POST OPERATIONAL CHEMICAL CLEANING OF BOILER

BY DILIP KUMAR ,CHEMISTRY NTPC KAHALGAON

Post Operational Chemical Cleaning
of 210 MW Boiler
Unit No.3 at NTPC Kahalgaon SEPT-201

BY
CHEMCLEAN SERVICES
A-6, Sagar Co-op Hsg. Society, Near
Sushrut Hospital,
Chendhare, Alibag - 402201
DISTT. RAIGAD (MAHARASHTRA)
(INDIA)
 INTRODUCTION
Water-side scale build-up in boilers is
a progressive, inevitable process.
Even with stringent control of feed
water and condensate chemistry,
scale and deposition will occur.
The main problems caused by boiler
scales are:
1. Increase in tube wall temperature,
hence, boiler tube ruptures.
 PROBLEMS BY BOILER DEPOSITS
The increase in tube wall temperature is a
result of the low thermal conductivity of
scales as compared to metal. The
reduction in heat-transfer can lead to the
design temperature of the tube wall being
exceeded, which in turnMATERIAL
INSULATION may lead to failure
of the tube by creep rupture.
BOILER TUBES
FINS

FURNACE FLAME
 PROBLEMS BY BOILER DEPOSITS

Overall efficiency can be

defined as the ratio of
steam output to the fuel
consumption ratio.
Again, since scaling
impedes heat transfer,
more fuel is required to
produce a given amount
of steam, thus reducing
overall efficiency and
loss of energy.
REQUIREMENT OF CHEMICAL CLEANING

Removal of scale from the boiler becomes

essential if damage to the boiler is to be
prevented. One way of removing scale is to
chemically clean the boiler. Chemical
cleaning is a multiple stage process that
seeks to remove all the existing scale from
the boiler internals, leaving a clean,
passivated waterside system.
One step in the process involves the use
of inhibited acid to dissolve the scales.
THE CHEMISTRY OF BOILER SCALES

The primary constituent of boiler

scales is magnetite (Fe3O4), which is
formed as a result of the reaction of
metallic
Copper isiron with high-temperature
present due to corrosion of
steam.
the copper alloy, aluminium bronze
feed water condensers and pre-
heaters, often because of oxygen
ingress into these systems. Copper is
transported through the steam cycle
 THE CHEMISTRY OF BOILER SCALES
Other crystalline materials, some shown in Table
Table 1: Compounds Found in Boiler Scales
Compound
Formula
Anhydrite CaSO4
Aragonite CaCO3
Brucite Mg(OH)2
Copper Cu
Calcite CaCO3
Hematite Fe2O3
Hydroxyapetite
Ca10(OH)2(PO4)6
Magnetite Fe3O4
Quartz SiO2
Thenardite Na2SO4
 CHEMICAL CLEANING PROPOSAL

Chemical cleaning proposals must

take into consideration the
different compounds present in the
scale in order to formulate the
optimum cleaning solutions. This
recommendation should effectively
remove scale without damaging
the underlying metal.
 BOILER TUBE SAMPLES

Tube samples should be removed

from locations where heavy scaling
is suspected. The tube sample
should be at least three feet long
so the method of removal (cut-off
wheels and cutting torches) does
not contaminate the scale at the
centre of the sample with slag or
 ANALYSIS OF SCALES

The scale density is determined

gravimetrically after dissolution of
scale in inhibited HCl. Loss of
weight on firing in a furnace will
measure the percentage of
hydrocarbons present, which then
determines the need for alkaline
degreasing. The need to clean is
 SCALE DENSITY Vs ACTION PLAN

