Condensate Corrosion in Steam Generating Systems (51300-98718-Sg)

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Paper No.
718
CONDENSATE CORROSION IN STEAM GENERATING SYSTEMS
Tzu-Yu Chart, Carol B. Batton, Daniel M. Cicero and Robert D. Port

Nalco Chemical Company
One Nalco Center
Naperville. Illinois 60563-l 198
U.S.A.
ABSTRACT
Corrosion is one of the major problems in boiler condensate systems. Inadequate corrosion protection or
chemical treatment programs can result in system failures and increasing boiler operation cost. The causes of
corrosion as well as corrosion monitoring in boiler condensate systems are reviewed. Various water treatment
technologies for condensate corrosion inhibition are highlighted.
Keywords: condensate corrosion, condensate corrosion inhibition, condensate corrosion monitoring, carbonic
acid corrosion, oxygen corrosion, neutralizing amines, filming amines
INTRODUCTION
Driven by financial necessity, operators of steam boiler systems have sought ways to increase boiler
cycles of concentration to reduce energy and water losses through boiler blowdown. Improvements in
pretreatment technology, most notably in reverse osmosis, have provided the means, but new concerns have
arisen as a result. When boiler cycles are low, feedwater contaminants are removed from the boiler through the
blowdown before they deposit on heat transfer surfaces. As boiler cycles increase, contaminants - mostly iron
and copper returned with the condensate - remain in the boiler for longer periods of time, increasing the
likelihood of deposition. Chemical dispersants are oflen used to minimize deposition of iron and other
contaminants, but do nothing to address root causes which oflen reside in the condensate system.
Maximizing condensate return is a powerful cost reduction tool. Condensate can be extremely pure water.
It oflen requires no pretreatment to make it acceptable for boiler feedwater, although use of condensate polishers
is not uncommon. Because of its heat content - typically 180aF (82%) or greater - less fuel is needed to convert
it to steam. It is also “free” in the sense that the returned condensate takes the place of excess make-up water in
the system.
Condensate can be contaminated by release of corrosion products through metal dissolution or by

