Corrosion Damage in Power Plant & its

Prevention, Chemical cleaning of Boiler &

Condenser

23rd Dec 2016

 Corrosion Activities at NETRA

Cathodic
Protection
Corrosion of
Chemical
Turbines &
Development
Other
for CW System
Equipment

Health Corrosion
Assessment of Monitoring &
Boiler Tubes Audit
Corrosion
Analysis &
Research
Laboratory
Failure Water
Investigations Management

Acid Dew Point Selection of

Corrosion of Anticorrosive
2
HRSGs Coatings
Heat Transfer
Improvement
for Boilers & HE
 COST OF CORROSION

AS PER EPRI, USA, 2003 STUDIES:

Corrosion-related problems in fossil plant heat exchangers (condensers,

Feed-water heaters, service water heat exchangers, lube oil coolers, etc.)
have been estimated to cost approximately 360 million dollars per year
in 1998 in the United States.

Corrosion products picked up in the heat exchangers can lead to

increased deposition of copper and iron in the boiler, causing problems
such as under-deposit corrosion, and to copper deposition in high
pressure turbines, leading to power losses.

This aspect of the problem with condensers and heat

exchangers was estimated to cost approximately $150 million per year 3
 Power Plant Water Chemistry
Influenced Damages

Chemistry influenced component damage in fossil plant units is widespread and

includes the following mechanisms.

• Condenser tubes: steamside initiated stress corrosion cracking, pitting from the
steam side, condensate or ammonia grooving.
• Condenser structure: flow-accelerated corrosion of steam side shell, supports,
headers and piping.
• Deaerators: flow-accelerated corrosion, pitting, corrosion fatigue, and stress
corrosion cracking.
• Feedwater heaters and associated piping: general corrosion and pitting, corrosion
fatigue, flow-accelerated corrosion, stress corrosion cracking, and deposits.
• Economizer tubes: pitting, flow-accelerated corrosion and corrosion fatigue.
• Boiler tubes: hydrogen damage, acid phosphate corrosion, caustic gouging,
corrosion fatigue, pitting, and deposit induced overheating.
• Superheaters and reheaters: pitting, stress corrosion cracking, and corrosion
fatigue.
• Turbines: corrosion fatigue, erosion and corrosion, stress corrosion cracking, 4

crevice corrosion, pitting, and deposits (reducing efficiency and capacity).

 NETRA

WHAT IS CORROSION
CORROSION IS A NATURAL PROCESS BY VIRTUE OF
WHICH THE METALS TEND TO ACHIEVE THE
LEAST ENERGY STATE – I.E. COMBINED STATE

M M2+ + 2e-
ANODIC REACTION
N 2+ + 2e- N
CATHODIC REACTION
 NETRA

CORROSION
Anode
Fe  Fe2+ + 2e-
Fe2+ + 2OH-  Fe (OH)2
Fe (OH)2 + H2O + 1/2 O2  Fe (OH)3
Fe (OH)3  Fe2O3 . H2O + 2H2O

Cathode
2 H+ + 2e-  H2
4H+ + O2 + 4e-  4 OH-
O2 + 2H2O + 4e-  4 OH-
 Corrosion in boilers is a result of such operation which
can not be eliminated completely but can definitely be
minimized, by adopting various standard practices, to
such levels which result in efficient, reliable, consistent,
economic, and safe operation.

 The various practices include selection of proper cycle

chemistry (AVT, Phosphate, OT etc.), strictly adhering to
cycle chemistry parameters, boiler layup during idle
periods, chemical addition during hydro test, post
operational chemical cleaning whenever required, regular
boiler blowdown, use of condensate polishing, strict
control on make up water quality, strictly following the
boiler shutdown practices, and so on.
 Corrosion damage falls into two general categories:
chemical and electrochemical.
 Direct chemical corrosion is associated with highly
corrosive environments, such as those where metal
surfaces come into contact with strong acids or alkalis,
high temperatures, or both.
 Electrochemical corrosion, involves an oxidation-
reduction (redox) reaction, in which one metal, or area of
a metal surface, functions as an anode and another as a
cathode. Through this process, the metal dissolves in an
anodic reaction, producing positively charged metal ions,
which are plated out in the cathodic reaction. The
presence of dissolved oxygen in water is a major cause
of corrosion in utility boilers.
Potential - pH diagram for carbon steel
at 350°C and 165 kg/cm2
Black, thin internal magnetite protective layer
Internal deposit layer showing cracks
helps in wick boiling phenomena
Porous internal deposit layer in water
wall tube
Non uniform thick internal deposit layer
in water wall tube
Whitish, thick, adherent internal
deposit in water wall tube
 Factors influencing deposit in tubes
• Number of startups / shutdown
• Ingress of raw water from Condenser leakages
or seepages.
• Change in Feed / makeup water quality
• Crud formation due to corrosion at LP side and
transfer to the Boiler.
• Boiler water chemistry deviations
• Preservation of boilers during idle period
• Boiler cycle metallurgy
Values of Thermal Conductivities
Material W/m°C at Room temp.
Air 0.024
Carbon Steel 45
Boiler Scale 2.32
Cu-Ni 70:30 30
Cu-Ni 70:10 44
Copper 90
Titanium 16
Aluminium 0.04
Stainless steel 15
Steam 0.038
Red Brick 0.81-0.7
Water 0.55
VARIOUS PRACTICES ADOPTED FOR MINIMIZING THE
BOILER CORROSION

 SELECTION OF PROPER CYCLE CHEMISTRY

 CYCLE CHEMISTRY PARAMETERS
 BOILER LAYOUT DURING IDLE PERIODS
 CHEMICAL ADDITION DURING HYDRO TEST
 POST OPERATIONAL CHEMICAL CLEANING
 REGULAR BOILER BLOWDOWN
 CONDENSATE POLISHING
 MAKE UP WATER QUALITY
 BOLIER SHUTDOWN PRACTICES
SELECTION OF PROPER CYCLE CHEMISTRY

Proper cycle chemistry will help in minimizing the internal system corrosion to a large
extent. The various cycle chemistry treatment practices like AVT based on hydrazine and
ammonia, phosphate treatments, caustic treatment, and oxygenated treatment should be
selected based on system metallurgy, drum operating pressure, type of boiler i.e., drum
type or once through, subcritical or supercritical etc.

