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Boiler Feedwater Treatment (Part II): Water Treatment Fundamentals

Contents

1. Removing impurities from boiler feedwater


2. Filtration
3. Coagulation and flocculation
4. Reaction of lime soda in softening process
5. Ion exchange
6. Deaeration of water
7. Combination of ion exchange and lime process
8. Reverse osmosis
9. Internal treatment of boiler feedwater
10. Blowdown
11. Corrosion in steam condensate system
12. Care of out-of-service boilers

Removing impurities from boiler feedwater


Feedwater is filtered to remove suspended matter and if the suspended solids are very fine, a flocculation step
may be needed to enable effective filtration. The water is then subjected to other treatments to make it suitable
for the boiler. Depending on the quality of water, it may be subjected to one or more treatments like chemical
precipitation, lime-soda softening, ion exchange, deaeration, and reverse osmosis.

Filtration
Filtration is the essential first step before the chemical treatment and conditioning of the boiler feedwater.
Filtration removes or minimizes all types of suspended solid impurities. If rust, sand (silica) etc. are not filtered
out, they lead to severe scale formation, which is difficult to clean and reduce boiler efficiency. Even the
condensate feedwater must be filtered before returning to the boiler. The boiler itself and the steam piping
produce rust particles etc. due to corrosion and other reactions. Filtration is also necessary for any water
treatment process to work properly. For example, softening resins get coated with suspended matter, loosing
their effectiveness and capacity to regenerate. Reverse osmosis membranes get fouled up leading to reduced
efficiency and shorter life. If the water is very dirty, sand filtration is first done followed by cartridge filtration.

Coagulation and flocculation


Some times the suspended particles in water are so fine that even cartridge filters are unable to remove them. In
such a situation, before cartridge filtration, the water is first treated with coagulants. Coagulation is charge
neutralization of finely divided and colloidal impurities in water into masses that can be filtered. In addition,
particles have negative electrical charges, which cause them to repel each other and resist adhering together.
Coagulation, therefore, involves neutralizing the negative charges and providing a nucleus for the suspended
particles to adhere to. Flocculation is the bridging together of coagulated particles.

Types of coagulants

Iron and aluminum salts such as ferric sulfate, ferric chloride, aluminum sulfate (alum), and sodium aluminate
are the most common coagulants. Ferric and alumina ions each have three positive charges and therefore their
effectiveness is related to their ability to react with the negatively charged colloidal particles. These coagulants
form a floc in the water that serves like a net for collecting suspended matter. Polyelectrolytes, which are
synthetic materials, have been developed for coagulation purposes. These consist of long chain-like molecules
with positive charges. In some cases organic polymers and special types of clay are used in the coagulation
process to serve as coagulant aids. These assist in coagulation by making the floc heavier.
Chemical precipitation
Chemical precipitation is a process in which chemical added reacts with dissolved minerals in the water to
produce a relatively insoluble reaction product. Precipitation methods are used in reducing dissolved hardness,
alkalinity, and silica. The most common example is lime-soda treatment.

Reaction of lime and soda in softening process


Calcium hydroxide (hydrated lime) reacts with soluble calcium and magnesium carbonates to form insoluble
precipitates. They form a sludge that can be removed by settling and filtration. Lime, therefore, can be used to
reduce hardness present in the bicarbonate form (temporary hardness) as well as decrease the amount of
bicarbonate alkalinity in water. Lime reacts with magnesium sulfate and chloride and precipitates magnesium
hydroxide, but in this process soluble calcium sulfate and chlorides are formed. Lime is not effective in
removing calcium sulfates and chlorides (permanent hardness). Soda ash is used primarily to reduce non-
bicarbonate hardness (permanent hardness). The calcium carbonate formed by the reaction precipitates as
sludge and can be filtered out. The resulting sodium sulfate and chloride are highly soluble and non-scale
forming.