separation of accumulated oxide layers from the metal surface during system startups or shutdowns. Corrosion
Copyright
01998 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be made I” writing to NACE
International, Conferences Division, P.O. Box 218340, Houston, Texas 77218-8340. The material presented and the views expressed in this
paper are solely those of the author(s) and are not necessarily endorsed by the Association. Printed in the U.S.A.
products tend to deposit on boiler heat transfer surfaces (Figure 1)’ reducing heat transfer efficiency and Musing
boiler tube failures. Condensate corrosion control is required to protect process equipment, lines and tanks as
well as to maintain the condensate as a good quality source of feedwater.
In order to maximize the benefits of returned condensate, it is important to understand the condensate
system corrosion mechanisms which can degrade condensate quality and, ultimately, boiler operation and
reliability. This paper discusses those mechanisms, several case histories illustrating failures, a summary of
corrosion protection technologies, and typical and state-of-the-art methods for corrosion monitoring in the
condensate systems.
CORROSION IN STEAM CONDENSATE SYSTEMS
Corrosion of metals is the consequence of exposure to environments in which the metals are
thermodynamically unstable. Certain metals, such as stainless steels, aluminum, and titanium, form a passive
oxide film which effectively separates the underlying bare metal from the environment, thereby preventing a
continuous corrosion reaction. Plain carbon steels at high temperatures tend to be protected in this manner.
Copper and copper-base metals do not form passive films in the classic sense, but depend upon their intrinsic
nobility for corrosion resistance in most aqueous industrial systems. Under certain conditions, a porous oxide
layer formed on copper metal surfaces in the presence of oxygen acts as a diffusion barrier to provide some
corrosion protection. Copper is noble to the hydrogen ion and therefore does not displace it from aqueous
solutions in the absence of oxidizing species.
One of the major problems in boiler condensate systems is corrosion of carbon steel pipes. Two
corrodents, carbon dioxide and oxygen, either acting alone or in combination, account for the majority of steel
corrosion problems in the condensate systems. Failures of heat exchangers made of copper and copper alloys
are primarily caused by ammonia, especially when oxygen is also present.
Corrosion of Carbon Steels
In pure water in the absence of oxygen, iron corrodes according to the following reactions:
Anodic Reaction: Fe = Fe’* + 2e- (1)
Cathodic Reaction: 2Hz0 + 2e‘ = 20H- + H2 (2)
Net Reaction: Fe + 2H20 = Fe(OH)* + HZ (3)
Hydrogen gas is generated as iron is corroded. Iron hydroxide can further be converted to magnetite, Fej04, by
the Schikorr’s reaction:2
3Fe(OH)* = Fe304 + 2H20 + Hz (4)
The stability of ferrous hydroxide and the rate of the Schikorr’s reaction are temperature dependent.= Leussing
and Kolthoff’ repotted that ferrous hydroxide remains stable at room temperature for periods up to several
weeks. However, at higher temperatures, the rate of Schikorr’s reaction is greatly enhanced, resulting in a
passive magnetite film to protect the underlying metaLal Water chemistry parameters, such as pH and
dissolved oxygen concentration, play an important role in the overall corrosion process affecting the stability of
iron and iron oxides. Maintaining pH within a certain range and removing oxygen from the system are required
for the formation of a stable passive film. It has been well established in the,$ky industry that in the absence of
oxygen a pH in the range of 9.3 to 9.4 is adequate to protect iron and steels. However, corrosion will be
increased when the condensate is contaminated with gases, such as carbon dioxide and oxygen.
Effect of Carbon Dioxide. The effect of carbon dioxide on steel corrosion is through its influence on
solution pH and its effect on the cathodic reaction of the overall corrosion process.
1. Source of Carbon Dioxide--Most steam generating systems require continual addition of make-up water to
replace losses through boiler blowdown, process consumption, unreturned contaminated condensate and leaks.
The make-up water usually contains bicarbonates and carbonates. These species can accumulate and
decompose in boilers at high temperatures to form carbon dioxide:
PHCOJ‘ + Heat = H20 + CO;* + CO2 (5)
7lSl2
CO3.* + Hz0 + Heat = CO2 + 20K (6)
2. Carbonic Acid Corrosion-The carbon dioxide produced in the boilers can be carried and distributed by the
steam to the steam/condensate system. When the steam condenses, part of the carbon dioxide gas dissolves
in the condensate and forms carbonic acid:
CO2 + H20 = H2C03 (7)
Carbonic acid is a weak acid which dissociates in water by hydrolysis in two steps:
H2C03 = H+ + HCO3 (8)
HCOj = H+ + CO;* (9)
Condensate starts as pure water without any buffering capacity. The small amount of H’ produced by
dissociation of H&03 is sufficient to significantly decrease the pH. For example, at 140°F (60°C) only 1 ppm
of dissolved carbon dioxide can depress the condensate pH from approximately 6.5 to 5.5. The solubility of
carbon dioxide decreases with increasing temperature at a given CO2 partial pressure. Figure 2 shows the pH
values of solutions of carbon dioxide in pure water at various concentrations. Pure water saturated with carbon
dioxide contains approximately 1,450 ppm CO2 at 77OF (25°C) with a pH of approximately 3.8.19 Although air
contains only 0.03-0.049/o carbon dioxide, pure water saturated with air can dissolve enough carbon dioxide to
lower the pH to approximately 5.6. If bicarbonate alkalinity is also present, then the pH is dependent on the ratio
of methyl orange alkalinity of the water to the free carbon dioxide content, as shown in Figure 3.M From this
figure, the free carbon dioxide concentration can be calculated if the pH and the bicarbonate alkalinity are
known.
Carbon dioxide can produce a reduction in pH, causing the corrosion rates of metals to increase.
Consequently, the concentrations of soluble species, such as iron and copper, and dissolved solids in the
condensate will increase. It was reported*’ that the corrosion rates of steels increased with increasing CO2 partial
pressure at various temperatures. Based on Henry’s law, this was a result of the increased solubility as the
partial pressure of the gas increased.
3. Mechanism of Carbonic Acid Corrosion-In acidic solutions in the absence of oxygen, the dominant cathodic
reaction for corrosion of metals is reduction of hydrogen ions to evolve hydrogen gas:
2H* + 2e‘ = HZ (10)
This would cause the solution pH to increase. In systems containing CO*, the cathodic reaction is complicated.
De Waard and Milliams** suggested the following mechanism for the cathodic reaction for pH’s in the range of
3.0 to 4.4:
2H2C03 + 2em = 2HCO; + 2Had. (Rate-Limiting Step) (11)
PHCO< + 2H+ = 2H2C03 (12)
2Htis = HZ (13)
Instead of the reduction of protons to hydrogen gas on the metal surface, reaction (11) was suggested as the
rate-limiting step at the corrosion potential for steel corrosion in the absence of oxygen. Undissociated carbonic
acid molecules are first adsorbed on the metal surface where they are cathodically reduced to form bicarbonate
ions and adsorbed hydrogen atoms (Ha&. The subsequent recombination of the bicarbonate ion with H’
diffusing from the bulk of the solution to the metal surface is a fast reaction and will not be the rate-limiting step.
The combination of adsorbed hydrogen atoms to produce Hz, reaction (13) is also much faster than reaction
(11). It can be seen that the net reaction of equations (1 l), (12) and (13) is the reduction of hydrogen ions,
reaction (10).
Nesic et al.23 investigated the corrosion of steel in deaerated solutions with and without CO2 using rotating
cyiindrical steel electrodes in the pH range of 3 to 6 at various temperatures. They confirmed the existence of an
additional cathodic reaction: the direct reduction of H&03. They proposed a cathodic reaction mechanism
716/3
similar to that suggested by De Waard and Milliams. However, they found that the cathodic reaction is a function
of pH and rotation speed. At pH 4 in systems containing C02, both H’ and H2COJ reductions were of similar
magnitude at low rotation speeds while hydrogen reduction dominates at higher rotation speeds. At pH 5,
reduction of H2C03 was the dominant cathodic reaction. The pH had no significant effect on the anodic
dissolution of iron in CO*-containing solutions at pH’s between 4 and 8.
Whitman et al. reported24 that dissolved carbon dioxide increased corrosion of steels as the pH was
decreased, and that at a given pH carbon dioxide was more corrosive than a completely dissociated acid25 (e.g.,
hydrochloric acid). At a given pH, experiments were performed in two solutions for comparisons. One solution
was purged with CO2 and pH adjusted by NaHCOs and the other one was purged with N2 and pH adjusted by
HCI. The cathodic current density on steel in the former was greater than that in the latter. This was also
explained as a Wiult of the addition of a cathodic reaction represented by equation (11) the reduction of H2C03,
to the hydrogen reduction reaction in the cathodic region at pH’s between 4 and 6.
For the corrosion of iron, Bockris et al? proposed a pH-dependent mechanism for the anodic reaction:
Fe + OK = FeOH + em (14)
FeOH = FeOH’ + e- (15)
FeOH’ = Fe** + OH- m
The above mechanism was accepted by De Waard and Milliams*’ for steels in waters containing C02.
Combining equations (1 l), (14) (15) and (16) the net reaction for corrosion of iron in carbonic acid solutions can
be represented as:
Fe + 2H2C03 = Fe’* + 2HCO; + HZ (17)
4. Characteristics of Carbonic Acid Corrosion--Carbon dioxide is highly volatile and its solubility is greater at
lower temperatures. Therefore, it tends to cause corrosion of system components, such as heat exchangers, in
the far ends or areas of lower temperatures in a system, leaving equipment in the initial hot condensate areas
relatively unattacked. Also, more corrosion problems are usually observed for systems that operate
intermittently or undergo hot-cold cycles.
The appearance of carbonic acid corrosion at the attack site is typically smooth, featureless metal surface
contours, often incorporating islands of intact metal that form plateaus within the surroundi;rl wastage (Figure 4).
It can result in trough-like thinning on the bottom of horizontal condensate pipes (Figure 5) and, sometimes,
channeling and pin hole leaks at pipe threads. The corrosion products, which are soluble in the immediate
vicinity of the corrosion site, may become insoluble downstream of the attack site, where temperature, pH, and
carbon dioxide content are altered. As a result, the corrosion products, consisting of hydroxides, carbonates and
oxides, may precipitate out of the solution at these locations.
Effect of Oxvqen. At room temperature, the corrosion rate of iron in deaerated water is very low, typically,
less than 0.2 mils per year (5.1~10~ millimeters per yeaa. However, under air-saturated conditions, the
corrosion rate of iron in water can be 100 times greater. Two forms of corrosion, namely, general corrosion and
pitting corrosion, can occur on steel surfaces in condensate systems containing oxygen. Pitting of condensate
steel pipes tends to occur at higher pH levels (near neutral or greater). At lower pH values, under the combined
effects of carbonic acid and oxygen, the form of corrosion will usually appear as severe general corrosion
showing rough surfaces, possibly with some pits present.
1. Source of Oxygen-The primary source of oxygen in the condensate system is air in-leakage at various
locations. This includes threaded and other mechanical joints, packing glands of condensate retum pumps,
faulty steam traps, and areas under vacuum or areas where the system pressure is lower than the atmospheric
pressure. Another source of oxygen is dissolved oxygen in the feedwater due to an inadequate oxygen
scavenging process. Corrosion of steels in waters containing sufficient quantities of dissolved oxygen is
thermodynamically and kinetically favored.
2. General Corrosion--In aqueous solutions containing oxygen, the cathodic reaction is a function of pH:
718l4
O2 + 4H* + 4ee = 2H20 (Acidic Solutions) (1 W
O2 + 2H20 + 4ee = 40H. (Neutral and Alkaline Solutions) (1 W
The reduction reaction proceeds as rapidly as oxygen reaches the surface of the metal resulting in an increase in
pH. Combining equation (1) and (18) making use of the reaction Hz0 = H’ + OK yields
2Fe + 2H20 + 02 = 2Fe(OH)* (19)
General corrosion in the presence of water containing sufficient levels of dissolved oxygen, and in the absence of
a sufficiently protective layer covering the metal surface, occurs according to the above reaction (19). The
ferrous hydroxide formed tends to be unstable in most condensate systems and reacts with oxygen to form ferric
hydroxide:
4Fe(OH)* + 2H20 + 02 = 4Fe(OH)3 (20)
The solubility of Fe(OH)3 in water is very low, resulting in precipitation of a nonprotective oxide layer of Fe20B:
2Fe(OH)3 = Fe203 + 3H20 (21)
Uhlig et aI.% studied the effect of oxygen on corrosion of mild steels in slowly moving distilled water at 77°F
(25%). They reported that below the air-saturated level, the corrosion rate increased with increasing oxygen
concentration.
General corrosion produces almost uniform metal loss over the exposed metal surface (Figure 6 ). The
color of hydrous ferric oxide is orange to red brown. A black hydrous ferrous ferrite FejOinH20 intermediate
layer may be observed between hydrous Fe0 and hydrous Fe203. This threefold corrosion product layer is
usually called rust with hydrous ferric oxide layer being the majority of the rust.
3. Pitting Corrosion--Pitting is an intensive and localized form of corrosion. Failure of system components or
equipment due to pitting corrosion often occurs with suddenness. The protective form of iron oxide is magnetite,
Fea04. Breaches in the magnetite layer furnish pit initiation sites at which condensate carrying dissolved oxygen
can establish an anodic metal dissolution reaction. The magnetite layer surrounding the breach site produces a
large, protected, cathodic area, which localizes and intensifies the anodic dissolution reaction at the breaches
due to a large cathode to anode area ratio. The result is the formation of pits (Figure 7) and associated high
corrosion rates. The anodic site can be covered with a dome-shaped mound of corrosion products referred to as
a tubercle, Figure 8. Tubercles are highly structured and eventually establish fairly complex, autocatalytic
corrosion reactions.3’.32 Their growth rate is difficult to predict.
Svnemistic Effect between Carbon Dioxide and Oxvaen. Skaperdas and Uhlig= reported that both
dissolved carbon dioxide and oxygen in steam condensate can cause failures of returned condensate pipes and
that for steels at 140°F (00%) oxygen is relatively six to ten times more corrosive than equal molar concentration
of carbon dioxide. However, the simultaneous presence of oxygen and carbon dioxide in condensate can
produce a synergistic interaction, resulting in corrosion rates that are 10 to 40 percent greater than the sum of the
corrosion rates of the two gases acting separately.” The synergistic effect is greater at lower values of 02/C02
concentration ratio.%
Figures 9 and 10 show the typical appearance of attack by carbon dioxide and oxygen. In Figure 9,
smooth attack on carbon steel revealed corrosion by carbonic acid. The entire metal surface was covered by red
hematite, indicating high oxygen concentrations in the condensate. Figure 10 shows jagged fir-tree pattern of
corrosion inside a tilted steel pipe caused by condensing steam containing high concentrations of carbon dioxide
and oxygen.
Corrosion of Copper and Copper Alloys
Effect of Carbon Dioxide and Oxvqen. Since copper is noble to the hydrogen ion, its wrrosion pathway
differs from that of carbon steels, which is less noble than the hydrogen ion. The primary cathodic reaction
involved in the corrosion of copper is oxygen reduction. In pure water containing oxygen, a porous layer
consisting of cuprous oxide and cupric hydroxide provides some corrosion protection by acting as a barrier to
715/5
oxygen diffusion.” Corrosion of copper will generally increase with increasing fluid velocity due to enhanced
mass transfer of oxygen to the metal surface.38 It was also reporh# that in a flowing solution at pH 5 and 77°F
(25%) the corrosion rate of a QO/lO copper-nickel alloy first increased with increasing oxygen concentration.
However, beyond a critical oxygen concentration the corrosion rate decreased due to the formation of a more
protective film which reduces the availablity of oxygen to the reacting interface. It is commonly accepted that
under normal operating conditions, corrosion of copper in hot pure water is negligible. Nevertheless, long-term
corrosion of copper heat exchangers can cause pluggage and loss of heat transfer efficiency due to
accumulation of copper oxides in the industrial water system.qO
For copper in solutions containing oxygen, the morphology, porosity and the protectiveness of the oxide
layer formed on the metal surface as a result of corrosion is a function of oxygen concentration, fluid velocity and
pH. The effect of dissolved carbon dioxide is to promote capper corrosion by lowering the pH to solubilize the
copper oxides. Corrosion of copper and its alloys by dissolved carbon dioxide and oxygen typically produces
smooth-walled metal loss. Accumulations of corrosive condensate at baffles, tube supports and tube sheets,
often produce the type of grooving illustrated in Figure 11.
Effect of Ammonia and Oxvaen. The primary source of ammonia in the condensate system is the thermal
decomposition of nitrogen-containing organic contaminants and the partial breakdown of chemicals, such as
hydrazine, for boiler water treatment. In some industries, ammonia is used as a neutralizer to raise the
condensate pH for corrosion control of steel components. Wilde4’ reported that at high temperatures the
corrosion rates of steels decreased with increasing NH3 content in the range of 1 to 100 ppm NH3. This was
attributed to the significant reduction in the limiting diffusion rate of H’ because of a simple pH effect.
While ammonia is not corrosive to steels, it degrades the corrosion resistance of copper and copper alloys.
Chen and Chen” investigated the effect of ammonia concentration on the corrosion of a copper electrode in
deaerated solutions at 178°F (80%) and pH 9 with a rotating cylinder system. They repotted that the anodic
dissolution of copper increased while the corrosion potential decreased with increasing ammonia concentration.
They concluded that under field conditions in the presence of oxygen the corrosion rate of copper and copper
alloys will be accelerated by ammonia, and the detrimental effect will increase with increasing ammonia
concentration.
Dissolution of copper in aqueous solutions containing ammonia and oxygen was wnsideredq a process
involving the formation ot,“n oxide which then reacted with ammonia to produce highly soluble cupric complex
ions of the type Cu(NH& . The value of n in the cupric ammonia complex varies between 1 and 5 and is a
function of the ammonia concentration.” The net reaction for the case of n=4 can be represented as:
2Cu + 8NH3 + O2 + 2H20 = 2Cu(NH&,+* + 40K (22)
It has been well-established that the cu&.$c ammonia complex ions can read with copper on the metal surface to
form cuprous ammonia complex ions:
Cu(NH&+* + CU(S”fface)= 2Cu(NH&+ (23)
The cuprous ammonia complex ions are not stable in the presence of oxygen and will be oxidized and reverted
to cupric ammonia complex ions?*
4Cu(NH3)*+ + 8NH3 + O2 + 2H20 = ~CU(NH&+~ + 40K (24)
Reaction (24) proceeds very rapidly throughout the solution since cuprous ammonia complexes are strong
reducing agents.% The cupric ammonia complex ions produced are then reduced on the copper metal surface
as shown in reaction (23). The net cathodic reaction is reduction of oxygen but it is accomplished through a rapid
intermediate reaction (24). It has also been reported that the rate of reduction of CU(NH~)~ * is much faster than
that of the direct reduction of oxygen on the metal surface.”
The overall process is autocatalytic since it not only regenerates but also multiplies cupric ammonia
complex ions. For this reason, the combination of ammonia and oxygen is extremely aggressive to copper-base
metals. This can cause severe corrosion in condensers, feedwater preheaters and other components made of
copper and copper alloys. The increase in corrosion rate of copper was further explained by Bertgcci based on
an enhanced mass transport mechanism involving the above copper-ammonia Wmptex Species.
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Impact of Condensate Corrosion
Condensate corrosion causes damages of the system components and can affect the performance of
boiler operation. The consequence of corrosion in the condensate system includes:
1. Higher Maintenance Cost--Failed components due to wrrosion must be replaced by maintenance personnel.
The overall operation cost increases due to increased demand on labor and capital spending. Severe failures
may cause production losses which can be very costly.
2. Poor Quality Condensate--Condensate can be contaminated by corrosion products produced in the

