UNIT-II

 BOILER PROBLEM AND

SOFTENING METHOD
BOILER WATER (WATER FOR STEAM GENERATION):

 A boiler is a closed vessel in which water under pressure is

transferred into steam by the application of heat.

 In the boiler furnace, the chemical energy in the fuel is

converted into heat, and it is the function of the boiler to
transfer this heat to the contained water in the most efficient
manner.
 Boiler should also be designed to generate high
quality steam for plant use.

 A boiler must be designed to absorb the maximum

amount of heat released in the process of
combustion.

This heat is transferred to the boiler water through

radiation, conduction and convection.
Convection:-

 The movement caused within a fluid by the

tendency of hotter and therefore less dense
material to rise, and colder, denser material to
sink under the influence of gravity, which
consequently results in transfer of heat.
 B0ILER FEED WATER:-

1. It should be free from suspended solid and

dissolved gases such as- CO2,SOx,NOx,halogen
and hydrogen halide.
2. Hardness should be less than 0.1 ppm.
3. Alkalinity should be in the range 0.1to1 ppm.0.5
alkalinity is preferable.
4. Free from oily/soapy matter that reduce the
surface tension of water.
5. Free from hardness producing substance.
Excess of impurities, if present, in boiler feed water
generally cause the following problems:

BOILER PROBLEM:
1. SLUDGE & SCALE FORMATION
2. PRIMING & FOAMING
3. CARRY OVER
4. BOILER CORROSION
5. CAUSTIC EMBRITTLEMENT
Sludge and Scale Formation in Boilers
In boiler, water is converted to steam. during this
process ,when the volume of water decrease and
saturation point is reached and all dissolved salts
precipitate out.

If the precipitates formed are soft loose and slimy,

these are known as sludges, while if the precipitate is
hard and adhering on the inner walls, it is called as
scale.
 SLUDGE:-
Sludge is a soft, loose and slimy precipitate formed
within the boiler.

Sludge are formed by substances which have greater

solubility in hot water than in cold water, e.g.
MgCO3, MgCl2, CaCl2,MgSO4 etc.

They are formed at comparatively colder portions of

the boiler get collected at places where the flow rate
is slow; they can be easily removed (scrapped off)
with a wire brush.
Disadvantages of Sludge formation:-
(i) Sludges are poor conductors of heat, so they tend
to waste a portion of heat generated and thus decrease
the efficiency of boiler.

(ii) 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, there by causing even choking
of the pipes.
Prevention of sludge formation:-

By using softened water.

By frequently ‘blow-down operation’, (i.e.
partial removal of concentrated water
through a )tap at the bottom of boiler and
replacing it by fresh water.
 SCALES:-
 Scales are hard deposits firmly sticking to the inner
surfaces of the boiler.
 They are difficult to remove, even with the help of hammer
and chisel, and are the main source of boiler troubles.

Decomposition of calcium bicarbonate:-

 Ca(HCO3)2 CaCO3 + H2O + CO2
(scale)
 Calcium carbonate is soft and is the main cause of scale
formation in low-pressure boilers. But in high-pressure
boilers, CaCO3 is soluble due to the formation of Ca(OH) 2
 CaCO3 + H 2O Ca(OH)2 + CO2
(soluble)
Deposition of calcium sulphate:-

 CaSO4 is soluble in cold water, but almost completely

insoluble in super-heated water. It may be due to increase
ionization at high temperature.

 Consequently, CaSO4 gets precipitated as hard scale on

the hotter parts, of the boiler.

 This type of scale causes troubles mainly in high pressure

boilers.

 Calcium sulfate scale is quite adherent and difficult to

remove, even with the help of hammer and chisel.
Hydrolysis of magnesium salts
MgCl2 + 2H2O Mg(OH)2 + 2HCl
(scale)
Presence of silica:-
Even if a small quantity of SiO2 is present, it may deposit
as calcium silicate (CaSiO3) and / or magnesium silicate
(MgSiO3). These deposits adhere 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.
Disadvantage of Scale-
Wastage of fuel:-
Scales have a poor thermal conductivity so the rate of heat
transfer from boiler to inside water is greatly reduced.
The wastage of fuel being dependent on the thickness and
the nature of scale.
Lowering of boiler safety:-
Due to scale formation, over-heating of boiler is done in
order to maintain a steady supply of steam. It makes the
boiler material softer and weaker. This cause distortion of
boiler tube and also makes the boiler unsafe to bear the
pressure of the steam, especially in high-pressure boilers.
Decrease in Efficiency:-
Deposition of scales in the valves and condensers of
the boiler, choke them partially. This results in
decrease in efficiency of the boiler.