CYCLE CHEMISTRY PARAMETERS

The various steam-water cycle chemical parameters (e.g., pH, conductivity, sodium,
oxygen, silica etc.) must be adhered to the prescribed limits all the times. Deviations
should be strictly monitored and corrective actions to be taken immediately to bring the
cycle parameters within limits.
BOILER LAYOUT DURING IDLE PERIODS

 Follow good layup practice to prevent cycle corrosion. Inconsistent

layup practices contribute to a variety of problems, particularly
damage in condensers and copper fouling in turbines. Plants
following proper layup and startup procedures can expect
significantly less corrosion while units are offline, and subsequently
lower corrosion product transport during startup.
 The purpose of any layup procedure is to prevent corrosion during
the time that equipment is idle, and to ensure a rapid and uneventful
return to operation. Different steps are taken, depending on whether
a short or long-term idle period is expected. Short term is applied to
downtimes ranging from a few days to as long as two weeks and
anything longer than two weeks is termed as long term. Proper short-
term practice always involves the boiler, superheater, feedwater
heaters, dearator, and condenser. Long term steps involve the
turbine and other equipments.
BOILER LAYOUT DURING IDLE PERIODS
cont.
 Wet layup procedure is used for short term outages and dry layup for
long term outages. Wet layup protects better than dry layup,
because it can address boiler areas such as the superheater and
reheater, which are difficult to get to and keep completely dry. On the
downside , a wet layup requires additional time and manpower to
monitor and ensure that the unit is properly passivated.
 Both wet and dry layup, applied correctly and monitored closely, can
protect the steam cycle from corrosion but if improperly implemented,
either method can lead to corrosion and damage.
 CHEMICAL ADDITION DURING HYDRO TEST

 Chemical addition (ammonia and hydrazine) should be done to DM

water used for boiler hydro test. This will reduce boiler corrosion and
corrosion products carryover to the turbine.
 POST OPERATIONAL CHEMICAL CLEANING

 The oxide/deposits thickness on heat transfer surfaces should be

regularly monitored and chemical cleaning to be performed wherever
the thickness exceeds the limiting values in order to maintain the
proper heat transfer and avoid under deposit corrosion. Proper
chemical cleaning methods should be adopted and strictly followed.

 REGULAR BOILER BLOWDOWN

 To take care of accumulation of pre-boiler corrosion products

transported to boiler drum in the form of crud, regular boiler
blowdown practices should be followed.
 CONDENSATE POLISHING

 Condensate polishing units improves the quality of boiler feed water

by using ion exchange to remove soluble species and filtration to
remove insoluble species from cycle condensate. This improvement
in steam water cycle chemistry minimizes the corrosion in the
system. Besides their usefulness in normal operating conditions
these units offer very good protection under startup and condenser
leak conditions.

 MAKE UP WATER QUALITY

 Good makeup water quality (cond. <0.1S/cm, silica <10ppb) will

introduce minimum amount of impurities in the system and thus
minimizing corrosion. Proper attention to be given to water pre-
treatment and demineralization to achieve good makeup water
quality.
BOLIER SHUTDOWN PRACTICES
 When a boiler is taken out of service, take special precautions to
prevent mechanical damage. These precautions will also help
minimizing water side deposition as a result of suspended solids
baking on to internal surfaces during the cooling process. To avoid
mechanical damage as a result of thermal stresses, follow the
manufacturer’s instructions for the rate of boiler cooling as well
as any other recommended procedures.
 In operation, boiler water contains solids suspended by water
circulation. Unless suitable procedures are observed during the
entire shutdown process, these suspended solids will settle on boiler
surfaces to form an adherent deposit that may require special
removal methods. In addition, unless such deposition is examined
carefully, it may be incorrectly assumed to be scale that was formed
during operation. Proper care is imperative during shutdown, both for
correct evaluation of treatment processes and to eliminate
unnecessary boiler cleaning.
VARIOUS CORROSION RELATED
DAMAGE MECHANISMS
 CHEMICAL CLEANING DAMAGE
 CORROSION FATIGUE
 FIRESIDE CORROSION

 UNDERDEPOSIT CORROSION
 ACID PHOSPHATE CORROSION (PHOSPHATE HIDEOUT AND
RETURN)
 CAUSTIC GOUGING
 HYDROGEN DAMAGE
 GRAPHITIZATION
 PITTING
 SHORT-TERM OVERHEATING
 LONG-TERM OVERHEATING/CREEP
CHEMICAL CLEANING DAMAGE
 Acid cleaning, typically with hydrochloric acid, is routinely performed
to remove built-up deposits on boiler tube steam-side surfaces. Steel
corrodes in low pH environments, and for this reason inhibitors are
usually added along with the acid to reduce corrosion of the tube
metal. If not carefully controlled, however, the cleaning process can
lead to extensive tube corrosion. Temperature excursions can cause
the inhibitor to break down and become ineffective. Use of
inappropriate cleaning agents, excessively high acid concentration or
long cleaning times, or failure to completely neutralize, drain, and
rinse after cleaning can also result in tube corrosion.

