4.

28 Boiler and Feedwater Treatment

A. Banweg
Nalco Company, 1601 W. Diehl Road, Naperville, IL 60563, USA

2010 Elsevier B.V. All rights reserved.

4.28.1 Introduction 2972

4.28.2 Make up Water Treatment 2973
4.28.3 Feedwater Treatment 2975
4.28.3.1 Dissolved Oxygen Control 2975
4.28.3.2 pH Control 2977
4.28.3.3 All Volatile Treatment (Reducing) (AVT(R)) 2977
4.28.3.4 Flow Accelerated Corrosion 2977
4.28.3.5 All Volatile Treatment (Oxidizing) (AVT(O)) 2978
4.28.3.6 Oxygenated Treatment 2979
4.28.4 Boiler Water Treatment 2980
4.28.4.1 Residual Phosphate Treatment 2980
4.28.4.2 Steam Purity 2980
4.28.4.3 Chelant Treatments 2981
4.28.4.4 All Polymer Treatment 2982
4.28.4.5 Coordinated Phosphate Treatment 2982
4.28.4.6 Congruent Phosphate Treatment 2983
4.28.4.7 Phosphate Continuum Treatment (Formerly Equilibrium Phosphate Treatment) 2984
4.28.4.8 All Volatile Treatment 2985
4.28.4.9 Caustic Treatment 2986
4.28.5 Condensate Treatment 2986
4.28.6 Boiler Treatment During Out-of-Service Conditions 2988
4.28.7 Miscellaneous (But Important) Comments 2988
References 2988

Glossary feedwater heaters are typically located

Attemperation The process for reducing and
controlling the temperature of superheated
steam.
Cation conductivity The measurement of the
electrical conductivity of a water
sample after it has been passed through a
strong acid cation resin that is in the
hydrogen form.
Decarbonator A degasifier used to remove carbon
dioxide.
Desuperheat Removing superheat from steam
typically by injecting high-purity water or
steam condensate.
Duct burner A means of auxiliary firing in many
combined cycle plant heat recovery steam
generators (HRSGs).
Feedwater heater A heat exchanger used to raise
the feedwater temperature. Low pressure
ahead of the deaerator; high pressure
feedwater heaters are typically located after
the deaerator.
Mud drum The lower drum in a boiler circuit
that acts as a point of recirculation and
collects solids for removal by bottom
blowdown.
Mud drum attemperator A steam to water heat
exchanger located in the mud drum used to
control steam temperature.
Specific conductivity The measure of the ability of
water to conduct an electric current. Often
related to the dissolved solids content of the
water.
Steam blanketing A condition in a boiler tube
where the steam water mixture stratifies into
separate layers. This is more likely to occur in
an inclined tube.

2971
2972 Environmental Modification
Sweetwater condenser A heat exchanger that
cools a portion of generated steam so that
the resultant condensate can be used for
attemperation of the superheated steam.
Abbreviations
ASME American Society of Mechanical Engineers
AVT All volatile treatment
AVT(O) All volatile treatment, oxidizing
AVT(R) All volatile treatment, reducing
ED Electrodialysis
EDI Electrodionization
EDR Electrodialysis reversal
EDTA Ethylenediaminetetraacetic acid
EPRI Electric power research institute
FAC Flow accelerated corrosion
JIS Japanese Industrial Standards
NTA Nitrilotriacetic acid
ORP Oxidation reduction potential
OT Oxygenated treatment
RO Reverse osmosis
TDS Total dissolved solids
VGB Vereinigung Grosskraftwerk Betreiber
(Germany)
4.28.1 Introduction
Water is abundant on our planet. However, very little
is suitable for human consumption (potable) without
pretreatment. It is very rare that even potable quality
water is suitable for makeup water to a boiler system
without additional pretreatment.
There are many technical organizations around
the world that publish guidelines on recommended
feedwater and boiler water specifications. There
are the European Standard1 and the Vereinigung
Grosskraftwerk Betreiber (VGB)2 in Europe, the Amer-
ican Society of Mechanical Engineers (ASME)3 and
Electric Power Research Institute (EPRI)4 in the United
States, and the JIS5 in Asia. These guidelines are gener-
ally developed by a consensus of committee members
that can include equipment manufacturers, industrial
equipment operators, water treatment companies, and
experienced consultants. Some of these guidelines
focus more on a particular segment of the industry
than another. For example, the EPRI guidelines focus
on boiler systems in the electric utility industry,
whereas ASME focuses on boiler systems in industrial
applications. Others may try to cover the entire scope
of boiler applications. These guidelines are, for the
most part, very general, and only in rare cases do these
guidelines specify a treatment chemistry or treatment
chemical to use. This is because the actual treatment
chemistry used is a function of the makeup water quality
available, the desired steam purity to be produced, and
economic considerations. For instance, the ASME
guidelines relate steam purity to the appropriate boiler
water limits but do not specify feedwater purity in terms
of total dissolved solid content. This is an economic
decision left to the individual boiler system operator
to decide how much is invested in the pretreatment
system to purify the water as opposed to higher blow-
down rates to maintain the boiler water dissolved solid
limits. The EPRI guidelines are an example of such an
exception from these more general types of guidelines,
in that they are intended for a very specific audience of a
narrowly defined type of boiler system in this case, the
electric utility industry.
Finally, since these guideline committees are con-
tinually updating their guidelines based on the most
current information available and the latest operating
experience, they will only be referenced in the chapter.
For actual guidelines, the most current relevant issue
of the chosen guideline should be obtained for use in
a particular boiler system.
This chapter addresses the subject of makeup water,
feedwater, boiler water, and steam and condensate
treatment in steam boiler systems. Feedwater by defi-
nition is the combination of returned condensate and
fresh makeup water (Figure 1). This combination can
Makeup Steam
Feedwater
Continuous
blowdown
Condensate
Intermittent
blowdown
Figure 1 Schematic of typical boiler flows.

range from 0% to 100% in industrial steam-generating
systems, in which the steam-generating system is gen-
erally part of an industrial or manufacturing plant.
Figure 2 is a typical field-erected water tube industrial
boiler. Notably different are steam-generating systems
in the electric utility industry, which are dedicated only
to the production of electric power and have conden-
sate return rates consistently greater than 95% of the
feedwater by design. Figure 3 is a typical drum-type
utility boiler.
4.28.2 Make up Water Treatment
The type of pretreatment will dictate the necessary
further chemical treatment that the water will require
prior to use in the particular steam-generating sys-
tem. The possible types of pretreatment are
clarification,
cold lime softening,
hot lime softening,
zeolite (ion exchange) softening,
demineralization,
reverse osmosis (RO).
Figure 2 Field erected water tube industrial boiler.
Boiler and Feedwater Treatment 2973
Clarification is used to reduce the suspended solids
of the water; cold lime, hot lime, and zeolite softening
are used to reduce only the hardness, that is, the
calcium and magnesium content of the water; reverse
osmosis (RO) and demineralization are used for a
more effective reduction of the total dissolved solids
content of the water.
When precipitating processes for hardness
removal such as cold or hot lime softening are used
as pretreatment, the effluent water pH is inherently
high, in excess of a pH of 10.0. pH control is a very
important aspect of water treatment to protect
the materials of construction of these systems.
A secondary benefit of these precipitation processes
is the partial reduction of the waters silica content.
When these precipitating processes are used to
reduce water hardness, it is important to remember
to measure the total hardness of the effluent water.
This involves an acid digestion step, as opposed to the
normal soluble hardness tests, since there can be
suspended solids of hardness in the effluent from
these systems that the soluble hardness test would
not detect and must be accounted for in the chemical
treatments applied.
2974 Environmental Modification

Steam drum

Reheat
Platen superheater
secondary
superheater
Primary
Secondary superheater
superheater

Economizer
Wing
walls

Furnace
Overfire
SCR
air ports
Low NOx
burners

Trisector
air heater

B&W roll wheelTM Forced Primary

pulverizers draft fans air fans

Figure 3 Natural circulation drum type utility boiler.