condensate system. The corrosion products tend to deposit in boilers, causing operation problems. In many
cases contaminated condensate must be dumped to the sewer due to its poor quality. This would increase the
boiler operation cost by increasing the demand of the make-up water and its treatment. The fuel cost will also
increase due to losses of the heat value of the dumped condensate.
3. Reduced Efficiency and Reliability of Boiler Operation--Corrosion products generated in the condensate
system have a great tendency to deposit in boilers, especially in high heat transfer areas. This will reduce the
heat transfer efficiency and reliability of boiler operation.
4. Unexpected Boiler Shutdowns--Deposition of wrrosion products on boiler tube surfaces requires acid
cleaning. Deposition can also cause localized overheating and boiler tube failures. This will result in unexpected
system shutdowns and costly production losses.
The corrosion problems caused by carbon dioxide and oxygen can be reduced by mechanical means, for
instance, fixing air in-leakages, establishing steam trap maintenance programs and providing adequate venting.
A wmmon solution to minimizing corrosion in the condensate system is to apply chemical treatments, such as
neutralizing amines and filming amines, to protect against corrosion problems caused by carbon dioxide and/or
oxygen. The effectiveness and types of amines used depend on the characteristics of the entire steam/
condensate system and can vary from one plant to another. In some cases, regulatory issues may limit the use
of certain chemicals in the steam that may be in contact with the product. For these cases, precautions must be
taken in selecting and applying the chemical treatment pmgrams.
CONDENSATE CORROSION PROTECTION TECHNOLOGIES
As stated earlier, the two primary causes of condensate corrosion that affect ferrous metals are carbon
dioxide and oxygen in-leakage. Mechanical methods for dealing with these problems are available.
To reduce carbon dioxide in the steam, the alkalinity of the feedwater should be reduced. This can be
accomplished by a well-controlled lime softening program, dealkalization, demineralization, or degasification
processes. Lime softening involves the removal of calcium and magnesium with a precipitation process. These
hardness components are removed as CaC03 and Mg(OH)2. Dealkalization involves passing the condensate or
feedwater through an anion exchanger to remove alkaline anions, such as carbonates, bicarbonate and sulfate.
Demineralization involves passing water through cation and anion exchanger resins. In the cation process,
hydrogen is substituted to all the cations. The anion exchanger operates on the hydroxide cycle replacing anions
with hydroxide. The final effluent from this process consists of hydrogen/hydroxide ions or essentially pure
water. Degasification is a process that can be used to remove troublesome gas such as oxygen, carbon dioxide,
or ammonia via a venting, deaeration, scrubbing or mechanical mechanism.
Alkalinity can certainly be reduced; however, a certain amount is required to maintain proper boiler water
alkalinity. Therefore, carbon dioxide will always be present in the steam. Available chemical treatment solutions
for the condensate, such as neutralizing amines, should be used in conjunction with proper mechanical solutions.
When oxygen is present in the condensate system, it is typically due to air in-leakage. The source of oxygen
should be located and corrected. Likewise, chemical solutions to the problem, such as filming amines, can be
used.
Neutralizing Amines
Neutralizing amines are nitrogen-containing compounds that are added to the steam system to neutralize
carbonic acid and raise the condensate pH. Neutralizing amine programs are generally effective when fed to
maintain a pH of 859.0. This range will maximize corrosion protection since carbon dioxide does not exist
above pH 8.3. This pH range also offers maximum protection of copper and copper alloys. In systems
containing no copper or copper alloys, a somewhat higher pH value will improve mild steel corrosion control.
Common neutralizing amines include morpholine, cyctohexylamine (CHA), monoethanolamine (MEA),
diethylaminoethanol (DEAE), methoxypropylamine (MOPA), dimethylisopropanolamine (DMIPA), and
aminomethylpropanol (AMP).
Neutralizing amines are dosed in direct proportion to the amount of carbon dioxide in the steam. Carbon
dioxide content of the steam can be measured or calculated based upon feedwater and boiler alkalinity. Typical
neutralizing programs are monitored based on measurements of condensate pH. In high alkalinity feedwater
systems, the generation of carbon dioxide is appreciable and this will require feeding excessive amounts of
neutralizing amines to neutralize the carbonic acid. Another treatment option under these conditions is to
consider filming amines.
Neutralizing amines are characterized% by a specific volatility, acid neutralization ability, basicity and
thermal stability. These parameters must be considered when selecting a condensate corrosion inhibition
program.
Volatility. All gases in the condensate system have a specific volatilityn,5B or vapor to liquid distribution
ratio (V/L). The V/L distribution ratio is defined as follows:
[Concentration in the Vapor or Steam Phase]