 The entire cleaning operation, including temperature, cleaning agent

concentration, and the iron and copper content of the cleaning
solution during and after the operation, should be carefully
monitored. A visual inspection of tube and drum internals should be
performed following the cleaning.
200MW unit, W/W tube, Internal oxide containing copper
 CORROSION FATIGUE
 Corrosion fatigue is caused by the combined action of thermally induced
stresses from load cycling and corrosive boiler water conditions. On the
steam-side, cracks that are formed from oxygen or acid cleaning pits, or
along cracks in the protective iron oxide coating as a result of cyclic stress,
can act as stress concentrators. These cracks may also become anodic
and prone to localized corrosion.
 Corrective actions
 Redesign of tube attachments
 to eliminate or reduce differences in thermal expansion between joining
components
 timely chemical cleaning to remove tube deposits before pitting occurs—
while avoiding overly aggressive cleaning; eliminate impurity ingress (e.g.,
condenser leaks)
 restore water chemistry stability, with a focus on limiting the dissolved
oxygen level to <5 ppb and main-taining pH within limit
 Restrictions on the amount of cyclic operation may also be necessary if
corrosion fatigue failures are frequent.
 FIRESIDE CORROSION
 Corrosion of external superheater or reheater tube
surfaces is most often caused by
 low-melting-point, complex alkali compounds in coal and
oil ash. In the case of corrosive coal ash, an alkali-iron-
trisulfate layer covering an iron sulfide/iron oxide scale
is commonly observed in the deposit. For oil ash
corrosion, sodium vanadates or vanadylvanadates are
generally found.
 This corrosion mechanism occurs after the tubing has
reached a sufficiently high temperature (to melt the
corrosive alkali compound. Melting points between
approximately 550°C to 620°C have been measured. It
is, thus, expected that regions of tubing operating above
540°C are prone to this type of attack. The liquid ash will
readily attack both ferritic and austenitic tubing.
 Fireside corrosion of SH/RH by sulfidation
mechanism when reducing conditions exist.
This form of corrosion has been observed on
austenitic stainless steel tubing. Discrete iron
sulfides have been found in the grain
boundaries on the corroded region of the
tubes, which also exhibit surface
carburization.
 FIRESIDE CORROSION (CONTD.)
 Corrective actions depend on the
 severity of the ash corrosion problem.
 The presence of a liquid ash, which would provide a measure of ash
corrosivity, can be confirmed by measuring the melting temperatures
of the fireside scale/ash constituents.
 Long-term solutions to fireside corrosion problems include fuel blending
or use of additives. Lowering the tube crown temperatures of the
hottest tubes through burner tuning or steam flow redistribution, or
replacing tubes using more corrosion resistant materials or thicker
walls can also be effective.
 If corrosion is occurring under reducing/carburizing conditions,
maintaining sufficient and proper air delivery,
 secondary, and tertiary air will assure complete combustion and will
minimize the carbon monoxide and hydrogen sulfide levels relative to
the oxygen concentration.
 Excessive oxygen concentration must also be avoided, as this will
increase the likelihood and rate of liquid ash corrosion.
UNDERDEPOSIT CORROSION

 The general category of under deposit corrosion represents a subset

of corrosion damage that includes
 Acid phosphate corrosion,
 Caustic gouging, and
 Hydrogen damage.

 Each is characterized by localized concentration of a corrosive

agent, typically in regions of high heat flux or high deposit buildup
such as weld backing rings, protrusions, and crevices.
 ACID PHOSPHATE CORROSION (PHOSPHATE HIDEOUT AND
RETURN)
 Phosphate corrosion is caused by a combination of high boiler pressure,
high inside surface metal temperature, and high local concentrations of
monosodium or disodium phosphate. It has only been observed in boilers
in which monosodium and disodium phosphate was added. It has also
been observed in boilers that use only trisodium phosphate.
 Phosphate corrosion is also associated with phosphate hideout and
return, where phosphate concentrations fluctuate with pressure. During
boiler shutdown or pressure reduction, the phosphate that hide out in the
boiler during pressure increase is returned to the system.
 The return of phosphate can cause a pH depression in the boiler
water, which can lead to depletion of the tube surface protective layer,
and ultimately the base metal of boiler tubes.
 In high-pressure boilers (above 180 kg/cm2) and at high heat fluxes,
sodium phosphate can become concentrated within deposits, leading to
rapid corrosion of the underlying metal. This corrosive condition involves
a phosphate concentrating mechanism, such as local steam blanketing or
boiling within porous deposit, and buildup of a thermal barrier (from local
steam blanketing or from the buildup of an internal deposit).
 ACID PHOSPHATE CORROSION (PHOSPHATE HIDEOUT AND
RETURN) (CONTD.)
 Corrective actions center around improving control of boiler water
chemistry
 by switching to low level or equilibrium phosphate control
 using only trisodium phosphate;
 minimizing the ingress of feed water corrosion products into the
boiler; and
 removal of corrosion product deposits by periodic chemical cleaning.
 Boiler operating conditions that result in local hot spots, such as
excessive over firing or under firing, misaligned burners,
 Eliminating welds with backing rings or other internal surface contour
irregularities can help in reducing internal deposits that can cause a
thermal barrier.
 In cases where inadequate circulation produces local steam
blanketing, design modifications may even be necessary.
 Caustic Gouging
• High degree of localised concentration is necessary
for caustic corrosion.
• Caustic generated due to decomposition of TSP
dosing in the boiler.
• Caustic reacts with the magnetite and forms sodium
ferrite (NaFeO2) and sodium Ferroate (Na2FeO2).
• Ferroate / ferrite changes to magnetite and caustic in
the boiler. Loose magnetite settles in drum or down
comers.
• Carbon steel shows the gouging where as stainless
steel shows inter-granular or trans-granular corrosion.
Internal and whitish deposit
formation due to caustic attack
Gouging and thickness reduction in
w/w tube adjacent to weld zone
Gouging and thickness reduction in
w/w tube near the weld zone after
chemical cleaning in laboratory
 CAUSTIC GOUGING
 Caustic gouging is caused by localized concentration of sodium
hydroxide (NaOH) to high pH levels, which solubilizes the protective
magnetite layer of the tubing steel and leads to rapid dissolution of the
underlying tube metal.
 Susceptible boiler locations include high heat flux regions, horizontal or
inclined tubing, and sections that have flow disruptions such as weld
backing rings, protrusions, and crevices.
 In the case of high heat flux areas, feed water corrosion products deposit
and accumulate in these locations and act as concentrators of NaOH
through a process known as wick boiling, in which feed water is drawn to
the tube surface underneath the porous deposit where boiling is
enhanced, leaving behind any dissolved salts. In inclined or horizontal
tubes, steam tends to accumulate on the upper surface of the tube,
creating a steam blanket in which soluble salts, such as NaOH, can
become concentrated. The protective oxide is then attacked by the high
pH conditions, and the underlying metal is rapidly corroded, usually in a
localized region centered on the crown of the tube where temperatures
are highest. The locally thinned tube often corrodes through or succumbs
to ductile rupture.
 CAUSTIC GOUGING (CONTD.)
 Typical reactions of caustic with iron oxide and iron are:

 Fe3O4 + 4NaOH ---> 2NaFeO2 + Na2FeO2 + 2H2O

 2NaOH + Fe ---> Na2FeO2 + H2

 Preventive actions center around improvements in boiler water

chemistry,
 minimizing the ingress of feed water corrosion products and
condenser leakage products,
 removing corrosion product deposits through periodic chemical
cleaning.
 In addition, boiler operating conditions that lead to local hot spots,
such as excessive over firing or under firing, misaligned burners, and
gas channeling, should be modified.
60MW unit, W/W tube, Gauging from internal surface
210 MW unit, W/W tube, Under deposit corrosion
 Hydrogen Damage
• Bulk boiler water pH remains alkaline.

• Acidic condition generated on tube surface beneath

the deposits. Presence of chloride was confirmed
• Acidic condition develops due to presence of
hydrolysable chloride concentrated by wick boiling
phenomena.
• Hydrogen generated due to localised corrosion
enters tube metal and forms methane with carbon.
• Fissures were generated in the tubes which
combines and failure due to hydrogen damage takes
place.
Hydrogen damage mechanism
H+ + Cl- = HCl
HCl + Fe2O3 = FeCl2 +
FeCl3
Fe + 2 HCl = FeCl2
H+ + e- = H°
(Atomic Hydrogen)

H° + Fe3C = Fe + CH4
Cementite (Methane gas)

Methane gas forms fissures on

grain boundary and form inter
granular cracks which when joins,
the tube fail.
Cracks develop in water wall tube
due to hydrogen damage
 HYDROGEN DAMAGE
 Hydrogen damage results from low pH (acidic) conditions,
either in localized areas or in overall boiler water chemistry,
that lead to corrosion and subsequent diffusion of hydrogen
into the steel tubing.
 Under low pH conditions, the protective surface oxide of the
tubing steel breaks down and exposes the base metal to
attack. This corrosion reaction produces hydrogen at the
metal surface, which diffuses into the steel and reacts with
iron carbide (Fe3C) to form methane gas. This reaction also
produces weakened regions due to local decarburization of
the steel. The large methane molecules, which cannot easily
diffuse through the metal lattice, become trapped at grain
boundaries. As the gas accumulates, the pressure builds,
and networks of internal fissures form, which link up over time
to cause through-wall fractures.
Thick and adherent deposit in water
wall tube and crack generated due to
hydrogen damage
Window opening due to Hydrogen damage
in Water wall tube
 Fissures and Cracks developed in the
• tube due to Hydrogen damage
 Fissures and Cracks developed in the
tube due to Hydrogen damage
•
 Fissures and Cracks developed in the
tube due to Hydrogen damage
•
 Fissures and Cracks developed in the
tube due to Hydrogen damage
•
 HYDROGEN DAMAGE (CONTD.)
 Corrective actions include
 maintaining boiler water chemistry at the proper values;
 promptly reacting to contaminant ingress and removing the boiler
from service if the pH drops below 7;
 elimination of hot spots or flow disrupters where excessive deposition
can take place.
 Chemical cleaning can be employed to remove the internal deposits
and to stop further generation of hydrogen on the tube surface. It
should be considered when the boiler water pH has been below
seven for more than one hour due to the ingress of saline
condenser cooling water or acidic chemicals into the boiler, or
from breakdown of boiler water conditioning elements. If
significant wall thinning has occurred, the damaged tubing sections
must be replaced to prevent repeat failures later in service. The use
of low alloy steel tubes will reduce the likelihood of hydrogen
damage. Pad weld repairs, which can lead to deposit buildup, should
be avoided.
210MW unit, W/W tube, H2 damage
210MW unit, W/W tube, H2 damage
 GRAPHITIZATION