Softened makeup water is generally acceptable
for lower-pressure boiler systems. Higher-pressure sys-
tems will require more purified water such as that
treated by RO or a demineralization processes. A high
percentage of condensate return in the feedwater can
also produce high-purity feedwater.
Zeolite softening, an ion exchange process using
strong acid cation resin in the sodium form, can also
be used to remove the hardness from the water. This
process can be applied in conjunction with one of
the precipitating softening processes or alone. Ion
exchange softening can also include a dealkalizer for
the alkalinity reduction of the makeup water. This is
typically done using anion resin in the chloride form,
but several configurations are possible.
Conventional ion exchange demineralization of
makeup water typically involves a two-bed deminer-
alization system. Most common is a strong base cat-
ion resin bed in the hydrogen form, followed by a
strong base anion bed in the hydroxide form. There
may or may not be a decarbonator in between.
There are many configurations of these systems
available, which vary from cocurrent to counter cur-
rent regeneration configurations. They may also
include alternative resin types, weak acid resin, or
weak base resin with multiple cation and anion units,

depending on the starting water composition, the
final desired water purity and local economics. For
the highest water purity requirements, a mixed-bed
resin unit is applied at the end of the process.
RO, a membrane-based water purification system,
can be used to reduce the total dissolved solids con-
tent of the water. There are numerous configurations
of the RO process available that can be chosen based
on the waters composition to be treated, the level of
effluent purity required versus the percentage of
recovery required and the local economics of chemi-
cal cost, power cost, and labor cost. The details of
these systems are beyond the scope of this chapter
and will not be addressed in this chapter. The reader
is directed to numerous literature sources available
on these topics for specific information.
RO, a semipermeable membrane process, red-
uces the dissolved substances in water, but this
removal is not complete, and effluent or permeate
may not yet be suitable for boiler makeup water.
A conventional mixed-bed resin polisher, electrodi-
alysis (ED), or some modification of this process can
follow the RO.
ED is a membrane process in which mineral salts
and other ions are transported through ion-perme-
able membranes from one solution into another
under the influence of a direct current electrical
potential. Electrodeionization (EDI) is a modification
of the ED process that combines ED with self-regen-
erating mixed-bed ion exchange resins installed
between the membranes. Electrodialysis reversal
(EDR) is another modification of ED in which the
electrical field is periodically reversed to provide a
self-cleaning process that can run at increased recov-
ery rates.
Though these electrochemical processes are avail-
able commercially and are capable of producing
high-purity water, they are rarely used in the boiler
makeup water treatment application and are more
likely to be seen in the microchip manufacturing
industry. Conventional mixed-bed resin deionization
is much more common in the production of high-
purity boiler makeup water.
4.28.3 Feedwater Treatment
Corrosion protection in the feedwater system is gen-
erally achieved by mechanically and chemically
removing dissolved oxygen from the feedwater and
buffering the feedwater pH into a range suitable for
the system materials of construction. Feedwater must
Boiler and Feedwater Treatment 2975
generally be deaerated for industrial steam boiler
applications, but there are special circumstances in
which full deaeration is not recommended. These are
discussed separately.
4.28.3.1 Dissolved Oxygen Control
Dissolved oxygen removal from the feedwater is typ-
ically accomplished in a deaerating heater or deaera-
tor in which steam is used to remove the dissolved
oxygen from the feedwater. Each of these pieces of
equipment has its own dissolved oxygen removal
efficiency. In some very low-pressure applications,
there may only be a feedwater tank in which makeup
water and condensate are mixed, which may or may
not be actively steam sparged or otherwise heated to
try to remove the dissolved oxygen.
The goal of the mechanical deaeration process is
to reduce the dissolved oxygen content of the feed-
water to less than 7 ppb for a system using a true
deaerator. Dissolved oxygen in the feedwater can
cause pitting corrosion damage of the feedwater sys-
tem components. More complex feedwater systems
can include both low- and high-pressure feedwater
heaters in addition to an economizer.
Additionally, vacuum degasifiers or deaerating
condensers can be used for dissolved oxygen removal.
Recently, a semipermeable membrane process6 has
also been developed to reduce the dissolved oxygen
content of water. These membrane systems have been
used in laboratory environments for more than
25years but have only recently become commercially
feasible for industrial applications. This membrane
process can use a combination of vacuum and strip-
ping gas arrangements to deaerate the water. The
membrane modules can be arranged in series to pro-
duce ppb level oxygen concentrations in the final
water. These membranes, dependant on the pH of
the water, can also remove carbon dioxide. RO pre-
treatment is recommended ahead of the gas mem-
brane to prevent fouling. A conventional deaerator
also provides only limited removal of carbon dioxide,
based on the pH of the water.
After any of these mechanical/thermal deaeration
processes, a chemical oxygen scavenger can be
applied to further reduce the dissolved oxygen con-
tent of the feedwater (Table 1).
Sodium sulfite is the most common chemical
oxygen scavenger used in low-pressure boiler sys-
tems. It is also available in a catalyzed form, which
increases the speed of reaction with the dissolved
oxygen. This can be important when the mechanical
2976 Environmental Modification

Table 1 Oxygen scavengers used in steam-generating systems

Scavenger Primary reaction Comments

Hydrazine N2H4 + O2 ! 2N2 + 2H2O Toxicity and handling issues

Hydrazine decomposition 3N2H4 ! 4NH3 + N2 At temp. >200  C
Sodium Sulfite 2Na2SO3 + O2 ! 2Na2SO4 Also NaHSO3, Na2S2O5,
NH4HSO3
Carbohydrazide (H2N-NH)2CO + 2O2 ! 2N2 + Forms hydrazine at temp.
3H2O + CO2 >150  C, NH3, N2, and H2 on
decomposition
N,N-Diethylhydroxylamine 4(CH3CH2)2NOH + 9O2 ! Frequently fed with hydroquinone,
8CH3COO + 9H+ + 2N2 + 6H2O acetic acid, CO2, acetaldehyde,
NH3 at temperatures above
275  C
Hydroquinone C6H4(OH)2 + 1/2O2 ! C6H4O2 + Acetates, CO2 decomposition
H2O products, toxicity issues
Erythorbate C6H4 O6 + 1/2O2 ! C6H5O8 + H2O CO2, lactic acid, decomposition
products
Methyl ethyl ketoxime 2CH3(C2H5)CNOH + O2 ! N2O + Frequently fed with hydroquinone,
2CH3(C2H5)CO + H2O NH3, CO2, ketones, aldehydes
on decomposition

deaeration process does not provide sufficient resi-
dence time. Sodium sulfite is a nonvolatile inorganic
compound that does contribute dissolved solids to
the feedwater and the boiler water. This dissolved
solids contribution prevents its use in feedwater that
is to be used as attemperator spray or desuperheat
spray for steam temperature control, as these solids
would become impurities in the steam.
The control of sodium sulfite is generally based on
maintaining a sulfite residual concentration in the
boiler water. This can be a problem in a system
where the feedwater system deaeration process and
chemical injection point do not provide sufficient
residence time and temperature for the chemical
oxygen scavenging reaction to be completed prior
to the feedwater entering the steam drum of the
boiler. Oxygen scavengers and dissolved oxygen can
coexist in the feedwater, in such a situation, pitting
corrosion can occur. Because of the dissolved oxy-
gens high volatility, the oxygen preferentially goes
into the steam phase when the feedwater enters the
boiler steam drum, leaving the unreacted sulfite
residual in the boiler water.
Another point of oxygen ingress into the sys-
tem not to be overlooked is a leak path through
the boiler feed pump seals. It is wise not only to
monitor the temperature and pressure operating
conditions of the deaerating device for proper opera-
tion but also to periodically measure the feedwater
dissolved oxygen content directly at the boiler or
economizer inlet.
Sodium sulfite can also produce some acidic gas-
eous decomposition products, such as sulfur dioxide,
that will be carried out of the boiler in the steam. This
can be significant at boiler operating pressures above
4.1 MPa g (600 psi g). These decomposition products
can cause low steam condensate pH.
Hydrazine is another available oxygen scavenger
that has been used primarily in higher-pressure
boiler applications. It is a volatile compound that
can be used in feedwater that is used for steam
temperature control by attemperation or desuper-
heating. However due to its status as a suspect car-
cinogen, its use in industry has declined. When it is
used, a closed feed system is typically required.
Given these health concerns, alternatives to
hydrazine have been developed. The most common
of these are carbohydrazide, erythorbate, diethylhy-
droxylamine, hydroquinone, and methylethyl ketox-
ime. Many of these oxygen scavengers also function
as passivating corrosion inhibitors. Each is an organic
compound that has its own temperature limitations.
Decomposition products can vary from only carbon
dioxide to several organic acids and other organic
compounds. Some decomposition products are more
undesirable than others, and the amount of these
decomposition products can be application-specific,
depending on system temperatures and metallurgy.
Each application should be evaluated based on the
benefit provided versus the potential undesirable
effects of the decomposition products. As a note,
commercially available erythorbate can be either in