Scale Density Ranges and Required Action

Scale Density g/ft2 or (mg/cm2) Recommended Action

< 23 (25) No action required

23 70 (25 75) Chemically clean within one year
70 93 (75 100) Chemically clean within three months
> 93 (100) Chemically clean before further operation
 NTPC- NETRA
ANALYSIS OF SCALES DONE AT
NETRA( NTPC Energy Technology
Research Alliance) GREATER
NOIDA AND RECOMMENDED
TWO SAGE BOILER CHEMICAL
CLEANING OF KhSTPP U#3
 CHEMICAL CLEANING RECOMMENDATIONS
BY NETRA
Internal deposit 18.6-
52.5mg/cm2 at hot side of
surfaces and 15.6-48.6
mg/cm2 at cold side of
surfaces which is more than
40 mg/cm2 as per the limit if
IS-10391 and copper in
deposit is > 20%. On the
basis of internal deposit
quantity
Deposits and
and scale maydeposit
consist of silicates, sulphates, sulphites, carbonates, calcium,
analysis,
organic growths, two stage
etc. and all have post to cause tube wall damage and/or
the potential
decrease efficiency.
operational chemical
THE STEPS TO BOILER CHEMICAL CLEANING
AND TREATMENT SELECTION

Cleaning a boiler usually consists

of a combination of the following
stages:

o Mechanical cleaning
o Water flushing
o Alkaline treatment
o Solvent cleaning
o Neutralization and Passivation
 THE STEPS TO BOILER CHEMICAL CLEANING

MECHANICAL CLEANING: Mechanical cleaning and

water flushing can remove loose scale and other debris
from the boiler.

ALKALINE TREATMENT: Alkaline treatment removes oils

and hydrocarbons that might interfere with the
dissolution of the scale by acid solvents.

SOLVENT CLEANING: The solvent cleaning stage is the

process in which inhibited acid is used to remove scale
form the boiler.
Once the scale is removed in the solvent stage, fresh
active metal is exposed.
 HOT ALKALINE TREATMENT SELECTION

If oil, grease, carbon or other

organic compounds are present,
they must be removed during
chemical cleaning. Selection
depends on the degree of
contamination. Use hot alkaline
treatment only when organic
deposits interfere with solvent
cleaning. If solubility of deposits is
PROPOSED SCHEME FOR CHEMICAL
CLEANING
CHEMICAL CLEANING SITE
CHEMICAL CLEANING SITE
(TOP VIEW)
CHEMICAL RECIRCULATION PUMPS
 CHEMICAL CLEANING TECHNIQUE
Chemical cleaning shall be carried out
by circulation method using adequate
capacity and head pumps for achieving
desired velocity in each down comer and
riser tubes as well as the other parts of
the boiler. In general, circulating water
pumps will take suction from chemical
mixing tank and discharge is connected
to feed water line inlet to economizer.
The return from boiler is taken from
 SEQUENCE OF CLEANING OPERATION
The following sequence of operations shall be
carried out for complete removal of various
post-operational deposits such as Copper
Oxide, Iron oxide and other water side
impurities:
1. Preservation of super heater.
2. Water Rinse (Cold & Hot)
3. Copper Removal 1st Stage.
4. Acid Pickling / Iron & Copper
Removal
5. Citric Acid Rinsing
 PRESERVATION OF SUPER HEATER

The Super Heater Tubes Outlet is to be

plugged from inside of drum first and
Super Heater Coils are preserved by
filling of Ammoniated Hydrazine Solution
through Super Heater Drain Pipe Line.
Hydrazine concentration is to be
maintained at 200ppm and pH>10.This
system is to be kept under Constant
pressure by pumping the preservation
 TEST SAMPLES

Water wall tube pieces 1 2 3 4 5

of about 4-6 long
should be cut from
boiler and hanged
inside the boiler drum
by steel wire to see
the efficacy of
chemical cleaning just
BOILER TUBES SAMPLE BEFORE CHEMICAL CLEANING
after the completion
 COLD WATER RINSE
Cold D.M. Water flushing of the
system are carried out to
remove the loose deposit and
water soluble impurities from
the system. Turbidity should
be observed visually.
The process is to be
terminated once the water is
 DRUM

