COOLING SYSTEMS

DON’T UNDERESTIMATE THE PROBLEMS CAUSED BY CONDENSER

TUBE LEAKS
solids levels well above the low part- ically of a porous nature, on boiler tube

T
per-billion (ppb) concentrations required surfaces. Deposits play an important
for trouble-free operation. part in chemistry and chemistry control,
To understand how impurities cause as we shall see.
problems, it is first necessary to under- Feedwater piping and boiler water
stand some of the basics, and subtle- wall tubes exhibit minimal corrosion with-
he changing nature of ties, of steam generation chemistry. The in a pH range of approximately 8.5 to 12.
employment in this coun- typical material of construction for boiler Common for high-pressure steam gen-
try, with its downsizings, feedwater piping and boiler tubes is erators is pH control within or slightly
early retirements, and movement of peo- mild carbon steel, while feedwater tubes above a range of 9.0 to 9.7. Various
ple to different careers, has had an may be stainless steel, carbon steel, or treatment methods are available to main-
impact at electric utilities and many oth- copper-alloy. When a boiler is first tain a mildly alkaline pH in steam gener-
er industries. People who know the placed into operation, the carbon steel ators. For feedwater, the most common
plants well and are experienced in solv- piping reacts with water to form a thin treatment scheme is injection of ammo-
ing problems are often no longer with a layer of the iron oxide, magnetite (Equa- nia or an amine to adjust pH and per-
company. tion 1). (Editor’s note: All article equa- haps an oxygen scavenger (hydrazine
One of the primary concerns at utility tions appear together in an Equations or an organic substitute) to minimize
and industrial steam generating plants table, and not within the text.) oxygen corrosion. In once-through
is that of condenser tube leaks, but Magnetite serves as a protective coat- steam generators and some drum-type
often the author hears of situations where ing for the underlying base metal, and units, these chemicals also serve as the
plant management does not recognize chemical treatment programs for many boiler water conditioners as well. For
the danger that can result from tube years have been designed to minimize the majority of drum units, tri-sodium
failures. Major leaks have been known magnetite corrosion. (A later section on phosphate (Na3PO4) or TSP serves as
to cause millions of dollars in boiler tube deposition influenced by chemical treat- the primary boiler water-conditioning
damage in only a few days, while even ments discusses an alternative program, agent. TSP performs two major purpos-
minor leaks can be very troublesome if oxygenated treatment.) However, even es in that it produces a mildly alkaline
they are not corrected over time. This in well-treated steam generators, grad- pH, and it, or the alkalinity generated
article reviews this critical issue. ual corrosion of the magnetite layer and thereby, reacts with contaminants. The
Cooling water for steam surface con- transport of the iron oxide products to basic chemistry of these actions is out-
densers can vary widely in quality. Many the boiler induces deposit buildups, typ- lined in Equations 2 through 4.
plants use once-through cooling with
lake or river water as a source. These
supplies, whose quality can be greatly
influenced by climatic and seasonal
weather variations, typically contain a
few hundred parts-per-million (ppm) of
dissolved and suspended solids. Table
A outlines several snapshot water anal-
yses from various points around the
country.
At facilities with cooling towers, where
cooling water cycles several times, the
impurity concentrations are substantial-
ly greater. Infiltration of cooling water
into condensate can increase dissolved

By Brad Buecker
Kansas City Power & Light Co.

ISSN:0747-8291. COPYRIGHT (C) Tall Oaks Pub-

lishing, Inc. Reproduction in whole, or in part,
including by electronic means, without permission
of publisher is prohibited. Those registered with the Figure 1. Tube failure due to hydrogen damage.
Copyright Clearance Center (CCC) may photocopy Photo courtesy of GE Betz.
this article for a flat fee of $1.50 per copy.

30 ULTRAPURE WATER® DECEMBER 2003--UP201030

 Figure 3. Caustic attack of boiler tube metal.
Photo courtesy of GE Betz.

