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#6 Hydrogen Damage

One of most disturbing tube failure mechanisms in HRSG


and conventional boiler

Caused by the reaction of the iron carbide (FeC) in the tube


microstructure with hydrogen from under deposit
corrosion process- which produces methane (CH4) at the
grain boundaries of tube steel

#6 Hydrogen Damages: Features

Thick Edged
Brittle final fracture
Often window opening

Multi layered deposits


Major: magnetite

Microstructural decarburization

Source: B. Dooley, PPChem101Boiler and HRSG Tube Failure:


Hydrogen Damage, PP Chem
2010 , 12(2)

#6 Hydrogen Damages: Features

Source: B. Dooley, PPChem101-Boiler and HRSG Tube Failure: Hydrogen Damage, PP Chem 2010 , 12(2)

#6 Hydrogen Damages: Features

Source: B. Dooley, PPChem101-Boiler and HRSG Tube Failure: Hydrogen Damage, PP Chem 2010 , 12(2)

#6 Hydrogen Damages: Mechanisms

1. Excessive Deposition
2. Acidic Contamination

#6 Hydrogen Damages: Location

HP & IP Evaporator

Water flow is disrupted


Welded join
Internal deposition
Thermal hydraulic flow disruption
- Local steam blanketing

Overheating of the tube

#6 Hydrogen Damages
Root Causes & Action to Confirm

Excessive deposits
High iron in BFW and evaporator increasing potential for concentration
mechanism
- Condenser tube leaks where Cl and SO4 enter the boiler

Selective tube sampling

Flow disruption
Selective tube sampling

Gas side issue


Tube heat flux & temperature measurement

Influence of acidic contamination

#6 Hydrogen Damages
Root Causes & Action to Confirm

Minor condenser leaks over an extended period


High cation conductivity
High chloride and / or sulfates

Major condenser leaks one serious event


pH depression in Boiler

Water treatment plant upset


High cation conductivity

Errors in chemical cleaning process

H2 Damages, Caustic Gouging & Acid PO4 Corrosion


Characteristic

H2 Damage

Features of Failure Gouged. thick


deposit
Thick edged
window opening

Caustic Gouging

Acid Phosphate
Corrosion

Gouged, thick
deposit
Ductile, thin
edged, pin hole

Gouged, thick
deposit
Ductile, thin
edged, pin hole

Deposit

Metal oxide

Rich in caustic
Na-feroate , Naferoite

Acid PO4
2-3 distinct layer
Maricite

Cycle Chemistry

Source of low pH
exist

Source of high pH
exist

DSP, MSP, or
Na:PO4<3.0

Attack Rate

Very rapid10
mm/year

Rapid up to 2
mm/year

Rapid up to 2
mm/year

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#7 Oxygen Pitting

Localized dissolution of metal.

Relatively small amount of metal loss that initiate failure


with catastrophic results

Type of pitting in Boiler


Oxygen pitting
Pitting caused by improper chemical cleaning
Pitting caused by carry over of sodium sulfate

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#7 Oxygen Pitting: Features

Pit shape: broad, rounded

Pit distribution can be numerous


or random

Corrosion product and deposit


are present primarily Fe2O3

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# 7 Oxygen Pitting: Features

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc., 1991

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#7 Oxygen Pitting: Mechanisms

1. Moisture
2. Oxygen

Source: EPRI, Heat Recovery Steam Generator Tube Failure Manual, 2002

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#7 Oxygen Pitting: Location

Prevalent in economizer

Any wet surface, especially no-drainable


horizontal surfaces

Poor lay-up procedures

Can be found in Superheater and reheater


tubes where condensate collects in bends

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#7 Oxygen Pitting
Root Causes & Action to Confirm

Stagnant, oxygenated water with no protective environment


due to improper layup
Review the procedure
Selective tube sampling
Corrosion product analysis

#7 Oxygen Pitting Corrosion: Case History


Case History
Industry: Chemical process
Location: Economizer
Orientation: Horizontal
Pressure: 41 bar
Tube metallurgy: Carbon steel
Treatment Program: Polymer & O2 Scav
Time in Service: 7 years
The reddish color & the presence of turbecles
capping iron oxide-filled pits is typical of exposure
of steel to water containing excessively high level
of dissolved oxygen, Pitting & perforation of
economizer tubes was a recurrent problem at this
plant. Failures were occurring every 3 or 4 months.
Excursions to high levels of oxygen was suspected
but could not be documented. The boiler was
operated continuously.
Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#8 Stress Corrosion Cracking