 Graphitization is a diffusion process whereby graphite nodules form

as carbon atoms migrate from supersaturated ferrite. Although the
microstructure of a typical boiler tube is metastable, it will remain
essentially unchanged below about 430°C. If the tube sustains long-
term exposure with metal temperatures between 430°C and 720°C,
the pearlitic microstructure will decompose by spheroidization of the
peralitic lamellae, and by graphitization if the steel contains less than
about 0.6% chromium. Graphitization occurs preferentially between
the two competing mechanisms at temperatures below
approximately 550°C. Graphitization is most damaging when the
graphite particles form continuous planes of weakness, which has
been observed in the grain refined region of weld heat affected
zones.
110MW unit, W/W tube, Graphitization
 GRAPHITIZATION (CONTD.)
 The extent and cause of the graphitization can be determined by
metallographic examination, mechanical tests, chemical composition
analysis, and temperature exposure measurements. Steels with
more than about 0.6% chromium are immune. Steels containing less
than 0.6% chromium (i.e. SA-209-T2) may need to be replaced if
used under conditions where long-term exposure promotes graphite
formation. In susceptible steels, aluminum contents above 0.025%
increase the tendency for graphitization. Weld joints can be stabilized
to resist chain like graphitization by a post-weld heat treatment
between 720°C and 730°C for a minimum of four hours.
 PITTING
 Pitting occurs when small imperfections or cracks develop in a tube’s
protective oxide layer, exposing the underlying metal to localized
corrosion. The corrosion can result from either acidic conditions, or
high dissolved oxygen at the tube surface, which cause small anodic
regions to form on the tube surface with the adjacent metal acting as
the cathode.
 Pitting commonly results from two sources, both associated with unit
shutdown. The first involves poor shutdown procedures, which
produce locations with stagnant oxygenated water. Forced cooling
and/or improper draining and venting procedures can result in
excess moisture throughout the boiler. Economizer tubes and the
bottom of pendant loops of superheaters and reheaters are common
locations where stagnant conditions can occur. The second source of
pitting occurs primarily in reheater tubes because of deposited
Na2SO4 compounds. Reheater circuits are particularly susceptible
locations because the temperature and pressure conditions increase
the solubility of Na2SO4 compounds, which acidify during shutdown
periods.
 PITTING (CONTD.)
 Corrective actions focus on protecting tubing during non operating
periods. Proper draining and venting after shutdown will reduce the
amount of moisture that condenses in the tubing as the boiler cools.
Nitrogen blankets or caps of the steam-cooled circuits can provide
protection during outages of less than four days, while long-term
protection involves filling the superheater and reheater tubing with
condensate that contains hydrazine and ammonia
210MW unit, W/W tube, Pitting corrosion
210MW unit, W/W tube, Pitting corrosion
Overheating of tube due to internal
oxide/deposition
 SHORT-TERM OVERHEATING

 This type of failure is usually indicated by a ‘thin-lipped’ burst of the

boiler tube.
 These failures occur
 when water circulation in the tube is interrupted, and the
 flue gas temperature cause a rapid overheating of the metal to a
point where the metal becomes highly plastic and a violent burst
occurs.
 Typical causes of short term overheating are circulation
problems caused by poor operation (sudden incraese in steam
demand or low water level) or design, and tube blockage. Tube
blockage normally occurs from deposition in the tube or supply
header.
 LONG-TERM OVERHEATING/CREEP

 This type of failure is usually indicated by a ‘thick-lipped’ burst of

the boiler tube.
 Long term overheating can result from excessive deposition,
 flame impingement,
 mild flow restrictions, or
 poor water or flue gas circulation patterns.
 Probably the most common of these is excessive deposition, which
prevent proper heat transfer and excessive metal temperatures. This
prolonged overheating of the tube causes metal degradation to the
point that it can no longer handle the operating pressure and a thick-
lipped failure occurs.
 Increase in metal temperature due to
internal scale
T T
E H
M I
P C
E K
R N
A E
T S
U S
R
E

HEAT FLUX KW/m2

Mechanism of local concentration in Water wall
tubes due to under deposit corrosion and tube
thickness reduction by Wick Boiling
Swelling in Water wall tubes due to under deposit
corrosion and tube thickness reduction
Mechanism Chemistry influence
Corrosion fatigue Poor water chemistry, shut down
and lay up practices, improper
chemical cleaning
Hydrogen damage Excessive deposits from feed
water corrosion products combined
with acids or salts
Caustic Gouging Excessive deposits from feed
water corrosion products combined
with acids or salts

Fire Side corrosion Mechanism accelerated tube metal

temp. resulting from excessive
deposits
Mechanism Chemistry influence

Short and long term Increased tube metal temp.

Overheating resulting from excessive
deposits; orifice plugging by
feed water corrosion products
prevent cooling

