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Filming Amines

Why Use a Filming Amine?

• High CO2 loading makes neutralizing amines costly


• Film barrier provides some protection against
oxygen corrosion
• Filming Amines may protect against erosion
• Filming Amines may improve heat transfer
Why Not Use a Filming Amine?
• Hard to Feed
• Little Selection Available
• Possible Fouling
• Program must start slowly
• Not completely effective against oxygen
Filming Amines
CO2 O2 O2

O2 CO2
O2
CONDENSATE
O2 O2 CO2
CO2 O2
O2 O2
CO2
O2 O2 CO2
CO2
CO2
O2 CO2
Metallic wall

Protective filming amine


layer
Different Filming Molecules
Primary Amines
RNH2

Secondary Amines
(R)2NH

Tertiary Amines
(R)3N
Filming Amines
Feeding Requirements
• May need to be diluted with Condensate
prior to feeding
• Must be Fed to Steam Header
• Must be Fed through Injection Nozzle
• Feed Pump Interlocked to Steam Flow Meter
Filming Amines Fail When The
Film Breaks Down
Factors that Break Down Filming Amines
– Hard Water Contamination
– pH too low (< 6.5)
– pH too high (8.5)
– Organic Contamination
NALCO ACT

Advanced Condensate Treatment

“The World’s Most Innovative


Corrosion Inhibitor”
ACT: Something New in
Filming Agents
• ACT is an Ondeo Nalco patented condensate treatment
technology
• Its a blend of emulsifiers used in the Food Industry
(contains no amines or other nitrogen- containing
compounds)
• Provides a comparable barrier to the historically used
amines; pH control range 5.5 to 7.5
• Much reduced fouling potential
• Fully approved by regulatory agencies
• Effective in inhibiting CO2 and O2 corrosion
ACT Feeding Requirements
• Steam Header Feed
• Stainless steel slotted retractable quill injector
(P4634 and P4694)
• Quill orientation is important
• Fed neat or in dilution
• Should be fed continuous
• Max pressure 600 psig (41 bar)
• Max Temp 486oF (252oC)
Summary of Condensate
Filming Treatments
• Useful when CO2 loading prevents economic
application of neutralizing amines
• Are effective in inhibiting oxygen corrosion
• Make the commitment to feed properly
• May have merit to prevent erosion in certain
applications
• Poor reputation due to fouling potential
Oxygen Scavenging -
Metal Passivation in Condensate Treatment
• Given the lack of effectiveness of other treatments on
oxygen, the application of some feedwater oxygen
scavenging technology in the condensate area is a
good fit
• After taking all possible mechanical corrective
measures, the application of a chemical treatment can
be effective
Molecules Available
• Hydrazine
• Carbohydrazide
• DEHA
• Hydroquinone
Operating Mechanism of
Scavenger / Passivator
• “Conditioning” of metal surface to prevent
corrosion, even if oxygen is present
• Conversion of ferric oxidation state to
reduced oxide form i.e. Fe3O4 (magnetite)
• Direct removal of oxygen
When a Scavenger/Passivator
Should be Applied
• After all steps taken to limit oxygen entry
• Cost analysis between condensate dumping and
treatment application
• Trial conducted on small part of system, monitoring
iron throw before and after treatment use
• Can be beneficial when electromagnetic polishing is
in use
Problems with Passivation
• Supplemental feed to steam system is usually
required
• Condensate Systems are dymanic and may
not operate at trial conditions
• Oxygen ingress may be sporadic
• Results may not meet expectation
Summary of Scavenging /
Passivation Treatment
• Most applicable in batch processes, where known
oxygen intrusion will occur
• Feed point selection is critical to get
coverage/performance
• Good monitoring required to justify
• May avoid capital expense of supplemental
condensate purification or excessive dumping
Supplemental / Mechanical
Condensate Purification
TYPE OF DEVICE OPERATING STRENGTH WEAKNESS
MECHANISM
A) SODIUM-CYCLE ION VERSATILE ALTERS BOILER CHEMISTRY
CONDENSATE EXCHANGE
POLISHER

