UNIT I - Water Treatment

Introduction :
Water is the most abundant and most useful compound. It plays an
important part in a wide variety of natural processes and is essential for the growth of all
animals and plants. Water is the basic material needed by almost all industries. Water is
used as a coolant in power and chemical plants. As engineering material water is mainly
used in the steam generation in boiler and hydro-electric power. A large quantity of water
is also required in the industries like paper, textile, sugar, chemical pharmaceutical and
ice manufacturing for their routine operations.

Hardness of water:
“Hardness of water is that property which prevents the lather
formation with soap.”
This is due to the presence of bicarbonates, chlorides, sulphates of calcium and
magnesium and heavy metals dissolve in water. A sample of hard water when treated
with soap (sodium or potassium salt of higher fatty acid like stearic/ palmitic / oleic )
does not produce lather but forms a “white scum” or “curdy precipitated”. This
precipitate is formed due to the formation of insoluble stearates calcium and magnesium.
The reactions of soap (sodium stearate) with the salts causing hardness to the water are
given as fallows:
2 C17H35COONa + Ca(HCO3)2 Ca(C17H35COO)2 + 2 NaHCO3
(Soluble sodium stearate) (Insoluble Ca-stearate)
Soap

2C17H35COONa + CaCl2 (C17H35COO)2 Ca + 2NaCl

Sodium stearate)(Hardness) Calcium stearate
(Sodium soap) (Insoluble)

2C17H35COONa+MgSO4 (C17H35COO)2 Mg +Na2SO4

Magnesium stearate
(Insoluble)
• It should be noted that presence of sodium compounds in water does not
contribute to hardness.
• Thus, water which does not produce lather with soap solution readily, but forms a
white-scum (or curd) is called ‘hard water’. On the other hand, water which
produces lather easily with soap solution is called ‘soft water’.
“Soap consuming capacity of water”.

Types Of Hardness :-
1. Temporary (or carbonate) hardness :-
Temporary hardness is caused by the presence of dissolved
bicarbonates of calcium, magnesium, and other heavy metals and the carbonate of iron.
Temporary hardness is generally removed by mere boiling of water.
By boiling the bi-carbonates are decomposed with the formation of insoluble carbonates
(or hydroxides) with the evolution of carbon dioxide. HCO3-

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 Ca (HCO3)2 CaCO3 + H2O + CO2
Calcium bicarbonate calcium carbonate
(Insoluble)

Mg(HCO3)2 MgCO3 + H2O + CO2

Magnesium bicarbonate magnesium carbonate
(Insoluble)
OR

Mg(HCO3)2 Mg(OH)2 + 2CO2

Magnesium hydroxide
The insoluble calcium and magnesium carbonate (or hydroxide) thus formed are
deposited in the form of crust or precipitate at the bottom of the vessel while carbon
dioxide escapes out.

2. Permanent (or non-carbonate hardness ):-

The permanent hardness is due to the presence of chlorides(Cl-) and
Sulphates(SO42-)of calcium and magnesium in water. Sometimes permanent hardness is
due to the presence of Cations like Fe++, Fe+++, Al+++ and anions like nitrates and
silicates. Unlike temporary hardness, the permanent hardness cannot be removed by mere
boiling of water, but it requires certain chemical treatment.

Softening of water :-
Water used for industrial purposes, such as for steam generation,
should be sufficiently pure. It should be free from Ca, Mg, and Fe salts, otherwise
troubles like scale ( “ scale are hard deposits, which stick up very firmly to the inner
surface of the boiler.” It is so hard & adherent that it is difficult to remove then, even with
the help of hammer and chisel. It is the main cause of boiler troubles) and sludge
(“sludge-forming a soft loose and slimy deposits within the boiler, which do not stick up
permanently. It can be removed by simply wire –brushing). Corrosion ( corrosion – the
gradual eating away, disintegration, decaying or deterioration of metal by a chemical or
electrochemical reaction with its environment or metals are exposed to atmospheric
condition they react with an or water in the environment to form undesirable compounds
usually oxides ) etc. occur in boilers,
Therefore, the industrial water should be free from hardness producing salts before it is
put to use.
“The process of removing hardness-producing salts from water, is known as
softening of hard water.”
In industry, mainly three methods are used for softening water –
1) Lime-soda process
2) Zeolite process
3)Demineralization(Ionexchange)process
.
1) Lime-soda process :-
In this process, the soluble Ca and Mg salts present in the
water are chemically converted into insoluble compounds.. These insoluble compounds

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are removed by filtration .The insoluble compounds formed by adding lime, Ca (OH)2
and soda, Na2CO3 are calcium carbonate (CaCO3) and magnesium hydroxide, Mg (OH)2.
In this method, the hard water is treated with calculated
quantities of slaked lime, Ca (OH)2 and soda- ash, Na2CO3 in reaction tanks provided
with stirrers. The chemicals and water are thoroughly mixed when water get softened.
Most of the heavy precipitates of [CaCO3 and Mg (OH)2] settle down as sludge at the
bottom of the tank and are removed from time to time. The softened water (containing
some of the precipitate) is then filtered. The following reactions take place.
(i) lime removes the temporary hardness:
Ca (HCO3)2 + Ca (OH)2 2CaCO3 + 2H2O
(Calcium bicarbonate) lime