Flow-Accelerated corrosion Reducing condition and

low pH water

Pitting in economizer stagnant, oxygenated water

during shut down

Pitting in re-heater Concentration of salts or

H2SO4 at lower bends during
lay up; carry over or flue gas
 Remedial Measures
• Periodic Post operational acid cleaning of
boilers to remove the existing internal oxide
layer and formation of protective magnetite
layer.
• Control the ingress of impurities i.e.
cooling water through condenser, which will
reduce the phenomena of salt concentration
by “wick boiling”.
 Recommendations
• To control such failures, attempts have been made in
NTPC and worldwide to use condensate polishing
units (CPU)
• Maintain the boiler water chemistry parameters
suggested by manufacturers to reduce the internal
corrosion.
• Control of cooling water ingress from condenser.
• Follow the guidelines of Boiler preservation during
shutdown.
• Periodic chemical cleaning of water wall in boilers.
• DM water washing of super heater tubes.
• maintain the parameters during startups and
shutdown of boiler.
 Boiler water treatment by Tri sodium
phosphate in 200 / 500 MW boilers
Addition of TSP either by itself or in conjunction with
NaOH provide the pH necessary to minimise the
corrosion of carbon steel tubes.
TSP also provide the sufficient chemical buffering
capacity to cope with small system upset e.g. a small
condenser leaks.
Phosphate also has the ability to significantly curtail the
incidents of caustic embrittlement.
It is economical and easy to handle.
It requires a need to get tighter control.
MAIN ADVANTAGES OF OXYGENATED BOILER
WATER TERATMENT
RELIABLE FORMATION OF PASSIVE LAYERS,
RESULTING IN A LOW PRESSURE DROPS
IRON CONTENT IN FEED WATER IS REDUCED
PRECIPITATION ON BOILER SURFACES IS KEPT LOW
POST – OPERATIONAL ACID CLEANING IS
DRASTICALLY REDUCED
AMMONIA CONTENT IS LOW RESULTING IN LONGER
OPERATIONAL CYCLES FOR CPU & LOW CHEMICAL
CONSUMPTION
FOUR PREERQUISITE CONDITION FOR OT IN
ONCE-THROUGH AND DRUM

1. ALL-FERROUS FEEDWATER HEATER

METALLURGY (COPPER ALLOYS MAY BE
USED ONLY IN CONDENSER TUBING)
2. CATION CONDUCTIVITY <0.15 µS/cm IN
CONDENSATE, FEEDWATER AND STEAM
3. HYDRAZINE AND OTHER OXYGEN
SCAVANGERS ARE NOT USED

4. CONDENSATE POLISHING UNITS

OT REDUCES OR ELIMINATES MOST OF THE
TYPICAL AVT PROBLEMS
1. FLOW ACCELERATED COROSION
2. DEPOSITION OF FEEDWATER CORROSION
PRODUCTS
3. CORROSION PORDUCT TRANSPORT INTO THE
BOILER RESULTING IN ORIFICE FOULING,
BOILER DEPOSITS, OVERHEATING AND
FREQUENT TUBE CLEANING
4. TURBINE FOULING
5. COPPER ALLOY CONDENSER TUBE FAILURES
(WHEN OPERATING WITH OT AT REDUCED
AMMONIA LEVEL)
Corrosion Control
 Choice of different metal
 Design modification
 Application of Coating
 Change of environment
 Intervention in the reaction
 Changing inprocedure
 POST-OPERATIONAL CHEMICAL
CLEANING OF BOILER
 NETRA

CORROSION IN CW SYSTEM

• PIPELINES
• CONDENSER WATER BOXES
• TUBE PLATES
• TUBE - TUBE PLATE JOINTS
• CONDENSER TUBES - INTERNALS
• CONDENSER TUBES - EXTERNALS
• INLET END OF CONDENSER TUBES
• PUMPS
• BOILER TUBES (CARRY OVER)
• AUXILLIARY COOLING WATER SYSTEM
• HEAT EXCHANGERS
• PLATE HEAT EXCHANGERS
Metals to be considered

98
 NETRA
Causes of Corrosion
 Dissolved Oxygen
 Dissolved and suspended solids
 Acidity – Alkalinity
 Water velocity
 Temperature
 Microbiological Growth
 Presence of CO, NH3, H2S and Chlorine
 High Chloride /sulphate
 Galvanic Action
 Pollutants
 Fouling/ Under deposit corrosion
The pH or alkalinity of the water is extremely important as it
affects corrosion significantly.
As a general rule corrosion potential decreases when pH
increases, but as the pH increase so does the potential
for scale.
 NETRA
CORROSION CONTROL
 pH adjustment
 Effective aeration
 Effective Chlorination
 Balancing the chloride and hardness
 Polyphosphate dosing
 Ferrous sulphate dosing
 Cathodic Protection
 Corrosion inhibitors
 Correct design
 Corrosion resistant materials
 Anti corrosive coating
 Avoid galvanic coupling
 Keeping the system clean
 NETRA
Corrosion Control
Corrosion inhibitors are used to control the
corrosion in CW system, which are
Phosphates -When added to the system in
presence of calcium hardness will form a cathodic
inhibitor.
 Chromates : Anodic inhibitor
 Zinc : Cathodic inhibitor, which provides excellent
pitting corrosion protection.
 Tiazoles : An anodic inhibitor that specifically
protects system yellow metals.
 Phosphonates : Cathodic inhibitor which that lays
down monomolecular film on metal surfaces.
 Molybdates : A non toxic heavy metal that is
excellent anodic inhibitor
 NETRA

CORROSION INHIBITORS

ANODIC CATHODIC

Chromate Polyphosphate
Zinc
Orthophosphate
Molybdate
Nitrite Polysilicate
Phosphonates
Orthosilicate
 NETRA

Corrosion Monitoring

System corrosion rates can be measured

with the use of:

 Corrosion Coupons
 Corrator Readings
 Water chemistry tests
 NETRA

CORROSION RATE BY WEIGHT LOSS

22.3 x W
C.R. (mpy) =
DxAxT

MPY = Mils Per Year

W = Weight Loss (mg)
D = Specific Gravity (gm / cm2)
A = Exposed Area (inch2)
T = Time (Days)

1 MM = 40 Mils
1 MIL = 25 Microns
 PROBLEMS DUE TO LEAKAGE
FROM CONDENSER TUBES
Many of the corrosion problems in fossil fuel boilers, LP steam turbines
and feedwater heaters have been traced to leaking condensers.

