Professional Documents
Culture Documents
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INDEX
1. Introduction
2. Boilers
Boilers water treatment three factors
3. Boilers water fundamental knowledge
4. Ships heat generation plant
5. Boilers
Boilers water treatment
6. Main problems in boilers caused by water
7. Unex boilers
boilers water recommendations
8. Lessons learned
9. Water chemistry terms
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1. INTRODUCTION
If boilers water doesnt receive proper treatment, the boiler will suffer from
carryover, sludging, scale and corrosion, leading to weak and dangerous
machinery.
Long before the boiler fails, water-related problems will cause:
Correct boiler water treatment and follow-up of the water and steam condition,
are of utmost importance for keeping the heat generation systems in good
condition.
The present report characterizes a ship heat generation system, its water
treatment procedures and maintenance required. The main objective is to
document the system and to establish optimal and standard operation processes.
It is also an important piece of digital information, part of the ship information
system, shareable and available for present and future crews, and a helpful tool to
support company management.
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2. BOILERS
BOILERS WATER TREATMENT - THREE FACTORS
1. CHEMICAL TREATMENT
Water normally contains various levels of contaminants, dissolved solids
(minerals) and dissolved gases. These contaminants cause major operational
problems and damage to boilers unless they are removed or controlled on a
continuing basis. Correct application of chemical treatment programs can
eliminate many problems associated with boiler operations.
But other problems can and do impact operations.
They are into two major areas:
Management concerns - Addresses the administration of boiler water operations.
Operator performance - Addresses the hands-on operation of boilers.
2. MANAGEMENT CONCERNS
Every installation has its own mode of operation and style of management.
Boiler water treatment is one small area of operations but is so critical that
complete base operations may cease if boilers are not operated properly.
Observations indicate that major difficulties found in boiler water treatment
systems can be traced to management actions.
3. OPERATORS PERFORMANCE
The successful operation of boilers requires accurate analysis of the water that is
used, proper treatment to remove corrosive minerals and gases, and careful
attention to the controls and procedures for the taking of water samples, their
testing, and all required inspections.
The key players are the boiler operators and, of course, assigned supervisors.
A basic knowledge of boiler mechanics and water chemistry is an absolute
requirement, whether through formal training or on the job training.
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3. BOILERS
BOILERS WATER FUNDAMENTAL KNOWLEDGE
A boiler is a device for generating steam, which consists of two principal parts: the
furnace, which provides heat, usually by burning a fuel, and the boiler proper, a
device in which the heat changes water into steam. The steam is then recirculated
out of the boiler for use in various processes in heating applications.
There are basically two types of boilers:
A. WATER TUBE (20% of boilers in use)
Water is fed through a bundle of tubes inside the boiler, and heat is applied to the
outside of the tubes to heat the water.
B. FIRE TUBE (80% of boilers in use)
Heat travels through a bundle of tubes inside the boiler to heat the water
surrounding the tubes.
The bundle of tubes which carries water in the Water Tube Boiler and heat in the
Fire Tube Boiler is called the Heat Transfer Surface.
Both the Water Tube and the Fire Tube Boiler have the following components:
HEAT SOURCE - A gas, oil, or coal burner heats the water in the oiler.
HOTWELL - Tank that receives make-up water from ship water tanks and steam
condensate from the condenser, feeding the boiler with water. The hotwell is
heated to drive off dissolved oxygen and carbon dioxide gases before the water
enters the boiler. Since these gases dissolve more readily in cold water, heating
helps to eliminate them. Dissolved gases cause corrosion in the boiler. Scale and
corrosion prevention chemicals are added at the hotwell to condition the water
before it enters the boiler.
CONDENSER Equipment where steam return from consumers and is condensed
by lowering its temperature, through sea water circulation and heat transfer.
FEED WATER - The water entering the boiler from the hotwell.
Feedwater = Make-up Water + Condensate Return
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MAKE-UP WATER - The fresh water entering the hotwell from ship water tanks, to
compensate steam losses and blow-down. It could be raw water received from
shore or distilled water produced on ship.
Make-up Water = Blow-Down + Condensate Loss
FEED WATER PUMP - When heated water from the boiler is given off as steam,
and the pump feeds water into the boiler from the hotwell. The feed water pump
must generate sufficient pressure to overcome the pressure in the boiler.
BLOW-DOWN VALVE - This valve allows some of the water carrying accumulated
solids ("sludge") in the boiler to drain off. The act of removing water and sludge
from the boiler is called "blow-down."
WATER LEVEL CONTROL - The Water Level Control maintains the proper water
level inside the boiler. This water level can be visually checked at the sight glass.
The boiler tubes will become overheated if the water level is too low to keep the
heat transfer surface covered. Low water level will cause excessive stress to the
boiler. High water level will allow water to get into the steam lines, reducing the
efficiency of the boiler system.
SAFETY VALVES - These valves automatically releases any excess pressure that
builds up in the boiler. Every boiler has several safety mechanisms that will shut it
off in the event of malfunction.
The boiler receives the feed water, which consists of varying proportion of
recovered condensed water (return water) and fresh water, which has been
purified in varying degrees (make-up water).
The make-up water is usually distilled water or natural water, either in its raw
state, or treated by some process before use. Feedwater composition therefore
depends on the quality of the make-up water and the amount of condensate
returned to the boiler.
The steam, which escapes from the boiler, frequently contains liquid droplets and
gases. The water remaining in liquid form at the bottom of the boiler picks up all
the foreign matter from the water that was converted to steam. The impurities
must be blown down by the discharge of some of the water from the boiler to the
drains. The permissible percentage of blow-down is strictly limited by running
costs and initial outlay. The tendency is to reduce this percentage to a very small
figure.
REPORT: ALVARO SARDINHA
MARINE ENGINEER
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Pag |6 - 94
SCALE
As water flows over rock formations and through the earth, it picks up and
dissolves calcium and other metallic salts. When water enters a boiler, where it is
heated to produce steam, these dissolved solids precipitate out of solution. The
precipitates are left behind in the boiler water - they do not travel with the steam.
If they are allowed to accumulate, they will settle out as scale on the boiler metal.
This is what happens when water in a pan on the stove is allowed to boil dry, or
when water in a glass is allowed to evaporate completely. A residue of salts will be
left, which is scale.
When chemical treatment is not used, scale forms in a boiler. If scale is allowed to
build up, it reduces the heating efficiency of the boiler. A heavily scaled boiler
heats water to steam at a slower rate, because the scale acts as an insulator. This
increases operating costs.
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The amount of scale depends on the amount of dissolved solids in the water. If
water is added, the scale residue will not go back into solution. The U.S. Bureau of
Mines has determined that a thickness of only 2,82 mm scale in a boiler increases
fuel costs in 16%.
CORROSION
Gases in the air are soluble in water. The two that cause the most problems are
oxygen and carbon dioxide.
Dissolved oxygen in water entering the boiler causes corrosion, which will pit and
weaken the boiler. Rust is formed as a by-product. Rust deposits interfere with the
boiler's heating efficiency. This slower heating ability increases the boiler's
operating cost.
Carbon dioxide corrosion occurs in the condensate return system. Carbon dioxide
is released as a gas when water is converted to steam. This gas travels with the
steam. When steam liquefies and enters the condensate return lines, the carbon
dioxide gas is absorbed in the condensate water, forming a weak acid which will
eventually "groove" or wear away the metal.
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Hardness is expressed in ppm, which stands for parts per million. Let's say the
result of the Hardness test is 20 ppm. This means that for every 1 million Kg of
water, there are 20 Kg of hardness salts (dissolved calcium and magnesium).
Hardness must be precipitated out of water so that scale does not form. When
high alkalinity is present in the water, hardness is precipitated as soft sludge that
is held in suspension until blow-down. When low alkalinity is present in the raw
water, the alkaline builders in added chemical products provide the alkalinity
necessary to precipitate the hardness as soft sludge. A smaller dosage of
chemicals will be used if the make-up water is highly alkaline.
ALKALINITY TEST - Sodium hydroxide provides a highly alkaline environment in the
boiler. This is about the only environment where water and steel get along well.
Heat magnifies the normally corrosive effect water has on steel, since it speeds up
chemical reactions. Maintaining the correct alkalinity range minimizes this highly
corrosive effect of water. Alkalinity also plays a critical part in various chemical
reactions in the boiler. Frequently, most of boiler water alkalinity comes from the
addition of sodium hydroxide in the chemical program. Some of the alkalinity
comes from naturally occurring alkalinity found in raw water supplies. If it is
present naturally, it contributes to the required alkalinity in the boiler and
decreases the amount of sodium hydroxide needed.
Alkalinity is typically measured as either P-Alkalinity (Phenylthalein Alkalinity),
M-Alkalinity (Methyl Orange Alkalinity), or OH-Alkalinity (Hydroxide Alkalinity).
