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Do Neutralizing Amines

Have a Role in the


Treatment of High Purity
Boiler Feedwater?
J ames Robinson
Luis Carvalho
Anthony Rossi
GE Power & Water
Volatile Alkaline Treatments Are
Commonly Used To Treat High
Purity Feedwater
Boost Feedwater and Condensate pH
Boost pH in AVT Treated Boiler Water
Volatile Alkaline Treatments
Ammonia
Neutralizing Amines
Morpholine
Cyclohexylamine
Diethylaminoethanolamine
Methoxypropylamine
Ethanolamine
Advantages of Neutralizing
Amines
Distribution of Amines in 2- Phase Systems
Ability of Amines to Boost pH at the
Temperature of the System.
Steam-Water Distribution Ratio as a Function of
System Pressure -- Water pH
25C
= 9.0
0
1
2
3
4
5
6
7
0 500 1000 1500
System Pressure, PSIG
D
i
s
t
r
i
b
u
t
i
o
n

R
a
t
i
o
Ammonia
Cyclohexylamine
Ethanolamine
Common 2-Phase Systems
Boilers
Flash tanks
Heat Exchangers
Lines mixtures of steam and condensate
pH of Pure Water as a Function of Temperature
0
1
2
3
4
5
6
7
8
25 50 75 100 125 150 175 200
Temperature (C)
p
H
Increase of pH at Temperature Compared to that of
Pure Water as a Function of Boiler Operating
Pressure When pH at 25 C is Adjusted to 9.0 with
Various Alkalizing Agents
0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 500 1000 1500
System Pressure, PSIG
p
H

