Power Plants Steam Quality

The Babcock & Wilcox Company
Chapter 42
Water and Steam Chemistry,
Deposits and Corrosion
Steam generation and use involve thermal and

physical processes of heat transfer, fluid flow, evaporation, and condensation. However, steam and water
are not chemically inert physical media. Pure water
dissociates to form low concentrations of hydrogen and
hydroxide ions, H + and OH, and both water and
steam dissolve some amount of each material that they
contact. They also chemically react with materials to
form oxides, hydroxides, hydrates, and hydrogen. As
temperatures and velocities of water and steam vary,
materials may dissolve in some areas and redeposit in
others. Such changes are especially prevalent where
water evaporates to form steam or steam condenses
back to water, but they also occur where the only
change is temperature, pressure, or velocity. In addition, chemical impurities in water and steam can form
harmful deposits and facilitate dissolution (corrosion)
of boiler structural materials. Therefore, to protect
vessels, tubing, and other components used to contain
and control these working fluids, water and steam
chemistry must be controlled.
Water used in boilers must be purified and treated
to inhibit scale formation, corrosion, and impurity contamination of steam. Two general approaches are used
to optimize boiler water chemistry. First, impurities in
the water are minimized by purification of makeup
water, condensate polishing, deaeration and
blowdown. Second, chemicals are added to control pH,
electrochemical potential, and oxygen concentration.
Chemicals may also be added to otherwise inhibit scale
formation and corrosion. Proper water chemistry control improves boiler efficiency and reduces maintenance and component replacement costs. It also improves performance and life of heat exchangers,
pumps, turbines, and piping throughout the steam
generation, use, and condensation cycle.
The primary goals of boiler water chemistry treatment and control are acceptable steam purity and
acceptably low corrosion and deposition rates. In addition to customized boiler-specific guidelines and procedures, qualified operators are essential to achieving
Steam 41 / Water and Steam Chemistry, Deposits and Corrosion
these goals, and vigilance is required to detect early

signs of chemistry upsets. Operators responsible for
plant cycle chemistry must understand boiler water
chemistry guidelines and how they are derived and
customized. They must also understand how water
impurities, treatment chemicals, and boiler components
interact. Training must therefore be an integral, ongoing part of operations and should include management,
control room operators, chemists, and laboratory staff.
General water chemistry control limits and guidelines
have been developed and issued by various groups of
boiler owners and operators (e.g., ASME,1,2,3 EPRI4 and
VGB5 ), water treatment specialists6,7,8 utilities and industries. Also, manufacturers provide recommended
chemistry control limits for each boiler and for other
major cycle components. However, optimum water and
steam chemistry limits for specific boilers, turbines, and
other cycle components depend on equipment design
and materials of construction for the combination of
equipment employed. Hence, for each boiler system,
boiler-specific water chemistry limits and treatment
practices must be developed and tailored to changing
conditions by competent specialists familiar with the
specific boiler and its operating environment.
Chemistry-boiler interactions
To understand how water impurities, treatment
chemicals and boiler components interact, one must
first understand boiler circuitry, and steam generation
and separation processes.
Boiler feed pumps provide feedwater pressure and
flow for the boiler. From the pumps, feedwater often
passes through external heaters and then through an
economizer where it is further heated before entering
the boiler. In a natural circulation drum-type unit,
boiling occurs within steel tubes through which a
water-steam mixture rises to a steam drum. Devices
in the drum separate steam from water, and steam
leaves through connections at the top of the drum.
This steam is replaced by feedwater which is supplied
42-1

by the feedwater pumps and injected into the drum
just above the downcomers through a feedwater pipe
where it mixes with recirculating boiler water which
has been separated from steam. By way of downcomers, the water then flows back through the furnace
and boiler tubes. Boiler water refers to the concentrated water circulating within the drum and steam
generation circuits. Chapters 1 and 5 provide detailed
descriptions of steam generation and boiler circulation.
Boiler feedwater always contains some dissolved
solids, and evaporation of water leaves these dissolved
impurities behind to concentrate in the steam generation circuits. If the concentration process is not limited, these solids can cause excessive deposition and
corrosion within the boiler and excessive impurity
carryover with the steam. To avoid this, some concentrated boiler water is discarded to drain by way of a
blowdown line. Because the boiler water is concentrated, a little blowdown eliminates a large amount
of the dissolved solids. Since steam carries very little
dissolved solids from the boiler, dissolved and suspended solids entering in the feedwater concentrate
in the boiler water until the solids removed in the
blowdown (boiler water concentration times the
blowdown rate lb/h or kg/s) equal the solids carried in
with the feedwater (lb/h or kg/s).
A small amount of dissolved solids is carried from
the drum by moisture (water) droplets with the steam.
Because moisture separation from steam depends on
the difference between their densities, moisture separation is less efficient at high pressures where there
is less difference between the densities. Therefore, to
attain the same steam purity at a higher pressure, the
dissolved solids concentration in boiler water must
generally be lower.
In a drum boiler, the amount of steam generated is
small compared to the amount of water circulating
through the boiler. However, circulation is also largely
driven by the difference in densities between the two
fluids, so as pressure increases the ratio of water flow
to steam flow decreases. At 200 psi (1379 kPa), water
flow through the boiler must be on the order of 25,000
pph (3 kg/s) to produce just 1000 pounds per hour of
steam. Even at 2700 psi (18.6 MPa), 2500 to 4000 pounds
of water circulates to produce 1000 pounds of steam. By
contrast, most or all of the water entering a once-through
boiler is converted to steam without recirculation.
Some boiler operators have asked why boiler water concentrations change so slowly once a source of
contamination is eliminated and the continuous
blowdown rate is increased. How quickly can excess
chemical be purged from a boiler? How much impurity or additive is needed to upset boiler water chemistry? How quickly do chemical additions circulate
through the boiler? To answer these questions and
explore some other chemistry-boiler interactions, consider for example a typical 450 MW natural circulation boiler, generating 3,000,000 pounds of steam per
hour. It has a room temperature water capacity of
240,000 pounds and an operating water capacity of
115,000 pounds. The furnace wall area is 33,000
square feet, about 5800 of which are in the maximum
heat flux burner zone.
42-2
Impurities purge slowly from the boiler because the

boiler volume is large compared to the blowdown rate.
For example, at maximum steaming capacity with a
blowdown rate 0.3% of the steam flow from the drum,
17 hours may be required to decrease the boiler water concentration of a non-volatile impurity by 50%.
Almost two hours are required to effect a 50% reduction in the boiler water concentration even at a
blowdown rate of 3%. Without blowdown, dissolved
sodium with a fractional carryover factor of 0.1%
would have a half life of 52 hours. While long periods
of time are generally required to purge impurities,
mixing within the boiler is rapid. For the boiler being
used as an example, the internal recycle rate is about
one boiler volume per minute, and steam is generated
at a rate of one boiler volume every 5 minutes.
The rate of steam generation is such that replacement feedwater must be essentially free of hardness
minerals and oxides that deposit in the boiler. For
example, feedwater carrying only 1 ppm of hardness
minerals and oxides could deposit up to 25,000 lb
(11,340 kg) per year of solids in the boiler, so the boiler
might require chemical cleaning as often as 3 or 4 times
per year. Also, small chemical additions have a large
effect on boiler water chemistry. For example, addition of 0.2 lb (0.09 kg) of sodium hydroxide to the
boiler water increases the sodium concentration by 1
ppm, which can significantly affect the boiler water
chemistry. Similarly, a small amount of chemical hideout can have a large effect on boiler water concentration. Hideout or hideout return of only 0.01 gram per
square foot (0.1 g/m2 ) in the burner zone can change
the boiler water concentration by 1 ppm.
Control of deposition, corrosion, and

steam purity
The potential for deposition and corrosion is inherent to boilers and increases with boiler operating pressure and temperature. Evaporation of water concentrates boiler water impurities and solid treatment
chemicals at the heat transfer surfaces. During the
normal nucleate boiling process in boiler tubes, small
bubbles form on tube walls and are immediately swept
away by the upward flow of water. As steam forms,
dissolved solids in the boiler water concentrate along
the tube wall. Additionally, the boundary layer of
water along the wall is slightly superheated, and
many dissolved minerals are less soluble at higher temperatures (common phenomenon referred to as inverse
temperature solubility). Both of these factors favor
deposition of solids left behind by the evolution of
steam in high heat flux areas, as illustrated in Fig. 1.
These deposits in turn provide a sheltered environment which can further increase chemical concentrations and deposition rates. In a relatively clean boiler
tube, concentration of chemicals at the tube surface
is limited by the free exchange of fluid between the
surface and boiler water flowing through the tube.
Wick boiling as illustrated in Fig. 2 generally produces
sufficient flow within the deposits to limit the degree
of concentration. However, as heavy deposits as illus-
Fig. 1 Three years of operation resulted in light deposits because of

good water treatment. The upper right figure is the heated side, and
the lower right figure is the unheated side.
trated in Fig. 3 accumulate, they restrict flow to the

surface. Some boiler water chemicals concentrate on
tube walls during periods of high load and then return to the boiler water when the load is reduced. This
is termed hideout and hideout return. This can greatly
complicate efforts to control boiler water chemistry.
Typical boiler deposits are largely hardness precipitates and metal oxides. Hardness, easily precipitated
minerals (mainly calcium and magnesium), enters the
cycle as impurities in makeup water and in cooling
water from condenser leaks. Metal oxides are largely
Fig. 2 Schematic of the wick boiling mechanism (adapted from

Reference 9).
from corrosion of pre-boiler cycle components. Scaling

occurs when these minerals and oxides precipitate and
adhere to boiler internal surfaces where they impede
heat transfer. The result can be overheating of tubes,
followed by failure and equipment damage. Deposits
also increase circuitry pressure drop, especially detrimental in once-through boilers. Effective feedwater
and boiler water purification and chemical treatment
minimizes deposition by minimizing feedwater hardness and by minimizing corrosion and associated iron
pickup from the condensate and feedwater systems. Also,
phosphate and other water treatment chemicals are used
in drum boilers to impede the formation of particularly
adherent and low thermal conductivity deposits.
Some chemicals become corrosive as they concentrate. Corrosion can occur even in a clean boiler, but
the likelihood of substantial corrosion is much greater
beneath thick porous deposits that facilitate the concentration process. Concentration at the base of deposits can be more than 1000 times higher than that in
the boiler water and the temperature at the base of these
deposits can substantially exceed the saturation temperature. Hence, as deposits accumulate, control of
boiler water chemistry to avoid the formation of corrosive concentrates becomes increasingly important. Since
chemistry upsets do occur, operation of a boiler with
excessively thick deposits should be avoided.
Because local concentration of boiler water impurities and treatment chemicals is inherent to steam generation, water chemistries must be controlled so the
concentrates are not corrosive. On-line corrosion is
often caused by concentration of sodium hydroxide,
concentration of caustic-forming salts such as sodium
carbonate, or concentration of acid-forming salts such
as magnesium chloride or sulfate.10 Effective feedwater and boiler water treatment minimizes corrosion
by minimizing ingress of these impurities and by add-
Fig. 3 An example of internal deposits resulting from poor boiler

water treatment. These deposits, besides hindering heat transfer,
allowed boiler water salts to concentrate, causing corrosion.
42-3

ing treatment chemicals (such as trisodium phosphate)
that buffer against acid or caustic formation. However,
corrosion and excessive precipitation can also be caused
by improper use of buffering agents and other treatment chemicals. For example, underfeeding or overfeeding of treatment chemicals, out-of-specification sodiumto-phosphate ratios, or out-of-specification free-chelant
concentrations can cause corrosion.
Dissolved carbon dioxide and oxygen can also be
corrosive and must be eliminated from feedwater.
Carbon dioxide from air in-leakage and from decomposition of carbonates and organic compounds tends
to acidify feedwater and steam condensate. Oxygen
is especially corrosive because it facilitates oxidation of
iron, copper, and other metals to form soluble metal ions.
At higher temperatures, oxygen is less soluble in water
and the rate of chemical reaction is increased. As boiler
feedwater is heated, oxygen is driven out of solution and
rapidly corrodes heat transfer surfaces. The combination
of oxygen and residual chloride is especially corrosive,
as is the combination of oxygen and free chelant.
Carryover of impurities from boiler water to steam
is also inherent to boiler operation. Though separation
devices remove most water droplets carried by steam,
some residual droplets containing small amounts of dissolved solids always carry through with the steam. Also,
at higher pressures, there is some vaporous carryover.
Excessive impurities can damage superheaters, steam
turbines, or downstream process equipment.
Boiler feedwater
To maintain boiler integrity and performance and
to provide steam of suitable turbine or process purity,
boiler feedwater must be purified and chemically conditioned. The amount and nature of feedwater impurities that can be accommodated depend on boiler operating pressure, boiler design, steam purity requirements, type of boiler water internal treatment,
blowdown rate, and whether the feedwater is used for
steam attemperation. Feedwater chemistry parameters to be controlled include dissolved solids, pH, dissolved oxygen, hardness, suspended solids, total organic carbon (TOC), oil, chlorides, sulfides, alkalinity,
and acid or base forming tendencies.
At a minimum, boiler feedwater must be softened
water for low pressure boilers and demineralized water for high pressure boilers. It must be free of oxygen and essentially free of hardness constituents and
suspended solids. Recommended feedwater limits are
shown in Table 1. Use of high-purity feedwater minimizes blowdown requirements and minimizes the potential for carryover, deposition, and corrosion problems throughout the steam-water cycle.
Operation within these guidelines does not by itself
ensure trouble-free operation. Some feedwater contaminants such as calcium, magnesium, organics, and carbonates can be problematic at concentrations below the
detection limits of analytical methods commonly used
Table 1
Recommended Feedwater Limits
Once-Through
Boilers
Drum Boilers
Oxygen
Pressure,
psig (MPa)
with AVT*
AVT
Treatment
15 to 300
(0.10 to 2.07)
301 to 600
(2.08 to 4.14)
601 to 900
(4.14 to 6.21)
901 to 1000
(6.21 to 6.90)
1001 to 1500
(6.90 to 10.34)
>1500
(>10.34)
All
All
All
pH, all ferrous

heaters
9.3 to 10.0
9.3 to 10.0
9.3 to 10.0
9.3 to 9.6
9.3 to 9.6
9.3 to 9.6
9.3 to 9.6
9.3 to 9.6
8.0 to 8.5
pH, copperbearing heaters
8.8 to 9.2
8.8 to 9.2
8.8 to 9.2
8.8 to 9.2
8.8 to 9.2
8.8 to 9.2
8.8 to 9.2** 8.8 to 9.2
Total hardness,
as ppm CaCO3,
maximum
0.3
0.2
0.1
0.05
0.003
0.003
0.003
0.003
0.001
0.007
0.007
0.007
0.007
0.007
0.007
0.007
0.007
0.030 to 0.150
Iron, ppm
maximum
0.1
0.04
0.02
0.02
0.01
0.01
0.01
0.010
0.005
Copper, ppm
maximum
0.05
0.02
0.01
0.01
0.005
0.002
0.005
0.002
0.001
Organic, ppm
TOC max.
1.0
1.0
0.5
0.2
0.2
0.2
0.2
0.200
0.200
Cation conductivity,
S/cm max.
0.5
0.2
0.2
0.15
0.15
Oxygen, ppm
maximum***
N/A
* All volatile treatment.

