MEE374 PROCESS PLANT UTILITIES

Dr. S. K. Behera
School of Chemical Engineering
VIT, Vellore, TN, India – 632 014.
 Module 1

Methods of Softening of Water

Need for water softening
Presence of hardness causing ions in water leads to several
disadvantages:

 Effects on cooling towers:

 Hard water makes scale and corrosion.

 Scale formation due to the presence of calcium and magnesium

reduces water flow, and heat transfer due to temperature drops.
Hence, repairing cost increases.

 Different types of ions are present in hard water. When two different
types of metal are present in hard water; these ions can act as
electrolyte. As a result, it leads to corrosion.
• Effects in boiler:
 When hard water is used in boiler, hard crystalline deposits of
calcium carbonate, calcium sulfate, magnesium carbonate are
formed.
 The resulting scale reduces the heating efficiency. Hence, it
needs further heating. This overheating may damage the
boiler.

• Effects in beverage industries

 Water used in beverages industries should be free from any
contaminants and microorganisms as they can change the
color, taste and odor of soft drinks.
 So, water must be conditioned before using in beverage
industries.
• Methods of Water softening

a) Pre-boiling of water

b) Lime soda process

c) Zeolite or Permutit process

d) Phosphate treatment

e) Ion exchange process

Preboiling of water
• Generally water fed to boilers is passed through heat exchanger and it
is preboiled.

• During preboiling the dissolved gases are removed.

• Bicarbonates of Ca and Mg causing temporary hardness are

decomposed to insoluble carbonates and removed from water.
Lime – Soda Process
• Most commonly used water softening method.

• In this method, all soluble hardness causing impurities are chemically

converted into insoluble precipitate which is removed by settling or
filtration.

• Hard water is treated with slaked lime - Ca(OH)2 and soda ash -
Na2CO3 in reaction tanks provided with stirrer.

• Water gets softened and the precipitates of CaCO3 and Mg(OH)2

settle down as sludge at the bottom of the tank.
Lime – Soda Process
Chemical reactions taking part in lime soda process are as follows:
Lime – Soda Process
Lime – Soda Process
• Reaction of lime with Ca and Mg salts are slow. Reactions produce
very fine particles which require sufficient time to settle down.

• Coagulating reagents like sodium aluminate or alum are used to

coagulate the precipitates at a faster rate.

• Lime soda process does not introduce new soluble salts to water. It
is best suited to treat both types of hardness, especially temporary
hardness.
Cold Lime soda process

• In this method, a calculated quantity of lime and soda ash are mixed
with water at room temperature.

• At this temperature, the precipitates formed are very fine and require
more time for settling which may be about 24 hours. It is not possible
to remove the fine precipitates by filtration.

• Some coagulants like alum or sodium aluminate or aluminium

sulphate are added to water. These coagulants hydrolyze to flocculent,
gelatinous precipitate of Al(OH)3 which bring together fine precipitate
particles.

• Use of sodium aluminate as coagulating agent removes silica & oil

present in water.
Cold Lime soda process
• Batch process:
Cold Lime soda process
• Batch process:
Cold Lime soda process
• Continuous process:
Cold Lime soda process
• Continuous process:

• Raw water and calculated quantities of chemicals are continuously fed

from the top into the inner chamber of vertical circular tank provided
with a stirrer.

• Raw water and chemicals flowing down the chamber come into close
contact because of continuous stirring and the chemical reaction takes
place to soften the water.
The sludge formed settles down to the bottom of the outer chamber
from where it is removed through sludge outlet. The softened water
rising up passes through the fiber filter which removes traces of sludge
and the filtered soft water passes through the outlet.

Soft water obtained from cold lime soda process still contains 50-60
ppm of residual hardness.
Hot Lime soda process
Hot Lime soda process
• In this process, raw water is treated with softening chemicals at a
temperature of 80 oC to 100 oC. At this temperature, the chemical
reactions are much faster than in cold process.

• Hot lime soda softeners are much faster in operation and require less
storage capacity tank.

• Elevated temperature accelerates the rate of actual chemical reaction,

increases the rate of aggregation of particles and reduces the viscosity
of water. Thus, rate of settling and filtration is increased.

• The sludge formed settles down rapidly and hence there is no need of
adding coagulants. In this process, the dissolved gases are driven out
due to high temperature treatment.

• The water softened by hot lime soda process contains residual

hardness of 15 – 30 ppm.
Advantages of Lime soda process
• Economical.

• Process increases pH value which reduces the corrosion of tanks and

pipe lines.

• Removes dissolved salt and gases along with hardness.

• Does not introduce any new salts to water.

• Can be used with lower quantity of coagulants as required.

Zeolite or Permutit process
• Zeolite is used to refer certain group of minerals consisting of hydrated
aluminosilicates of sodium, potassium, and calcium.

• They can be readily dehydrated and rehydrated and are used as cation
exchangers.

