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THE CHALLENGES OF INDUSTRIAL

BOILER WATER TREATMENT
POSTED BY CHEMTREAT ON 12/15/2020

By Brad Buecker, Senior Technical Publicist and Tim Hughes, Senior Technical Staff
Consultant

몭is article was originally published in PPCHEM® Journal; PPCHEM® 2020, 22(6), 252–259;

https://journal.ppchem.com/

Abstract
High-pressure steam generators for power production require high-purity makeup and
feedwater and controlled boiler water chemistry to minimize corrosion and scale
formation in the boilers, superheater/reheater circuits, and turbines. Numerous articles in
the PPCHEM® journal over the last two decades have outlined these chemistries and
their evolution.

However, while many heavy industries have high-pressure steam generators for co-
generation needs, these plants and many other smaller facilities also have low-pressure
boilers that produce process steam. 몭e lower heat fluxes and pressures in these steam
generators somewhat alleviate the stringent treatment requirements necessary for
high-pressure units but offer more complexity in the choice of optimum treatment
methods.

몭is article provides an overview of modern methods for protecting lower-pressure

steam generators from factors that typically do not plague their high-pressure
counterparts.

Introduction

High-pressure steam generators for power production require high-purity makeup and
feedwater and controlled boiler water chemistry to minimize corrosion and scale
formation in the boilers, superheater/reheater circuits, and turbines. However, while
many heavy industries have high-pressure steam generators for co-generation needs,
these plants and many other smaller facilities also have low-pressure boilers (boilers of
less than 4.14MPa (600psig)) that produce process steam. 몭e lower heat fluxes and
pressures in these steam generators somewhat alleviate the stringent treatment
requirements necessary for high-pressure units but offer more complexity in the choice
of optimum treatment methods. Potential issues such as contaminated condensate
return and makeup water treatment system malfunctions can increase the complexity
of steam generation water/steam treatment.

몭is article provides an overview of modern methods for protecting lower-pressure

steam generators from factors that typically do not plague their high-pressure
counterparts.

The Complexities of Makeup, Condensate Return, and Feedwater Chemistry

In utility systems, the steam is condensed and returned to the boiler after performing its
work in the turbine. 몭e complete water/steam circuit is nearly a closed loop with
approximately 0.5–2% water loss and corresponding makeup additions. Mature
technologies such as reverse osmosis (RO) and ion exchange are available to produce
high-purity makeup (≤2μg∙L–1 of sodium and chloride, ≤10μg∙L–1 of silica, and ≤0.1μS∙cm–1
specific conductivity). In the absence of a condenser tube leak or, less frequently,
makeup system upset, the feedwater remains highly pure on its path to and through the
steam generator and turbine, and for that small portion utilized for steam attemperation.

Now consider the realm of low-pressure steam generation, where the boilers do not
require demineralized makeup. For decades, and even today, sodium zeolite softening
has been a common primary treatment method for industrial boiler makeup. In this
process, the makeup passes through a bed of ion exchange resin that trades calcium
and magnesium hardness ions for sodium. 몭e softened stream, with the remaining
impurities including bicarbonate alkalinity (HCO3–), chloride (Cl–), sulfate (SO42–), silica
(SiO2), and others, then feeds the boiler. Some softening makeup systems include a
splitstream de-alkalizer, or perhaps a forced-draft decarbonator, to remove most of the
alkalinity. 몭is can be beneficial, as will be outlined.

Basic softening offers both advantages and drawbacks. Compared to complete

demineralization, softening saves plants money in equipment and operating costs.
Regenerating softening resins with brine is straightforward and does not require storing
and handling dangerous acids and caustic. 몭e major difficulty with softening is that the
ions not removed by the process can become problematic upon reaching the steam
generator. Alkalinity is a prime example. If it is not removed from the makeup, alkalinity
will at least partially convert to carbon dioxide (CO2) in the boiler, carrying over with the
steam. Upon steam condensation, the CO2 can lower the pH, leading to potential
condensate corrosion issues for carbon steel piping.