P-Alkalinity is determined by a relatively simple titration procedure. OH-Alkalinity
is determined by either using a modified version of the P-Alkalinity test, or by
calculation using P and M-Alkalinity (2xP-M=OH). OH-Alkalinity is primarily the
most important. However, P-Alkalinity is more convenient to test. If P-Alkalinity is
in range, the OH-Alkalinity will be also. Boiler alkalinity is directly related to boiler
pH so if the alkalinities are in range, the pH will be also.
"M" ALKALINITY TEST - This is used to determine the Total Alkalinity of the raw
water in ppm. The result of the "M" Alkalinity test is used to determine how much
chemical products should be added to feedwater.
SULFITE TEST - This test indicates the amount of Sulfite in the water. Sulfite and
oxygen cannot coexist; therefore, by keeping an excess of sulfite in the boiler
water, we can be sure there is no oxygen is present. If no oxygen is present, no
acid can be formed and there will be no corrosion.
Sulfite is used to consume dissolved oxygen in steam boiler systems. If dissolved
oxygen is permitted to exist in the boiler, it attacks the steel in the boiler forming
REPORT: ALVARO SARDINHA
MARINE ENGINEER
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Pag |9 - 94
oxygen pits. This pitting causes serious damage and eventually tube failure. This is
the most common form of corrosive attack in steam boilers. Dissolved oxygen can
also flash-out with the steam and cause corrosion throughout the condensate
return system. Sulfite reacts with dissolved oxygen to form sulfate, thus making
the oxygen unavailable to damage system metals. Sulfite is best fed into the feed
water system as far upstream as possible. The optimum feed location is at the
storage portion of a deaerator. A long distance in the feed water stream increases
the reaction time of the sulfite with the oxygen decreasing the possibility of
oxygen getting into the boiler. Consequently, much of the feed water system also
gets protected.
PHOSPHATES TEST - Phosphates are used to react with calcium and magnesium
hardness to produce controllable materials removable by blow-down. Phosphates
should be added to low pressure boilers to maintain a residual of 30 to 60 ppm as
ortho-phosphate. Any calcium or magnesium present will consume the orthophosphate. Hard make-up water requires enough phosphate to maintain the 30 to
60ppm residual in addition to that needed to neutralize all of the calcium and
magnesium hardness in the boiler water. Soft make-up water only requires
enough phosphate to maintain the same 30 to 60 ppm residual. A boiler on soft
make-up can be operated at higher cycles of concentration, thus requiring less
blow-down and less chemical treatment in general.
CONTROL TEST FOR ISOMINE - Phenolphthalein is an indicator which is colorless
below and pink above a pH of 8.2. When the pH of the condensate is higher than
8.2, pink indicates that corrosion is being prevented effectively. A red color
indicates excess chemical is being used; therefore, the feed rate should be
reduced.
CONDUCTIVITY TEST - Conductivity testing is used to monitor the amount of
material dissolved in water by measuring its ability to conduct electricity. The
more material dissolved in the water, the higher its conductivity will be. As a
boiler approaches its maximum allowable cycles, it will also approach its maximum
allowable conductivity. If boiler water's conductivity gets too high, indicating
excessive dissolved material is present, steam will start to have trouble escaping
the water's surface. This phenomenon is due to increased water surface tension
from higher dissolved solids concentrations. The boiler at this point will begin to
prime, or foam and bounce, resulting in tiny droplets of boiler water carrying over
with the steam. Good quality steam is essentially distilled water. Carryover
reduces the BTU content of the steam resulting in excess fuel consumption and
reduced efficiency.
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CHLORIDE TEST - When water is converted to steam, the dissolved solids do not
travel with the steam, but are left behind in the boiler water. Water enters the
boiler to replace the amount lost through steam evaporation. When this new
water is converted to steam, more solids are left behind. As steam is continually
produced, evaporated, and replaced with new water, the amount of solids in the
boiler continues to increase.
For every Kg of steam generated, a Kg of water must be replaced. The amount of
solids in the water will have doubled when the amount of new water that has
entered the boiler is equal to the amount of water that was used to originally fill
the boiler. When the amount of solids has doubled, there are 2 cycles of
concentration in the water; when the amount of solids has tripled, there are 3
cycles of concentration. Cycles of concentration is an indicator of the amount of
solids build-up in the water.
Chloride is chosen as the indicator for cycles of concentration because, 1) it is
always present in the make-up water, 2) it does not change character when
heated, 3) it is not affected by chemical treatment, and 4) like the other dissolved
solids, it does not leave the water in the boiler when steam is produced.
If the Chloride in the water doubles, all the solids have doubled. Elevated levels of
chlorides (over 200 ppm) in the water of steam boilers will accelerate water side
corrosion and shorten the operating life of the boiler.
DISPERSANTS - Phosphate precipitates (sludge) must be dispersed thoroughly to
prevent them from baking on to the heat transfer surfaces of boilers. A variety of
dispersants are used for this purpose and must be fed in a proper ratio to the
phosphate treatment.
AMINES - Return condensate is naturally corrosive because of its purity. The pH of
pure water is easily decreased in the presence of carbon dioxide. Carbon dioxide
dissolves in the water to form carbonic acid. Oxygen readily dissolves in pure
water also. Both low pH and dissolved oxygen lead to corrosion in any water
system especially in the presence of heat. The amount of carbon dioxide depends
primarily on the amount of carbonates present in the make-up water. Various
amines are used to neutralize the resulting carbonic acid in condensate causing
the pH to stabilize at higher less corrosive levels. The return condensate system is
then protected from carbonic acid corrosion.
Reducing corrosion decreases the amount of corrosion products that would
normally return to boiler and form deposits. These deposits can be the most
difficult to remove.
REPORT: ALVARO SARDINHA
MARINE ENGINEER
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The heat generating plant in a ship, may include oil-fired steam boilers with firetubes (auxiliary boiler) and exhaust gas boilers with water tubes.
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CONDENSATE SYSTEM
The heat generation plant includes a condensator. It is circulated by sea water to cool and
condensate steam returning from several consumers. The condensates return then to the
water feed tank (hotwell).
May also be available one observation tank that receives the return steam, used to heat
fuel for main engines, diesel generators and oil-fired boilers, and steam used to heat the
fuel oil and lubricating oil, at purifiers plant. At this tank is possible to check if there is oil
or fuel contamination of steam.
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5. BOILERS
BOILERS WATER TREATMENT
Correct use and careful maintenance of the boiler, increase its service life.
Maintenance of the burner and careful cleaning of the boiler are the most
important prerequisites for faultless operation. Also important for safety, working
life and security of boiler, are the correct treatment and maintenance of boilers
water.
The quality of water and functioning of the treatment equipment must be
regularly observed and any potential defects must be immediately eliminated.
A book of water values and functioning of devices must also be kept. In case of
potential malfunctioning, conclusions on reasons for them can be drawn on this
basis.
Characteristics of boiler feed water
Water absorbs more heat for a given temperature rise than any other common
inorganic substance. It expands 1600 times as it evaporates to form steam at
atmospheric pressure. The steam is capable of carrying large quantities of heat.
These unique properties of water make it an ideal raw material for heating and
power generating processes.
All natural waters contain varying amounts of dissolved and suspended matter
and dissolved gases. Since water impurities cause boiler problems, careful
consideration must be given to the quality of the water used for generating steam.
The composition of boiler feed water must be such that the impurities in it can be
concentrated a reasonable number of times inside the boiler, without exceeding
the tolerance limits of the particular boiler design. If the feed water does not meet
these requirements it must be pre-treated to remove impurities. The impurities
need not be completely removed in all cases, however, since chemical treatment
inside the boiler can effectively and economically counteract them.
Feedwater purity is a matter both of quantity of impurities and nature of
impurities: some impurities such as hardness, iron and silica are of more concern,
for example, than sodium salts. The purity requirements for any feedwater
depend on how much feedwater is used as well as what the particular boiler
design (pressure, heat transfer rate, etc.) can tolerate. Feedwater purity
requirements therefore can vary widely. A low-pressure fire-tube boiler can
usually tolerate high feed-water hardness with proper treatment while virtually all
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where the heat is greatest; principally in the fire box where the highest heat
concentration occurs. Normal acids have no effect in dissolving this scale.
MAGNESIUM SULFATE (MgSO4)
Magnesium sulfate is one of the most soluble of salts, having a solubility of 20% in
cold water and 42% in boiling water. It exists only in water of low pH.