the acid form or in the sodium salt form. The sodium
salt form is nonvolatile, which restricts its use if the
feedwater is used as spray attemperation or in
desuperheating.
4.28.3.2 pH Control
Feedwater pH adjustments to slightly alkaline condi-
tions are used to minimize corrosion of the feedwater
system piping and components, and the resultant cor-
rosion product transport to the boiler. Caustic, neu-
tralizing amines or ammonia are commonly used for
this task. Obviously, caustic cannot be used where the
feedwater is used as spray attemperation for steam
temperature control. The more common amines in
use are morpholine, cyclohexylamine, monoethanola-
mine, diethanolamine, and methoxypropylamine.
4.28.3.3 All Volatile Treatment (Reducing)
(AVT(R))
The feedwater target pH range is a function of the
feedwater system metallurgy. In the past, a target pH
range of 8.89.2 had been specified for feedwater
systems containing mixed metallurgy typically
heat exchanger components constructed of copper
alloys. Recent work79 has shown that reducing con-
ditions in the feedwater system, an oxidation
reduction potential (ORP) of 300 to 350 mV at
25  C (77  F), measured between a Pt electrode and a
Ag/AgCl (saturated KCl) reference electrode, at the
deaerator inlet, are necessary to minimize copper
corrosion and corrosion product transport in these
mixed-metal feedwater systems. This work showed
that the feedwater pH is a secondary control param-
eter, which should be restricted to a pH range of
9.09.3. EPRI has used the terminology AVT(R), all
volatile treatment (reducing) to describe this treat-
ment chemistry. In practice, many systems are not
able to reach these low levels of ORP, but copper
corrosion and copper corrosion product transport have
been successfully reduced in some systems with feed-
water ORP levels of even 200 to 100 mV at 25  C
(77  F), measured between a Pt electrode and a
Ag/AgCl (saturated KCl) reference electrode.
This treatment chemistry is expected to reduce
corrosion production transport to the boiler system
for all operating pressure boiler systems, but is most
critical for the very high-pressure boiler systems used
by the electric utility industry, where at their
operating pressures (>16.4 MPa g (>2400 psi g)),
Boiler and Feedwater Treatment 2977
copper has volatility properties into the high-pressure
saturated steam and has caused deposition problems in
the high-pressure steam turbine. This deposition in
the steam turbine can limit steam throughput and
megawatt output. Although the consequences of high
copper corrosion product transport to most industrial
boiler systems are not as dire as in the very high
pressure electric utility boiler systems, only more fre-
quent chemical cleaning of the boilers may be
required; this new information on copper corrosion
and strategies to minimize it should also be applied
to industrial mixed metallurgy feedwater systems.
Theoretically these reducing conditions should be
maintained by lay up practices even when the system
is out of service, to prevent the reversion of the more
protective, more reduced form of copper oxide,
cuprous oxide, Cu2O, formed in service, to the
more oxidized and less protective form of copper
oxide, cupric oxide CuO. Based on the actual circum-
stances of the out-of-service period, it may not be
practical to maintain a reducing environment.
This work7,8 also showed that the desired reducing
environment could not be achieved by the addition
of excessive amounts of a chemical reducing agent
such as an oxygen scavenger to compensate for a
mechanical problem in the system such as a malfunc-
tioning DA or high levels of air in leakage into a
condenser or hotwell.
For an all-steel metallurgy feedwater system, the
feedwater pH target range is somewhat more alkaline
pH 9.39.6. For most industrial boiler feedwater
systems, definitely those with softened water make up
even those with demineralized make up water or high
percentages of condensate return, it is still advisable
to fully deaerate the feedwater and treat the system
with a chemical oxygen scavenger to prevent dis-
solved oxygen pitting corrosion damage to the feed-
water system components, as previously discussed.
4.28.3.4 Flow Accelerated Corrosion
In boiler systems in dedicated electric utility service,
where the typical percentage of condensate return in
the feedwater is over 95%, the feedwater most likely
will be pure enough to make the system susceptible
to flow accelerated corrosion (FAC) damage.1013
FAC is a corrosion mechanism that can cause cor-
rosion damage and failures in feedwater systems in-
cluding economizers, feedwater heaters, and piping.
EPRI has compiled a significant amount of informa-
tion on this topic as it relates to boiler systems in
dedicated electric utility service.14
2978 Environmental Modification
FAC is a very localized damage mechanism that
affects predominantly areas of flow turbulence in the
feedwater system. It is a primarily hydrodynamic
phenomenon that prevents the formation of the nor-
mal protective oxide (magnetite) coating to form on
carbon steel and prevent any further metal loss. FAC
is a process whereby the normally protective oxide
surface dissolves into a moving fluid. The most sus-
ceptible systems are typically all-steel, and employ
very high-purity feedwater, due to the purity prereq-
uisite of the steam purity required by the steam
turbine in these systems. A significant amount of
research has been done on this topic in power plants
and is very well documented.14 FAC is possible at a
water temperature range of 100250  C (212482  F),
but there seems to be a maximum susceptibility at
about 150  C  28  C (300  F  50  F). Even though
FAC is primarily a hydrodynamic phenomenon, those
mechanical parameters that control velocity and tur-
bulence are fixed and not easily changed in an existing
system. The research work has identified two water
chemistry parameters that influence FAC behavior
that can be optimized feedwater pH and ORP.
4.28.3.5 All Volatile Treatment (Oxidizing)
(AVT(O))
EPRI has developed a feedwater treatment philoso-
phy for boilers in the electric utility service industry
that has been termed AVT(O),4 all volatile treatment
(oxidizing), to minimize the potential for FAC in
these systems. With AVT(O) treatment, no chemical
oxygen scavenger is fed and a nominal amount of
dissolved oxygen, (typically <10 mg l1, <10 ppb) is
considered acceptable. This is expected to result in
an ORP of 50 to 50 mV, measured between a Pt
electrode, and a Ag/AgCl (saturated KCl) reference
electrode. This condition is considered less suscepti-
ble to FAC than the completely oxygen deficient-
reducing conditions of AVT(R) in this high-purity
feedwater. Feedwater cation conductivity required for
AVT(O) is less than 0.2 mS cm1.
All the discussion on ORP measurement of feed-
water up to this point has been regarding the measure-
ment of the ORP of a sample cooled to room
temperature, 25  C (77  F). Room temperature ORP
measurements have had problems with a lack of sensi-
tivity and response. The capability to measure the
feedwater ORP at system temperature has
been developed, AT ORP (originally known as
@T ORP).15,16 The potential is measured against
an external pressure balanced reference electrode
(Ag/AgCl//0.1 N KCl). This technology is much
more responsive to system changes that affect ORP.
These at temperature ORP measurements can be made
at feedwater temperatures up to 260  C (500  F).
Feedwater pH is another chemistry parameter that
affects FAC, and for an all-steel feedwater system,
typically the more alkaline the better (pH > 9.2 up to
about 10.0). Even though the feedwater system may
be all-steel, there may be a copper alloy condenser
that could limit the feedwater pH adjustment to
prevent yellow metal attack of the condenser that
can occur when ammonia is the alkalizing agent or
a decomposition product.
This near-neutral ORP control, AVT(O), is quite
acceptable for high-purity boiler feedwater systems
such as those in the electric utility industry, in which
the level and consistency of feedwater purity is
high. Industrial boiler feedwater systems employing
high-purity feedwater are also potentially susceptible to
FAC, but the possible chemistry-related corrective
actions are not nearly as clear. In industrial boiler
systems, even when make-up water is demineralized, the
required level of purity for this treatment <0.2 mS
cm1 is rarely achieved. Additionally, because of the
lower percentage of condensate return and the very
significant potential for constant low levels and periodic
high levels of contamination, feedwater purity can be
very inconsistent. For these industrial systems, the
simultaneous presence in the feedwater of dissolved
oxygen and any feedwater contamination provides
the potential for oxygen pitting damage of the feedwater
system, especially heat exchanger components, such
as an economizer. From the existing research work, it
is unclear how pure feedwater must be in order
for dissolved oxygen to act as a corrosion inhibitor
rather than cause the pitting damage common in indus-
trial systems. From the experience with AVT(O) and
oxygenated treatment (OT), feedwater cation conduc-
tivity of <0.2 and <0.15 mS cm1 respectively are con-
ditions in which dissolved oxygen acts as a corrosion
inhibitor. But even the OT guidelines recommend
ceasing oxygen feed and going to an AVT(O) treatment
when cation conductivity exceeds 0.3 mS cm1. There
are no further guidelines for acceptable higher levels
of cation conductivity in the feedwater for AVT(O).
OT is discussed in the next section.
This FAC mitigating philosophy of AVT(O) near-
neutral ORP can also be accomplished in industrial
systems by feeding a very low level of one of the
available organic oxygen scavengers/passivators. In
this treatment scheme, the oxygen scavenger/passiva-
tor is not fed in the stoichiometric ratio to scavenge the