Methods of lime-soda softening

The older method of intermittent softening consists of mixing the chemicals with the water in a tank, allowing
time for reaction and forming of sludge, and filtering and drawing off the clear water. The modern method of
continuous lime-soda softening involves use of compartmented tanks with provision for (a) proportioning
chemicals continuously to the incoming water, (b) retention time for chemical reactions and sludge formation,
and © continuous draw-off of softened water. Lime-soda softening is classified as hot or cold, depending on
the temperature of the water. Hot process softeners increase the rate of chemical reactions, increase silica
reduction, and produce over-all better quality water.

Coagulants used in lime-soda process

In the initial clarification process, coagulants are used to agglomerate fine suspended particles, which can then
be filtered out. Likewise, in the softening process, coagulants speed up settling of sludge by 25-50%. Sodium
aluminate used as a coagulant in lime-soda softening being alkaline, also contributes to the softening reactions,
particularly in reducing magnesium. Proper uses of coagulants help remove silica in the softening process.
Silica tends to be adsorbed on the floc produced by coagulation of sludge.

Disadvantages of lime-soda softening

The main disadvantage is that while hardness is reduced it is not completely removed. Variations in raw water
composition and flow rate also make control of this method difficult since it involves adjusting the amounts of
lime and soda ash being fed.

Advantages of lime-soda softening

The main advantage is that in reducing hardness, alkalinity, total dissolved solids, and silica are also reduced.
Prior clarification of the water is not usually necessary with the lime-soda process. Another advantage is that
with continuous hot process softening some removal of oxygen and carbon dioxide can be achieved. Fuel
savings can be realized with hot process softening because of solids reduction. This reduction decreases the
conductivity of the feedwater, thereby decreasing blowdown and conserving heat.

Ion Exchange
Minerals dissolved in water form electrically charged particles called ions. Calcium carbonate, for example,
forms a calcium ion with positive charges (a cation) and a bicarbonate ion with negative charges (an anion).
Some synthetic and natural materials have the ability to remove mineral ions from water in exchange for
others. For example, in passing water through a simple cation exchange softener all the calcium and
magnesium ions are removed and replaced with sodium ions. Ion exchange resins usually are small porous
beads that compose a bed several feet deep through which the water is passed.

Types of ion exchange resins

Ion exchange resins are two types: cation and anion. Cation exchange resins react only with positively charged
ions like Ca+2 and Mg+2. Anion exchange resins react only with the negatively charged ions like bicarbonate
(HCO3-) and sulfate (SO4-2). Although there are many types of cation exchange resins, they usually operate
on either a sodium or hydrogen ‘cycle’. That is, they are designed to replace all cations in the water with
either sodium or hydrogen. The anion resins are of two types: weak base and strong base. Weak base resins will
not take out carbon dioxide or silica, but will remove strong acid anions by a process more similar to
adsorption than ion exchange. Strong base anion resins, on the other hand, can reduce carbon dioxide and silica
as well as strong acid anions to very low values. Strong base anion resins are normally operated on a hydroxide
cycle. Chloride anion exchange resin is also used in dealkalization where alkalinity is reduced.

Ion exchange regeneration

Ion exchange resins have a certain capacity for removing ions from water and when their capacity is used up
they have to be regenerated. The regeneration is essentially reversing the ion exchange process. Cation
exchangers operating on the sodium cycle, salt (NaCl) is added to replenish the sodium capacity. Resins
operating on the hydrogen cycle are replenished by adding acid (H2SO4 or HCl). Anion exchangers are
normally regenerated with caustic (NaOH) or ammonium hydroxide (NH4OH) to replenish the hydroxide ions.
Salt (NaCl) may also be used to regenerate anion resins in the chloride form for dealkalization. Regeneration
process involves taking the vessel off line and treating it with concentrated solution of the regenerant. The ion
exchange resin then gives up the ions previously removed from water and these ions are rinsed out of the
vessel. After the regeneration has been completed, the vessel is ready for further service.

Split-stream softening

When the effluents from a cation exchanger operating on sodium cycle are blended with effluents from a cation
exchanger operating on a hydrogen cycle. The purpose is to reduce the alkalinity of the water. Since the
hydrogen cycle produces acid water while the sodium cycle does not affect alkalinity, the two effluents can be
blended together to give the desired reduction in alkalinity.