몭e introduction of other water impurities to the boiler can lead to higher conductivity,
increasing the general corrosion potential of the water, especially because the ions “cycle
up” in drum boilers as steam is produced. While some accumulation of these impurities
is tolerable, in many cases, plant personnel do not track deposit buildup in boilers,
particularly of iron oxide corrosion products transported from elsewhere, e.g.,
condensate return systems. Boiler water impurities can concentrate under these
deposits to much higher levels than in the bulk water, and induce under-deposit
corrosion.

Heavy deposits also restrict heat transfer, and in areas of high heat flux may lead to tube
overheating and mechanical failure as shown in Figure 1, where iron oxides from
condensate return created thick deposit layers followed by fishmouth opening of the
tube from overheating [1].

RO technology offers a reliable option for producing makeup water with very low
dissolved solids. At many power plants, RO serves as the primary demineralization step
dissolved solids. At many power plants, RO serves as the primary demineralization step
with mixed-bed ion exchange or continuous electrodeionization (CEDI) polishing as the
final stage, but RO as a stand-alone process can suffice for many low-pressure boilers.
몭e process removes the bulk of impurities (often 99% or more), including silica, which
can allow for higher boiler water cycles of concentration, thus saving costs via reduced
makeup and blowdown.

Figure 1: Iron oxide deposits in boiler tubes leading to tube bursts with the typical
fishmouth openings.

Sufficient pretreatment to remove suspended solids ahead of RO membranes and a

well-designed chemical treatment program to minimize scale formation are important
to successful RO unit operation. Careful RO feedwater analysis is critical for proper
pretreatment equipment and chemical selection. Also, RO generates a nearsteady
wastewater stream that must be disposed of. For plants with cooling towers, the tower
basin may serve as a good repository. Otherwise, alternative disposal methods may be
needed.

몭ere are many examples of makeup system upsets wherein plant personnel operated
the systems in failed mode or sometimes even bypassed malfunctioning systems and
fed raw water to the boiler. A mindset of “water is water” seems to prevail in these cases.
Such assumptions can lead to disastrous consequences, and boiler tubes have been
known to fail within days or sometimes hours of such decisions.

Feedwater and Condensate Return Issues

Apart from whatever method is utilized for makeup water production, significant
impurities can enter the steam generator via condensate return from plant processes.
몭e percent condensate return may range from slight to very large depending on plant
design and operation. In a classic example of contaminated condensate observed years
ago by one of the authors, superheater bundle replacement of four package steam
boilers at an organic chemicals plant was required every 1.5–2 years because of internal
deposition and overheating failures. 몭e root cause was excessive organic ingress to the
condensate return, which induced foaming in the boiler drums and solids carryover to
the superheaters. No systems were in place either to polish the condensate or to dump it
during impurity excursions.

Depending on the chemical processes at the plant and the ability of impurities to enter
the condensate, a wide variety of contaminants can potentially enter the boiler. A
program should be in place to detect chemical leakage from heat exchangers, reactors,
or other vessels, and to make repairs as needed. Testing condensate return for pH,
hardness, and specific conductivity is common. And, it might be prudent to check the
return condensate for organics in specific cases. With such monitoring, the condensate
can be diverted to drain if the measurement exceeds a predetermined limit, e.g.,
50μS∙cm–1 continuous on-line conductivity. Setpoints for dump or reuse of return
condensate should be defined for all site-specific parameters that might impact boiler
feedwater quality. Condensate dumping can be expensive considering the costs for
makeup water production and heating water to produce steam; however, plant
personnel may rely too much on the boiler water treatment program to alleviate
problems. Excessive contamination can overload any treatment program.

