Thermo Lecture 3 - Water Conditioning

Iswor Bajracharya, PhD
Department of Mechanical Engineering

Pulchowk Engineering Campus
1.5 Water Conditioning
Water as a universal solvent, water dissolves gases from
the air and mineral matter from the soil and rock with
which it comes in contact. If untreated water is fed to the
boiler, various problems such as scale formation,
corrosion, fouling, foaming and embrittlement may occur
which eventually reduces the performance of boiler.
Therefore, water is treated to improve the quality of
water at certain standard acceptable for boiler operation
before it is fed to the boiler in order to remove the
dissolved solids, dissolved gases, suspended particles and
to chemically modify the dissolved substances that are
potentially harmful to the boiler. This is called water
conditioning.
12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 2
 Water conditioning is the process of removing or
altering minerals, chemicals, and contaminants from a
water at a certain level acceptable for smooth operation
of boiler before feeding into the boiler for steam
generation.
 Applying the proper type(s) of water conditioning
creates clean water that can be used in boiler.

Boiler Feed Water Quality
Parameter Acceptable Limits
Appearance Clear, without residue
Residual hardness < 5 ppm
Dissolved Oxygen < 0.02 mg/l
Temporary CO2 0 mg/l
Permanent CO2 < 25 mg/l
Silica < 0.5
Iron < 0.05 mg/l
Copper < 0.01 mg/l
pH (@ 20°C) 8.0 – 9.0
Water Temp. > 90° C
1.5.1 Water Problems and Benefits of Water
Conditioning
 Water is a good solvent. While flowing through its course,
it dissolves gases from the air and mineral substances and
chemical compound from the soil and rock with which it
comes in contact and carries suspended matters. It is also
subject to contamination with trade wastes, oils and process
materials. In general, water contains the following
impurities:
a) Dissolved solids: magnesium, calcium, aluminum,
iron, silica
b) Dissolved gases: oxygen, carbon dioxide, carbon
monoxide, ammonia
c) Suspended solids: silts, clay, sand

1.5.1 Water Problems and Benefits of Water Conditioning
 In general, the type of impurities water contains

depends on what it contacts; the amount of impurities
depends upon the contact time.
 As water is heated in a boiler, dissolved solids become
concentrated and form deposits inside the boiler. This
deposit and other impurities accumulate on tubes, valves,
pumps and pipe lines (formation of scale), restricting flow
and affecting heat transfer.
This leads to poor heat transfer and reduces the
efficiency of the boiler as well as reduces the life of boiler.
This also increases the quantity of fuel to be burnt.
 Therefore, raw water is unsuitable for use in boiler.
 Dissolved gasses such as oxygen and carbon dioxide will

react with the metals in the boiler system and lead to
boiler corrosion. In order to protect the boiler from these
contaminants, they should be controlled or removed,
trough external or internal treatment of water.
 Effect of impurities :
IMPURITY EFFECT ON A BOILER
1. Dissolved gases Corrosion
2. Calcium salts and These salts results in scale formation. Some salts
magnesium salts can also cause corrosion
3. Silica Can form a very hard scale.
4. Suspended solids and
Contribute to, or cause, carryover
dissolved solids
Water Problems
If raw water is used in the boiler without conditioning,
following problems occur in the boiler and accessories
which reduces the efficiency of boiler and shortens the
boiler life.
1) Scale Formation
 Deposition of different salts dissolved in the water leads
to scale formation.
Scale acts as an insulator that reduces the heat transfer
rate, increases water pressure drop through the heat
exchanger and leads excessive fuel consumption
More serious effect is the overheating of tubes which
ultimately reduces the tube life.
Water Problems
 Fuel wasted due to scale may be approximately 2-5 %
depending upon the scale thickness.
Fig: Scale formation in boiler

Water Problems
2) Corrosion
 Corrosion can be caused partly by absorption of gases
from the air and partly by the dissolved oxygen and carbon
dioxide in water.
 Grease and oil from animal or vegetable sources in
feedwater has a specific ultimate corrosive effect.
 Much of the organic and sewage content of impure
water also tends to increase corrosion.
 Low alkalinity also trigger corrosion in boiler tubes.
 In industrial areas this is frequently a major problem
because of heavy pollution of the air by flue gases.

Water Problems
 High temperatures and stresses in the boiler metal tend

to accelerate the corrosive mechanisms.
 In the steam and condensate system corrosion is
generally the result of contamination with carbon dioxide
and oxygen.
 Specific contaminants such as ammonia or sulphur also
may increase attack on copper alloys in the boiler.
 Low pH corrosion is seen in the condensate return
system.
 It reduces the thickness of metallic tubes which
ultimately leads to the failure of parts. It also reduces the
heat transfer and system efficiency.
Water Problems
3. Growth of Slime and Algae

Sometimes there is possibility of the organic growths of
slime and algae inside the boiler tubes and other heat
exchanges. These organic substances reduce the heat
transfer rate by forming an insulating coating or can
promote corrosion by pitting.

Water Problems
4. Carryover
 Carryover is a collective term to describe the transport
of a relatively small quantity of boiler-water solids along
with steam.
 Carryover occurs as a result of either foaming, priming
or by a combination of both.
 Foaming is the formation of bubbles on the surface of
the boiler resulting in the throwing over of slugs of boiler
water with the steam. This is similar to the 'bumping'
experienced when water is boiled in an open vessel.