COPPER
Copper is introduced into the system by corrosion of copper piping and copper
alloys. In cooling systems this may be caused by excessive use of water treatment,
causing highly alkaline conditions. In boilers, the source of this corrosion is
excessive use of hydrazine, or leaking internal de-super-heater elements in boiler
drums, which allow alkaline boiler water to enter the de-super-heater steam
system and corrode copper and copper alloys, bringing the copper to the boiler.
Copper in the boiler displaces tube steel or plates out. This condition frequently
takes place under scale or sludge deposits and is often described as under
deposit corrosion.
SILICA (Si02)
Silica is not generally found in marine boilers except in minute quantities. Silica
will produce a very hard scale and may be admitted to systems only if severe
carryover has occurred from evaporators distilling water from rivers where the
silica content is high, or if feed water is taken from cement washed tanks. In
certain cases, when row water is evaporated and is high in silica, carryover may
admit silica into the distilled water system.
On some new vessels where silicate coatings have been used in distilled water
storage tanks, initial silica readings may be high and should be tested often and
controlled by blow-down. Silica may cause difficulty in cooling water systems by
forming calcium and magnesium silicate scale.
IRON OXIDES (FeO - Fe2O3 - Fe3O4)
Iron may enter the boiler as a result of corrosion in the pre-boiler sections or parts
of the feed system, or may redeposit as a result of corrosion in the boiler itself.
Often, iron oxide will deposit and retard heat transfer within a boiler tube,
sometimes resulting in tube failure. When iron is not present in the row water
feed, its presence in the boiler or cooling system indicates active corrosion, a
more serious problem than its presence in scale in which it appears by occlusion.
Pag |24 - 94
Rust, the reddish form, is fully oxidized. More often, in a boiler with limited
oxygen, it is in the reduced or black form (Fe3O4). Fe3O4 is magnetic and can be
readily detected with a magnet.
OIL
To prevent oil from entering condensate and feedwater systems, certain safety
equipment is generally incorporated to remove or arrest such contamination if
this should arise. There are certain occasions due to mechanical failure (for
example, faulty oil deflectors at turbine glands passing lube oil to gland seal
condensers and main condensers, etc., or leaks at tank heating coils) causing oil to
enter a boiler.
Any oil film on internal heating surfaces is dangerous, impairing heat transfer
drastically to the extent that comparable heat retarding effects can be likened to
considerable dense scale build-up. Oil films therefore cause overheating of tube
metal, resulting in tube blistering and failure, or cracking of engine parts. If oil
contamination is suspected, immediate action must be undertaken for its removal.
DISSOLVED GASES
Dissolved gases are present in distilled water in the form of oxygen and carbon
dioxide. Each enters the condensate system from leaks in the vacuum side or open
exposure to the atmosphere, the atmospheric drain tank, surge tank, or feed filter
tank. Due to chemical reactions in water, carbon dioxide can form carbonic acid
(H2CO3), lowering the pH of the condensate, making it corrosive.
Oxygen is highly corrosive causing localized pitting and attack of boiler metal.
Mechanical deaerating equipment, if installed, is designed to remove the
majority of these dissolved gases. However, the most efficient deaerating
equipment still passes about 5 ppb (parts per billion) of dissolved gases. Chemical
treatment is required to render these gases harmless.
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In the following tables are presented lists of the common boiler feed water
contaminants, their effect and their possible treatment.
IMPURITY
RESULTING IN
GOT RID OF BY
SOLUBLE GASSES
Hydrogen sulphide (H2S)
Oxygen (O2)
IMPURITY
RESULTING IN
GOT RID OF BY
SUSPENDED SOLIDS
Sediment & Turbidity
Organic Matter
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IMPURITY
RESULTING IN
GOT RID OF BY
DISSOLVED SOLIDS
Oil & Grease
Sulfates (SO4)
Chlorides, (Cl)
Silica (SiO2)
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boiler with the feed water (hardness, oxygen, silica, etc.). In many cases external
treatment of the water supply is not necessary and the water can be treated only
by internal methods.
Internal treatment
Internal treatment is the conditioning of impurities within the boiler system. The
reactions occur either in the feed lines or in the boiler proper. Internal treatment
may be used alone or in conjunction with external treatment. Its purpose is to
properly react with feed water hardness, condition sludge, scavenge oxygen and
prevent boiler water foaming.
Internal treatment can constitute the unique treatment when boilers operate at
low or moderate pressure, when large amounts of condensed steam are used for
feed water, or when good quality raw water is available. The purpose of an
internal treatment is to:
1) React with any feedwater hardness and prevent it from precipitating on the
boiler metal as scale;
2) Condition any suspended matter such as hardness sludge or iron oxide in the
boiler and make it non-adherent to the boiler metal;
3) Provide anti-foam protection to allow a reasonable concentration of dissolved
and suspended solids in the boiler water without foam carryover;
4) Eliminate oxygen from the water and provide enough alkalinity to prevent
boiler corrosion.
In addition, as supplementary measures an internal treatment should prevent
corrosion and scaling of the feedwater system and protect against corrosion in the
steam condensate systems.
During the conditioning process, which is an essential complement to the water
treatment program, specific doses of conditioning products are added to the
water. The commonly used products include:
Phosphates-dispersants, polyphosphates-dispersants (softening chemicals):
reacting with the alkalinity of boiler water, these products neutralize the hardness
of water by forming tricalcium phosphate, and insoluble compound that can be
disposed and blow-down on a continuous basis or periodically through the bottom
of the boiler.
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protects condensate pipelines. Sodium sulfate is not poisonous and is suitable for
use in boilers with working pressure below 40 bar. This compound does not
evaporate in the boiler and does not give the same level of protection to the
condensate piping as hydrazine.
Control of salinity
The salinity of boiler water is maintained within ratings by means of periodical
blow-out. The salinity of feed water is controlled automatically by a salinometer.
Standard values
Using a UNITOR water treatment kit, the recommended values for boiler water
are:
Alkalinity
Chlorides
pH
9.5 11
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The major function of 'OH' alkalinity in the boiler water is to create proper
conditions for scale control reactions. If the OH is below established control limits,
converting and precipitating scaling impurities won't be fully accomplished.
Corrective actions should not be taken until all your water tests are run
and you have interpreted your reading.
Hotwell Temperature Control
Very few motor vessels have deaerators fitted to reduce oxygen in the boiler feed.
Those that have still require an oxygen scavenger but use less. Dissolved oxygen
can be greatly reduced by maintaining high hotwelI temperatures approaching
boiling point. This is due to the fact that dissolved oxygen levels decrease as water
temperatures approach boiling point. The excess oxygen is released to
atmosphere at the tank surface.
Many systems are operated with no control of this temperature. Hotwells are
often over-cooled or the other extreme where they are boiling, which is a direct
waste of energy as water vapour is released to the atmosphere.
The over-cooled hotwell leads to high oxygen levels and also means that a loss of
thermal energy has taken place. Ideally the temperature is controlled at 80-90 oC,
either by bypassing the drain cooler, or reducing cooling water flow, dependant
on system design. Very often, the maximum acceptable temperature, prior to
wasteful loss of vapour is a function of feed pump design.
In view of this, the ideal temperature for any particular vessel must be evaluated
with respect to the risk of feed pump cavitation caused by "boil off' of feed water
at the low pressure area of the pump impeller suction. Experience indicates that
80 oC can be safely used on most motor vessels.
Please remember that this form of control reduces oxygen and therefore requires
less chemical products, but it also means that less energy is required in the
auxiliary boiler or exhaust gas economiser to produce steam. Thus, it is a
significant fuel saving device, where an oil fired unit is operating.
This also reduces the risk of reaching "dew point" on gas side of the exhaust gas
economiser. This in turn will greatly reduce corrosion in that area.
Blow-down control
Blow-down is necessary to lower the boiler water concentration by removing
dissolved and suspended solids. Without controlled blow-down, oil solids in the
boiler water would build-up. Excessive build-up can cause priming and carryover
REPORT: ALVARO SARDINHA
MARINE ENGINEER
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Pag |36 - 94
and could choke boiler tubes and headers with sludge, resulting in poor
circulation, over-heating and possible tube failures.
When chemicals are added to boiler water to protect the internals, it is obvious
that an increase in dissolved solids will occur. As the treatment reacts with the
contaminants in the water, sludge is formed. Additionally, solids, dissolved and
suspended, are carried into the boiler by the make-up water, and concentration of
these continues. Eventually there is a need for blow-down and it is necessary to
monitor this rate of concentration. A positive method of determining total
dissolved solids of boiler water is the measurement of specific conductance using
a dissolved solids meter.
Blow-down is conducted depending upon the degree of solids by the following
methods:
Continuous Blow-down: Used when dissolved solids are high. This method is
usually adopted through the sampling line, if a continuous blow-down line is not
installed, and can safely be used when a boiler is steaming.