As with high-pressure steam generators, establishing and maintaining a moderately

basic pH range (in general, pH 9–10) is an important issue for feedwater and condensate
return systems in low-pressure units to prevent general carbon steel corrosion. In the
power industry, the common pH conditioner is ammonia, which raises feedwater pH via
the following reaction:
몭is is a reversible reaction, so the alkalinity increase is limited, which usually minimizes
excessive steel corrosion in the event of a chemical feed upset. (High ammonia
concentrations, especially in the presence of oxygen, can be very detrimental to copper
alloys.) Conditions are often different in low-pressure boilers. If the makeup water is
sodium-softened only, sufficient alkalinity may be present to maintain a basic pH.
Sometimes a bit of caustic feed may be employed to boost feedwater pH, although care
must be taken when using this strong chemical.

However, the wild card for industrial systems is condensate return, in which the pH may
be significantly depressed by carbon dioxide carryover. Accordingly, neutralizing amine
injection to condensate return is often employed to minimize corrosion in carbon steel
piping networks.

A common injection point is the storage section of the deaerator or directly to the steam
header, which may be better. 몭e chemical or chemical blend not only protects the
condensate but carries through the system. Table 1 details several of the most common
neutralizing amines.

Table 1: List of common neutralizing amines.

몭e amines all have a higher molecular weight than ammonia, and thus will not flash off
as readily, although each has its own distribution ratio (the amount remaining in the
water vs. that departing with steam) whose properties are a function of temperature and
pressure. 몭e products also have different basicities, providing flexibility in treatment
program selection. Careful evaluation of condensate return system operating and design
conditions is necessary to select the most appropriate amine or amine blend.

Some compounds are not allowed if the steam can directly contact food or other
consumable products.

As discussed in a previous issue of the PPCHEM® journal, monitoring total iron

concentrations in condensate is highly recommended to evaluate feedwater chemistry
efficacy [2]. We will return to this idea again later in this article.

Dissolved Oxygen Control

In the middle of the last century, the consensus about dissolved oxygen (DO) in boiler
feedwater was uniform: oxygen should be eliminated because it is highly corrosive. But
European and Russian researchers in the late 60s and early 70s discovered that some
dissolved oxygen (at concentrations up to 300μg·L–1) introduced to high-purity water
during normal operation induced formation of a tight α-hematite oxide layer on carbon
steel piping. Corresponding particulate and dissolved feedwater iron concentrations
could be driven to very low values of 1μg·L–1 or even less. 몭e program became known as
oxygenated treatment (OT) and was widely applied to once-through supercritical units
in Europe and, eventually, in the United States and elsewhere. 몭e caveat for OT is that it
requires exceptionally high-purity feedwater (≤0.15μg·L–1 cation conductivity); otherwise,
oxygen corrosion may occur. Figure 2 illustrates this concept.
Figure 2: Oxygen corrosion rates as a function of dissolved solids content. [3]

Drum units continued to operate with feedwater chemistry anchored to dissolved

oxygen removal by mechanical deaeration and reducing agent (also known as oxygen
scavenger) treatment until failures from flow-accelerated corrosion (FAC) began to
emerge in the 1980s. A number of these failures caused injuries and fatalities at power
plants over the next three decades. FAC chemistry has been well documented in the
PPCHEM® journal [4] and other publications, but a key point is that it led to the
development of a cousin to OT for drum units named all-volatile treatment, under
oxidizing conditions (AVT(O)), which also relies on a small concentration of dissolved
oxygen in the feedwater. AVT(O) also requires high-purity feedwater (≤0.2μg·L–1 cation
conductivity) to develop the proper oxide layer on carbon steel while minimizing oxygen
corrosion.

몭e upshot of this brief discussion about OT and AVT(O) is that industrial boilers are
usually supplied with less than high-purity makeup, and often recover condensate that
contains some impurities, so neither AVT(O) nor OT can be utilized because of the
potential for severe oxygen corrosion of carbon steel components. Most industrial
feedwater systems are equipped with mechanical deaerators, which, when operating
properly, should reduce the DO concentration to 7–10μg·L–1. A common layout for
industrial low-pressure steam generation is displayed in Figure 3.
Figure 3: A common industrial steam generation layout. Note the makeup water
and condensate return feeds to the deaerator.