Metal failure resulting from a


synergistic interaction of a
tensile stress and a specific
corrodent to which the metal is
sensitive

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#8 Stress Corrosion Cracking: Features

Thick-edged, brittle failure

May often involve the blow out of small window-type


pieces

Little or no loss of wall thickness

Cracks
Can initiate either inside or outside surfaces
Can be oriented circumferentially or longitudinally
May have significant branching

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#8 Stress Corrosion Cracking - Features

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc., 1991

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#8 Stress Corrosion Cracking: Mechanisms


Can occur if 2 (two) conditions exist:

The existence of a critical system of material and corrosive


medium i.e., a specific corrosive medium must be present
for a given material

The presence of tensile stress


Static tensile stress
Tensile stresses which increase over time
Tensile stresses which change at a low frequency over time

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#8 Stress Corrosion Cracking: Mechanisms

Source: H.G. Seipp, Damage in Water/Steam Cycle-Often Matter of Solubility, PP Chem 2005 (7)

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#8 Stress Corrosion Cracking: Mechanisms

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Stress Corrosion Cracking:


Material & Corrodents

Austenitic Stainless Steel (300 series)


Chlorides
Sodium hydroxide
Hydrogen sulfide

Carbon Steel
Sodium hydroxide

Copper-based Alloys
Ammonia

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#8 Stress Corrosion Cracking: Location

Potential for the highest concentration of contaminants


Condensate can form during shutdown

High stress locations


Bends, welds, tube attachment, supports, near weld, spacers; etc
Especially where a change in thickness occur

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#8 Stress Corrosion Cracking


Root Causes & Action to Confirm

Environmental Effects
Chloride: Condenser in-leakage & chemical cleaning
Caustic: Carry over

Stress Effects
Residual stresses: fabrication/welding/heat treatment/bend
Service stresses: especially at attachment & supports

Susceptible Material Effects

#8 Stress Corrosion Cracking: Case History


Case History
Industry: Petrochemical
Location: Superheater, first stage
Orientation: Vertical
Pressure: 41 bar
Tube metallurgy: 304 stainless steel
Treatment Program: Phosphate
Time in Service: 3 weeks
The original tubes were CS that cracked after 9
months of service. SS tubes were specified to
replace CS. Moderate bends were put to relieve
the thermal expansion and contraction stress that
had caused cracking in the CS tubes.
SS failed because caustic stress corrosion
cracking (lacked adequate devices for separation
and load swings- carry over of ) boiler water. In
addition , the bends provided high residual stress
(no stress-reilef-annealed apply on the bend)
Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#9 Short Term Overheating

Occur when the tube metal temperatures are well above


the design temperature for the tubing

In SH/RH tubing occur when the normal flow of cooling


steam is blocked or partially blocked

Excessive temperatures and subsequent tube failures can


occur in very short period of time

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#9 Short Term Overheating: Features

Thin-edged, ductile final failures

Longitudinal fish mouth or rupture

Tube bulging is often

Scale not necessarily thick or can be absent

Localized hardening near the rupture

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#9 Short Term Overheating - Features

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#9 Short Term Overheating - Features

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#9 Short Term Overheating: Mechanisms

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#9 Short Term Overheating: Mechanisms

Source: EPRI, Heat Recovery Steam Generator Tube Failure Manual, 2002

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#9 Short Term Overheating: Location

Can occur in steam-cooled tubing (SH/RH) or the hotter


sections of the water cooled tubing (evaporator)

Susceptible locations:
Tubing nearest to the gas inlet, especially down stream of supplemental
burner (most common leading row SH)
Tubing down steam of bends;etc- where potential blockage is exit

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#9 Short Term Overheating


Root Causes & Action to Confirm

Excessive gas temperature


Visual examination of flame pattern
Operating condition (gas temperature measurement; etc)
Metallurgical analysis