Dealkalization

One of the ion exchange processes for reducing water alkalinity is referred to as dealkalization. In this process
the water passes through an ion exchanger operating on the chloride cycle. The exchanger removes alkaline
anions such as carbonate, bicarbonate, and sulfates, replacing these ions with chloride. Cation exchange
softening precedes dealkalization process.

Demineralization

When the water is passed through both cation and anion exchange resins it is known as demineralization. In
this process the cation exchange is operated on the hydrogen cycle. That is, hydrogen is substituted for all the
cations. The anion exchanger operates on the hydroxide cycle, which replaces hydroxide for all of the anions.
The final effluent from the process consists essentially of hydrogen ions and hydroxide ions or pure water. The
demineralization process can be done by several methods. In the mixed-bed process, the anion and cation
exchange resins are intimately mixed in one vessel. Multi-bed arrangements may consist of different
combinations of cation exchange beds, weak and strong-based anion exchange beds, and degasifiers.

Disadvantages of ion exchange


Sodium cycle ion exchange softening disadvantage is that the total solids, alkalinity, and silica contents of the
raw water are not reduced. In the case of cation exchange on the hydrogen cycle, the disadvantage is the
corrosion from the acid pH of the effluent. With demineralization, the main difficulty is higher cost,
particularly on high solids raw water. Without an excellent pre-filtration arrangement, fouling of the ion
exchange material with suspended and colloidal matter in the raw water can produce short runs, ion-exchange
degradation, and regeneration difficulties.

Advantages of ion exchange

A major advantage of ion exchange softening is the ease of process control. Variations (within reasonable
limits) of hardness in raw water or in flow rate do not have an adverse effect on the completeness of softening.
The ion exchange system takes up less space than the lime-soda system. Generally the ion exchange
demineralization has the ability to produce better quality boiler feedwater at an economical cost than most
other methods.

Deaeration of water
Dissolved oxygen in water is a major cause of boiler system corrosion. It should be removed before the water is
put in the boiler. Feedwater deaeration removes oxygen by heating the water with steam in a deaerating heater.
Part of the steam is vented, carrying with it the bulk of the dissolved oxygen.

Combination of ion exchange and lime process

As mention earlier, water containing suspended solids, organics, or turbidity requires filtration/clarification
prior to ion exchange. Because simple cation exchange does not reduce the total solids of the water supply, it is
sometimes used in conjunction with precipitation softening. A common combination treatment is the hot lime-
zeolite process. This involves pretreatment of the water with lime to reduce hardness, alkalinity, silica, and
subsequent filtration and a cation exchange softening. This combination accomplishes several functions like
softening, alkalinity and silica reduction, some oxygen reduction, and removal of suspended matter and
turbidity.

Reverse osmosis
To understand reverse osmosis (RO), one must first understand osmosis. Osmosis uses a semi-permeable
membrane that allows ions to pass from a more concentrated solution to a less concentrated solution without
allowing the reverse to occur. Reverse osmosis overcomes the osmotic pressure with a higher artificial pressure
to reverse the process and concentrate the dissolved solids on one side of the membrane. Operating pressures of
about 300 to 900 psi are required to achieve this. Reverse osmosis reduces the dissolved solids of the raw
water, making the final affluent ready for further treatment. This process is suitable for any type of raw water,
but sometimes the installation and operation cost may not be economical.

Internal treatment of boiler feedwater


Internal treatment of water inside the boiler is essential whether or not the feedwater has been pretreated.
Internal treatment compliments external treatment and is required regardless of whether the impurities entering
the boiler with the feedwater are large or small in quantity. In some cases feedwater supply needs to be only
filtered without the need for any other external treatment. Internal treatment can constitute the sole treatment
when boilers operate at low pressure, large amounts of condensed steam are used for feedwater, or the raw
water available is of good quality. However, in moderate or high-pressure boilers, External treatment of the
make-up water is mandatory for good results. With today’s boilers having higher heat transfer rates, even a
small deposit can cause tube failure or wasted fuel.

