Corrosion Control in

Condensate Systems Reprint R-741

By Daniel M. Cicero, Nalco Company

Boiler systems, at the core of every process plant, are The value of condensate
constantly exposed to elements that cause scaling, A well-controlled boiler system should have condensate
fouling and, ultimately, corrosion. Excessive mainte- that is low in dissolved solids. Corrosion products such
nance, premature replacement and gradual demise as iron and copper contribute to the deterioration of
are the consequences of neglect or failure to see the equipment and negatively impact boiler efficiency.
“red flags” of corrosion in a facility. This article dis-
cusses the use of chemistry to combat corrosion in When properly treated, condensate returned to the
condensate systems. Methods of treatment, which in- boiler can be a valuable resource. Aside from its high
clude neutralizing amines, filming amines and “green purity, it also has high heat content. Thus, an im-
chemistry” technologies, are compared and contrasted. provement in the quality of condensate returned to
the boiler boosts efficiency and reduces operating
costs. Condensate temperatures are typically 180°F
The combined assault or greater. With a heat value of 148 Btu/lb (relative
to a 32°F base at this temperature), condensate re-
Regardless of the mechanical complexity of a system,
quires less energy to convert to steam. The “free” Btus
condensate corrosion can almost always be ascribed
contribute to lower overall energy requirements and
to the presence of carbon dioxide (CO2) and oxygen
operating costs.
(O2).1 Each has its own sources, and its own impact
on condensate-system chemistry (Box, p. 2). Amine compounds are commonly used today to con-
trol condensate-system corrosion. These compounds
The presence of either CO2 or O2 by itself, in conden-
generally fall into two different categories — neutral-
sate systems can be problematic; but together, these
izing amines and filming amines. Amine treatments
gases can accelerate
vary, depending on the type of corrosion in the system.
corrosion by 10 to
40% more than the
sum of the rates of
Neutralizing amines
the individual gases
(Figure 1). Neutralizing amines are
nitrogen-containing com-
Perhaps the best way pounds added to the
of dealing with corro- steam to neutralize corro-
sive gases is to pre- sive carbonic acid and
vent their entry into raise system pH (Figure
the boiler system. 2), so that CO2 levels are
Mechanical measures kept to a minimum. Ex-
for preventing infil- amples of neutralizing
tration include de- amines include morpho-
aeration, the use of line, cyclohexylamine and
Figure 2 — Carbonic
leak-free pumps, and acid attacks internal diethylaminoethanol
Figure 1 — Carbonic acid venting, which allows pipe surface (DEAE). Ammonia is also
and oxygen attack conden- air and corrosive
sate piping employed as a neutralizing amine.
gases to escape to the
atmosphere. Chemical treatment systems, which in-
clude filming and neutralizing amines or “green” cor-
rosion inhibitors, are also deemed effective.

Reprinted from Chemical Engineering, March 2000, 2000 by Chemical Week Associates,
L.L.C. with all rights reserved.
 CORROSION CHEMISTRY
Sources for condensate-system corrosion are often right
under the operator’s nose. Easy-to-overlook equipment
shortcomings, and sources of otherwise innocuous CO2 and
O2, which fuel corrosive reactions, are inherent to every
system.
Take, for instance, the feedwater source. All condensate
systems use one to replenish losses that result from boiler
blowdown, process consumption, unreturned condensate
and leaks. The quality of this makeup water can vary dra-
matically, since sources may include raw untreated water,
zeolite-softened water, demineralized water, lime-soda soft-
ened water, and of course, returned condensate. In most
boiler feedwaters, some carbonate alkalinity is present. Figure 3 — Oxygen pitting on
the internal surface of piping
Under boiler pressures and temperatures, a portion of the
carbonate molecules breaks down, forming carbon dioxide,
which is carried along with the steam. When the steam
condenses, some of the CO2 dissolves in the condensate and
forms carbonic acid. It is not the carbon dioxide, per se, Figure 4 — Low-pH
corrosion
that is harmful, but the carbonic acid that results from its
dissolution in the condensate. However, the impact of metal corrosion is not limited to
Carbon dioxide forms through thermal decomposition of thinning of condensate piping. The iron dissolved by the
carbonate molecules in the boiler, via either of the follow- low pH of condensate is then returned to the feedwater via
ing two reactions:2 the following equation:

2HCO3– + Heat → H2O + CO3–2 + CO2 ↑ (1) Fe + 2H+ + 2HCO3– → Fe(HCO3)2 + H2 (6)

or This reaction, coupled with the dynamics of the boiler sys-

tem, removes iron from condensate piping and deposits it
CO3–2 + H2O + Heat → CO2 ↑+ 2OH– (2) in areas near boiler heat-transfer surfaces, presenting fur-
Carbon dioxide is liberated from the boiler with the steam. ther problems: costly replacement of condensate piping,
When the steam condenses, the carbon dioxide gas dissolves reduced boiler tube life and ultimately, boiler shutdown.
into the condensate, forming carbonic acid according to the
following equation: Oxygen attacks
CO2 + H2O → H2CO3 (3) In most condensate systems, air in-leakage is the primary
source of oxygen. Mechanical joints, packing glands on con-
Carbonic acid is a weak acid, which dissociates in water
densate-return pumps, faulty steam traps, and areas un-
via the following equations:
der vacuum are possible sources for oxygen contamination.
H2CO3 → H+ + HCO3– (4) While many condensate systems employ deaerators to scav-
enge oxygen from feedwater, resulting in oxygen concen-
HCO3– → H+ + CO3– (5)
trations of below 10 ppb, faulty or inefficient equipment
Condensate has almost no buffering capacity, so the small can contribute to total oxygen content. Even at 10 ppb, oxy-
amount of H+ produced by dissociation of the carbonic acid gen is still capable of causing severe corrosion. Sulfite, hy-
is sufficient to significantly decrease the pH. The low pH drazine, or organic reducing agents can be used to further
values enhance corrosion in the piping and equipment that reduce oxygen content. Oxygen launches a two-pronged
contacts the condensate, as shown in Figure 4. Made of assault on ferrous surfaces. First, it reacts with iron ac-
such species as iron and copper, these components may form cording to the following reaction:
corrosive by-products, which increase the concentration of
2Fe0 + 2H2O + O2 → 2Fe(OH)2 (7)
dissolved solids in the condensate. In addition, carbonic acid
may cause thinning of condensate piping. Notable charac- Then, ferrous hydroxide reacts with combustion oxygen to
teristics include trough-like thinning at the bottom of the form ferric hydroxide according to the reaction below:3
pipe, worming or roughness on metal surfaces.
4Fe(OH)2 + 2H2O + O2 → 4Fe(OH)3 (8)
Even small concentrations of carbon dioxide dissolved in
These reactions compound corrosion problems by attack-
condensate can create big problems. As little as 1 part per
ing ferrous surfaces in a manner that results in pitting and
million (ppm) CO2 dissolved in condensate can result in a
localized corrosion (Figure 3). At the same time, the low
pH of 5.5 at typical condensate temperatures. A pH of 5.5
solubility of ferric oxide in water results in precipitation of
is 10,000 times more aggressive to mild steel than a pH of
ferric oxide (hematite) on surfaces, and subsequent opera-
7.5, and 1,000,000 times more aggressive than a pH of 8.5.
tional and maintenance problems.

