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Abstract
Organic amines have been widely used to treat high-purity boiler feedwater since at least the 1940s. Alt-
hough notable benefits have been derived, some consider the use of these amines to be risky. In addition,
the use of organic chemicals for boiler feedwater treatment often causes steam and condensate cation
conductivity levels to exceed current power industry guidelines. The benefits that can be derived and ques-
tions concerning the use of both neutralizing and filming amines are presented to help plant operators as-
sess the potential value to be gained from using these amines in their systems.
Figure 1 The steam-water distribution ratios of ammonia and various amines vary as a function
of system pressure (temperature) and pH.
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Also, the high temperature in most parts of the boiler-steam system affects the temperature of the water
under operating conditions. Compared to ammonia, certain amines are better able to maintain alkaline pH
levels at the temperature of the water in steam generators (Figure 2).
1.4
pH Increase Over Pure Water
1.2
1 Ammonia
0.8 Cyclohexylamine
0.6
Ethanolamine
0.4
0.2
0
0 500 1000 1500
Figure 2 The effect of boiler pressure (temperature) on pH at temperature when otherwise pure water
is adjusted to a pH 9.0 at 25C with various volatile alkalizing chemicals.
Figure 3 FAC caused serious damage to this low-pressure evaporator steam separator.
To illustrate the effects of the steam-water distribution ratio and the at-temperature basicity of volatile alka-
line treatments in LP evaporators, models were developed using Water & Process Technologies Computer
Modeling System (CMS)1 software. To develop the models, the CMS program calculates the steam-water dis-
tribution constants and acid dissociation constants of the feedwater contaminants and alkalizing agents at
the operating temperature of the evaporator. It then uses flow data to project the distribution of the constit-
uents in the water and steam phases and calculates the pH of each stream at both the temperature of the
system (pHt) and at 25C (pH25C).
For the purposes of this illustration, an LP evaporator model that converts 10 percent of the feedwater into
100 psig (700kPa) steam and riser tubes that develop a steam-to-liquid weight ratio of 0.1 was used. Figures
3a through 3d show the projected pHt and pH25C developed at various locations in the LP evaporator when
ammonia or ETA is fed to the feedwater. The projected chemistry of each of the LP evaporator streams is
provided in Tables 1a through 1d.
Figure 4a shows that when ammonia is used to control the feedwater pH25C at 9.2, the expected pH at tem-
perature in the liquid exiting the riser tube is 6.4. By comparison, Figure 4b shows that when ETA is used to
control the feedwater pH25C at 9.2, the expected pH at temperature in the liquid exiting the riser tube is 6.7.
Although this 0.3 unit difference in pH does not seem large, experience has shown that it is enough to dra-
matically reduce FAC problems in many systems. To develop the same 6.7 pHt in the liquid exiting the riser
tube when using ammonia, the feedwater pH25C must be increased to 9.6, as shown in Figure 4c. Dooley
and Anderson have suggested that the pH25C should be at least 9.8 to control two-phase FAC when ammonia
is used.2 This is to boost the pH at temperature one full unit above that of pure water, which is 5.8 at 100 psig
(700kPa)
Figure 4b The use of ETA to control LP feedwater pH25C at 9.2 usually controls FAC in riser
tubes. However, the use of ETA alone can produce a low pH in the condensed steam.
Figures 4b and 4c show that the use of ETA or ammonia alone may not provide satisfactory results through-
out the system. The use of ETA alone may effectively protect the LP evaporator riser tubes from FAC, but re-
sult in low steam pH. By contrast, feeding enough ammonia to control FAC in the LP evaporator riser tubes
may cause excessive ammonia in the steam. For these systems, a blend of amines or ammonia and an
amine may prove desirable. The model in Figure 4d illustrates how a blend of ETA and ammonia can provide
a better pH balance throughout the LP evaporator.
Figure 4d - A blend of ETA and ammonia produces a nearly uniform pH throughout the LP system.
Figure 5 - HP evaporator with 5 ppb acidic chloride (cation conductivity of 0.17 S/cm)
contamination of the boiler feedwater.
Since much on-load corrosion of 1500 psig evaporators is due to underdeposit corrosion (Figure 6), CMS
models were designed to show the effect of different treatment chemistries on pH in both the bulk boiler wa-
ter and boiler water that has been concentrated 10 fold beneath a deposit. This information is presented in
Figures 7a through 7d.
Figures 7a and 7b show the projected results for all volatile treatment (AVT) with ammonia and ETA, respec-
tively. Figure 7a shows that with ammonia treatment, although the pH25C of the bulk boiler water is 8.3, the
pHt is 5.0, well below the pHt of 5.7 for pure water. In addition, the concentrated water beneath the deposit is
projected to be highly corrosive, with a pHt of 3.8.
By contrast, in the ETA treated system, Figure 7b shows that the bulk boiler water pH25C is projected to be 9.6
and the pHt is projected to be 6.0, slightly above that of pure water at this temperature. The pHt of the con-
centrated water beneath the deposit is projected to be 5.3. Although this is still not optimum, it is significantly
better than the pHt of 3.8 that is projected for the ammonia-treated system.