Tube blockage
Oxide from exfoliation tube material, chemical cleaning and /or improper
repair
Videoscope & metallurgical analysis to confirm

Start up with condensate filled tubes


Thermocouple measurement
Review start up procedure

#9 Short Term Overheating: Case History


Case History
Industry: Utility
Location: Water wall, nose arch
Orientation: Slanted
Pressure: 124 bar
Material: Carbon steel
Treatment Program: Coordinated Phosphate
Time in Service: 5 years
Rupture occurred shortly after start-up.
Microstructural evidence indicated that the tube
metal near the rupture exceed 870 0C. No
significant thermally formed oxide was found
anywhere on the received section.
The burst was caused by insufficient coolant flow
on start-up.
Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#10 Long Term Overheating

Occur when metal temperature exceed design limits for


days, weeks, months or longer

Because steel loses much strength at elevated


temperature, rupture caused by normal internal pressure
becomes more likely as temperature rise

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#10 Long Overheating: Features

Thick-edged, brittle final failure

Bulging and plastic deformation

Scale
Internal: Extensive, multilaminated & exfoliating
External: Thick, laminated & often longitudinally cracked

May have wastage flats

Extensive sign of tube material degradation

Localized softening near the rupture is typical

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#10 Long Term Overheating - Features

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#10 Long Term Overheating - Features

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#10 Long Term Overheating: Mechanisms

Thermal Oxidation (metal burning)


Excessive if temperatures > certain value for each alloy
Cause crack and exfoliated patches
Cyclic thermal oxidation & spalling resulting wall thinning
Process can continue until the entire wall is converted to oxide,
creating a hole

Creep Rupture
Plastic deformation during overheating
Produce thick-lipped rupture

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#10 Long Term Overheating : Mechanisms

Source: EPRI, Heat Recovery Steam Generator Tube Failure Manual, 2002

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#10 Long Term Overheating: Location

Near the material changes just before the change to a


higher grade of material

Tubing nearest to the flue gas inlet, especially for


supplementary-fired units

Final leg of tubing just before the outlet header

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#10 Long Term Overheating


Root Causes & Action to Confirm

Excessive gas temperature


Visual examination of flame pattern
Operating condition (gas temperature measurement; etc)
Metallurgical analysis

Tube blockage
Oxide from exfoliation tube material, chemical cleaning and /or improper
repair
Videoscope & metallurgical analysis to confirm

Start up with condensate filled tubes


Thermocouple measurement
Review start up procedure

#10 Long Term Overheating: Example


Case History
Industry: Power Plant
Location: Primary SH Inlet
Pressure: 83 bar
Orientation: Horizontal
Treatment Program: Phosphate
Time in Service: 20 years
Creep rupture caused by prolong overheating at
temperature above 570 0C. Coolant flow
irregularities immediately downstream of a partially
circumferential weld, along with internal deposition,
which reduced heat transfer were contributing
factors. Additionally, a switch from oil to coal firing
likely changed fire-side heat input.
The superheater had a history of boiler water
carryover and load swing were common.
Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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Short Term vs Long Term Overheating

Source: R.Port, The Nalco Guide to Boiler Failure Analysis, Mc Graw Hill, Inc.,
1991

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#11 Exfoliation: Location

Superheater and Reheater Tubes

Results of long term overheating of tubes

Significant impact is the type and quality of the tube metal

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#11 Exfoliation: Results

Exfoliated particles will collect in bends and can cause


blockage of tubes

Excessive exfoliation can result in particulate erosion of


turbine components, especially the nozzle block

May result in impacting the following:


Plant availability

EPRI: Road Map for Analyzing BTF

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Determine the Extend of Damage


Failure Mechanisms

Recommended Test

Corrosion Fatigue

Ultrasonic Testing UT)


Selective Tube Sampling

Thermal/Mechanical Fatigue

Fluorescence magnetic partcle


examination (WFMT) or Fluorescence
penetrant (WFPT)
Thermal stress analysis

Deposit

Selective tube sampling


Deposit Weight Density (DWD)

FAC

Ultrasonic Testing (UT)

H2 Damage, Caustic & Acid


Phosphate Corrosion

Ultrasonic Testing (UT)