V/L = (25)
[Concentration in the Liquid or Condensate Phase]
The V/L ratio is an indication of how much of the amine will be present in the steam phase compared to what is
present in the liquid or condensate phase. In other words, the V/L ratio indicates whether the species would
condense with the condensate or stay with the steam. To neutralize carbon dioxide, the amine must be in the
condensate as the carbon dioxide dissolves. The V/L ratio governs the distribution of carbon dioxide or
neutralizing amine present at different locations. For example, an amine having a V/L ratio of 4.0 indicates that
4.0 ppm of amine must be present in the steam to get 1 .O ppm in the condensate. The higher the V/L ratio, the
higher the amine concentration in the steam.
The V/L ratio is dependent on temperature, pressure, pH and other operating conditions. Table 1
summarizes the V/L ratio of two wmmon neutralizing amines and carbon dioxide. The significance of V/L ratios
becomes important when a phase separation occurs. For example, in a flash tank, condensate enters the vessel
while both condensate and steam exit the vessel. The low volatility amines, such as morpholine, will tend to be
present in greater concentration in the condensate exiting the flash tank and neutralize the carbonic acid at that
point. The higher volatility amines, such as cyclohexylamine, will tend to be present at higher concentrations in
the steam exiting the flash tank to be carried through the system. When final condensation occurs the higher
volatility amines will then condense to offer protection. V/L ratios are not significant when total condensation
occurs. Total condensation takes place when all the carbon dioxide and amines in the steam entering a unit are
dissolved into the condensate with no phase separation.
Acid Neutralizina Ability. Another characteristic of amines that is important in the selection of an amine for
treatment is the acid neutralizing ability. This is the amount of amine required, based upon weight, to neutralize
the carbonic acid in the water. The amine reacts with the carbonic acid in solution to form an amine bicarbonate
according to the following reaction:
RNH2 + H’ + HCO$ = RNHj + HCO3 (26)
This acid neutralizing ability is dependent upon the molecular weight of the amine. Lower molecular weight
amines will neutralize more carbonic acid than higher molecular weight amines on a pound-for-pound basis.
Basicity. When all the acid in the condensate system has been neutralized, amine basicity becomes
important. At thisgoint the condensate system is typically at a pH of 8.3. Basrcrty refers to the measure of
amine hydrolysis. Any additional amine added to the condensate system at this point will hydrolyze and raise
the condensate pH:
RNH2 + Hz0 = RNH; + OH
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Basicities of neutralizing amines also vary. Cyclohexylamine is a stronger base than morpholine. Over a certain
pH level, additional quantities of the weaker neutralizing amines, such as morpholine, will have little effect on
further increasing the pH. Figure 12 shows the combined effect of acid neutralizing ability and basicity for three
commonly used amines.BO
Thermal Stability. Different amines show widely different thermal stability and amounts of breakdown to
ammonia under high temperature/high pressure conditions. Jacklit’?’ tested amines at various pressures up to
1500 psi (10.3 MPa) at saturated temperatures in an experimental boiler. The amount of each amine in the
feedwater was 34 ppm. He reported that cyclohexylamine, 2-diethylaminoethanoI and morpholine showed
relatively low thermal breakdown rates among the 15 materials tested. 2-diethylaminoethanol revealed good
stability at 1500 psi (10.3 MPa) and steam temperatures up to 800°F (427OC). Above 800°F (427°C) the amount
of breakdown increased rapidly. However, morpholine is relatively stable at boiler pressures up to 2500 psi
(17.2 MPa) and steam temperatures up to 1200°F (849°C). The amount of breakdown of morpholine increased
very slowly and uniformly up to 1200°F (849OC). Argawala= reported low decomposition of morpholine. At
583OF/1350 psi (308W9.27 Mpa) and 801°F/1530 psi (318WlO.5 MPa), morpholine decomposed only by 24%
and 3-5%, respectively. Gilbert et al.63 reported that the kinetics of the thermal decomposition of morpholine was
first order at temperatures ranging from 500°F to 572°F (28O’C to 3OOOC). The major breakdown products were
identified as ammonia, ethanolamine, 2-(2-aminoethoxy)ethanol, methylamine, ethylamine, ethylene glywl, and
acetic and glywlic acids. Table 2 summarizes the amount of amine decomposed obtained in a decomposition
study on several amines by Shenberge$4 at 1000 psi (8.88 MPa) without and with oxygen. Except for
morpholine and DAE (1, Pdiaminoethane), oxygen was found to enhance the thermal decomposition. The
amount of ammonia generated for each amine is listed in Table 3.= Other major decomposition products for
each amine are summarized in Table 4.66
Filming Amines
Neutralizing amines are used to neutralize carbonic acid. They have no significant effect on oxygen
corrosion. Filming amines are recommended for protecting condensate piping from both oxygen and carbonic
acid corrosion. Filming amines do not neutralize carbon dioxide. Performance is accomplished by laying down a
very thin nonwettable film on the surface (Figure 13).67 The film acts as a barrier between the metal surface and
the corrosive condensate.
In order for fllmers to work, the condensate pH must be high enough for the film to form.
OctadecylamineW is a commonly used filmer. It requires that the condensate pH be controlled within a range of
8.5 to 8.0. If the pH is outside this range, the film strips off and can cause deposits in the steam traps and
condensate lines. Octadecylamine is not volatile and therefore must be fed to the steam header. The amount of
surface area to be covered is the prime consideration in determining dosage. Typical filming amine programs
are monitored based upon product residual in the condensate. In addition to octadecylamine, several proprietary
filming amines are available. These may include tallow or soya based amines. These filmers are stable over a
wider pH range of 8.5 to 9.5.
In almost all cases, the filmer treatment is supplemented with a neutralizing amine. The filmer alone is
incapable of neutralizing or buffering the condensate pH into the required pH range where filming can effectively
take place. Therefore, most filmers are offered as a combination treatment of filming/neutralizing amines to
alleviate corrosion problems. Due to the nature of the program, filmer/neutralizer programs can provide
protection at a pH lower than a straight neutralizer program. This may allow a plant to use less neutralizer and
thereby reduce treatment costs. The ultimate basis for this decision is the individual plant’s treatment
performance and operating history.
There may be some difficulties in the use of filming amines. Filming amines can cause formation of a
sticky deposit or “gunk balls” when overfed or if the pH is not properly maintained in a certain range. These
deposits can cause pluggage in steam traps, pump strainers, control valves and low flow areas of the system. In
addition, care must be taken when starting up a filming program in a previously untreated system due to
corrosion product clean-up and the possibility of overfeed. It is not unwmmon to see a large amount of
corrosion products present in the condensate as the filmer cleans the ditty lines. It is recommended to start at a
low dosage and gradually increase feed.
718l9
Oxygen Scavengers
An alternative treatment to filming amines for condensate oxygen corrosion protection is an oxygen
scavenger chemistry. Some typical oxygen scavenger chemistries include carbohydrazide, diethylhydmxylamine
and hydroquinone. The oxygen problem is addressed directly by using an oxygen scavenger to treat the steam/
condensate system. In other words, the scavengers react directly with and reduce the oxygen that is present in
the system. One problem of the oxygen scavenger chemistry is its distribution in the condensate system. Some
oxygen scavengers are volatile with each being characterized by its specific volatility. The scavenger tends to
distribute unevenly depending on how the temperature changes across the entire condensate system. Uneven
distribution of scavengers provides corrosion protection in one area while leaving other areas in the condensate
system unprotected. In addition, oxygen corrosion can occur in the condensate phase, but it can also occur in
the vapor phase as long as moisture and/or condensation is present above the waterline. Distribution ratio of an
oxygen scavenger between the vapor phase and the water phase is another concern. Low volatility and
nonvolatile oxygen scavengers tend to provide protection only in the water phase.
Oxygen scavengers do not provide protection against carbon dioxide. Carbonic acid when present will
attack the passive magnetite film on steel surfaces. At a pH above 8.3, carbonic acid is not present and
passivation is improved. For that reason, when using an oxygen scavenger chemistry, the condensate pH must
be maintained above 8.3 for stable passivation. A combination of neutralizing amines and an oxygen scavenger
chemistry can be used to maintain the wrrect condensate pH for optimum protection and product performance.
If feedwater alkalinities are high, a neutralizer/filmer program may be more economical. The trade-off between
ease of control (favoring neutralizer/oxygen scavenger) and economics (favoring neutralizer/filmer) is system
dependent.
Application
A question frequently raised on the application of condensate wrrosion inhibitors is whether a neutralizing
amine product should be fed to the feedwater or directly to the steam header. Using a computer model on a
simple steam system where all the steam is condensed and a portion is returned to the deaerator, a general rule
of thumb was obtained.69 If the V/L ratio of the amine is greater than 1 .O. the preferred feed point is the
feedwater due to its ease of application. If the V/L ratio of the amine is less than 1 .O, the preferred feed point is
the steam header due to its low volatility. Feeding a neutralizing product to the steam header helps ensure that
all the amine is going into the steam to minimize product loss through blowdown. If steam header feed is not
possible, then the product can be fed to the boiler feedwater or the boiler steam drum. This will result in product
loss through the deaerator vent or through the boiler blowdown but the amount lost is minimal in industrial
boilers.
All amines suffer some loss in the boiler blowdown. The amount of a specific amine lost will vary
according to the V/L ratio as well as the boiler pressure, boiler cycles of concentration, and azeotrope formation.
Figure 14 summarizes losses of various amines in the boiler blowdown at 10 cycles of wncentration.70 Higher
cycles of concentration significantly reduce the loss.” Many condensate treatment programs use a blend of
amines. When fed to the boiler feedwater, a greater percentage of the low volatility amines will be lost via
blowdown. Higher V/L ratio amines that reach the condensate system will only protect the final condensation
areas of the system. Corrosion could occur in the initial condensation areas. From this, the total amine loss is
not as important as the disproportionate loss of the individual amines in the product.
Filming amines must be injected into the steam header. Typical filming amines are not totally volatile and
in fact in most cases are considered non-volatile. Injection into the steam header also assures distribution
throughout the entire system. Feed to the boiler or boiler feedwater will result in loss of the filmer in the boiler
blowdown.
Under all treatment programs, the inhibitors must be fed continuously to prevent wrrosion of the
condensate system. For optimum application and distribution throughout the condensate system, all condensate
corrosion inhibitors should be fed neat (undiluted) to the system. Neat feed of chemical allows for accurate
measurement of the exact amount of chemical being fed. Dilution water can introduce impurities to the steam
system which can result in other system problems. These may include turbine deposition, steam hammer,
erosion and line failure. Depending upon the source of dilution water, if the dilution water temperature is greater
than 90°F (32%) the high V/L ratio amines will flash from the dilution tank, causing release of amine vapors and
disproportionate amine feed.
Satellite feed is always a viable alternative when dealing with any of these programs, especially in light of
the fact that condensate systems typically are extensive. Satellite feed consists of injecting the chemical just
before areas of condensation, for instance, prior to a heat exchanger. Due to multiple condensation points along
the pipe, amine could be lost to the condensate at the exchanger. The steam continuing to the outlying areas of
the condensate network may not have enough amine to protect the remaining system components. Satellite
feed of product will help protect the entire system.
Care must always be taken in controlling condensate treatment programs. The appropriate pH range must
be individually specified by professionals with regard to system metallurgy and corrosion control requirements.
The specified pH will typically be within the range of 8.5-9.0 for neutralizing amines and 8.5-9.0 for filming
amines. If excess neutralizing amine is fed, the condensate pH will be high. When the pH reaches above 9.2,
corrosion of copper and copper alloys becomes appreciable. The problem can be worsened if high pH and
oxygen are both present. If a filming amine is overfed, “gunk balls” of excess materials could cause plugging of
traps and lines.
In a number of applications, such as food industry, hospitals, Co-Gen, or pharmaceutical, the use of
amines is limited due to federal regulations. One of the wncems is the toxicitr20f most amine treatments.
Table 5 lists the symptoms due to exposures to various amines and ammonia. Many neutralizing amines are
irritating to eyes, skin, and muwus membranes. Some can cause severe bums. Morpholine may cause kidney
and liver damage in animals. Because of this concern. in many applications no chemical treatment program is
used. There is a tremendous need to develop new corrosion inhibition programs for these specific areas.
Octadecylamine and octadecylamine acetate are filming amines that can be used in FDA and USDA
applications. For plants that require FDA or USDA approval, Table 8 summarizes the acceptable amines
permitted and their limits. They can be used in combination or simultaneously provided that each does not
exceed its individual tolerance and the total does not exceed 25 ppm (per 1982 FDA interpretation of Federal
Regulation 21CFRl73.31O(d)).
CONDENSATE CORROSION CASE HISTORIES
Case History No. 1 - Industry: Refinery
Specimen - Reboiler
Specimen Orientation - Horizontal
Environment -
Internal: Steam/Condensate, Pressure: 10 psi (0.089 MPa), pH: 8.5-8.5,
Oxygen: 2.5 ppb
External: Volatile organic materials
Sample Specification - Carbon steel, heat exchanger
A midwest refinery plant experienced corrosion problems in several reboilers. A 10 psi (0.089 MPa) steam
line was introduced to the reboilers for process heating through a carbon steel heat exchanger inside each
reboiler. The steam condensate then passed through a vent and returned to a condensate receiver. Through-
the-wall corrosion has occurred in the heat exchangers, causing leakage of process chemicals into the steam/
condensate system.
A corrosion monitoring system, including a corrosion monitorJ3 a stainless steel corrosion cell enclosing a
carbon steel corrosion probe, a pH meter and an oxygen probe, was set up as a diagnostic tool. The entire
system was enclosed in an explosion-proof aluminum box which was continuously purged with air. A stainless
tube was connected to a condensate sampling point, which was located downstream from the vent, to supply the
test water to the corrosion cell at a flow rate of approximately 100 ml/minute.
Figure 15 and 18 show the variation of pH/oxygen concentration and corrosion rate with time curves,
respectively. The effect of venting on corrosion rate was investigated, Closing the vent caused an increase in
CC2 concentration and a decrease in pH from approximately 9.2 to a value fluctuating between p.5 and 8.5
(average pH = 7.2) (Figure 15). The average corrosion rate increased from 0.78 mpy (1.98x10- mm/year) to
3.92 mpy (0.1 mm/year) due to the reduction in pH (Figure 18). Opening the vent provides a means to decrease
7Wll
CO2 content and reduces corrosion for the areas after the vent. However, because the vent was located
downstream from the reboiler, opening the vent will not reduce the wrrosion in the heat exchanger inside the
&oiler. Since the oxygen concentration was very low (2.5 ppb in average), the plant decided to satellite feed a
neutralizing amine product to protect the heat exchanger.
Case History No. 2 - Industry: Steam Heat-Building
Specimen - Condensate Return Line to Receiver Tank

