LNCT GROUP OF COLLEGES

Name of Faculty:Dr. Anjali Tiwari

Designation: Professor
Department: Engineering Chemistry
Subject: Engineering Chemistry
Unit:II
Topic: Boiler Problems and Softening
Methods
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Water is mainly used in boilers for the generation of steam for industries and power
houses. A boiler is an apparatus in which water under pressure is converted into steam by the
application of heat and this steam is utilized for various purposes like electricity generation.
For boiler feed water all the impurities are not necessarily eliminated, and only those
impurities which lead to operational troubles in boilers are eliminated or kept within the
tolerable limits.
Boiler-feed water should correspond with the following composition:
• Its hardness should be below 0.2 ppm.
• Its caustic alkalinity (due to OH-) should be between 0.15 and 0.45 ppm.
• Its soda alkalinity (due to Na2CO3) should be 0.45 – 1 ppm.
Excess of impurities, if present, in boiler feed water generally cause some boiler-problems
like Scale and sludge formation, corrosion, priming and foaming, caustic embrittlement.

I. Sludge and Scale Formation in Boilers:

In a boiler, water is continuously evaporated to form steam. This increases the concentration
of dissolved salts. Finally a stage is reached when the ionic product of these salts exceeds
their solubility product and hence they are thrown out as precipitates.
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 wall of boiler, it is called as scale.
Suldge formation: Sludge is a soft, loose and slimy precipitate formed within the boiler.
Sludges 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
scrapped off with a wire brush. If sludges are formed along with scales, then former gets
entrapped in the latter and both get deposited as scales.
Disadvantages of sludge formation:-
• Sludges are poor conductors of heat, so they tend to waste a portion of heat generated
and thus decrease the efficiency of boiler.
• 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:-
• By using softened water
• By frequent ‘blow-down operation’ i.e. partial removal of concentrated water through
a tap at the bottom of boiler, when extent of hardness in the boiler becomes
alarmingly high and ‘Make-up’ water is addition of fresh softened water to boiler after
blow down operation.
Scale Formation: 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. Scales are mainly formed by;
(i) Decomposition of Temporary Hardness like magnesium bicarbonate, calcium
bicarbonate:-
Mg(HCO3)2 → Mg(OH)2+2CO2
Ca(HCO3)2 CaCO3 + 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 due to the formation of Ca(OH)2
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CaCO3 + H2O Ca(OH)2 + CO2
(ii) Deposition of calcium sulphate:- The solubility of CaSO4 in water decreases with
increase in temperature. CaSO4 is soluble in cold water, but almost completely insoluble in
super-heated water. It may be due to increase ionization at high temperature so ksp < kionic
product and less availability of water molecules for solvation 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 sulphate scale is quite
adherent and difficult to remove, even with the help of hammer and chisel.
(iii) Hydrolysis of magnesium salts:- Dissolved magnesium salts get hydrolyzed at prevailing
high temperature inside the boiler, forming magnesium hydroxide precipitate, which forms a
soft type of scale, e.g.
MgCl2 + 2H2O Mg(OH)2 + 2HCl
(iv) 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.
Disadvantages of Scale formation;
1. Wastage of fuel. Scales have a poor thermal conductivity so the rate of heat transfer
from boiler to inside water is greatly reduced. In order to provide a steady supply of
heat to water, excessive or over- heating is done and these causes increase in fuel
consumption.
The wastage of fuel being dependent on the thickness and the nature of scale:
Thickness of scale
0.325 0.625 1.25 2.5 12
(mm)
Wastage of fuel 10% 15% 50% 80% 150%
2. 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.
3. 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.
4. 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.
Prevention of scale formation:
Scales are removed by mechanical or by chemical methods like if the scales are loosely
adhering, it can be removed with the help of scraper or piece of wood or wire brush followed
by frequent blow-down operation.,
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 adherent and hard, they can be removed by dissolving them by adding
chemicals e.g., CaCO3 scales can be dissolved by using 5-10% HCl. Calcium sulphate scales
can be removed by adding EDTA, since the Ca – EDTA complex is highly soluble in water.

II. Priming, Foaming and Carry over process:

The process of carrying water by steam along with impurities is called
“carry over”. This is mainly due to priming and foaming. These processes are objectionable
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and usually occur together.
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. Due to priming, 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. It is caused by the presence of considerable
quantities of dissolved and suspended impurities in water, High steam velocities, sudden
boiling, Faulty design of boiler, etc.
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, filtration, by
blowing off sludge or scales from time to time.
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 these impurities greatly lower the surface tension of
water, and thus increase the foaming tendency of the liquid. Due to foaming the maintenance
of the boiler becomes difficult because of improper judgment of actual height of water
column.
Foaming can be avoided by: (i) the addition of anti-foaming agents like castor oil which
spreads on the surface of water and therefore neutralizes the surface tension reduction (ii) the
removal of foaming agent like oil from boiler water by using coagulants which entrap oil
drops.