Selective Tube Sampling
Boroscope
Pressure Test after chemical cleaning

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Determine the Extend of Damage


Failure Mechanisms

Recommended Test

Stress Corrosion Cracking

Fluorescence magnetic particle


examination (WFMT) or Fluorescence
penetrant (WFPT)
Thermal stress analysis

Short & long term overheating

Radiography
Tube removal
Tube diameter measurement (wall
thickness)

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Nalco SEA
Recent Case of Boiler Tube Failure

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Case #1: HRSG Tube Failure

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Case #1: Plant Data

Combined Cycle Power Plant, 110 MW Thailand

HRSG, Multiple Pressure (HP:62 bar, LP: 5 bar), Capacity:


67 tons/hr (HP), 11 tons/hr (LP)

Condensing steam turbine

Surface condenser with admiralty tubes and Cu:Ni=90:10


for air removal section

Boiler make-up: demineralized water from mixed bed

Condensate polisher: no

Two HRSG HP
Evaporator - tube failure in
1 week!

Important Events

November 2010
and confirmed

: Condenser in-leakage has identified

May 23-25, 2011


leakage become bigger

: Major ingress due to condenser in-

May 28-29, 2011


in condenser. Drum

: Plant shutdown. Plugged leak tubes


inspection

May 30, 2011 : Plant is running back

Sept 8 22, 2011


inspection

Sept 18, 2011 : Tube failure of HP evaporator section.

Sept 22-23, 2011


HRSG tube failure.of HP Evap

Sept 25, 2011 : Plant is running back

: Major schedule shutdown. Drum

: Unscheduled plant shutdown due to

Deposit Sampling Analysis Result


Elements/
Compounds
Iron (Fe2O3)
Copper (CuO)
Phosporus (P2O5)
Calcium (CaO)
Magnesium (MgO)
Sulfur (SO3)
Silicon (SiO2)
Zinc (Zn)
Carbonate (CO2)
Manganese (Mn)
Sodium (Na2O)
Loss at 925 0C
Major compounds
Minor compounds

Steam Drum
May 11
33 wt%
12 wt%
23 wt%
15 wt%
8 wt%
2wt%
4 wt%
1 wt%
<1 wt%
1 wt%
1 wt%
2 wt%
Magnetite-Fe3O4
Magnesium Iron
Oxide (MgFe2O4)

Steam Drum
Sept 11
22 wt%
8 wt%
32 wt%
26 wt%
6 wt%
1 wt%
1 wt%
<1 wt%
1 wt%
1 wt%
1 wt%
Magnetite-Fe3O4
Ca PhosphateCa3PO4

HP Evap-Sept11
(Sample #1)
50 wt%
15 wt%
14 wt%
8 wt%
5 wt%
2 wt%
1 wt%
1 wt%
<1 wt%

HP Evap-Sept11
(Sample #2)
90 wt%
3 wt%
2 wt%
1 wt%
<1 wt%

1 wt%
Magnetite-Fe3O4
Hematite-Fe2O3

Magnetite-Fe3O4
Iron Oxide - FeO
Hematite-Fe2O3

Screen Analysis Fracture/Appearance


Excessive/
thick deposit

No tube
bulging

Thick edge

Metal loss
under
deposit

Rectangular
Window

Metal loss
under
deposit

Thick edge

Rectangular
Window

Determine the Root Cause


Major Root Cause Influences

Confirmation

Remarks

Influence of excessive deposits

Yes.

Flow disruption: deposits, DNB, bend/sharp


changes in tube direction, locally high heat
transfer; etc
Influence of acidic contamination
Condenser leaks minor but occurring over
an extend period
Condenser leaks major ingress, generally
one serious event

Yes

Deposit in steam drum (boiler inspection


May and September 2011)
Heavy deposition in sampling tube
(September 2011)
Flow disruption only influenced by
deposition

Water treatment plant up set leading to


low pH condition
Errors in chemical cleaning process

Yes.
Yes.
Yes.
May 2011

pH of boiler dropped to ~8.5 on May 2011


Condenser leaks occurred November 2010
May 2011
pH of boiler dropped to ~8.5
Hardness in condensate went up >0.5
ppm
Chloride concentration in HP evaporator
went up > 10 ppm

No.
No.

