Microsoft PowerPoint - Feed Water Treatment

Boiler Feed Water Treatment
Essential Expertise for Water, Energy and Air SM
SM
Essential Expertise for Water, Energy and Air 1
Agenda
• Boiler make-up water system
• Objective of boiler feed water treatment
• Type of corrosion in feed water system
• Corrosion control in boiler feed water system
• Sampling and Testing
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Typical Boiler Make-up System
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Best Practices of Boiler Make Up
Parameter Softener Co-current Counter Mixed Power

Dual Bed Current Bed Plant
Total Hardness, ASME <0,02 <0,02 Trace Trace
ppm CaCO3
Conductivity, - 2–5 <1 < 0.5 < 0.1
µS/cm
Silica, ppb - <50 < 20 < 10 < 10
Sodium, ppb - 100 -500 10 – 50 < 10 < 10
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Typical Boiler Feed Water System
SM
Objective of BFW and Condensate Chemistry
• To control corrosion in
boiler feed water system
• Prevent boiler deposition

by minimizing metal
transport (iron) into the boiler
• Extend equipment life time
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Preboiler System
Heaters Economizer
Pitting Corrosion
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BFW Corrosion & Iron Deposition
• Corrosion in feed water system

will cause:
– High metal transport into the boiler
and boiler deposition
– Unscheduled outages, lost production
& profits
Caustic Corrosion
• Boiler deposition will lead to:

– Under deposit corrosion
– Overheating/tube failures
– Unscheduled outages, lost production
& profits
– Higher frequency of boiler acid
cleanings
Acid PO4 Corrosion
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Type of Corrosion
• Oxygen Corrosion
• Flow Accelerated Corrosion (FAC)
Oxygen Corrosion FAC
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Oxygen Corrosion
• Generally occurs as pitting

corrosion that lead to tube
failure
• O2 corrosion attack
commonly occur in heaters &
economizer – before entering
the “boiler”
• Rare occur in operating

boiler. Unless result of un-
proper lay up when boiler in
idle condition
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O2 Corrosion is not Common
Occur in Running Boiler
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Corrosion Control in Feed Water System
• Use corrosion resistant

materials
• Remove the oxygen
• Metal passivation (pH

and oxidizing-reduction
potential adjustment)
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Dissolved Oxygen Removal
• Mechanical
– Prevent air in-leakage in condenser
– Mechanical dearation
» Condenser deaeration
» Deaerator
– Dearator should be able to remove
most of all DO in BFW until < 10 ppb
• Chemical (O2 Scavenger)

– Polishing of mechanical dearation
process
SM
Boiler Feed Water System
Deaerator
• Primary oxygen removal

mechanisms in most of all
steam generation systenm
• To mechanically remove
oxygen to prevent
corrosion in boiler feed
water and internal
• Also can be act as feed

water tank
SM
Principles of Mechanical Deaeration
1. Only uncharged
species are removed
• O2, CO2 and NH3
• But not HCO3 (from CO2) or

NH4OH (from NH3)
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2. Temperature
• O2 solubility decreases as temperature increases
PAC-2 Sales Blitz

Essential Expertise for Water, Energy and Air
SM
16
3. Relative partial pressure

• Amount of O2 in the water is
depend on amount of O2 in
the vapor
PAC-2 Sales Blitz

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17
4. Agitation
• Small droplets heat easier and provide greater surface
area for removal of gases
PAC-2 Sales Blitz

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18
Deaerator Types
Spray Tray
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Deaerator: Key Performance Indicator
• DO < 10 ppb
• DO>15 ppb typically caused

by mechanical malfunction or
improper operation
• These problems usually

indicated by:
– Temperature of storage > 2.80C
(5 0F) of dome temperature
– Temperature of dome is > 2.20C
(4 0F) of saturated steam
temperature at operating
pressure
SM
Typical Dearator Mechanical/Operational Problem
• Inadequate venting
• High or low feed water temperature

• Too high à less steam flow à
inadequate stripping
• Too low à excessive steam rate à
Inadequate Venting
carry over & damage the equipment
• Inadequate quantity of steam or

fluctuating steam pressure
Invisible
• Wide fluctuations in feed water plume
(15-40 cm)
flow or flow rates outside design
• Feed water << design will cause poor
water spray in nozzle Adequate Venting
SM
Typical Dearator Mechanical/Operational Problem
• Short circuiting
• Plugged, broken or missing
spray nozzles and/or trays
• Air in-leakage at boiler feed

pump
• Recirculation line recycles
problem back to deaerator
• Air or hydrocarbon binding