2
Carbon dioxide gas is liberated from a boiler with the boiler, neutralizing only the carbonic acid that is
steam. When the steam condenses, the carbon diox- formed there. To neutralize carbonic acid, the amine
ide dissolves in the condensate, forming carbonic acid. must be present in the condensate as the carbon
Although weak, carbonic acid depresses the conden- dioxide dissolves.
sate pH, making it corrosive. Neutralizing amines,
added to the steam to inhibit corrosion, are volatile. The distribution ratio dictates whether the amine will
They also condense with the steam, raising pH and condense or remain in the vapor phase, under exist-
neutralizing the carbonic acid. An amine reacts with ing conditions. Consider, for instance, a phase sepa-
carbonic acid to form an amine bicarbonate accord- ration, when steam and condensate exist together at
ing to the following equation:1 150 psig in a flash tank. Suppose the steam has been
treated with cyclohexylamine, an amine with a V:L
RNH2 + H+ + HCO3– → RNH3– + HCO3– (9) ratio of 4:1 at that pressure. An analysis of the con-
Neutralizing amines can be introduced to the boiler densate would reveal that it contains 20% of the origi-
system via addition to the feedwater or directly into nal amine. The remaining 80% would exist as a vapor
the steam. Since these amines are volatile, they in the steam. Under those same conditions, if the
quickly and thoroughly disperse. Neutralizing amines steam were treated with an amine with a relatively
provide the greatest protection when they are used low V:L ratio like morpholine (V:L = 0.5:1 at 150 psig),
to maintain a pH of 8.5–9.0 — a range in which car- 67% of the amine would be found in the condensate
bonic dioxide cannot exist (CO2 cannot prevail at a and 33% would be found in the steam.
pH higher than 8.3). However, in copper-free systems, The choice of which neutralizing amine is appropri-
somewhat higher pH values (8.8–9.2) improve con- ate depends on the dynamics of the steam system
trol of mild-steel corrosion. being treated. The goal is to have slightly higher con-
The amount of a neutralizing amine fed to a system centrations of amine than carbonic acid across the
is directly proportional to the amount of carbon entire steam system. In almost every case, more than
dioxide present in the steam. In high-alkalinity one neutralizing amine is needed to obtain this goal.
feedwater systems, where carbon dioxide generation Most specialty-chemical manufacturers blend several
is appreciable, chemical treatments can be expensive. amines, combining those with high, intermediate and
The engineer may consider investing in a dealkalizer low volatilities, to obtain uniform distribution
(see p. 5) to reduce the concentration of carbon diox- throughout the steam system.
ide generated by the boiler. One must decide whether
it is feasible to use a filming amine (discussed later),
which will permit lower condensate pH’s, or whether Determining amine strength
replacing the existing mild-steel condensate piping An amine’s acid-neutralizing ability is measured by
with more corrosion-resistant materials would be the amount of amine required, on a weight basis, to
more sensible. neutralize the carbonic acid present in the system.
On a pound-for-pound basis, lower-molecular weight
amines neutralize more carbonic acid than higher-
The condensation game molecular weight amines.
The efficiency of an amine in neutralizing carbonic Once all the carbonic acid has been neutralized —
acid is related to its volatility.4,5 All the steam in a resulting in a pH of 8.2–8.3 — amine basicity becomes
steam system does not condense at the same place or important. Basicity, a measure of amine hydrolysis,
time. As the steam travels through the steam sys- results in the formation of hydroxyl ions (OH–). After
tem, giving up energy in various processes, conden- neutralization is complete, any amine added to amine
sate and carbonic acid are formed. The measure of a will hydrolyze, raising the condensate pH.
neutralizing amine’s volatility, or its vapor-to-liquid
distribution ratio (V:L), dictates when, under a given RNH2 + H2O → RNH3– + OH– (11)
set of conditions, the amine will condense. The ratio Use of neutralizing amines can disrupt some indus-
is defined by the equation below: trial processes. In refining or chemical processes
V amine concentration in the vapor phase where steam is used directly, neutralizing amines can
= (10) potentially initiate undesirable chemical reactions.
L amine concentration in the liquid phase For example, the amine can contaminate or “poison”
Amines with high volatilities or distribution ratios a catalyst used in polymerization.
tend to remain in the vapor phase longer, controlling Neutralizing amines also present a number of han-
corrosion downstream from the boiler. Less-volatile dling and safety concerns, as exposure to large doses
amines condense soon after the steam has left the can cause irritation to eyes, skin, and mucous mem-