Tube leaks allow the ingress of cooling water into the steam-water cycle.

The very nature of the condenser tends to increase a problem with cooling
water leakage, in that the condensate side of the condenser operates in a
vacuum and thus any leak in a tube wall or other connection will allow
cooling water to be drawn into, and contaminate, the pure condensate.

The acceptable impurity levels in cooling water are much higher than
those acceptable for the condensate.

This can be a problem in both once-through systems and in recirculating

systems.
105
 PROBLEMS DUE TO LEAKAGE
FROM CONDENSER TUBES
For example, in the event of a leaking tube, cooling tower water can present
a contamination problem nearly as bad as seawater because of its high
hardness and high concentrations of other dissolved solids.

Cooling water also often contains chemicals added to control biofouling,

scale and silt. Condenser corrosion problems have increased in the past few
years, in part, as a result of higher pollution in cooling water.

Use of treatment plant effluent as tower makeup is growing and also

increases the risk of problems.

Condensate polishers can provide some protection against impurity ingress

to the cycle; however, their capability can be overwhelmed by condenser
leaks and, during larger leaks, can be exhausted within minutes.

The effect of condenser tube leaks and damage are manifest. These include
106
effects on cycle chemistry, steam generators and boilers, the turbine, and
plant discharges.
 EFFECTS OF CONDENSER
TUBE LEAKS AND DAMAGE

The ingress of cooling water into the steamside of the condenser will result in its
subsequent distribution into the water-steam cycle.

Carried throughout the cycle, there is a significant potential for damage to the steam
generator or boiler, and turbine.

Steam generators and boilers are typically the components most susceptible to damage by
contaminants from condenser leakage.

In some cases degradation of steam generator materials has progressed to the point that
replacement of the steam generators has been required.

A number of studies have demonstrated the incentive to minimize aggressive impurities

introduced into the steam generator feedwater by leakage of cooling water and/or air into
the condenser.

Boiler tube failure mechanisms in fossil-fueled power plants that are

107
influenced by condenser tube leaks include: hydrogen damage, corrosion
fatigue, pitting and stress corrosion cracking.
 CONDENSER TUBE DAMAGE
MECHANISMS
Screening Table for Condenser Tube Water-side Damage Mechanisms
Damage Mechanism Most Commonly Affected
Material(s)
Erosion-Corrosion Copper alloys

Sulphide Attack Copper alloys

Pitting Some Stainless Steels, Copper alloys
Crevice Corrosion Copper alloys, some Stainless Steels
Dealloying Copper alloys
Microbiologically Copper alloys, Stainless Steels
Induced Corrosion 108

Galvanic Corrosion Requires susceptible combination of

metals
 CONDENSER TUBE DAMAGE
MECHANISMS
Screening Table for Condenser Tube Water-side Damage Mechanisms

Damage Mechanism Most Commonly Affected

Material(s)
Hydriding Titanium

Hydrogen Ferritic Stainless steels

Embrittlement
Cleaning Damage Copper alloys most affected by
mechanical Cleaning damage.
Copper alloys & Stainless steels most
affected by chemical cleaning damage109
Cavitation Damage All materials potentially susceptible
from Tube Vibration
 CONDENSER TUBE DAMAGE
MECHANISMS
Screening Table for Condenser Tube Steam-side Damage Mechanisms
Damage Mechanism Most Commonly Affected
Material(s)
Steam side Erosion Copper alloys are most affected but
(Impingement SS and Titanium can also be affected
damage)
Impact damage Any Tube Material is susceptible
Condensate corrosion Copper alloys
(Ammonia Grooving)
Steam side SCC Copper alloys 110

Fretting and Fretting All materials potentially susceptible,

Corrosion from Tube although thin-walled titanium tubes
 CONDENSER TUBE DAMAGE
MECHANISMS
Screening Table for Condenser Tube Steam-side Damage Mechanisms

Damage Mechanism Most Commonly Affected

Material(s)
Tube Impact Damage All materials potentially susceptible;
from Tube Vibration thin Walled titanium tubes have been
more susceptible if Support spacing
is inadequate.
Fatigue & Fatigue All materials potentially susceptible;
Corrosion from Tube thin Walled titanium tubes have been
Vibration more susceptible if Support spacing
111
is inadequate.
 Losses in Pipelines due to Friction Head &
consequent Energy Losses

Pump designed for 630 m3/hr was delivering 450 m3/hr due to
Severe fouling. Corrosion products 112
Losses in Pipelines due to Friction Head &
consequent Energy Losses

113
Losses in Pipelines due to Friction Head &
consequent Energy Losses
• Corrosion due to water flowing inside the pipe results in
development of rough surfaces and additionally the
corrosion products reduce the effective internal diameter of
the pipe.

• In many small diameter pipes the nodular growth

(tuberculation) causes reduction of diameter of pipe to
almost 1/10th or lesser of the original diameter besides
creating highly rough surface.

• This results in very high-energy losses and non-availability

of sufficient water required for specific purpose such as
cooling or drinking.