dissolved oxygen but rather is fed at a rate to passivate
the steel and provide the neutral ORP target. The
feedwater concentration needed to accomplish this
ORP is unique to each of the scavengers (hydroqui-
none, erythorbate, carbohydrazide, diethylhydroxyla-
mine, methylethyl ketoxime). In this treatment, when
there is an excursion in the chemistry or dissolved
oxygen concentration due to mechanical problems,
the scavenger feed is able to compensate. We note
that sodium sulfite, although it is an oxygen scavenger,
cannot be used for this purpose, as it does not appear
to have any passivating properties for steel.
Finally, monitoring feedwater ORP does not supply
quantitative information regarding FAC, only qualita-
tive information. It has been found that measuring the
soluble iron concentration of the feedwater1719 at
various points in the system can provide more quanti-
tative information regarding FAC. Given that FAC is a
very localized damage mechanism related to flow tur-
bulence, it is important to sample the feedwater before
and after a feedwater system component with a large
surface area subjected to local flow turbulence for this
soluble iron testing. Such a component is typically an
economizer or feedwater heater with heat transfer
surfaces constructed of carbon steel. Detecting a sig-
nificant increase in the soluble iron content of the
feedwater between the inlet and outlet indicates a
potential for FAC in the system. Then optimizing
feedwater treatment chemistry parameters (feedwater
pH, ORP/oxygen scavenger feed) individually and
reviewing their impact on the change in feedwater
soluble iron content demonstrates the potential impact
that feedwater chemistry changes can have on FAC in
the feedwater system.
As soluble iron in the water is relatively unst-
able, soluble iron determination requires careful sam-
ple handling to minimize the potential to oxidize
the soluble iron in the sample. Feedwater dissolved
oxygen content should be less than 20 ppb, and it has
been found that it is best to take the sample directly
into the reagent to preserve the iron in the soluble
state. There have been a number of different ferroin
compounds used to determine iron spectrophotomet-
rically.17,18 One of the most widely used compounds
is 3-(2-pyridyl)-5-6-bis (4-phenylsulfonic acid)-1,2,
4-triazine, monosodium salt. The test procedure in-
volves collecting samples directly into an acid-cleaned,
iron-free container containing the ferroin reagent.
Stainless steel sample lines are required.
Even though this soluble iron testing gives a more
quantitative picture of the FAC susceptibility of a
system and this information can be used to optimize
Boiler and Feedwater Treatment 2979
feedwater chemical treatment, it cannot identify a spe-
cific feedwater system component that could be experi-
encing a particularly high local rate of FAC damage.
For this reason, it is still recommended that such a
system have periodic nondestructive testing performed
on susceptible components (tees, elbows, piping, down-
stream of valves, flow orifices, etc.) especially those that
are in the more prone temperature environment, with
water at 150  C  28  C (300  F  50  F).
It has been found that in most cases, feedwater
chemistry optimization has been able to reduce FAC
rates in high-purity industrial boiler feedwater systems
prone to FAC but not eliminate them, even in some
cases where the treatment has been converted to
AVT(O). But as the research work10 on FAC has
shown, commercially available low-chrome alloys
(>1% chromium content) are much less susceptible to
FAC than carbon steel. Replacing a carbon steel compo-
nent found to be thinning due to FAC with one of these
low-chrome alloy alternatives has eliminated future
FAC damage in all but the most extreme situations.
4.28.3.6 Oxygenated Treatment
2025
OT is a feedwater treatment developed for once-
through boilers in the electric utility industry in
Germany in the 1960s. Prior to OT, these boilers
were treated with all volatile treatment (AVT) using
ammonia and hydrazine. With this conventional AVT
treatment, these boilers required frequent chemical
cleaning to prevent the accumulation of corrosion
products from the feedwater system (primarily iron
oxide) in the boiler. These deposits caused pressure
drop increases in the boilers flow circuitry and
insulating deposits on high heat transfer areas of the
boiler, which could lead to overheating damage.
A once-through boiler is an inherently high-purity
feedwater system, since the feedwater purity must
meet the steam turbines steam purity requirement.
Most of the once-through boilers in Germany operate
at subcritical pressures, whereas most of the once-
through boilers in the United States operate at super-
critical pressures. Most of these systems have all-steel
feedwater systems and full-flow condensate polishing.
In these systems, it was found that low levels of
dissolved oxygen added to this high-purity feedwater
acted as a corrosion inhibitor, producing a more
protective oxide on the steel than conventional AVT.
This reduced corrosion product transport to and accu-
mulation in these boilers. Most of the once-through
boilers in operation worldwide today have now been
converted to OT. Some boilers on OT treatment in
2980 Environmental Modification
Germany have never required chemical cleaning.
Once-through boilers in the United States that have
converted to OT have significantly extended the time
required between required chemical cleanings.
Typical control parameters for OT are a feedwater
cation conductivity of less than 0.15 mS cm1; feed-
water pH and dissolved oxygen can be controlled by
either what is termed the neutral method, which
involves maintaining the pH in the range of pH 78
and a dissolved oxygen content of 50250 mg l1
(50250 ppb), or the combined method in which the
feedwater pH is 89 and the dissolved oxygen con-
tent is 30150 mg l1 (30150 ppb). Only ammonia
can be used in this treatment as the alkalizing treat-
ment chemical; dissolved oxygen degrades the more
complex amines, increasing the cation conductivity.
OT is only occasionally used on high-pressure
drum-type boilers because they rarely have the pre-
requisite feedwater system metallurgy and the consis-
tent level of feedwater purity required, which typically
requires a full flow condensate polishing system.
Finally, the required chemical cleaning requirements
for drum-type boilers that do meet the metallurgy and
feedwater purity requirements are already quite long;
therefore, OT does not provide the same economic
benefit as it does to once-through boilers. OT for these
drum boilers could provide a benefit regarding FAC
potential in their feedwater systems, but this benefit is
also provided by the AVT(O) feedwater treatment.
4.28.4 Boiler Water Treatment
4.28.4.1 Residual Phosphate Treatment
Boiler water internal treatment options are depen-
dant on the type of makeup water pretreatment,
percent condensate return, and boiler operating pres-
sure. For softened makeup water systems, one of the
most common internal treatments is residual phos-
phate treatment, a precipitating treatment for the
hardness contaminants in the feedwater.
This treatment chemistry is designed to purpose-
fully precipitate the feedwater hardness contaminants
into more desirable, less adherent forms than if they
precipitated on their own in the boiler due to their
retrograde solubility characteristics. The intent is
to precipitate calcium as basic calcium phosphate
and magnesium as magnesium hydroxide by main-
taining an appropriate boiler water orthophosphate
residual and a free hydroxide concentration. The
orthophosphate concentration must be measured on
a filtered boiler water sample.
A synthetic organic polymer or naturally occur-
ring organic material such as lignins or tannins may
be used to help disperse the resultant precipitated
suspended solids. The precipitated calcium and mag-
nesium contaminants, though in a more desired form,
are still difficult to remove from an operating boiler
via the continuous blowdown. This is because they
are entrained in the boilers internal circulation
between the downcomer and riser circuitry, which is
many times the flow rate of the steam that the boiler
actually produces. This circulation continually passes
the particulates past the high heat transfer areas of
the boiler, where they can form deposits. Suspended
solids caught up in the boilers internal circulation
are also not removed very effectively by a boilers
intermittent blowdown system (mud drum blow-
down), if the boiler has this capability. Because of
the limited effectiveness of the boiler blowdown sys-
tems in removing suspended solids, the success of
residual phosphate treatment is very much depen-
dent upon minimizing the hardness contaminants in
the feedwater and potentially cleaning the boiler,
chemically or mechanically, periodically, to control
deposit accumulation in the boiler.
Residual phosphate chemistry is controlled by
maintaining an orthophosphate residual in the boiler
water that is chosen as a function of the boilers
operating pressure, Table 2. Free hydroxide levels
in the boiler water are typically maintained at a level
of three times the boiler water silica concentration to
aid in maintaining silica mineral solubility in the
boiler water. In higher-pressure boiler applications
(>4.1 MPag (>600 psi g)) where volatile silica trans-
port into the saturated steam is a concern, or any-
time the steam being produced is for use in a
condensing steam turbine, maximum boiler water
silica concentrations are maintained to limit the silica
concentration in the saturated steam to the speci-
fied limit for the turbine (typically 1020 mg l1
(1020 ppb)) silica in the steam).
4.28.4.2 Steam Purity
Boiler water total dissolved solids are maintained at or
below a maximum value to control the overall purity
of the saturated steam required. More stringent steam
purity limits are required for that steam when it is to
be used in a condensing steam turbine application as
opposed to a process heating application. With the
exception of silica, which has vaporous solubility char-
acteristics in saturated steam, all other nonvolatile
species of concern in boiler applications at less than
 Boiler and Feedwater Treatment 2981