Danger of Explosion :-
When thick scales crack due to uneven expansion,
the water comes suddenly in contact with over-heated
portion and large amount of steam is formed
instantaneously. This results in development of
sudden of sudden high-pressure which may cause
explosion of the boiler.
Removal of Scales:
 Scales are removed by mechanical methods and by
Chemical Methods .

 If the scales are loosely adhering, it can be removed with the help of
scraper or piece of wood or wire brush,

 If the scales are brittle, it can be removed by giving thermal shocks (i.e.,
heating the boiler and then suddenly cooling with cold water).

 If the scales are loosely adhering, they can also be removed by frequent
blow-down operation. Blow-down operation is partial removal of hard
water through a ‘tap’ at the bottom of the boiler and add soft water.

 If the scales are adherent and hard, they can be removed by dissolving
them by adding chemicals e.g., CaCO 3 scales can be dissolved by using
5-10% HCl. Calcium sulfate scales can be removed by adding EDTA,
since the Ca – EDTA complex is highly soluble in water.
s.no. SLUDGE SCALE

1. Sludges are soft, loose and slimy Scales are hard deposits.
precipitate.

2. They are non-adherent deposits They stick very firmly to the inner
and can be easily removed. surface of boiler and are very
difficult to remove.

3. Formed by substances like CaCl2, Formed by substance like CaSO4,

MgCl2, MgSO4, MgCO3 etc. Mg(OH)2 etc.

4. Formed at comparatively colder Formed generally at heated portions

portions of the boiler. of the boiler.

5. They decrease the efficiency of Decrease the efficiency of boiler

boiler but are less dangerous. and chances of explosions are also
there.

6. Can be removed by blow-down Cannot be removed by blow-down

operation. operation.
 Priming and Foaming

Priming:-
 When steam is produced rapidly in the boilers, some droplets of the
liquid water are carried along-with the steam. This process of ‘wet-
steam’ formation is called priming.

 The moisture contamination in the steam is expressed in percentage

by weight of Steam.

 For example, if steam contains 0.2% moisture, its steam quality will
be reported as 100 – 0.2 = 99.8%.
 Priming is caused by:
 Mainly due to suspended impurities and due
to dissolved impurities in water.
 Steam velocities high enough to carry
droplets of water into the steam pipe;
 Sudden boiling;
 Faulty design of boiler.
 Priming can be avoided by:
Controlling rapid change in steaming velocities,
 The proper design of boilers (maintaining low
water levels in boilers)
Ensuring efficient softening and Filtration of the
boiler-water carried over to the boiler.
 By blowing off sludge or scales from time to time.
 Foaming:-
 Foaming is the formation of small but persistent foam or bubbles at the
water surface in boilers, which do not break easily.

 Foaming is caused by the presence of oil and alkalis in boiler-feed water.

 Actually oils and alkalis react to form soap, which greatly lowers the
surface tension of water, and thus increase the foaming tendency of the
liquid.

 With respect to foaming, water can be following grades:

 (i) Foaming water:- It is that water which produces foam even in two
days, if blowing off operation is not done.
 (ii) Semi-Foaming water:-. It is that water which does not produce
any foam in locomotive boilers for two days.
 (iii) Non-Foaming water:- It is that water which does not produce any
foam in locomotive boilers for one week.
 Foaming can be avoided by:

 The addition of anti foaming agent, for example addition of castor

oil (which spreads on the surface of water and therefore) neutralizes
the surface tension reduction.

 Traces oils are generally introduced in boiler feed water through the
lubricating materials used for pumps etc. the removal of foaming
agent (Lubricating oil) from boiler water.