III. Boiler Corrosion:

Boiler corrosion is “decay” or “disintegration” of boiler material either by chemical or
by electrochemical reactions with its environment.
The disadvantages of corrosion are: Shortening of boiler life, Leakages of the joints and
rivets,
Increased cost of repairs and maintenance, etc.
Corrosion in boilers is due to the following reasons:
a. Dissolved oxygen: This is the most usual corrosion causing factor. In Boilers, oxygen
is introduced 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 and the boiler starts corroding. Dissolved oxygen reacts with the iron of boiler in
presence of water and under prevailing high temperature to form ferric oxide (rust).
Fe + H2O + 1/2O2 Fe(OH)2
Ferrous hydroxide
4Fe(OH)2 + O2 2 [Fe2O3.2H2O]
Rust
Removal of dissolved oxygen:
1. By adding hydrazine or sodium sulphite or sodium sulphide. Thus:
N2H4 + O2 N2 + 2H2O
Na2SO3 + 1/2O2 Na2SO4
Na2S + 2O2 Na2SO4
Hydrazine is an ideal chemical for the removal of dissolved oxygen. It reacts with oxygen,
forming nitrogen and water. Nitrogen is harmless. Consequently hydrazine removes oxygen
without increasing the conc. of dissolved solids/salts.
Pure hydrazine is not used in water treatment because it is an explosive inflammable liquid so
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40% aqueous solution of hydrazine is used which is quite safe.
Excess hydrazine must not be used because excess of it decomposes to give NH3, which
causes corrosion of some alloys like brass etc. used in condenser tubes.
3 N2H4 4 NH3 + N2
On the other hand, if sodium sulphite or sodium sulphide is used, the sodium sulphate is
formed. Under high pressure it decomposes giving SO2. The SO2 enters the steam pipes and
appears as corrosive sulphurous acid (H2SO3) in steam condensate. So as a rule a very low
concentration of 5-10 ppm of Na2SO3 in the boiler is maintained, rather adding it
intermittently.
2. By mechanical de-aeration. This process consists of spraying water over preheated
perforated plates stacked in a degasifier. Removal of dissolved O2 is ensured by
applying high temperature and vacuum.

b. 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 Mg(OH)2 + 2CO2
Carbon dioxide in presence of water forms carbonic acid which has a corrosive effect on the
boiler material like any other acid.
H2O + CO2 H2CO3
Carbonic acid
CO2 can be removed by mechanical de-aeration along with O2 or Addition of appropriate
quantity of ammonium hydroxide
CO2 + 2NH4OH (NH4)2 CO3 + H2O
c. 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 FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl
2Fe(OH)2 + O2 Fe2O3 . H2O
Thus, a small amount of HCl may cause extensive corrosion since HCl is produced in a
chain-like manner. Consequently presence of even a small amount of MgCl2 causes
corrosion of iron to a large extent.
As the boiler water is generally alkaline and hence the acid is usually neutralized. In case the
amount of acid is more, calculated quantity of alkali is added from outside to neutralize the
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acid for preventing this corrosion.
IV. 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
ferroate (Na2FeO2).
From its place of formation, sodium ferroate decomposes a short distance away as per the
following equation.
3 Na2FeO2 + 4 H2O 6 NaOH + Fe3O4 + H2
Further dissolution of iron takes place because of the precipitation of Fe3O4, and the
regeneration of NaOH. This causes embrittlement of boiler walls more particularly at stressed
parts like bends, joints, rivets, etc., causing even failure of the boiler.
Mechanically embrittlement arises due to the setting up of a concentration cell with the iron
surrounded by dil. NaOH acting as the Cathode, while the iron surrounded by conc. NaOH
acting as the anode. The iron in the anodic part gets dissolved or corroded.
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 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. It has been observed that caustic
cracking can be prevented if Na2SO4 is added to boiler water so that the ratio of [Na2SO4
conc.] and [NaOH conc.] is kept as 1:1, 2:1 and 3:1 in boilers working respectively at
pressures up to 10, 20 and above 20 atmospheres.