Table 2 Typical control limits for residual phosphate treatment

Boiler water component (ppm) Drum pressure (psi g; MPa g)

150 (1.0) 300 (2.1) 600 (4.1) 900 (6.2)

a
TDS (max) 4000 3500 3000 2000
Phosphate (as PO4) 3060 3060 2040 1520
Hydroxide (as CaCO3) 300400 250300 150200 120150
Sulfite 3060 3040 2030 1520
Silica (as SiO2) maxb 100 50 30 10

a
The limits on TDS will vary with the design of the boiler and with the needs of the system with regard to steam purity.
b
Example silica values are listed but if silica volatility is a concern, such as condensing steam turbine applications, available pressure
dependant and pH dependant control curves on boiler water silica concentration should be used. Silica may be carried at higher levels if
there are no condensing turbines in the cycle. In any case, maintain an OH/SiO2 ratio of at least 3/1 to inhibit silica deposition.

13.7 MPa g (2000 psi g) end up in the steam as a result 4.28.4.3 Chelant Treatments
of mechanical carryover of boiler water droplets that
Realizing the shortcomings of residual phosphate
pass through the mechanical separating equipment in
chemistry in the way it handles feedwater hardness
the steam drum. Therefore, the steam purity is directly
contamination (precipitation), alternative treatment
proportional to the boiler water purity.
chemistries were developed.
The restrictions on boiler water total dissolved solid
The first was the use of chelants to solubalize the
limits to maintain the same steam purity do vary with
hardness contaminants. The most common chelants
boiler operating pressure and are more restricted at
used were ethylenediaminetetraacetic acid (EDTA)
higher operating pressures because the mechanical
and nitrilotriacetic acid (NTA). Both EDTA and
steam/water separation process is more efficient when
NTA form soluble complexes with calcium and mag-
the density difference between the steam and water
nesium that are stable to relatively high temperatures,
phases is greater.
up to 6.8 MPa g (1000 psi g). The removal of hardness
Sodium salts and copper oxides, considered non-
contaminants from the boiler, now in a soluble form,
volatile at lower operating pressures exhibit volatility
are no longer limited by the continuous blowdowns
characteristics above 16.4 MPa g (2400 psi g). This
limited ability to remove suspended solids from the
mode of transport into the steam must also be con-
circulating boiler water. If the species in question is
sidered and controlled by the appropriate measures
soluble in the feedwater, remains soluble in the boiler
to maintain the desired steam purity.
water and is nonvolatile, the continuous blowdown
In addition, when attemperation is used for final
removes that species at 100% efficiency.
steam temperature control, the impact of that attem-
Theoretically, if the required stoichiometric ratio of
peration water on the final steam purity must also
chelant to hardness were maintained, there would be
be considered, in the design stage as well as while
no accumulation of hardness-based deposits in the
diagnosing steam purity problems. The potential
boiler. However in practice, there are variations
sources of attemperation water are feedwater (if it
in the level of hardness contaminants in the feedwater,
is pure enough), condensate and a sweetwater con-
and some overfeed must be applied continually to
denser. A sweetwater condenser is typically a shell
account for these variations. This overfeed is typically
and tube heat exchanger that condenses saturated
controlled to result in a small residual chel-
steam with incoming feedwater. That condensed
ant concentration in the boiler water above that
saturated steam is then used as attemperation water
required for the actual hardness. It was found that
for steam temperature control. Each of these sources of
this boiler water chelant residual must be controlled
attemperation water can be potentially contaminated
very tightly because high levels of the residual can
and impact on steam purity. A mud drum attemperator
result in corrosion of the boiler base material. This
may also be used for steam temperature control. This
corrosion is most likely to occur in areas of high
is typically a heat exchanger located in the mud
fluid velocity or turbulence in the boiler. For this
drum. By design, there is no intended contact between
reason, chelant residual control limits vary as a
the steam and the boiler water, but in the event of a
function of boiler operating pressure and range from
leak in the exchanger boiler water can contaminate
about 15 mg l1 (15 ppm). Chelants have been
the steam.
2982 Environmental Modification
applied at boiler pressures over 6.8 MPa g (1000 psi g)
early in their history but later were only commonly
applied up to about 2.7 MPa g (400 psi g) for EDTA
and about 6.2 MPa g (900 psi g) for NTA.
Today, chelants are rarely used for several reasons.
NTA is classified as a suspected carcinogen, the
potential corrosions problems, and challenges in
controlling the required residual level and alternative
treatment chemicals have been developed.
4.28.4.4 All Polymer Treatment
Technically, the ability of the chelant chemistry to
maintain the solubility of feedwater hardness con-
taminants is a much more effective way to control
hardness deposit accumulation in boiler systems
than residual phosphate treatment. Synthetic organic
polymer chemistries have been developed that also
have chelating abilities for hardness control. These
are based typically on polyacrylate or polymethacry-
late polymers. Such synthetic organic polymers can
be applied in what is termed an all-polymer treat-
ment, the purpose of which is the same as the chelant
chemistry: form a soluble complex with calcium and
magnesium and maintain that soluble complex at
boiler water conditions to allow for the efficient
removal of these contaminants from the boiler in
the continuous blowdown as dissolved solids. In addi-
tion to the ability of these polymers to maintain
soluble hardness contaminants, they are typically
anionically charged, whereas suspended solid con-
taminants such as iron oxide tend to be cationically
charged. The polymers also have the ability to dis-
perse particulate contaminants. This dispersion mini-
mizes their ability to agglomerate into larger particles
as well as adhere to the heat transfer surfaces of the
boiler. But as a suspended solid, there is still the same
physical limitation on the ability of the continuous
blowdown to remove even these dispersed contami-
nants from the boiler.
There are many synthetic organic polymers in use
in boiler water treatment. It is important to note that
not all of these polymers have chelant properties
relative to calcium and magnesium, and it is only
those that do that can be used as an all-polymer
treatment for feedwater hardness contamination.
And even those polymers that do have this chelating
ability must be of an appropriate molecular weight
for the boiler operating pressure and saturation tem-
perature to function as intended. Polymers that do
not have the chelant properties with respect to hard-
ness tend to act only as dispersants and therefore do
not have the same effectiveness in handling feedwater
hardness contamination.
Even though the polymers used in the all-poly-
mer technology have chelant properties, they are
much weaker chelants than EDTA or NTA. As
much weaker chelants, the need to control the excess
polymer residual relative to the hardness is much less
critical. However as with all solubalizing treatments,
the potential for corrosion of the boilers base material
must be recognized and an appropriate control strat-
egy used.
As there are many synthetic polymer treatments on
the market today and most are offered as proprietary
treatment chemistries by water treatment companies,
hopefully the end user can ask the appropriate ques-
tions based on the information provided, such as what
the purpose and abilities of their available products are
and what the control limits and control strategies are,
to decide while choosing between various offerings to
best meet his/her needs.
Polymeric dispersants are also used within other
treatment philosophies, such as in chelant treatments
to disperse iron oxide contaminants and in residual
phosphate treatment to disperse the resultant cal-
cium and magnesium precipitated suspended solids.
In these cases, however, the concentration of the
polymers to hardness is much less than the stoichio-
metric requirement to solubalize the hardness, and as
such they only act as a dispersant and do not compete
with the primary intended purposes of the chelant or
phosphate chemistry.
In industrial boiler systems, there have been many
mixed treatment chemistries that have had mixed
success chelant/polymer, chelant/phosphate,
polymer/chelant/phosphate, etc. There are too many
to address specifically.
4.28.4.5 Coordinated Phosphate
Treatment
In the past, it was more common to find high-purity
feedwater in only high-pressure boiler applications
>6.8 MPa g (>1000 psi g). Today the use of high-
purity makeup water in low-pressure boilers is much
more common.
Coordinated phosphate chemistry26 was devel-
oped as a response to caustic embrittlement failures
of boiler drums. In the early days of boiler water
treatment, prior to the development of efficient
make-up water pretreatment systems, coagulation
internal treatments were used. This type of treatment
used soda ash (Na2CO3) to precipitate the hardness