I
n
c
r
e
a
s
e

O
v
e
r

P
u
r
e

W
a
t
e
r
Ammonia
Cyclohexylamine
Ethanolamine
Where are the differences in
distribution ratio and pH at
temperature important?
CMS
Evaluates all constituents in the system
Calculates at temperature
Acid dissociation constants
Vapor-liquid distribution constants
Uses flow data to project the concentrations
in the liquid and the vapor phases
Calculates pH
25C
and pH
t
of each stream
LP Evaps in Gas Turbine HRSGs
Many preclude the use of phosphate or caustic for
liquid phase pH control
Volatile chemicals used for pH control
2-phase FAC became a common problem
LP Evap Flow Accelerated
Corrosion Principally in the
Risers and Steam-Water
Separators
44
4/20/2010
Feedwater
3 ppb CO
2
530 ppb NH
3
pH
25
= 9.2
Blowdown
pH
25
= 9.1
pH @T = 6.5
Riser Liquid
pH
25
= 9.0
pH @T = 6.4
LP Evap Steam
NH
3
= 1990 ppb
pH
25
= 9.6
FAC
100 psig LP evaporator
Blowdown = 90% of feedwater
Replacing Ammonia with ETA
Reduces 2-Phase FAC!
45
4/20/2010
Feedwater
3 ppb CO
2
1500 ppb ETA
pH
25
= 9.2
Blowdown
pH
25
= 9.2
pH @T = 6.6
Riser Liquid
pH
25
= 9.3
pH @T = 6.7
LP Evap Steam
pH
25
= 7.8
100 psig LP evaporator
Blowdown = 90% of feedwater
What if we increase the feed of
ammonia to produce the same
pH @T (6.7) in the riser as we
have with ETA?
46
4/20/2010
Feedwater
3 ppb CO
2
2300 ppb NH
3
pH
25
= 9.6
Blowdown
pH
25
= 9.5
pH @T = 6.8
Riser Liquid
pH
25
= 9.4
pH @T = 6.7
LP Evap Steam
NH
3
= 9890 ppb
pH
25
= 9.9
100 psig LP evaporator
Blowdown = 90% of feedwater
45
4/20/2010
Feedwater
3 ppb CO
2
1200ppb MEA
300 ppb NH
3
pH
25
= 9.3
Blowdown
pH
25
= 9.2
pH @T = 6.6
Riser Liquid
pH
25
= 9.3
pH @T = 6.7
LP Evap Steam
pH
25
= 9.4
100 psig LP evaporator
Blowdown = 90% of feedwater
High Pressure Evaporators
47
4/20/2010
Feedwater
20 ppb CO
2
5 ppb Cl
pH
25
= 9.4
Cat Cond = 0.17 uS/cm
0.5% Blowdown
1 ppm Cl
Riser Liquid
1500 PSIG Steam
48
3/30/2010
Fe
3
O
4
Ammonia Feedwater Treatment to pH of 9.4
10 Concentrations Under Deposit
Porous Iron Deposit
Water
Steam
Heat
NH
3
=560 ppb
Cl = 1000 ppb
pH
25
= 8.26
pH
t
= 4.95
pH
25
= 3.7
pH
t
= 3.8
49
3/30/2010
Fe
3
O
4
ETA Feedwater Treatment to pH = 9.4
10 Concentrations Under Deposit
Porous Iron
Water
Steam
Heat
MEA =9500 ppb
Cl = 1000 ppb
pH
25
= 9.6
pH
t
= 6.0
pH
25
= 9.4
pH
t
= 5.3
48
3/29/2010
Fe
3
O
4
Ammonia Feedwater Treatment to pH of 9.4
10 Concentrations Under Deposit
TSP to 0.5 ppm PO4 + 0.5 ppm NaOH
Porous Iron Deposit
Water
Steam
Heat
NH
3
=400 ppb
Cl = 1000 ppb
pH
25C
= 8.6
pH
t
= 5.4
pH
25C
= 4.1
pH
t
= 4.4
Treatment
Program
pH
t
in Boiler
Tube
pH
t
Beneath
Deposit
Low-Level
Phosphate-NaOH-
NH
3
5.4 4.4
AVT - ETA
6.0 5.7
5 ppb Acidic Chloride Contamination
of Boiler Feedwater
50
3/24/2010
Fe
3
O
4
Ammonia Feedwater Treatment to pH = 9.4
TSP to 6 ppm PO
4
in Boiler Water
10 Concentrations Under Deposit
Porous Iron
Water
Steam
Heat
Cl = 1000 ppb
pH
25
=9.8
pH
t
=7.7
pH
25
= 10.4
pH
t
8.7
Steam Turbines
Steam Inlet
CO
2
20 ppb
Chlorides 5 ppb
pH
25C
= 9.4
1
st
Condensate
Temperature 212F
Effect of % Steam Condensation on the pH at
Temperature of the First Turbine Condensate
(St eam Inlet - pH
25C
= 9.4 f or Ammonia and ETA, Chlor ide = 5 ppb)
0
2
4
6
8
10
0.001 0.01 0.1 1
Percent of Steam Condensed in the
First Condensate
p
H

a
t

T
e
m
p
e
r
a
t
u
r
e
Pure Water
Ammonia
ETA
Limitation of Neutralizing
Amines
Thermal Decomposition
Boilers
Superheaters and reheaters
Thermal Decomposition Products
Carbon dioxide
Formate, Acetate, Proprionate, etc.
Ammonia
Affect of Decomposition
Products on Corrosion
Carbon dioxide corrosion problems are well
known
Limited reports of organic acid corrosion as
well
Priority for control of this corrosion is to
maintain pH throughout.
Affect of Decomposition
Products on Cation Conductivity
Carbon dioxide and organic acids contribute
to cation conductivity
Reduces effectiveness for detecting
feedwater contamination
Exceeds turbine manufacturers steam purity
specifications
Steam Purity Monitoring
Turbine manufacturers specify steam cation
conductivity limits, usually of 0.2 or 0.3 uS/cm.
0.2 to 0.3 uS/cm is equivalent to 16 to 25 ppb of
chloride in otherwise pure water!
Degassed cation conductivity measurement is
gaining in popularity
No form of cation conductivity detects caustic
contamination
Conclusions
Yes, neutralizing amines provide improved
corrosion protection compared to ammonia
in many applications
Thermal instability limits amine
applications mostly because of the effect on
cation conductivity measurements
Improved steam purity monitoring methods
are needed