Figure 2. Magnetite solubility as a function of ammonia

concentration and temperature. Figure 4. Acid phosphate corrosion of boiler tube metal.
Source: Electric Power Research Institute. Photo courtesy of GE Betz.

While feedwater and boiler water centrations. The reaction outlined in event, hydrogen damage began caus-
chemicals protect the steam generator Equation 6 becomes very localized with ing so many forced outages that the
against general corrosion and mitigate resulting attack of tube metal. utility scheduled an emergency replace-
mild contaminant intrusion in the short As drastic as this chemistry seems, it ment of virtually all of the water wall
term, they are not a cure for fundamen- may be overshadowed by an even more tubes at great cost. Operation with the
tal problems. insidious problem. Hydrogen molecules condenser tube leak was a classic ex-
produced by acid attack are very small ample of treating the symptoms and not
Effects of Condenser Tube Leaks and can penetrate the tube metal. Once the root cause.
A condenser tube leak will obviously inside the tube wall, hydrogen will react
introduce the contaminants listed in with carbon to produce voluminous Deposition Directly Influenced
Table A into the condensate, feedwater, methane molecules that impart stress to by Condenser Tube Leaks
and steam generator. Even when con- the metal and initiate cracks (Equation Many of the other impurities introduced
taminant levels are not extremely high, 7). by a condenser tube leak will form re-
the progressive increase in tempera- This phenomenon is known as hydro- versibly soluble salts as they are ex-
ture initiates a number of reactions. One gen damage, and is almost impossible posed to increasing temperatures dur-
of the most troublesome is illustrated in to detect through simple visual inspec- ing the journey to the boiler. One of the
Equation 5. tion. Sudden tube failures are often the most notable reactions, which should
The production of hydrochloric acid result of hydrogen damage (Figure 1), be familiar to readers dealing with cool-
can lower the boiler water pH in a very and usually if it occurs in one area, then ing water scale control, is outlined in
short time (1). other areas are also afflicted. A very Equation 8.
If boiler tubes were completely clean, important point to note is that while large Boiler water chemical programs may
general corrosion might be the result, condenser leaks can initiate hydrogen minimize such scale formation if a tube
but the typical presence of deposits, damage, chronic small leaks can have leak is small, but large leaks that con-
and especially porous iron oxide mate- the same effect. Reference 1 at the end sume the protective chemicals will allow
rials, drastically increases the complex- of this article includes a case history hard scales to form. Other potential
ity of the situation. Boiler water will enter where the chemists diligently maintained deposits include magnesium and silica
porous deposits and as it nears the tube pH and phosphate concentrations in a compounds. All deposits have a much
wall where the temperature is higher, medium-pressure (1,250 pounds per lower thermal conductivity than steel,
the water will flash to steam and escape. square inch gauge) boiler that suffered and even a very thin deposit layer will
Contaminants often remain behind in through a three-week long, moderate restrict heat transfer. For example the
the deposits and build up to high con- condenser leak. Two months after the thermal conductivities of some selected

ULTRAPURE WATER® DECEMBER 2003--UP201030 31

 materials are as follows:
EQUATIONS
2 o
Carbon steel: 360 Btu/ft /hr- F-in
Magnetite: 20 Btu/ft2/hr-oF-in 3Fe + 4H2O → Fe3O4 + 4H2↑ Eq. 1
Calcium carbonate: 7 Btu/ft2/hr-oF-in Na3PO4 + H2O ⇔ NaOH + Na2HPO4 Eq. 2
Porous silica: 0.6 Btu/ft2/hr-oF-in
Btu/ft2/hr-oF-in = British thermal units per square foot 10Ca+2 + 6PO4-3 + 2OH- → 3Ca3(PO4)2·Ca(OH)2↓ Eq. 3
per hour-degrees Fahrenheit-inch 3Mg+2 + 2SiO3- + 2OH- + H2O → 3MgO·2SiO2·2H2O↓ Eq. 4