Internal water treatment program

The purpose of an internal water treatment program is:


1. To react with incoming feedwater hardness and prevent it from precipitating on the boiler metal as scale
2. To condition any suspended matter such as hardness sludge in the boiler and make it nonadherent to the
boiler metal
3. To provide antifoam protection to permit a reasonable concentration of dissolved and suspended solids
in the boiler water without foaming
4. To eliminate oxygen from the feedwater
5. To provide enough alkalinity to prevent boiler corrosion
6. To prevent scaling and protect against corrosion in the steam-condensate systems.

Chemicals used in internal treatment

Phosphates used to be the main conditioning chemical, but nowadays chelate and polymer type chemicals are
mostly used. These new chemicals have the advantage over phosphates of maintaining scale-free metal
surfaces. All internal treatment chemicals, whether phosphate, chelate, or polymer, condition the calcium and
magnesium in the feedwater. Chelates and polymers form soluble complexes with the hardness, whereas
phosphates precipitate the hardness. Sludge conditioners are also used to aid in the conditioning of precipitated
hardness. These conditioners are selected so that they are both effective and stable at boiler operating pressures.
Synthetic organic materials are used as antifoam agents. For feedwater oxygen scavenging, chemicals used are
sodium sulfite and hydrazine. Condensate system protection can be accomplished by the use of volatile amines
or volatile filming inhibitors. A reputable company supplying treatment chemicals should be consulted. These
companies supply the chemical formulations under their brand names and they provide details on the dosage
and methods.

Internal treatment for hardness

At boiler operating temperatures, calcium carbonate in the feedwater breaks down to form calcium carbonate.
Since it is relatively insoluble, it precipitates. Sodium carbonate in the water partially breaks down to sodium
hydroxide and carbon dioxide. Internal treatment with phosphates transforms calcium bicarbonate to calcium
phosphate and sodium carbonate. In the presence of hydroxide alkalinity, magnesium bicarbonate precipitates
as magnesium hydroxide or reacts with silica to form magnesium silicate. These minerals are precipitated from
solution in form of sludge, which must be conditioned to prevent its sticking to the boiler metal. The
conditioned sludge is then removed from the boiler by blowdown. When chelate is used for internal treatment,
it reacts with calcium and magnesium salts to form soluble complexes. These complexes are in the form of
dissolved solids and are removed by blowdown. Dispersant polymers used in conjunction with chelate
produces reaction products, which are better conditioned. They do not precipitate and are more easily removed
by blowdown. Use of polymers further aids in conditioning any suspended solid contamination that may have
entered with the boiler feed water.

Internal treatment for sulfates

The boiler temperature makes the calcium and magnesium sulfates in the feedwater insoluble. With phosphates
used as internal treatment, calcium reacts with the phosphate producing hydroxyapatite, which is much easier
to condition than calcium sulfate. With chelates or polymer used as internal treatment, calcium and magnesium
react with these materials producing soluble complexes that are easily removed by blowdown.

Internal treatment for silica

If silica is present in the feedwater, it tends to precipitate directly as scale at hot spots on the boiler metal and or
combines with calcium forming a hard calcium silicate scale. In the internal treatment for silica, the boiler
water alkalinity has to be kept high enough to hold the silica in solution. Magnesium, present in most waters,
precipitates some of the silica as sludge. Special organic materials or synthetic polymers are used to condition
magnesium silicate from adhering to the boiler metal.