Bottom Flash Blow: When giving a boiler a bottom flash blow, all fires must be
extinguished to prevent blistering of tubes, due to upset circulation. Bottom flash
blows are given when quick dilution of boiler water is required and to remove
sludge. Boilers should be allowed to cool and pressure lowered to no more than
75% of working pressure. This allows suspended solids to drop to the mud drum
so they can be removed when the blow-down valve is opened.
The blow-down valve should be opened quickly and immediately closed to
prevent boiler tube damage. Boiler should be allowed to stand for 5 minutes,
which allows more solids to gravitate to mud drum and blow-down should be
repeated by quickly opening and closing bottom blow-down valve. This procedure
should be repeated allowing about 5 minutes between each blow, until desired
quantity of sludge has been removed or replaced.
It should be stressed that too little blow-down is dangerous for reasons already
stated and excessive blow-down is costly in the form of wasted water, heat, fuel
and chemicals.
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SCALING IN BOILERS
Boiler scale is caused by impurities being precipitated out of the water directly on
heat transfer surfaces or by suspended matter in water settling out on the metal
and becoming hard and adherent. Evaporation in a boiler causes impurities to
concentrate. This interferes with heat transfers and may cause hot spots, leading
to local overheating.
Scaling mechanism is the exceeding of the
solubility limits of mineral substances due to
elevated temperature and solids concentration at
the tube/water interface. The deposition of
crystalline precipitates on the walls of the boiler
interferes with heat transfer and may cause hot
spots, leading to local overheating. The less heat
they conduct, the more dangerous they are.
Common feed water contaminants that can form
boiler deposits include calcium, magnesium, iron,
aluminium, and silica. Scale is formed by salts that
have limited solubility but are not totally insoluble
in boiler water. These salts reach the deposit site
in a soluble form and precipitate.
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CaSO4
CaCO3
SiO2
Scaling is mainly due to the presence of calcium and magnesium salts (carbonates
or sulfates), which are less soluble hot than cold, or to the presence of too high
concentration of silica in relation to the alkalinity of the water in the boiler.
Pag |40 - 94
Pag |41 - 94
Pag |42 - 94
CORROSION IN BOILERS
Corrosion is one of the main causes of reduced reliability in steam generating
systems. It is estimated that problems due to boiler system corrosion cost industry
billions of euros per year.
Many corrosion problems occur in the hottest areas of the boiler, the water wall,
screen, and superheater tubes. Other common problem areas include deaerators,
feedwater heaters, and economizers.
Methods of corrosion control vary depending upon the type of corrosion
encountered. The most common causes of corrosion are dissolved gases (primarily
oxygen and carbon dioxide), underdeposit attack, low pH, and attack of areas
weakened by mechanical stress, leading to stress and fatigue cracking.
These conditions may be controlled through the following procedures:
Maintenance of proper pH and alkalinity levels
Control of oxygen and boiler feedwater contamination
Reduction of mechanical stresses
Operation within design specifications, especially for temperature and
pressure
Proper precautions during start-up and shutdown
Effective monitoring and control
Pag |43 - 94
Pag |44 - 94
Pag |45 - 94
Oxygen pitting, particularly in the pendant loop area, is another major corrosion
problem in superheaters. It is caused when water is exposed to oxygen during
downtime. Close temperature control helps to minimize this problem. In addition,
a nitrogen blanket and chemical oxygen scavenger can be used to maintain
oxygen-free conditions during downtime.
TYPES OF CORROSION
Corrosion control techniques vary according to the type of corrosion encountered.
Major methods of corrosion control include maintenance of the proper pH,
control of oxygen, control of deposits, and reduction of stresses through design
and operational practices.
Galvanic Corrosion
Galvanic corrosion occurs when a metal or alloy is electrically coupled to a
different metal or alloy.
The most common type of galvanic corrosion in a boiler system is caused by the
contact of dissimilar metals, such as iron and copper. These differential cells can
also be formed when deposits are present. Galvanic corrosion can occur at welds
due to stresses in heat-affected zones or the use of different alloys in the welds.
Anything that results in a difference in electrical potential at discrete surface
locations can cause a galvanic reaction. Causes include:
Scratches in a metal surface
Differential stresses in a metal
Differences in temperature
Conductive deposits
Pitting of boiler tube banks has been encountered due to metallic copper
deposits. Such deposits may form during acid cleaning procedures if the
procedures do not completely compensate for the amount of copper oxides in the
deposits or if a copper removal step is not included. Dissolved copper may be
plated out on freshly cleaned surfaces, establishing anodic corrosion areas and
forming pits, which are very similar to oxygen pits in form and appearance. This
process is illustrated by the following reactions involving hydrochloric acid as the
cleaning solvent.
Pag |46 - 94
Magnetite is dissolved and yields an acid solution containing both ferrous (Fe+)
and ferric (Fe+) chlorides (ferric chlorides are very corrosive to steel and copper)
Fe3O4
magnetite
8HCl
hydrochloric acid
FeCl2
2FeCl3
4H2O
water
Cu
ferric chloride
copper
CuCl
FeCl2
cuprous chloride
ferrous chloride
Fe
cuprous chloride
iron
FeCl2
2Cu0
ferrous chloride
copper oxide
Thus, hydrochloric acid cleaning can cause galvanic corrosion unless the copper is
prevented from plating on the steel surface. A complexing agent is added to
prevent the copper from redepositing. The following chemical reaction results:
FeCl3
ferric chloride
copper
ferrous chloride
CuCl
cuprous chloride complex
This can take place as a separate step or during acid cleaning. Both iron and the
copper are removed from the boiler, and the boiler surfaces can then be
passivated.
In most cases, the copper is localized in certain tube banks and causes random
pitting. When deposits contain large quantities of copper oxide or metallic copper,
special precautions are required to prevent the plating out of copper during
cleaning operations.
Pag |47 - 94
Caustic Corrosion
Concentration of caustic (NaOH) can occur either as a result of steam blanketing
(which allows salts to concentrate on boiler metal surfaces) or by localized boiling
beneath porous deposits on tube surfaces.
Caustic corrosion (gouging) occurs when caustic is concentrated and dissolves the
protective magnetite (Fe3O4) layer. Iron, in contact with the boiler water, forms
magnetite and the protective layer is continuously restored. However, as long as a
high caustic concentration exists, the magnetite is constantly dissolved, causing a
loss of base metal and eventual failure.
Steam blanketing is a condition that occurs when a steam layer forms between
the boiler water and the tube wall. Under this condition, insufficient water
reaches the tube surface for efficient heat transfer. The water that does reach the
overheated boiler wall is rapidly vaporized, leaving behind a concentrated caustic
solution, which is corrosive.
Porous metal oxide deposits also permit the development of high boiler water
concentrations. Water flows into the deposit and heat applied to the tube causes
the water to evaporate, leaving a very concentrated solution. Again, corrosion
may occur.
Caustic attack creates irregular patterns, often referred to as gouges. Deposition
may or may not be found in the affected area.
Boiler feedwater systems using demineralized or evaporated makeup or pure
condensate may be protected from caustic attack through coordinated
phosphate/pH control. Phosphate buffers the boiler water, reducing the chance of
large pH changes due to the development of high caustic concentrations. Excess
caustic combines with disodium phosphate and forms trisodium phosphate.
Sufficient disodium phosphate must be available to combine with all of the free
caustic in order to form trisodium phosphate.
Disodium phosphate neutralizes caustic by the following reaction:
Na2HPO4
NaOH
Na3PO4
trisodium phosphate
H2O
water
Pag |48 - 94
discussed later) does not occur, because high caustic concentrations do not
develop.
Different forms of phosphate consume or add caustic as the phosphate shifts to
the proper form. For example, addition of monosodium phosphate consumes
caustic as it reacts with caustic to form disodium phosphate in the boiler water
according to the following reaction:
Na2HPO4
NaOH
Na2HPO4
H2O
water
trisodium phosphate
H2O
water
Na2HPO4
disodium phosphate
NaOH
sodium hydroxide
Control is achieved through feed of the proper type of phosphate to either raise or
lower the pH while maintaining the proper phosphate level. Increasing blow-down
lowers both phosphate and pH. Therefore, various combinations and feed rates of
phosphate, blow-down adjustment, and caustic addition are used to maintain
proper phosphate/pH levels.
Elevated temperatures at the boiler tube wall or deposits can result in some
precipitation of phosphate. This effect, termed "phosphate hideout," usually
occurs when loads increase. When the load is reduced, phosphate reappears.
Clean boiler water surfaces reduce potential concentration sites for caustic.
Deposit control treatment programs, such as those based on chelants and
synthetic polymers, can help provide clean surfaces.
Where steam blanketing is occurring, corrosion can take place even without the
presence of caustic, due to the steam/magnetite reaction and the dissolution of
magnetite. In such cases, operational changes or design modifications may be
necessary to eliminate the cause of the problem.