** AVT not recommended for copper-bearing cycles and associated low feedwater pH where the drum pressure is less than 400 psig.
*** By mechanical deaeration before chemical scavenging of residual.
Note:
ppm = mg/kg
42-4

for industrial boilers. Also, operators must be sensitive
to changes in feedwater chemistry and boiler operating conditions, and must adapt accordingly.
Makeup water
Boiler feedwater is generally a mix of returned
steam condensate and fresh makeup water. For utility boilers, most of the steam is usually returned as
condensate, and only 1 to 2% makeup is necessary.
However, for some industrial cycles, there is little or
no returned condensate, so as much as 100% makeup
may be necessary.
Chemistry requirements for makeup water depend
on the amount and quality of returned steam condensate. Where a large portion of the feedwater is uncontaminated condensate, makeup water can generally
be of lesser purity so long as the mixture of condensate and makeup meet boiler feedwater requirements.
The feedwater concentration for each chemical species is the weighted average of the feedwater and
makeup water concentrations:
Feedwater concentration = (condensate concentration flow
(1)
+ makeup concentration makeup flow) / total feedwater flow
The selection of equipment for purification of

makeup water must consider the water chemistry requirements, raw water composition, and quantity of
makeup required. All natural waters contain dissolved
and suspended matter. The type and amount of impurities vary with the source, such as lake, river, well
or rain, and with the location of the source. Major dissolved chemical species in source water include sodium,
calcium, and magnesium positive ions (cations) as well
as bicarbonate, carbonate, sulfate, chloride, and silicate
negative ions (anions). Organics are also abundant.
The first steps in water purification are coagulation
and filtration of suspended materials. Natural settling
in still water removes relatively coarse suspended solids. Required settling time depends on specific gravity, shape and size of particles, and currents within
the settling basin. Settling and filtration can be expedited by coagulation (use of chemicals to cause agglomeration of small particles to form larger ones that
settle more rapidly). Typical coagulation chemicals are
alum and iron sulfate. Following coagulation and settling, water is normally passed through filters. The
water is chlorinated to kill micro-organisms, then activated charcoal filters may be used to remove the final traces of organics and excess chlorine.
Subsequently, various processes may be used to
remove dissolved scale-forming constituents (hardness
minerals) from the water. For some low pressure boilers, removal of hardness minerals and scale-forming
minerals is adequate. For other boilers, the concentration of all dissolved solids must be reduced or nearly
eliminated. For low pressure boilers, the capital and
operating cost for removal must be weighed against
costs associated with residual dissolved solids and
hardness. These include increased costs for boiler water
treatment, more frequent chemical cleaning of the
boiler, and possibly higher rates of boiler repair. Demineralized water nearly free of all dissolved solids is
recommended for higher pressure boilers and espeSteam 41 / Water and Steam Chemistry, Deposits and Corrosion
cially for all boilers operating at pressures greater than

1000 psi (6.9 MPa).
Sodium cycle softening, often called sodium zeolite
softening, replaces easily precipitated hardness minerals with sodium salts, which remain in solution as
water is heated and concentrated. The major hardness
ions are calcium and magnesium. However, zeolite ionexchange softening also removes dissolved iron, manganese, and other divalent and trivalent cations. Sodium held by a bed of organic resin is exchanged for
calcium and magnesium ions dissolved in the water.
The process continues until the sodium ions in the resin
are depleted and the resin can no longer absorb calcium and magnesium efficiently. The depleted resin
is then regenerated by washing it with a high concentration sodium chloride solution. At the high sodium concentrations of this regeneration solution, the
calcium and magnesium are displaced by sodium.
Variations of the process, in combination with chemical pre-treatments and post-treatments, can substantially reduce hardness concentrations and can often
reduce silica and carbonate concentrations.
For higher pressure boilers, evaporative or more
complete ion-exchange demineralization of makeup
water is recommended. Any of several processes may
be used. Evaporative distillation forms a vapor which
is recondensed as purified water. Ion exchange demineralization replaces cations (sodium, calcium, and
magnesium in solution) with hydrogen ions and replaces anions (bicarbonate, sulfate, chloride, and silicate) with hydroxide ions. For makeup water treatment, two tanks are normally used in series in a cation-anion sequence. The anion resin is usually regenerated with a solution of sodium hydroxide, and the
cation resin is regenerated with hydrochloric or sulfuric acid. Reverse osmosis purifies water by forcing it
through a semi-permeable membrane or a series of
such membranes. It is increasingly used to reduce total
dissolved solids (TDS) in steam cycle makeup water.
Where complete removal of hardness is necessary,
reverse osmosis may be followed by a mixed-bed demineralizer. Mixed-bed demineralization uses simultaneous cation and anion exchange to remove residual
impurities left by reverse osmosis, evaporator, or twobed ion exchange systems. Mixed-bed demineralizers
are also used for polishing (removing impurities from)
returned steam condensate. Before regenerating
mixed-bed demineralizers, the anion and cation resins must be hydraulically separated. Caustic and
acids used for regeneration of demineralizers
and other water purification and treatment
chemicals present serious safety, health, and
environmental concerns. Material Safety Data
Sheets must be obtained for each chemical and
appropriate precautions for handling and use
must be formulated and followed.
Dissolved organic contaminants (carbon-based
molecules) are problematic in that they are often detrimental to boilers but are not necessarily removed by
deionization or evaporative distillation. Organic contamination of feedwater can cause boiler corrosion,
furnace wall tube overheating, drum level instability,
carryover, superheater tube failures, and turbine cor42-5

rosion. The degree to which any of these difficulties
occurs depends on the concentration and nature of the
organic contaminant. Removal of organics may require activated carbon filters or other auxiliary purification equipment.
Returned condensate condensate polishing

For many boilers, a large fraction of the feedwater
is returned condensate. Condensate has been purified
by prior evaporation, so uncontaminated condensate
does not generally require purification. Makeup water can be mixed directly with the condensate to form
boiler feedwater.
In some cases, however, steam condensate is contaminated by corrosion products or by in-leakage of
cooling water. Where returned condensate is contaminated to the extent that it no longer meets feedwater
purity requirements, mixed-bed ion-exchange purification systems are commonly used to remove the dissolved impurities and filter out suspended solids. Such
demineralization is referred to as condensate polishing. This is essential for satisfactory operation of oncethrough utility boilers, for which feedwater purity
requirements are especially stringent. While high
pressure drum boilers can operate satisfactorily without condensate polishing, many utilities recognize the
benefits in high pressure plants. These benefits include
shorter unit startup time, protection from condenser
leakage impurities, and longer intervals between acid
cleanings. Condensate polishing is recommended for
all boilers operating with all volatile treatment (AVT)
and is essential for all boilers operating with all volatile treatment and seawater cooled condensers. Provisions for polishing vary from adequate capacity for
100% polishing of all returned condensate to polishing only a portion of the condensate. However, all must
be adequate to meet feedwater requirements under
all anticipated load and operating conditions.
Most of the pressure vessels that contain ion exchange resins have under-drain systems and downstream traps or strainers to prevent leakage of ion
exchange resins into the cycle water. These resins can
form harmful decomposition products if allowed to
enter the high temperature portions of the cycle. Unfortunately, the under-drain systems and the traps
and strainers are not designed to retain resin fragments that result from resin bead fracture. Also, the
resin traps and strainers can fail, resulting in resin
bursts. Resin intrusion can be minimized by controlling flow transients, reducing the strainers screen
size, increasing flow gradually during vessel cut-in,
and returning the polisher vessel effluent to the condenser during the first few minutes of cut-in.
Feedwater pH control
Boiler feedwater pH is monitored at the condensate
pump discharge and at the economizer inlet. When
the pH is below the required minimum value, ammonium hydroxide or an alternate alkalizer is added.
Chemicals for pH control are added either downstream
of the condensate polishers or at the condensate pump
discharge for plants without polishers. For high purity demineralized feedwater, ammonium hydroxide
42-6
injection pumps or alternative feedwater pH control

is achieved using a feedback signal from a specific conductivity monitor. Conductivity provides a good measure of ammonium hydroxide concentration, and automated conductivity measurement is more reliable
than automated pH measurement. Also, the linear
rather than logarithmic relationship of conductivity
to ammonia concentration gives better control. Fig. 4
shows the relationship between ammonium concentration, pH, and conductivity of demineralized water.
While an equilibrium concentration of ammonium
hydroxide remains in the boiler water, much of the
ammonium hydroxide added to feedwater volatilizes
with the steam. Conversely, the solubility of ammonium hydroxide is such that little ammonia is lost by
deaeration. Hence, returned condensate often has a
substantial concentration of ammonium hydroxide
before further addition.
Common alternative pH control agents include neutralizing amines, such as cyclohexylamine and
morpholine. For high pressure utility boilers with superheaters, the more complex amines are thermally
unstable and the decomposition products can be problematic.
Deaeration and chemical oxygen scavengers

Oxygen and carbon dioxide enter the cycle with undeaerated makeup water, with cooling water which
Fig. 4 Approximate relationship between conductivity and pH for

ammonia solutions in demineralized water.

leaks into the condenser, and as air leaking into the
vacuum portion of the cycle.
For turbine cycles, aeration of the feedwater is initially limited by use of air ejectors to remove air from
the condenser. Utility industry standard practice is to
limit total air in-leakage to less than one standard
cubic foot of air per minute per 100 MW of generating capacity (approximately 0.027 Nm3/100 MW), as
measured at the condenser air ejectors. Final removal
of oxygen and other dissolved gases adequate for boiler
feedwater applications is generally accomplished by
thermal deaeration of the water ahead of the boiler
feed pumps. Thermal deaeration is accomplished by
heating water to reduce gas solubility. Gases are then
carried away by a counter flow of steam. The process
is typically facilitated by the use of nozzles and trays
which disperse water droplets to increase the steamto-water interfacial area. Thermal deaeration can reduce feedwater oxygen concentration to less than 7
parts per billion (ppb). It also essentially eliminates
dissolved carbon dioxide, nitrogen, and argon.
Chemical agents are generally used to scavenge residual oxygen not removed by thermal deaeration. Traditional oxygen scavengers have been sodium sulfite for
low pressure boilers and hydrazine for high pressure
boilers. Sulfite must not be used where the boiler pressure is greater than 900 psig (6.2 MPa). Other oxygen
scavengers (erythorbic acid, diethylhydroxylamine, hydroquinone and carbohydrazide) are also used. Hydrazine has been identified as a carcinogen and this has
increased the use of alternative scavengers. Scavengers
are generally fed at the exit of the condensate polishing
system and/or at the boiler feed pump suction.
Attemperation water
Water spray attemperation is used to control steam
temperature. Attemperation for utility boilers is discussed in the Steam temperature adjustment and control section of Chapter 19, Boilers, Superheaters and
Reheaters. The spray water is feedwater, polished feedwater, or steam condensate. As the spray water evaporates, all chemicals and contaminants in the water
remain in the steam. This addition must not be excessive. It must not form deposits in the attemperator
piping, and it must not excessively contaminate the
steam. If a superheated steam purity limit is imposed,
the steam purity after attemperation must not exceed
this limit. To meet this requirement, the weighted
average of the spray water total solids concentration
and the saturated steam total solids concentration
must not exceed the final steam total solids limit. Additionally, spray water attemperation must not increase the steam total solids concentration by more
than 0.040 ppm. Independent of other considerations,
the spray water solids concentration must never exceed 2.5 ppm. Ideally, the purity of attemperation
water should equal the desired purity of the steam.
Drum boilers and internal boiler water

Boiler water that recirculates in drum and steam
generation circuits has a relatively high concentration
of dissolved solids that have been left behind by wa-
ter evaporation. Water chemistry must be carefully

controlled to assure that this concentrate does not
precipitate solids or cause corrosion within the boiler
circuitry. Boiler water chemistry must also be controlled
to prevent excessive carryover of impurities or chemicals with the steam.
Customized chemistry limits and treatment practices must be established for each boiler. These limits
depend on steam purity requirements, feedwater
chemistry, and boiler design. They also depend on
boiler owner/operator preferences regarding economic
tradeoffs between feedwater purification, blowdown
rate, frequency of chemical cleaning, and boiler maintenance and repair. Direct boiler water treatment
(usually referred to as internal treatment) practices
commonly used to control boiler water chemistry include all volatile treatment, coordinated phosphate
treatments, high-alkalinity phosphate treatments,
and high-alkalinity chelant and polymer treatments.
In all cases, when treatment chemicals are mixed, the
identity and purity of chemicals must be verified and
water of hydration in the weight of chemicals must
be taken into account. The specific treatment used
must always be developed and managed by competent water chemistry specialists.
Feedwater is the primary source of solids that concentrate in boiler water, and feedwater purity defines
the practical limit below which the boiler water solids
concentration can not be reduced with an acceptable
blowdown rate. Additionally, hardness and pre-boiler
corrosion products carried by the feedwater play major roles in defining the type of boiler water treatment
that must be employed. Where substantial hardness
is present in feedwater, provision must be made to
ensure that the hardness constituents remain in solution in the boiler water or to otherwise minimize the
formation of adherent deposits. This is often accomplished by use of chelant, polymer, or high-alkalinity
phosphate boiler water treatment. Where substantial
hardness is not present, boiler water treatment can be
optimized to minimize impurity carryover in the steam
and to minimize the potential for boiler tube corrosion.
Because boiler water impurities and treatment
chemicals carry over in the steam, steam purity requirements play a major role in defining boiler water
chemistry limits. Boiler specifications normally include
a list of boiler-specific water chemistry limits that must
be imposed to attain a specified steam purity. Limits
must always be placed on the maximum dissolved
solids concentration. Limits must also be placed on
impurities and conditions that cause foaming at the
steam-water interface in the drum. These include limits on oil and other organic contaminants, suspended
solids, and alkalinity. The carryover factor is the ratio
of an impurity or chemical species in the steam to that
in the boiler water.
Blowdown
The dissolved solids concentration of boiler water
is intermittently or continuously reduced by blowing
down some of the boiler water and replacing it with
feedwater. Blowdown rate is generally expressed as a
percent relative to the steam flow rate from the drum.
42-7
Traditional all volatile treatment