Minor scale buildups can lead to effi- MgCl2 + 2H2O → Mg(OH2)↓ + 2HCl Eq. 5
ciency losses and long term overheat- 2HCl + Fe → FeCl2 + H2↑ Eq. 6
ing, the latter of which causes gradual C + 2H2 → CH4 Eq. 7
tube deformation. Bulges develop that
Ca +2
+ 2HCO → CaCO3↓ + CO2↑ + H2O
3
-
may take a long time to fail. Heavy scale
formation can induce short term over-
heating, where the tubes may fail in
weeks, days, or in extreme cases, hours. fatalities at several plants. FAC has also directly attacked the tube metal (Figure
Contaminant in-leakage severe enough become troublesome in the low-pres- 3). So, the phosphate programs of the
to cause short-term overheating will also sure boilers of many heat recovery steam middle 20th Century evolved into coordi-
initiate other failure mechanisms, such generators (HRSG). The low-pressure nated and congruent programs where
as hydrogen damage. boilers typically have many short-radius chemists blended di-sodium phosphate
Another potential difficulty presented elbows and operate near the tempera- (Na2HPO4) and occasionally even some
by condenser tube leaks is steam con- ture of maximum iron dissolution shown mono-sodium phosphate (NaH2PO4) to
tamination, particularly in units not in Figure 2. drive Equation 3 to the left and reduce
equipped with a condensate polisher. An alternative and popular treatment caustic concentrations. However, hide-
In most modern high-pressure steam scheme for once-through units, some out makes these programs difficult to
generators, feedwater is sprayed into standard drum boilers, and even some control, and there is now overwhelming
main and reheat steam to control tem- HRSGs is oxygenated treatment (OT), in evidence that phosphate deposits are
perature. This offers a direct path for which oxygen is deliberately injected often acidic in nature and cause direct
contaminant introduction to the turbine. into the condensate and feedwater to corrosion of boiler tubes. This acid
While none of the impurities introduced produce a dissolved oxygen residual of phosphate corrosion often resembles
by a condenser leak are beneficial in around 50 ppb. A pre-requisite for OT is caustic attack (Figure 4).
the turbine, some are notorious bad very pure condensate. When conden- Many plant chemists have switched to
actors, and in particular chloride. Chlo- sate conditions are carefully controlled, a program known as equilibrium phos-
ride ions induce pitting in stainless steels, OT generates a tight oxide film contain- phate treatment (EPT), in which tri-sodi-
and in turbines they can also initiate ing ferric oxide hydrate (FeOOH). Years um phosphate is the only compound
stress corrosion cracking. Sulfate ions worth of data from around the world added to boiler water, where the phos-
will cause similar problems, although shows that the oxide film produced by phate concentration is maintained be-
not to the same extent as chloride. The OT is much stronger than magnetite. low 2 ppm and free hydroxide alkalinity
Electric Power Research Institute (EPRI) The program cannot be used in systems is held below 1 ppm. This scheme
now recommends a maximum limit of 2 with copper alloy feedwater heater minimizes hideout and under-deposit
ppb for chloride and sulfate in main and tubes, as rapid corrosion would result. caustic attack. The primary drawback
reheat steam. This is an extremely low Phosphate treatment for boiler water to EPT is that a condenser leak will
value, which indicates how problematic corrosion prevention may cause prob- quickly eat up the treatment chemical,
these contaminants can be. lems on its own. Phosphates, and par- leaving the boiler tubes vulnerable to
ticularly tri-sodium phosphate came into attack and scaling. Advanced research
Deposits and Corrosion Induced use in the 1930s, as the chemicals on phosphate treatment programs is
by Chemical Treatments proved superior to previous treatments still underway. By the time this article is
As was previously mentioned, the once for controlling pH and contaminant dep- published, EPRI will probably have come
popular feedwater treatment method osition. However, as boiler technology out with their Phosphate Continuum
using oxygen scavengers/metal passi- improved and pressures and tempera- guidelines. These will be the definitive
vators has fallen into some disfavor. tures increased, two major problems word on phosphate treatment.
This is due to the tendency of iron disso- became evident. First, while TSP solu- Another topic that is still being hotly
lution to occur in strongly reducing en- bility increases up to about 300oF, the debated is the use of organic pH condi-
vironments at typical feedwater temper- solubility rapidly decreases beyond this tioners and oxygen scavengers/metal
atures (Figure 2) with a subsequent temperature. Thus, in high-pressure, passivators for feedwater treatment.
transport of iron oxide to the boiler. The high-temperature boilers, most of the While many of the products work well in
mechanism also contributes to wall thin- phosphate precipitates on the tube walls. the steam generator, research has
ning at feedwater and economizer el- This phenomenon is known as hideout. shown that most at least partially break
bows and other flow disturbances in a A problem that once occurred with tri- down in the boiler and steam network to
phenomenon known as flow-assisted- sodium phosphate feed alone was caus- produce organic acids and carbon di-
corrosion (FAC). FAC-induced failures tic attack in which excess sodium hy- oxide. Some experts believe that these
over the last decade have resulted in droxide built up under deposits and decomposition products initiate or ex-