Mg (HCO3)2 + 2Ca (OH)2 Mg(OH)2 + 2CaCO3 + 2H2O

(ii) lime removes the permanent magnesium hardness

MgCl2 + Ca (OH)2 Mg (OH)2 + CaCL2

MgSO4 + Ca (OH)2 Mg(OH)2 + CaSO4

(iii) lime removes dissolved iron and aluminium salts:

FeSO4 + Ca (OH)2 Fe(OH)2 + CaSO4

2 Fe (OH)2 + H2O + O 2 Fe(OH)3

Al2 (SO4)3 + 3 Ca (OH)2 2Al(OH)3 + 3CaSO4

(iv) lime removes free mineral acids:

2HCl + Ca (OH)2 CaCl2 + 2H2O

H2SO4 + Ca(OH)2 CaSO4 + 2H2O

(v) To convert bicarbonate ions into carbonates

2NaHCO3 + Ca (OH)2 CaCO3 + Na2CO3 + H2O

(vi) lime removes dissolved CO2 and H2S

Ca (OH)2 + CO2 CaCO3 + H2O

Ca (OH)2 + H2S Ca S + 2H2O

(vii) soda removes all the soluble calcium permanent hardness (i.e. that which is
originally present as well as that which is introduced during the removal of
Mg2+, Fe2+,Al3+,HCl, H2SO4 etc by lime).

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 CaCl2 + Na2CO3 CaCO3 +2NaCl

CaSO4 + Na2CO3 CaCO3 + Na2SO4

Since natural water generally contain a large proportion of temporary hardness, it is often
convenient and economical to remove temporary hardness by lime treatment. Lime is
rather cheap and it removes temporary hardness efficiently without introducing any
soluble salts in the water. Magnesium hydroxide produced in the above reactions
precipitates as an insoluble sludge. The reaction of soda with the permanent calcium
hardness produces insoluble CaCO3, addition of a coagulant such as sodium aluminates
or alum helps in accelerating the coagulation of the carbonate sludge, which is
subsequent removed by filtration, water softened by this process contain appreciable
concentrations of soluble salts, such as sodium sulphate and cannot be used in high-
pressure boiler installation.
Notes:-
1. When the impurities are given as CaCO3 and MgCO3, these should
be considered due to bicarbonates of calcium and magnesium.
2. If only ward temporary hardness is given, it means Ca(HCO3)2
3. The substances like NaCl, KCl, Na2SO4, SiO2, Fe2O3 etc do not
impart any hardness and therefore do not consume any lime soda.
4. Co-agulant like FeSO4, 7H2O or Al2 (SO4)3 when used, should be
treated as dissolved salts of iron and aluminium.
Function of soda :-
The added soda- ash (Na2CO3) react with calcium permanent hardness [including
calcium hardness introduced during the reaction of lime with HCl,H2SO4,MgCl2 or
MgSO4,Al(SO4)3,FeSO4 etc]

CaCl2 2NaCl
+ 2Na2CO3 2CaCO3 +
CaSO4 Na2SO4

It may also be noted that bicarbonate ions (NaHCO3/ KHCO3 ), if present produce
carbonate ions (as Na2CO3/K2CO3)( during their reaction with lime and this may be
imagined to be equivalent to production of Na2CO3. Hence the amount of carbonate
ions thus produce from bicarbonate ions are to be subtracted from the total
requirement of soda for softening.
106 parts of soda (Na2CO3) = 100 parts of CaCO3

Soda requirement for softening = 106/100 [ perm. Ca++ + perm. Mg++ + Perm(Mg++
+ Fe+ + + Al+++) + HCl + H2SO4 - HCO3- all in terms of CaCO3- equivalents]
The weights of different substances are converted into equivalents of CaCO3
100 parts of CaCO3 = 74 parts of Ca(OH)2
Lime requirement for softening =74/100 [ temp.Ca++ +2x temp.Mg++ + perm.(Mg+ + +
Fe++ + Al +++) + CO2 + HCl + H2SO4 + HCO3- all in terms of CaCO3 equivalents ]

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 The lime soda process may carried out in either cold or hot.

1) Cold lime-soda process :

There are four basic types of cold lime soda soften:

1) The intermitted type (batch process)
2) The conventional type (continuous process )
3) The catalyst or spiractor type
4) The sludge blanket type.

Cold lime – soda process :

In this method, calculated quantity of lime and soda are mixed
with water at room temp. The precipitates formed are finely divided, so they do not settle
down easily and requires about 24 hours for setting. They can not even filter easily.
Hence, it is essential to add small amounts of coagulants (like alum, NaAlO2, Al2 (SO4)3
etc.)
These co-agulants hydrolyse to flocculent, gelatinous precipitate of
Al(OH)3, which entraps the fine precipitates formed by the reactions of lime and soda.

NaAlO2 + 2H2O NaOH + Al(OH)3

Sod-aluminate coagulant flocculant gelatinous precipitate.

Al2 (SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4+ 6CO2

Cold lime-soda process provides water of 50-60 ppm residual hardness.

1] Intermittent or Batch process :-

It is carried out in a large steel tank provided with stirrers for proper
mixing. A calculated quantity of lime and soda are added to water in the tank. The
mixture is thoroughly mixed by mechanics stirrer.