Pag |49 - 94
Acidic Corrosion
Low make-up or feedwater pH can cause serious acid attack on metal surfaces in
the pre-boiler and boiler system. Even if the original makeup or feedwater pH is
not low, feedwater can become acidic from contamination of the system.
Common causes include the following:
Improper operation or control of demineralizer cation units
Process contamination of condensate
Cooling water contamination from condensers
Acid corrosion can also be caused by chemical cleaning operations. Overheating of
the cleaning solution can cause breakdown of the inhibitor used, excessive
exposure of metal to cleaning agent, and high cleaning agent concentration.
Failure to neutralize acid solvents completely before start-up has also caused
problems.
In a boiler and feedwater system, acidic attack can take the form of general
thinning, or it can be localized at areas of high stress such as drum baffles, "U"
bolts, acorn nuts, and tube ends.
Oxygen Attack
Without proper mechanical and chemical deaeration, oxygen in the feedwater will
enter the boiler. Much is flashed off with the steam; the remainder can attack
boiler metal. The point of attack varies with boiler design and feedwater
distribution. Pitting is frequently visible in the feedwater distribution holes, at the
steam drum waterline, and in downcomer tubes.
Oxygen is highly corrosive when present in hot water. Even small concentrations
can cause serious problems. Because pits can penetrate deep into the metal,
oxygen corrosion can result in rapid failure of feedwater lines, economizers, boiler
tubes, and condensate lines. Additionally, iron oxide generated by the corrosion
can produce iron deposits in the boiler.
Oxygen corrosion may be highly localized or may cover an extensive area. It is
identified by well defined pits or a very pockmarked surface. The pits vary in
shape, but are characterized by sharp edges at the surface. Active oxygen pits are
distinguished by a reddish brown oxide cap (tubercle). Removal of this cap
exposes black iron oxide within the pit.
Pag |50 - 94
Fe2+
2e
H2O
2e
Cathode:
O2
2OH
Overall:
Fe
O2
H2O
Fe(OH)2
Pag |51 - 94
Caustic Embrittlement
Caustic embrittlement (caustic stress corrosion cracking), or inter-crystalline
cracking, has long been recognized as a serious form of boiler metal failure.
Because chemical attack of the metal is normally undetectable, failure occurs
suddenly-often with catastrophic results.
For caustic embrittlement to occur, three conditions must exist:
The boiler metal must have a high level of stress
A mechanism for the concentration of boiler water must be present
The boiler water must have embrittlement-producing characteristics
Where boiler tubes fail as a result of caustic embrittlement, circumferential
cracking can be seen. In other components, cracks follow the lines of greatest
stress. A microscopic examination of a properly prepared section of embrittled
metal shows a characteristic pattern, with cracking progressing along defined
paths or grain boundaries in the crystal structure of the metal. The cracks do not
penetrate the crystals themselves, but travel between them; therefore, the term
"inter-crystalline cracking" is used.
If boiler water possesses embrittling characteristics, steps must be taken to
prevent attack of the boiler metal. Sodium nitrate is a standard treatment for
inhibiting embrittlement in lower-pressure boiler systems. The inhibition of
embrittlement requires a definite ratio of nitrate to the caustic alkalinity present
in the boiler water. In higher-pressure boiler systems, where demineralized makeup water is used, embrittling characteristics in boiler water can be prevented by
the use of coordinated phosphate/pH treatment control, described previously
under "Caustic Corrosion." This method prevents high concentrations of free
sodium hydroxide from forming in the boiler, eliminating embrittling tendencies.
Pag |52 - 94
Fatigue Cracking
Fatigue cracking (due to repeated cyclic stress) can lead to metal failure. The
metal failure occurs at the point of the highest concentration of cyclic stress.
Examples of this type of failure include cracks in boiler components at support
brackets or rolled in tubes when a boiler undergoes thermal fatigue due to
repeated start-ups and shutdowns.
Thermal fatigue occurs in horizontal tube runs as a result of steam blanketing and
in water wall tubes due to frequent, prolonged lower header blow-down.
Corrosion fatigue failure results from cyclic stressing of a metal in a corrosive
environment. This condition causes more rapid failure than that caused by either
cyclic stressing or corrosion alone. In boilers, corrosion fatigue cracking can result
from continued breakdown of the protective magnetite film due to cyclic stress.
Corrosion fatigue cracking occurs in deaerators near the welds and heat-affected
zones. Proper operation, close monitoring, and detailed out-of-service inspections
(in accordance with published recommendations) minimize problems in
deaerators.
Steam Side Burning
Steam side burning is a chemical reaction between steam and the tube metal. It is
caused by excessive heat input or poor circulation, resulting in insufficient flow to
cool the tubes. Under such conditions, an insulating superheated steam film
develops. Once the tube metal temperature has reached 400 C in boiler tubes or
510 - 540 C in superheater tubes (assuming low alloy steel construction), the rate
of oxidation increases dramatically; this oxidation occurs repeatedly and
consumes the base metal. The problem is most frequently encountered in
superheaters and in horizontal generating tubes heated from the top.
Erosion
Erosion usually occurs due to excessive velocities. Where two-phase flow (steam
and water) exists, failures due to erosion are caused by the impact of the fluid
against a surface. Equipment vulnerable to erosion includes turbine blades, lowpressure steam piping, and heat exchangers that are subjected to wet steam.
Feedwater and condensate piping subjected to high-velocity water flow are also
susceptible to this type of attack. Damage normally occurs where flow changes
direction.
Pag |53 - 94
4H2O
Fe3O4 +
4H2
water
magnetite
hydrogen
Pag |54 - 94
copper
O2
oxygen
2H2O
water
4Cu2O
cuprous
2H2
oxide hydrogen
The oxide that develops on the copper surfaces is comprised of two layers. The
inner layer is very thin, adherent, nonporous, and comprised mostly of cupric
oxide (CuO). The outer layer is thick, adherent, porous and comprised mainly of
cuprous oxide (Cu2O). The outer layer is formed by breakup of the inner layer. At a
certain thickness of the outer layer, an equilibrium exists at which the oxide
continually forms and is released into the water.
Maintenance of the proper pH, elimination of oxygen, and application of metalconditioning agents can minimize the amount of copper alloy corrosion.
Metal Passivation
The establishment of protective metal oxide layers through the use of reducing
agents (such as hydrazine, hydroquinone, and other oxygen scavengers) is known
as metal passivation or metal conditioning. Although "metal passivation" refers to
the direct reaction of the compound with the metal oxide and "metal
conditioning" more broadly refers to the promotion of a protective surface, the
two terms are frequently used interchangeably.
The reaction of hydrazine and hydroquinone, which leads to the passivation of
iron-based metals, proceeds according to the following reactions:
N2H4
6Fe2O3
hydrazine
hematite
C6H4 (OH)2
+ 3Fe2O3
hydroquinone hematite
4Fe3O4
magnetite
2Fe3O4
magnetite
2H2O +
N2
water
nitrogen
C6H4O2 +
H2O
benzoquinone
water
Pag |55 - 94
4CuO
hydrazine
cupric oxide
C6H6O2
Hydroquinone
cuprous oxide
2CuO
cupric oxide
2Cu2O
Cu2O +
cuprous oxide
2H2O +
N2
water
nitrogen
C6H6O2
benzoquinone
H2O
water
Magnetite and cuprous oxide form protective films on the metal surface. Because
these oxides are formed under reducing conditions, removal of the dissolved
oxygen from boiler feedwater and condensate promotes their formation. The
effective application of oxygen scavengers indirectly leads to passivated metal
surfaces and less metal oxide transport to the boiler whether or not the scavenger
reacts directly with the metal surface.
A significant reduction in feedwater oxygen and metal oxides can occur with
proper application of oxygen scavengers.
Pag |56 - 94
Amine concentration
Ammonia concentration
Flow rate
The impact of each of these factors varies depending on characteristics of each
system. Temperature dependence results from faster reaction times and greater
solubility of copper oxides at elevated temperatures. Maximum temperatures
specified for various alloys range from 90 to 150 C.
Methods of minimizing copper and copper alloy corrosion include:
Replacement with a more resistant metal
Elimination of oxygen
Maintenance of high-purity water conditions
Operation at the proper pH level
Reduction of water velocities
Application of materials which passivate the metal surfaces
pH Control
Maintenance of proper pH throughout the boiler feedwater, boiler, and
condensate systems is essential for corrosion control. Most low-pressure boiler
system operators monitor boiler water alkalinity because it correlates very closely
with pH, while most feedwater, condensate, and high-pressure boiler water
requires direct monitoring of pH. Control of pH is important for the following
reasons:
Corrosion rates of metals used in boiler systems are sensitive to
variations in pH
Low pH or insufficient alkalinity can result in corrosive acidic attack
High pH or excess alkalinity can result in caustic gouging/cracking and
foaming, with resultant carryover
Speed of oxygen scavenging reactions is highly dependent on pH levels
Pag |57 - 94
Pag |58 - 94
to allow ample time for the scavenger/oxygen reaction to occur. The deaerator
storage system and the feedwater storage tank are commonly used feed points.