• Venting is required for heating
make-up water
• Leaking deaerator by-pass

valve
PAC-2 Sales Blitz

SM
22
Dearator Problem: Dearator Cracking
• Catasthropic failure in
• ~40% of 700 dearators

that inspected by NACE in
1980’ at US have serious
cracking problem
• Dearator inspection using

WFMT every 3-5 years
(NACE guide line)
• NACE Task Group: Standard

RP0590-96, “Recommended
practice for prevention, detection
and correction of deaerator
cracking”, NACE, (1996)
SM
Why Use Oxygen Scavenger Chemical?
• To remove remaining
oxygen after
mechanical deaeration
to prevent oxygen
pitting corrosion
• To enhance passivation
in preboiler system
(second generation
oxygen scavenger)
SM
Passivation
• Passivation:
“Continuous formation of a protective
film of metal oxide that significantly
reduces the corrosion rate”
- Iron oxides to magnetite (Fe3O4)
- Copper oxides to cuprous form
(Cu2O)
• Iron will self passivate in water, if no

contaminants are present
– Reaction is very slow below 100 0C
– Reaction become fast above 204 0C
• Passivation can be accelerated by

some oxygen corrosion inhibitors
SM
Oxygen Scavenger Chemicals
• Sulfite
• Hydrazine
• Hydroquinone
• DEHA
• MEKO
• Carbohydrazide (Elimin-ox®)
• Erythorbic Acid (Surgard)
SM
O2 Scavenger & Passivator Guide Line
Oxygen All DEA Max Turbine Spray FDA

Scavenger Volatile absolutely Pressure Attemp. Approved
needed (psig)
Sulfite No No 900 No No Yes
Hydrazine Yes Yes No limit Yes Yes No
Elimin-ox® Yes Yes No limit Yes Yes No
DEHA Yes Yes 1800 Yes Yes No
Hydroquinone Yes Yes 2800 Yes Yes No
MEKO Yes Yes 1000 Yes Yes No
SURGARD® No Yes 1800 Yes Yes Yes
SM
Key Factors to Select O2 Scavenger Chemicals
• Safety, Health & Environment

• Solids contribution
– Cycles
– Attemperation
• Not breakdown at boiler
pressure/temperature Main concern of Hydrazine
• Meet process requirement
– Turbine
– Superheater
• Provide metal passivation
– O2 scavenger is minomer
• Regulatory issues
– FDA/USDA
SM
Hydrazine vs Elimin-ox ® - Health & Safety Concern
Acute Toxicology
Study Performed 35% Hydrazine Elimin-ox®

Acute oral LD50 - Rats 370 mg/kg >5000 mg/kg
Acute dermal LD50 – 420 mg/kg >2000 mg/kg
Rabbits
Primary eye irritation – Irritating Non-irritating (0.33/110)
Rabbits (24 hours)
Primary dermal irritation Severe irritant (7.0/8.0). Mild irritant
- Rabbits May be corrosive (most
of suppliers ship as
corrosive liquid
SM
Hydrazine vs Elimin-ox ® - Health & Safety Concern
Regulatory Status
Federal Regulation 35% Hydrazine Solution Elimin-ox®
OSHA’s Hazard Requires labeling as Not Hazardous
Communication Rule (29 KNOWN CARCINOGEN
CRF1910.1200)
CERCLA 40CRF117,302 3 pounds spill requires Spill notification NOT
National Response Center required
Notification
Resource & Recovery Act HAZARDOUS WASTE NOT HAZARDOUS WASTE
(RCRA) 40CFR261 under RCRA criteria under RCRA criteria
Subparts C&D
Federal Water Pollution Hydrazine is covered by None of its ingredients
Control Act 40CFR401.15 The Clean Water Act are listed
and 40 CFR116 section 311
SM
Oxygen Scavenging Performance
Simulated boiler feedwater conditions in the lab:
MEKO
MEKO
DEHA DEHA
HYDRAZINE Hz
ELIMIN-OX
CHz
SUR-GARD
EA
HYDROQUINONE
HQ
SULPHITE
SO3
0% 20% 40% 60% 80% 100%

OXYGEN SCAVENGING PERFORMANCE
PAC-2 Sales Blitz

SM
31
Passivation Performance
Simulated boiler feedwater through economizer:
HYDROQUINONE HQ
SULPHITE SO3
DEHA DEHA
HYDRAZINE Hz
MEKO
MEKO
SUR-GARD EA
ELIMIN-OX CHz
Poor Good Excellent
SM
Oxygen Scavenger - Breakdown Products
Oxygen Scavengers %C Break down Products