For all volatile treatment (AVT), no solid chemicals
are added to the boiler or pre-boiler cycle. Boiler water chemistry control is by boiler feedwater treatment
only. No chemical additions are made directly to the
drum. Feedwater pH is controlled with ammonia or
an alternate amine. Because ammonia carries away
preferentially with the steam, the boiler water pH may
be slightly lower (0.2 to 0.4 pH units) than the feedwater pH. For traditional all volatile treatment, as opposed to oxygen treatment, hydrazine or a suitable
alternate is added to scavenge residual oxygen. Table
1 shows the recommended AVT feedwater control limits. Because all volatile treatment adds no solids to the
boiler water, solids carryover is generally minimized.
All volatile treatment provides no chemical control
for hardness deposition and provides no buffer against
caustic or acid-forming impurities. Hence, feedwater
must contain no hardness minerals from condenser
leakage or other sources. It must be high-purity condensate or polished condensate with mixed-bed quality demineralized makeup water.
All volatile treatment can be, but rarely is, used
below 1000 psig (6.9 MPa). Normally it is used only
for boilers operating at or above 2000 psig (13.8 MPa)
drum pressure. It is not recommended for lower pressure boilers where other options are feasible. While
all volatile treatment is one of several options for drum
boilers, it is the only option for once-through boilers.
Oxygen treatment
Even in the absence of dissolved oxygen, steel surfaces react with water to form some soluble Fe ++ ions
which may deposit in the boiler, superheater, turbine,
or other downstream components. However, in the absence of impurities, oxygen can form an especially protective Fe +++ iron oxide that is less soluble than that
formed under oxygen-free conditions. To take advantage
of this, some copper-free boiler cycles operating with ultra pure feedwater maintain a controlled concentration
of oxygen in the feedwater. Most of these are high pressure once-through utility boilers, but this approach is also
used successfully in some drum boilers.
Oxygen treatment was developed in Europe, largely
by Vereinigung der Grosskesselbetreiber (VGB),11 and
there is also extensive experience in the former So42-8
viet Union (FSU). It can only be used where there is

no copper in the pre-boiler components beyond the
condensate polisher, and where feedwater is consistently of the highest purity, e.g., cation conductivity
< 0.15 S/cm at 77F (25C). A low concentration of oxygen is added to the condensate. The target oxygen concentration is 0.050 to 0.150 ppm for once-through
boilers and 0.040 ppm for drum boilers. With oxygen
treatment, the feedwater pH can be reduced, e.g.,
down to 8.0 to 8.5. An advantage of oxygen treatment
is decreased chemical cleaning frequencies for the
boiler. In addition, when oxygen treatment is used in
combination with lower pH, the condensate polisher
regeneration frequency is reduced.
Coordinated phosphate treatment

Coordinated phosphate-pH treatment, introduced
by Whirl and Purcell of the Duquesne Light Company,12 controls boiler water alkalinity with mixtures
of disodium and trisodium phosphate added to the
drum through a chemical feed pipe. The objective of
this treatment is largely to keep the pH of boiler water and underdeposit boiler water concentrates within
an acceptable range. Fig. 5 indicates the phosphate
concentration range that is generally necessary and
sufficient for this purpose. Phosphate treatment must
not be used where the drum pressure exceeds 2800
psig (19.3 MPa). All volatile treatment is recommended
at the higher pressures.
In sodium phosphate solutions, an H+ + PO4
HPO4= balance buffers the pH (i.e., retards H+ ion concentration changes). Solution pH depends on the
phosphate concentration and the molar sodium-tophosphate ratio. The relationship between pH, phosphate concentration, and molar sodium-to-phosphate
ratio is shown in Fig. 6. Where solutions contain other
dissolved salts (e.g., sodium and potassium chloride
and sulfate), sodium phosphate can still be used to control pH, and the curves of Fig. 6 are still applicable.
However, for such solutions, the sodium-to-phosphate
ratio labels on these curves are only apparent values
with reference to pure sodium phosphate solutions.
Measured sodium concentrations can not be used in
calculating sodium-to-phosphate ratios for control of
100
Phosphate, ppm
Blowdown is accomplished through a pressure letdown

valve and flash tank. Heat loss is often minimized by
use of a regenerative heat exchanger.
The ratio of the concentration of a feedwater impurity in the boiler water to its concentration in the
feedwater is the concentration factor, which can be estimated by use of Equation 1. However, a more complex formula must be used where there is substantial
carryover.
If there is no blowdown, solids concentrate until
carryover with the steam is sufficient to carry away
all of the solids that enter the boiler with the feedwater. For example, where the feedwater silica concentration is 0.01 ppm and 10% of the silica in the
boiler water carries over with the steam, the equilibrium boiler water silica concentration is 0.1 ppm.
10
10
100
1000
10000
Dissolved Solids, ppm
Fig. 5 Phosphate concentrations to control boiler water chemistry

(little or no residual hardness in the feedwater). Indicates phosphate
range at a given dissolved solids concentration.

11
10.5
pH
Na/PO4 = 3.0 + 1ppm NaOH

Na/PO4 = 3.0
10
Na/PO4 = 2.8
Na/PO4 = 2.6
Na/PO4 = 2.4
9.5
10
Phosphate, ppm
100
Fig. 6 Estimated pH of sodium phosphate solutions. Note: pH values

can differ by up to 0.2 pH units, depending on the choice of chemical
equilibrium constants used, but more often agree within 0.05 pH units.
boiler water pH because measured sodium concentrations include non-phosphate sodium salts. While dissolved sodium chloride and sulfate do not alter boiler
water pH, ammonia does alter the pH. Hence, the
presence of ammonia must be taken into account
where ammonia concentrations are significant compared to phosphate concentrations.
Historically, the initial goal of coordinated pH-phosphate control was to keep the effective molar sodiumto-phosphate ratio just below 3, to prevent caustic stress
corrosion cracking, acid corrosion, and hydrogen damage. This proved to be an effective method for control
of deposition and corrosion in many boilers. However,
caustic gouging of furnace wall tubes occurred in some
boilers using coordinated pH-phosphate control, and
laboratory tests indicated that solutions with molar
sodium-to-phosphate ratios greater than about 2.85 can
become caustic when highly concentrated. Subsequently, many boilers were operated under congruent
control with a target effective sodium-to-phosphate
ratio of less than 2.85, generally about 2.6, and often
less than 2.6. Again, this proved to be an effective
method of control for many boilers, but some of the
boilers operating with low molar sodium-to-phosphate
ratios experienced acid phosphate corrosion. Instances
of boiler tube corrosion generally occurred in boilers that
experienced substantial phosphate hideout and hideout-return when the boiler load changed.
Phosphate hideout, hideout-return, and associated
corrosion problems are now addressed by equilibrium
phosphate treatment.13 The concentration of phosphate
in the boiler water is kept low enough to avoid hideout and hideout return associated with load changes,
thus it is always in equilibrium with the boiler. The
effective molar sodium-to-phosphate ratio is kept
above 2.8. The free hydroxide, as depicted in Fig. 6,
is not to exceed the equivalent of 1 ppm sodium hydroxide. Concern about caustic gouging at the higher
ratios is largely reduced by experience with this treat-
ment regime and by experience with caustic boiler

water treatment.
Tables 2 and 3 show recommended boiler water
chemistry limits. Customized limits for a specific boiler
depend on the steam purity requirements for the
boiler. Boiler and laboratory experience indicate that,
under some conditions, phosphate-magnetite interactions can degrade protective oxide scale and corrode
the underlying metal. To minimize these interactions,
the pH must be greater than that corresponding to the
2.6 sodium-to-phosphate ratio curve of Fig. 6, and
preferably greater than that corresponding to the 2.8
curve. The pH must always be above the 2.8 curve
when the drum pressure is above 2600 psig (17.9
MPa). The maximum pH is that of trisodium phosphate plus 1 ppm sodium hydroxide. Additionally, the
boiler water pH is not to be less than 9 nor greater
than 10. As discussed below, it may be necessary to
reduce the maximum boiler water phosphate concentration to avoid hideout and hideout return, and to
avoid associated control and corrosion problems.
Table 2
Boiler Water Limits
Pressure
Range,
psig (MPa)
Maximum
TDS, ppm
Maximum
Suspended
Solids, ppm
Maximum
Silica, ppm
15 to 50*
(0.10 to 0.35)
1250
15
30
15 to 50**
(0.10 to 0.35)
3500
15
150
51 to 325
(0.35 to 2.24)
3500
10
150
326 to 450
(2.25 to 3.10)
3000
90
451 to 600
(3.11 to 4.14)
2500
40
601 to 750
(4.14 to 5.17)
2000
30
751 to 900
(5.18 to 6.21)
1500
20
901 to 1000
(6.21 to 6.90)
1250
* For natural separation with no diffuser baffles in the

steam drum.
** Where the drum includes baffles that separate water
droplets from steam.
Notes:
1. Operation outside the limits defined in this table is not
recommended. Within these broad limits, more restrictive
limits must be imposed, consistent with the type of boiler
water treatment method chosen to control deposition,
corrosion, and carryover. For example, the boiler water pH
range of 8.5 to 9.0 is only acceptable with all volatile
treatment (AVT).
2. ppm = mg/kg
42-9
Table 3
Boiler Water Limits for Coordinated Phosphate Boiler Water Treatment
Pressure, psig (MPa)
15 to 1000
(0.10 to 6.90)
Maximum
TDS, ppm
Maximum
sodium, ppm
Maximum
silica, ppm
Defined by Table 2 or as
necessary to attain required
steam purity, whichever is less
1001 to 1500
(6.90 to 10.34)
1501 to 2600
(10.35 to 17.93)
100 ppm or as necessary to 50 ppm or as necessary to

attain required steam
purity, whichever is less
2601 to 2800
(17.93 to 19.31)
15 ppm or as necessary to
Maximum sodium concentration (if any) as necessary to attain required steam purity
Defined by Table 2 or as
necessary to attain required
steam purity, whichever is less
2 ppm or as necessary to
0.5 ppm or as necessary to

0.1 ppm or as necessary to

purity, whichever is less.
Phosphate as
PO4, ppm
See Fig. 5
"Effective"
Na/PO4
molar ratio
2.6 to 3.0
2.6 to 3.0 + 1 ppm NaOH
2.6 to 3.0 + 1 ppm NaOH
2.8 to 3.0 + 1 ppm NaOH
pH
See Figs. 6 and 7
9.4 to 10.5 and as dictated

by Figs. 6 and 7

by Figs. 6 and 7

by Figs. 6 and 7
Maximum
specific conductivity, S/cm
Twice the maximum TDS (ppm).
Note:
ppm = mg/kg
Phosphate treatment chemicals may hide out during periods of high-load operation, then return to the
boiler water when the load and pressure are reduced.
This type of hideout makes control of boiler water
chemistry difficult and can cause corrosion of furnace
wall tubes. This hideout and return phenomena is
caused by concentration of phosphate at the tube/
water interface in high heat flux areas. In these areas, phosphates accumulate in the concentrated liquid. The concentrated phosphates then precipitate, or
they adsorb on or react with surface deposits and
scale.13,14,15 Where excessive deposits are not present,
this hideout and hideout return associated with load
and pressure changes can be eliminated by decreasing the phosphate concentration in the boiler water
or possibly by increasing the sodium-to-phosphate
ratio. Where hideout and hideout-return are caused
by excessive deposits, the boiler must be chemically
cleaned. The amount of phosphate hideout or return
accompanying load changes must not be more than 5
ppm. Corrective action is necessary if the amount of
phosphate hideout or return accompanying load
changes is more than 5 ppm and/or the boiler water
pH change is more than 0.2 pH units, or where there
are changes in the hideout/hideout-return behavior.
This phenomenon must be distinguished from loss of
phosphate to passive film formation. As the passive oxide film reforms following a chemical cleaning of the
boiler, some phosphate is irreversibly lost from the boiler
water. This is minimized if chemical cleaning is followed
by a phosphate boilout repassivation of the boiler.
Operators should not over-correct for deviations of
42-10
pH and phosphate concentration from target values.

