Overview

• The value of condensate

• Condensate corrosion

• Condensate treatment

• Condensate monitoring,
sampling and control
Condensate System
Condensate Treatment Technology is the Implementation of
an Integrated Chemical, Mechanical and Monitoring
Program to Derive Significant Operating Cost Savings in
Plant Operation
 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
 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
The Risks of Returning
Condensate
• Process Contamination
– Oil
– Process Constituents
• Raw Water Constituents
– Oxygen
– Hardness
• Corrosion Products
– Iron
– Copper
Why is Condensate Treatment
Needed?
Condensate Treatment is the Battle Against Three
Dissolved Gases:
CO2 O2 NH3
Carbon Dioxide Sources

•Breakdown of feedwater alkalinity

2 HCO3 - heat
CO3 -2 + H 2O + CO 2
Bicarbonate Carbonate Water Carbon Dioxide

heat
CO3 -2 + H2O 2OH - + CO 2
Carbonate Water Hydroxide Carbon Dioxide

•Air inleakage
•Breakdown of organic compounds present in the
feedwater
Where CO2 Corrosion Occurs

CO2(g) + H2O(g) --> No Reaction

CO2(g) + H2O(l) --> H2CO3(l) (carbonic acid)

Then, H2CO3(l) <--> H+ + HCO3-
Wastage Caused by CO2
Softened Water used for Boiler Makeup
produces a considerable CO2 concentration in
the condensate. Consider revising the
external treatment system to reduce the CO2
loading.

Demineralized Water greatly reduces the CO2

loading in the system, but there is still
sufficient present to depress condensate pH
and still require treatment.
Feedwater Alkalinity Reduction
To Control CO2 Generation

• Lime softening
• Dealkalization
• Degasification
• Demineralization
• Increased condensate return
Oxygen Corrosion in
Condensate
Sources of Oxygen in
Condensate Systems
• Systems under vacuum
• Intrusion into Batch Processes
• In and out of Service Equipment
• Leakage past Pump Seals
• Service water used to “Quench”
• Alternate heating/cooling cycles
 Mechanical Corrections to
Oxygen Intrusion

Causes of O2 Entry Means of Detection Remedy

Into Vacuum Systems Check Gauges Repair Leaks

Out-of-Service Test at Start-up Dump Condensate

Systems
Open Receivers Identify Repipe Below Liquid
Level
Pump Seal Leakage Test In-Service Repack, or Install New
Seals
Quench Water Test/Observe Remove Source

Alternate Identify Dump Condensate

Heating/Cooling
Ammonia is the Third Dissolved
Gas to be Considered
• Ammonia only attacks copper alloys
• Sources of Ammonia
– Ammonia added as a treatment
– Amine-based treatment decomposition
– Thermal decomposition of hydrazine
– Nitrogen containing organics present in make water
Mechanism of Ammonia Attack
• Ammonia Dissolution in Liquid Phase
NH3(g) + H2O(l) --> NH4OH
• Ammonia Ionization
NH4OH <---> NH4+ + OH-
• Copper/Ammonia Complexation
Cu+2 + 6NH4+ --> Cu(NH4)6
 Ammonia

Dissolved oxygen Maximum allowable

ppb ammonia, ppm

0 to 20 0.5

20 to 50 0.3

>50 Any level may be

a problem
 Remedies for Ammonia Attack
• Alloy Selection (You’ll never see copper piping in an
ammonia plant)
• Consider a hydrazine substitute
• Evaluate neutralizing amine selection
• Sewer contaminated condensate (i.e. air injector drains)
• There is no treatment for ammonia attack
 System Survey
Id e n tify E q u ip m en t
S te a mC/ o n d e n s aStey ste m s C a n B e E x te n s iv e
M a ke - up ◆ R e b o ilerasn d
h e at
Pr o ce s s ex c h a n g ers
P r o ce s s ◆ K et tl es
e ttl a n d re a cto r s
◆ C o n d en ssee rs
P r o ce s s

Low
B low d ow n F l a sh ◆ Tank h ea ter s
fl a s h t a nk t a nk
p re s su re
st e a m
◆ S t ea m tr ap s
C o nd e n s a te
R e c e iv e r
◆ F la sh ta
t a n k s a n d re ce ive rs

• A complete system survey is the key to any effective

treatment strategy
• The survey defines system needs and limitations
Steam Traps
Condensate Treatment
 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
 Neutralizing Amines
• Neutralizing amines are the most universally
used chemical treaments to prevent CO2
corrosion

• Neutralizing amines are organic compounds with

an amino functionality attached (-NH2;
NHR; -NR2)

• The organic group may be cyclic, a straight chain

or a branched chain.
Why Amines are So Popular
• Direct Neutralization of CO2
• Direct elevation of pH
• Easy to feed
• Easy to Control
• Many options available
• Few “Side Effects”
• Compatible with other system treatments
• Treatment Recycles
• Blends Available
 Weaknesses of Amines
• Selection requires system knowledge
• Presumed performance doesn’t always occur
• Can be expensive if CO2 loading is high
• No impact on oxygen contamination
• Some systems cannot tolerate nitrogen
• Adds conductivity to condensate
Amine Selection in a “Simple” System
Amine Volatility is not as big an
issue when condensation is “one
and done”