Water Problems
 Foaming is caused by high concentration of any solids in
the boiler water. Substances such as alkalis, oils, fats,
greases, certain types of organic matter and suspended
solids are particularly conducive to foaming. Substances
such as alkalis, oils, fats, greases, certain types of organic
matter and suspended solids are particularly conducive to
foaming.
 Priming is the carryover of small amounts of droplets of
water in the form of spray or mist with steam, which
lowers the energy efficiency of the steam and leads to the
deposit of salt crystals on the super heaters and in the
turbines.
Water Problems
 Priming is aggravated by the presence of certain organic

substances, suspended and dissolved solid in the boiler-
water.
 Priming is common cause of high levels of boiler water
carryover. These conditions often lead to super heater
tube failures as well.
 Some mechanical entrainment of minute drops of
boiler water in the steam always occurs. When this boiler
water carryover is excessive, steam-carried solids produce
turbine blade deposits. The accumulations have a
composition similar to that of the dissolved solids in the
boiler water.
Water Problems
 It is harmful to the valves and pistons, as lubrication is

washed away, and can be dangerous as any water
collecting in the cylinders is not compressible and if
trapped may fracture the cylinder head or piston.

Water Problems
Effect of Scaling, Corrosion & Carryover
Classification Troubles in operation of boiler Causes of troubles
of problems system
1) Scaling • Reduction of boiler efficiency by  Leakage of hardness and/or
adhesion of hardness or silica silica from softener /demineralizer
scale  Inadequate quality control of
•Expansion or bursting of feedwater or boiler water
evaporation tubes by heavy scale  Application of inadequate
adhesion chemical treatment
2) Corrosion  Corrosion damage of piping of  Insufficient Deaeration of

feedwater and condensate, feedwater
evaporation tube by dissolved  Reduction of boiler water or
oxygen or carbon dioxide condensate pH
 Corrosion damage of  Iron contamination of feedwater
evaporation tube under from condensate line
deposition of metal oxides  Oxygen incoming to boiler
during idle time

Water Problems
Classification Troubles in operation of boiler Causes of troubles
of problems system
3) Carryover  Reduction of steam purity  Rapid fluctuation of

 Reduction of turbine efficiency by boiler operation load
silica scale  Excess concentration of
 Deterioration of product quality boiler water
treated with the steam  Boiler water
contamination with
organic matters
Source: Handbook of Water Treatment , KARUTA

Water Problems
Benefits of Water Conditioning
Water conditioning controls the amounts of different
types of impurities present in the water to a level
acceptable to the boiler operation. It brings the following
types of benefits:
1. All the problems in boiler caused by impurities so far
discussed is reduced.
2. Boiler efficiency increases.
3. Over heating of boiler tubes and hence thermal stress
is minimized.
4. Life of boiler tubes and accessories will lengthen.
5. Reduction in maintenance cost.
6. Steam quality increases.
Water Problems
Main Reasons of Water Conditioning
1. Prevention of Corrosion in feed boiler, steam

and condensate systems.
2. Elimination of Scale.
3. Economic boiler operation without
carryover.

1.5.2 Constituents and Characteristics of Water
 Water is a good solvent. It dissolves the rocks and soil

it contacts. It dissolves gases from the air and gases given
off from organics in the soil. Picks up suspended matter
from the earth and also subject to contamination with
trade wastes, oils and process materials. In general, the
type of impurities water contains depends on what it
contacts; the amount of impurities deepens on the
contact times.

1.5.2 Constituents and Characteristics of Water
Constituents of Water Impurities
Dissolved Solids Dissolved Liquid or gases Suspended Matter

CaCO3 (Limestone) O2 Organic Matter
MgCO3 (Dolamite) (decayed organic waste,
CO2 vegetation, algae,
CaSO4 (Gypsum)
slime, bacteria etc.)
MgSO4 (Epsom Salts)
SiO2 (Silica) Sediment (silt, clay ,
CO2 forms carbonic acid sand)
NaCl & attack the metal Oil, fat, grease, Sewage
NaSO4 (Glaubers salts) surface. O2 forms the iron
Small qty of Fe, Ca, Mg, oxide on mild steel These impurities cause
Na, K, Cl, Fl, Al,Mn surface. deposits on heat transfer
HCO3 surface, responsible for
NO3, SO4 foaming and carryover.
These minerals deposit on the
metal surface and form scale.
Dissolved Gases
 The two gases which cause corrosion are oxygen and

carbon dioxide.
 The carbon dioxide does so by dissolving in the water
and forming a weak carbonic acid (H2CO3) which attacks
the metal in feed systems, boiler or condensate system.
CO2 + H2O H2CO3
 Oxygen forms red iron oxide on a mild steel surface
immersed in water. This rusting occurs until the metal is
corroded away.
 If the amount of oxygen in the water is restricted, the
oxide film does not form so readily; but instead, the
surface of the steel tarnishes.
Dissolved Gases
 This tarnish is usually the development of a thin film of

iron oxide on the metal surface which is not so fully
oxidized as the red iron oxide, and is more dense, thus
tending to resist further corrosive attack.