• Chemical structure of sodium zeolite: Na2OAl2O3.SiO2.H2O.

• These are capable of exchanging their sodium ions for multivalent ions of
calcium & magnesium present in water.

• Removes dissolved salt and gases along with hardness.

• Can be used with lower quantity of coagulants, if required.

Zeolite or Permutit process
Zeolite or Permutit process
Zeolite or Permutit process
 For softening of water
by zeolite process, hard
water is percolated at a
specified rate through
a bed of zeolite, kept in
a cylinder.

 The hardness causing

ions (Ca2+ ,Mg2+ ,etc.)
are retained by the
zeolite as CaZe and
MgZe; while the
outgoing water
contains sodium salt.
Zeolite or Permutit process
Regeneration
• After some time, the zeolite is completely converted into calcium and
magnesium zeolite and it ceases to soften water.
• At this stage, the supply of hard water is stopped and the exhausted
zeolite is reclaimed by treating the bed with a concentrated (10%) brine
(NaCl) solution.
• CaZe (or MgZe) + 2NaCl  Na2Ze + CaCl2 (or MgCl2)

The washing (containing CaCl2 and MgCl2 ) are led to drain and the
regenerated zeolite bed is again used for softening purpose.
Zeolite or Permutit process
Advantages:
1. It removes the hardness almost completely and water of about 10 ppm
hardness is produced.
2. The equipment used is compact, occupying a small space.
3. No impurities are precipitated, so there is no danger of sludge formation in
the treated water at a later stage.
4. It is quite clean.
5. It requires less time for softening.
6. It requires less skill for maintenance as well as operation.
Zeolite or Permutit process
Disadvantages:
1. The treated-water contains more sodium salts than in lime-soda process.
2. The method only replaces Ca2+ and Mg2+ ions, but leaves all the acidic ions
(like HCO3- and CO32-) as such in the softened water.
3. When such softened water (containing NaHCO3, Na2CO3, etc.) is used in
boilers for steam generation, NaHCO3 decomposes producing CO2 , which
causes corrosion ; and Na2CO3 hydrolysis to NaOH causes caustic
embrittlement.
4. High turbidity water cannot be treated efficiently by this method because
fine impurities get deposited on the zeolite bed, thereby creating problem
for its working.
Zeolite vs. Lime Soda process
Phosphate Treatment
• Water treated by lime-soda or Permutit process has traces of
impurities left in them which may cause scale formation in boiler.

• In high pressure boilers, scale formation can be avoided by addition of

phosphate to boiler water.

• The soluble phosphates for this purpose are:

Disodium hydrogen phosphate Na2HPO4
Sodium dihydrogen phosphate Na2H2PO4
Trisodium phosphate Na3PO4
Sodium ortho phosphate Na2P2O7

These sodium phosphates react with calcium and magnesium impurities

to convert them to their insoluble phosphate as Ca3(PO4)2 which are
deposited and removed as sludge. This avoids scale formation.
Phosphate Treatment

• For effective phosphate treatment, pH of water should be in the

range of 9.5 to 10.5.
Ion exchange process
• Water treated by lime-soda or Permutit process has lots of dissolved
sodium salts left in them.

• Water to be used in boiler must be free from all types of dissolved

impurities and must be very near to distilled water. Such a quality of
water can be obtained by demineralization or deionization process.

• Soft water is free from Ca & Mg ions but can contain Na, K, Cl,
SO4 ions. However, the dimineralized water does not contain any ion.

• Hence, every soft water is NOT dimineralized water but every

dimineralized water is a soft water.
Ion exchange process
• Ion exchange resins are insoluble cross linked long chain organic
polymers and the functional groups attached to chains are
responsible for ion exchanging properties.

• The resins containing acidic functional group such as –COOH, -

SO3H are capable of exchanging their H+ ions with cations coming in
their contact and the resins containing basic functional group such as
–NH2=NH2 are capable of exchanging their anions with other anion
coming in their contact. Hence, there are two types of ion exchange
beds in this process:
a) Cation exchange resins
b) Anion exchange resins
Ion exchange process
a) Cation exchange resin: These are capable of exchanging cations in
water by hydrogen ions. Resins such as sulphonated coals, tannin
formaldehyde represented as RH2 are the examples. Their exchange
resins are given as:

Cation exchange beds, when exhausted, can be regenerated by passing

an excess of strong acid solution through their bed.
Ion exchange process
b) Anion exchange resin: These are capable of exchanging anions in
water by hydroxyl ions. Their exchange resins are given as:

Anion exchange beds, when exhausted, can be regenerated by

passing an excess of strong alkali solution through their bed.
Ion exchange process
Ion exchange process
• Hard water is first passed through the cation exchange bed and then
through anion exchange bed. Consequently the resulting water will be
free from both cations and anions.

• Water obtained through the process is free of all ions.

• Water obtained by this process has a hardness less than 2 ppm