Then, a small amount of coagulant like alum is added in order to coagulate and settle

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down the precipitate formed. The contents of the tank are kept undisturbed for about 2
hours, so as to settle down the precipitate completely. The softened water so obtained is
then pumped out & filtered through a sand filter. The sludge formed at the bottom of tank
is removed and tank is washed with water, so that it can be used again for treating another
batch.

2] Continuous or Conventional type:

This is a continuous process and therefore time is not washed during the
operations. In this process, raw water and calculated quantities of chemicals (lime + soda
+ coagulant) are fed from the top into the inner vertical circular chamber, filled with a
vertical circular chamber, filled with a vertical rotating shaft carrying a number of
paddles. As the raw water and chemicals flow down, there is a vigorous stirring and
continuous mixing, whereby softening of water takes place.
As the softened water comes into the outer coaxial chamber, it rises
upwards. The heavy sludge (or precipitated flock ) settle down in the outer chamber by
the lime the softened water then passes through a filtering media ( usually made of wood
fiber ) to ensure complete removal of sludge. Filtered soft water finally flows out
continuously through the outlet at the top the sludge setting at the bottom of the enter
chamber is drown of periodically.

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 3) Catalyst or Spiractor type:- cold lime soda water softener.

It consist of a conical tank which is about two thirds filled with finely divided granular
catalyst. The tank used may be either open (for gravity operation ) or closed ( for
operation under pressure). In both the cases the raw water & the calculated quantities of
chemicals enter the tank tangentially near the bottom of the cane & spiral upwards
through the suspended catalyst bed. The catalyst employed is a finely granuled ( 0.3 to
0.6 mm diameter)insoluble mineral substance such as graded calcite or sand or green
sand. The retention time is about 8 to 12 minutes. The sludge formed during the softening
reactions. Deposited on the catalyst grain in an adherent form and hence the granules
grow in size. The softened water rises to the top from where it is drawn off.
The catalyst or spiractor type of continuous water softener is of interest as it gives
a granular sludge which drains & dries rapidly & can be landler easily.

4] Sludge blanket type :- Diagram

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Raw water and chemicals enter into a primary mixing and reaction compartment formed
by the conical part of an inverted funnel. Further agitation and mixing takes place as the
solution flows upward through the wide stem of funnel into the secondary reaction zone .
the liquid and the suspended particles are formed through the space between the skirting
of the inverted cylinder, forming the secondary reaction vessel and the slopping sides of
the primary reactor. Part of the mixture flows upward towards the out led and part is
recycled through the primary reaction zone. Heavy particles having a rate of
sedimentation grater than the linear upward flow of the water will sink and colleted into
bottom while the fine particles with sedimentations rate less than the upward flow of the
water will move upward. Particles having a settling velocity just equal to the rate of the
moving water will form a stationary layer which acts as floating filter. The fine particles
are entrapped and form aggregates with the suspended particles in the stationary layer.
The agglometrates being larger than the critical size are removed by sedimentation.

(i) Hot lime- soda process :-

It involves in treating water with softening chemicals at
the temperature of 80 to 150C . Since hot process is operated at a temperature close to the
boiling point of the solution, so:

(a) The reaction proceeds faster;

(b) The softening capacity of hot process is increased to many fold;
(c) The precipitate and sludge formed settle down rapidly and hence no coagulants
are needed;
(d) Much of the dissolved gases ( such as CO2 and air ) driven out of the water;
(e) Viscosity of softened water is lower, so filtration of water becomes much easier.
This in-turn increases the filtering capacity of filters, and
(f) Hot lime soda process produces water of comparatively lower residual harness of
15 to 30 ppm.

Hot lime-soda plant consists of 3 parts:

(i) ‘Reaction tank’ –for mixing thoroughly raw water, chemicals and steam.

(ii) ‘Conical sedimentation vessel’ for setting down sludge.

(iii) ‘Sand filter’ for complete removal of sludge from softened water.

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The continuous softener for hot process consists of high tank with two concentric
cylindrical chambers. The upper end of the inner circular vertical chamber (or reaction
tank) is funnel – shaped, while the lower end is open. It consist of there inlets for feeding
raw water, chemicals and passing steam) to increase the temp. of water). The outer
chamber is big with larger cross-section at the top than at the bottom, which facilitates the
rise of water from bottom. Raw water, lime and soda fall into the funnel and get mixed
steam is then passes through inlet. The treated water rises upwards in the outer tank from
the open bottom of chamber and in outer tank sludge settles down by the time the
softened water reaches up. There is continuous supply of soft water through the water
outlet. The sludge is withdrawn from the bottom of outer tank. The soften water is then
passed through sand filters to ensure complete removal of sludge.
Advantages of lime-soda process
1) It is very economical.
2) If this process is carried out with the combination of sedimentation and
coagulation, lesser amounts of coagulants will be required.
3) The pH value of treated water increases by this process thereby, corrosion of pipe
lines is reduced.
4) Due to the alkaline nature of treated water, amount of pathogenic bacteria’s in
water is considerably reduced.
5) Besides the removal of hardness, the quantities of minerals in the water are also
reduced.
6) Viscosity of softened water becomes low and hence its filtration becomes easier.
Disadvantages of lime-soda process
1) This process can remove hardness only up to 50 ppm. which is not good for
boilers.
2) Disposal of large amounts of sludge is a big problem.