Corrective action must be taken with an understanding of system response times, the amounts of impurities being neutralized, and the amount of treatment
chemicals likely to be required.
Where phosphate treatment is used, pH is an especially critical parameter, so the accuracy of pH measuring devices and temperature corrections must be
assured. The boiler water pH must also be corrected
to discount the pH effect of residual ammonia in the
boiler water. Fig. 7 shows the estimated effect of ammonia on boiler water pH. The figure indicates the
expected pH for solutions with different concentrations
of sodium phosphate and 0.2 ppm ammonia. Where
these species dominate the solution chemistry, such
figures may be used to estimate sodium-to-phosphate
molar ratios.
With high purity feedwater, the recommended boiler
water pH can be attained with appropriate additions
of trisodium phosphate. If the recommended boiler
water pH can not be maintained within the above limits using trisodium phosphate or a mixture of trisodium and disodium phosphate, this is indicative of
alkaline or acid-forming impurities in the feedwater
or excessive hideout, and the root cause must be addressed. An exception is low level equilibrium phosphate treatment, where the small amount of trisodium
phosphate added to the boiler water may at times be
insufficient to achieve the recommended pH. A small
amount of sodium hydroxide may be added to attain
the recommended pH, but the excess sodium hydroxide must not exceed 1.0 ppm.13 Even 1.0 ppm sodium

used where waterside deposits are excessively thick,
where there is steam blanketing or critical heat flux
(see Chapter 5), or where there is seepage (e.g.,
through rolled seals or cracks).
Fig. 8 shows phosphate concentration limits for
high-alkalinity phosphate treatment. With some
feedwaters (e.g., high-magnesium low-silica), lower
phosphate concentrations may be advisable. The required pH is attained by adjusting the sodium hydroxide concentration in the chemical feed solution. The
total (M alkalinity in calcium carbonate equivalents)
must not exceed 20% of the actual boiler water solids
concentration.
NH3 PO4 + 1ppm NaOH

Na/PO4 = 3.0
9.8
pH
9.6
Na/PO4 = 2.8
Na/PO4 = 2.6
9.4
9.2
8.8
Phosphate, ppm
Fig. 7 Estimated pH of sodium phosphate solutions containing 0.2

ppm ammonium hydroxide. Note: pH values can differ by up to 0.2 pH
units, depending on the choice of chemical equilibrium constants
used, but more often agree within 0.05 pH units.
hydroxide may be excessive for some units, for example oil-fired boilers with especially high heat fluxes
in some areas of the furnace.
When mixing boiler water treatment chemicals,
operators should verify the identity and purity of the
chemicals and take into account water of hydration
in the weight of the chemicals. Neither phosphoric acid
nor monosodium phosphate should be used for routine boiler water treatment. If monosodium phosphate
is used to counter an isolated incident of alkali contamination of the boiler water, it must be used with
caution, and at reduced load.
High-alkalinity phosphate treatment

(low-pressure boilers only)
Minimal carryover and deposition are achieved
with demineralized makeup water and minimal dissolved solids, but this is not necessarily cost-effective
for all low pressure industrial boilers. Where softened
water with 0.02 to 0.5 ppm residual hardness (as
CaCO3) is used as makeup water for low pressure industrial boilers, high alkalinity or conventional phosphate treatment may be used to control scale formation. This high alkalinity treatment must only be used
for boilers operating below 1000 psig (6.9 MPa). The
pH and phosphate concentrations are attained by
addition of a trisodium phosphate and (if necessary)
sodium hydroxide solution through a chemical feed
line into the drum. With high-alkalinity phosphate
treatment, the boiler water pH is maintained in the
range of 10.8 to 11.4. This high pH precipitates hardness constituents that are less adherent than those
formed at lower pH.
Where high alkalinity boiler water is excessively
concentrated by evaporation, the concentrate can become sufficiently caustic to produce caustic gouging
or stress corrosion cracking of carbon steel. Hence,
high-alkalinity boiler water treatment must not be
Dispersants, polymers, and chelants

(low pressure boilers only)
Where substantial hardness (e.g., 0.1 ppm as
CaCO3) is present in feedwater, chelant treatment is
often used to ensure that the hardness constituents
remain in solution in the boiler water, or polymer
treatment is used to keep precipitates in suspension.
Blowdown of the dissolved contaminants and colloids
is more effective than that of noncolloidal hardness
precipitates and metal oxides.
While phosphate treatment precipitates residual
calcium and magnesium in a less detrimental form
than occurs in the absence of phosphate, chelants react with calcium and magnesium to form soluble compounds that remain in solution. Chelants commonly
employed include ethylene-diaminetetraacetic acid
(EDTA) and nitrilotriacetic acid (NTA). Because of concern about thermal stability, the use of chelants and
polymers should be limited to boilers operating at less
than 1000 psi (6.9 MPa).
To be most effective, chelant must mix with the feedwater and form thermally stable calcium and magnesium complexes before there is substantial residence
time at high temperature, where free chelant is not
thermally stable. Because the combination of free
chelant and dissolved oxygen can be corrosive, chelant
must be added only after completion of oxygen removal
and scavenging. Also, there must be no copper-bearing components in the feedwater train beyond the
chelant feed point.
Control limits depend on the feedwater chemistry,
specific treatment chemicals used, and other factors.
However, the boiler feedwater pH is generally be70
60
Phosphate, ppm
10
50
Maximum
40
Optimum
30
Minimum
20
10
0
(0)
200
(1379)
400
(2758)
600
(4137)
800
(5516)
1000
(6895)
Operating Pressure, psig (kPa)
Fig. 8 Phosphate concentration limits for high-alkalinity phosphate

treatment.
42-11

tween 9.0 and 9.6 and hardness as calcium carbonate is less than 0.5 ppm. The boiler water pH is generally maintained in the range of 10.0 to 11.4. The
boiler water pH is attained by a combination of alkalinity derived from the chelant feed (e.g., as Na 4
EDTA), evolution of CO2 from softened feedwater, and
addition of sodium hydroxide. Polymeric dispersants
are generally used to impede formation of scale by
residual solids.
Once-through universal pressure boilers

In a subcritical once-through boiler, there is no
steam drum. As water passes through boiler tubing,
it evaporates entirely into steam. Because steam does
not cool the tube as effectively as water, the tube temperature increases beyond this dry-out location. Subcritical once-through boilers are designed so this transition occurs in a lower heat flux region of the boiler
where the temperature increase is not sufficient to
cause a problem. However, because the water evaporates completely, it must be of exceptional purity to
avoid corrosion and rapid deposition, and carryover
of dissolved solids.
Similarly stringent water purity requirements must
be imposed for supercritical boilers. While there is no
distinction between water and steam in a supercritical boiler, the physical and chemical properties of the
fluid change as it is heated, and there is a temperature about which dissolved solids precipitate much as
they do in the dry-out zone of a subcritical oncethrough boiler. This is termed the pseudo transition
zone. (See Chapter 5.)
Satisfactory operation of a once-through boiler and
associated turbine requires that the total feedwater
solids be less than 0.030 ppm total dissolved solids with
cation conductivity less than 0.15 S/cm. Table 1 lists
recommended limits for other feedwater parameters.
Feedwater purification must include condensate polishing, and water treatment chemicals must all be volatile. Ammonia is typically added to control pH. For traditional all volatile treatment, hydrazine or a suitable
volatile substitute is used for oxygen scavenging. Iron
pickup from pre-boiler components can be minimized
by maintaining a feedwater pH of 9.3 to 9.6. Prior to
plant startup, feedwater must be circulated through the
condensate polishing system to remove dissolved and
suspended solids. Temperatures should not exceed 550F
(288C) at the convection pass outlet until the iron levels are less than 0.1 ppm at the economizer inlet.
Utility once-through boilers with copper-free cycle
metallurgy commonly use oxygen treatment. Table 1
includes recommended limits for other feedwater chemical parameters for oxygen treatment. Startup is with
increased pH and no oxygen feed. Oxygen addition to
feedwater is initiated and pH is reduced only after feedwater cation conductivity is less than 0.15 S/cm.
System transients and upsets inevitably cause excursions above recommend limits. Increased rates of
deposition and corrosion are likely to be in proportion
to the deviations. Small brief deviations may individually be of little consequence, but the extent, duration,
and frequency of such deviations should be minimized.
42-12
Otherwise, over a period of years the accumulative effects will be significant. Potential effects include increased deposition, pitting, pressure drop, and fatigue
cracking. Particular care is required to minimize the
extent and duration of chemistry deviations for cycling
units where operational transients are frequent.
Steam purity
Purity or chemistry requirements for steam can be
as simple as a specified maximum moisture content,
or they can include maximum concentrations for a
variety of chemical species. Often, for low-pressure
building or process heater steam, only a maximum
moisture content is specified. This may be as high as
0.5% or as low as 0.1%. Conversely, some turbine
manufacturers specify steam condensate maximum
cation conductivity, pH, and maximum concentrations
for total dissolved solids, sodium and potassium, silica,
iron, and copper. Turbine steam must generally have
total dissolved solids less than 0.050 ppm, and in some
cases less than 0.030 ppm. Individual species limits
may be still lower. If steam is to be superheated, a
maximum steam dissolved solids limit must be imposed
to avoid excessive deposition and corrosion of the superheater. This limit is generally 0.100 ppm or less.
Even where steam purity requirements are not imposed by the application, steam dissolved solids concentrations less than 1.0 ppm are recommended at
pressures up to 600 psig (4.1 MPa), dissolved solids
concentrations less than 0.5 ppm are recommended at
600 to 1000 psig (4.1 to 6.9 MPa), and dissolved solids concentrations less than 0.1 ppm are recommended
above 1000 psig (6.9 MPa).
Up to 2000 psig (13.8 MPa), most non-volatile chemicals and impurities in the steam are carried by small
water droplets entrained in the separated steam. Because these droplets contain dissolved solids in the same
concentration as the boiler water, the amount of impurities in steam contributed by this mechanical carryover
is the sum of the boiler water impurities concentration
multiplied by the steam moisture content. Mechanical
carryover is limited by moisture separation devices placed
in the steam path, as described in Chapter 5.
High water levels in the drum and boiler water
chemistries that cause foaming can cause excessive
moisture carryover and therefore excessive steam
impurity concentrations. Foaming is the formation of
foam or excessive spray above the water line in the
drum. Common causes of foaming are excessive solids or alkalinity, and the presence of organic matter
such as oil. To keep dissolved solids below the concentration that causes foaming requires continuous or
periodic blowdown of the boiler. High boiler water alkalinity increases the potential for foaming, particularly in the presence of suspended matter.
Where a chemical species is sufficiently volatile, it
also carries over as a vapor in the steam. Total carryover is the sum of the mechanical and vaporous carryover. Vaporous carryover depends on solubility in
steam and is different for each chemical species. For
most dissolved solids found in boiler water, it is negligible by comparison to mechanical carryover at pres-

sures less than 2000 psig (13.8 MPa). An exception is
silica for which vaporous carryover can be substantial at lower pressures. Fig. 9 shows typical vaporous
carryover fractions (distribution ratios) for common
boiler water constituents under typical conditions over
a wide range of boiler pressures. Fig. 10 shows expected total dissolved solids carryover for typical highpressure boilers. Vaporous carryover depends on pressure and on boiler water chemistry. It is not affected
by boiler design. Hence, if vaporous carryover for a
species is excessive, the carryover can only be reduced
by altering the boiler water chemistry. Only mechanical carryover is affected by boiler design. Non-interactive gases such as nitrogen, argon, and oxygen
carry over almost entirely with the steam, having no
relationship to moisture carryover.
Excessive steam impurity concentrations can also
be caused by feedwater and boiler water chemistries
that favor volatile species formation. Carryover of
volatile silica can be problematic at pressures above
1000 psig (6.9 MPa). Fig. 11 shows boiler water silica
concentration limits recommended to obtain steam
silica concentrations less than 0.010 ppm at pressures
up to 2900 psig (20.0 MPa) where the pH may be as
low as 8.8. Vaporous silica carryover at a pH of 10.0
is 88% of that at a pH of 8.8. The vaporous silica carryover at a pH of 11.0 is 74% of that at 8.8. The only effective method for preventing excessive silica or other vaporous carryover is reduction of the boiler water concentrations. Another common source of excessive impurities
in steam is inadequate attemperation spray water purity. All impurities in the spray water enter directly into
the steam. Procedures for measuring steam quality and
purity are discussed in Chapter 40.
Fig. 9 Impurity carryover coefficients of salts and metal oxides in

boiler water (adapted from Reference 16).
Fig. 10 Solids in steam versus dissolved solids in boiler water.
Water sampling and analysis

A key element in control of water and steam chemistry is effective sampling to obtain representative
samples, prevent contamination of the samples, and
prevent loss of the species to be measured.17 References
18 and 19 provide detailed procedures. In general,
sample lines should be as short as possible and made
of stainless steel, except where conditions dictate otherwise. Samples should be obtained from a continuously flowing sample stream. The time between sampling and analysis should be as short as possible.
Samples should be cooled quickly to 100F (38C) to
avoid loss of the species of interest. Sample nozzles and
lines should provide for isokinetic sample velocity and
maintain constant high water velocities [minimum of
6 ft/s (1.8 m/s)] to avoid loss of materials. Sample
points should be at least 10 diameters downstream of
the last bend or flow disturbance.
Guidelines and techniques for chemical analysis of
grab samples are listed in Table 4. The detailed methods are readily available from the American Society for
Testing and Materials (ASTM) in Philadelphia, Pennsylvania, U.S. and the American Society of Mechanical Engineers (ASME) in New York, New York, U.S.
Wherever practical, on-line monitoring should be
considered as an alternative to grab samples. This
gives real-time data, enables trends to be followed,
and provides historical data. However, on-line monitors require calibration, maintenance, and checks with
grab samples or on-line synthesized standard samples
to ensure reliability. Table 5 lists important on-line
monitoring measurements and references to specific
methods. In addition to the measurements listed, in-
42-13

100
Table 4
Guidelines for Measurements on Grab Samples
Measurement
Maximum Boiler Water Silica, ppm
10
pH
Electrometric
ASTM D 1293
Method A
Conductivity
Dip or flow type conductivity

cells energized with
alternating current at a
constant frequency
(Wheatstone Bridge)
ASTM D 1125
Methods A or B
Dissolved
oxygen
Colorimetric or
titrimetric
ASTM D 888
Methods A, B, C
Suspended
iron oxides
Membrane comparison
charts
ASME PTC 31
Ion exchange
equipment
Iron
Photometric
(bathophenanthroline)
or atomic absorption
(graphite furnace)
ASTM D 1068
Method C, D
Copper
Atomic absorption
(graphite furnace)
ASTM D 1688
Method C
Sodium
Atomic absorption or
flame photometry
ASTM D 4191 or
ASTM D 1428
Silica
Colorimetric or
atomic absorption
ASTM D 859 or
ASTM D 4517
Phosphate
Ion chromatography or
photometric
ASTM D 4327 or
ASTM D 515
Method A
Ammonia
Colorimetric
(nesslerization) or
ion-selective electrode
ASTM D 1426
Method A or B
Hydrazine
Colorimetric
ASTM D 1385
Chloride
Colorimetric,
ion-selective electrode
or ion chromatography
ASTM D 512 or
ASTM D 4327
Sulfate
Turbidimetric or ion
chromatography
ASTM D 516 or
ASTM D 4327
Calcium and
magnesium
Atomic absorption;
gravimetric or
titrimetric
ASTM D 511 or
ASTM D 1126
Fluoride
Ion-selective electrode
or ion chromatography
ASTM D 1179 or
ASTM D 4327
Morpholine
Colorimetric
ASTM D 1942
Alkalinity
Color-change titration
ASTM D 1067
Method B
Hydroxide ion
in water
Titrimetric
ASTM D 514
Total organic
carbon
Instrumental (oxidation
and infrared detection)
ASTM D 4779
0.1
0.01
0
(0)
500
(3447)
1000
(6895)
1500
(10,342)
2000
(13,790)
2500
(17,237)
3000
(20,684)
Drum Pressure, psig (kPa)
Fig. 11 Boiler water silica concentration limit, where maximum steam

silica is 0.010 ppm and boiler water pH is greater than 8.8.
strumentation is commercially available to monitor

chloride, dissolved oxygen, dissolved hydrogen, silica,
phosphate, ammonia and hydrazine.
Adequate water chemistry control depends on the
ability of boiler operators to consistently measure the
specified parameters. Hence, formal quality assurance
programs should be used to quantify and track the
precision and bias of measurements. Detailed procedures should be in place to cover laboratory structure,
training, standardization, calibration, sample collection/storage/analysis, reporting, maintenance records,
and corrective action procedures. Further discussion
is provided in Reference 20.
Common fluid-side corrosion problems

Water and steam react with most metals to form
oxides or hydroxides. Formation of a protective oxide
layer such as magnetite (Fe3O4) on the metal surface
causes reaction rates to slow with time. Boiler cycle
water treatment programs are designed to maintain
such protective oxide films on internal surfaces and
thus prevent corrosion in boilers and other cycle components. With adequate control of water and steam
chemistry, internal corrosion of boiler circuitry can be
minimized. Yet, chemistry upsets (transient losses of
control) do occur. Vigilant monitoring of system chemistry permits quick detection of upsets and quick remedial action to prevent boiler damage. Where these
measures fail and corrosion occurs, good monitoring
and documentation of system chemistry can facilitate
identification of the root cause, and identification of the
cause can be an essential step toward avoiding further
corrosion. Where corrosion occurs and the origin is
unknown, the documented water chemistry, location of
42-14
Technique(s)
Reference/
Comment
(Notes 1 and 2)
Notes:
1. ASME PTC refers to Performance Test Codes of the American
Society of Mechanical Engineers, New York, New York.
2. ASTM refers to testing procedures of the American Society for
Testing and Materials, Philadelphia, Pennsylvania.