3
 Figure 6 — Filming amine providing non-
Figure 5 — Pitting caused by oxygen attack wettable surface

branes. On the other hand, neutralizing amines offer are able to function at pH levels as high as 9.5, in-
several advantages to alternative treatment methods: creasing their range of applicability.
they are low in cost, are easy to feed into a system,
and are available in a wide variety of chemicals to Octadecylamine, which has been approved by the
meet specific process needs. Food and Drug Administration (Washington, D.C.)
under 21 CFR 173.310 for safe use in steam that con-
tacts food, is one filming amine that is particularly
Filming amines impacted by pH excursions, requiring a system pH of
7.0–7.5. If the pH is significantly below or above this
Oxygen, another major cause of corrosion, presents a range, the protective film will be compromised.
different set of challenges to the corrosion engineer
(Figure 5). While mechanical approaches, such as the Since all filming amines are essentially nonvolatile,
use of deaerators, help to reduce oxygen content in it is necessary to inject them directly into the steam
condensate systems, they are seldom 100% effective. as the steam leaves the boiler. This is often a chal-
Oxygen in-leakage is a reality in most boiler systems. lenging task for pipefitters, and requires a high-pres-
While effective at eliminating the deleterious effects sure chemical feed pump. In addition, filming amines
of CO2, neutralizing amines have virtually no effect also do not form their protective barrier instanta-
on oxygen corrosion. Other strategies must be em- neously. Initial dosages must be carefully controlled.
ployed to deal with this problem. Starting too quickly will result in the formation of
sticky deposits; starting too slowly leaves the system
Filming amines, or filmers, for short, were developed unprotected for longer periods than necessary.
to address oxygen-induced corrosion, and, in fact, can
also be used to control carbonic acid corrosion. These Filming amines are often used in conjunction with
amines form a thin, nonwettable film on the metal neutralizing amines. Filmers alone do not have
surfaces inside the condensate system. The film acts enough neutralizing capability to buffer condensate
as a barrier between the surface and the corrosive pH into a range where filming can effectively take
condensate (Figure 6).6 Octadecylamine is a typical place (6.5–8.0). A combination filmer-neutralizer pro-
filming amine. gram can work more effectively at a lower pH than a
straight neutralizer, enabling a plant to utilize less
Filming amines are sensitive to system pH. In order neutralizer and reduce total treatment costs. Film-
for a film to form, the system pH must be controlled ing amines also enhance heat transfer — thanks to
over a range of 6.5–8.0. Acidic environments inhibit film formation — resulting in nucleate condensation.
film formation, while basic environments (pH > 8.0)
remove any film that has formed. Aside from amine treatment consideration, the pH
at which the condensate was maintained would de-
Under some conditions, filming amine molecules have pend on the metallurgy used in the system. For in-
a greater affinity for other filming amine molecules stance, the solubility of mild steel is at its lowest point
than for metal surfaces. If overfed or controlled at a at a pH of approximately 11.0, whereas the corrosion
improper pH, filming amines can agglomerate, form- rate of copper, from which many heat exchangers are
ing sticky deposits. These deposits can clog steam fabricated, is lowest at a pH of about 8.8. If a filming
traps, strainers, and other condensate system equip- amine is used instead of a neutralizing amine, the
ment, creating a sticky, fouling mass. Boiler-water pH of the system should be lower, because the film-
foaming and carryover can also occur under these ing amines provide better protection at lower pHs.
conditions. However, some proprietary filming amines