Hydrazine 0 Nitrogen, water, ammonia
Elimin-ox® (CHZ) 13.3 Hydrazine, nitrogen, water, ammonia
Hydroquinone 65.5 Benzoquinone, light alcohols, ketone, low
MW organic acids, carbon dioxide
DEHA 5.39 Acetaldehyde, acetic acid, dialkylamines,
ammonia, nitrate, nitrite
MEKO 53.9 Methyethylketone, hydroxylamine,
nitrogen, nitrous oxide, ammonia, CO2
Surgard ®(Erythorbic Acid) 55.2 Lactic and glycolid acid, carbon dioxide
Eliminox is the only hydrazine alternative which not produce organic acids!
SM
What is FAC ?
• Dissolving of protective
magnetite layer (Fe3O4)
• Influenced by several factors:

– Velocity
– Flow geometry,
– Two phase flow
– Temperature
– pH
– Oxygen concentration
– Metallurgy
that contribute to magnetite
solubility
SM
Factors Affecting FAC - Temperature
• Extremely temperature dependent:
– Occurs in HRSG IP & HP Economizer tubes & headers, and in LP
evaporators & drums.
– Occurs in cold re-heat return lines, FW heater drip lines.
Tendency for Saturation

Temperature
FAC Pressure
Deg C Deg F psia
Moderate Range 80 176 7
150 302 70
Severe Range 150 302 70
180 356 146
Moderate Range 180 356 146
230 446 409
SM
Factors Affecting FAC – pH
SM
Factors Affecting FAC –
Oxidizing & Reducing Environment
Source: EPRI, Cycle chemistry Guidelines for Fossil Plants, Phosphate Continuum and Caustic Treatment, 2004.
SM
FAC Solution
• Material upgrade to 1 or 2% chrome
• Maintain pH in proper range with ammonia or amines

• Higher end of range is better!
• Pay attention to amine distribution ratio in multi-pressure HRSGs
• Avoid a highly reducing environment!

• Do not allow excess feed of oxygen scavenger
• Monitor feedwater ORP, consider control of passivator to ORP
• Monitor with soluble iron tests before and after suspect

areas
• Need proper sample points!
SM
pH Role
Corrosion of Fe & Cu Vs pH
Fe & Cu Fe
ppb
10
• Elevating pH of feed water
. using volatile amines will
. reduce corrosion by oxygen
8
. corrosion and FAC
Cu
6 .. .
• Best Practices
. ... ...
• Industrial
4 ..
.
.. .
• Power Plant
2 . . . o 9.2 – 9.6: All Steel
. .. . .. o 9.0 – 9.3: Mixed
. .
. . . Cu Corrosion
0
8.9 9.1 9.3 9.5 9.7
8.8 9.0 9.2 9.4 9.6 9.8
pH CONDENSATE
SM
Injection Point of Oxygen Scavenger
• Between deaerator and

storage section is ideal
– Optimum mixing
– Holding time in the DA
tank allows scavenging
reaction to process
• Alternatively, feed directly

to storage section, insuring
even distribution
• For attemperation, injection

point will vary if using non-
volatile scavenger
SM
Condensate Treatment
SM
Extended Condensate System
SM
The Value of Returning Condensate
• Condensate is Hot Water!

– Most Industrial Condensate Systems are pressurized
– Utilities and some process systems are under vacuum
• Condensate is (reasonably) Pure Water!

– Low conductivity water replaces additional demineralized
makeup water for boiler feedwater
– Replaces softened water and allows boiler to operate at
higher cycles of concentration
SM
Typical % Condensate Return
Industry Typical % Return
Chemical 30-60
Cogen 20-80
Paper 40-65
Petrochemical 65-85
Power 95-99
Refining 10-60
Steel 5-50
SM
Why Condensate Treatment is Needed?
• Condensate treatment is
battle against three
dissolved gases
1. Carbon Dioxide
– Source: breakdown of
alkalinity and organics + air
in-leakage
– Forming carbonic acid in
condensate system and
dropping the pH
– Corrosion form: thinning or
grooving
SM
Why Condensate Treatment is Needed?
2. Oxygen
– Sources: air in-leakage (vacuum system, pump seal; etc)
– Attacking CS and copper
– Corrosion form: pitting corrosion
3. Ammonia
– Sources: treatment program (ammonia, breakdown of amine,
hydrazine, carbohydrazide; etc)
– Attacking copper (high DO, complexing CuO)
SM
Condensate Treatment Alternatives
• Neutralizing Amines
– Distribute throughout systems
– Neutralize CO2
– Elevate condensate pH
• Filming Agents
– Both amines and non-amines are used
– Create a barrier between condensate and piping
• Scavenger/Passivating Agents
– Primarily condition metal surfaces
SM
Neutralizing Amines
How its Work?
• Neutralizing amines are volatile,

alkaline compounds that are added
to steam generation system.
• They function by volatilizing into the

steam and redissolving in the
condensate
• Amines neutralize carbonic acids or

any other acids present in the
condensate and raise the pH to a
Morpholine
level least corrosive to the system
metal
SM
Neutralizing Amines
Simple Acid/Base Neutralization
• CO2 dissolving in condensate