Table 5
On-line Monitoring Measurements
Measurement
Technique(s)
Reference
pH
Electrometric
ASTM D 5128
Conductivities
(general, cation
and degassed)
Electrical conductivity
ASTM D 4519
measurement before and
after hydrogen cation
exchanges and at atmospheric boiling water
after acidic gas removal
Sodium
Selective ion electrode

flame photometry
ASTM D 2791
Total organic
carbon
Instrumental (oxidation
and measurement
of carbon dioxide)
ASTM D 5173
the corrosion, appearance of the corrosion, and chemistry of localized deposits and corrosion products often
suggest the cause. Common causes are flow accelerated
corrosion, oxygen pitting, chelant corrosion, caustic
corrosion, acid corrosion, organic corrosion, acid phosphate corrosion, hydrogen damage, and corrosion assisted cracking. Figs. 12 and 13 show typical locations
of common fluid-side corrosion problems. Further dis-
Fig. 13 Boiler convection pass showing typical locations of various

types of water-side corrosion.
Fig. 12 Typical locations of various types of water-side corrosion in

a boiler furnace water circuit.
cussion of corrosion and failure mechanisms is provided

in References 21, 22, 23, and 24. For EPRI members,
Boiler Tube Failures: Theory and Practice25 provides an
especially thorough description of utility boiler corrosion problems, causes, and remedial measures.
One distinguishing feature of corrosion is its appearance. Metal loss may be uniform so the surface
appears smooth. Conversely, the surface may be
gouged, scalloped, or pitted. Other forms of corrosion
are microscopic in breadth, and subsurface, so they
are not initially discernible. Subsurface forms of corrosion include intergranular corrosion, corrosion fatigue,
stress corrosion cracking, and hydrogen damage. Such
corrosion can occur alone or in combination with surface wastage. In the absence of component failure, detection of subsurface corrosion often requires ultrasonic, dye penetrant, or magnetic particle inspection
(Chapter 45). These forms of corrosion are best diagnosed with destructive cross-section metallography.
Another distinguishing feature is the chemical composition of associated surface deposits and corrosion
products. Deposits may contain residual corrosives such
as caustic or acid. Magnesium hydroxide in deposits can
suggest the presence of an acid-forming precipitation
process. Sodium ferrate (Na2FeO4) indicates caustic
conditions. Sodium iron phosphate indicates acid phosphate wastage. Organic deposits suggest corrosion by
organics, and excessive amounts of ferric oxide or hydroxide with pitting suggest oxygen attack.
Flow accelerated corrosion is the localized dissolution of feedwater piping in areas of flow impingement.
It occurs where metal dissolution dominates over protective oxide scale formation. For example, localized
42-15

conditions are sufficiently oxidizing to form soluble
Fe ++ ions but not sufficiently oxidizing to form Fe +++
ions needed for protective oxide formation. Conditions
known to accelerate thinning include: flow impingement on pipe walls, low pH, excessive oxygen scavenger concentrations, temperatures in the range of
250 to 400F/121 to 204C (although thinning can occur at any feedwater temperature), chemicals (such
as chelants) that increase iron solubility, and thermal
degradation of organic chemicals. Thinned areas often have a scalloped or pitted appearance. Failures,
such as that shown in Fig. 14, can occur unexpectedly and close to work areas and walkways. To assure
continued integrity of boiler feedwater piping, it must
be periodically inspected for internal corrosion and
wall thinning. Any thinned areas must be identified
and replaced before they become a safety hazard. The
affected piping should be replaced with low-alloy chromium-bearing steel piping, and the water chemistry
control should be appropriately altered.
Oxygen pitting and corrosion during boiler operation largely occur in pre-boiler feedwater heaters and
economizers where oxygen from poorly deaerated
feedwater is consumed by corrosion before it reaches
the boiler. A typical area of oxygen pitting is shown in
Fig. 15. Oxygen pitting within boilers occurs when
poorly deaerated water is used for startup or for accelerated cooling of a boiler. It also occurs in feedwater
piping, drums, and downcomers in some low pressure
boilers which have no feedwater heaters or economizer. Because increasing scavenger concentrations
to eliminate residual traces of oxygen can aggravate
flow accelerated corrosion, care must be taken to distinguish between oxygen pitting and flow accelerated
Fig. 14 Rupture of 6 in. (152 mm) feedwater pipe in an area thinned

by internal corrosion.
42-16
corrosion which generally occurs only where all traces

of oxygen have been eliminated.
Chelant corrosion occurs where appropriate feedwater and boiler water chemistries for chelant treatment are not maintained. Potentially corrosive conditions include excessive concentration of free chelant
and low pH. (See prior discussion of boiler water treatment with dispersants, polymers, and chelants.) Especially susceptible surfaces include flow impingement
areas of feedwater piping, riser tubes, and cyclone
steam/water separators. Affected areas are often dark
colored and have the appearance of uniform thinning
or of flow accelerated corrosion.
Corrosion fatigue is cracking well below the yield
strength of a material by the combined action of corrosion and alternating stresses. Cyclic stress may be
of mechanical or thermal origin (Chapter 8). In boilers, corrosion fatigue is most common in water-wetted surfaces where there is a mechanical constraint
on the tubing. For example, corrosion fatigue occurs
in furnace wall tubes adjacent to windbox, buckstay,
and other welded attachments. Failures are thick lipped.
On examination of the internal tube surface, multiple
initiation sites are evident. Cracking is transgranular.
Environmental conditions facilitate fatigue cracking
where it would not otherwise occur in a benign environment. Water chemistry factors that facilitate cracking
include dissolved oxygen and low pH transients associated with, for example, cyclic operation, condenser leaks,
and phosphate hideout and hideout-return.
Acid phosphate corrosion occurs on the inner steamforming side of boiler tubes by reaction of the steel with
phosphate to form maricite (NaFePO4 ). Fig. 16 shows
ribbed tubing that has suffered this type of wastage.
The affected surface has a gouged appearance with
maricite and magnetite deposits. Acid phosphate corrosion occurs where the boiler water effective sodiumto-phosphate ratio is less than 2.8, although ratios as
low as 2.6 may be tolerated at lower pressures.
Though not always apparent, common signs of acid
phosphate corrosion include difficulty maintaining
target phosphate concentrations, phosphate hideout
and pH increase with increasing boiler load or pressure, phosphate hideout return and decreasing pH
with decreasing load or pressure, and periods of high
iron concentration in boiler water. The potential for
acid phosphate corrosion increases with increasing
internal deposit loading, decreasing effective sodiumto-phosphate molar ratio below 2.8, increasing phosphate concentration, inclusion of acid phosphates (disodium and especially monosodium phosphate) in
phosphate feed solution, and increasing boiler pressure. To avoid acid phosphate corrosion, operators
should monitor boiler water conditions closely, assure
accuracy of pH and phosphate measurements, assure
purity and reliability of chemical feed solutions, assure that target boiler water chemistry parameters are
appropriate and are attained in practice, and watch
for aforementioned signs of acid phosphate corrosion.
Under-deposit acid corrosion and hydrogen damage occur where boiler water acidifies as it concentrates
beneath deposits on steam generating surfaces. Hydrogen from acid corrosion diffuses into the steel where
Fig. 17 Schematic of hydrogen attack, showing steps that occur

and the final result. Hydrogen attack can occur in both carbon and
low alloy steels in acidic or hydrogen environments.
Fig. 15 Oxygen pitting of economizer feedwater inlet.
it reacts with carbon to form methane as depicted in

Fig. 17. The resultant decarburization and methane
formation weakens the steel and creates microfissures.
Thick lipped failures like that shown in Fig. 18 occur
when the degraded steel no longer has sufficient
strength to hold the internal tube pressure. Signs of
hydrogen damage include under deposit corrosion,
thick lipped failure, and steel decarburization and
microfissures. The corrosion product from acid corrosion is mostly magnetite. Affected tubing, which may
extend far beyond the failure, must be replaced. The
boiler must be chemically cleaned to remove internal
tube deposits, and boiler water chemistry must be altered or better controlled to prevent acid-formation as
the water concentrates. Operators should reduce acidforming impurities by improving makeup water, reducing condenser leakage, or adding condensate polishing. For drum boilers, operators should use phosphate treatment with an effective sodium-to-phosphate
molar ratio of 2.8 or greater.
Fig. 16 Acid phosphate corrosion of ribbed tubing.
Caustic corrosion, gouging and grooving occur

where boiler water leaves a caustic residue as it evaporates. In vertical furnace wall tubes, this occurs beneath deposits that facilitate a high degree of concentration and the corroded surface has a gouged appearance as shown in Fig. 19. In inclined tubes where the
heat flux is directed through the upper half of the
tube, caustic concentrates by evaporation of boiler
water in the steam space on the upper tube surface.
Resulting corrosion is in the form of a wide smooth
groove with the groove generally free of deposits and
centered on the crown of the tube. Deposits associated
with caustic gouging often include Na2FeO4. To prevent
reoccurrence of caustic gouging, operators should prevent accumulation of excessive deposits and control
water chemistry so boiler water does not form caustic
as it concentrates. The latter can generally be achieved
by assuring appropriate feedwater chemistry with coordinated phosphate boiler water treatment, taking
care to control the effective sodium-to-phosphate molar ratio as appropriate for the specific boiler and the
specific chemical and operating conditions. In some instances, where caustic grooving along the top of a sloped
tube is associated with steam/water separation, such
separation can be avoided by use of ribbed tubes which
cause swirling motion that keeps water on the tube wall.
Caustic cracking can occur where caustic concentrates in contact with steel that is highly stressed, to
or beyond the steels yield strength. Caustic cracking
is rare in boilers with all welded connections. This
Fig. 18 Brittle tube failure in hydrogen damaged area.
42-17

extent that a tube no longer retains adequate strength
and bulges or ruptures. Internal tube deposits generally cause moderate overheating for extended periods
of time, causing long-term overheat failures. Shortterm overheat failures generally occur only when there
is gross interruption of internal flow to cool the tube,
or grossly excessive heat input.
Out-of-service corrosion is predominantly oxygen
pitting. Pitting attributed to out-of-service corrosion
occurs during outages but also as aerated water is
heated when boilers return to service. Especially common locations include the waterline in steam drums,
areas where water stands along the bottom of horizontal pipe and tube runs, and lower bends of pendant superheaters and reheaters. Pinhole failures are more
common in thinner walled reheater and economizer tubing. Such corrosion can be minimized by following appropriate layup procedures for boiler outages and by improving oxygen control during boiler startups.
Pre-operational cleaning
Fig. 19 Caustic gouging initiated along weld backing ring.
generally occurs in boilers using a high alkalinity

caustic boiler water treatment, and it is normally associated with unwelded rolled joints and welds that
are not stress relieved. On metallographic examination, caustic cracking is intergranular and has the
branched appearance characteristic of stress corrosion
cracking as illustrated in Fig. 20. It can generally be
avoided by use of coordinated phosphate treatment.
Where a high alkalinity caustic phosphate boiler water treatment is used for low pressure boilers, nitrate
is often added to inhibit caustic cracking.
Overheat failures like that shown in Fig. 21 occur
where deposits impede internal heat transfer to the
Fig. 20 Schematic of stress corrosion cracking.
42-18
In general, all new boiler systems receive an alkaline boilout, i.e. hot circulation of an alkaline mixture
with intermittent blowdown and final draining of the
unit. Many systems also receive a pre-operational
chemical cleaning. The superheater and reheater
should receive a conventional steam blow (a period of
high velocity steam flow which carries debris from the
system). Chemical cleaning of superheater and reheat
surfaces is effective in reducing the number of steam
blows to obtain clean surfaces, but is not required to
obtain a clean superheater and reheater.
Alkaline boilout
All new boilers should be flushed and given an alkaline boilout to remove debris, oil, grease and paint.
This can be accomplished with a combination of trisodium phosphate (Na3PO4) and disodium phosphate
(Na2HPO4), with a small amount of surfactant added
as a wetting agent. The use of caustic NaOH and/or
soda ash (Na2CO3) is not recommended. If either is
used, special precautions are required to protect boiler
components.
Chemical cleaning
After boilout and flushing are completed, corrosion
products may remain in the feedwater system and
boiler in the form of iron oxide and mill scale. Chemical cleaning should be delayed until full load operation has carried the loose scale and oxides from the
feedwater system to the boiler. Some exceptions are
units that incorporate a full flow condensate polishing system and boilers whose pre-boiler system has
been chemically cleaned. In general, these units can
be chemically cleaned immediately following pre-operational boilout.
Different solvents and cleaning processes are used
for pre-operational chemical cleaning, usually determined by boiler type, metallic makeup of boiler components, and environmental concerns or restrictions. The
four most frequently used are: 1) inhibited 5% hydrochloric acid with 0.25% ammonium bifluoride, 2) 2%

hydroxyacetic/1% formic acids with 0.25% ammonium
bifluoride and a corrosion inhibitor, 3) 3% inhibited
ammonium salts of ethylene-diaminetetraacetic acid
(EDTA), and 4) 3% inhibited ammoniated citric acid.
Steam line blowing