Environment -
Internal: Steam/Condensate, Pressure:15 psi (0.103 MPa), pH: 7.5-8.5
External: Ambient
Time in Service - 20 years
Sample Specification - Carbon steel, 15/a in. (4 cm) outside diameter
The internal surface of this condensate return line was covered with iron oxide corrosion products,
Figure 17. Complete plugging of the line had occurred over a 2 ft (81 cm) section, Figure 18.
Close examinations on the internal surface in open areas revealed tubercles, Figure 19, some of which
capped corrosion sites which penetrated approximately one-third of the wall thickness. X-ray fluorescence and
x-ray diffraction analyses on these corrosion products showed that they were composed of 97% iron in the form
of iron oxide hydroxide (FeOOH), magnetite (Fe304), and hematite (Fe203).
Corrosion of this form is caused by exposure of the metal to water containing dissolved oxygen. It is
probable that most of the corrosion occurred during summer idle periods. Proper lay-up procedures were not
implemented during this time.
Pluggage of the line probably resulted from dislodgment of tubercles, which then accumulated in
downstream regions where the flow was retarded. Retarded flow can be caused by large, intact tubercles which
occlude the pipe bore, especially in small diameter lines.
Case History No. 3 - Chemical Process Industry
Specimen - Condensate Recovery End of Soda Ash Steam Dryer

Environment -
Internal: Product - Soda Ash
External: Steam/Condensate, Pressure:185 psi (1.3 MPa), Reported Condensate pH: 9.2,
Condensate contained Neutralizing Amines
Sample Specification - Carbon steel, 23/4 in. (7 cm) outside diameter
Figure 20 illustrates the metal loss on the dryer tube surface exposed to the condensate. Numerous, deep,
overtapping depressions, some of which perforate the tube wall, are present. Most of this surface is covered with
a thin layer of reddish corrosion products. Both carbonates and iron oxide were detected in the corrosion
products covering the surface.
The contours of the wasted surface, coupled with analysis of the corrosion products, revealed that the
metal had been exposed to corrosive levels of dissolved oxygen and dissolved carbon dioxide. As discussed
previously, oxygen and carbon dioxide in condensate can produce a synergistic interaction resulting in corrosion
rates that is greater than the sum of the corrosion rates of the two gases acting separately. Hence, even low to
moderate concentrations of these gases may produce substantial corrosion. Neutralizing amines alone wilt not
significantly reduce corrosion by dissolved oxygen. A filming amine would be more successful in mitigating this
type of corrosion problems.
7W12
Case History No. 4 - Industry: Plastics
Specimen - Surface Condenser Tube Near Air Ejectors

Environment -
Internal: Cooling Water
External: Steam/Condensate, Pressure: -13 psi (-0.091 MPa), Temperature: 104°F to
113°F (40°C to 45’C), pH: 8.5-9.5, Condudivity: 8.5 pmhoskm, Condensate treated with a
Neutralizing Amine.
Sample Specification - Admiralty Brass, 3/4 in. (1.9 cm) outside diameter
A series of seven failures in a two-month period generated considerable wncem as to the integrity and
reliability of this large surface condenser. Figures 21 and 22 illustrate the severe corrosion of external surfaces
of tubes located in the vicinity of the air ejectors.
Circumferential grooving adjacent to baffles or tube supports is apparent in Figure 21. Baffles and tube
supports ad as collection sites where condensate can form relatively stable pools. Figure 22 shows parallel,
transverse grooves apparently caused by gravity-oriented flow of corrosive condensate. Pale-blue carbonates
were deteded on tube surfaces, indicating that corrosion involved dissolved carbon dioxide.
Failure of the neutralizing amine to adequately proted the condenser could result from such circumstances
as insuffkient amine feed rates, use of an amine having an improper distribution ratio or volatility, or inadequate
amine feed points.
CONDENSATE CORROSION MONITORING
Corrosion monitoring tools are often employed to evaluate and ensure the performance of the condensate
treatment programs. In fad, a good chemical treatment program should be one that also provides good
monitoring instrumentation. This is essential to optimizing the dosage of the chemicals to obtain the best
performance. Corrosion monitoring techniques that can be used in the condensate systems include water
chemistry analyses, coupon weight loss measurements, electrochemical corrosion-measuring methods,
electrical resistance measurements, and other corrosion products monitoring techniques.
Water Chemistry Analyses
Conventional condensate corrosion monitoring involves wlleding condensate samples and performing
water chemistry analyses to determine the wrrosivity or quality of the water. These are all indirect corrosion
measurements and do not determine the corrosion rates (mpy or mm/year) of metals encountered in the
condensate system.
Samolinq Procedures. Sarn$tg technique is an essential part for water chemistry analyses. Operators
should consult existing guidelines for sampling requirements and procedures. In general, the precaubons
listed below should be followed.
1. Metallurgy of Sample Cooler-The sample coolers must be made of stainless steel with corrosion resistance at
least as good as 18% chromium, 8% nickel steel.” Use of plain carbon steel or copper coil for cooling samples
should be avoided. The diameter of the tube should be as Small as practical so that the time lag of the sample
through the sample cooler is minimal?’
2. Sample Temperature-Loss of volatile species can greatly change the chemistry, such as pH and conductivity,
of the collected condensate if the sample temperature is too hot. Samples should be cooled to lower than 90°F
(32°C) to avoid flashing and losses of amines, carbon dioxide and other gaseous species from the condensate
sample.
3. Sample Flow and Purging Time-Condensate should run continuously through the sample cooler to assure
that representative samples are obtained. Tests should be run as soon as possible after samples are collected.
When sampling streams under pressure, the sample line should be flushed at a sufficiently high flow rate to
71#13
remove all sediments and gas pockets prior to sample wlledion.79 The minimum purging times for various sizes
of sampling lines can be calculated as follov+@
Purging Time per Foot of Sample Line (Seconds) = (Inside Diameter of Sample Line in mm / 3)2
For example, for one-inch Schedule 40 sample lines, the minimum purging time is 80 seconds per foot of sample
line. These minimum purging times provide three to four times the sample line volume. If samples are collected
for detecting species at very low concentrations, increasing the conditioning time to significantly longer than the
above minimum recommended times may be necessary.
4. Sample Contamination by Air--Care must be taken to avoid exposures of samples to the air to prevent
contamination, especially during measurements of dissolved oxygen concentration, dissolved carbon dioxide
concentration and pH. Also, these measurements should be conducted on site.
5. The Number of Sampling Points--Most condensate treatment programs require maintaining the pH within
certain range to minimize corrosion. As discussed earlier, corrosion of metals in aqueous solutions can cause an
increase in pH due to the reduction of hydrogen ion or oxygen. Corrosion at one location may raise the pH in the
downstream areas. As a result, conformance in pH at one location does not always guarantee that the entire
system is protected. Severe corrosion may be taking place in an upstream area.
As mentioned previously, neutralizing amines with higher volatilities tend to remain in the gas phase at
higher temperatures. They will dissolve in the condensate and protect the metal when the system temperature is
low enough. On the other hand, amines with lower volatilities start to dissolve in the water in the early
condensate system where the temperature is higher. Consequently, combinations of amines with various
volatilities are usually used for corrosion protection in large condensate systems where the temperature changes
significantly across the system. For these reasons, an adequate number of sampling points must be installed for
performance monitoring to ensure corrosion protection of the entire system.
Testing. The following tests are commonly run on condensate samples to locate problem areas in the
condensate systems. The results can be used to improve or optimize the chemical treatment program.
1. Condensate pH--Most condensate treatment programs require pH to be maintained in a certain range.