salt contaminants into the desired form and then
added organic materials (tannins and lignin) to con-
dition this precipitated material (sludge) where hope-
fully it would settle in the mud drum and be removed
from the boiler via the intermittent blowdown (mud
drum blowdown) practice.
The use of soda ash introduced high levels of alka-
linity, including free hydroxide or caustic alkalinity,
into the boiler water, and at that time boiler drums
were constructed by riveting rolled sections of steel
plate together. These mechanical joints were prone to
leaking. When a leak did occur, the leaking boiler water
containing free hydroxide would flash to steam, result-
ing in very high local caustic concentrations at the site
of the leak. Carbon steel is susceptible to stress corro-
sion cracking failure when it is highly stressed and in
contact with high concentrations of caustic. The geom-
etry of the riveted construction provided a location of
stress concentration, and the flashing boiler water
provided the environment that resulted in the potential
for stress corrosion cracking or caustic embrittlement
failure of the steel. In the early days of boiler water
treatment, these embrittlement failures and sometimes
resultant boiler explosions were not uncommon, and
there were fatalities. Coordinated phosphate chemistry
control was developed as a chemical solution to this
problem. Coordinated phosphate chemistry balances
the boiler water pH and orthophosphate concentration
to a maximum Na:PO4 molar ratio of 3.0:1 to theoreti-
cally prevent the formation of free hydroxide in the
boiler water. For control, a minimum Na:PO4 ratio of
2.2:1 is chosen to buffer low pH concerns. It is
10.7
10.5
10.3
10.1
9.9
9.7
9.5
9.3
pH
9.1
8.9
8.7
8.5
8.3
8.1
7.9
7.7
7.5
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42
Total Orthophosphate as PO4, ppm (mg l1)
Na/PO4 = 3.0 Na/PO4 = 2.8
Na/PO4 = 2.30 Na/PO4 = 2.20
Figure 4 pH vs. PO4 graph at different Na/PO4 molar ratios.
Boiler and Feedwater Treatment 2983
important to note that the Na:PO4 molar ratio used in
this treatment as well as the other high-purity phos-
phate chemistries is not determined by directly mea-
suring both the boiler water sodium and phosphate
concentration and calculating the ratio but rather is
determined by measuring the boiler water pH and
orthophosphate concentrate and then plotting that
data on a graph similar to Figure 4.
The reason for this is that in most boiler systems,
there are neutral sodium salts present that do not
affect the boiler water pH. There can also be con-
taminants in the makeup water such as organic mate-
rials that can decompose to form organic acids in the
boiler water, affecting boiler water pH but with no
contribution of sodium.
With this in mind it is also important to realize that
what affects the boiler water pH and phosphate
relationship is that which is added intentionally as
the treatment chemicals and that other contaminants
may concentrate in the boiler water and affect pH
(organic materials in the makeup water or sodium
leakage [NaOH] from the make up demineralizer).
Sodium salts of various phosphate species and
sodium-to-phosphate molar ratios and sodium hydrox-
ide may have to be used to buffer the pH into the
desired control range in these situations.
4.28.4.6 Congruent Phosphate Treatment
Caustic problems in boiler systems were not totally
alleviated by the adoption of coordinated phosphate
chemistry. This was thought to be due to the
Control vectors
NaOH Na PO
3 4
Na2HPO4
Blowdown NaH2PO4
Na/PO4 = 2.60
2984 Environmental Modification
solubility characteristics of sodium phosphate salts
a characteristic known as incongruent precipitation.
Studies27 showed that precipitation of phosphate
from a high temperature (300  C, 572  F) sodium
phosphate solution having a Na:PO4 molar ratio
greater than 2.85:1 always results in an increase in
the Na:PO4 ratio of the remaining solution, toward or
further into the free caustic region above the 3.0:1
ratio boundary. Conversely, when phosphate is pre-
cipitated from a solution having a Na:PO4 ratio less
than 2.85:1, the Na:PO4 ratio decreases in the remain-
ing solution, further away from the free caustic
region. With a solution Na:PO4 ratio of exactly 2.85,
the Na:PO4 ratio in the precipitated phosphate solids
is identical, that is, congruent.
Subsequent studies showed that at higher tem-
peratures, the congruent point could be at a Na:PO4
ratio as low as 2.6:1. Again, control is based entirely on
the relationships of boiler water pH and orthophos-
phate concentration, endeavoring to keep their plot-
ted coordinates within the appropriate zones on a
control diagram (see Figure 1).28 Congruent phos-
phate29 then is a refinement of the original coordi-
nated phosphate treatment with new boundaries on
the Na/PO4 molar ratio; a maximum ratio of 2.6:1
and a minimum ratio of 2.3:1. The actual PO4 con-
centration control range is typically chosen based on
boiler operating pressure and the degree of control
capability in the plant and the consistency of feed-
water quality (purity). Generally, higher phosphate
control ranges (1020 mg l1 (1020 ppm)) at lower
boiler operating pressures and lower phosphate con-
trol ranges (510 mg l1 (510 ppm) at higher boiler
operating pressures are employed.
When the chosen PO4 control range is less than
2 mg l1 (2 ppm) in the boiler water, the effect of
ammonia or neutralizing amines must be taken into
account due to their effect on the boiler water pH
measurement at room temperature.
Even though boiler drums are constructed using
welded joints today, most industrial boilers operating
at less than 6.8 MPa g (l000 psi g) are constructed
with mechanical roll expanded joints to connect the
tubes between the steam drum and the mud drum.
Therefore, there is still the possibility of a local
caustic embrittlement failure of the drum if one
of these mechanical joints were to leak and the
boiler water contained free hydroxide. Congruent
phosphate chemistry provides a level of protection
for these boilers from this failure mechanism and
would be a preferred choice provided the feed-
water purity requirements are met and the boiler
is not experiencing phosphate hideout behavior
(see the following section) due to the congruent
phosphate treatment.
4.28.4.7 Phosphate Continuum Treatment
(Formerly Equilibrium Phosphate Treatment)
Congruent phosphate programs can be difficult to
control because of phosphate hideout.30 Phosphate
hideout is the simultaneous decrease in the phosphate
concentration of the boiler water and an increase in
boiler water pH during a load or heat flux increase.
Hideout return is the reverse during a load decrease
phosphate concentration increases and boiler water
pH decreases. Equilibrium phosphate control solves
this problem and has therefore gained acceptance with
electric utility drum boiler operators.
As phosphate hideout occurs, the phosphate con-
centration in the bulk boiler water is reduced down to
very low remaining equilibrium levels. The boiler
water phosphate might drop from a normal 5 mg l1
(5 ppm) down to 2 mg l1 (2 ppm) or even less during
hideout. Attempts to maintain the original boiler water
phosphate levels by adding phosphate during hideout
are usually futile, because ongoing hideout simply
continues to remove boiler water phosphate down to
the equilibrium level.
In the past, phosphate hideout had been thought
to be associated with the retrograde solubility behav-
ior and incongruent precipitation behavior of sodium
phosphates, but laboratory research work31 has
shown that phosphate hideout is actually the temper-
ature-dependent reaction of low Na:PO4 molar ratio
compounds in the boiler water with magnetite. These
reactions are significant when boiler water Na:PO4
molar ratios are 2.32.6:1, but are essentially nonexistent
when the boiler water Na:PO4 molar ratio is greater
than 2.85:1.
During phosphate hideout, phosphate wastage of
the boiler metal can result due to the concentration
of low Na:PO4 molar ratio materials in high-heat flux
zones. Maracite (NaFePO4) and/or Iron Phosphate
(FePO4) are the residual corrosion products found on
boiler tubes damaged by the phosphate wastage
mechanism.32
Phosphate hideout and phosphate wastage are more
likely at higher boiler operating pressures but are also
possible in lower-pressure boilers with high local heat
fluxes. Phosphate wastage corrosion predominantly
occurs in conventional boilers operating at greater
than 13.8 MPa g (2000 psi g), although it has been seen
in an industrial boiler operating at 6.9 MPa g

