Softening process: The process of removing dissolved salts of calcium and magnesium that cause hardness

in water is called as Softening of water OR converting dissolved salts of calcium and magnesium into
insoluble precipitates or salts is called as softening of water.

Types of Softening Methods: 1. Zeolite 2. Ion Exchange 3. Lime Soda

1. Zeolite Process or Permutit Process:

Principle: Zeolite is micro-porous mineral which is used as catalyst in many industrial purposes such as
water purification and air purification. Zeolites are naturally occurring sodium aluminium silicates. They are
represented as- Na2O.Al2O3.xSiO2.yH2O where x and y varies from 2 to 10 and 2 t 6 respectively. There
are two types of Zeolites.

Natural zeolites: These are non porous in nature. eg. Natrolite Na2OAl3O34SiO2.2H2O

Synthetic Zeolites: These are porous and gel like structure. Prepared by heating China Clay, Faldspar and
Soda Ash.

For softening of water by zeolite process, hard water is percolated at a specified rate through a bed of zeolite.
Zeolite holds sodium ion loosely and can be represented as Na2Ze or Na2P or Na2Z, where Z represents
insoluble radical frame work of zeolite.

Method: When the water passes through zeolite the hardness causing ions (Ca+2, Mg+2 etc.) are retained by
the zeolite as CaZ and MgZ respectively, while the outgoing water contains equivalent amount of sodium
salts. After some time, when the zeolite is completely changed into calcium and magnesium zeolites, then it
gets exhausted (saturated with Ca+2 and Mg+2 ions) and it ceases to soften water. It can be regenerated and
reused by treating it with a 10% brine (sodium chloride) solution. The block diagram and chemical reactions
taking place in zeolite softener is:

Chemical Reactions: Ca(HCO3)2 + Na2Z → CaZ + 2NaHCO3

Mg(HCO3)2 + Na2Z → MgZ + 2NaHCO3
CaSO4 + Na2Z → CaZ + Na2SO4
CaCl2 + Na2Z → CaZ + 2NaCl
MgSO4 + Na2Z → MgZ + Na2SO4
MgCl2 + Na2Z → MgZ + 2NaCl

Regeneration Reactions: CaZ + 2NaCl → Na2Z + CaCl2

MgZ + 2NaCl → Na2Z + MgCl2

Diagram: Zeolite softening is carried out in large cylindrical tank as shown in dia. holding Ze material on a
perforated platform. The tank has two inlets for feeding raw water and passing saturated NaCl solution.
There are two outlets for softened water and removing CaCl2,MgCl2,CaSO4,MgSO4 and the wash water
formed during the regeneration.

Dr. H.V.PATILE Page 1

 Dia. 1 Zeolite Softner

Merits of Zeolite Process:

• It removes the hardness almost completely (about 10 ppm hardness only).
• 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.
• The equipment is compact and requires less space.
• It requires less skill in maintenance as well as operation.
• Water obtained is quiet clear.

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.
• Highly acidic water is not suitable as it affects mineral.
• Zeolites of iron and manganese cannot be easily regenerated by passing NaCl solution. Hence iron
and manganese impurities in the water to be treated must be minimum.

2. Ion Exchange or Demineralization or Deionization Process:

Principle: The ion-exchange resins have been used to remove all minerals from water. It is a process by
which ions held on a porous, essentially insoluble solid are exchanged for ions in solution that is brought
in contact with it. Ion-exchange Resin is nothing but a cross linked organic polymer network having
some ionizable group. It may be of two types depending upon the nature of the ionizable group.

Dr. H.V.PATILE Page 2

 (i) Cation Exchange Resin or Cation Exchanger - Such resins are having - SO3H, -- COOH or -OH
(phenolic) group as the ionizable group. Since these resins exchange the cationic portion of minerals by
their hydrogen atom, they are known as cation exchangers. It is represented as RH+. Eg. Styrene divinyl
benzene copolymer which on sulphonation or carboxylation become capable to exchange H+ with
cations.

(ii) Anion Exchange Resin or Anion Exchanger – These resins are having -NH2, -NHCH3, -N(CH3)2 or
-OH group. They exchange the anionic portion of the minerals and they are known as anion exchanger.
Uses of Ion-exchange Resin – Water treatment by ion-exchange resin includes softening deionization and
de-alkalization of water. Therefore, hard water can be converted into soft water by making use of ion
exchange resins. It is represented as R’ OH-. Eg. Styrene divinyl benzene copolymer or amine
formaldehyde copolymers which contain amino/quaternaryammonium/phosphonium or tertiary
sulphonium group as an integral part of resin. After treatnment with NaOH can exchange OH-

Process – In this process first we passed hard water through cation exchange column, which removes all the
cations (like Ca+2, Mg+2 etc.) from it and equivalent amount of H+ ions are released from this column to
water. Thus,
2RH+ + Ca+2 -> R2Ca+2 + 2H+
2RH+ + Mg+2 -> R2Mg+2 + 2H+
After this process, hard water is passed through anion exchange column, which removes all the anions (like
SO4-2, Cl- etc.) from it, and equivalent amount of OH- ions are released from this column to water. Thus,

Dr. H.V.PATILE Page 3

 R'OH-2 +Cl-2 -> R'Cl-+ OH-
2R'OH- + SO2-4 -> R'2 SO2-4 + 2OH-
2R'OH- + CO2-3 -> R'2 CO2-3 + 2OH-
+ -
Hence, H and OH ions get combined to produce water molecule
H+ + OH- + H2O
The water coming out from the exchanger is free from cations as well as anions. Ion-free water is known as
deionized or demineralized water.