Determining pH will indicate if the program is within the control range. In addition, measuring condensate pH’s at
various locations can ensure that the entire condensate system is properly treated for wrrosion pmtedion. Use
of low conductivity pH electrodes is recommended.
pH is an indication of hydrogen ion concentration or acidity in the water. It is commonly determined by

measuring the potential difference between a thin pH-sensitive glass membrane eledrode and a calomel
reference electrode. The pH measurement circuit is completed externally through the water sample. A critical
component in the pH measurement circuit is the reference junction in the reference electrode. The jundion is
usually made of a porous material and a solution of potassium chloride is allowed to bleed slowly through the
junction to maintain the electrical continuity. Some pH electrodes with a non-flowing type reference junction can
quickly lose its electrolyte in the junction in high purity waters. This will result in a high resistance path in the
measurement circuit, causing unstable, fluctuating and erroneous pH readings. Some commercial pH-measuring
systems provide a pump to continuously supply the KCI electrolyte to the reference electrode cell junction for
high purity water applications. Others use a gel-type cell containing a KCI electrolyte which diffuses very slowly
through the reference junction. The gel-type cell is useful for an extended period of time, typically, several
months.
It should also be noted that a high pH value does not always indicate low corrosion rates in the condensate.
McCoy” pointed out that it is wmmon to find pH values above eight in actual condensate samples with corrosion
rates as high as several hundred mils per year. His explanation was that the hydrogen ions produced in equation
(8) (dissociation of carbonic acid) rapidly oxidize iron according to equation (28):
H3CO3 = H’ + HC03 (8)
Fe + 2H’ = Fe+2 + H3 (28)
The net reaction of equations (8) and (28) is:
71w14
Fe + 2H3CO3 = Fe+* + 2HCO; + H2 (17)
Hydrogen gas is formed as a result of corrosion, leaving a dominance of bicarbonate ion in the solution. He
considered the equilibrium equation for reaction (8) and showed that
k = {[H+IWCOJII / iH2C031
pH = - log [H+] = - log K, + log {[HCO3-]/[HzC03]} (29)
where Kt is the first dissociation constant of carbonic acid, and [H’], [HC03-] and [H2C03] are concentrations of
hydrogen ion, bicarbonate and carbonic acid, respectively. From equation (29), it can be seen that the pH of a
solution depends on the ratio of (HCO3-] to [&CO3] rather than on the concentration of H2C03 alone. The
reduction of hydrogen ions by iron through equation (28) continuously increases the ratio of [HCC3-] to [H2C03]
and raises the pH as shown in equations (18) and (29). Condensate pH, as all the other parameters listed b&w,
should not be used alone to determine the wrrosivity of the condensate. Results obtained from other
measurements, such as conductivity, oxygen, and iron and copper concentrations should also be considered.
2. Conductivity-The conductivity is affected by the amount of soluble corrosion products, pH, amines, amine
bicarbonate and amine carbonate in the sample. This is generally used as an indication of the condensate
quality. Many plants use conductivity value to determine whether to return the condensate to the boiler or to
dump it to the sewer. This test is also very useful in identifying a boiler carryover problem. Resistivity, which is
sometimes used as the primary measurement, is simply l/conductivity.
3. Dissolved Oxygen--This test will reveal an air in-leakage contamination problem and/or an inadequate
deaeration process.
4. lronS233 and Copper Concentrations--These tests determine the amount of corrosion pmduds in the
condensate. These corrosion products tend to form deposits on boiler heat transfer surfaces if returned to the
boiler. Dissolved, insoluble, and total iron or copper measurements can also indicate condensate treatment
performance. Sampling is very important. Continuously flowing samples are preferred, but when not available,
the sample lines should be flushed before sample collection.
5. Dissolved Carbon Dioxide--This test will determine the actual content of CO3 in the condensate sample.
8. Total Hardness--This test can reveal a cooling water or service water contamination problem.
7. Total Organic Carbon--This test can indicate a process contamination problem.
8. Product Residuals--This test will measure the residual amount of the treatment chemicals, such as filming
amines, in the condensate. The product residual test should be run where applicable to determine program
control.
9. Ammonia--This test will allow the operators to determine the potential of copper corrosion problems.
lg. Condensate Quality--The ASME ‘Consensus on Operating Practices for Control of Feedwater and Boiler
Water Quality in Modem Industrial Boilers”, issued in 1994, uses the limits on feed water shown In Table 7.e4
When condensate contaminants interfere with the feedwater quality limits, the condensate should not be returned
to the boiler.
The above system performance measurements are indications of wrrosivity and quality of the condensate.
Actual corrosion rates of metals, in terms of penetration rate (millimeters per year, mm/year; or milS per year,
mpy), are typically determined by coupon weight loss measurements and/or electrochemical sensors.
Coupon Weight Loss Measurement
Coupon weight loss measurement is very oflen used to monitor wrrosion of metals in Various industrial
plants. The practices recommended by ASTM should be followed.85B7 Coupons of different metallurgies are
commercially available. Specimens are immersed in the condensate for a certain period of time, typically 90 to
180 days. They were then retrieved to determine the type and the extent of corrosion. Some important
considerations are listed below.
718l15
1. The specimens should be easily accessible without having to disturb the system.
2. Metal specimens should be electrically isolated from other metallic components to avoid galvanic corrosion.
3. The specimens should be property positioned for simulating complete immersion, partial immersion, or for
vapor phase corrosion studies.
4. Hydrodynamic effects should be taken into consideration in selecting the test location, for example, elbows
versus straight pipe.
5. The immersion test should follow the empirically derived minimum exposure time requirement:8889
Minimum Exposure Time (Days) = 85/mpy (30)
A formula for converting the weight loss data to a corrosion rate in mm/year (millimeters per year) or mpy (mils
per year) has been derived by Fontana and Greene?
mm/year = 13.8 W/(pAt) or (31)
mw = 534W/(pAt) (32)
where W = the weight loss (mg),

p = the density of the specimen $g/cm?,
A = the area of the specimen (in ), and
t = the exposure time (hour).
The coupon weight loss method is very time-consuming. The disadvantage of this is that corrective
actions cannot be taken in a timely manner.
Electrochemical Corrosion Rate Measurements
Eledrochemical techniques have widely been employed for measuring instantaneous corrosion rates of
metals in aqueous solutions. Most eledrochemical techniques for corrosion rate measurements, such as linear
polarization (LP) technique and electrochemical impedance spectroscopy (EIS), are based on the Stem-Gea#
equation:
i,= P.303) UP. P34P. + PC)) W%J (33)
where i,,, = corrosion current density (mA/cm2),

pp = anodic Tafel slope (mv),
PC = cathodic Tafel slope (mv), and
RP
= polarization resistance (ohm x cm*)
Based on Faraday’s law, the corrosion current density, i,, can further be converted to mm/year
(millimeters per year) and mpy (mils per year):
mm/year = 3.15x1 O5{M/(nFd)} x i,,, (34)

= 1 .37x105 {M/(nFd)) x (B/Rp)
mpy = 1.24~10’ {M/(nFd)) x i, (35)

= 5.39~10~ {M/(nFd)} x (B/Rp)
where M = molecular weight of metal (g/mole)

n = number of electrons involved in the corrosion reaction (mole),
F= Faraday’s constant,
d = density of metal (g/cm?, and
B = (P. l%MP. + P3 (mv)
Substituting the values of M, n, and d for iron (M = 55.85 g/mole Fe, n = 2 moles e-/mole Fe, d = 7.88
g/cm?, Faraday’s constant (98,500 coulombs/mole of e). and assuming that 8. = pC = 120 mV, equations (34)
and (35) become
718l18
mm/year = (3.03x1 OZ)/Rp (for iron) (38)
mpy = (1 .19x1 03/R, (for iron) (37)
Similar equations can be derived for copper and other metals.
Linear Polarization ILP) Techniaue. In linear polarization (LP) measurements, a small potential signal (for
example, f10 mV) is applied to the metal surface at a very slow potential scan rat&& typically 0.1 mV/sewnd, to
measure R,+R, (sum of solution resistance, R., and polarization resistance, Rp). ’ In highly conductive
solutions, such as seawater and cooling water environments, the value of Rs is very small. Therefore, (R,+Rp) a
R, and we can determine wrrosion rate with LP from equation (38) or (37).
LP is very simple and convenient to use for corrosion monitoring in high-wndudivity solutions. For high
purity or low-wndudivity waters, such as boiler condensate, the value of the solution resistance &is very large.
In this case, R, is not negligible and LP which measures (Rs + RP) will significantly underestimate the corrosion
rate. For this reason, many corrosion sensors based on LP technique without compensation for the solution
resistance are not suitable for corrosion rate measurements in low-wndudivity waters such as boiler condensate.
Electrochemical ImDedance SDedroscoDv (EIS). In EIS measurementsgqg6 typically, a small ac potential

excitation of different frequencies is applied at the corrosion potential to measure Rs as the high frequency limit
and (Ra+Rp) as the low frequency limit. The polarization resistance, R,, can then be calculated by subtracting the
value of the high frequency limit from that of the low frequency limit. The advantage of EIS is that it measures
the solution resistance so that the polarization resistance and the wrrosion rate can be accurately determined.
However, due to the long measuring-time required for EIS measurements, the system being measured has to be
very stable to obtain meaningful data. Furthermore, the instruments involved in EIS are expensive and
complicated and may not be suitable for long-term corrosion monitoring in the plants.
Corrosion Sensors for Field ADDlications. VanOUS electrochemical corrosion monitoring instrument and
wrrosion probes for field applications are available from several suppliers.“W’w Most of the simple units are
based on the linear polarization technique. Systems capable of measuring corrosion rates of metals in low-
conductivity solutions also determine the solution resistance. Methods for compensating solution resistance vary
among these systems. This includes a high frequency impedanceiW measurement, a current interrupt’” method
and a potential step/peak detedor’06~‘07 technology.
Electrical Resistance Probe
Conventional electrical resistance probes for corrosion rate measurements consist of a metal wire element
of fixed length embedded in a water resistant material. The value of the electrical resistance, r, is related to the
cross-sectional area of the wire element:
r=a(L/A) (38)
where r = electrical resistance (ohm),