Internal treatment for sludge conditioning


Internal treatment for hardness results in insoluble precipitates in the boiler that form sludge. In addition,
insoluble corrosion particulate (metal oxides) are transported to the boiler by condensate returns and from
preboiler feedwater corrosion resulting in suspended solids. Suspended solids, carried to the boiler by
feedwater or subsequently formed within the boiler, adversely affect both boiler cleanliness and steam purity.
These solids have varying tendency to deposit on the boiler metal. Conditioners prevent these solids from
depositing and forming corrosive or insulating boiler scale. Some of the principal types of sludge conditioners
are:

1. Starches – effective on high silica feedwater and where oil contamination is a problem
2. Lignins – effective on phosphate type sludge
3. Tannins – fairly effective on high hardness feedwater
4. Synthetic polymers – Highly effective sludge conditioners for all types of sludges

Internal treatment advantages

Internal treatment is basically simple and with the help of a qualified consultant an effective program is easily
established. Scales or deposits, corrosion and carryover are minimized thereby improving efficiency and
reducing energy consumption, preventing tube failures and unscheduled costly repairs, and reducing deposits,
corrosion and contamination in the downstream equipments or processes.

Internal treatment – chemical dosage

Chemical dosages are based on the amount and type of impurities in the feedwater. For example, the amount of
boiler treatment chemicals depends on the feedwater hardness; the amount of sodium sulfite depends on the
amount of dissolved oxygen in the feedwater. In addition, a certain amount of extra chemicals are added to
provide a residual in the boiler water. Feeding methods include chemical solution tanks and proportioning
pumps with the chemicals being added directly before entrance to the boiler. Ortho type phosphates are fed
through a separate line directly into the steam drum of the boiler. Chemicals used to prevent condensate system
corrosion can be fed directly to the feedwater, boiler, or steam, depending on the type of chemical used.
Continuous feeding is the preferred method but intermittent feeding may also suffice in some cases.

Tests for treatment control

Boiler water control tests include tests for alkalinity, phosphate, polymer, hydrazine, chelate, sulfite, pH,
organic colour, and total dissolved solids. If sulfite test shows adequate residual is present (this test is not valid
with use of uncatalyzed sodium sulfite), the feedwater oxygen has been removed. Testing for organic colour
gives an indication for both sludge conditioner and antifoam level. Chelate testing can be either for total chelate
or residual chelate.

Tests for checking contaminants

These tests depend on what type of contaminants is suspected. Common checks are for iron, oil and silica.
Total iron test serves as a check on corrosion products brought back by the condensate return. This test is also
used to check iron present in the make up water. Laboratory facility is required for oil test but visual inspection
can reveal gross contamination. Periodic checking should be done to detect unusual silica contamination and to
determine when blowdown is needed.

Blowdown
Blowdown is the discharge of boiler water containing concentrated suspended and dissolved feedwater solids.
As the blowdown water is replaced with lower solids feedwater, the boiler water is diluted. With proper
regulation of blowdown, the amount of solids in the boiler water can be controlled. The amount of blowdown
needed depends on how much feedwater impurities a given boiler can tolerate. For example if a particular
boiler can tolerate 500 ppm maximum dissolved solids, and the feedwater contains 50 ppm, it can be
concentrated only about 10 times. This means that for every 100 pounds of water fed to the boiler about 10
pounds of boiler water must be blown down to keep the dissolved solids from exceeding 500 ppm. Total
dissolved solids is not the only limiting factor in determining blowdown, other considerations include
suspended solids, alkalinity, silica and iron.

Test for regulating blowdown

A practical method for regulating blowdown is by routinely checking the electrical conductivity of the water
with a simple measuring instrument. Electrical conductivity gives an estimate of the dissolved solids in the
boiler water. By checking both the feedwater and boiler water dissolved solids, one can easily calculate the
number of feedwater concentrations.

Continuous and intermittent blowdown

Boilers incorporate blowdown valves at low points where sludge is likely to collect. Opening these blowdown
valves for short intervals provides intermittent removal of sludge and concentrated solids. In addition, some
boilers also have a blowdown off take located slightly below the water level in the steam release area. A small
amount of water is continuously removed through these connections. The use of continuous blowdown in
addition to manual (bottom) blow down maintains the residuals at more consistent levels in the boiler water.
Continuous blowdown also minimizes the amount of bottom blowdown required, with resultant savings in fuel
and chemicals. Continuous blowdown helps minimize upsets in boiler water circulation and operation.