A chemical reducing agent is also typically employed to further lower DO levels. For
steam generators at or below a pressure of 4.14MPa (600psi), either un-catalyzed or
catalyzed sodium sulfite (Na2SO3) is a popular reducing agent. 몭is non-volatile oxygen
scavenger adds some inorganic dissolved solids to the feedwater.

A common injection point is the deaerator storage tank.

But as has already been observed many times in the power industry, complete DO
removal leads to conditions that promote FAC. 몭is raises an important question, “Can
FAC occur in industrial feedwater systems if the DO concentration is reduced to very low
values?” 몭e answer is yes, and reference [5] outlines mild cases of FAC at a co-
generation facility in the United States. To summarize, recent non-destructive testing
revealed some wall loss at elbows on both the suction and discharge side of several
boiler feedwater pumps as well as at a nozzle and a weld seam. None require immediate
repair, but they prompted plant personnel to plan additional testing to ensure other
locations are not seriously damaged. Undoubtedly, a mitigating factor in the mild nature
of those spots suffering from FAC is that plant personnel have strived to maintain
feedwater pH within a mid- to upper-9 range, in accordance with data presented by
Sturla [6] nearly five decades ago (Figure 4).

Figure 4: Influence of temperature and pH on iron dissolution from carbon steel [5]. 몭e
temperature aspect is why FAC is typically most pronounced in the feedwater systems
and economizers of many conventional steam generators and the LP evaporators of
multi-pressure heat recovery steam generators (HRSGs).

An important point to note is that this elevated pH range would be too high for most
systems containing copper alloys and would need to be lowered to the low 9s for
combined iron and copper corrosion control. It is in such situations that analytical
techniques like corrosion product sampling can be quite valuable, where the solution
concentration of both metals can be evaluated. For all-ferrous systems, straight iron
monitoring techniques are possible, and reference [1] outlines several of these
techniques. 몭e International Association for the Properties of Water and Steam (IAPWS)
has generated a Technical Guidance Document (TGD) [7], which discusses the variety of
analytical methods that can be used for these tests. At the facility highlighted in
reference [5], personnel make spot checks of condensate and feedwater iron
concentrations via the well-known Millipore test method, in which a known volume of
the sample is passed through a very small-pore (0.45μm) white filter paper, whose color
is compared to standard samples after drying. 몭e Millipore procedure was in large
measure pioneered and promoted years ago by the boiler manufacturer Babcock &
Wilcox for quick calculations of feedwater iron concentrations during unit startups [8]. In
utility boilers, virtually all of the particulates will be iron oxides, but in industrial steam
utility boilers, virtually all of the particulates will be iron oxides, but in industrial steam
generators with complex steam and condensate return networks, other impurities that
mask the results may exist.

In many complex industrial steam generation/condensate return systems, it is desirable

to have proper pH control throughout the network, but a single compound may not be
sufficient to achieve this control. 몭e authors’ colleagues have developed blended amine
products that can provide wide-ranging coverage. A thorough analysis of system design,
metallurgy, current chemistry, and operating temperatures is a prerequisite for proper
program selection.

Film-Forming Chemistry for Corrosion Protection

Film-forming amines (FFA) were introduced by the water treatment industry decades
ago, and recent years have seen a re-emergence of film-forming substances (especially
octadecylamine or C18H39N) for corrosion protection. 몭e amine group on each molecule
attaches to the metal substrate, and the long-chain organic portion of the molecule
extends into the water and acts as a barrier. However, poor control and lack of detailed
knowledge of the overall chemistry have often led to problems, including formation of
“gunk balls” that fouled steam generators [9]. Advancements in chemical synthesis
techniques and analytical instrumentation have led to the development of new film-
forming substances, both amines and other compounds, that are much more effective
at protecting metal surfaces. 몭is includes the FFA products of ChemTreat’s TITAN360™
series. Figure 5 shows a protected metal surface (during off-line conditions). Note how
the water beads rather than wetting the surface.
Figure 5: Protected metal surface with FFA.