 Oils can be removed by the addition of aluminum compounds, like

Sodium Aluminate and Aluminum sulphate which is hydrolyzed
to form Aluminum hydroxide flocks which entrap oil drops.
 The flocks of Al(OH)3 containing oil droplets are removed by
filtration through anthracite (Anthracite, also known as hard
coal,)filter bed.
 Carry Over:-
The phenomenon of carrying of water along with impurities by steam is called
“carry over”.
 This is mainly due to priming and foaming .
 Priming and foaming usually occur together.

Dissolved salts or suspended solids in boiler water are

carried by the wet steam to super heater and turbine blades,
where they get deposited as water evaporates. This deposit
decreases the efficiency of boiler.
Dissolved salts may enter the parts of other machinery,
thereby decreasing their life;
The maintenance of the boiler pressure becomes difficult
because of improper judgment of actual height of water colum.
 Boiler Corrosion:-
Boiler corrosion is “decay” or “disintegration” of
boiler body material either due to chemical or
electrochemical reaction with its environment.
The disadvantages of corrosion are:-

(i) Shortening of boiler life,

(ii) Leakages of the joints and rivets;
(iii) Increased cost of repairs and maintenance
 Corrosion in boilers is due to the following reasons:-

Dissolved oxygen:-
This is the most usual corrosion causing factor.
 Inboiler oxygen is introduce through the raw water supply. Water
usually contains about 8 PPM of dissolved oxygen at room temp.

 As the water is heated, the dissolved oxygen is set free .

 Dissolved oxygen reacts with the iron of boiler in presence of
water and under prevailing high temperature to form ferric oxide
(rust).

 4Fe + 2H2O+ O2 4Fe(OH)2

 4Fe(OH)2 + O2 2 [Fe2O3 . 2H2O]
Ferric Oxide (Rust)
 Mineral acids
 Magnesium Chloride, if present in boiler feed water, can undergo
hydrolysis producing HCl.

 MgCl2 + 2H2O Mg(OH)2 + 2HCl

 The liberated acid reacts with iron material of the boiler to form ferrous
hydroxide which in turn is converted to rust in the following way:
 Fe + 2HCl FeCl 2 + H2
 FeCl2 + 2H2O Fe(OH)2 + 2HCl
 2Fe(OH)2 + O2 Fe2O3 . H2O
 Removal of dissolved oxygen :

 By adding hydrazine or Sodium Sulfate or Sodium Sulfide.

Thus:
N2H4 +O 2 N + 2H2O
2

 Hydrazine is an ideal chemical for the removal of dissolved

oxygen. It reacts with oxygen, forming nitrogen and water.
Nitrogen is harmless.
(a) Pure hydrazine is not used in water treatment because it is
an explosive inflammable liquid so 40% aqueous solution of
hydrazine is used.
(b) Excess hydrazine must not be used because excess of it
decomposes to give NH3, which causes corrosion of some
alloys like brass etc.
3 N2H4 4 NH3 + N2
Carbon dioxide:-
There are two sources of CO2 in boiler water, viz. dissolved CO2 in raw
water and CO2 formed by decomposition of bicarbonates in H2O
according to the equation:
Mg(HCO3)2 MgCO3 + H2O + CO2
Carbon dioxide in presence of water forms carbonic acid which has a
corrosive effect on the boiler
H2O + CO2 H2CO3
(Carbonic acid)
CO2 can be removed by:
(i) Mechanical de-aeration along with O2.
(ii) Filtering water through lime-stone
CaCO3 + H2O + CO2 Ca(HCO3)2
Lime stone

But this method increases hardness

(iii) Addition of appropriate quantity of ammonium hydroxide
De-aeration Mechanism
 Caustic Embrittlement:-
 Caustic embrittlement is the phenomenon during which the boiler
material becomes brittle due to the accumulation of caustic
substances.
 This type of boiler corrosion is caused by the use of highly alkaline
water in the high pressure boiler.
 During softening by lime-soda process, it is likely that some
residual Na2CO3 is still present in the softened water.
 In high pressure boilers Na2CO3 decomposes to give
sodium hydroxide and CO2, and Sodium hydroxide
thus produced makes the boiler water “caustic”.
 Na2CO3 + H2O 2NaOH + CO2
 This caustic water flows into the minute hair-cracks,
present in the inner side of boiler, by capillary action.
 On evaporation of water the dissolved caustic soda
concentration increases progressively which attacks
the surrounding area, thereby dissolving iron of
boiler as Sodium ferrote (Na2FeO2).