(J = resistivity of metal (ohm/cm),
L = length of wire element (cm), and
A= cross-sectional area of the wire element (cm*).
The electrical resistance is inversely proportional to the cross-sectional area of the metal wire. As
corrosion proceeds, the cross-sectional area of the metal element decreases, resulting in an increase in the
electrical resistance. For known values of CI and L, by measuring the change in the electrical resistance, Ar, we
can determine the change in the cross-sedional area and the corrosion rate.lW This technique can be used for
wrrosion rate measurements in low-wndudivity solutions. The disadvantage is that it takes a long time to
obtain a significant change in the electrical resistance in typical boiler condensate environments. Fluduations in
the condensate temperature and pitting corrosion can complicate the analysis of the data.
Corrosion Product Monitoring
Condensate can be contaminated by the release of oxide particles from the metal surfaces into the water,
especially during plant/machine startups or shutdowns. These corrosion product particles, such as iron and
copper oxides, can be carried to the boiler by returned condensate. They tend to deposit in high heat flux zones
71al17
of the boiler. Consequently, periodic off-line chemical cleanings are often necessary to ensure reliable operation.
Continuous corrosion product monitoring can detect condensate contamination events. It provides important
information to plant operators, or as a feedback to an automatic on/off valve, to determine when to dump or
reuse the condensate. It is also a good performance measurement of condensate treatment programs for
corrosion protection. Conventional techniques for monitoring oxide particulate concentrations in condensate
have been reviewed by Chen et atlog Methods that have been used in the past and that are currently being used
are summarized below.
Babcock and Wilcox Millipore Filter Method. This method consists of passing one liter of water sample
through a 0.45 micron membrane fitter. The color as well as the darkness of the fitter pad is then compared with
a standard, such as the Babcock and Wilcox comparison chart. Although semi-quantitative, this test is a good
tracking method for insoluble iron particulate.
Calorimetric/Photometric Methods. These laboratory tests determining corrosion product levels can
provide very accurate results which are good trend indicators. The methods usually involve a digestion
procedure to convert insoluble metal oxide particles to the soluble metal ion complexes.
Atomic Absorption. This is an accurate method, but it can be very time-consuming. The samples are
usually sent to a laboratory and several days pass before the results are known. This makes the data useless to
operators who must make decisions about corrosion product transport events that occur over minutes or hours.
Turbidimeters. Turbidimeters have been used in some plants to deted the presence of patticulates for on-
line condensate quality analysis. Turbidity is affeded by the size, color, shape and composition of particles in
the test water. The color of the sample fluid and the wavelength of the incident light also affect the
measurement. The glass sample cell must not have any scratches, dust, condensation and deposit film to avoid
interference.
Figure 23 shows the schematic diagram ‘I0 of the basic light scattering device known as nephelometers
used in many turbidimeters. The turbidity is determined by measuring the light scattered at an angle (usually
90 degrees) to the incident light beam. It should be noted that for a given mass concentration of particles, the
turbidity is smaller with larger sized particles. This implies that larger particles could be in a sample, but not
contribute much to the turbidity reading giving a false impression of the presence of particulates.
Particle Counters. Particle counters are more precise than turbidimeters. Many,particle counters use
detectors that measure the total intensity of transmitted or scattered light (Figure 24). They can deted both
the size and number of particles. Some are designed to determktrt the total particle concentration while others
are optimized to provide information on particle size distribution.
Particle Monitor. A particle monitor has been reported’13 as an excellent tool for on-line corrosion product
transport monitoring in a paper mill. This on-line particle monitor operates on the principle of dynamic light
obscuration1’“16 with a cell shown in Figure 25.” Particles passing between the light source and the detector
cause random fluctuations in the intensity of the light beam at the detector. Higher numbers of particles in the
sample will create greater magnitudes in the intensity fluctuations. The particle monitor measures particle
concentration from the magnitude of these intensity fluctuations not the total intensity of transmitted or scattered
light as in turbidimeters or particle counters. The particle monitor was reported”’ to be more accurate and
sensitive than a turbidity meter.
CONCLUSIONS
Cost Reduction by Increasing Condensate Return
Monitoring, control and chemical treatment of the condensate system is frequently a negleded, not well-
understood area of the steam cycle. The mechanisms of corrosion, although well-documented in the technical
literature, are difficult to measure in the operational environment. Even relatively high corrosion rates can take
years to cause failures in many facilities. Therefore, systems are often operated without adequate treatment and
monitoring until problems occur. Severe problems or failures may cause produdion losses which can be very
costly. The importance of proper condensate corrosion inhibition and monitoring can be realized if the benefits
such as return on investment and cost reduction can be shown. Consider a system operating under the
conditions listed below:
718/18
Steam flow rate 50,000 Ibs/hr (22,727 kglhr)
Boilerwater conductivity 4000 pmhoslcm
Feedwater conductivity 80 umhos/cm
Condensate wndudivity 20 pmhos/cm
Make-up water conductivity 185 pmhos/cm
Temperature of condensate 18o’F (82’C)
Temperature of make-up 70°F (21’C)
Boiler efficiency 82%
Fuel cost S0.47Itherm
Heat value of condensate 148 BtuWlb
Feedwater flowrate 51,020 Ibs/hr (23,109 kglhr)
Concentration Ratio 50
% Condensate Return 84%
1 therm = 100,000 Btu’s. 1 therm costs $0.34-$0.40
The savings associated with a 2% increase in the amount of condensate returned as a percentage of
feedwater flow can be calculated as follows:
% condensate return (current) 84%

% condensate return (proposed) 88%
% condensate return improvement
Concentration ratio ET
Condensate return improvement (Ibs ,./hr) 1,020 Ibs/hr (484 kglhr)
Energy output saved (MM BTU’s/hr) 150,980 BtuWhr
Energy input saved (MM BTUWhr) 184,098 BtuWhr
Units of fuel saved 1.84 therms/hr
Cost of fuel ($/unit or $/therm) $0.40
Fuel cost savings per day $17.88
Fuel cost savings per year $8,477
The amount shown above is a dired fuel cost savings associated with a 2% increase in condensate return.
An increase of 10% condensate return would result in a savings of approximately $32,400 per year. The total
savings can be much greater if other cost factors, such as raw water treatment cost, maintenance cost, capital
spending, frequency of boiler cleaning and shutdowns, etc., are also taken into account.
Condensate Corrosion Inhibition and Corrosion Monitoring
Maintaining the purity of steam condensate is essential to the efficient and reliable operation of boiler
systems. Chemical treatment programs, such as neutralizing amines and filming amines, provide corrosion
protection against carbon dioxide and/or oxygen in the condensate system. Adequate corrosion protedion of a
condensate system can be achieved if the program is correctly selected and applied. This requires
understanding of condensate corrosion mechanisms and a detailed system survey by establishing sufficient
sampling points across the condensate system.
Corrosion monitoring plays an important role in condensate corrosion control. It can help the facility
managers and engineering staffs in managing the risks by identifying trouble areas. Installation of accurate
corrosion monitoring programs will also help optimize and ensure system performance to increase condensate
return. A good condensate treatment program should be one with good monitoring instrumentation that provides
a powerful tool for cost reduction by maximizing the condensate return.
Safety/Regulation Issues
In many applications, such as food industry and hospitals, the use of amines and other chemicals is limited
due to federal regulations. One of the concerns is the toxicity of most chemical treatments. This
safety/regulation issue should also be considered when managing condensate corrosion control programs. For
the industries subject to federal regulations, the condensate systems are very oflen operated without any
treatment for corrosion inhibition. There is a tremendous need to develop new wrrosion inhibition programs for
these specific areas.
71SllQ
ACKNOWLEDGEMENTS
The authors would like to thank Roger W. Fowee, Deborah M. Bloom, Dolores J. Soto and Richard A.
Peterson for many useful discussions and suggestions.
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71 W2g
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718/21
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718/22
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718l24
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48, December, 1992.
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TABLE 1
V/L RATIOS OF CYCLOHEXYLAMINE, MORPHOLINE AND CARBON DIOXIDE’
71W25
TABLE 2
PERCENT AMINE DECOMPOSITION64
DAE = 1, Z-Diaminoethane ETA = Ethanolamine AMP = Aminomethylpropanol

MPA = Methoxypropylamine 3HQ = 3-Hydroxyqoinuclidine
TABLE 3
AMMONIA GENERATION (MOLE NH3 PER MOLE AMINE)=
DAE = 1, 2-Diaminoethane ETA = Ethanolamine

AMP = Aminomethylpropanol MPA = Methoxypropylamine
3HQ = 3-Hydroxyquinuclidine
TABLE 4
DECOMPOSITION PRODUCTS=
Amine Other Major Decomposition Products

DAE ETA. Methylamine
ETA Ethylamine
Morpholine Methylamine, 2-(2-aminoethoxy)ethanol, Ethylamine
AMP Methylamine, Ethylamine
MPA Propylamine
3HQ Methylamine, Trimethylamine, Triethylamine, Piperidine
DAE = 1, P-Diaminoethane ETA = Ethanolamine