When correctly applied, film-formers can protect metal surfaces during normal
operation and unit downtimes. However, it must be noted that implementing FFA
programs requires proper system oversight and control. Less-than-knowledgeable
vendors have been known to suggest that such chemicals could be injected into the
unit, after which corrosion issues would magically disappear. Severe problems were the
result instead. A careful analysis of system operation and past/present chemistry is
necessary beforehand, with careful monitoring and control required after FFA chemistry
is introduced, as it is explicitly described and recommended in section 8 of the IAPWS
TGD11-19 [9].

Boiler Water Treatment

In the 1930s, as power generating units increased in number and size, tri-sodium
phosphate (Na3PO4, also known as TSP) became a popular boiler water conditioning
chemical for drum boilers. At that time, phosphate treatment served two primary
functions. 몭e first was to establish moderately alkaline conditions in the boiler to
minimize general corrosion of carbon steel boiler tubes, drums, and headers.

몭is function is still quite critical today.

A second function of phosphate was, and in many cases still is for industrial boilers,
important for scale control where hardness ingress occurs. Eq. (4) below outlines the
most common of these scale-forming reactions, which has probably been observed ever
since humans began heating water for personal and then industrial use.

Calcium carbonate (CaCO3) deposition, often accompanied by other minerals, still

plagues many industrial steam generators when makeup systems malfunction but
remain in operation or are bypassed.

Phosphate and the alkalinity produced by its reaction with water will react with
hardness ions to form soft sludges as opposed to hard scale. However, in the early days
of power unit operation, some boilers were plagued by under-deposit caustic corrosion
generated by the rather high concentrations of TSP needed for scale control. 몭is led to
the development of coordinated and congruent phosphate treatment programs that
utilized blends of tri-, di-, and sometimes even a small amount of monosodium
phosphate. Subsequent research has shown that these chemistries can generate acidic
phosphate deposits in high-pressure steam generators. Utility boiler treatment
programs have returned to TSP (or, in some cases, caustic treatment), albeit in low
dosages of perhaps no greater than 2mg·L–1. 몭is is possible because modern makeup
treatment systems are quite reliable, such that hardness in-leakage is very rare. 몭us,
phosphate treatment is used for pH control only.

For industrial boilers, phosphate treatment remains a strong choice, particularly because
the potential for hardness ingress to many industrial units is much greater. 몭e lower
heat fluxes in these steam generators allow higher phosphate dosages than in utility
units. And it may be possible to sometimes employ phosphate blends rather than TSP
alone for more flexibility in pH control. Sludge conditioners consisting of water-soluble
polymers that help keep solids in suspension by a combination of dispersion, crystal
modification, and sequestration are often recommended alongside phosphate
treatment. Iron particulates from condensate return system corrosion can be
problematic, but sludge conditioners help to keep the particles in suspension for
subsequent blowdown. 몭ese polymers can sometimes serve as a standalone treatment,
particularly if hardness ingress is not an issue.

In former days, chelants were sometimes employed in industrial drum units. 몭ese
chemicals directly bind with metals to keep them suspended.
Ethylenediaminetetraacetic acid (EDTA) is the most widely known chelant and has been
used for many applications both inside and outside industrial applications. However,
improper chelant use can cause localized corrosion of boiler components. Chelant
programs are very rare now and should only be used with well-deaerated feedwater,
excellent pretreatment control, and low feedwater iron concentrations.

몭e upshot is that several possibilities, namely phosphate/polymers, polymers alone, and,
rarely, chelating agents, exist for boiler water treatment, but the proper choice depends
on a variety of factors that include boiler design and pressure, makeup water treatment
sophistication and reliability, and the potential for impurity ingress and iron oxide
carryover from condensate return. 몭ese factors must be evaluated carefully for each
case. A “one size fits all” approach to treatment selection can lead to problems.

Conclusion

몭e lower pressures and heat fluxes in industrial steam generators make them less
susceptible to high-temperature corrosion mechanisms than those in utility units.
However, chemical treatment of these lower-pressure units may be more complicated
because of several factors, including:

• The potential for impurity ingress from complex steam feed and condensate return
systems.
• Inadequate attention to makeup water treatment system performance, which allows
unwanted impurities such as hardness to enter boilers.

