut down and allowed to cool slowly
Blr drained at 95 C under atm press
Coupons & blr drum inspected for smooth coating of magnetite layer

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Effluent Neutralization Schematic

ABO & Neutralization of pickled surface:

pH of the solution is lowered to less than 9.0 by sufficient
dilution with water.
Acid pickling:
Neutralized with caustic soda Lye & Lime powder (pH 5.5 to
9.0 and fluoride content < 2.0 ppm)
Citric Rinse:
Neutralized with caustic soda Lye (pH 5.5 to 9.0)
Passivation:
Hydrazine & Ammonia neutralized with bleaching powder

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ACID CLEANING
Boiler units can be acid cleaned by either the "circulation" or
"fill and soak" method. The circulation method can be used to
clean units with positive liquid flow paths, such as forced circulation
boilers. The inhibited acid solution is circulated through the unit at
the correct temperature until test analyses of samples from the
return line indicate that the acid strength has reached a
balance and no further reaction with the deposits is taking
place. Because the strength of the acid solution can be determined
frequently during the cleaning process, this method can be more
THANKS
accurately controlled and can use lower strength solutions than the
fill-and-soak method
The fill-and-soak method is used for cleaning units with natural
circulation. The boiler unit is filled with the inhibited acid solution at
the correct temperature and allowed to soak for the estimated
time. It is not possible to obtain accurate representative samples of
the cleaning solution during the soaking period

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