CO2 + H2O à H2CO3
Carbon doxide water Carbonic acid
• Amine hydrolysis in water:

R-NH2 + H2O à R-NH3+ + OH-
Neut. amine water Neut. amine hydroxide
• Net reaction:
R-NH2 + H2CO3 -à R-NH3+ + HCO3-
Neut. Amine Carbonic acid Neut. amine bicarbonate
SM
Corrosion of Iron and Copper at Varying pH
Fe & Cu Fe
ppb The lowest corrosion
10
rate of Fe & Cu
.
metallurgy
8 . pH = 9.0 – 9.3
. Cu
6 .. .
. ... ...
4 ..
.
.. .
2 . . .
. .. . ..
. . . .
. Cu Corrosion
0
8.9 9.1 9.3 9.5 9.7
8.8 9.0 9.2 9.4 9.6 9.8
pH CONDENSATE
SM
Neutralizing Amines
Limitation and Considerations
• Not effective against

oxygen
• May not best choice in

high alkalinity boiler
feed waters (>20 ppm)
• Not all locations will

have same pH - a blend
of amines is typically
Cyclohexamine required
SM
Neutralizing Amines Characteristics
• V/L Distribution Ratio
• Neutralizing Capability
& Basicity
• Thermal Stability
SM
Neutralizing Amine Characteristics
V/L Distribution Ratio
• The V/L distribution ratio

indicates how much of each
species will condense with the
condensate or stay with the
steam
• Vary with pressure,

temperature, pH and other
operating condition
• Only significant when a phase

separation occurs – not when
total condensation occurs
SM
SM
Steam & Condensate Equipment
Non Cascading - Simple Steam/Condensate System
5 bar
DEAE
20 bar
DEAE
DEAE
DEAE
0.5 bar
Centrifugal pump
Tank
DEAE
Centrifugal pump
• Not difficult to protect

• Single amine product could work
SM
Cascading – Complex Steam/Condensate System
60 bar 20 bar
CHA
DEAE
CHA
CHA
DEAE 5 bar
MOR
5 bar
DEAE
MOR
Heat exchanger 40 bar MOR DEAE

DEAE
CHA
MOR
MEA
Tank
MOR
CHA
MOR 0.7 bar
MEA
• More difficult to protect

• Mixed Amines (2 or 3 amines) is required
• Amine satellite injection sometimes is needed to achieve desired pH
• Could lead to air in-leakage (paper dryer) à O2 Scavenger satelite injection
SM
Neutralizing Capability
This is the amount of amine required on a mass basis to

neutralize the carbonic acid
RNH2 + H+ + HCO3- → RNH3+ + HCO3-
• Depend upon the molecular

ppm per weight of the amine and the
Product MW
CO2 number of neutralizing
100% NH3 17.00 0.66 groups
100% CHA 99.00 1.52
100% MEA 61.09 1.12 • In general, lower MW
amines will neutralizes more
100% MOPA 89.14 1.00 carbonic acid than higher
100% MOR 87.12 3.96 MW amines
Note: pH~8.5
SM
Basicity
Amine basicity is a measure of amine hydrolysis à OH
RNH2 + H2O → RNH3+ + OH- (pH > 8.3)
• Once all of carbonic acid is

neutralized (pH>8.3) amine
basicity is represented by pKa
Product MW pKa
100% NH3 17.00 9.24
• Any additional amine added is
hydrolyzed and will further 100% CHA 99.00 10.58
increase the pH to pKa 100% MEA 61.09 9.5
100% MOPA 89.14 10.11
• If pKa< target pH, excessive 100% MOR 87.12 8.49
amount of amine may need to
be fed
SM
Neutralizing Amines Characteristic
Thermal Stability
• Amines have specific Amines Temperature

temperature limitations, above Limit* (0C)
which they will thermally
decompose CHA 593
DEAE 454
• Primarily dependent on time at
temperature also oxygen EA or MEA 593
MOPA 593
• Relative stability (EPRI
MOR 593
Research) : MEA > MOPA>
MOR AMP 399
Ammonia No limit
• Above 165 bar, 600 0C: NH3 is
*50% decompose
recommended
SM
Factors to Consider in Selecting Neutralizing Amines
• Regulatory
• pH Target
• Steam pressures and

temperature (thermal
stability)
• Equipment in steam/
condensate system
• Cascading system
• Flash tank
• Steam turbine
• Metallurgy
• Reboiler
• Vented receiver; etc
SM
pH Target - Feed Water and Condensate
Nalco Best Practices