The steam line blow procedure depends on unit
design. Temporary piping to the atmosphere is required with all procedures. This piping must be anchored to resist high nozzle reaction force.
All normal startup precautions should be observed for
steam line blowing. The unit should be filled with treated
demineralized water. Sufficient feedwater pump capacity and condensate storage must be available to replace
the water lost during the blowing period.
Numerous short blows are most effective. The color
of the steam discharged to the atmosphere provides
an indication as to the quantity of debris being removed from the piping. Coupons (targets) of polished
steel attached to the end of the exhaust piping are
typically used as final indicators.
Periodic chemical cleaning

Cleaning frequency
Internal surfaces of boiler water-side components (including supply tubes, headers and drums) accumulate
deposits even though standard water treatment practices are followed. These deposits are generally classified
as hardness-type scales or soft, porous-type deposits.
To determine the need for cleaning, tube samples
containing internal deposits should be removed from
high heat input zones of the furnace and/or areas
where deposition problems have occurred. The deposit
weight is first determined by visually selecting a
heavily deposited section. After sectioning the tube
(hot and cold sides), the water-formed deposit is removed by scraping from a measured area. The weight
of the dry material is reported as weight per unit area:
either grams of deposit per square foot of tube surface
or mg/cm2. Procedures for mechanical and chemical
methods of deposit removal are provided in ASTM
D3483.26 General guidelines for determining when a
boiler should be chemically cleaned are shown in Table
6. The deposit weights shown are based on the mechanical scraping method. This removes the porous
deposit of external origin and most of the dense inner
oxide scale. Values are slightly lower than those obtained from the chemical dissolution method.
Because of the corrosive nature of the fuel and its
combustion products, furnace tubes in Kraft recovery
and refuse-fired boilers are particularly susceptible to
gas-side corrosion which can be aggravated by relatively modest elevated tube metal temperatures. (See
Chapters 28 and 29.) Through-wall failures due to
external metal corrosion can occur in these tubes at
water-side deposit weights much less than 40 g/ft2 (43
mg/cm2 ). In addition, for Kraft recovery boilers there
are significant safety concerns for water leakage in
the lower furnace. (See Chapters 28 and 43.) For these
units, a more conservative cleaning criterion is recommended for all operating pressures.
Fig. 21 Short-term overheat thin edged failure.
Chordal thermocouples
The chordal thermocouple (see Chapter 40) can be
an effective diagnostic tool for evaluating deposits on
operating boilers. Properly located thermocouples can
indicate a tube metal temperature increase caused by
excess internal deposits, and can alert the operator to
conditions that may cause tube failures. Thermocouples are often located in furnace wall tubes adjacent to the combustion zone where the heat input is
highest and the external tube temperatures are also
high. (See Fig. 22.)
Deposition inside tubes can be detected by instrumenting key furnace tubes with chordal thermocouples. These thermocouples compare the surface
temperature of the tube exposed to the combustion
process with the temperature of saturated water. As
deposits grow, they insulate the tube from the cooling
water and cause tube metal temperature increases.
Beginning with a clean, deposit-free boiler, the instrumented tubes are monitored to establish the temperature differential at two or three boiler ratings; this
establishes a base curve. At maximum load, with clean
tubes, the surface thermocouple typically indicates
metal temperatures 25 to 40F (14 to 22C) above saturation in low duty units and 80 to 100F (44 to 56C) in
high duty units as shown in Fig. 23. The temperature
variation for a typical clean instrumented tube is dependent upon the tubes location in the furnace, tube
thickness, inside fluid pressure, and the depth of the
Table 6
Guidelines for Chemical Cleaning
Unit Operating
Pressure, psig (MPa)
Water-side
Deposit Weight*
(g/ft2 )
Below 1000 (6.9)
20 to 40
1000 to 2000 (6.9 to 13.8) including all

Kraft recovery and refuse-fired boilers
12 to 20
Above 2000 (13.8)
10 to 12
* Deposit removed from hot or furnace side of tube using

the mechanical scraping method. (1 g/ft2 = 1.07 mg/cm2 )
42-19
Clean Tube
500F
(260C)
Chemical Recovery Boiler
583F
(306C)
Saturation Temp
500F (260C) at
665 psi (4.6 MPa)
Heat Input
120,000 Btu/h ft2
(378,550 W/m2)
510F
(266C)
Typical Locations for

Chordal Thermocouples
Outer
Casing
Side
Furnace
Side
Scaled Tube
80 g/ft2
Fossil Fuel-Fired Boiler
877F
(469C)
785F
(418C)
500F
(260C)
500F
(260C)
Typical Locations for

Chordal Thermocouples
Fig. 22 Typical locations of chordal thermocouples.
surface thermocouple. Internal scale buildup is detected by an increase in temperature differential

above the base curve. Chemical cleaning should normally be considered if the temperature differential at
maximum boiler load reaches 100F (56C).
Initially, readings should be taken weekly, preferably using the same equipment and procedure as used
for establishing the base curve. Under upset conditions, when deposits form rapidly, the checking frequency should be increased.
Chemical cleaning procedures and methods

In general, four steps are required in a complete
chemical cleaning process:
1. The internal heating surfaces are washed with a
solvent containing an inhibitor to dissolve or disintegrate the deposits.
2. Clean water is used to flush out loose deposits,
solvent adhering to the surface, and soluble iron
salts. Corrosive or explosive gases that may have
formed in the unit are also displaced.
42-20
3. The unit is treated to neutralize and passivate the

heating surfaces. This treatment produces a passive surface, i.e., it forms a very thin protective film
on freshly cleaned ferrous surfaces.
4. The unit is flushed with clean water to remove any
remaining loose deposits.
The two generally accepted chemical cleaning
methods are: 1) continuous circulation of the solvent
(Fig. 24), and 2) filling the unit with solvent, allowing it to soak, then flushing the unit (Fig. 25).
Circulation cleaning method

In the circulation (dynamic) cleaning method (Fig.
24), after filling the unit with demineralized water,
the water is circulated and heated to the required
cleaning temperature. At this time, the selected solvent is injected into the circulating water and recirculated until the cleaning is completed. Samples of the
return solvent are periodically tested. Cleaning is considered complete when the acid strength and the iron
Soaking method
The soaking (static) cleaning method (Fig. 25) involves preheating the unit to a specified temperature,
filling the unit with the hot solvent, then allowing the
unit to soak for a period of time, depending on deposit
conditions. To assure complete deposit removal, the
acid strength of the solvent must be somewhat greater
than that required by the actual conditions; unlike the
circulation method, control testing during the course
of the cleaning is not conclusive, and samples of solvent drawn from convenient locations may not truly
represent conditions in all parts of the unit.
The soaking method is preferable for cleaning units
where definite liquid distribution to all circuits (by the
circulation method) is not possible without the use of
many chemical inlet connections. The soaking method
is also preferred when deposits are extremely heavy,
or if circulation through all circuits at an appreciable
rate can not be assured without an impractically-sized
circulating pump. These conditions may exist in large
natural circulation units that have complex furnace
wall cooling systems.
Advantages of this method are simplicity of piping
connections and assurance that all parts are reached
by a solvent of adequate acid strength.
Solvents
Many acids and alkaline compounds have been
evaluated for removing boiler deposits. Hydrochloric
acid (HCl) is the most practical cleaning solvent when
using the soaking method on natural circulation boilers. Chelates and other acids have also been used.
An organic acid mixture such as hydroxyacetic-formic (HAF) is the safest chemical solvent when applying the circulation cleaning method to once-through
boilers. These acids decompose into gases in the event
of incomplete flushing.
For certain deposits, the solvent may require additional reagents, such as ammonium bifluoride, to promote deposit penetration. Alloy steel pressure parts,
particularly those high in chromium, should generally
not be cleaned with certain acid solvents. A general
guideline for solvent selection can be found in Table 7.
Prior to chemically cleaning, it is strongly recommended that a representative tube section be removed
and subjected to a laboratory cleaning test to determine and verify the proper solvent chemical, and concentrations of that solvent.
200
With Internal
Deposits
After Operation
T, F
150
Base Curve
Clean Condition
100
50
50
100
Firing Rate, %
Low Duty Units
200
With Internal
Deposits
After Operation
150
T, F
content of the returned solvent reach equilibrium (Fig.

26), indicating that no further reaction with the deposits is taking place. In the circulation method, additional solvent can be injected if the dissipation of the
solvent concentration drops below the recommended
minimum concentration.
The circulation method is particularly suitable for
cleaning once-through boilers, superheaters, and
economizers with positive liquid flow paths to assure
circulation of the solvent through all parts of the unit.
Complete cleaning can not be assured by this method
unless the solvent reaches and passes through every
circuit of the unit.
100
50
Base Curve
Clean Condition
0
50
100
Firing Rate, %
High Duty Units
Fig. 23 Temperature difference between surface and saturation

thermocouples.
Deposits
Scale deposits formed on the internal heating surfaces of a boiler generally come from the water. Most
of the constituents belong to one or more of the following groups: iron oxides, metallic copper, carbonates, phosphates, calcium and magnesium sulfates,
silica, and silicates. The deposits may also contain
various amounts of oil.
Pre-cleaning procedures include analysis of the
deposit and tests to determine solvent strength and
contact time and temperature. The deposit analyses
should include a deposit weight in grams per square
foot (or milligrams per square centimeter) and a spectrographic analysis to detect the individual elements.
X-ray diffraction identifying the major crystalline constituents is also used.
If the deposit analysis indicates the presence of copper (usually from corrosion of pre-boiler equipment,
such as feedwater heaters and condensers), one of
three procedures is commonly used: 1) a copper
complexing agent is added directly to the acid solvent,
2) a separate cleaning step, featuring a copper solvent,
is used followed by an acid solvent, and 3) a chelantbased solvent at high temperature is used to remove
iron, followed by addition of an oxidizing agent at re42-21

duced temperature for copper removal. The decision
to use one of these methods depends on the estimated
quantity of copper present in the deposit.
When deposits are dissolved and disintegrated, oil
is removed simultaneously, provided it is present only
in small amounts. For higher percentages of oil contamination, a wetting agent or surfactant may be added to
the solvent to promote deposit penetration. If the deposit is predominantly oil or grease, boiling out with
alkaline compounds must precede the acid cleaning.
Inhibitors
The following equations represent the reactions of
hydrochloric acid with constituents of boiler deposits:
Fe3 O4 + 8HCl 2FeCl3 + FeCl 2 + 4H2O
(2)
CaCO3 + 2HCl CaCl 2 + H2O + CO2
(3)
At the same time, however, the acid can also react

with and thin the boiler metal, as represented by the
equation:
Fe + 2HCl FeCl 2 + H2
Fig. 24 Chemical cleaning by the circulation method simplified

arrangement of connections for once-through boilers.
Fig. 25 Chemical cleaning by the soaking method simplified

arrangement of connections for drum-type boilers.
42-22
(4)
unless means are provided to slow this reaction without affecting the deposit removal. A number of excellent commercial inhibitors are available to perform this
function. The aggressiveness of acids toward boiler
deposits and steel increases rapidly with temperature.
However, the inhibitor effectiveness decreases as the
temperature rises and, at a certain temperature, the
inhibitor may decompose. Additionally, all inhibitors
are not effective with all acids.
Determination of solvent conditions

Deposit samples The preferred type of deposit
sample is a small section of tube with the adhering
deposit, though sometimes tube samples are not easily obtained. Selection of the solvent system is made
from the deposit analyses. After selection of the solvent system, it is necessary to determine the strength
of the solvent, the solvent temperature, and the length
of time required for the cleaning process.
Solvent strength The solvent strength should be
proportional to the amount of deposit. Commonly used
formulations are:
1. Natural circulation boilers (soaking method)
(a) pre-operational inhibited 5% hydrochloric
acid + 0.25% ammonium bifluoride
(b) operational inhibited 5 to 7.5% hydrochloric
acid and ammonium bifluoride based on deposit analysis
2 Once-through boilers (circulation method)
(a) pre-operational inhibited 2% hydroxyacetic1% formic acids + 0.25% ammonium bifluoride
(b) operational inhibited 4% hydroxyacetic-2%
formic acids + ammonium bifluoride based on
deposit analysis
Solvent temperature The temperature of the solvent
should be as high as possible without seriously reducing the effectiveness of the inhibitor. An inhibitor test
should be performed prior to any chemical cleaning

to determine the maximum permissible temperature
for a given solvent.
When using hydrochloric acid, commercial inhibitors generally lose their effectiveness above 170F
(77C) and corrosion rate increases rapidly. Therefore,
the temperature of the solvent, as fed to the unit,
should be 160 to 170F (71 to 77C). In using the circulation method with a hydroxyacetic-formic acid mixture, a temperature of 200F (93C) is necessary for
adequate cleaning. Chelate-based solvents are generally applied at higher temperatures (about 275F/
135C). In these cases, the boiler is fired to a specific
temperature. The chelate chemicals are introduced
and the boiler temperature is cycled by alternately
firing and cooling to predetermined limits.
Steam must be supplied from an auxiliary source to
heat the acid as it is fed to the unit. When using the
circulation method, steam is also used to heat the circulating water to the predetermined and desired temperature before injecting the acid solution. Heat should
be added by direct contact or closed cycle heat exchangers. The temperature of the solvent should never be
raised by firing the unit when using an acid solvent.
Cleaning time When cleaning by the circulation
method, process completion is determined by analyzing samples of the return solvent for iron concentration and acid strength. (See Fig. 26.) However, acid circulation for a minimum of six hours is recommended.
In using the soaking method, the cleaning time
should be predetermined but is generally between six
to eight hours in duration.
Preparation for cleaning