DRUM VENT
RI S E R TUBE

ECONOMISER
DO W N C O M E R
DM WATER

PUMP
W / W TUBES

ACID R/C TANK

BOTTOM RING HEADER

Eff
Pit TEMPORARY HEADER

TO ECONOMISER INLET
 HOT WATER RINSE

Hot Water Flushing shall be

done at 60-65C using external
steam for heating of the system
to removed the loose deposit
and water soluble impurities.
Turbidity should be observe
visually. The process is to be
 1st STAGE COPPER REMOVAL
Copper removal shall be carried out by using the
following chemicals quantity as in % with D.M.
Water and temperature maintained 65-70C.
a] Add Liquid Ammonia 1% (approx.) to raise pH
9.5 10.0
b] Sodium Nitrite (0.75%)
c] Ammonia Bi Carbonate (0.25%)
Add chemicals in following sequence after get
desired temp.
1. Add Liquid Ammonia 1%w/v.
2. Add 0.75% w/v Sodium Nitrite slowly, which acts
as an oxidizing agent.
 DRUM

DRUM VENT
AMMONIA,
SODIUM
NITRITE RI S E R TUBE

ECONOMISER
AMMONIUM

DO W N C O M E R
BICARBONATE

STEAM

PUMP W / W TUBES

ACID R/C TANK

BOTTOM RING HEADER

To Effluent Pit
TEMPORARY HEADER

TO ECONOMISER INLET
CHEMICAL REACTIONS IN COPPER REMOVAL
 D.M. WATER FLUSHING

D.M. Water filled and re-

circulation establish along with
temp.60C raising and drained
off the entire system and
analyzed the alkalinity nil traces
and pH normal.
Terminated the process at get
 IRON AND COPPER REMOVAL

Iron & Copper removal shall be carried

out by the using of following
Chemicals quantity as in
% with D.M. water.

1. Acid Inhibitor .(0.25%) Rodine 213Spl

2. Hydrochloric Acid (5%)
3. Ammonium Bi-fluoride (0.25%)
4. Thio-Urea (1.0%)
 IRON AND COPPER REMOVAL

Inhibited hydrochloric acid is a most

widely used solvent since it produces
good solubility with a wide variety of
scales, is economical and is easy to
handle. It shows good corrosion
characteristics when adequately
inhibited and the process is controlled
within the accepted limits.
The process is flexible and can be
tailored to complex copper by the
 IRON AND COPPER REMOVAL PROCEDURE

1.Fill the boiler system by DM water and establish

recirculation.
2. Raise the temperature of circulating water about
65-700C in return line.
3. Cut off steam and add a small quantity of HCl and
immediately followed by required quantity of acid
inhibitor. Acid concentration not exceeded by 6%.
4. Add required quantity of thio-urea into the
circulation tank and circulate the system for complete
mixing of chemicals.
5. Add calculated quantity of Ammonium bi-fluoride in
the mixing tank slowly and circulate the system for
complete mixing of chemical.
IRON AND COPPER REMOVAL REACTIONS
CHEMICALS

HYDROCHLORIC ACID

THIO-UREA

AMMONIUM BI-FLUORIDE
IRON AND COPPER REMOVAL REACTIONS
 DM WATER RINSE

Fill the system with the D.M. Water

and raise the temp up to 60C.
charging steam to the circulating
water. Analyze the samples from
inlet sampling point and a system
return line for acid, copper and iron
concentration. Terminated the
process after circulate the system
for half an hour. And drain the
 CITRIC ACID RINSE
Fill the system with the D.M.water.
Charges steam in the Mixing tank and
raise the temp. Of circulating water to
60-65C. Add. 0.2% w/v Citric Acid and
Liquid Ammonia to raise the pH to 3.5-
4.0

Terminated the process after circulate

the solution for 2 hrs. Analyzed the
 CITRIC ACID RINSE
The normal reasons for Citric Acid
selection are:
oPresence of austenitic materials of
construction.

oExtremely effective copper removal

from high copper- content scales.