Softening Methods

I. Zeolite/Permutit process:
Zeolite is micro-porous inorganic mineral. For odour removal and the softening of hard water
generally sodium zeolites are used. It is capable of exchanging its sodium ions with hardness
causing cations reversibly. It is hydrated sodium alumino silicates and its chemical formula is
Na2O. Al2O3.xSiO2.yH2O here x may be 2-10 and y may be 2-6. Zeolites are of two types
natural and synthetic. The natural zeolites are generally non or less porous while synthetic
zeolites are more porous, glassy, gelatinous and have higher softening capacity than natural
zeolites. Zeolites are characteristically soft to moderately hard, light in density, insoluble in
water but can act as base exchangers in contact with water containing cations. Hence these
can remove Ca2+ and Mg2+ ions from water when hard water is passed through it.
Zeolite process for water softening: When Ca2+ and Mg2+ ions containing hard water is
passed through a bed of sodium zeolite, the sodium ions are replaced by the calcium and
magnesium ions.
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Na2Ze + Ca(HCO3)2 → 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 → 2NaHCO3 + MgZe
Na2Ze + CaSO4 → Na2SO4 + CaZe
Na2Ze + MgSO4 → Na2SO4 + MgZe
Na2Ze + CaCl2 → 2NaCl + CaZe
Na2Ze + MgCl2 → 2NaCl + MgZe
Na2Ze + Fe(HCO3)2 → 2NaHCO3 + FeZe
Na2Ze + Mn(HCO3)2 → 2NaHCO3 + MnZe
When all sodium ions are replaced by calcium and magnesium ions, the zeolite becomes
inactive. Then the zeolite needs to be regenerated. zeolite can be easily regenerated by
passing brine solution (10% NaCl) through the bed of inactivated zeolite. The following
reactions are taken place and form Na2Ze.
CaZe + 2NaCl → Na2Ze + CaCl2
MgZe + 2NaCl → Na2Ze + MgCl2

Merits of Zeolite Process:

Used equipment is compact.
It removes the hardness upto 10 ppm.
The process automatically adjusts 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.

II. Ion exchange process Or Demineralization process Or Deionization

process:
Ion exchange resins are insoluble, micro porous, cross linked, long chain, higher molecular
weight, functional group containing organic copolymers. The functional groups attached to
the chains are involved in the ion-exchanging properties.
Types of ion exchanger;
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Cation exchange 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 hard water. These have acidic functional groups like -SO3H, -COOH

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 complex anions in water. These resins contain basic
functional groups like amino, quaternary ammonium or tertiary sulphonium or quaternary
phosphonium groups.

Ion exchange process

It is 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 : (RH+ = Cation exchange resin)
2RH+ + Ca2+ R2Ca2+ + 2H+

2RH+ + Mg2+ R2Mg2+ + 2H+

Anion exchange resins : (R’OH- = Anion exchange resin)

R’OH + Cl- R’Cl- + OH-

2R’ OH- + SO42- 4

R’2SO 2-
4 + 2OH
-

2R’ OH- + CO32- R’2CO3 2- + 2OH-

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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 complex cations and anions 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 exchange resin is regenerated by passing dilute NaOH solution.
Regeneration Chemical reaction
R2Ca2+ + 2H+ 2RH+ + Ca2+ (washing)
R’2 SO42- + 2OH- 2R’OH- + SO42-

The columns are washed with deionised water and washing (which contain Ca2+, Mg2+ ,
SO42-, Cl- ions) are passed to sink or drain. The regenerated resins are again used.
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, exchangers 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.