In boilers operating below 70 bar, sodium sulfite and a concentrated liquid
solution of catalyzed sodium bisulfite are the most commonly used materials for
chemical deaeration due to low cost and ease of handling and testing. The oxygen
scavenging property of sodium sulfite is illustrated by the following reaction:
2Na2SO3
sodium sulfite
O2
oxygen
2Na2SO4
sodium sulfate
Pag |59 - 94
hydrazine
O2
oxygen
2H2O +
N2
water
nitrogen
Because the products of this reaction are water and nitrogen, the reaction adds no
solids to the boiler water. The decomposition products of hydrazine are ammonia
and nitrogen. Decomposition begins at approximately 200C and is rapid at 300C.
The alkaline ammonia does not attack steel. However, if enough ammonia and
oxygen are present together, copper alloy corrosion increases. Close control of the
hydrazine feed rate can limit the concentration of ammonia in the steam and
minimize the danger of attack on copper-bearing alloys. The ammonia also
neutralizes carbon dioxide and reduces the return line corrosion caused by carbon
dioxide.
REPORT: ALVARO SARDINHA
MARINE ENGINEER
alvarompsardinha@gmail.com
Pag |60 - 94
Hydrazine is a toxic material and must be handled with extreme care. Because the
material is a suspected carcinogen, federally published guidelines must be
followed for handling and reporting. Because pure hydrazine has a low flash point,
a 35% solution with a flash point of greater than 90C is usually used.
Theoretically, 1.0 ppm of hydrazine is required to react with 1.0 ppm of dissolved
oxygen. However, in practice 1.5-2.0 parts of hydrazine are required per part of
oxygen.
The factors that influence the reaction time of sodium sulfite also apply to other
oxygen scavengers. The reaction is also dependent upon pH (the optimum pH
range is 9.0-10.0).
In addition to its reaction with oxygen, hydrazine can also aid in the formation of
magnetite and cuprous oxide (a more protective form of copper oxide), as shown
in the following reactions:
N2H4
hydrazine
6Fe2O3
hematite
4Fe3O4
magnetite
N2
nitrogen
2H2O
water
and
N2H4
hydrazine
4CuO
cupric oxide
2Cu2O +
cuprous oxide
N2
2H2O
nitrogen
water
Because hydrazine and organic scavengers add no solids to the steam, feedwater
containing these materials is generally satisfactory for use as attemperating or
desuperheating water.
The major limiting factors of hydrazine use are its slow reaction time (particularly
at low temperatures), ammonia formation, effects on copper-bearing alloys, and
handling problems.
Organic Oxygen Scavengers. Several organic compounds are used to remove
dissolved oxygen from boiler feedwater and condensate. Among the most
commonly used compounds are hydroquinone and ascorbate. These materials are
less toxic than hydrazine and can be handled more safely. As with other oxygen
scavengers, temperature, pH, initial dissolved oxygen concentration, catalytic
effects, and scavenger concentration affect the rate of reaction with dissolved
REPORT: ALVARO SARDINHA
MARINE ENGINEER
alvarompsardinha@gmail.com
Pag |61 - 94
oxygen. When fed to the feedwater in excess of oxygen demand or when fed
directly to the condensate, some organic oxygen scavengers carry forward to
protect steam and condensate systems.
Hydroquinone is unique in its ability to react quickly with dissolved oxygen, even
at ambient temperature. As a result of this property, in addition to its
effectiveness in operating systems, hydroquinone is particularly effective for use
in boiler storage and during system start-ups and shutdowns. It is also used widely
in condensate systems.
Hydroquinone reacts with dissolved oxygen as shown in the following reactions:
C6H4(OH)2
hydroquinone
O2
oxygen
C6H4O2
benzoquinone
H2O
water
O2
benzoquinone
polyquinones
oxygen
These reactions are not reversible under the alkaline conditions found in boiler
feedwater and condensate systems. In fact, further oxidation and thermal
degradation (in higher-pressure systems) leads to the final product of carbon
dioxide. Intermediate products are low molecular weight organic compounds,
such as acetates.
Oxygen Level Monitoring. Oxygen monitoring provides the most effective means
of controlling oxygen scavenger feed rates. Usually, a slight excess of scavenger is
fed. Feedwater and boiler water residuals provide an indication of excess
scavenger feed and verify chemical treatment feed rates. It is also necessary to
test for iron and copper oxides in order to assess the effectiveness of the
treatment program. Proper precautions must be taken in sampling for metal
oxides to ensure representative samples.
Due to volatility and decomposition, measurement of boiler residuals is not a
reliable means of control. The amount of chemical fed should be recorded and
compared with oxygen levels in the feedwater to provide a check on the control of
dissolved oxygen in the system. With sodium sulfite, a drop in the chemical
REPORT: ALVARO SARDINHA
MARINE ENGINEER
alvarompsardinha@gmail.com
Pag |62 - 94
residual in the boiler water or a need to increase chemical feed may indicate a
problem. Measures must be taken to determine the cause so that the problem
can be corrected.
Sulfite residual limits are a function of boiler operating pressure. For most lowand medium-pressure systems, sulfite residuals should be in excess of 20 ppm.
Hydrazine control is usually based on a feedwater excess of 0.05-0.1 ppm. For
different organic scavengers, residuals and tests vary.
Pag |63 - 94
If a continuous oxygen meter is not installed, periodic testing with spot sampling
ampoules should be used to evaluate deaerator performance and potential for
oxygen contamination from pump seal water and other sources.
For the boiler water, the following tests should be performed:
Phosphate (if used)
P-alkalinity or pH
Sulfite (if used)
Conductivity
Sampling
It is critical to obtain representative samples in order to monitor conditions in the
boiler feedwater system properly. Sample lines, continuously flowing at the
proper velocity and volume, are required. Generally, a velocity of 1,5 mt/sec and a
flow of 800-1000 ml/min are satisfactory. The use of long sample lines should be
avoided. Iron and copper sampling should be approached with extreme care
because of the difficulty of obtaining representative samples and properly
interpreting results. Trends, rather than individual samples, should be used to
assess results. Copper sampling requires special precautions, such as acidification
of the stream. Composite sampling, rather than spot sampling, can also be a
valuable tool to determine average concentrations in a system.
Oxygen sampling should be performed as close to the line as possible, because
long residence time in sampling lines can allow the oxygen scavenger to further
react and reduce oxygen readings. Also, if in-leakage occurs, falsely high data may
be obtained. Sampling for oxygen should also be done at both the effluent of the
deaerator and effluent of the boiler feedwater pump, to verify that oxygen ingress
is not occurring.
Results and Action Required
All inspections of equipment should be thorough and well documented.
Conditions noted must be compared to data from previous inspections. Analytical
results and procedures must be evaluated to ensure that quality standards are
maintained and that steps are taken for continual improvement. Cause-and-effect
diagrams can be used either to verify that all potential causes of problems are
reviewed, or to troubleshoot a particular corrosion-related problem.
Pag |64 - 94
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compressed gas. Particular care should be taken to purge water from long
horizontal tubes, especially if they have bowed slightly.
Heat is applied to optimize drying. After drying, the unit is closed to minimize air
circulation. Heaters should be installed as needed to maintain the temperature of
all surfaces above the dew point.
Immediately after surfaces are dried, one of the three following desiccants is
spread on water-tight wood or corrosion-resistant trays:
Quicklime-used at a rate of 0,90 Kg/10 m of boiler volume
Silica gel-used at a rate of 2,5 Kg/10 m of boiler volume
Activated alumina-used at a rate of 4,0 Kg/10 m of boiler volume
The trays are placed in each drum of a water tube boiler, or on the top flues of a
fire-tube unit. All manholes, handholes, vents, and connections are blanked and
tightly closed. The boiler should be opened every month for inspection of the
desiccant. If necessary, the desiccant should be renewed.
Wet Storage
For wet storage, the unit is inspected, cleaned if necessary, and filled to the
normal water level with deaerated feedwater.
Sodium sulfite, hydrazine, hydroquinone, or another scavenger is added to control
dissolved oxygen, according to the following requirements:
Sodium sulfite. 0,36 Kg of sodium sulfite and 0,36 Kg of caustic soda should be
added per 1000 liters of water contained in the boiler (minimum 400 ppm Palkalinity as CaCO3 and 200 ppm sulfite as SO3).