(1000 psi g) that was experiencing steam blanketing.
It is also common in vertical shell-and-tube steam
generators; these are commonly unfired process boilers
with flat tube sheets and deep oxide sludge deposits on
the tube sheet, which is generally at the inlet of the
highest process gas temperature. In addition, heat
recovery steam generators (HRSG) commonly used
in combined cycle plants with duct burners are also
prone to phosphate hideout and the potential for phos-
phate wastage, especially when duct burners are in use.
Equilibrium phosphate control30 makes no attempt
to carry boiler water phosphate concentration above its
hideout equilibrium level. Equilibrium phosphate levels
vary from boiler to boiler, depending on the severity of
hideout conditions and must be determined by testing
for each unit. EPRI has recently revised and renamed
the Equilibrium Treatment philosophy to what is
now termed Phosphate Continuum Treatment4 as illu-
strated in Figure 5. The maximum Na/PO4 ratio con-
trol boundary is a Na/PO4 equal to 3.0 plus 1 mg l1
(1 ppm) NaOH and the minimum Na/PO4 control
boundary is Na/PO4 3.0. Additionally, there is a
minimum pH 9.0 and a minimum boiler water ortho-
phosphate concentration of 0.2 mg l1 (0.2 ppm).
For mixed-bed makeup water systems with no
significant sodium leakage and low organic contami-
nation of the makeup and condensate, only trisodium
phosphate and caustic soda (when needed) are
recommended for Phosphate Continuum Treatment.
Monosodium, disodium, and polyphosphates should
10.2
10.0
9.8
9.6
pH at 25 C
9.4
9.2
9.0
8.8
8.6
0 1 2 3 4 5
PO4 (mg l1)
Figure 5 Phosphate continuum control chart.
Boiler and Feedwater Treatment 2985
not be needed. But for many industrial boiler systems
that can have significant sodium leakage from the
makeup system or significant organic contaminants
in the makeup water or condensate, a wide range of
Na:PO4 molar ratio treatment chemicals might be
required to maintain the desired control in a particu-
lar boiler system situation.
Phosphate continuum treatment does include the
presence of free hydroxide in the boiler water and
therefore does present the known concerns associated
with caustic in boilers. There is the potential for
under deposit caustic gouging in the boiler, the
potential for stress corrosion cracking of steam sys-
tem components in the event of boiler water carry
over and the potential for embrittlement damage to
the drums if the boiler has mechanical rolled tube
joints if one were to leak.
4.28.4.8 All Volatile Treatment
33,34
AVT helps achieve sufficiently high pH to protect
boiler steel without introducing any dissolved solids. It
is based on the use of entirely volatile, solid-free che-
micals, such as hydrazine or carbohydrazide for oxygen
scavenging, plus neutralizing amines or ammonia for
boiler water pH control. AVT may be used in drum
boilers that have the appropriate feedwater purity and
is the only program that can be used in once-through
boilers. In drum boilers, AVTmay be used for simplic-
ity where phosphate hideout has caused control
TSP + 2 PPM NaOH
TSP + 1 PPM NaOH
Na/PO4 = 3.0
Na/PO4 = 2.8
Na/PO4 = 2.6
Note:
1. Minimum PO4
> 0.2 (mg l1)
6 7 8 9 10
2986 Environmental Modification
problems on phosphate-pH control programs or where
ultra pure steam is required.
A disadvantage of all-volatile treatment for drum
boilers is that the boiler water is unbuffered and thus
subject to extensive and rapid pH excursions in the
event of feedwater contamination. Prompt detection
and remedial action is required in the event of any
feedwater contamination. A condensate polishing sys-
tem, either for continuous polishing or for start-up
and emergency polishing, is very desirable. Some uti-
lities do operate high pressure drum cycles on AVT
without the benefits of polishers, but their systems
have extensive instrumentation that allows immediate
remedial action to be taken in the event of cycle
contamination (including feeding phosphate until the
problem is resolved). A mixed-bed polisher is essential
in the makeup system.
The AVT program control is simple and highly
effective as long as feedwater quality is maintained.
Feedwater contamination of an otherwise solid-free
system produces undesirable effects immediately.
With essentially no buffering capacity in the system,
boiler water pH values can reach free acidity levels
(pH<4.3) very rapidly following contamination. This
is particularly true in systems using seawater or
brackish water for condenser cooling.
Cation conductivity measurements of the boi-
ler water are used to monitor any dissolved solids
contamination of the cycle. Cation conductivity is
also preferred for condensate and feedwater moni-
toring since it is very sensitive to changes in dissol-
ved solids concentrations and is not affected by
changing the amine or ammonia levels. Specific con-
ductance is used primarily to monitor the level of
ammonia or neutralizing amine present in the cycle.
Continuous pH monitoring of the boiler water is
desirable, as pH provides another indication of a
contamination problem. Boiler water pH values will
typically be lower than the feedwater pH because of
the volatilization of the amine or ammonia from the
boiler water; pH control in the feedwater cycle will
vary with cycle metallurgy.
4.28.4.9 Caustic Treatment
Sodium hydroxide alone can also be used as the solid
alkali in internal boiler water treatment for pH control.
It is a common practice in high-pressure drum boilers
in the United Kingdom, and many of these are high-
pressure drum boilers in the electric utility service
industry.4,35 A typical boiler water pH control range
is 9.09.4. Caustic can still be very corrosive to carbon
steel under concentrated conditions, such as under
porous metal oxide deposits on a boilers heat transfer
surfaces, and can cause under deposit corrosion dam-
age. It is therefore very important to keep the boilers
heat transfer surfaces clean by minimizing the feed-
water corrosion product transport into the boiler and
periodic chemical cleaning. There is also a concern
that chloride contamination may increase this corro-
sion potential, and individual operators have also
restricted boiler water chloride limits.
4.28.5 Condensate Treatment
Condensate is a very valuable commodity (resource)
in a boiler system, not only because of its energy
content but also because of its high purity. Therefore,
the more condensate that can be returned as part of
the boiler feedwater, the more efficient the econom-
ics are of operating the boiler system.
As condensate is very pure water, very small
amounts of contamination can render it extremely
corrosive and unsuitable as feedwater. One of the
more common contaminants that can depress the pH
of the condensate is carbon dioxide. Carbon dioxide
can originate from the bicarbonate alkalinity in the
makeup water, which decomposes at boiler operating
pressure, contributing the carbon dioxide to the steam
or from air in leakage into the system. The latter is most
likely to occur when the pressure in the condensate
system is at or below atmospheric pressure.
In addition, organic materials in the makeup water
can decompose in the boiler water, resulting in the
formation of low molecular weight organic acids such
as acetic, formic, and glycolic acids. These organic acids
have volatility characteristics that are a function of
pressure. All are considerably stronger acids than car-
bonic acid and will increase the demand for the neu-
tralizing amine treatment that is commonly employed
to neutralize acids and so elevate the condensate pH.
Hydrogen sulfide and sulfur dioxide, the products of
decomposition of the sodium sulfite oxygen scavenger,
that can occur at boiler operating pressures >4.1 MPa g
(>600 psi g), can also depress condensate pH and con-
tribute to the amine demand. Depressed pH conditions
of the condensate can cause significant corrosion dam-
age to condensate system components.
Dissolved oxygen either not removed by the
deaeration processes or that has leaked into the sys-
tem at points where the pressure is at less than