Figure 7a The pH at temperature is acidic in both the bulk boiler water and beneath a deposit in a 1500 psig boiler
tube with ammonia-based AVT feedwater treatment, when 5 ppb of acidic chloride contamination (cation conductivity
of 0.17 S/cm) is in the boiler feedwater.
Figures 7c and 7d illustrate the advantages of using ETA compared to ammonia for feedwater pH control
under the following conditions: The boiler water is treated with 0.5 ppm of trisodium phosphate and 0.5 ppm
of sodium hydroxide, and the feedwater is contaminated with 5 ppb of acidic chloride.
Figure 7c shows that with ammonia feedwater treatment, the 5 ppb of feedwater chloride produces an acid-
ic pHt of 5.4 in the bulk boiler water and 4.4 beneath the deposit. Acidic corrosion is very likely under these
conditions even though the bulk boiler water has an alkaline pH25C of 8.4.
By contrast, as illustrated in Figure 7d, if ETA is used for feedwater treatment, the bulk boiler water pHt is pro-
jected to be 6.3, which is slightly alkaline, and the pHt of the water concentrated beneath the deposit is pro-
jected to be only slightly acidic at 5.7.
Figure 7c The pH at temperature is acidic in both the bulk boiler water and beneath a deposit in a 1500 psig boiler
tube with low-level trisodium phosphate, caustic and ammonia feedwater treatment, when 5 ppb of acidic chloride
contamination (cation conductivity of 0.17 S/cm) is in the boiler feedwater.
The information extracted from Figures 7b and 7c and presented in Table 3 of the appendix shows that at
the model conditions, the AVT treatment using ETA for feedwater pH elevation provides better protection
from acidic chloride corrosion than does low-level phosphate and caustic treatment when ammonia is used
for feedwater pH control. The pHt of the bulk boiler water is maintained at 6.0 with the ETA-based AVT
treatment, while it drops to 5.4 when using low-level phosphate and caustic treatment with ammonia for
feedwater pH control. Beneath the deposit, the pHt of the AVT treatment using ETA becomes slightly acidic
at 5.7. By comparison, the pHt beneath the deposit with the low-level phosphate, caustic and ammonia
treatment is 4.4.
Boilers designed with adequate circulation so that phosphate hideout is not an issue can obtain significantly
greater protection from acidic chloride contamination by maintaining an increased level of trisodium phos-
phate in the boiler water. As shown in Figure 7e, the feed of trisodium phosphate to maintain 6 ppm of
phosphate in the boiler water maintains alkaline water with a pHt of 7.7 in the bulk boiler water and 8.7 when
concentrated 10 times beneath a deposit, in the presence of 5 ppb acidic chloride feedwater contamination.
The increased protection from acidic corrosion provided by ETA or increased TSP is afforded without the
need for adding caustic to the system, reducing the risk of steam system damage.
Filming Amines
Filming amines have been used almost as long as neutralizing amines to protect equipment by forming a
non-wettable film on metal surfaces. Figure 8 shows the protection polyamine application afforded corro-
sion coupons exposed to 100 ppb of oxygen at 230F (110C) for 7 days.4
Figure 8 Filming amines form a non-wettable film on metal surfaces, providing protection against oxygen corrosion.
The above coupons were exposed to a filmer-neutralizer treatment and 100 ppb of dissolved oxygen in demineralized
water at 230F for seven days. The average corrosion rate was measured to be 0.23 mils/yr with no noticeable pitting
observed.
Why are Organic Amines not more Widely Used in the Power Industry?
In spite of the benefits that can be derived by employing properly selected neutralizing amines, their use is
restricted from many power plant systems for numerous reasons. One major reason is the thermal decom-
position of neutralizing amines in steam superheaters and reheaters. The amount of decomposition that
occurs depends on the particular chemicals used, the temperature of the superheat and reheat steam, and
the time of exposure at those temperatures.
Ammonia, carbon dioxide, acetate and formate are some of the most commonly formed decomposition
products. Carbon dioxide, acetate and formate have been of concern due to their potential for causing cor-
rosion in the steam-condensate system and because of their masking effect on cation conductivity meas-
urements. Ammonia formation is also of concern due to the increased potential for corrosion in systems
with copper alloys.
CORROSION CAUSED BY CARBON DIOXIDE AND ORGANIC ACIDS - Carbon dioxide is well known for the nu-
merous acidic condensate corrosion problems it has caused in boiler systems with sodium zeolite softened
make-up water. On a much more limited basis, there have been reports of acidic organic contamination of
boiler feedwater also causing corrosion. While not all answers are known, investigations of these reports 3,
operating experiences reported by Carvalho8,9 and discussions from recent conferences have concluded that
the priority for control of carbon dioxide and organic acid corrosion is maintaining sufficient pH throughout
the system.10
CATION CONDUCTIVITY - Cation conductivity is widely used in the power industry to detect contamination of
condensate, feedwater and steam. It has proven very useful for identifying the presence of anions such as
chloride and sulfate in the condensate as the result of condenser tube leaks. However, it also provides an
undifferentiated indication when carbon dioxide, formate and acetate are also present. Consequently, this
makes cation conductivity a less effective tool for detecting the potentially more damaging chloride and
sulfate contaminants.