Hydrazine. 0,59 Kg of a 35% solution of hydrazine and 0,012 Kg of ammonia or
0,37 Kg of a 40% solution of neutralizing amine can be added per 1000 liters
(minimum 200 ppm hydrazine and 10.0 pH). Due to the handling problems of
hydrazine, organic oxygen scavengers are normally recommended.
Hydroquinone. Hydroquinone-based materials are added to achieve
approximately 200 ppm as hydroquinone in previously passivated on-line systems.
In new systems, or those considered to have a poorly formed magnetite film, the
minimum feed rate is 400 ppm as hydroquinone. pH should be maintained at 10.0.
No matter which treatment is used, pH or alkalinity adjustment to minimum levels
is required.
REPORT: ALVARO SARDINHA
MARINE ENGINEER
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Pag |66 - 94
After chemical addition, with vents open, heat is applied to boil the water for
approximately 1 hour. The boiler must be checked for proper concentration of
chemicals, and adjustments made as soon as possible.
If the boiler is equipped with a non-drainable superheater, the superheater is
filled with high-quality condensate or demineralized water and treated with a
volatile oxygen scavenger and pH control agent. The normal method of filling nondrainable superheaters is by back-filling and discharging into the boiler. After the
superheater is filled, the boiler should be filled completely with deaerated
feedwater. Morpholine, cyclohexylamine, or similar amines are used to maintain
the proper pH.
If the superheater is drainable or if the boiler does not have a superheater, the
boiler is allowed to cool slightly after firing. Then, before a vacuum is created, the
unit is filled completely with deaerated feedwater.
A surge tank (such as a 208 liters drum) containing a solution of treatment
chemicals or a nitrogen tank at 5 psig pressure is connected to the steam drum
vent to compensate for volumetric changes due to temperature variations.
The drain between the non-return valve and main steam stop valve is left open
wide. All other drains and vents are closed tightly.
The boiler water should be tested weekly with treatment added as necessary to
maintain treatment levels. When chemicals are added, they should be mixed by
one of the following methods:
Circulate the boiler water with an external pump
Reduce the water level to the normal operating level and steam the boiler for a
short time
If the steaming method is used, the boiler should subsequently be filled
completely, in keeping with the above recommendations.
Although no other treatment is required, standard levels of the chemical
treatment used when the boiler is operating can be present.
Boilers can be protected with nitrogen or another inert gas. A slightly positive
nitrogen (or other inert gas) pressure should be maintained after the boiler has
been filled to the operating level with deaerated feedwater.
Pag |67 - 94
Pag |68 - 94
Pag |69 - 94
7. UNEX BOILERS
BOILERS WATER RECOMMENDATIONS
RECOMMENDATIONS
Pag |70 - 94
Pag |71 - 94
c) Hydrazine or Sodium Sulfite feed for eliminating the residual oxygen to reduce
corrosion
In addition to the above, the out-blow arrangement is considered to be part of
water treatment. Furthermore it is presumed that all feed water is led through a
water softener, if evaporated water is not available.
Gas removing and feedwater tank
Feedwater and returning condensate shall flow as evenly as possible into the feed
water tank. At the bottom of the water space in feedwater tank, there must be
arranged feed of steam through an automatic temperature regulator. With the aid
of steam, blow water in the feed water tank is kept moving and hemothermal. It
can also be used to heat up the water quickly, if it has got cool.
Dosing of Trisodium Phosphate (Na3PO4)
The amount of dosing depends of the volume of out-blow and is directly in
proportion to it. The aim is to maintain the P205 content of boiler water between
20-40 mg/l. If the volume of out-blow is approximately 5 %, the amount of
phosphate to be added to feed water is 5 - 10 g/m3. Trisodium Phosphate contains
approximately 19 % of P205.
Dosing of Sodium Hydroxide (Alkali) (NaOH)
If the volume of out-blow is 5 % of the additional water amount, dosing of alkali
can be started with the amount 20 g/m3. If the volume of out-blow is smaller, the
dosing is correspondingly smaller, as well. The rating table shows the boiler water
pH, which should be achieved. In addition to pH also the p-value must be
observed. It may not exceed the value 15.
Dosing of hydrazine or Sodium Sulfite
a) The aim of the dosing is that there is a slight surplus of hydrazine (N2H4) in
boiler water of 0,1 - 0,3 mg/l. Hydrazine is a powerful reducer which changes
together with free oxygen in water into nitrogen and water. Theoretically 1 g of
hydrazine binds 1 g of oxygen, but in practice, at least a tripled value is
recommended.
Hydrazine dissolves as ammonia and nitrogen, if there is not oxygen in water.
Ammonia moves with steam and increases the pH value of the condensate, which
value protects the condensate pipings from corrosion.
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20 g / ton
90 C
18 g / ton
95 C
15 g / ton
96 C
13 g / ton
97 C
10 g / ton
98 C
7 g / ton
> 99 C
4 g / ton
b) The aim of the dosing is that there is always Sodium Sulfite in boiler water.
30-60 g/m3 is regarded as a suitable amount. If there is no thermal degassing,
dose must be 50-200 g/m3. The Sodium Sulfite used should be so-called activated
Sodium Sulfite, made for the purpose.
Blow-out
The boiler blow-out is used for maintaining the quality of boiler water within
desired limits, which have been given in the rating table. It is important that the
proportion of out-blown water and additional water remains constant, because
the chemical dosing succeeds only on that condition. On the other hand, the
volume of blow-out should be as small as possible and, however, sufficiently large
to prevent exceeding of critical analysis values in boiler water.
The volume of blow-out can be roughly calculated as the proportion of the
additional water salinity and the biggest allowed salinity of boiler water. If, e.g. the
salinity of additional water is 50 mg/l and biggest allowed concentration of boiler
water is 1000 mg/l, the volume of blow-out is 50/1000 = 0,05 or 5 % of the
additional water volume.
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CONTROL
Chemical analyses are used to control functioning of water treatment equipment
of the boiler plant and dosing of chemicals. In addition, mechanical functioning of
the devices is controlled, as well.
SAMPLING
Before a chemical analysis there is always a sampling to be analysed. The correct
sampling is as important as the analysis itself. The sampling is performed in such a
way that the sample really contains the water to be examined.
Therefore, before sampling, water is let run with considerable speed so long that
it is changed 3-4 times in the sampling pipeline (30 seconds at the minimum) and
only then the actual sample needed for analysing is taken.
It is best to take boiler water sample through a special condensing coil designed
for this purpose. If this is not available, the analysis results must be multiplied by
the following numbers in order to correct the fault caused by evaporation loss:
Boiler pressure bar coefficient:
6
8
10
15
20
0,88
0,86
0,84
0,81
0,7826
RATINGS
The following table shows the water treatment ratings for boilers. While starting
up a new boiler or after a downtime, analyses must be performed more frequently
than stated in the table. After finding out that sampling continuously give the
same results, the analyses can be done according to the table. Hardness of
softened water must be defined the more often the longer the softening filter has
been in use, counted from regeneration.
The table also includes other ratings beside those, for which more detailed
definitions and analysis instructions have been given. This is to give a more
detailed description of the facts to be paid attention to while maintaining the
boiler.
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Feed water
pH
daily
8,5 - 9,5
Oxygen 02
mg/l
monthly
< 0,05
Hardness
dH
daily
< 0,1
Oil
mg/l
daily
<2
mg/l
monthly
< 0,1
Salinity
mg/l
daily
< 100
daily
9 - 11,5
Boiler water
pH
p-value
mval/l
daily
5 - 15
Salinity NaCl
mg/l
weekly
< 1000
Be
weekly
0,35
Phosphate
mg/I
daily
20 - 40
KMn04 consumption
mg/l
monthly
500
Hydrazine N2H4
mg/I
weekly
0,1 - 0,3
Conductivity
S/cm
daily
< 5000
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8. LESSONS LEARNED
Boilers are common equipment in ships and in land installations. There are many
reports and communications available, full of lessons learned that must be
considered and that are strategic to a successful water treatment program.
LESSONS LEARNED - I
Three serious auxiliary boiler explosions have been reported to the Department
and in two cases there was loss of life. The three boilers were of different types
and make.
(a) Vertical smoke tube boilercombined exhaust and oil fired.
(b) Vertical combined water tube/smoke tube oil fired boiler.
(c) Double evaporation boiler (steam heated low pressure drum exploded).
These boilers contained large amounts of water and at the time of the incident
were 10 to 15 years old.
On investigation it was noted that all had been suffering from general corrosion
and pitting on the waterside for sometime. In two cases large cracks developed
from small crevices next to welding seams in the shell plating due to high oxygen
content in the boiler water over a period.