No chemical cleaning conducted on 20102011.

Root Cause

Condenser in-leakage
Increase chloride and sulfate level in BFW and boiler water
Introduce hardness salts into BFW
Introduce O2 into condensate and BFW

Deposition
Hardness
Iron
Copper
Phosphate

Determine the Extend of Damage

Ultrasonic test not applicable for finned tube

Visual inspection by using fiber optic (boroscope/


videoscope) - not applicable

Selective tube sampling ?

Chemical cleaning & pressure test ?

Immediate Solution

Isolate the condenser and plug all the leaking tubes


and tubes with high depth wastage. Ensure there is
no cooling water in-leakage by checking condensate
quality (cation conductivity, hardness, chloride; etc)

Selective tube sampling for deposit measurement.


Inspection using fibre optic (boroscope) can provide
useful information

Tube replacement for all tubing with hydrogen


damage and/or significant wall loss be replaced

Check the efficacy of chemical cleaning

Long Term Solution

Chemical cleaning
Proper chemical cleaning method/procedure.

Pressure test 1.5x than normal operating pressure

Replace all tube failed in pressure test

Improving integrity of surface condenser

Install on-line instrumentation to improve condenser


leakage detection capability & control

Develop specific cycle chemistry targets, action


levels and shutdown policies to maintain HRSG
cleanliness.

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Case #2: Coal Fired Boiler Tube Failure (BTF)

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Case #2: Plant Data

Cogeneration Plant (Coal Fired) for Paper Mill

3x35 MW + 1x65 MW Indonesia

Boiler #6, 300 tons/hr, 100 bar

Condensing steam turbine

Surface condenser with admiralty tubes

Boiler make-up: demineralized water from mixed bed

Condensate polisher: yes, for process condensate

Case #2:Important Events

July 2011
program

: Change boiler chemical treatment

July December 2011

15th December 2011 : Low pH Boiler water (~ 5.7)

18th December 2011 : 1st boiler tube failure (water wall)

24th December 2011 : 2nd boiler tube failure (water wall)

:Total iron in BFW > 10 ppb

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Screen Analysis: Location

Location of BTF:
Water Wall
Radiant heat transfer in
front of buner
Highest temperature areas

Deposit Sampling Analysis Result

Screen Analysis Fracture/Appearance

Screen Analysis Fracture/Appearance

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Metallurgical Analysis Result


(~3 weeks after the incident)

Confirm the Root Cause


Major Root Cause Influences

Confirmation

Remarks

Influence of excessive deposits

Yes.

Flow disruption: deposits, DNB, bend/sharp


changes in tube direction, locally high heat
transfer; etc
Influence of acidic contamination

Yes

Deposit in steam drum (Boiler


inspection)
Deposition in sampling tube
High iron in BFW (>10 ppb)
Flow disruption only influenced by
deposition

Condenser leaks minor but occurring over


an extend period
Condenser leaks major ingress, generally
one serious event
Water treatment plant up set leading to
low pH condition
Errors in chemical cleaning process

Yes.
?

pH of Boiler dropped to <8.0 after start up


in December 2011
Need to confirm by conducting condensate
analysis by IC

No
Yes
No.

Contamination from pretreatment (possibly


organic acids

Determine the Extend of Damage

Selective tube sampling

Chemical cleaning followed by boiler pressure test (1.5x


than normal operation pressure)

Immediate Solution

Conducting proper chemical cleaning


1,8 tons of iron has removed from the boiler during cleaning
DWD test after cleaning = clean

Followed by boiler pressure test (1.5x than normal)


Some tubes were failed during pressure test

Replacing all the tubes with significant metal losses

Long Term Solution

Minimize deposit build up on boiler tubes by ensuring


minimum corrosion product formation in BFW and transport
into the boiler
Total Iron < 10 ppb (ASME), EPRI < 2 ppb
Total copper < 10 ppb (ASME), EPRI < 2 ppb

Use adequate chemistry related instrumentation and


installation

Preventing acidic contamination into the boiler system

Preventing upset of the water treatment plant


- UF-RO-Ion Exchange for all boilers to minimize TOC intrusion
- Use appropriate on-line instrumentation to monitor performance of plant

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THANK YOU!