Corrosion in steam condensate system

Corrosion in steam condensate system is caused by carbon dioxide and oxygen carried into the system by
steam. Dissolved carbon dioxide in condensed steam forms corrosive carbonic acid. If oxygen is present with
carbon dioxide, the corrosion rate is much higher, and is likely to produce localized pitting. Ammonia, in
combination with oxygen, attacks copper alloys.

Prevention of steam condensate corrosion

Generally corrosion prevention is by removing oxygen from the feedwater by mechanical (deaerator) means,
by use of suitable chemicals, and pretreatment of the make-up water to minimize potential carbon dioxide
formation in the boiler. Further boiler water treatment is done by use of volatile amines to neutralize carbon
dioxide or volatile filming inhibitors to form a barrier between the metal and the corrosive condensate.
Mechanical conditions need to checked and corrected, like poor trapping and draining of lines. Deaerator can
reduce oxygen to as low as 0.007 ppm. Since very small amounts of oxygen can cause boiler and steam
condensate system corrosion, chemical treatment is needed to assure complete oxygen removal. Sodium sulfite
and hydrazine chemicals are commonly used for this purpose. Catalysts are sometimes also used to speed up
the reaction.

Prevention of deposits and water corrosion in feedwater systems

Deposits in feedwater systems are usually caused by hardness precipitation as the water goes through feedwater
heaters or as the feed lines enter the boilers. Deposits can also occur from premature reaction of treatment
chemicals with hardness in the feedwater. Prevention is by means of the use of stabilizing chemicals fed
continuously to retard hardness precipitation. The corrosion of feedwater system is due to the low alkalinity or
dissolved oxygen in the water. Raising the pH of the water with caustic or amines and feed of catalyzed sodium
sulfite minimizes this problem.

Prevention of caustic embrittlement

Organic materials like lignins applied to the boiler water are effective in preventing caustic embrittlement of
boiler metal. Sodium nitrate inhibits embrittlement at low concentrations ranging to 0.4 part of sodium nitrate
per part of caustic soda in boiler water. Maintaining an organic content of 50-100 ppm and a sodium nitrate
content of 50 ppm is a commonly used embrittlement prevention program.
Oil contamination, problem & remedies

Main problems caused by oil in the boiler water are:

1. Oil can coat metal surfaces, cut down heat transfer, and produce metal overheating
2. Oil can cause sludge to become sticky and adhere to heat transfer surfaces
3. Oil can produce foaming and boiler water carryover

Oil contamination should be completely eliminated whenever possible. Organic chemicals help counteract the
effects of small amounts of oil contamination, but not of gross contamination. When sudden boiler water oil
contamination is experienced, normal procedure is to blow down heavily to remove oil and to check for the
source of contamination. In case of severe contamination, the boiler needs to be taken off the line and cleaned
out to remove the oil from the boiler surfaces. When oil contamination is continuous and unavoidable, some of
the methods used are:

1. Free oil can be reduced by passing the water through absorbent cartridge filters
2. Emulsified oil is broken down by chemical additives and filtered
3. Special filters are used with aids like diatomaceous earth
4. Flotation method
5. Coalescence method

Care of out-of-service boilers


Much of the corrosion damage to boilers and condensate equipment results during idle periods due to corrosion
caused by the exposure of wet metal to oxygen in the air. Wet boiler lay-up method is of storing boilers full of
water. Extra chemicals (alkalinity, oxygen scavenger, and a dispersant) are added to the boiler water and the
water level is raised in the idle boiler to eliminate air spaces. Nitrogen gas can also be used on airtight boilers
to maintain positive pressure on the boiler, thereby preventing oxygen from entering. Dry boiler lay-up method
is usually for longer boiler outages. The boiler is drained, cleaned and dried out. Material, such as hydrated
lime or silica gel, which absorb moisture, is placed in trays inside the boiler. The boiler is then sealed to
prevent air from entering. Periodic replacement of the drying chemical is required during long storage periods.