Merits of ion-exchange process:

➢ The process can be used to soften highly acidic or alkaline water.
➢ It produces water of very low hardness (say 2ppm).
➢ It is very good for treating water for use in high-pressure boiler.

Demerits of ion-exchange process:

➢ The equipment is costly and more expensive chemicals are needed.
➢ If water contains turbidity, then the output of the process is reduced
➢ Turbidity must be below 10 ppm. If it is more, it has to be removed first by coagulation and
filtration.

3. Lime soda process: There are again two types of process, Cold L-S Process and Hot L-S
process. Cold lime Soda process are of again two types; batch Process and Continuous process.

Reactions of Lime:

1. It can remove all temporary 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

Dr. H.V.PATILE Page 4

2. It can remove permanent Magnesium Hardness:

MgSO4 + Ca(OH)2 → Mg(OH)2 + CaCl2

MgCl2 + Ca(OH)2 → Mg(OH)2 + CaSO4

3. It can remove iron and Aluminium Salts:

FeSO4 + Ca(OH)2 → Fe (OH)2 + CaSO4

2AlCl3 + 3 Ca(OH)2 → 2 Al(OH)3 + 3 CaCl2

4. It can remove CO2 And H2S gas:

Ca(OH)2 + CO2→ CaCO3 + H2O

Ca(OH)2 + H2S →CaS + 2H2O

5. It can remove Free acids:

Ca(OH)2 + HCl→ CaCl2 + H2O

Ca(OH)2 + H2SO4 → CaSO4 + 2H2O

Reactions of Soda: It can only remove permanent calcium hardness.

CaSO4 + Na2CO3→ CaCO3 + Na2SO4

MgSO4 + Na2CO3→ MgCO3 + Na2SO4

Method: Lime soda process is one of the water softener systems. In this system calcium hydroxide and soda
ash are used as reagents. By this process soluble magnesium and calcium salts are removed as calcium
carbonate and magnesium hydroxide precipitated. After removal of this precipitated, we obtain soft water.
Both temporary water hardness and permanent water hardness are removed by this lime softening water
softener systems. Before water treatment calculate the amount of temporary and permanent water hardness,
and then estimate the amount of lime and soda ash and added control with careful.

Formula:

Cold Lime Soda Process: In the cold lime soda process the reactions take place at normal temperature. The
raw water is passed into a tank with a static continuous flow, at the same time a calculated amount of
chemical mixture of lime and soda ash are also added a static continuous flow and then thoroughly mixed
with a stirrer in this mixture tank. Afterward this water is allowed to settle. When the settlement becomes
complete the water is passed by continuous up-flow process into another tank which is called filter bed. Then
we get soften water.
The cold lime soda process is not suitable for all purposes. It is limited for those purposes where partially
softened water needed because this process fails to precipitate completely all the hardness forming salts. The
Dr. H.V.PATILE Page 5
cold lime soda process is used for municipal water and cooling water softener systems. The reason in case of
municipal purpose, it is not necessary to remove all water hardness forming ions. Same way cooling water
should be free from temporary water hardness. In this process it is possible to remove magnesium water
hardness nearly completely but calcium hardness may be remains more than 40ppm.

Coagulant is necessary because at room temperature precipitate is finally divided. But do not settle easily &
cannot easily filtered. Mechanical stirrer is used to increase mixing & rate of precipitate formation.
NaAlO2+2H2O−−→NaOH+Al(OH)3NaAlO2+2H2O−−→NaOH+Al(OH)3

a) Batch Process.

b) Continuous Process.

Dr. H.V.PATILE Page 6

Hot Lime Soda Process: In the hot lime soda process the reactions take place at higher temperature near
about boiling point of water. The chemical mixing process is same as the cold lime soda process, but steam is
applied in mixture tank. As a result precipitation becomes almost complete very quickly. This process is
more effective than cold lime soda process. The hot lime soda process water softener systems are exclusively
used for boiler purpose. In this process it is possible to remove magnesium water hardness completely and
calcium hardness may be remains very low. Moreover dissolved corrosive gases also removed by this hot
lime soda process. It is carried out at temperature 80−150∘c80−150∘c. It is used when small quantity of
water is required. But it takes place at low hardness ie. 15-25 ppm.

Due to hot condition OR advantages over Cold Lime soda Process:

• Reactions take place faster.

• No need of coagulant
• Hardness is low
• Dissolved gases are expelled out at high temperature

Advantages:
• It is more economical
• Less amount of coagulant is required.
• It increases pH value, there by corrosion is reduced.
• Also Fe, Mn & minerals are reduced.
• Pathogenic bacteria are reduced.

Disadvantages:

• The hardness is 50-60 ppm by cold process & about 15-30 ppm by hot process
• Careful operation & skilled supervision are required.
• Disposal of large quantity of sludge formed during process is a problem.

Dr. H.V.PATILE Page 7