Water and Steam Chemistry, Deposits and Corrosion.
Water and Steam Chemistry, Deposits and Corrosion.
Water and Steam Chemistry, Deposits and Corrosion.
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 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.
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. 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.
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 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.
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 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 x concentration flow + makeup concentration x makeup
flow) / total feedwater flow (1)
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 especially 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 two-bed-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 corrosion. 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.
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 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.
Attemperation water
Water spray attemperation is used to control steam temperature. 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.
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.
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, the water concentration factor into the boiler is 100 and 10% of the
silica in the boiler water carries over with the steam, the equilibrium silica concentration into the
steam is 0.1 ppm.
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.
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++ PO43- HPO42- balance buffers the pH (i.e., retards H+ ion
concentration changes). Solution pH depends on the phosphate concentration and the molar
sodium-to-phosphate 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 cannot be used in calculating sodium-to-phosphate ratios for control of 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
sodium to- 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
treatment 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.
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 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.
Steam purity
Purity or chemistry requirements for steam
can be as simple as a specified maximum
moisture content, or they can include
Fig. 10 Solids in steam versus dissolved solids in boiler water.
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
Fig. 11 Boiler water silica concentration limit, where maximum solids concentrations less than 1.0 ppm are
steam silica is 0.010 ppm and boiler water pH is greater than 8.8. recommended at pressures up to 600 psig (4.1
MPa), dissolved solids concentrations less than
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.
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.
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 discussion 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. 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 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.
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. 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 steam forming 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 sodium to- phosphate
diffuses into the steel where 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.
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 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 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. Short-term overheat failures generally occur only when there is gross interruption
of internal flow to cool the tube, or grossly excessive heat input.
Pre-operational cleaning
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
Chordal thermocouples
The chordal thermocouple 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 22oC) above saturation in
low duty units and 80 to 100 F (44 to 56 oC) 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 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 100 F (56 oC).
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.
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.
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).
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
Fig. 25 Chemical cleaning by the soaking method
be assured without an impractically-sized
simplified arrangement of connections for drum-type
boilers. 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.
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 chelant-based solvent at high temperature is used to remove iron, followed by addition of an
oxidizing agent at reduced 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:
Fe3O4 + 8HCl 2FeCl3 + FeCl2 + 4H2O (2)
CaCO3 + 2HCl CaCl2 + 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 FeCl2 + H2 (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.
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. isolation of the system to be cleaned,
2. hydrostatic testing for leaks,
3. leak detection during each stage of the process,
4. back flushing of the superheater and forward flushing of the economizer,
5. preheating of the system and temperature control,
6. solvent injection/circulation (if circulation is used),
7. draining and/or displacement of the solvent,
8. neutralization of residual solvent,
9. passivation of cleaned surfaces,
10. flushing and inspection of cleaned surfaces, and
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
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.
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
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
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
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.
*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.
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.
source: Steam/its generation and use, John B. Kitto and Steven C. Stultz, The Babcock & Wilcox Company, 2005.
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