Dissolved Calcium and Magnesium Salts
There are two forms of hardness- temporary and

permanent.
 Temporary hardness is due to carbonates and
bicarbonates of calcium and magnesium breaks down into
carbonates when the water is heated. In the boiler the
following chemical reaction takes place :
Ca(HCO3)2 + Heat → CO2 + H2O + CaCO3
 Carbonates are insoluble and therefore precipitate as a
fine white powder. This precipitate will bake unto the
heating surface of a boiler and form a scale.

Permanent hardness
Permanent hardness is due to calcium and magnesium
sulphate, chlorides and nitrates, and these salts cannot be
removed by boiling.
 Over a period of time, these deposit on the hottest part
of the heating surface and form permanent hardness
scale. Some salts like salts of magnesium tend to cause
corrosion instead of hard scale formation, e.g. magnesium
chloride in an untreated boiler hydrolyzes to form
corrosive hydrochloric acid.

Silica forms scale in a similar way to the permanent
hardness salts. When the scale formed is a mixture of
silica, calcium and magnesium salts, it is very hard and
therefore presents a difficult problem at inspection time.

Characteristics of Water
The major characteristics of water with reference to the

boiler feed water conditioning are:
1) pH Value
2) Alkalinity
3) Hardness and
4) Specific conductance

1. pH Value
The pH value is one of the most important control
factors in water treatment.
 It is an arbitrary symbol adopted to express the degree
of acidity or alkalinity of a water sample. Neutral water has
a pH of 7.0.
 Values below 7.0 and approaching 0 are increasingly
acid while values from 7.0 to 14.0 are increasingly alkaline.
14 0
7
Alkaline Acidic
(Neutral)
 Most natural waters have a pH of 6.0 to 8.0.

 Water containing free mineral acids may have pH values

below 4.5.
 A pH below 7.0 gives rise to corrosion of equipment
with which water comes in contact.
 When the pH is high (above 7.5 or 8.0), CaCO3 scale is
deposited more readily.
 The pH is usually measured by an electrometric pH
meter in the laboratory. It can also be determined by the
use of color indicators, comparing the solution with
standard shades of colors over the range of a particular
indicator. There are several standard indicator slides to
cover the range from 0 -14.0 pH.
 The pH is defined as the logarithm of the reciprocal of

the hydrogen ion concentration (moles per liter).
where H+ is the hydrogen ion concentration.

 When pure water (H2O) ionizes into H+ and OH- ions,
0.0000001 grams of hydrogen ions per liter are liberated.
This can be written as 1×10-7, or as a pH of 7.0.

2. Alkalinity
 Alkalinity is the most important characteristic of a water
when determining the scale forming tendency.
 Generally, alkalinity is a measure of the acid neutralizing
power of a water, and is determined by titration indicator.
 Alkalinity is classified with respect to a pH value.
Alkalinity
Phenolphthalein alkalinity Methyl orange (total) alkalinity
It is a measure of the carbonate and caustic It is a measure of all the alkaline

hydroxyl ions. It is determined by titrating substances (total alkaline),
down to a pH of 8.3. In natural waters this including the phenolphthalein
alkalinity is usually absent; but found in water alkalinity. It is determined by
which has been softened by lime or soda ash. titrating down to a pH of 4.3.
Interpretation of Methyl orange and phenolphthalein
Alkalinities
1. When there is no indication of phenolphthalein
alkalinity, this means that all of the alkalinity is caused
mainly by calcium, magnesium and sodium
bicarbonates. This water has a pH value less than 8.5
2. If twice the phenolphthalein alkalinity is less than or
equal to the methyl orange alkalinity, the alkalinity is
assumed to be caused by calcium, magnesium and
sodium carbonates and bicarbonates. This water has a
pH greater than 8.5.

3. When twice the phenolphthalein alkalinity exceeds the
methyl orange alkalinity, there is no bicarbonate
alkalinity and the alkalinity is caused by calcium,
magnesium and sodium hydroxides and carbonates.
Such water has a pH value greater than 8.5.
The amount of alkalinity and its type in a water

determine to a large extent the type of water
conditioning required.

Examples
Example 1-Bicarbonate Alkalinity
Methyl orange (MO) alkalinity =100 ppm as CaCO3
Phenolphthalein (P) alkalinity= 0 ppm as CaCO3
Since this analysis indicates 0 ppm of phenolphthalein
alkalinity, all of the alkalinity in the water is caused by
bicarbonates.
Example 2-Bicabonate and Carbonate Alkalinity
Methyl orange (MO) alkalinity = 100 ppm as CaCO3
Phenolphthalein (P) alkalinity = 5 ppm as CaCO3
Twice the phenolphthalein alkalinity is less than the
methyl
Orange alkalinity. Therefore, the alkalinity is caused by
bicarbonates and carbonates.

Example 3- Carbonate and Hydroxide Alkalinity

Phenolphthalein (P) alkalinity= 55 ppm as CaCO3
Since twice the phenolphthalein alkalinity (2×55)
exceeds the methyl orange alkalinity, there is no bicarbonate
alkalinity present. All of the alkalinity is present as carbonates
and hydroxides.