3 Na2FeO2 + 4 H2O 6 NaOH + Fe3O4 + H2

Caustic Embrittlement can be prevented:-

 By using sodium phosphate as softening reagent, instead of

sodium carbonate in external treatment of boiler water.
 By adding tannin or lignin(decomposed part of plants or
nature organic matter) to boiler water which blocks the
hair-cracks in the boiler walls thereby preventing
infiltration of caustic soda solution into these areas, by
adding sodium sulphate to boiler water.
 Na2SO4 also blocks hair-cracks, thereby preventing
infiltration of caustic soda solution in these areas.
 Tannin and lignin blocks the heir line cracks and thus
prevent penetration of NaOH in these areas .
 ZEOLITE PROCESS:-
 Zeolite is micro-porous mineral which is used as catalyst in
many industrial purposes such as water purification and air
purification.
 Zeolites are two types natural and synthetic.
 The natural zeolite that is used for water softening is
glauconite or greensand / a greenish clay
 Permutit is the synthetic zeolite that is most used in water
softening and its chemical formula is Na2O. Al2O3. nSiO2.
xH2O.
 Permutit are more porous, glassy , and have higher softening
capacity than greensand.
Zeolite process for water softening:-
Zeolite process for water softening has become a
commercial success for the reason that zeolite can
be easily regenerated.
When Ca2+ and Mg2+ ions containing hard water is
passes through a bed of sodium zeolite, the sodium
ions are replace by the calcium and magnesium
ions.
 Na2Ze + Ca(HCO3)2 → 2NaHCO3 + CaZe
 Na2Ze + Mg(HCO3)2 → 2NaHCO3 + MgZe
Na2Ze + CaSO4 Na2SO4 + CaZe
 When all sodium ions are replaced by calcium and
magnesium ions, the zeolite becomes inactive. Then the
zeolite needs to be regenerated. Brine solutions are passing
through the bed of inactivated zeolite.
 The following reactions are taken place and form Na2Ze
 CaZe + 2NaCl → Na2Ze + CaCl2
 MgZe + 2NaCl → Na2Ze + MgCl2

ZEOLITE SOFTNER:-
 Merits of Zeolite Process:
 It removes the hardness almost completely .
 The process automatically adjust itself for variation in
hardness of incoming water.
 This process does not involve any type of precipitation, thus,
no problem of sludge formation occurs.
 Demerits of Zeolite Process:
 The outgoing water (treated water) contains more sodium
salts.
 This method only replaces Ca+2 and Mg+2 ions by Na+ ions.
 High turbidity water cannot be softened efficiently by Zeolite
process.
 LIME SODA PROCESS:-
 PRINCIPLE:- The basic principle of this process is to
chemically convert all the soluble hardness causing
impurities into insoluble precipitates, which may be
removed by settling and filtration . for this purpose, a
suspension of milk of lime Ca(OH)2,with soda Na2CO3 is
added in fix amount .proper mixing of water and chemical
carried out. Calcium carbonate Ca(OH)2, Mg(OH)2,
Fe(OH)3, Al(OH)3 precipitated and filtered out .
Temporary water hardness :
 Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
 Mg(HCO3)2 + Ca(OH)2 2CaCO3 + MgCO3 + 2H2O
 MgCO3 + Ca(OH)2 Mg(OH)2 + CaCO3
PERMANENT WATER HARDNESS:-
CaSO4 + Na2CO3→ CaCO3 + Na2SO4
MgSO4 + Na2CO3→ MgCO3 + Na2SO4
MgSO4 + Na2CO3→ MgCO3 + Na2SO4

