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More TOC (> 1 ppm) in feed water will contribute to lowering pH due to

formation weak acids (organic) due to decomposition of TOC at 350 deg. C.


Boiler pH
Natural water is usually between 6.5 and 7.5 pH. A common
recommendation is to maintain boiler water at 8.5 pH.
Acidic water is corrosive. Alkalinic water is more prone to scaling.
Alkalinity is a measure of the bicarbonate (HCO3), carbonate (CO3)
and hydroxyl (OH) ions in the water. pH and alkalinity ratings are
NOT the same and are NOT proportional. pH is rated on the Scale
and alkalinity is measured in parts per million (ppm). A typically
recommended alkalinity rating is 140 - 700 ppm for boilers
operating below 300 psi.

Low pH
Background Use of deionized water as a makeup source has increased the need
for operator awareness of boiler water chemical control, testing, and response. High
purity makeup water does not contain measurable alkalinity, therefore boiler water
usually contains a very low to zero level of hydroxide alkalinity. Boiler water
alkalinity acts as a buffer. Caustic can be added to increase alkalinity in boiler water;
however as operating pressures increase over 1000 psig, this can lead to a problem
of caustic concentration and corresponding corrosion. Boiler water alkalinity is a pH
buffer against feedwater contamination. A buffer is defined as a substance in
solution which accepts either hydrogen ions (acids) or hydroxyl ions (bases)
entering the system, thereby minimizing a change in pH. With very low hydroxide
alkalinities, the buffering capacity of the boiler water becomes reduced and
feedwater contamination more significantly influences the pH. Where a coordinated
phosphate program is being used, buffering capacity is minimal and pH can change
rapidly with the slightest amount of feedwater contamination.
Contamination sources Contamination of high purity feedwater can occur from
several sources. 1. Salts entering the feedwater from condenser leaks or
demineralizer leakage. If the leakage is high in magnesium chloride (brackish water)
the chance of a low pH condition is greater. A small amount of hard water leakage
could cause a pH of 4 or less in an unbuffered boiler water. 2. Demineralizer
regenerant leakage. Cation exchange resin requires a strong acid for regeneration,
usually sulfuric or hydrochloric. The regenerant can enter the feedwater when
valves do not close properly during regeneration. The most common causes of this
phenomenon are a power outage and leaking valves or both. 3. In boilers over 1000
psig pressure, black liquor contamination may cause the boiler water pH to drop due
to organic acids, high magnesium, or high sulfidity.
Immediate action Low pH exclusions require immediate action to minimize the
effects on boiler waterside surfaces. A summary of pH levels and appropriate
actions to be taken are shown. Boiler water pH tests should be conducted frequently

until the problem is corrected. For the following boiler water pH ranges, continuing
actions should include:
pH 8.6 to 9.2
Action Add trisodium phosphate and back out any monosodium phosphate
being fed. Begin aggressive search for contaminant source including
alignment of regeneration valves, hardness checks on boiler feedwater, and
black liquor contamination. Maintain phosphate in normal range.
pH 8.0 to 8.6
Action Start feeding caustic to re-establish normal operating pH. Increase
continuous blowdown to maximum allowable rate. If dispersant is being fed,
increase feed to match increased blowdown. Add or increase boiler water antifoam
to minimize carryover. Monitor steam purity:
(A) Monitor condensed steam for sodium level
(B) Monitor condensed steam for conductivity level
(C) Monitor superheater outlet temperature.
3. pH 7.0 to 8.0
Action Notify downstream users of potential impact to their system. Continue
actions shown in Step 2. Reduce boiler steaming rate by 20%.

4. pH 6.0 to 7.0
Action Reduce steaming rate by an additional 20% (total 40%). Start to use all
possible blowdown, both continuous and manual.
5. pH 5.0 to 6.0
Action Prepare to take boiler offline. If pH continues to decrease (below 5) the fire
needs to be pulled immediately. Continue heavy blowdown of boiler and drain at
proper time. Refill with treated demineralized water, caustic, trisodium phosphate,
or regular water treatment chemicals.

If the boiler is continuing to run at pH lower than 5 for more than 4 h and the pH
was brought back up with caustic addition, large amounts of iron (corrosion product)
will precipitate as iron hydroxide. Iron deposits will form on the hot surfaces of the
radiant section and could cause tube failure short-term (within weeks) or long-term
(within months). Chemical cleaning as soon as practical is recommended to remove
the deposited iron.

Boiler blowdown is the removal of water from a boiler. Its purpose is to control boiler water parameters within
prescribed limits to minimize scale, corrosion, carryover, and other specific problems. Blowdown is also used to
remove suspended solids present in the system. These solids are caused by feedwater contamination, by internal
chemical treatment precipitates, or by exceeding the solubility limits of otherwise soluble salts.
In effect, some of the boiler water is removed (blowndown) and replaced with feedwater. The percentage of boiler
blowdown is as follows:

quantity blowdown water

X 100 = % blowdown

quantity feedwater

The blowdown can range from less than 1% when an extremely high-quality feedwater is available to greater than
20% in a critical system with poor-quality feedwater. In plants with sodium zeolite softened makeup water, the
percentage is commonly determined by means of a chloride test. In higher-pressure boilers, a soluble, inert material
may be added to the boiler water as a tracer to determine the percentage of blowdown. The formula for calculating
blowdown percentage using chloride and its derivation are shown in Table 13-1.
The primary purpose of blowdown is to maintain the solids content of boiler water within certain limits. This may be
required for specific reasons, such as contamination of the boiler water. In this case, a high blowdown rate is
required to eliminate the contaminants as rapidly as possible.
The blowdown rate required for a particular boiler depends on the boiler design, the operating conditions, and the
feedwater contaminant levels. In many systems, the blowdown rate is determined according to total dissolved solids.
In other systems, alkalinity, silica, or suspended solids levels determine the required blowdown rate.
For many years, boiler blowdown rates were established to limit boiler water contaminants to levels set by the
American Boiler Manufacturers' Association (ABMA) in its Standard Guarantee of Steam Purity. These standards
were used even though they were of a general nature and not applicable to each individual case. Today, the ASME
"Consensus on Operating Practices for the Control of Feedwater and Boiler Water Quality in Modern Industrial
Boilers," shown in Table 13-2, is frequently used for establishing blowdown rates.
This consensus applies to deposition control as well as steam quality. Good engineering judgment must be used in
all cases. Because each specific boiler system is different, control limits may be different as well. There are many
mechanical factors that can affect the blowdown control limits, including boiler design, rating, water level, load
characteristics, and type of fuel.
In some cases, the blowdown control limits for a particular system may be determined by operating experience,
equipment inspections, or steam purity testing rather than ASME or ABMA water quality criteria. In certain cases, it is
possible to exceed standard total solids (or conductivity), silica, or alkalinity limits. Antifoam agents have been
applied successfully to allow higher-than-normal solids limits, as shown in Figure 13-1. Chelating and effective
dispersant programs also may allow certain water criteria to be exceeded.
The maximum levels possible for each specific system can be determined only from experience. The effect of water
characteristics on steam quality can be verified with steam purity testing. However, the effects on internal conditions
must be determined from the results observed during the turnaround for the specific unit.
Certain boilers may require lower than normal blowdown levels due to unusual boiler design or operating criteria or
an exceptionally pure feedwater requirement. In some plants, boiler blowdown limits are lower than necessary due
to a conservative operating philosophy.

MANUAL BLOWDOWN
Intermittent manual blowdown is designed to remove suspended solids, including any sludge formed in the boiler
water. The manual blowdown take-off is usually located in the bottom of the lowest boiler drum, where any sludge
formed would tend to settle.
Properly controlled intermittent manual blowdown removes suspended solids, allowing satisfactory boiler operation.
Most industrial boiler systems contain both a manual interm

Blowdown Control

Blowdown from industrial steam boilers is typically


controlled automatically using a continuous system.
Automatic systems usually maintain the specific conductance
of the boiler water at a specified level, especially if
sodium zeolite softened makeup water is used. Other
boiler water constituents such as chlorides, sodium, and
silica are also used as a means of controlling blowdown.
Continuous blowdown is supplemented by manual
blowdown to discharge suspended solids from the low
points in the boiler system.
Here are some guidelines for blowdown control [9]:
Dissolved solids specific conductance gives an indirect measure of dissolved
solids and can usually be used for blowdown control. Conductance is caused by the
ionization of the various salts that are present; in dilute solutions there is almost
complete ionization; however, in concentrated solutions ionization is suppressed.
Therefore, it is best to correlate specific conductance with dissolved solids for each
system. For a rule of thumb estimate, very dilute solutions such as condensate
may be calculated with
a factor of 0.5 to 0.6 ppm of dissolved solids per microsiemens of specific
conductance. For a more concentrated solution such as boiler water, the factor
varies between 0.55 and 0.90 ppm of dissolved solids per microsiemens of specific
conductance. It is common practice to neutralize any hydroxide ions
with gallic acid or boric acid prior to measuring conductivity.
Chloride if the chloride concentration in the feedwater is high enough to
measure accurately, it can be used to control blowdown and to calculate the rate of
blowdown.
Chlorides do not precipitate in the boiler water, therefore the relative chloride
concentrations provide an accurate basis for calculating the rate of blowdown. The
chloride test is unsuitable when the feedwater chloride is too low for accurate
determination.
Silica on-line methods of silica monitoring are primarily applicable to boilers
operating at 600 psig or greater, utilizing a demineralized makeup and where the
steam is used in turbines. Silica in the steam must be limited to 0.01 to 0.02 ppm;
to do this the silica in the boiler water must be limited to a specified maximum that
is dependent on boiler pressure and system design.

Caustic Embrittlement
Whenever free caustic (NaOH) is present in a boiler, failure from caustic
embrittlement may occur. Embrittlement is a form of stress corrosion cracking. It
occurs in areas where there are specific stress conditions and free NaOH in the
boiler water. Boiler tubes usually fail from caustic embrittlement at points where
tubes are rolled into sheets, drums, or headers. However, it also occurs at weld
cracks and if there is tube-end leakage.
Sodium nitrate is usually used to inhibit embrittlement in boilers operating at low
pressures. The US Bureau of Mines recommends that the ratio of sodium nitrate to
sodium hydroxide be maintained in accordance with Table 9-5. At pressures above
7000 kPa (1000 psig), coordinated phosphate/pH control is usually employed which
precludes the development of high concentrations of caustic.
Calculate the ratio using the following formula:

Conductivity versus Dissolved Solids


For a quick estimate of total dissolved solids (TDS) in
water one can run a conductivity measurement. The unit
for the measurement is mhos/cm. A mho is the reciprocal
of an ohm. The mho has been renamed the Sieman (S) by
ISO. Both mhos/cm and S/cm are accepted as correct
terms. In water supplies (surface, ground, etc.) conductivity
will run about 10_6 S/cm or 1 mS/cm.
Without any data available the factor conductivity to
TDS is:

However, the local water supplier will often supply TDS


and conductivity data. Table 9-4 gives conductivity
factors for common ions found in water supplies.