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 3) For efficient and economical softening the careful operation and experts
supervision is required.

Cold-lime soda process Hot – lime soda process

1. Water with chemicals treated at room 1. Water with chemicals treated at a temp of
temperature 800 to 1500 C

2. As it is operated at room temp, 2. As it is operated at boiling temp,

the reaction taken place slowly the reaction proceeds faster
(nearly 1 hour) ( nearly 15 min)

3. The softening capacity is low 3. The softening capacity is high

4. The coagulant must be added to settle 4. No need of coagulant

down the sludge and precipitate
5. Much of the dissolved gases remain 5. Much of the dissolved gases (such as CO2
in the softened water H2S, air) are driven out
6. It provides water of 50-60 ppm hardness. 6. It provides water of 15-30 ppm hardness

2] Zeolite process :- or Permutit:-

This is the modern process used for removing both temporary and
permanent hardness of water. Permutit or Zeolite is a hydrated sodium aluminium
orthosilicate.

Na2 Al2Si2O8X H2O i.e. Na2 Ze (where Ze=Zeolite)

Ze
Or P or Na2 P (where P= permutit)

Zeolite or permutit hold sodium ions loosely and can easily exchange their Na+ ions with
the hardness producing ions Ca++, Mg++ etc in water.

Process: - Zeolite softener consists of a steel tank packed with a thick large of Zeolite.
Hard water is percolated through the zeolite, when the hardness causing ions (Ca++, Mg++
etc) are retained by exchanging its Na+ ions in the form of insoluble salts of calcium and
magnesium zeolites. The resulting soft water collected at the top of tank is removed from
the tap T, only the harmless sodium salts are left in the water. The reaction taking place
during the softening process is:

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For temporary hardness:

Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3

Mg (HCO3)2 + Na2Ze Mg Ze + 2NaHCO3

For permanent Hardness:-

CaCl2 + Na2Ze CaZe + 2NaCl

CaSO4 + Na2Ze CaZe + Na2SO4

MgCl2 + Na2Ze MgZe + 2NaCl

MgSO4 + Na2Ze MgZe + Na2SO4

Thus, the process removes both temporary and permanent hardness.

Regeneration:-
After a long time (about 12 hrs) when the zeolite is completely converted into calcium
and magnesium zeolites i.e. it get exhausted, it ceases to soften water. However the
Zeolite can be regenerated by passing 10% brine (NaCl) solution from above for few
minutes.

CaZe + 2NaCl Na2Ze + CaCl2

MgZe + 2NaCl Na2Ze + MgCl2

(Exhausted Zeolite) (regenerated Zeolite)

The washings ( containing CaCl2 & MgCl2) are led to drain and the regenerated Zeolite
bed ( Na2Ze), thus obtained is used again for softening more hard water.

Limitations of Zeolite process:-

1. If the supply of water is turbid, then the turbidity may clog the pores of Zeolite bed
and it restricts the flow of water.
2. If hard water contains mineral acids, then it may destroy the zeolites.
3. If hard water contains large quantities of coloured ions, such as Fe++ and Mn++, these
ions will produce FeZe and MnZe such zeolites cannot be regenerated easily.

Advantages of Zeolite process

1. It removes the hardness completely and water of 10 ppm. Hardness is produced.
2. The equipment used is compact, occupying a small space.
3. The process automatically adjusts itself for different hardness of incoming water.
4. No sludge formation during the process.

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5. It is a clean process.
6. It requires less time for softening.
7. It removes iron and manganese from water.
8. It requires less skill for maintenance as well as operation.

Disadvantages of Zeolite process:

1. The treated water contains more sodium salts than in lime-soda process.
2. The method only replaces the cation (like Ca2+ and Mg2+ ions) by Na+ ions,
but leaves all the anions (like CO32-and HCO3-) as such in the softened water.
3. When the softened water (containing NaHCO3 and Na2CO3 etc) is used in
boilers for steam generation, NaHCO3 decomposes producing CO2, which
causes corrosion, and Na2CO3 hydrolyses to NaOH, which causes caustic
embrittlement.
4. Water having high turbidity cannot be treated efficiently by this process, because
fine impurities may get deposited in the Zeolite bed, thereby creating problem
for its working.
Diagram

De-mineralization or De-ionization by synthetic ion-exchange resins :-

In boiler a pure water (ie. Free from all types of impurities) is required. Water of
such quality can be obtained by de-mineralization process, since it removes almost all the
ions (cation and anions) present in water.
“Ion exchange resins are insoluble, cross-linked, long chain organic
polymers with micro porous structure and the ‘functional groups’ attached to the chains
are responsible for the ion-exchanging properties”
There are two types of resins-

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(i) Cation exchange resins (RH2):
Resins containing acidic functional groups (-COOH, -SO3H) etc. are capable for
exchanging their H+ ions with other cations, which comes in their contact, these are
reprensented as RH2. so their exchange reaction with cation (eg. Ca++, Mg++ ) can be
shown as:
RH2 + Ca++ RCa + 2H+

(ii) Anion exchange resins [ R’(OH)2]:-

Resins containing basic functional groups (-NH2, = NH) etc) are capable of exchanging
their anions with other anions, which comes in their contact.
These are represented as R’(OH)2 so their exchange reaction with anions
(eg SO4-- , CO3--, Cl-) can be shown as
R’(OH)2 + SO4--- R’SO4+ 2OH-