External
Treatment
System Condenser Steam Turbine

Economizer

Makeup Water

Boiler
Superheater
Deaerating
Heater

Boiler Feedwater
Pump
 A Typical Paper Machine Dryer
Configuration Represents a Complex
Condensate System
Neutralizing Amine Selection Criteria
• Need for Volatility
• Amount of CO2 Expected
• FDA Regulations Applicable?
• Pressure of Steam System
• Process Considerations
• Direct Contact with Process?
• Steam used for Humidification
 Neutralizing Amine
Operating Mechanism
• Volatility - As measured by Distribution Ratio at
the pressure of two phase conditions
• Neutralizing Capacity - As determined by the
molecular weight of the amine molecules present
• pH Elevation - As determined by the basicity
constant of the molecules present
The Importance of Volatility

• Volatility positions the amines in complex systems

• Amine volatility is always compared to CO2

• Volatility is measured by V/L Ratio or Distribution Ratio

• Volatility is not as important in “simple” systems

 Amine Volatility is Very
Temperature & Pressure Dependent
 Amine Volatility vs. Pressure
Name V /L R a i t o v s B o i l e r p r e ssu r e ( p si g ) **
0 50 150 450 600 900
CO 2 3 4 .8 8 .5 8 .5 1 5 .8 >9 9 .0
NH3 6 .7 7 .0 5 .0 4 .3
MEA 0 .1 1 0 .1 7 0 .2 4 0 .2 5
A min o m e th y lp r o p a n o l 0 .6 5 0 .6 5 0 .7 7 0 .8 6
Mo r p h o lin e 0 .4 0 0 .4 4 0 .9 9 1 .1 0 1 .2 2 1 .2 2
MO PA 2 .1 2 .0 2 .3 2 .0
DEA E 5 .8 6 .3 5 .2 4 .5
DMA IP 7 .3 4 .8 4 .9 4 .2
Cy c lo h e x y la m in e 4 .0 3 .0 9 .0 9 .4 8 .2 7 .0
** Ex p e r ime n ta l B o ile r Re s u lts
 Using Concept of Volatility
• Evaluate System to determine if volatility matters
• Amine blends provide for most comprehensive coverage
• Look for places of steam venting (flashed steam), and
pick amine to avoid loss
• Focus on amines in locations of maximum condensate
return
 Neutralizing Amines
• Neutralizing capacity determines amount of CO2
(actually carbonic acid) that the amine can
counteract
• Neutralizing capacity is specified by the
molecular weight of the amine
Molecular Weight of Amines

Amine MW
Morpholine 87
Cyclohexylamine 99
MOPA 89
DEAE 119
MEA 61
Corrosion of Carbon Steel and Copper
Depends on pH of Water
After neutralization, the final
function of the amine is to boost
condensate pH into the range
where total metal solubility is
minimized.
The measure of an amine’s
capability to boost pH is
specified by its basicity
constant.
PH Control Ranges For Neutralizing Amines

Typical Preferred
Mixed iron-copper 8.5-9.2 8.8-9.2
metallurgy
Ferrous Metallurgy 8.5-9.5 9.0-9.5
 Amine Ionization

R-NH2 <---> RNH3+ + OH-

Amines that stay in the R-NH2 form contribute little to pH

elevation. Amines that ionize more completely are more
cost-effective.
Ionization Properties of Different
Amines, NH3 and CO 2
Name pKa*
CO2 4.3
NH3 9.3
Monoethanolamine, MEA or EA 9.5
Aminomethylpropanol, AMP 9.5
Morpholine 8.4
Methoxypropylamine, MOPA 10.1
Diethylaminoethanol, DEAE 9.6
Cyclohexylamine 10.6
Dimethylamino-2-propanol, DMAIP 9.6
Diethanolamine, DEA 8.9
Dimethylpropylamine, DMPA 10.7
Dimethylaminoethanol, DMAE 9.6

* pKa indicates base strength of the amine. The higher the pKa the stronger the base.
 Amine Neutralizing Ability

11

9
pH

5
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
ppm Amine / ppm CO2

Cyclohexylamine Morpholine Diethylaminoethanol

Regulatory Issues
 FDA Applications

• Amines cannot be used to treat steam which

could contact milk or milk products
Cyclohexylamine 10 ppm

Diethylaminoethanol 15 ppm

●
Only four amines are FDA Morpholine 10 ppm
approved
Octadecylamine 3 ppm
●
Steam concentrations are
limited
 OSHA* Restrictions
OSHA PEL Limits

Morpholine 20 ppm

Diethylaminoethanol 10 ppm

Cyclohexylamine 10 ppm

• Establishes the concentration of amines in air to which a healthy

worker could be exposed for an eight hour period
• Known as the PEL (Permissible Exposure Limit)
* Occupational Safety and Health Administration
 Summary of
Neutralizing Amine Use
• Determine the regulatory limitations
• Determine type of system - single pressure(simple) or multiple
flash (complex)
• Select Amine Volatility to get Treatment where needed
• Ascertain amount of CO2 to justify selection based on
Neutralization Capacity
• Select condensate pH control range on basicity of amines in use
• Satellite fed maybe necessary
• Monitor throughout the system