Special examination of such boilers has been carried out since. In a number of
cases cracks/fractures have been found in the lower section of the water space in
REPORT: ALVARO SARDINHA
MARINE ENGINEER
alvarompsardinha@gmail.com
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Pag |77 - 94
LESSONS LEARNED - II
MANAGEMENT CONCERNS
Pag |78 - 94
Suggested Actions
Base management should ensure the assignment of single-point responsibility.
Specific duties would include development and maintenance of:
A Preventative Maintenance Plan.
Accurate records of tests and repair activities.
A training schedule for personnel.
A safety program.
A schedule for general housekeeping activities to be followed.
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Pag |80 - 94
OPERATOR PERFORMANCE
Pag |81 - 94
react with oxygen before the oxygen gets into the boiler and it also helps to
protect feed water lines.
Sulfite should be fed continuously as a function of feed water flow as opposed to
slug dosages. This allows for a proper residual in the operating boiler at all times
and avoids conditions of overtreatment and under treatment swings.
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The proper amine or blend of amines is dependent upon the length of condensate
piping runs to be protected. Morpholine for example is more effective for short
runs of say 250 meters or less. Diethylaminoethanol (DEAE) is more effective for
runs of up to 1500 meters while cyclohexylamine is more effective for runs over
1500 meters.
Neutralizing amines should be fed directly into the boiler or into feed water
piping. It should not be fed into the deaerator where it can escape via vent piping.
For long and complex condensate systems (over 1600 meters with multiple
locations for steam demands), satellite amine feed stations can augment amines
being fed at the boiler plant.
Neutralizing amines should be fed continuously as a function of feed water flow as
opposed to slug dosages. This allows for a proper pH in the condensate system at
all times and minimizes overtreatment and under-treatment swings.
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equipment for resin volume. The run time on a softener is measured by the
amount of water it can soften before regeneration is required. A running log of
softener capacity will show a trend of softener efficiency. As the realized capacity
drops below design capacity, regeneration needs to be performed more often to
prevent excursions of hardness or other unwanted ionic species. Resins may need
replacement or replenishment.
Feed phosphate and dispersant treatments continuously as a function of feed
water as opposed to slug dosages. This allows for a proper residual in the
operating boiler at all times and minimizes overtreatment and under-treatment
swings.
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Use bottom blow-down to remove sludge. It is not used to control TDS unless it is
the only blow-down option available. The frequency of bottom blow-down
depends on feed water quality and the type of treatment program being followed.
Boiler load also impacts blow-down requirements. The heavier the load, the more
frequent bottom blow-down is required.
Excessive blow-down is a common problem with boiler operations. The general
attitude is that blow-down will avoid trouble. However, the cost in wasted
energy, water, and chemicals along with the possible replacement of boiler
elements can be significant. Proper blow-down is achieved when adjustments are
made to match boiler load changes, while maintaining the specific control ranges
for TDS, alkalinity, and/or silica.
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Chemical test results are only as accurate as the sample collected. Therefore the
sample collected must be truly representative of the system conditions. A poor
sample will yield results that call for unwarranted or insufficient adjustments to
the program.
Suggested Actions
Specific rules apply to good sampling and test procedures:
Sample Point
Boiler samples should be collected at the continuous surface blow-down line using
a sample cooler for operator safety and to prevent flashing (water converting to
steam). If there is no continuous blow-down line then a sample can be collected
from the water column beneath the sight glass which again should be cooled.
Sampling Technique
Sample lines should be flushed thoroughly to minimize contaminants from
stagnant water in the lines. Sample containers should be clean prior to taking a
sample. Containers should be dedicated for sample type i.e. boiler, feedwater,
condensate etc. Heavy duty, high temperature, polypropylene, wide mouth
bottles are recommended over glass. Tests for trace metals like iron and copper
require special preparation. The sample needs to be preserved with acid to bring
the pH down to 2.0 or less. This is necessary to prevent the trace amount of metal
from being absorbed into the walls of the container.
Interval Between Sample Collection and Analysis
For some constituents in boiler water, it is critical that the interval between
sample collection and analysis be as short as possible. Long intervals may allow
some chemicals to continue reacting so that smaller than actual amounts will be
found. An example of this is Sulfite which continues to react with oxygen from the
atmosphere over time. Different constituents in boiler water have different
degrees of stability. Some must be tested immediately after removal: Sulfite,
hydroxide, and pH. Others can last indefinitely when properly contained. The
order of testing should be as follows: 1.) Sulfite, 2.) causticity and pH, and 3.) all
others.
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Pag |87 - 94
Suggested Actions
Obtain documents from the previous inspection if applicable, to serve as a
reference for the present condition of the boiler.
Inspect the watersides of the boiler. In many cases the view will be limited
especially for water tube boilers. Fiber optics video inspection equipment is useful
for this purpose. Note the presence or absence of deposits. If present, note the
thickness of the deposit and obtain a sample for laboratory analysis. Good control
of external treatment, chemical treatment, and blow-down will prevent deposits
from forming.
Inspect the watersides for corrosion control effectiveness. The metal should have
a thin layer of magnetite (ferrous-ferric oxide), a self-limiting form of corrosion
that is a protective film. Magnetite has a grayish/brown appearance. Its presence
is indicative of good pH control. The metal should not show any pitting due to
oxygen corrosion attack.
Inspect the mud drum of the boiler. There should be no significant accumulation
of sludge which indicates that adequate bottom blow-down control has been
accomplished.
Safety inspections are above and beyond those described above which are to be
done by operators and must be done by experts in this area.
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Pag |89 - 94
Burette A long narrow titrating column that has been accurately calibrated
to indicate the exact volume of liquid dispenses in the test procedure.
Carryover The entrainment of small droplets of boiler water and associated
dissolved solids in the steam leaving the boiler.
Caustic This refers to caustic soda that is sodium hydroxide.
Chlorides Indicates the amount of solids build-up in the water, including salts of
calcium, sodium and potassium. If the Chlorides in the water doubles, all the solids
have doubled.
Chlorine A disinfecting oxidizing agent, which is most widely used in water
treatment.
Chlorine, Combined Available The chlorine residual, which exists in water
systems as a chemical combination with ammonia or organic matter after the
chlorine, has been satisfied.
Chlorine Demand The amount of chlorine consumed by organize matter and
bacteria in water systems.
Chlorine, Free Available The hypochlorous ions (OCI), hypochlorous acid (HOCI),
or any combination thereof present in water (the portion of chlorine in water
systems that is available for the immediate oxidation [killing] of bacteria and
organic matter).
Chlorine, Residual The total amount of free and combined chlorine remaining in
water systems after its chlorine demand has been satisfied.
Chlorine, Total The sum of free and combined chlorine.
Colour Standard A hermetically sealed glass tube containing a stable solution
equivalent in colour to the colour developed when an indicator is added to a
sample solution to determine the concentration of a chemical.
Colourimetric A name, which is given to a chemical test method where the results
of the test are determined by the amount or shade of colour that is developed.
Comparator The device for holding colour standards and a test sample in
adjacent positions so that the colours of each may be easily compared with
one another.
Concentration The amount of a substance per unit volume.
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Pag |91 - 94
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Scale A hard, crusty deposit that may be found inside boilers, tubes, pipes,
valves, etc.
Shelf Life The length of time that an analytical reagent can be stored
without its chemical composition deteriorating or it undergoing some change that
will make the reagent unacceptable for use.
Shock Treatment The application of extremely high concentrations of chlorine
to destroy bacteria and algae.
Sludge A 'mud-like' residue, which is formed from the chemical treatment of
hardness salts in water, and is considered to be a normal by-product of
water treatment.
Soft Water Water that has a very low calcium and magnesium content.
Soluble A substance, which is easily dissolved.
Standard Solution A solution with a precise known composition.
Suspended Solids Particles within a liquid solution, which can be removed by
filtration.
TDS Total dissolved solids.
Titration A chemical test method using a reagent that is chemically keyed
to the unknown factor being tested. Usually an indicator is added to the
test sample and then the titrating solution is added in measured amounts.
When sufficient titrating solution is added to bring about a colour change in the
sample (the endpoint) the amount of solution added is noted and its volume
multiplied by a standard factor gives the result in ppm of the chemical
compound being measured.
Turbidity A suspension of fine particles that obscures light rays but requires many
days for settling out because of the small particle size.
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Hydrazine
N2H4
Sodium Sulfite
Na2SO3
Sodium Sulfate
Na2SO4
Sodium Chloride
NaCl
Trisodium Phosphate
Na3PO4
NaOH
Calcium Carbonate
CaCO3
Calcium Sulfate
CaSO4
Magnesium Sulfate
MgSO4
Silica
SiO2
Carbonic Acid
H2CO3
Iron Oxides
Pag |94 - 94