From above, it is clear that if hard water is passed first through cation exchanger bed and
then through anion exchanger bed, the resulting water will be free from both cations and
anions and the water is said to be ‘de-ionized or demineralize water.
Process :
It consist of two cylindrical towers the first tower contains ‘cation’ exchanger (RH2) and
the other one contains ‘anion exchanger’ [R’ (OH)2]
The impure (or hard) water is passed first through the tower contains cation
exchanger bed, which removes all the cations like Ca++, Mg++, Na+) from it and
equivalent amount of H+ ions are released.
RH2 + Ca++ RCa + 2H+

RH2 + Mg++ RMg + 2H+

RH2 + 2Na+ RNa2 + 2H+

Thus, the H= ions combine with the anions like chlorines, sulphates and bicarbonates
present in water are converted into the corresponding acids like HCl, H2SO4 and H2CO3.
In other words, water from cation exchanger is free from all cations but it is acidic in
nature.
This acidic water is then passed through another tower containing anion
exchanger bed, where acids are converted into water.
R’(OH)2 + 2HCl R’Cl2 + 2H2O

R’(OH)2 + H2SO4 R’SO4 + 2H2O

R’(OH)2 + H2CO3 R’CO3 + 2H2O

In this way, the water4 coming out from anion exchanger becomes free from both cation
and anions and is virtually a distilled water.
The water is finally freed from the dissolved gases (like CO2,O2,) by passing it through a
‘degasifier’ which is a tower whose sides are heated with steam jacket and is connected

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to a vacuum pump. High temp and how pressure reduces the quantity of dissolved CO2
and O2 in water. Such softened water can be used for industrial purposes.

Regeneration :

When the capacities of resins to exchanges ions are lost, these are said to be ‘exhausted’.
The exhausted cation exchanger is regenerated by passing dilute solution of acid
(dil H2SO4 , dil HCl) through the first tower. The reaction in regeneration can be
represented as:

R Ca + 2HCl RH2 + CaCl2

R Mg + 2HCl RH2 + MgCl2

The washing containing CaCl2, MgCl2 (CaSO4, MgSO4) etc. is also passed to drain.
Similarly, the exhausted anion exchanger is regenerated by passing dilute solution of
alkali (dil NaOH or KOH) through the second tower. The reaction in regeneration can be
represented as :
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl

R’SO4 + 2NaOH R’ (OH)2 +Na2SO4

The washing containing NaCl, Na2SO4, is also pasted to drain. The regenerated ion
exchange resins are used again to soften more amount of hard water.
Advantages:

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 1. The process can be used to soften highly acidic or alkaline waters.
2. It produces water of very low harness (about 2 ppm). Hence, it is very
good for treating water, for the use in high pressure boilers.
Disadvantages :
1. The equipment is costly and more expensive chemical are needed.
2. If water contains turbidity then the efficiency of the process is reduced . the
turbidity must be below 10 ppm, if it is more, it has to be removed first by
co-agulation and filtration.

COMPARISON BETWEEN LIME-SODA, ZEOLITE AND EXCHANGER

PROCESS:-
Lime-soda process
1. Cost of plant and material is low
2. Plant occupies large space
3. Treated water contains less Na+ ions.
4. Softened water has hardness up to 15-20 ppm.
5. Turbidity and suspended matter causes no problem.
6. It can not be a very clean process.
7. Pressure has no effect.
8. Disposal of sludge is a problem.
9. Process removes both cations & anions.
10. No question of regeneration, However, it can be made faster & continuous in hot
condition.
Zeolite
1. Cost of plant and material is higher.
2. Plant occupies less space
3. Treated water contains higher connections of Na+ ions.
4. Softened water has hardness up to 5-10 ppm.
5. Turbidity badly affects the efficiency of plant.
6. It is compact clean and fast process.
7. Can be operated under pressure.
8. No sludge formation.
9. Process removes only cations like Ca2+,Mg2+ etc.
10. Exhausted Zeolite can be regenerated by treating the bed with 10% NaCl (brine)
solution.
Ion exchange Process
1. Cost of plant and material is much higher.
2. Plant occupies less space.
3. Treated water contains no Na+ ions.
4. Softened water has hardness up to 2 ppm.
5. Turbidity badly affects the efficiency of process.
6. It is compact, most clean process.
7. Can be operated under pressure.
8. No sludge formation.
9. Process removes all the types of ions/ mineral salts.
10. Exhausted resins are regenerated by passing dil HCl and dil NaOH solutions.

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Boiler Troubles :
The problem of making up feed water for boilers. (steam produced in a boiler is
condensed after use and returned as pure feed water to the boiler. There are inevitable
losses however; the “make up” water must be supplied from time to time. The term
:boiler feed-water make –up” means the treated water which is required to make up the
water losses from the boiler caused by use of open team in process work or steam
otherwise lost plus the water lost in the boiler blow-down.) is common to almost all
industries and has been a subject of detailed study by several workers, in treatment of
boilers feed water, total elimination of all the impurities is generally not attempted. Only
those impurities which give rise to certain operational troubles are either eliminated or
maintained within tolerable limits.
The major boiler troubles caused by the use of unsuitable water are
1.carry over: priming & foaming.
2. Scale formation.
3.Corrosion and
4.Caustic embitterment.