4
Cost is also a factor in setting the pH of a system. In densate system. Field applications have proven this
many instances, because the concentration of carbonic system to be highly effective in a wide variety of in-
acid in the condensate is very high, users will opt to dustrial condensate systems.
trade corrosion for chemical dollars: With operation
at a lower pH, chemical usage can be reduced with In selecting a corrosion-prevention strategy, one must
some incremental increases in corrosion rates. consider workplace safety, operating efficiency and
regulatory compliance. Neutralizing amines work
effectively in systems with low makeup requirements,
Alternative treatments low feedwater alkalinity, and good oxygen control.
Filming amines thrive in systems requiring higher
Although amine-based chemical solutions to corro- makeup, and with higher alkalinities and a propen-
sion problems are common in industry, many prefer sity to draw in air. In many cases, a combination of
to use “mechanical” means to eliminate the causes of neutralizing and filming amine treatments offers the
corrosion. The most common method of condensate most effective solution, while the new GCCIs offer
treatment is dealkalization. other regulatory, process and economic benefits.
An ion exchange process, dealkalization removes the
carbonate and bicarbonate ions in the boiler makeup
water by passing it through an ion-exchange resin References and other readings
bed. The resin, which has an affinity for such anions 11. Berk, A. A., Treating steam chemically to reduce
as carbonate and bicarbonate, exchanges them for return line corrosion, Industry and Power, Vol. 53,
chloride, which does not thermally decompose in the No. 5, Nov. 1947, pp. 79-81, 110, 112.
boiler to form carbon dioxide gas. By elimination of
these alkaline substances, the amount of carbon di- 12. Chen, T.Y., others, Condensate corrosion in steam
oxide liberated from the boiler is reduced. Less CO2 generating systems, Corrosion 1998 Conference,
translates into less carbonic acid formation in the Paper No. 718, NACE International, San Diego,
condensate, and a reduced demand for neutralizing Calif., 1998.
amine. 13. Webb, S. L. and Bohnsack, G., The kinetics of the
A chloride cycle dealkalizer uses an anion exchanger Schikorr Reaction on steel surfaces at low tem-
to remove bicarbonate ions from solution according peratures, Corrosion 1989 Conference, Paper No.
to the reaction below: 311, New Orleans, La., 1989.

NaHCO3 + XCl → XHCO3 + NaCl (12) 14. Obrecht, M. F., Effluent Water Treatment, J. Chem.
Eng. Data, Vol. 5, 1964.
where X is the anion resin. When the ion exchange
resin has been exhausted (i.e., no longer able to re- 15. Davison, R. R., others, J. Chem. Eng. Data, Vol. 5,
move anions), it is regenerated with NaCl. A satu- 1960.
rated brine solution is passed through the resin bed, 16. Bloom, D. M. and Wiltsey, D. G., Condensate system
reversing the process and exchanging CO3–2 for Cl–. troubleshooting and optimization, Boiler Water
NaCl + XHCO3 → XCl + NaHCO3 (13) Treatment for the 1990s Conference, Warrington,
England, 1992.
Once restored, the dealkalizer is again ready to ex-
change anions for chloride ions. 17. Batton, C. B., others, Corrosion Inhibitor, U.S.
Patent No. 5,849,220, Dec. 15, 1998.
Increasing environmental and health concerns sur-
rounding amines has spurred exploration into viable 18. Cicero, D. M., Regulatory issues in condensate
alternatives. New “green” condensate corrosion in- treatment, International Water Conference, Pitts-
hibitors (GCCIs) are being developed to meet the cor- burgh, Pa., 1997.
rosion-control needs of industrial and commercial 19. Wilson, A. M., Beyond condensate-system protec-
boilers (August 1998, p. 59). GCCIs are safe enough tion: Ensuring amine compliance, District Energy
to be used in facilities traditionally prohibited from Magazine, 1996.
using amine treatments, and are approved by the FDA
in applications where steam directly contacts food 10. Edgerton, S. A., others, Determination of amines
products. in indoor air from steam humidification, Environ-
mental Science Technology, Vol. 23, pp. 484-488.
GCCIs create a non-wettable barrier between the con-
densate and pipe surfaces, preventing carbonic-acid
and oxygen attack, even during short-term feed in-
terruptions. Also, because they are nonvolatile, GCCIs
can be applied selectively to various areas of a con-

5
Author
Dan Cicero is product manager for In 1991, Cicero left the Navy and joined Nalco as a
Nalco Company (1601 West Diehl district representative, concentrating on boiler and cool-
Road, Naperville, IL 60563-1198; ing water applications in the middle market. In 1994,
E-mail: [email protected]). After he was promoted to boiler products manager for Nalco’s
graduation from the University of middle market Unisolv Group. Two years later, Cicero
Michigan (Ann Arbor), Dan ac- advanced to his current position as new-product-devel-
cepted a commission in the U.S. opment team leader, managing all steam condensate
Navy where he served as an engi- treatment programs in North America, Latin America
neering officer responsible for the and Europe.
operation, maintenance and man-
agement of a high-pressure steam propulsion plant.

Nalco Company 1601 West Diehl Road • Naperville, Illinois 60563-1198

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