3. Hardness
 Hardness is represented by the sum of calcium and
magnesium salts in water although it may include
aluminum, iron, manganese, strontium, or zinc.
 Carbonate (temporary) hardness is attributed to
carbonates and bicarbonates of calcium and/or
magnesium expressed in ppm as CaCO3.
 The remainder of the hardness is known as non-
carbonate (permanent) hardness which is due to the
sulfates, chlorides, and/or nitrates of calcium and/or
magnesium expressed in ppm as CaCO3.

Classification of Hardness
Hardness (ppm as CaCO3) Classification
Less than 15 Very soft
15 to 50 Soft
50 to 100 Medium hard
100 to 200 Hard
Greater than 200 Very hard
Source: Water Conditioning, Carrier
 The accurate method for determining the hardness of
a water is from complete chemical analysis of the water.
 But soap solution is also used in water treatment
plants to determine hardness. This method is not
accurate.
Alkalinity Tests
Alkalinity test may be used to determine the amount of
carbonate and non-carbonate hardness for control
purposes.
1. When the methyl orange or total alkalinity exceeds
the total hardness, all of the hardness is caused by
bicarbonates and carbonates.
2. When the methyl orange or total alkalinity is less than
the total hardness:
a) Carbonate hardness equals the alkalinity.
b) Non-carbonate hardness equals the total hardness
minus the methyl orange alkalinity.

Example 4-Carbonate Hardness
Total hardness = 95 ppm as CaCO3.
Methyl orange alkalinity in this case exceeds the total
hardness. Therefore, all of the hardness is present as carbonate
hardness.
Example 5-Carbonate and Non-carbonate Hardness
Total hardness = 150 ppm as CaCO3
Total hardness exceeds the methyl orange alkalinity.
a) The carbonate hardness, therefore, equals the alkalinity, and is
equal to 100 ppm as CaCO3.
b) Non-carbonate hardness equals total hardness minus methyl
Orange alkalinity (150-100) or 50 ppm as CaCO3

4. Specific Conductance
 Specific Conductance is a measure of the ability of
water to conduct an electric current . The specific
conductance of a water indicates whether galvanic
corrosion may be a problem.
 Galvanic corrosion occurs when dissimilar metals are
present in a solution capable of carrying an electric
current. It is a form of electrochemical corrosion where a
difference in potential associated with the metals
themselves causes a small electric current to flow from
one metal to the other thru the electrolyte.

1.5.3 Types and Causes of Scale and Deposits
Introduction
 When water is evaporated in the boiler, the impurities
get deposited at the tubes, shell and other parts. When
the concentration of the impurities reaches saturation
point, they are seen on the inner walls of the boiler.
 Deposition can take place in two forms:
Deposition
Sludge Scale
If the deposition of impurities takes If the deposited matter forms a hard,

place in the form of loose, soft and adhering crust/coating on the inner
slimy layer, it is called sludge. walls of the boiler, it is called scale.

Sludge
 Sludge is formed within the comparatively colder
portions of the boiler and collects in areas of the system,
where the flow rate is slow or at bends.
 Sludge is formed by substances which have greater
solubility in hot water than in cold water, e.g., MgCO3,
MgCl2, CaCl2, MgSO4, etc.

Problems of Sludge
1. Sludges are poor conductor of heat, so they tend to
waste a portion of heat generated
2. If sludges are formed along with scales, then former
gets entrapped in the latter and both get deposited as
scales.
3. Excessive sludge formation disturbs the working of the
boiler. It settles in the regions of poor water circulation
such as pipe connection, plug opening, gauge-glass
connection, thereby causing even choking of the pipes.

Prevention of Sludge Formation

1) By using well softened water,
2) By frequently ‘blow-down operation’, i.e., drawing off a
portion of the concentrated water.

Scale Formation
 Scales are hard deposits, which stick very firmly to the
inner surfaces of the boiler. Scales are difficult to remove,
even with the help of hammer and chisel. Scales are the
main source of troubles.
 There are two types of scale.
Scale
CaCO3 Scale CaSO4 Scale Mg (OH)2 Scale Silicate Fe2O3 Deposit

Scale

Calcium Carbonate Scale
 The calcium carbonate scale is formed due to the
decomposition of calcium bicarbonate
Ca(HCO3)2 + Heat → CaCO3 (scale)↓ + H2O + CO2 ↑
However, scale composed chiefly of calcium carbonate
is soft and is the main cause of scale formation in low-
pressure boilers. But in high-pressure boilers, CaCO3 is
soluble.
CaCO3 + H2O → Ca(OH2)2 (soluble) + CO2 ↑

 Calcium carbonate and calcium sulfate have decreasing
solubility in water with rising temperature. So, high
temperature surfaces are more susceptible to scale formation
than the low temperature surfaces in the same water system.
Fig: Solubility of CaCO3 with temperature and pH (Source: Water Conditioning,

Carrier)
Factors Causing CaCO3 Scale
 The primary factors causing calcium carbonate scale in
a water system are:
1. High methyl orange alkalinity, ppm as CaCO3.
2. High calcium content, ppm as CaCO3
3. High pH
4. High temperature
5. High dissolved solids, ppm
 Normally, methyl orange alkalinity is a good measure
of the amount of calcium bicarbonate in the water.
Calcium carbonate is formed by the decomposition of
calcium bicarbonate.
Calcium Sulphate Scale
The solubility of calcium sulphate in water decreases with
rise of temperature. Thus, solubility of CaSO4 is 3,200 ppm
at 15oC and it reduces to 55 ppm at 230oC and 27 ppm at
320oC. In other words, CaSO4 is soluble in cold water, but
almost completely insoluble in super-heated water.
Consequently, CaSO4 gets precipitated as hard scale on the
heated portions of the boiler. This is the main cause of
scales in high-pressure boilers. Calcium sulphate scale is
quite adherent and difficult to remove even with the help
of hammer and chisel.