oReduces cleaning time by eliminating

the need to drain, flush and refill the
CITRIC ACID RINSE CHEMICAL REACTIONS

Citric acid is weak and tri-basic organic acid and forms complex
compound with Fe2+ and Fe3+ which are stable in solution.
 D.M. WATER RINSE
Fill the water with D.M.water by
circulating pump. Rise the
0
temperature up to 60 C.
Terminated the process on
getting Iron Concentration < 25
ppm, copper concentration <1
ppm and Acidity Nil. Drain the
total system under Nitrogen
 NEUTRALISATION
Fill the system with DM water and
establish circulation. Measure the iron
content in the water. When the iron
content is less than 25 ppm, Add 0.5% of
soda ash in the circulating tank to
neutralize the system. Raise the
temperature of circulating water to 80-85
C by addition of steam and circulate for
6 hours. Measure
The purpose the
of neutralization is topH in the
end acidic nature inlet and
of solution.
 PASSIVATION STAGE-1

Purpose of this activity is to

create a uniform layer of
protective iron oxide on the
freshly treated surface. Use the
same system as used in acid
cleaning and carry out first
passivation immediately after
 PASSIVATION STAGE-1
Fill the system with D.M. water. Raise Temp.
of circulating water to 80-90C by charging
steam. Add required quantity of Hydrazine
hydrate to maintain 200ppm and ammonia
added to maintain the pH above
9.0.circulate for 20 hrs. Measure the
Hydrazine concentration and Ph of
circulating water periodically. Add the
hydrazine into the solution when the
concentration
Inspect goescooling)
the drum (after below 200 ppm. Drain
for magnetite
the system
coating in hotdebris
and remove condition. Open vent,
if available.
PASSIVATION STAGE-1
 PASSIVATION STAGE-1

INSIDE VIEW OF BOILER DRUM AFTER STAGE-1 PASSIVATION

 PASSIVATION STAGE-1

BOILER TUBE SAMPLES BEFORE

BOILER
CLEANING
TUBE SAMPLES AFTE
 PASSIVATION STAGE-1

The magnetite layer of thickness

50-100A thickness is temporary
during this process so second
stage passivation is required.
After draining the system hot cut
bottom ring header stubs and
cool down the system under
 PASSIVATION STAGE-2
After the chemical cleaning the
drum, internals are restored and
the boiler is prepared for regular
operation.
Fill up the boiler with DM water
having N2H4 200ppm and for
pH>10.
Light up the boiler at 40kg press
and maintain the press for 24 hrs
during the process maintain N2H4
EFFLUENT NEUTRALISATION & DISPOSAL

Remnant Hydrochloric Acid can be

neutralized by adding Soda Ash in
Neutralizing pit.
Make arrangement to dispose the effluents
into the ash dyke. confirm regulation of
pollution control board norms. The large
ash pond with sufficient retention time can
help non-complex copper, Iron to precipitate
as their hydroxide.
The effluent after first stage passivation
EFFLUENT NEUTRALISATION & DISPOSAL

Effluent
Neutralization
System contains
Effluent pit,
Effluent recirculation
pump,
Effluent disposal
pump, and
Air compressor for
effluent mixing
EFFLUENT NEUTRALISATION AND DISPOSAL SYSTEM
 Chemical Cleaning Evaluation
Inspection of the boiler after the chemical
cleaning is crucial to determine if the
procedure has been successfully
completed. Visual and video boroscope
inspections determine the effectiveness of
the cleaning. There should be no visible
traces of water and loose or adherent scale
inside the boiler drums and tubes. Remove
the corrosion coupons and the polarization
probes, visually examine them, determine
 Chemical Cleaning Evaluation

Scale Density after cleaning - Cut a tube

sample after chemical cleaning and determine
the density of any deposit.
 CONCLUSION
It is essential to clean a boiler periodically for
efficient operation, corrosion control, reliability
and prevention of tube failures. Cleaning is
accomplished by a combination of steps. For
some boilers it may not be necessary to use all
the cleaning steps, since the degree of
contamination will vary from one boiler to
another. The exact procedure to be used
depends upon the scale density and its analysis,
tube bulging or failure, water treatment analysis,
inspection and history or the unit itself. The
formulations recommended do not override the
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