USE OF COAGULANTS:-
(NaAlO2 or Al2(SO4)3 or K2SO4. Al2(SO4)3.24H2O)
At room temperature ,the ppt formed are very fine ,they do
not settle down easily and cause difficulty in filtration. but if
small amount of coagulants is added like alum , aluminum
sulphate, they hydrolyze to ppt of aluminum hydroxide
which entraps the fine ppt of CaCO3,Mg(OH)2.
 Cold Lime soda process:-
When the chemicals lime or soda are added to hard
water at room temperature, the process is known as
cold lime soda process.
At room temperature, the precipitates are finely
divided and do not settle easily, nor can they be
easily filtered.
They help in the formation of coarse precipitates.
NaAlO2 + 2H2O NaOH + Al(OH)3
Cold lime soda process provides water containing a
residual hardness of 50-60 PPM
Cold lime soda softner:-
HOT L-S METHOD
In this process, water is treated with
chemicals at a tempertature of 94 0C – 100
0
C.
It is a rapid process.
Coagulants are not needed.
Softened water has residual hardness of
15ppm to 30 ppm.
Hot lime soda softner:-
Advantages
1. Itis very economical process.
2. Less amount of coagulants are required.
3. Certain quantity of minerals is reduced from water.
4. The level of carbon dioxide can also be reduced using
hot L-S Process. Fe and Mn are also removed from the
water.
5.The process increases the PH value of the treated water
thereby corrosion of the distribution pipes is reduced.
Disdvantages
6. Sludge disposal is problem.
7. This can remove hardness only up to 15 ppm, which is
not good for boilers.
8. Careful operations and skilled supervision are required
for economical and efficient softening.
Ion exchange process Or Demineralization process Or Deionization
process:-
 Ion exchanger resin are insoluble , cross linked, long chain higher
molecular weight organic polymers which are permeable due to their
micro porous structure, and the functional groups attached to the chains
are involved in the ion-exchanging properties.
 Types of ion exchanger resins

(i)Cation exchanger resins (RH+ ) :

These are usually styrene divinyl
benzene copolymers which on carboxylation or sulphonation
become capable of exchanging their H+ ions with the cations of the
solution. These have acidic functional groups like SO3H+, -COOH or
OH(phenolic)
(ii)Anion exchanger resins (ROH-) :
These are usually styrene divinyl
benzene or amine formaldehyde copolymers which on treatment with
dilute NaOH solution become capable to exchange their OH- anions
with anions in water. Which contains basic functional groups like
quaternary ammonium or quaternary sulphonium or quaternary
phosphonium groups
 Ion exchange process
Itis a two stage process, the water first passes
through the column containing hydrogen exchanger
(Cation exchanger) and then through second column
containing hydroxyl exchanger(Anion exchanger).
H+ and OH- ions released from cation exchanger and
anion exchanger columns get combined to produce
water molecule.
 Cation
exchange resins :
2RH+ + Ca2+ R2Ca2+ + 2H+
2RH+ + Mg2+ R2Mg2+ + 2H+
(RH+ = Cation exchange resin)
Ion exchange process Diagram
 Anion exchange resins :

 R’OH + Cl- RCl + OH-

 2R’ OH- + SO42- R2SO42- + 2OH-
 2R’ OH- + CO32- R2CO32- + 2OH-
(R’OH- = Anion exchange resin)
 H+ + OH- ions , combine and produce water
 H+ + OH- H2O
 Regeneration of exhausted resins:-
 After some time the cation and anion exchanging resins lose
the capacity to remove H+ ions and OH- ions respectively,
they are then said to be exhausted.
 When the resins are exhausted, the supply of water is stopped.
 The exhausted cation exchanger is regenerated by passing
dilute HCl or H2SO4 Solution and exhausted anion exchanger
resin is regenerated by passing dilute NaOH solution.
 Regeneration Chemical reaction


R2Ca2+ + 2H +
2RH+ + Ca 2+
(washing)
 R2SO2-4 + 2OH- 2ROH- + SO2-4
 Advantages:
 Highly acidic or alkaline water also can be softened by this
process.
 It produces water of low hardness (up to 2 ppm).
 If the output water is passed through de-gassifier, then the
gaseous impurities like O2 , CO2 also get expelled, to get
water of distilled water standard.
 Disadvantages:
 Costly equipment and costly chemicals are needed for
regeneration.
 Turbid water can not be used as it decreases the efficiency of
resins.
 It can be operated only small scale purification of water.
Internal Methods for Water Softening