It may be formed
(1) By the action of sulfur dioxide gas (SO2) from the air
dissolving in water to form sulfuric acid (H2SO4) which
in turn combines with calcium carbonate.
SO3(g) + H2O(l) → H2SO4(aq)
H2SO4 + CaCO3 → CaSO4 + H2CO3
(1) By feeding sulfuric acid for calcium carbonate scale
control.

Magnesium Hydroxide Scale
Dissolved magnesium salts undergo hydrolysis (at
prevailing high temperature inside the boilers) producing
magnesium hydroxide precipitate, which forms a soft
type of scale .
MgCl2 + 2 H2O → Mg(OH)2 ↓ + 2HCl ↑
Silicate Scale
When Silica (SiO2) combines with calcium or magnesium
salt, they form calcium silicate (CaSiO3) or magnesium
silicate (MgSiO3) which are very hard. These deposits stick
very firmly on the inner side of the boiler surface and are
very difficult to remove. One important source of silica in
water is the sand filter.
Iron Oxide
In the case of well water possessing a high natural iron
content, the ferrous bicarbonate reacts with the dissolved
oxygen in the boiler feed water and gets decomposed into
iron oxide. This iron oxide is deposited into the metal
surface.
4Fe(HCO3)2+O2 → 2Fe2O3 ↓ + 8CO2 + 4H2O

Disadvantages of Scale Formation
1. Wastage of fuel : Scales have a low thermal
conductivity, so the rate of heat transfer from boiler
to inside water is greatly decreased. In order to
provide a steady supply of heat to water, excessive or
over heating is required and this causes increase in
fuel consumption. The wastage depends upon the
thickness and the nature of scale :
Thickness of scale (mm) 0.325 0.625 1.25 2.5 12
Wastage of fuel 10% 15% 50% 80% 150%

2. Lowering of boiler safety : Due to scale formation,
over-heating of boiler is to be done in order to
maintain a constant supply of steam. The over-heating
of the boiler tube makes the boiler material softer and
weaker and this causes distortion of boiler tube and
makes the boiler unsafe to bear the pressure of the
steam, especially in high-pressure boilers.
3. Choking of pipes & valves: Scales may sometimes
deposit in the valves and condensers of the boiler and
choke them partially. This results in pressure in the
pipe lines.

4. Danger of explosion : When thick scales crack, due to

uneven expansion, the water comes suddenly in
contact with over-heated iron plates. This
causes formation of a large amount of steam suddenly.
So sudden high-pressure is developed, which may even
cause explosion of the boiler.
5. Decrease in efficiency: As the fuel consumption is
increased to generate the steady steam supply, the
overall efficiency of the boiler is decreased.

Removal of Scales
1. With the help of scraper or piece of wood or wire brush, if
they are loosely adhering.
2. By giving thermal shocks (i.e., heating the boiler and then
suddenly cooling with cold water), if they are brittle.
3. By dissolving them by adding chemicals, if they are
adherent and hard.
a) Calcium carbonate scales can be dissolved by using 5-
10% HCl.
b) Calcium sulphate scales can be dissolved by adding
EDTA (Ethylene Diamine Tetra Acetic Acid), with which
they form soluble complexes.
4. By frequent blow-down operation, if the scales are loosely
adhering.
1.5.4 Scale Deposit Prevention and Methods
1. External Treatment Method
 External treatment is the reduction or removal of
impurities from water outside the boiler for use as
boiler feed water. It consists of chemical and
mechanical treatment of water. The goal is to improve
the quality of water prior to its use as boiler feed water,
external to the operating boiler itself.
 Such external treatment normally includes:
a) Clarification (removes suspended solid, used in very
large boiler systems
b) Filtration (removes very fine suspended solids)
c) Softening and Demineralization (removes dissolved
minerals )
External Treatment Method
d) Dealkalization
e) Deaeration and Heating
 Any or all of these approaches can be used in boiler
feed water preparation.

Fig: Water treatment schematic

2. Internal Treatment Method
 Even after the best and most appropriate external
treatment of the water source, boiler feed water
(including return condensate) still contains impurities
that could adversely affect boiler operation. Internal
boiler water treatment is then applied to minimize the
potential problems and to avoid any catastrophic
failure, regardless of external treatment malfunction.
 It 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.
 It is also called sequestration. In this method, an ion is
prohibited to exhibit its original character by
'complexing’ or converting it into other more soluble
salt by adding appropriate reagent.
 An internal treatment is accomplished by adding a
proper chemical to boiler water either :
(a) to precipitate the scale forming impurities in the form of sludges,
which can be removed by blow-down operation, or
(b) to convert them into compounds, which will stay in dissolved form
in water and thus do not cause any harm.
 Internal treatments methods are, generally, followed
by 'blow-down operation', so that an accumulated
sludge is removed.