Heat transfer equipment All parts not to be cleaned
should be isolated from the rest of the unit. To exclude
acid, appropriate valves should be closed and checked
for leaks. Where arrangements permit, parts of the
unit such as the superheater can be isolated by filling with demineralized water. Temporary piping
should be installed to flush dead legs after cleaning.
In addition to filling the superheater with demineralized water, once-through type units should be pressurized with a pump or nitrogen. The pressure should
exceed the chemical cleaning pump head.
Bronze or brass parts should be removed or temporarily replaced with steel. All valves should be steel or
steel alloy. Galvanized piping or fittings should not be
Table 7
Comparative Cleaning Effectiveness
Makeup of Deposit
Type of
Cleaning
HCl
HAF
EDTA
Citric
Bromate
Iron
Copper
Silica
Hardness
(Ca/Mg)
Good
Good
Good
Good
N/A
Medium
Poor
Medium
Medium
Good
Medium
Medium
Poor
Poor
N/A
Good
Medium/poor
Medium/poor
Poor
N/A
used. Gauge and meter connections should be closed

or removed.
All parts not otherwise protected by blanking off or
by flooding with water will be exposed to the inhibited solvent. Vents to a safe discharge should be provided wherever vapors might accumulate, because
acid vapors from the cleaning solution do not retain
the inhibitor.
Cleaning equipment The cleaning equipment should
be connected as shown in Fig. 24 if the continuous
circulation method is used, or as shown in Fig. 25 if
the soaking method is used. Continuous circulation
requires an inlet connection to assure distribution. It
also requires a return line to the chemical cleaning
pump from the unit. The soaking method does not
require a return line. The pump discharge should be
connected to the lowermost unit inlet.
The filling or circulating pump should not be fitted
with bronze or brass parts; a standby pump is recommended. A filling pump should have the capacity to
deliver a volume of liquid equal to that of the vessel
within two hours at 100 psi (0.7 MPa). A circulating
pump should have sufficient capacity to meet recommended cleaning velocities. With modern oncethrough boilers, a capacity of 3600 GPM (227 l/s) at
300 psi (2.1 MPa) is common. A solvent pump, closed
mixing tank and suitable thermometers, pressure
gauges, and flow meters are required. An adequate
supply of clean water and steam for heating the solvent should be provided. Provision should be made for
adding the inhibited solvent to the suction side of the
filling or recirculating pump.
Cleaning solutions Estimating the content of the
vessel and adding 10% to allow for losses will determine the amount of solvent required. Sufficient commercial acid should then be obtained. An inhibitor
qualified for use with the solvent also needs to be procured and added to the solvent.
Cleaning procedures
The chemical cleaning of steam generating equipment consists of a series of distinct steps which may
include the following:
1.
2.
3.
4.
Fig. 26 Solvent conditions during cleaning by the circulation method.
isolation of the system to be cleaned,

hydrostatic testing for leaks,
leak detection during each stage of the process,
back flushing of the superheater and forward
flushing of the economizer,
5. preheating of the system and temperature control,
42-23

6.
7.
8.
9.
10.
11.
solvent injection/circulation (if circulation is used),

draining and/or displacement of the solvent,
neutralization of residual solvent,
passivation of cleaned surfaces,
flushing and inspection of cleaned surfaces, and
layup of the unit.
Every cleaning should be considered unique, and

sound engineering judgment should be used throughout the process. The most important design and procedural considerations include reducing system leakage,
controlling temperature, maintaining operational flexibility and redundancy, and ensuring personnel safety.
Precautions
Cleaning must not be considered a substitute for
proper water treatment. Intervals between cleanings
should be extended or reduced as conditions dictate.
Every effort should be used to extend the time between chemical cleanings. Hazards related to chemical cleaning of power plant equipment are fairly well
recognized and understood, and appropriate personnel safety steps must be instituted.27
Chemical cleaning of superheater, reheater and

steam piping
In the past, chemical cleaning of superheaters and
reheaters was not performed because it was considered unnecessary and expensive. With the use of
higher steam temperatures, cleaning procedures for
superheaters, reheaters and steam piping have gained
importance and acceptance.
When chemically cleaning surfaces that have experienced severe high-temperature oxide exfoliation
(spalling of hard oxide particles from surfaces), it is
important to first remove a tube sample representing
the worst condition. Oxidation progresses at about the
same rate on the outside of the tubes as on the inside;
exfoliation follows a similar pattern.
The tube sample should be tested in a facility capable of producing a flow rate similar to that used in
the actual cleaning. This allows development of an
appropriate solvent mixture.
To determine the circulating pump size and flows
required, it is usually necessary to contact the boiler
manufacturer.
Figs. 27 and 28 show possible superheater/reheater
chemical cleaning piping schematics for drum boiler and
once-through boiler systems, respectively.
If, in the case of a drum boiler, the unit is to be
cleaned along with the superheater and reheater, it
is usually necessary to orifice the downcomers to obtain the desired velocities through the furnace walls.
A steam blow to purge all air and to completely fill
the system must precede cleaning in all systems containing pendant non-drainable surfaces. Most
drainable systems also benefit from such a steam blow.
Presently, two solvent mixtures are available to
clean superheater, reheater and steam piping. One is
a combination of hydroxyacetic and formic acids containing ammonium bifluoride; the other is an EDTA
(ethylenediaminetetraacetic acid)-based solvent.
42-24
Fig. 27 Typical superheater/reheater chemical cleaning circuit for a

drum-type boiler.
Solvent disposal
General considerations A boiler chemical cleaning
is not complete until the resultant process waste water stream is disposed of. Selection of handling and
disposal methods depends on whether the wastes are
classified as hazardous or non-hazardous. Boiler
chemical cleaning wastes (BCCW) are different in
volume and frequency of generation and have different discharge regulations from other power plant waste
streams. Of all power plant discharges, BCCWs are
most likely to be classified as hazardous. Depending
upon the cleaning process, the resultant BCCW may
become one of the driving forces in solvent selection.
Under National Pollutant Discharge Elimination
System (NPDES) requirements, boiler cleaning wastes
are considered chemical metal cleaning wastes. The
primary parameters of concern are iron, copper, chromium and pH. In all cases, waste management must
be performed in accordance with current regulatory
requirements.
Waste management options Table 8 lists the handling practices for BCCW. In co-ponding, the BCCW
is mixed in an ash pond with other waste streams from
the power plant. Acid wastes are neutralized by the
alkaline ash, and the metals are precipitated as insoluble metal oxides and hydroxides, or absorbed on
ash particles. Co-ponding is the least expensive and
the easiest disposal option.
Incineration of organic-based cleaning wastes by
direct injection into the firebox of the utility boiler is
another common disposal practice. Potential emissions
from the boiler must be carefully monitored to ensure
regulatory compliance.
Large quantities of BCCW are often disposed of in a
secure landfill. Evaporation can reduce waste volume
and, thereby, reduce overall landfill disposal costs.
HCl cleaning wastes can be treated to NPDES standards using lime or caustic precipitation. It is more

Removing metal ions and reusing chemical cleaning waste are subjects receiving increased attention.
As the regulatory environment continues to change,
more emphasis will be placed on the treatment and
reuse of BCCW.
Layup
Fig. 28 Typical superheater/reheater chemical cleaning circuit for a

once-through boiler.
difficult to treat the organic cleaning agents (such as

EDTA) by current techniques. Treatment methods with
permanganate, ultraviolet light, and hydrogen peroxide (wet oxidation) have been used with limited
success. Several vendors have proprietary processes
which claim to successfully treat chelated wastes.28,29
Table 8
Boiler Chemical Cleaning Wastes
Practices/Options
Source Reduction
Optimize cleaning frequency
Reduce volume of cleaning solution
Improve boiler water chemistry
Alternate Solutions
Change the cleaning solvent
Disposal
Evaporation
Incineration
Co-ponding
Secured landfill
Treatment
Neutralization
Physical waste treatment
Chemical waste treatment
Recycle and Reuse
Recycle for metal recovery
Reuse acid in alternate applications
During periods when boiler operation is interrupted, substantial pitting and general corrosion can
occur within unprotected water-steam circuitry. When
boilers return to operation, corrosion products migrate
to high heat flux areas of the boiler or carryover to
the turbine. Out-of-service corrosion can therefore impede boiler startup and lead to operational problems
such as deposition, under-deposit corrosion, corrosion
fatigue, and cycle efficiency loss.
Preservation methods inhibit out-of-service corrosion by eliminating or controlling moisture, oxygen,
and chemical contaminants that cause corrosion. Table
9 provides a brief summary and comparison of common preservation methods.
These methods are designed to limit corrosion
caused by the normal range of boiler and atmospheric
contaminants. Gross contamination must be avoided
and, if it occurs, the contaminants must be immediately neutralized and removed. Respective vendors
should be contacted for specific recommendations for
balance-of-plant equipment (turbine, condensate,
feedwater, and atmospheric pollution control systems).
Vendor procedures should also be followed for boiler
auxiliary equipment such as pulverizer gearboxes,
sootblowers, fans, and motors.
Boiler shutdown for layup

Appropriate shutdown procedures can facilitate
preservation for subsequent idle periods. Reducing
load dissipates fluid-side salts that concentrate on
tube surfaces in high heat flux areas. As boiler load is
reduced, feedwater and boiler water pH should be
increased to the upper end of the target operating
range, preferably 9.6 or higher. Where an oxygen
scavenger/inhibitor is employed, concentration should
increase to 0.050 ppm hydrazine* or equivalent.
When boiler water is to remain in the boiler for a substantial cold layup period, the oxygen scavenger/inhibitor concentration in the water should be increased
to 20 ppm hydrazine or equivalent after the boiler
pressure has decayed to below 200 psig (1.4 MPa). At
higher pressures and associated temperatures, the
scavenger may rapidly decompose. An oxygen scavenger/inhibitor is not added to boilers that employ oxygen treatment. For boilers on oxygen treatment, the
oxygen feed should be stopped at least an hour be-
*WARNING: HYDRAZINE IS A PROVEN GENERIC

CHEMICAL FOR THIS APPLICATION. HOWEVER,
HYDRAZINE IS A KNOWN CARCINOGEN, AND CAN
BE REPLACED WITH OTHER PRODUCTS THAT
HAVE EQUIVALENT ABILITY TO SCAVENGE OXYGEN
AND INHIBIT CORROSION.
42-25
Table 9
Summary and Comparison of Boiler Lay-up Methods
Lay-up Method
Effectiveness
Costs
Safety and
Environmental Concerns
Strengths
Weaknesses
Drained and dry

for erection or
maintenance
Poor
Minimal
Minimal
Allows full access to

internal surfaces
Quick and easy
Not effective
Vaporous
corrosion
inhibitors
Variable,
generally
fair
Chemicals
Chemical application
Chemical removal
and disposal
Handling and disposal

of chemicals
Minimal maintenance
requirements
Remaining inhibitive
capacity is difficult
to monitor
Chemicals must be
replaced periodically
Difficult to distribute
through components
Nitrogen
blanketing
Excellent
Nitrogen distribution
system
Nitrogen
Nitrogen suffocation
Consistently effective
Easy to monitor
Safety concerns
Nitrogen leakage
Hot standby
Good
Heat
Residual temperature
and pressure
Fast restart
Not recommended for

more than 3 days
Cold standby
Poor
Minimal
Minimal
Fast restart
Not recommended for

more than 30 days
Wet, water-filled
Variable,
generally
good
Demineralized water
Chemical treatment
Disposal of treated
water
Handling of
chemicals
Disposal of treated
water
Easily applicable to
non-drainable
components
Facilitates rapid
return to service
Freeze damage
Valve seepage and
associated corrosion
damage
Difficult to monitor
and inspect
May corrode copper
alloys beyond boiler
Dry, dehumidified
air
Excellent
Dehumidifier and
blower unit
Air recirculation
piping
Minimal
Consistently effective
Safe
No disposal problems
Easy to monitor
Boiler must be
totally drained
Initial plumbing
and equipment
requirements
fore shutdown; there can be no oxygen leakage into

the cycle. Where possible, as steam pressure decays
to atmospheric pressure, nitrogen should be introduced
through upper vents to keep the internal pressure
positive and prevent air ingress. Boiler-specific operating instructions should be consulted for other important shutdown procedures and precautions.
Draining for boiler maintenance and inspection

Draining boilers without further preservation is
often necessary for maintenance and inspection, and
the unit should be drained and dried as thoroughly
as possible. Draining the boiler hot (for example, at
20 psig/0.14 MPa) will facilitate drying, but may leave
condensate in non-drainable superheater elements.
Boiler components that need not be open for maintenance should, where possible, be isolated and protected. For example, while the lower furnace is open
for maintenance, the superheater should, if possible,
be protected with an appropriate wet or dry layup
method. All openings should remain covered to prevent ingress of contaminants.
The unpreserved maintenance period should be as
42-26
brief as possible, preferably less than 3 weeks. Where

a long maintenance outage with minimal preservation is necessary, the boiler and open sections of the
pre-boiler system should generally be chemically
cleaned and repassivated to reform a protective oxide
film following the outage.
Hot standby and hot layup

When a boiler returns to operation while steam pressure remains above atmospheric pressure, preservation
requirements are minimal. If the shutdown period is
less than 72 hours and there is no air in-leakage, ammonia and oxygen scavenger/inhibitor concentrations
need only be raised to the high end of the normal operating range with an oxygen scavenger/inhibitor concentration equivalent to about 0.050 ppm hydrazine.
Oxygen scavengers are not used for boilers that employ oxygen treatment. However, a low oxygen concentration must be maintained by effective deaeration, and
water must remain at a high level of purity with cation conductivity less than 0.15 S/cm.
Extended hot standby is not recommended. Hot
layup can be extended by use of auxiliary heat, but

non-corrosive and non-depositing conditions can be
difficult to assure, especially in economizers, superheaters, and reheaters. If temperature is maintained
by injecting blowdown from an adjacent boiler, excessive blowdown solids can accumulate under low-flow
conditions in the standby boiler. When steam is injected from another boiler, deposition and corrosion
problems can arise from temperature and chemistry
differentials. Also, care must be taken to avoid cavitation and to control the chemistry of steam condensate. Water leakage across valves can cause corrosion
in seepage areas, and the corrosion is aggravated by
relatively high material and water temperatures.
Cold standby for up to thirty days