Scale And Sludge Formation In Boilers :-

In boiler, water evaporates continuously and the concentration of
dissolved salts increases progressively. When their concentration reaches to saturation
point, they are thrown out of water in the form of precipitates on the inner walls of the
boiler. If the precipitated matter forms a hard, adherent coating on the inner walls of the
boiler is called “boiler scale”.
On the other hand, if the precipitated matter forms a loose and slimy
deposit inside the boiler, witch does not stick up permanently is known as ‘sludge’.

[A] Sludge formation in boilers :-

“Sludge is a soft, loose and slimy precipitate formed within the boiler.”

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 Sludges are generally formed at comparatively cooler parts of the boiler. They
collect in areas of the system, where the flow rate is slow or there are bonds in a line. In
such parts, they build up the deposits which choke the steam pipes and valves. Sludge are
also formed by the substances which have greater solubility in hit water than in cold
water.
Eg. CaCl2 , MgCl2, MgSO4, MgCO3 etc.

Disadvantage of sludge formation :

(i) Sludges are poor conductor of heat so they tend to west apportion of heat
generated.
(ii) If sludges are formed along with scale, then they get entrapped in the scale
and both get deposited as scale.
(iii) Excessive sludge formation disturbs the working of boiler it settles in the
region of poor water circulation such as bends in a line, plug opening thereby
causing even chocking of the pipes and valves.
Prevention of sludge formation-
(i) By feeding of well softened water in boiler.
(ii) By frequent ‘blow-down operation’ ie. Drawing off a portion concentrated
water containing dissolved salts and replacing it by fresh water.
[B] Scale Formation in boiler :-
“Scales are hard deposits, which stick up very firmly to the inner surface of the
boiler.”
Scales are so hard and adherent that it is difficult to remove them, even
with the help of hammer and chisel. Scales are the main cause of boiler troubles.
The formation of scales may be due to:

(1) Decomposition of calcium bicarbonate :-

Forms insoluble CaCO3 which get precipitated as scale.

Ca(HCO3)2 CaCO3 + H2O + CO2

(scale)

However, scale formed due to CaCO3, is soft and can be scraped off with a wise brush.
This is the main cause of scale formation in low pressure boilers. But in high pressure
boilers, CaCO3 is soluble as it reacts with water to give soluble Ca(OH)2 and CO2.

CaCO3 + H2O Ca(OH)2 + CO2

(slaked lime)

(2) Deposition of calcium sulphate (CaSO4);

The solubility of CaSO4 in water decreases with rise of temperature when
hard water containing CaSO4 is heated in boiler; it is precipitated as hard scale on the hot
portion of boiler. This is the main cause of scale formation in high pressure boilers.
Calcium sulphate scale is quit adherent and difficult to remove even with the help of
hammer and chisel.

Dr. SANJOGTA MESHRAM Page 17

(3) Hydrolysis of magnesium salts:
Dissolved magnesium salts, particularly MgCl2, undergo hydrolysis at
prevailing high temp inside the boiler, forming Mg(OH)2 precipitate which form soft
scale.

MgCl2 + 2H2O Mg(OH)2 + 2HCL

(scale)
(4) presence of silica (SiO2) :-
Silica, even present in small quantity deposits as calcium silicate (CaSiO3)
or magnesium silicate (MgSiO3) these deposits stick very firmly on the inner surface of
boiler and are very difficult to remove.

Disadvantages of scale formation:

1. Wastage of fuel:- The scales are bad conductor of heat, hence, it does not allow the
ready transfer of heat from hot plates of boilers to the water inside. For ready supply
of steam more heat is to be applied which results in the increase of fuel consumption.
The wastage of fuel depends upon the thickness of the scale.

Thickness of scale (mm) wastage of Fuel

0.325 10%
0.625 15%
1.25 50%
2.5 80%
12 150%
2. Decrease in efficiency :-
Scale may sometimes deposits in the valves and condensers of boiler and
choking them partially which results in decrease in efficiency of boiler.
3. Danger of explosion : When thick scales crack due to uneven expansion of scale and
boiler material, the water comes suddenly in contact with overheated iron plates of boiler.
This causes the formation of large amount of steam suddenly inside the boiler. Hence,
sudden high pressure is developed which may cause the explosion of boiler.

Internal conditioning :
Internal treatment consists of adding chemicals directly to the water in the boilers
for removing dangerous scale forming salts which were not completely removed in the
external treatment for water softening. This is mainly used as a corrective treatment to
remove the slight residual hardness and also sometimes to remove the corrosive
tendencies in water. This treatment is not usually applied to raw waters, except for small
boilers, but it is usually practiced in larger power –stations. In modern heavy-duty high
pressure boilers, water of zero hardness is required, since even an egg-shell thickness of
scale may be extremely detrimental.