III. Soda lime process: It is the most common and economic water softening
method. It is very useful for the treatment of large volumes of hard water.
Addition of lime ie. Ca(OH)2 and soda ie.Na2CO3 to the hard water precipitates
calcium as the carbonate, and magnesium as its hydroxide. The amounts of the
two chemicals required are easily calculated from the analysis of the water and
stoichiometry of the reactions. The lime‐soda method uses lime, Ca (OH)2 and
soda ash, Na2CO3 to precipitate hardness from solution.
In case of Temporary hardness the following reactions are take places:
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 → Ca(HCO3)2 + Mg(OH)2
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In case of permanent hardness the following reactions are take places:
CaSO4 + Na2CO3→ CaCO3 + Na2SO4
CaCl2 + Na2CO3→ CaCO3 + 2NaCl
MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2 → Mg(OH)2 + CaSO4
In case of other impurities the following reactions are take places:
CO2 + Ca(OH)2 → CaCO3 + H2O
2HCl + Ca(OH)2 → CaCl2 + 2H2O
H2SO4 + Ca(OH)2 → CaSO4 + 2H2O
H2S + Ca(OH)2 → CaS + 2H2O
2Na(HCO3)2 + Ca(OH)2 → CaCO3 + Na2CO3 + 2H2O
Ca(NO3)2 + Na2CO3→ CaCO3 + 2NaNO3
Mg(NO3)2 + Ca(OH)2 → Mg(OH)2 + Ca(NO3)2
In case of coagulants the following reactions are take places:
FeSO4 + Ca(OH)2 → Fe(OH)2 + CaSO4
Al2(SO4)3 + 3Ca(OH)2 → 2Al(OH)3 + 3CaSO4
There are two types of lime-soda processes; cold lime soda process and hot lime soda
process.
Cold Lime soda process: When the chemicals (L Or S) 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 so small quantity of coagulant is also
added to water which 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.
Hot Lime soda process: When the chemicals are added to higher temperature (80o C to 150o
C) the process is known as Hot lime soda process. Hot L-S Method is proffered over the Cold
L-S Method because in hot lime soda method at higher temperature the reactions are fast,
precipitation is more complete, settling rate and filtration rates are increased. As a result the
precipitate and sludge formed settle rapidly and coagulants are not required and also
chemicals needed are in smaller quantities than that of cold L-S process. Dissolved gases are
eliminated from water to a certain extent. The softened water recovered from hot L-S process
has hardness of about 15 to 30 ppm.

Diagram of Cold L-S Method;

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Diagram of Hot L-S Method;

Advantages: It is very economical process.

Less amount of coagulants are required.
Certain quantity of minerals is reduced from water.
The level of carbon dioxide can also be reduced using hot L-S Process.
Fe and Mn are also removed from the water.
The process increases the PH value of the treated water thereby corrosion of the distribution
pipes is reduced.

Disdvantages: Sludge disposal is problem.

This can remove hardness only up to 15 ppm, which is not good for boilers.
Careful operations and skilled supervision are required for economical and efficient
softening.

List of References;
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Sr. Title of the Book Author/Publisher/Edition
No.

1 Engineering Chemistry [email protected]

2 Engineering Chemistry Dara S.S & Singh A.K, S Chand & Co..
3 Engineering Chemistry Jain & Jain, Dhanpat Rai & Co.
4 Engineering Chemistry Chawla S. ,Dhanpat Rai & Co.

Questions based on Unit II:

1. A water sample has the following composition data: Ca(HCO3)2=40.5 ppm,
Mg(HCO3)2=146 ppm, CaCl2=111 ppm, MgCl2=95 ppm, CaSO4=68 ppm, MgSO4=60
ppm. Calculate the quantity of lime (84%) and soda (90%) required for softening
100000 liters of water.

2. A water sample has the following composition data: Ca(HCO3)2=81 ppm,

Mg(HCO3)2=146 ppm, CaCl2=110 ppm, MgCl2=90 ppm, CaSO4=68 ppm, MgSO4=60
ppm, FeSO4.7H2O=139 ppm, CO2=44 ppm. Calculate the quantity of lime and soda
required for softening one million liter of water.

3. Calculate the amount of lime(88.3% pure) and soda(99.2 % pure) required to soften one
million liters of water containing the following impurities:-
CaCO3= 185 mg/L, CaSO4= 0.34 mg/L, MgCO3= 0.42 mg/L, MgCl2= 0.76 mg/L,
MgSO4= 0.90mg/L, NaCl= 2.34 mg/L, SiO2=2.34

4. A zeolite softener was completely exhausted and was regenerated by passing 100 L of
brine solution containing 200g/L of NaCl. How many litres of water of hardness 500
ppm can be softened by this softener?

5. Hardness of 20,000 L of water sample was completely removed by Zeolite softener.

The zeolite softener required 60 L of brine solution containing 1500 g/L of NaCl for
regeneration. Calculate hardness of water sample.

6. What are boiler troubles? Explain causes, effects and preventive methods of scale and
sludge formation.

7. Discuss Lime Soda process of softening hard water with the help of neat labeled
diagram and chemical reactions involved in it?

8. What are ion-exchangers. Discuss softening of hard water by ion exchange method with
the help of neat labeled diagram. Also write advantages and disadvantages of the
process.
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9. Discuss Zeolite method of softening hard water with diagram and chemical reactions
involved in it? Also write advantages and disadvantages of the process.

10. Discuss boiler corrosion and carry over processes of boiler with causes, effects and
preventive methods.