32 ULTRAPURE WATER® DECEMBER 2003--UP201030

 scale-forming and corrosive chemicals
TABLE A in a steam generator are very serious
Chemistry of Selected Water Supplies subjects. In today’s environment, where
(all values expect pH expressed as ppm) the key phrase seems to be “do more
with less,” neglect of issues such as
Well Water near Surface Water near Tombigbee River these can sometimes force a utility to do
Constituent Tecumseh, KS Beaumont, TX Alabama Sea Water “without” when a unit goes down.■
Calcium 120.0 8.7 16.2 400
Magnesium 23.5 2.8 4.1 1,272 References
Potassium 6.6 2.6 2.0 380
Sodium 73.4 14.8 15.3 10,561 1. B. Buecker; “Monitoring Condenser
Chemistry to Improve Steam Plant Opera-
Bicarbonate 297.6 34.6 54.3 tion”; ULTRAPURE WATER 19(9), pp. 24-32
Carbonate 0.0 0.0 0.0 (November 2001).
Chloride 99.3 19.0 16.4 18,980
Nitrate 0.0 0.0 1.5 Author Brad Buecker is the chemistry
Phosphate 0.0 0.0 supervisor at Kansas City Power & Light
Sulfate 150.0 17.0 30.2 2,652 Co.’s La Cygne, Kansas, power station.
Iron 0.4 2.3 3.6 He has previous experience as a chem-
Manganese 0.1 0.3 ical cleaning services engineer, a water
Silica 19.0 12.4 3.1 and wastewater system supervisor, and
TOC 0.0 6.7 a consulting chemist for an engineering
pH 7.7 7.7 7.2 8.0 firm. He also served as a results engi-
neer, flue gas desulfurization (FGD)
engineer, and analytical chemist for City
Water, Light & Power in Springfield, Ill.
acerbate turbine corrosion. Others claim cades or more. Safe systems can be
Buecker has written more than 50 arti-
that the effects are minimal or non-exis- designed that prevent personnel from
cles on steam generation, water treat-
tent. A problem this presents to utility being exposed to the chemical, and I
ment, and FGD chemistry, and he is the
personnel who believe organic treat- have observed several of these sys-
author of three books on steam genera-
ment chemicals are bad is that hydr- tems at plants around the country.
tion topics. Mr. Buecker has a B.S. in
azine (N2H4) is the only practical, non-
chemistry from Iowa State University.
organic oxygen scavenger/metal pas- Conclusion
sivator. Yet, it has been on the suspect- This article hopefully pointed out that
Key words: COOLING TOWERS, POW-
ed carcinogen list for perhaps two de- condenser tube leaks and production of
ER

ULTRAPURE WATER® DECEMBER 2003--UP201030 33

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