• Condensate return system corrosion that not only damages system piping and
equipment but sends iron oxide corrosion products to the boiler. These particulates
tend to deposit in high-heat locations, subsequently reducing heat transfer and
establishing sites for under-deposit corrosion and overheating failures because of
insufficient tube wall cooling.

Careful planning is necessary to establish the proper treatment programs for the entire
steam generation system and condensate return networks. A variety of methods are
available to optimize chemistry. Comprehensive monitoring is necessary to ensure
treatment programs are performing as intended.
Acknowledgement

몭e authors would like to greatly thank Frank Udo Leidich of the PPCHEM® journal
International Advisory Board for reviewing this article and providing valuable
information.

References

[1] Bursik, A., “Boiler Tube Failures in Industrial Drum-Type Steam Generators – Part 1:
Feedwater Treatment and Under-Deposit Corrosion Failures”, PowerPlant Chemistry
2001, 3(8), 459.
[2] Buecker, B., Kuruc, K., “Sampling Points and Parameters for Low-Pressure Industrial
Steam Generators”, PPCHEM 2020, 22(4), 142.
[3] Feed Water, Boiler Water and Steam Quality for Power Plants / Industrial Plants, 2011.
VGB PowerTech Service GmbH, Essen, Germany,
VGB-S-010-T-00;2011-12.EN.
[4] Dooley, B., Tilley, R., “Tube Failures in Conventional Fossil Plants and in HRSGs”,
PowerPlant Chemistry 2001 3(12), 703.
[5] Buecker, B., Murphy, F. P., Breakdown: Is Flow-Accelerated a Concern in Co-
Generation Steam Generators? Available from https://www.power-eng.com.
[6] Sturla, P., “Oxidation and Deposition Phenomena in Forced Circulating Boilers and
Feedwater Treatment”, presented at the Fifth National Feedwater Conference, 1973
(Prague, Czechoslovak Socialist Republic).
[7] Technical Guidance Document: Corrosion Product Sampling and Analysis for Fossil
and Combined Cycle Plants, 2014. International Association for the Properties of Water
and Steam, IAPWS TGD6-13(2014). Available from http://www.iapws.org.
[8] Membrane Filter Comparison Charts – Procedures and Test Methods, 1964. 몭e
Babcock and Wilcox Company, Barberton, OH, USA.
[9] Technical Guidance Document: Application of Film Forming Substances in Industrial
Steam Generators, 2019. International Association for the Properties of Water and Steam,
IAPWSTGD11-19. Available from http://www.iapws.org.

The Authors

Brad Buecker (B.S., Chemistry, Iowa State University, Ames, IA, USA) is a senior technical
publicist with ChemTreat. He has many years of experience
in or affiliated with the power industry, much of it in steam generation chemistry, water
treatment, air quality control, and results engineering
positions with City Water, Light & Power (Springfield, IL, USA) and the Kansas City Power
& Light Company’s (now Evergy) La Cygne, KS, USA, generating station. Most recently he
was a technical specialist with Kiewit Engineering Group Inc. He is a member of the
American Chemical Society, American Institute of Chemical Engineers, American Society
of Mechanical Engineers, Association of Iron and Steel Technology, National Association
of Mechanical Engineers, Association of Iron and Steel Technology, National Association
of Corrosion Engineers, the Electric Utility Chemistry Workshop planning committee, the
International Water Conference Advisory Council, and the Power-Gen International
planning committee. Mr. Buecker has authored many articles and three books on power
plant topics.

Tim Hughes (B.S., Petroleum and Natural Gas Engineering, Pennsylvania State
University, State College, PA, USA) is a senior technical staff consultant with ChemTreat.
He has 29 years of industrial water treatment experience and 8 years of oil & gas
experience. He previously held positions at Betz Laboratories, Universal Well Services and
National Fuel Gas Supply Corp.

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