Clarification
 Clarification is the removal of suspended matter from
water supplies.
 The suspended matter may consist of large particles
which settle out readily. In this case, clarification involves
the use of settling basins and/or filters.
 Clarification is commonly used for large boilers that
consume large volumes of water from surface water
sources.
 Clarification is commonly used in combination
with filtration for total removal of solids.

Coagulation
Coagulation is the clumping together of finely divided and
colloidal impurities in water into masses which will settle
rapidly and/or can be filtered out of the water. Colloidal
particles have large surface areas which keep them in
suspension and in addition the 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.

 Most often, however, suspended matter in water

consists of particles so small that they do not settle out
and even pass through filters. The removal of these finely
divided or colloidal substances therefore requires the use
of coagulants.

Coagulation
 Coagulation is the process of clumping together or
agglomerating of finely divided and colloidal particles in
water into masses which will settle rapidly and/or can be
filtered out of the water.
 Colloidal particles have large surface areas which keep
them in suspension and also the particles have negative
electrical charges which cause them to repel each other
and resist adhering together, dispersing almost
indefinitely.
 In coagulation, therefore, negatively charged particles
are neutralized so that they clump together.
Coagulation
Coagulants
 The most common coagulants (water soluble inorganic
compounds ) are iron and aluminum salts. The most
common inorganic coagulants are:
a. Alum-aluminum sulfate - Al2(SO4)3
b. Ferric sulfate - Fe2(SO4)3
c. Ferric chloride - FeCl3
d. Sodium aluminate - NaAlO2
In recent years synthetic materials called polyelectrolyte
have been developed for coagulation purposes.
In some cases organic polymers and special types of clay
are used in the coagulation in making the flock heavier,
causing it to settle out more rapidly.
Filtration
 After clarification and coagulation, water is passed
through filter. Clarification and coagulation remove most
of the suspended and colloidal particles, remaining
portion is filtered out in filtration.
 Filtration can be done several different ways. The most
common filters are granular media filters, made from
sand, anthracite (hard coal) and garnet. Filter media
choice, filter bed depth and other design parameters are
determined by the quality of the water and boiler
requirements.

Filtration
 Filtration does not remove dissolved solids, but may be

used together with a softening process, which does
reduce the concentration of dissolved solids. For example,
anthracite filtration is used to remove residual
precipitated hardness salts remaining after clarification in
precipitation softening.

Softening
 Water softening is a process of removing or reducing
raw water hardness, alkalinity, silica, and other
constituents. This is also called precipitation.
 The most commonly used softening method is the soda-
lime softening. The water is treated with lime or a
combination of lime and soda ash (carbonate ion).
 These chemicals react with the hardness and natural
alkalinity in the water and form insoluble compounds. The
compounds precipitate and are removed from the water
by sedimentation and, usually, filtration.

Softening
Temporary Hardness
 Waters with moderate to high hardness and alkalinity
concentrations (150-500 ppm as CaCO3) are often treated
in this fashion.
 Hydrated lime (calcium hydroxide) reacts with soluble
calcium and magnesium bicarbonates (temporary
hardness) to form insoluble carbonate precipitates. This is
shown by the following equations:
Ca(OH)2 + Ca(HCO3)2 ======> 2CaCO3 + 2H2O
Ca(OH)2 + Mg(HCO3)2 ======> Mg (OH)2+ 2CaCO3 + 2H2O
Ca(OH)2 + MgCO3 ======> Mg (OH)2 + CaCO3

Softening
 Most of the calcium carbonate and magnesium hydroxide
come out of solution as a sludge and 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 a water.
 Lime reacts with magnesium Sulphate and chloride and
precipitates magnesium hydroxides but in this process
soluble calcium sulphate and chloride are formed. Lime is
not effective in removing calcium sulphate and chlorides.
MgSO4 + Ca(OH)2 =====> Mg(OH)2 + CaSO4
MgCl2 + Ca(OH)2 =====> Mg(OH)2 + CaCl2
Softening
Permanent Hardness
 Soda ash (Na2CO3) is used primarily to reduce non-
bicarbonate hardness (also called Sulphate hardness or
permanent hardness). It reacts as follows:
Na2CO3 + CaSO4 =====> CaCO3 + Na2SO4
Na2CO3 + CaCl2 =====> CaCO3 + NaCl
 The calcium carbonate formed by the reaction tends to

come out of solution as a sludge. The sodium Sulphate and
chloride formed are highly soluble and non-scale forming.