For short periods (not more than a week), boilers
may remain on cold standby status with little or no
chemical additions. Moderate ammonia and oxygen
scavenger/inhibitor additions can extend this period up
to thirty days. Treated demineralized water for shortterm cold standby should have a minimum concentration of 10 ppm ammonia. The concentration of oxygen
scavenger/inhibitor normally used in the boiler should
be increased to the equivalent of 25 ppm of hydrazine.
Nitrogen blanketing (see below) is recommended.
For boilers employing oxygen treatment, no scavenger should be used for short cold standby periods. However, oxygen ingress must be avoided and low oxygen
concentrations must be maintained (for example, by use
of nitrogen blanketing of boiler and deaeration of
makeup water). Throughout the storage period, the pH
must be 9.2 or higher, and cation conductivity throughout the boiler must be less than 0.15 S/cm.
Boiler storage for more than seven days
Any of several layup practices are acceptable for
storage periods up to six months. Alternatives for fluidside layup include nitrogen blanketing, wet layup with
treated demineralized water, and dry dehumidified
layup. For extended outages, it is important that the
pre-boiler feedwater train, balance of the water-steam
cycle, auxiliary equipment, and fireside of the boiler
are adequately preserved. For idle periods longer than
six months, dry (dehumidified) storage is recommended. For boilers with non-drainable components,
water removal issues must be weighed against the
advantages of dry layup.
Reheaters all periods
Reheaters are generally stored dry because they
can not easily be isolated from the turbine. Wet storage requires installation of blanks or special valves in
the connecting lines. Drying can be performed by exposing reheaters to condenser vacuum after the fires
have been removed, the unit tripped, and the turbine
seals maintained. With approximately 20 in. (5 kPa)
of vacuum on the condenser, vents or drains on the
reheater inlet should be opened to allow air to pass
through and remove all moisture. Dehumidified dry
storage is recommended where the storage period exceeds 30 days. Alternatively, the evacuated reheater
may be isolated and nitrogen blanketed, or it may be
nitrogen blanketed in conjunction with the turbine.
Nitrogen blanketing
Even where water is present, corrosion can be prevented by eliminating oxygen from the environment.
Oxygen can be eliminated by sealing and pressurizing the entire boiler, or the space above water level,
with nitrogen to prevent air in-leakage. In the absence
of acids and other oxidants, eliminating air stops corrosion. Nitrogen blanketing is a highly effective
method for preventing corrosion. It is easy to monitor
and alarm, so effective preservation can be assured.
However, the boiler must be well sealed to prevent
excessive leakage.
It is absolutely imperative that working spaces
around nitrogen blanketed equipment be well ventilated. Venting of nitrogen during purging or water
filling operations can release large amounts of nitrogen into surrounding areas. Also, before entry, areas
that have been nitrogen blanketed must be well ventilated and the air tested to confirm that all parts have
adequate oxygen concentrations.
Wet (water-filled) layup
Wet layup in combination with nitrogen blanketing is often the most practical method of protection,
especially for boilers that are not fully or easily
drainable. However, for longer storage periods, advantages of wet layup are offset by accumulative corrosion in areas of valve seepage and by accumulative
cost of replacement water, chemicals, treated water
disposal, nitrogen cover gas, and heat in cold climates.
Consequently, dry layup is generally recommended for
storage periods longer than six months.
Before a boiler is flooded with layup water, provision
must be made to support the additional weight when
drum (if present), superheater, and steam piping are
filled. If the boiler is to be completely filled with layup
water, an expansion tank or surge tank above the highest vent is necessary to accommodate volume changes
that are caused by normal temperature fluctuations.
The expansion space at the top of the boiler (whether
in a drum or in a surge tank) should be nitrogen blanketed to assure that there is no air ingress. Where freezing conditions are expected or possible, provision must
be made for heating water-filled components.
Wet layup generally requires demineralized water
having a specific conductivity less than 1.0 S/cm before treatment chemicals are added. Use of demineralized water and all volatile treatment chemicals is
essential where boilers include non-drainable or stainless steel components. Use ammonium hydroxide to
raise water pH into the range of 10.0 to 10.4. Use an
oxygen scavenger/inhibitor to further retard corrosion.
Dry (dehumidified) layup
Dry layup requires the removal of all water and the
dehumidification of air to maintain a relative humidity less than 50%, and preferably less than 40%. This
prevents corrosion by hygroscopic salts. Dry-air (dehumidified) storage is highly effective, and its continued effectiveness is easy to monitor. Dry layup allows
easy and safe access for maintenance, with no potential for suffocation and no exposure to toxic chemicals.
42-27

It also eliminates the potential for biological activity,
damage from freezing water, and corrosion by leaking water. However, implementation requires that the
boiler be completely drained and dried, and this is a
major problem for boilers with non-drainable superheaters or other non-drainable circuits. Also, mechanical circulation and dehumidification equipment and
piping installation can be costly.
In preparation for dry storage, water must be
drained completely from all boiler circuits, including
feedwater piping, economizer, superheater, and
reheater. All non-drainable boiler tubes and superheater tubes should be blown with pressurized air.
Auxiliary sources of heat are used to dry fluid-side
surfaces. Deposits of sufficient thickness to retain
moisture must also be removed.
The preferred dry layup method is continuous recirculation of dehumidified air. Fans force air through
the dehumidifier, boiler fluid-side circuitry, and back
to the dehumidifier. The system must include instrumentation for measuring relative humidity. Recirculating dehumidification also requires external (usually flexible plastic) piping to complete the path. The
system must be sized to handle the residual moisture
and moist air in-leakage, and must be monitored to
assure that relative humidity remains less than 50%.

An alternative, but inferior, dry layup method is the
use of static desiccant to absorb moisture with no forced
air circulation. This method is effective for boiler components and small (package) boilers, but not generally adequate for large complex boiler circuitry.
Termination of the storage period requires removal
of the recirculation, dehumidification, and monitoring
materials and equipment. Any loose desiccant particles
or dust (which generally contain silica or sulfite
chemicals) must be cleaned from the boiler.
Vaporous corrosion inhibitors (VCI)

Vaporous corrosion inhibitors retard corrosion by
forming a thin protective film over metal surfaces.
Where such chemicals are sealed into a closed space,
they can retard corrosion even in the presence of both
water and oxygen. These inhibitors are not generally
used for completed boilers, where the size and complexity of boiler circuits precludes effective distribution of dry powders. However, they are often used to
inhibit internal corrosion of boiler components, as
supplements to dry storage for small boilers, and as
an alternative treatment for hydrotest water.
References
1. Klein, H.A., and Rice, J.K., A research study on internal corrosion in high pressure boilers, Journal of Engineering for Power, Vol. 88, No. 3, pp. 232-242, July, 1966.
2. Cohen, P., Ed., The ASME Handbook on Water Technology in Thermal Power Systems, The American Society of Mechanical Engineers, New York, New York, 1989.
3. Consensus on Operating Practices for the Control of
Feedwater and Boiler Water Quality in Modern Industrial
Boilers, The American Society of Mechanical Engineers,
New York, New York, 1994.
4. Interim consensus guidelines on fossil plant cycle
chemistry, Report CS-4629, Electric Power Research Institute, Palo Alto, California, June, 1986.
5. Guideline for Boiler Feedwater, Boiler Water, and
Steam of Steam Generators with a Permissible Operating Pressure > 68 bar, VGB PowerTech e.V., Essen, Germany, VGB-R 450 Le, (in German), 1988.
6. Betz Handbook of Industrial Water Conditioning,
Ninth Ed., Betz Laboratories, Trevose, Pennsylvania, September, 1991.
7. Drew Principles of Industrial Water Treatment, 11th
Ed., Drew Industrial Division, Ashland Chemical Co.,
Boonton, New Jersey, 1994.
8. Kemmer, F.N., Ed., The Nalco Water Handbook, Second Ed., McGraw-Hill, New York, New York, 1988.
9. Macbeth, R.V., et al., UKAEA Report No. AAEW-R711,
Winfrith, Dorchester, United Kingdom, 1971.
10. Goldstein, P., and Burton, C.L., A research study on
internal corrosion of high-pressure boilers final report,
Journal of Engineering for Power, Vol. 91, pp. 75-101,
April, 1969.
42-28
11. Freier, R.K., Cover layer formation on steel by oxygen in neutral salt free water, VGB Speiserwassertagung
1969 Sunderheft, pp. 11-17 (in German), 1969.
12. Whirl, S.F., and Purcell, T.E., Protection against
caustic embrittlement by coordinated pH control, Third
Annual Meeting of the Water Conference of the Engineers
Society of Western Pennsylvania, Pittsburgh, Pennsylvania, 1942.
13. Stodola, J., Review of boiler water alkalinity control,
Proceedings of the 47th Annual Meeting of The International Water Conference, Pittsburgh, Pennsylvania, pp.
235-242, October 27-29, 1986.
14. Economy, G., et al., Sodium phosphate solutions at
boiler conditions: solubility, phase equilibrium and interactions with magnetite, Proceedings of the International
Water Technology Conference, Pittsburgh, Pennsylvania,
pp. 161-173, 1975.
15. Tremaine, P., et al., Interactions of sodium phosphate
salts with transitional metal oxides at 360C, Proceedings
of the International Conference on Interaction of Iron
Based Materials with Water and Steam, Heidelberg, Germany, June 3-5, 1992.
16. Martynova, O.I., Transport and concentration processes of steam and water impurities in steam generating
systems, Water and Steam: Their Properties and Current Industrial Applications, J. Staub and K. Scheffler,
Eds., Pergamon Press, Oxford, United Kingdom, pp. 547562, 1980.
17. Nagda, N.L. and Harper, J.P., Monitoring Water in
the 1990s: Meeting New Challenges, STPl102, American
Society for Testing and Materials, Philadelphia, Pennsylvania, 1991.

18. Annual Book of ASTM Standards, Section 11, Water
and Environmental Technology, Vol. 11.01 (D 1192 Specification for Equipment for Sampling Water and Steam; D
1066 Practice for Sampling Steam; D 3370 Practice for
Sampling Water; and D 4453 Handling of Ultra-pure Water
Samples), American Society for Testing and Materials,
Philadelphia, Pennsylvania, 2004.
19. Steam and Water Sampling, Conditioning, and Analysis in the Power Cycle, ASME Performance Test Code
19.11, The American Society of Mechanical Engineers,
New York, New York, 1997.
20. Rice, J., Quality assurance for continuous cycle chemistry monitoring, Proceedings of the International Conference on Fossil Plant Cycle Chemistry, Report TR100195, Electric Power Research Institute, Palo Alto, California, December, 1991.
21. Uhlig, H.H., and Revic, R.W., Corrosion and Corrosion Control, Third Ed., John Wiley & Sons, New York,
New York, 1985.
22. Lamping, G.A., and Arrowood, Jr., R.M., Manual for
Investigation and Correction of Boiler Tube Failures, Report CS-3945, Electric Power Research Institute, Palo Alto,
California, 1985.
23. French, D.N., Metallurgical Failures in Fossil Fired
Boilers, Second Ed., Wiley, New York, New York, 1993.
24. Port, R.D., and Herro, H.M., The Nalco Guide to Boiler
Failure Analysis, McGraw-Hill Company, New York, New
York, 1991.
25. Dooley, R.B., and McNaughton, W.P., Boiler Tube
Failures: Theory and Practice, Electric Power Research
Institute, Palo Alto, California, 1996. LICENSED MATERIAL available to EPRI members.
26. Annual Book of ASTM Standards, Section 11, Water
and Environmental Technology, Vols. 11.01 and 11.02,
American Society for Testing and Materials, Philadelphia,
Pennsylvania, 2003.
27. Wackenhuth, E.C., et al., Manual on chemical cleaning of fossil-fuel steam generating equipment, Report CS3289, Electric Power Research Institute, Palo Alto, California, 1984.
28. Samuelson, M.L., McConnell, S.B., and Hoy, E.F., An
on-site chemical treatment for removing iron and copper
from chelant cleaning wastes, Proceedings of the 49th International Water Conference, Pittsburgh, Pennsylvania,
p. 380,1988.
29. Nalmet heavy metal removal program, Nalco Chemical Company, Naperville, Illinois, February, 1989.
42-29
Degassed conductivity analyzer for water quality analysis.
42-30

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The Babcock & Wilcox Company

Steam generation and use involve thermal and

these goals, and vigilance is required to detect early

The Babcock & Wilcox Company

Impurities purge slowly from the boiler because the

Control of deposition, corrosion, and

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

The Babcock & Wilcox Company

Fig. 1 Three years of operation resulted in light deposits because of

trated in Fig. 3 accumulate, they restrict flow to the

Fig. 2 Schematic of the wick boiling mechanism (adapted from

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

from corrosion of pre-boiler cycle components. Scaling

Fig. 3 An example of internal deposits resulting from poor boiler

The Babcock & Wilcox Company

pH, all ferrous

pH, copperbearing heaters

8.8 to 9.2** 8.8 to 9.2

* All volatile treatment.

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

The Babcock & Wilcox Company

The selection of equipment for purification of

cially for all boilers operating at pressures greater than

The Babcock & Wilcox Company

Returned condensate condensate polishing

injection pumps or alternative feedwater pH control

Deaeration and chemical oxygen scavengers

Fig. 4 Approximate relationship between conductivity and pH for

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

The Babcock & Wilcox Company

Drum boilers and internal boiler water

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

ter evaporation. Water chemistry must be carefully

The Babcock & Wilcox Company

Traditional all volatile treatment

viet Union (FSU). It can only be used where there is

Coordinated phosphate treatment

Blowdown is accomplished through a pressure letdown

Dissolved Solids, ppm

Fig. 5 Phosphate concentrations to control boiler water chemistry

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

The Babcock & Wilcox Company

Na/PO4 = 3.0 + 1ppm NaOH

Fig. 6 Estimated pH of sodium phosphate solutions. Note: pH values

Steam 41 / Water and Steam Chemistry, Deposits and Corrosion

ment regime and by experience with caustic boiler

* For natural separation with no diffuser baffles in the

The Babcock & Wilcox Company

100 ppm or as necessary to 50 ppm or as necessary to

0.5 ppm or as necessary to

0.1 ppm or as necessary to

2.6 to 3.0 + 1 ppm NaOH

2.6 to 3.0 + 1 ppm NaOH

2.8 to 3.0 + 1 ppm NaOH

See Figs. 6 and 7

9.4 to 10.5 and as dictated

9.0 to 10.0 and as dictated

9.0 to 10.0 and as dictated

pH and phosphate concentration from target values.

The Babcock & Wilcox Company

NH3 PO4 + 1ppm NaOH

Fig. 7 Estimated pH of sodium phosphate solutions containing 0.2

High-alkalinity phosphate treatment

Dispersants, polymers, and chelants