114
 Corrosion in RCC Structures

• Support structures of coal

conveyor belt - incorrect design
of the support member &
improper coating

Recommendations
• Modified design of base of the
support member so as to ensure
complete removal for coal slurry
from the joint of concrete & member
• Replacement of damaged members
by new members
• Application of coal tar based epoxy
coating after proper surface
preparation through qualified
115
applicators
• Avoidance of accumulation of coal
slurry at the base of the members
 Corrosion in pipelines carrying water
(internal side & external side)

• Internal side - water chemistry &

microbiological species,
stagnancy
• External Side – Soil, stray
current

Recommendations
• Design & execution of cathodic
protection systems.
• Replacement pipe material with
HDPE, SS
• Anticorrosive coatings
• Dosing of chlorine dioxide with
chlorine as biocide to control
microbiology.
116
• Water treatment
• Ensuring regular flushing of
pipelines
 Corrosion in Condenser &
heat exchanger tubes
• Condenser tubes (Brass) - stress corrosion
cracking. Dezincification & under deposit
corrosion due to water
chemistry/microbiological species
• Corrosion of Condenser Water Boxes:
Tube plates – Poor quality of cooling
water & poor corrosion protection
• Aluminum Brass tube failures by seawater
– Pitting, deposition, MIC
• Failure in transit/storage – Crevice
corrosion, pitting, thinning due to ingress
of seawater
Recommendations
• Replacement of brass tubes with copper- nickel
tubes for fresh water service.
• Replacement of brass tubes with titanium tubes
for seawater service.
• Application of anticorrosive coatings and
cathodic protection system for water boxes/tube
plates
117
• Replacement of damaged SS tubes with new
tubes.
 PREVENTION OF INGRESS OF
COOLING WATER IN FEED CYCLE
• Detailed failure analysis of condenser tubes to assess the cause of
failure.
• Checking of Baffles & proper control of boiler water chemistry to prevent
steam side corrosion.
• Development & execution of suitable site specific chemical treatment to
control corrosion, fouling, scaling & biofouling/MIC including biocides.
• Development & execution of cleaning methodology to remove deposits,
foulants, corrosion products to restore heat transfer/under deposit
corrosion.
• Design & Installation of Cathodic Protection systems for condenser
water boxes and tube plates.
• Recommendations of anti-corrosive coatings for condenser water
boxes, tube plates, CW ducts, etc.
• Recommendations for online monitoring equipment to assess the
corrosive, fouling, biofouling tendencies of cooling waters. 118

• Efforts are being made to develop suitable sensors/probes for

measurement of corrosion of boiler tubes on real time basis.
In-situ Integrity Assessment
of
Condenser Tubes
 In-situ integrity assessment of condenser tubes
In service, condenser tubes are subjected to reduction in
thickness due to corrosion, erosion etc.
• Significant wall thinning or localized deep pits could
cause tube leakage, which will provide path for mixing of
cooling water with DM water and would cause different
problems.
• Periodic monitoring of tube thickness is desirable
- To have feedback on general healthiness of tubes
- To plug the tubes, which are expected to leak before next
shutdown/ opportunity for tracking the tube thinning.
- To get time for planning for tube replacement
 Methods for in-situ integrity assessment of condenser tubes

Nature of Test Component (Condenser Tubes)

- Tubes might be in length from ~7.5 m to ~ 20 m and with

thickness from ~0.7 mm to 1 mm.
- Tubes are mostly made of non-magnetic but electrically
conductive material.
- Tubes are to be tested in in-situ condition
- OD of tubes are not accessible
- ID of the tubes are accessible for remote visual inspection
or for entry of sensing element.
Methods for in-situ integrity assessment of condenser tubes

Selection of Test Methods

• Another method, known as Eddy Current Testing (ECT)
can also be used with arrangement for taking probes from
one end to other. There is no need of couplant as also need
no revolution of probe as sensing coils are circular in close
proximity to ID of tubes.
• Remote visual inspection could also be used for internal
surface inspection for an idea of the tube deposit
 Visual Examination

• May be applied for exam. of single tube or for verifying

the results obtained by other NDE methods

• Videoimagescope could be used for the remote visual

exam.

• This type of examination will reveal the condition of the

inner surface of the examined tubes. The extent of
scale can be assessed and documented as well as the
extent of internal corrosion, general or local. If a tube is
blocked the visual examination can reveal the cause of
the block up.
 POST-OPERATIONAL CHEMICAL
CLEANING OF CONDENSER
 Condenser performance deteriorates with:
 time
 with off design operations and
 other interferences such as fouling, scaling
Condenser Chemical Cleaning-
Farraka Modified Procedure
 In case of sustained condenser scaling top part of the
condenser tubes are prone to hard scaling and it was not
possible to remove by chemical cleaning.(Farraka # 6 3
cleanings,Simhadri # 2 cleanings and dadri # 5),Even
after altering various factors such as conc,temperature
and flow duration etc.
 However on further investigation it was realise that flow
distribution could be an important factor.
 In Farraka the proper flow distribution was enforced by
plugging all tubes barring the top ones and cleaning
successful.
 Henceforth this method will be adopted.
 Farraka heat rate improved by ~ 10 K Cal and PG test is
possible.
 Before chemical cleaning of condenser
high pressure jet cleaning was carried out
at both passes, in which deposits, scale,
loose debris etc. were removed from
condenser.
 Two stage acid cleaning was done.
 First cycle was in normal way from bottom to top and
then top to bottom.
 In second cycle, lower condenser tubes (4500) of top
half were plugged to ensure the proper flow and
exposure of top half condenser tube to acid.
 Here flow was from top to top to facilitate thorough
cleaning of upper portion of the both passes.
 High pressure jet cleaning was done after chemical
cleaning; pressure was raised upto 600 PSI.
Plugging of lower Condenser tubes Removal of adherent scale layer after
acid cleaning
 Boroscopic
examination was
done. No significant
deposit was observed
Root Cause Analysis
 Deposits in condenser were comprised of
mainly Calcium Carbonate scale 50 – 90%
and organic fouling
 Dosing must be started during
commissioning stage.
 Some critical parameters may be
monitored online and integrated with Pi
server.
THANKS