Softening
However, non-carbonate magnesium hardness reduction
requires the use of both line and soda in cold process. The
reactions are as follows:
Na2CO3 + Ca(OH)2 + MgSO4 =====> CaCO3 + Mg(OH)2 + Na2SO4
Na2CO3 + Ca(OH)2 + MgCl2 =====> CaCO3 + Mg(OH)2 + NaCl

Demineralization
 Demineralization is the process of removing the
dissolved salts in raw water by an Ion Exchange Method
(chemical method and there by producing pure feed
water for boiler.
When minerals dissolve in water they form electrically
charge particles which are called ions. For example,
calcium carbonate forms a calcium ion with plus charges
(a Cation) and a carbonate ion with negative charges (an
Anion).
 Positively charged particles are known as Cation and
negatively charged particles are called Anion.
Demineralization
 Ion exchange method involves the exchanges one type

of ion (charged particle) for another.
 Certain natural and synthetic materials have the ability
to remove mineral ions from water in exchange for others.
 There are two types of Ion exchange materials:
1) Cation Exchangers
2) Anion Exchangers.
 Cation exchange materials react only with positively
charged ions such as Ca++ and Mg++. Anion exchanger
materials react only with the negatively charged ions such
as carbonate (CO3) and Sulphate (SO4).

Demineralization
Zeolite Ion Exchanger
 Zeolite material is used as Cation exchanger. It is a
naturally occurring insoluble minerals of sodium
aluminosilicate type complex (NaAlSiO4.3H2O ≈ NaZ).
 Sodium zeolite softening is the most widely applied use
of ion exchange.
Fig. Sodium Zeolite Bed

Demineralization
 In zeolite softening, water containing scale-forming

ions, such as calcium and magnesium, passes through a
resin bed in the sodium form. In the resin, the hardness
ions are exchanged with the sodium, and the sodium
diffuses into the bulk water solution.
 The hardness-free water, termed soft water, can then
be used for low to medium pressure boiler feed-water.

Demineralization
Principles of Zeolite Softening

The removal of hardness from water by a zeolite softening
process is described by the following reaction:
 In this way, calcium and magnesium ions responsible for

hardness are removed from the water, held by the resin,
and replaced by sodium ions in the water. This process
makes water “soft.”

Demineralization
Regeneration of Zeolites
 Eventually, a point is reached when very few sodium
ions remain on the resin, thus no more calcium or
magnesium ions can be removed from the incoming
water. The resin at this point is said to be “exhausted” or
“spent,” and must be “recharged” or “regenerated.”
 A high concentration of NaCl (generally 10% ) is passed
through the exhausted zeolites to replace calcium and
magnesium. The regeneration proceeds according to the
following equation:

Demineralization
Advantage
 Water from a properly operated zeolite softener is
nearly free from detectable hardness (0-2 ppm level).
 Process is simple and only one chemical is used.
 Regeneration of ion is possible.
Disadvantage
However, some small amounts of hardness, known as
leakage, are present in the treated water. Complete
demineralization of salt is difficult.

Synthetic Polymer Ion Exchanger

 The new type of synthetic polymer ion exchangers are
much more powerful than the zeolites and are widely
used in demineralization of water.
 These resins can remove all mineral salts to complete
demineralization of hard water.
 This synthetic polymer ion exchanger consists of two
types of Ion Exchangers:
a) Cation Exchangers
b) Anion Exchangers

Cation Ion Exchanger

Cation ion exchanger has replaceable H+ ion. The Cation
exchange resins are organic in nature, made up by
polymerization of polyhydric phenols with formaldehyde.
 These resins derive their functionality from sulfonic
acid groups (HSO3¯).
 These resins are also called Strong Acid Cation (SAC).
 When used in demineralization, these resins replace
nearly all the Cation of hard water by hydrogen ions
making the water an equivalent amount of acids.

 The removal of hardness from water by SAC is
described by the following reaction:
 Above equation shows that the resin has removed the

Ca, Mg and Na ions but the water has become acidic.
 Anion Exchange Resins are used to remove the acidity
of water by passing through the resin bed containing
Strong Base Anion (SBA).

Anion Ion Exchanger
 Anion exchanger has replaceable OH- ion. In this unit,
the acidity of water is removed by the anion by displacing
Cl-, SO4- from acid.
 The Strong Base Anion (SBA) derive their functionality
from quaternary ammonium functional groups.
 When in the hydroxide form, SBA resins remove all
commonly encountered anions as shown below:
 Thus the acidity of water is removed.

Fig: DM Plant

Dealkalization
 Boiler operation requires the removal of hardness as
well the reduction of alkalinity. Zeolite softening does
not reduce alkalinity, and demineralization is too costly.
 For these situations, a dealkalization process is used.
The most frequently used dealkalization process are:
a) Sodium/hydrogen zeolite (Split-Stream) dealkalization
b) Chloride-anion dealkalization
c) Weak acid cation dealkalization
 The softened water is passed through the Dealkalizers
to reduce the alkalinity of water through one of the
above dealkalization process.
Dealkalization
Sodium/Hydrogen Zeolite (Split-Stream)

Dealkalization
 In a split stream dealkalizer, a portion of the raw water
is passed through a sodium zeolite softener. The
remainder flows through a hydrogen-form strong acid
cation unit (hydrogen zeolite).
 The effluent from the sodium zeolite is combined with
the hydrogen zeolite effluent.
 The effluent from the hydrogen zeolite unit is acidic
(carbonic acid, sulphuric, hydrochloric acid) produced and
contains no alkalinity. The effluent from Sodium zeolite
contains sodium bicarbonates/carbonates.
Dealkalization
 When the two streams are combined, free mineral
acidity in the hydrogen zeolite effluent converts sodium
carbonate and bicarbonate alkalinity in the sodium
zeolite effluent to carbonic acid as shown below:
Effluent from Effluent from Carbonic Acid

sodiaum zeolite Hydrogen Zeolite
 Carbonic acid is unstable in water and forms carbon

dioxide gas and water. The blended effluents are sent to a
decarbonator or degasser, where the carbon dioxide is
stripped from the water
Deaeration and Heating

Refer Lecture Notes on Boiler Mountings and Accessories.