Carbonate conditioning
For a salt to be precipitated, sufficient amount of the ions forming the salt must be
present so that the product of their conc. (i.e. Ionic product) exceed a limiting value
known as the solubility product. Thus, for a salt like CaCO3 to be precipitated, the

Dr. SANJOGTA MESHRAM Page 18

product of the conc. of Ca2+ and CO32- must exceed the solubility product of CaCO3,
represented as KCaCO3. The formation of CaCO3 may be represented by

Ca++ + CO3-- CaCO3 CaCO3 …………………… (1)

Solution solid

When the equilibrium is established,

[Ca++] [CO3--] = KCaCO3

(Conc of Ca2+) (conc. of CO32--) solubility product of CaCO3

At any given temp.
If under these conditions, some Na2CO3 is added, the CO32—increase, then in
order to maintain the KCaCO3 constant some Ca2++ will get precipitated.
Similarly in a saturated CaSO4 solution ,
Ca++ + SO4-- CaSO4 CaSO4
Solution solid
And
[ Ca++] [SO4--] = KCaSO4 ……………………(2)
(Conc. of Ca2+ ) (conc. of SO42- ) solubility product of CaSO4.

Thus, if a solution is saturated with CaCO3 and CaSO4 ( as occurring in boiler water
conditions), both the relations (1) and (2) apply, and by dividing (1)by (2) we get

[CO3--] KCaCO3
>= ………………………………(3)
[SO4- -] KCaSO4

From this, it is clear that if

[CO3--] KCaCO3
> or K’;
--
[SO4 ] KCaSO4

Or in other words, if [CO3 - - ] > K’[SO4- -],

Then only CaCO3 will be precipitated in preference to CaSO4 ( because the solubility
product of CaSO4 cannot be attained under these conditions).
These principal are used in the carbonate conditioning. when sodium
carbonate solution is added to boiler water, the [CO3--] increase and when it becomes
greater than K’ X [SO4- -],only CaCO3 gets precipitated and CaSO4 remains in solution.
Thus the deposition of scale forming CaSO4 is prevented.

Na2CO3 + CaSO4 CaCO3 + Na2SO4

Carbonate conditioning is used only for low pressure boilers. In high pressure boilers the
excess Na2CO3 might be converted into NaOH due to hydrolysis as follows:

Dr. SANJOGTA MESHRAM Page 19

Na2CO3 + 2H2O 2 NaOH + H2CO3

H2CO3 H2O + CO2

NaOH causes caustic embitterment in high pressure boilers.

1) Calgon conditioning :-
Another approach for preventing scale formation is to convert the scale
forming salts into lightly soluble complexes which are not easily precipited under the
boiler conditions. In order to achieve this, sodium hexameta phosphate (NaPO3)6 or
Na2[Na4P6O18] ( its trade name is calgon is generally employed this substance interacts
with the residual calcium ions forming highly soluble calcium hexametaphosphate and
thus prevents the precipitation of scale- forming salts.

Na2 [Na4P6O18] 2Na+ + [Na4P6O18]2-

2Ca2+ + [Na4P6O18]2 - 4Na+ + [Ca2P6O18]2 –

3 Phosphate Conditioning ;-
Just as in the case of carbonate conditioning, if we consider a solution saturated with both
Ca3(PO4)2 and CaSO4, the solubility product equations for both salts must be satisfied.

Ca3(PO4)2 3 Ca++ + 2 PO4- - - ……………………(4)

[Ca++]3 [PO4- - - ]2 = KCa3(PO4)2 …………………(5)

solubility product of Ca3(PO4)2

Divide the above eq (5) by 3

[Ca++][PO4- - -]2/3 = [KCa3(PO4)2]1/3

similarly for CaSO4

CaSO4 = Ca++ + SO4- - ……………………..(6)

[Ca++][SO4 - - - ]= KCaSO4
solubility product of CaSO4

By dividing (5) by (6) we have

[PO4- - - ]2/3 [KCa3(PO4)2]1/3

= or K’…………………(7)
- -
[SO4 ] [KCaSO4]

or [PO4- - - ]2/3 > K’[SO4- -], only Ca3(PO4) will be precipitated in preference to CaSO4
(because the solubility product of CaSO4 cannot be exceeded under these conditions) and
hence CaSO4 scale will not form.

Dr. SANJOGTA MESHRAM Page 20

 These principles are made use in the phosphate conditioning. In this
excess of a soluble phosphate is added to the boiler water to precipitated the residual
calcium ion in the form of a non-adherent precipitate of calcium phosphate thus the scale
formation is prevented.
The three sodium orthophosphates viz. Na3PO4, Na2HPO4 and NaH2PO4
been used for phosphate conditioning also sodium pyrophosphate (Na4P2O7) sodium
metaphosphate (NaPO4). The typical reaction of the various phosphates with the hardness
represented as CaCO3, may be summarized as follows;

2Na3PO4 + 3CaCO3 Ca3(PO4)2 + 3Na2CO3

2 Na2HPO4 + 3 CaCO3 Ca3(PO4)2 + 2 Na2CO3 + CO2 + H2O

2 NaH2PO4 + 3 CaCO3 Ca3 (PO4)2 + Na2CO3 + 2CO2 + 2 H2O

2NaPO3 + 3 CaCO3 Ca3(PO4)2 + Na2CO3 + 2 CO2

The quality of the feed water dictates the choice of a particular phosphate to be
used. For instance, if the feed water tends to produce an acidic condition in the boiler, the
alkaline Na3PO4 should be chosen. This treatment could be supplemented with NaOH if
the required alkalinity could not be maintained with Na3PO4 alone. if the feed water
produces almost the right alkalinity desired in the boiler, it is preferable to use Na2HPO4
which is practically neutral. If the boiler water becomes too alkaline, the acidic NaH 2PO4
would be selected. Both sodium pyrophosphate and metaphosphate are rapidly
hydrolyzed under boiler water temp. to orthophosphate.