AMP = Aminomethylpropanol MPA = Methoxypropylamine
3HQ = 3-Hydroxyquinuclidine
718l28
TABLE 5
SYMPTOMS OF EXPOSURE TO AMINES AND AMMONIA”
Chemicals Symptoms
Morpholine Irritated Eyes, Skin, Nose, Respiratory System; Cough; Visual Disturbance;
Animals: Liver Damage, Kidney Damage
Cyclohexylamine Irritated Eyes, Skin, Mucous Membranes, Respiratory System; Eye and Skin
Bums; Cough, Pulmonary Edema; Drowsiness, Lightheadedness, Dizziness;
Diarrhea, Nausea, Vomiting
Diethylaminoethanol Irritated Eyes, Skin, Respiratory System; Nausea, Vomiting
Ammonia Irritated Eyes, Nose, Throat; Breathing Difficulty, Bronchospasm, Chest
Pain; Pulmonary Edema; Pink Frothy Sputum; Skin Bums, Vesiculation
TABLE 6
LIMITS OF FDA/USDA APPROVED AMINES
Amine Limit in Steam

Cyclohexylamine 10 ppm
Diethylaminoethanol 15 ppm
Morpholine 10 ppm
Octadecylamine 3 ppm
Hydrazine 0 ppm*
*Not FDA/USDA approved
TABLE 7
LIMITS USED TO DETERMINE CONDENSATE QUALITv84
I Clwratino I Dissolved 1 Total 1 Total 1 Total Oily Matter/ I

Iron 1 Copper 1 Hardness Nonvolatile TOC
wm Ppm wm mm
0.100 0.050 0.30 1.0
0.050 0.025 0.30
0.030 0.020 0.20
0.025 0.020 0.20
0.020 0.015 0.10
0.020 0.010 0.05
0.010 0.010 N. D.’
0.010 0.010 N. D:
l Nondetectable
718l27
NV-909039-P6V4K0, downloaded on 3/23/2015 7:00AM - Single-user license only, copying/networking prohibited.
7.0.
6.5.
----32°F (0°C)
-66°F (2oq
- 104°F (40 “(:
-140°F (60°C
---176°F (60°C
6.0.
5.5.
0.6 0.6 1.0

Concentration of Carbon Dioxide, ppm
FIGURE 1. Boiler tube with deposits.’ FIGURE 2. pH values of solutions of carbon dioxide
in pure water at various concentrations.‘8
1.
2.
a.0
a.
6.
1.
2.
7.0
6.
6.
1.
2 1.
6.0 6.0
.8 a.
.‘ ‘.
4 A
* *
5.0 5.0
.I 20 30 40 so 60 SO 100
FIGURE 3. Effect of free carbon dioxide on the pH of waters having bicarbonate alkalinity.20
FlGl JRE 4. Plateau of intact metal (upper left) surrounded by carbonic acid wastage lower right).
718/29
FIGURE 5. Trough-thinning by carbonic acid on the bottom of a horizontal steel pipe?*
FIGURE 6. General metal loss (lefl end of tube) on steel resulting from oxygen corrosion.
WrbOn
oxygen corrosion of
FIGURE 7. Pits caused by oxygen corrosion.
formed by localized
718131
tubercles
FI GURE 8. Flow-oriented
FIGURE 9. Corrosion caused by carbonic acid and oxygen.
FIGURE 10. Jagged fir-tree pattern of corrosion inside a tilted steel pipe caused by condensing steam
containing high concentrations of carbon dioxide and oxygen.
718J32
FIGURE 11. Grooving of a brass condenser tube at a baffle site by carbonic acid.
-.- Cyclohexylamine
- - - Morpholine
,..+.., Diethylaminoethanol
5 1 I r I I I 1
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4 3
ppm amine/ppm CO,
FIGURE 12. Amine neutralizing ability.60
71 &I33
FIGURE 13. Filming amine providing nonwettable sutface.67
16
a----
Aminomethylpropanol (AMP) L ,
\
\
--
12- --w
-. -. -. -.
6-
-mm.-*-
4-
Diethytaminoethanol(DEAE)
Dimethylisopropanolamine (DMIPA)
\**. .*.,. ..e . . . . . . .
---- -- Cyclohexylamine
0
I I I I
0 150 450 600 9oa
Pressure, psig
FIGURE 14. Percent amine lost in blowdown at 10 cycles.70

FIGURE 15. Variation of oxygen concentration and pH with time.
Vent Closed
Average Corrosion Rate = 3.92 mpy
8121197 at23197 8125197 m7i97 a/29/97 a/31/97 9l2i97 914197
TimerDate
FIGURE 16. Variation of corrosion rate in mpy with time.
718l35
tubercles.
products on internal surface.
of dislodged
caused by an accumulation
718136
17. Iron oxide corrosion
16. Pluggage
FIGURE
FIGURE
6X.
Magnification:
surface.
corroded external
on internal surface.
710137
FIGURE 20. Severely
19. Tubercles
FIGURE
FIGURE 22. Parallel grooves running down the side of the tube.
near a baffle or tube support
71 &I38
FIGURE 21. Severe grooving
Glass Sample Cell
1 1 Transmitted
I 0 b Light
L I
Light
Trap
FIGURE 23. The basic scattering device used in many turbidimeters

(Nephelometen measuring 90’ scattered light).“’
Sample In
Laser or
tight Source
Sample Out
FIGURE 24. Light obscuration particle counter.“’
718139
Water
Sample
_-__ .‘..i-
. .
.:’ _ ‘.m
_ .
.- . _ ..
..’ . .- .. .’
Infrared moto-
LED Detector
.. ‘:.,.:
*.. .-_*-
. .*-.. .
. I :-. ..: -:
_-_.. .*.
.:- . .* .
__ -.- . . i.
Sampling e
Tube
FIGURE 25. Particle monitor cell.“’
718140

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Abdullah M. Hammoud - Invoice INV-909039-P6V4K0, downloaded on 3/23/2015 7:00AM - Single-user license only, copying/networking prohibited.

CONDENSATE CORROSION IN STEAM GENERATING SYSTEMS

Tzu-Yu Chart, Carol B. Batton, Daniel M. Cicero and Robert D. Port

Condensate can be contaminated by release of corrosion products through metal dissolution or by

CORROSION IN STEAM CONDENSATE SYSTEMS

Corrosion of Carbon Steels

Anodic Reaction: Fe = Fe’* + 2e- (1)

Cathodic Reaction: 2Hz0 + 2e‘ = 20H- + H2 (2)

Net Reaction: Fe + 2H20 = Fe(OH)* + HZ (3)

3Fe(OH)* = Fe304 + 2H20 + Hz (4)

PHCOJ‘ + Heat = H20 + CO;* + CO2 (5)

CO2 + H20 = H2C03 (7)

H2C03 = H+ + HCO3 (8)

HCOj = H+ + CO;* (9)

2H* + 2e‘ = HZ (10)

2H2C03 + 2em = 2HCO; + 2Had. (Rate-Limiting Step) (11)

PHCO< + 2H+ = 2H2C03 (12)

FeOH = FeOH’ + e- (15)

FeOH’ = Fe** + OH- m

Fe + 2H2C03 = Fe’* + 2HCO; + HZ (17)

O2 + 2H20 + 4ee = 40H. (Neutral and Alkaline Solutions) (1 W

2Fe + 2H20 + 02 = 2Fe(OH)* (19)

4Fe(OH)* + 2H20 + 02 = 4Fe(OH)3 (20)

2Fe(OH)3 = Fe203 + 3H20 (21)

Corrosion of Copper and Copper Alloys

2Cu + 8NH3 + O2 + 2H20 = 2Cu(NH&,+* + 40K (22)

Cu(NH&+* + CU(S”fface)= 2Cu(NH&+ (23)

4Cu(NH3)*+ + 8NH3 + O2 + 2H20 = ~CU(NH&+~ + 40K (24)

2. Poor Quality Condensate--Condensate can be contaminated by corrosion products produced in the

CONDENSATE CORROSION PROTECTION TECHNOLOGIES

[Concentration in the Vapor or Steam Phase]

RNH2 + H’ + HCO$ = RNHj + HCO3 (26)

RNH2 + Hz0 = RNH; + OH

CONDENSATE CORROSION CASE HISTORIES

Case History No. 1 - Industry: Refinery

Case History No. 2 - Industry: Steam Heat-Building

Specimen - Condensate Return Line to Receiver Tank

Case History No. 3 - Chemical Process Industry

Specimen - Condensate Recovery End of Soda Ash Steam Dryer

Specimen - Surface Condenser Tube Near Air Ejectors

CONDENSATE CORROSION MONITORING

Water Chemistry Analyses

1. Condensate pH--Most condensate treatment programs require pH to be maintained in a certain range.

pH is an indication of hydrogen ion concentration or acidity in the water. It is commonly determined by

H3CO3 = H’ + HC03 (8)

Fe + 2H’ = Fe+2 + H3 (28)

The net reaction of equations (8) and (28) is:

pH = - log [H+] = - log K, + log {[HCO3-]/[HzC03]} (29)

7. Total Organic Carbon--This test can indicate a process contamination problem.

Coupon Weight Loss Measurement

Minimum Exposure Time (Days) = 85/mpy (30)

mm/year = 13.8 W/(pAt) or (31)

where W = the weight loss (mg),

Electrochemical Corrosion Rate Measurements

i,= P.303) UP. P34P. + PC)) W%J (33)

where i,,, = corrosion current density (mA/cm2),

mm/year = 3.15x1 O5{M/(nFd)} x i,,, (34)

mpy = 1.24~10’ {M/(nFd)) x i, (35)

where M = molecular weight of metal (g/mole)

mpy = (1 .19x1 03/R, (for iron) (37)

Similar equations can be derived for copper and other metals.

Electrochemical ImDedance SDedroscoDv (EIS). In EIS measurementsgqg6 typically, a small ac potential

Electrical Resistance Probe