Conclusions
Organic amines have been used for decades and continue to be used to protect steam plant equipment and
maintain reliable, efficient plant operations. Their proper use can provide increased corrosion protection not
available through the use of inorganic chemicals alone. The authors have found that these organic treat-
ments or their decomposition products have low corrosion risk as long as pH is adequately maintained
Thermal instability limits the application of organic chemicals, especially neutralizing amines in power plant
applications, because of the effect of the decomposition products on cation conductivity measurements.
This effect decreases the sensitivity of cation conductivity for detecting condenser tube leaks and often
boosts the steam cation conductivity above the steam turbine manufacturers specification.
The conundrum is that many avoid using organic chemical treatments because their use causes them to
exceed the turbine manufacturers steam cation conductivity limits. Yet, meeting those limits does not as-
sure that potentially acidic species, such as chloride and sulfate, are within an acceptable range. In addition,
one of the most damaging potential steam contaminants, sodium hydroxide, is not detected by cation con-
ductivity at all.
Improved criteria for steam purity and plant-friendly methods of monitoring those criteria are needed. For
now, plant operators must evaluate their own specific needs, compare those needs to the information avail-
able and select the treatment that is expected to provide the most value to their plant.
Table 1b (Figure 4b) LP Evaporator Steam Drum 100 psig (700 kPa) Steam Flow = 10% of Feedwater Flow CO2
Contamination of Feedwater - MEA Treatment to Feedwater pH25C of 9.2
Feedwater Blowdown Riser Steam
CO2, ppb (g/l) 3 <1 <1 30
ETA, ppb (g/l) 1550 1710 1830 83
Conductivity, 3.9 4.2 4.5 0.22
S/cm
Cation Conduc- 0.06 0.16
tivity, S/cm
pH @ 25C 9.2 9.2 9.3 7.8
pH @ T 6.6 6.6 6.7 5.9
Table 1c (Figure 4c) LP Evaporator Steam Drum 100 psig (700 kPa) Steam Flow = 10% of Feedwater Flow CO2
Contamination of Feedwater - Ammonia Treatment to pHt of 6.7 in Riser Tube
Feedwater Blowdown Riser Steam
CO2, ppb (g/l) 3 <1 <1 30
NH3, ppb (g/l) 2300 1460 950 9890
Conductivity, 11.0 8.4 6.4 25.1
S/cm
Cation Conduc- 0.06 0.16
tivity, S/cm
pH @ 25C 9.6 9.5 9.4 9.9
pH @ T 6.9 6.8 6.7 7.2
Table 2a (Figure 7a) HP Evaporator 1500 psig (10,500 kPa) Blowdown = 0.5% of Feedwater Flow - CO2 and Chloride
Contamination of Feedwater Ammonia Based AVT
Feedwater Riser Tube Under Deposit
CO2, ppb (g/l) 20 <1 <1
Chloride, ppb (g/l) 5 1,000 10,000
NH3, (g/l) 1,100 560 1,300
Conductivity, S/cm 5.1 4.7 98
Cation Conductivity, 0.17 12 119
S/cm
pH @ 25C 9.4 8.3 3.7
pH @ T 5.0 3.8
Table 2b (Figure 7b) HP Evaporator 1500 psig (10,500 kPa) Blowdown = 0.5% of Feedwater Flow - CO2 and Chloride
Contamination of Feedwater ETA Based AVT
Feedwater Riser Tube Under Deposit
CO2, ppb (g/l) 20 <1 <1
Chloride, ppb (g/l) 5 1,000 10,000
ETA, (g/l) 3,000 9,490 34,400
Conductivity, S/cm 6 12.8 39
Cation Conductivity, 0.17 11.9 119
S/cm
pH @ 25C 9.4 8.3 9.4
pH @ T 5.0 5.3
Table 2d (Figure 7d) HP Evaporator 1500 psig (10,500 kPa) Blowdown = 0.5% of Feedwater Flow - CO2 and Chloride
Contamination of Feedwater ETA Feedwater Treatment Low-Level Phosphate and Caustic Treatment of the Boiler
Water
Feedwater Riser Tube Under Deposit
CO2, ppb (g/l) 20 <1 <1
Chloride, ppb (g/l) 5 1,000 10,000
ETA, ppb (g/l) 3,000 8,600 24,700
PO4, ppb (g/l) 500 5,000*
NaOH, ppb ( g/l) 500 5,000
Conductivity, S/cm 6 14 49*
Cation Conductivity, 14 138*
S/cm
pH @ 25C 9.4 9.6 9.5
pH @ T 6.3 5.7
*Assumes phosphate remains soluble
Table 3 (Figures 7b and 7c) - AVT treatment with ETA provides better protection against acidic chloride corrosion than
low-level phosphate-caustic-ammonia treatment.
Treatment Program pHt in Boiler Tube pHt Beneath Deposit
Phosphate-NaOH-NH3 5.4 4.4
AVT - ETA 6.0 5.3