NaPO3 + H2O = NaH2PO4

Na4P2O7 + H2O = 2 Na2HPO4

Thus, their behavior within the boiler is identical with that of orthophosphates mentioned
above. However, NaPO3 solutions are practically neutral, whereas NaH2PO4 solutions are
acidic. Hence the former would be preferred if the use of NaH2PO4 causes feedline
corrosion.

Desalination of Sea water :-

(or Desalination of brackish water)
The process of removing common salt (sodium chloride) from the
water, is known as desalination.
The water, containing dissolved salts with a peculiar salty (or brackish)
taste, is called brackish water.
Sea water, containing on an average about 3.5% salts, comes under this category.
Brackish water is totally unfit for drinking purpose commonly used methods for the
desalination of brackish water are:
(1) Electro dialysis :-

Dr. SANJOGTA MESHRAM Page 21

 “It is a method in which the ions (of the salts present) are pulled out of the
salt water by passing direct current, using electrodes and thin rigid plastic membrane
pair( natural or synthetic)”.
When direct electric current is passed through saline water, the sodium
ions(Na+) start moving towards negative pole (cathode); while the chloride ions (Cl-) start
moving towards the positive pole (anode); through the membrane. As a result, the
concentration of brine decreases in the central compartment; while it increases in two
side compartments. Desalinated brine (or pure water) is removed from the central
compartment from time to time; while concentrated brine ( in the side compartments) is
replaced by fresh brine/ sea water

For more efficient separation, usually ions- selective membranes are employed. An ion-
selective membrane has permeability for only one kind of ions with specific charge. For
ex- a cation-selective membrane is permeable to cations only , because of the presence of
charged fixed ( inside the membrane) functional groups ( such as RCOO-, or R SO3-)
reject anions (having the same charge as that of fixed functional groups) similarly, anion-
selective membrane has positively charged fixed functional groups such as R4N+Cl-.
An electro dialysis cell, consist of a large number of paired sets of rigid
plastic membranes. Saline water is passed under a pressure ( of about 5-6 kg m-2)
between membrane pairs and an electric field is applied perpendicular to the direction of
water flow, just as magnets of like charges repel each other, the fixed positive charges
inside the membrane repel positively charged ions (Na+), yet permit negatively charged
ions (Cl-) to pass through. Similarly, the fixed negative charges inside the other type of
membrane repel negatively charged ions(Cl- ), yet permit positively charged ions (Na+) to
pass through. Therefore, water in one compartment of the cell is deprived of its salts.
While the salt concentration in adjacent compartment is increased. Thus, we get alternate
streams of pure water and concentrated brine.

Dr. SANJOGTA MESHRAM Page 22

Advantages:-
(1) It is most compact unit.
(2) The cost of installation of the plant and its operation is economical.
(3) If electricity is easily available, it is best suited.

When two solutions of unequal concentrations are separated by a semi permeable

membrane ( which selectively does not permit the passage of dissolved salute particles,
i.e. molecules, ions, etc.)flow of solvent takes place from dilute to concentrated sides, due
to osmosis. If , however , a hydrostatic pressure in excess of osmotic pressure is applied
on the concentrated side, the solvent flows reverse, i.e. solvent is forced to move from
concentrated side to dilute side across the membrane. This is the principle of reverse
osmosis. Thus, in reverse osmosis, pure solvent (water) is separated from its
contaminates, rather than removing contaminants from the water. This membrane
filtration is sometimes also called ‘Super-filtration’ or ‘hyper-filtration’.

Method:
In this process, pressure (of the order 15 to 40 Kg cm-2) is applied to the
sea-water/ impure water ( to be treated) to force its pure water out through the semi
permeable membrane; leaving behind the dissolved solids ( both ionic as well as non-
ionic). The principles of reverse osmosis, as applied for treating saline/ sea water,
membrane consist of a polymeric material film made of proper porosity.
The membrane consists of very thin films of cellulose acetate, affixed to
either side of a perforated tube. However, more recently superior membranes made of
polymethacrylate and polyamide polymers have came into use.

Dr. SANJOGTA MESHRAM Page 23

Advantages:-
(1) Reverse osmosis possesses a distinct advantages of removing ionic as well
as non-ionic colloidal and high molecular weight organic matter.
(2) It removes colloidal silica, which is not removed by demineralization.
(3) The maintains cost is almost entirely on the replacement of the semi
permeable membrane.
.

(4) The life time of membrane is quit high about 2 years.

(5) The membrane can be replaced within a few minutes, thereby providing
nearly uninterrupted water supply.
(6) Due to low capital cost, simplicity, low operating cost and high reliability,
the reverse osmosis is gaining ground at present for converting sea water
into drinking water and for obtaining water for very high-pressure boilers.
(7) Simple to operate.
(8) Pure water for high pressure boiler can be obtained.

Dr. SANJOGTA MESHRAM Page 24

Osmosis :- “A process in which solvent molecules from a dilute solution pass
through a semipermeable membrane to a concentrated solution is called osmosis”.

Dr. SANJOGTA MESHRAM Page 25