B) AMINE CYCLE ION PREVENT SODIUM COST


EXCHANGE CONTAMINATION
MIXED BED ION EXCELLENT LIMITED TO 120oF (49oC)
CONDENSATE EXCHANGE EFFLUENT
POLISHER QUALITY
CARTRIDGE FILTRATION INEXPENSIVE HIGH CHANGE-OUT RATE
FILTRATION WITH HIGH LOADING
PRECOAT FILTRATION COST-EFFECTIVE SUBJECT TO MECHANICAL
FILTRATION FAILURE
ELECTROMAGNETIC FILTRATION EXCELLENT COST, UNCERTAINTY OF
FILTRATION EFFLUENT COPPER REMOVAL
QUALITY
Comments on Condensate
Purification
• Hard to justify in normal operation, usually installed as
part of an expansion or upgrade
• May require chemical treatment for optimum
effectiveness
• May impact boiler water quality
• Many existing systems are poorly maintained, not that
effective
Condensate Sampling and
Monitoring
Where Do You Sample?
• Critical equipment and/or largest steam
users
• Composite streams prior to receivers or
flash tanks
• Known problem areas
• Return condensate streams
Sampling Requirements
• Cooled to less than 90oF (32oC)
• Sample flow throttled at outlet only
• Stainless steel sample lines
• Continuous flow
• Adequate velocity
• Throttle valve installed outlet side of
cooler
Sampling Horizontal Lines
Top
Sample tap

Sample tap
1/2 in. dam.
SS gate valve
45oF
1/4 in SS
sample line
Sample cooler
Sample line Gate valve

Throttle valve
Condensate monitoring is very
demanding
Monitoring Techniques Include:
• pH
• Iron Measurement
• Filtration Testing
• Conductivity
• Turbidity
• Corrosion Coupons
• Electrochemical Corrosion Monitoring
Measuring Condensate pH
Correctly Provides Powerful Data
• Sample temperature is critical
• Should use dedicated pH meter and electrode
• Sample collection isn’t as difficult as might be thought
• Meter calibration is required
Iron Analysis
• Many analytical methods available
– AA
– ICP
– Photometric Wet Chemistry
• Must employ a digestion step
• Sample collection is complex, since we are dealing with
particles
Filtration Testing of Condensate
• Standard technique is to use:
– 1 liter condensate sample
– 0.45 micron filter pore size
• Comparison charts available to
quantify results
• Best when fixed atop system
schematic to locate system
problems
Conductivity as a Condensate
Monitoring Tool
• Depends on process
– Paper mills have highly ionic process fluids
– Oil/petrochemicals may not be seen
• Realize impact of treatment
• Some systems use cation column to magnify presence of
ionic materials
• In critical system, install automatic dump based on
conductivity meter
Automatic Conductivity
Monitoring System
Turbidity is a Technique to Monitor
Particulate Iron On-Line
• Turbidity can be Correlated to Metals
Concentration
• Locate close to Equipment being Monitored to
cut Sample Lag Time
• Can be Incorporated with Diversion Valve
• Choose a meter that Scans the Surface of a
sample
Example of Turbidity
Diversion System
Summary of Condensate
Monitoring
• Match Monitoring Technique to type of program in use
• Look for consistency - high turbidity should correlate
with a highly colored Millipore
• Sampling protocol is more important for some
techniques that others
• Be Creative! - Find something unique about your
system
Key Takeaways
Key Takeaways
• Condensate Treatment Technology is the Implementation
of an Integrated Chemical, Mechanical and Monitoring
Program to Derive Significant Operating Cost Savings in
Plant Operation. Recycling or returning as much steam
condensate back as part of the boiler feedwater makes
good business sense. It’s already been paid for, generally
the quality is high purity, and it contains valuable heat
content.
Key Takeaways
• Condensate corrosion is caused by the presence of
dissolved carbon dioxide, oxygen and/or ammonia.
The three types of condensate treatment chemistries
used to inhibit these corrosive species are,
neutralizing amines, filming agents and passivating
oxygen scavengers.
Key Takeaways
• Neutralizing amine product selection requires that
you know the plant’s regulatory limitations with
respect to amine usage, and how complex the steam
condensate system is that you are trying to treat.
Select amine products based on their V/L ratio
characteristics, basicity and where the condensate is
returned from. Complex steam condensate systems
may require satellite feed of amines to control pH in
more remote areas.
Key Takeaways
• Filming amines and Ondeo Nalco’s non-amine
ACT chemistry lay down a protective barrier to
keep the corrosive species away from the metal
surface. Filming agents are typically used when
high CO2 loading makes neutralizing amines too
costly, or when the system is experiencing
dissolved oxygen problems.
Key Takeaways
• Certain passivating oxygen scavengers help reduce the
amount of iron returned in the condensate. They
condition the metal surface to slow down and inhibit
oxygen attack. Secondly they can react with oxygen
directly.
Key Takeaways
• The goal of installing sample points and monitoring
a condensate system is to be able to determine how
well it is being protected. They should enable you to
identify where problem areas are located in the
system and provide you with an effective way to
rapidly trouble shoot the system when new problems
arise. Things that need to be monitored include pH,
iron, conductivity and dissolved oxygen.