Internal Treatment Method
Phosphate Conditioning
 In high-pressure boilers, scale formation can be avoided
by adding sodium phosphate, which reacts with hardness
of water and forms non-adherent and easily removable,
soft sludge of calcium and magnesium phosphates. It can
be removed by blow - down operation.
3CaCl2 + 2Na3PO4 → Ca3(PO4)2 + 6 NaCl
 The main phosphates employed are : (a) NaH2PO4,
(Sodium dihydrogen phosphate (acidic); (b) Na2HPO4,
(Disodium hydrogen phosphate (weakly alkaline); (c)
Na3PO4 ( Trisodium phosphate (alkaline).
Carbonate Conditioning
 In low-pressure boilers, scale-formation can be avoided
by adding sodium carbonate to boiler water. CaSO4 is
converted into calcium carbonate in equilibrium.
CaSO4 +Na2CO3 → CaCO3 + Na2SO4
 Consequently, deposition of CaSO4 as scale does not

take place and calcium is precipitated as loose sludge of
CaCO3, which can be removed by blow-down operation.

Calgon Conditioning
Calgon conditioning involves in adding calgon [sodium
hexameta phosphate (NaPO3)6 to boiler water. It
prevents the scale and sludge formation by forming
soluble complex compound with CaSO4.
Na2[Na4(PO3)6] → 2 Na+ + [Na4P6O18]2-
Calgon
2CaSO4 + [Na4P6O18]2 − → [Ca2P6O18]2 − + 2 Na2SO4

Soluble complex ion

Treatment with Sodium Aluminates
 When Sodium Aluminates (NaAlO2) is mixed with water,
it gets hydrolyzed yielding NaOH and a precipitate
of aluminium hydroxide.
NaAlO2 + 2H2O → NaOH + Al(OH)3
 The sodium hydroxide, so-formed, precipitates some of
the magnesium as Mg(OH)2 ,
MgCl2 + 2NaOH → Mg(OH)2 + 2 NaCI
 The precipitate of Mg(OH)2 & Al(OH)3, produced inside
the boiler entraps finely suspended and colloidal particles,
including oil drops and silica. The loose precipitate can be
removed by blow-down operation.
Complex Metric Method

Complex metric method involves addition of 1.5 %
alkaline (pH = 8.5) solution of EDTA to feed-water. The
EDTA binds to the scale-forming Cations to form stable
and soluble complex. As a result, the sludge and scale
formation in boiler is prevented. Moreover, this
treatment : (1) prevents the deposition of iron oxides in
the boiler, (2) reduces the carryover of oxides with steam,
and (3) protects the boiler units from corrosion by wet
steam (steam containing liquid water).

END

Thermo Lecture 3 - Water Conditioning

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Thermo Lecture 3 - Water Conditioning

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Iswor Bajracharya, PhD

Department of Mechanical Engineering

12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 3

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 In general, the type of impurities water contains

 Dissolved gasses such as oxygen and carbon dioxide will

Fig: Scale formation in boiler

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 High temperatures and stresses in the boiler metal tend

3. Growth of Slime and Algae

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 Priming is aggravated by the presence of certain organic

 It is harmful to the valves and pistons, as lubrication is

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2) Corrosion  Corrosion damage of piping of  Insufficient Deaeration of

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3) Carryover  Reduction of steam purity  Rapid fluctuation of

Source: Handbook of Water Treatment , KARUTA

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Main Reasons of Water Conditioning

1. Prevention of Corrosion in feed boiler, steam

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 Water is a good solvent. It dissolves the rocks and soil

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Dissolved Solids Dissolved Liquid or gases Suspended Matter

 The two gases which cause corrosion are oxygen and

 This tarnish is usually the development of a thin film of

12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 24

There are two forms of hardness- temporary and

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The major characteristics of water with reference to the

12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 28

 Most natural waters have a pH of 6.0 to 8.0.

 Water containing free mineral acids may have pH values

 The pH is defined as the logarithm of the reciprocal of

where H+ is the hydrogen ion concentration.

12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 31

Phenolphthalein alkalinity Methyl orange (total) alkalinity

It is a measure of the carbonate and caustic It is a measure of all the alkaline

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The amount of alkalinity and its type in a water

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Example 3- Carbonate and Hydroxide Alkalinity

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If the deposition of impurities takes If the deposited matter forms a hard,

12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 42

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Prevention of Sludge Formation

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CaCO3 Scale CaSO4 Scale Mg (OH)2 Scale Silicate Fe2O3 Deposit

12/18/2015 Boiler Water Conditioning/Iswor Bajracharya 46

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Fig: Solubility of CaCO3 with temperature and pH (Source: Water Conditioning,