• Soft water m-up: 8.5 – 9.2
• Demin water: 9.0 – 9.2
Power Plant Best Practices

• All steel: 9.2 – 9.6
• Mixed: 9.0 – 9.3
SM
Steam Turbine – Advantages of Amines
• If not neutralized, organic acids may

drop the pH in initial condensation
zone & cause corrosion in steam
turbine Species Relative Destination
V/L
• Low V/L Amine is a better choice Carbonic High Final
I
than NH4OH to neutralize organic Acid condensation
acids in this particular area
Acetic & Low Early stage of
Formic Acid condensation
Ammonia High Final
condensation
Amines Low or Early & final

high stage of
condensation
(initial condensation)
SM
Metallurgy
Copper and Ammonia Corrosion
• One of thermal degradation

products of amines is
ammonia
Ammonia Grooving
• Ammonia is corrosive to
copper and copper alloys in DO Max Allowable
presence of O2 (ppb) Ammonia
(ppm)
0-20 0.5
• The main sources of NH3
present in the system with 20-50 0.3
Cu metallurgy should be
reduced or eliminated >50 Any level may cause
a problem
whenever possible
SM
Feed Water and Condensate Key Performance
Indicator
Parameter Industrial Power Plant

pH 8.8 – 9.2 9.2 – 9.6 (all steel)
9.0 – 9.3 (mixed)
Total Iron, ppb Fe < 10 <2
Total Copper, ppn Cu < 10 <2
Dissolved Oxygen, ppb <7 <5
SM
Boiler Feedwater & Condensate System Sampling
• Cooled to less than 32 0C
• Sample flow throttle at outlet

only
• Stainless steel sample lines

(1/4” tube)
• Proper flow as required by

test procedure
– 0.6 m/s – 1.8 m/s
– Particulates (iron and copper)
1.2-1.8 m/s
SM
Thank You!
SM

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Boiler Feed Water Treatment

Essential Expertise for Water, Energy and Air SM

• Boiler make-up water system

• Objective of boiler feed water treatment

• Type of corrosion in feed water system

• Corrosion control in boiler feed water system

• Sampling and Testing

Parameter Softener Co-current Counter Mixed Power

• Prevent boiler deposition

• Extend equipment life time

• Corrosion in feed water system

• Boiler deposition will lead to:

• Flow Accelerated Corrosion (FAC)

Oxygen Corrosion FAC

• Generally occurs as pitting

• Rare occur in operating

• Use corrosion resistant

• Remove the oxygen

• Metal passivation (pH

• Chemical (O2 Scavenger)

• Primary oxygen removal

• Also can be act as feed

• O2, CO2 and NH3

• But not HCO3 (from CO2) or

PAC-2 Sales Blitz

3. Relative partial pressure

PAC-2 Sales Blitz

PAC-2 Sales Blitz

• DO>15 ppb typically caused

• These problems usually

• High or low feed water temperature

• Inadequate quantity of steam or

• Air in-leakage at boiler feed

• Air or hydrocarbon binding

• Leaking deaerator by-pass

PAC-2 Sales Blitz

• ~40% of 700 dearators

• Dearator inspection using

• NACE Task Group: Standard

• Iron will self passivate in water, if no

• Passivation can be accelerated by

• Erythorbic Acid (Surgard)

Oxygen All DEA Max Turbine Spray FDA

• Safety, Health & Environment

Study Performed 35% Hydrazine Elimin-ox®

0% 20% 40% 60% 80% 100%

PAC-2 Sales Blitz

Simulated boiler feedwater through economizer:

Poor Good Excellent

Oxygen Scavengers %C Break down Products

• Influenced by several factors:

Tendency for Saturation

• Maintain pH in proper range with ammonia or amines

• Avoid a highly reducing environment!

• Monitor with soluble iron tests before and after suspect

• Between deaerator and

• Alternatively, feed directly

• For attemperation, injection

• Condensate is Hot Water!

• Condensate is (reasonably) Pure Water!

Industry Typical % Return

• Neutralizing amines are volatile,

• They function by volatilizing into the

• Amines neutralize carbonic acids or