atmospheric pressure can also cause corrosion dam-
age in the condensate system.
Ammonia can also be considered a contaminant in
the condensate if there are copper alloys in the con-
densate system that can be attacked by the ammonia.
Chemically, four types of treatment are used for
condensate system corrosion control: ammonia or neu-
tralizing amines, filming amines, oxygen scavengers/
metal passivators, and nonamine filming treatment.
Neutralizing amines and ammonia are volatile,
alkaline compounds that are added to either the boiler
feedwater or the steam. They function by volatilizing
into the steam and redissolving into the condensate.
The amines and ammonia chemically neutralize the
carbonic acid or any other acid present in the conden-
sate. Then they raise the pH of the condensate to
minimize the corrosion of the materials of construc-
tion of the condensate system. The most common
neutralizing amines in use today are cyclohexylamine,
morpholine, diethylaminoethanol, methoxypropyla-
mine, and monoethanolamine. Each has a unique
volatility and basicity characteristic.
Industrial boiler systems can have very extensive
and complex steam/condensate systems. Complex
steam systems that operate at multiple pressure
levels, especially where high-pressure condensate is
flashed to produce additional low-pressure steam,
can concentrate a single treatment amine to one
part of the system while simultaneously depleting
its concentration in another part of the system due
to its unique single, pressure-dependent vapor-to-
liquid distribution ratio characteristic. This leads to a
situation in which some parts of the complex system can
be undertreated, even though from the pH measure-
ment of the combined condensate sample the system
appears to be sufficiently treated. The common solution
to this situation is the use of an amine treatment product
that may be a combination of multiple amines, each
with a different vapor-to-liquid distribution character-
istic. In the most complex steam systems, satellite feed to
a particular point in the system may still be required to
provide adequate corrosion protection. In a simple
steam condensate system such as the typical electric
utility situation, a single amine or ammonia may provide
adequate protection. But there have been many cases
where a low volatility amine or the industrial multiple
amine philosophies of treatment have provided better
protection as measured by a reduction in corrosion
product transport, in even the simple system.
Neutralizing amine treatment does not provide
protection for the system from dissolved oxygen
Boiler and Feedwater Treatment 2987
attack. The feed of an oxygen scavenger/passivator
to the condensate can protect the system against
dissolved oxygen attack. Sodium sulfite is typically
not used for this application since it contributes non-
volatile solids. More typically, one of the volatile
organic oxygen scavenger/passivator materials can
be used in this application. Preferably though, the
source of the oxygen in leakage should be found and
corrected.
There can also be situations in which the carbon
dioxide content of the steam is so high because of the
natural bicarbonate alkalinity of the makeup water,
and that treating the condensate with neutralizing
amine technology is prohibitively expensive. In this
case, a filming amine technology can be used. In the
filming amine treatment, the carbon dioxide is not
neutralized, but the filming amine forms a nonwetta-
ble barrier on the condensate system components
preventing the low pH condensate from coming
into contact with the materials. Filming amines also
provide protection from dissolved oxygen attack. The
amount of filming amine required is related to the
surface area of the system. Octadecylamine is a com-
monly used filming amine. Filming amines have the
ability to move corrosion products from the surface
of the piping. It is therefore advisable to start with
low dosages, which are gradually increased until
residual limits are met. There are also proprietary
filming amines.
There may be restrictions on amine concentrations
in steam when there is contact of that steam with food or
food products, when the steam is used for humidifica-
tion of air or when it can contact certain catalysts used
in industrial processes. A nonamine filming corrosion
inhibitor technology36 has been developed for when
there is a prohibition on amines in the treated steam.
There are also mechanical means of treating con-
densate to remove contaminants and preserve its purity
for reuse. If corrosion products typically iron oxides
and copper oxides exist as suspended solids in the
condensate, they can be filtered out. Cartridge filters
can be used. Condensate polishers, an ion exchange
process in which strong acid cation resin is in the
sodium or amine form in industrial situations, act pri-
marily as a filter but can also remove hardness that
may have come from cooling water contamination of
the condensate. In electric utility boiler situations
where condensate temperatures are considerably
lower, mixed-bed resin polishers (typically a mixture
of strong acid cation resin in the hydrogen form and
strong base anion resin in the hydroxide form) are used.
2988 Environmental Modification
These can be deep bed regenerable units or they can be
of the powdered resin, one-time-use type. In addition,
high gradient electromagnetic filters have been used to
remove corrosion products of iron and some copper
that are magnetic.
As a final alternative, contaminated condensate
can be discarded or diverted rather than returned to
the system. The condensate diversion system (con-
densate dumps) is a system of sensors, valves and
piping to detect the contamination of the condensate
and divert it to waste. These condensate diversion
systems must be properly engineered to detect and
divert the contamination in a timely manner to pre-
vent the contamination of the feedwater. This tech-
nique is only applicable to systems where the makeup
water system capacity can compensate for this lost
condensate.
4.28.6 Boiler Treatment During
Out-of-Service Conditions
Boilers constructed out of carbon steel and low chro-
mium alloys up to about 9% chromium content are
prone to corrosion at ambient temperatures in contact
with untreated, typically aerated, water. The maxi-
mum corrosion rate occurs where carbon steel is in
contact with a waterair interface. This waterair
interface occurs when an operating boiler is taken
out of service and the vents are opened to the atmo-
sphere during the cooling process and air displaces the
condensing steam. Even if the boiler is drained at this
point, depending on the boiler design configuration
there may be areas of the boiler that do not drain
completely. In addition, in many boiler designs that
incorporate superheaters and reheaters, heat transfer
surfaces can be of a pendant or other design config-
uration that is inherently nondrainable. Nondrainable
components require special treatment if a wet lay-up
method is employed. Water purity must be very high
condensate or demineralized quality and any treat-
ment chemicals used in the water must be volatile.
Guidelines37,38 are available for the proper treat-
ment of a boiler in the out-of-service condition. The
goal of the guidelines is to use a procedure that gener-
ally eliminates the airwater interface. This can be
accomplished in a number of ways by draining the
boiler under a positive nitrogen pressure or draining
the boiler and installing a desiccant, for example. The
appropriate procedure depends on many variables,
including the configuration of the boiler and the
expected duration of the out-of-service period.
4.28.7 Miscellaneous (But Important)
Comments
Proper sampling is a prerequisite of effectively mon-
itoring a system. Effective monitoring of the makeup
water, feedwater, boiler water, steam, and condensate
is necessary to control deposition and corrosion
within the system. No matter how accurate or precise
the analysis of a sample obtained is, if the sample is
not truly representative of the stream being sampled,
the results are useless.39 Effective monitoring
requires a proper sampling system, adequate sample
system purging, the required sample velocity, and
appropriate sample handling.40
A particular case in point is sampling steam to
determine its purity. Isokinetic sampling nozzles and
procedures are required.41 When sampling super-
heated steam, sample cooling considerations are espe-
cially important. The distance between the sampling
nozzle and the primary cooler must be minimized no
more than 7 m (20 ft) and any sample line length
between the nozzle and the cooler must be insulated.
The proper sampling and analysis of condensate is
especially critical, because of its inherent high purity
and the volatility characteristics of both the treatment
chemicals and some of the contaminants it might
contain.
A stainless steel injection quill must be used to
inject treatment chemical into the system. Concen-
trated treatment chemicals in contact with carbon
steel at elevated system operating temperatures pres-
ent a corrosive situation for the carbon steel.
A properly designed and installed chemical injection
quill admits the chemical into the fluid stream, so that
it is properly diluted in the stream.
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