HARDNESS REMOVAL TECHNOLOGIES OF WATER

Hardness is due to the presence of multivalent cations in water. Hardness in water is

principally caused by the solution in water of carbonate, bicarbonate, and sulfate of
calcium, and magnesium. Sometimes iron and aluminum cause hardness to a lesser degree.
In other words, it is a property of water, which prevents the lathering of the soap. Hardness
is usually expressed in mg/litre or p.p.m. of calcium carbonate in water. Hardness is of two
types.

1. Temporary hardness: It is caused due to the presence of carbonates and sulfates of

calcium and magnesium. It is removed by boiling.
2. Permanent hardness: It is caused due to the presence of chlorides and nitrates of calcium
and magnesium. It is removed by zeolite method.

Generally a hardness of 100 to 150 mg/l is desirable. Excess of hardness leads to the
following effects.
1. Large soap consumption in washing and bathing
2. Fabrics when washed become rough and strained with precipitates.
3. Hard water is not fit for industrial use like textiles, paper making, dye and ice cream
manufactures.
4. The precipitates clog the pores on the skin and make the skin rough
5. Precipitates can choke pipe lines and valves
6. It forms scales in the boiler tubes and reduces their efficiency and cause in
encrustations
7. Very hard water is not palatable

Softening is practices when hardness exceeds 300mg/l. Hardness > 600 mg/l rejected for
drinking purpose.

METHODS OF REMOVAL OF HARDNESS

There are several general methods used for water softening

1. Boiling (Heating)
2. Lime addition (Lime process)
3. Lime soda process (lime and soda ash process)
4. Excess Lime treatment
5. Caustic soda process
6. Zeolite process
7. Demineralization or exchange process (base-exchange process).

Methods 1 and 2 are suitable for removal of temporary hardness and 3 to 7 for both
temporary and permanent hardness.

1
Removal of temporary Hardness:

1. Boiling: Boiling or heating is effective only for the removal of bicarbonate hardness.
Heating of water breaks down bicarbonate into carbonate, water and carbon dioxide.

heat heat
i) Ca(HCO3)2 ------> CaCO3+ CO2+ H2O ii) Mg(HCO3)2 ------> MgCO3+ CO2+ H2O

CaCO3 is insoluble and settles down and excess CO 2 escapes from water. Similarly
hardness by Mg(HCO3)2 can also be removed by simple heating.

2. Addition of lime: The lime process, also known as the Clark Process, reduces only
carbonate hardness. The principle involved is to neutralize with milk of lime, i.e
Ca(OH)2, forming normal carbonates which precipitate out when present in excess
amount and removed by sedimentation and filtration.
Ca (HCO3)2 + Ca(OH)2 -----------> 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 -----------> CaCO3 + MgCO3 + 2H2O

Removal of permanent Hardness:

1. Lime soda process: In this method, the lime and sodium carbonate or soda is used to
remove permanent hardness from water. Lime has no effect on sulfate of calcium and
magnesium, which are responsible for causing most non-carbonate hardness found in
natural waters. The non-carbonate hardness is removed by the addition of soda ash
(Na2CO3). The chemical reactions involved in this process are as follows.
MgSO4 + Ca(OH)2 ----------> Mg(OH)2 + CaSO4 {conversion of MgSO4 to CaSO4}
CaSO4 + Na2CO3 ----------> CaCO3 + Na2SO4 {removal of sulfates}
MgCl2 + Ca(OH)2 ----------> Mg(OH)2 + CaCl2 {removal of chlorides}
CaCl2 + Na2CO3 ----------> CaCO3 + 2NaCl
MgCl2 + Na2CO3 ----------> MgCO3 + 2NaCl {removal of chlorides}

Some of the insoluble materials formed in the process may remain in the water in a finely
divided state and may be found deposited on the filter sand or in the distribution pipelines
at a later time. This difficulty may be overcome by treating the water with carbon dioxide, a
process called recarbonation.

Advantages of lime soda process

1. The pH value of water treated by this process bring down to 9 and which results in
decrease in corrosion of the distribution system.
2. Less quantity of coagulant will be required, if this process is adopted
3. Removal of iron and manganese to some extent
4. Reduction of total mineral content of water
5. Hardness of water is reduced to 40mg/l (of CaCO3) and magnesium upto 10mg/l
6. The process is economical
2
Disadvantages

1. Large quantity of sludge formed during this process to be disposed off by some
suitable method
2. This process requires skilled supervision for its successful working
3. If recarbonation is omitted, a thick layer of calcium carbonate will be deposited in the
filtering media, distribution pipes etc.

2. Zeolite process:

This is also known as the base-exchange or Ion exchange process. The hardness may be
completely removed by this process.

Principle
Zeolites are compounds (silicates of aluminum and sodium) which replace sodium ions
with calcium and magnesium ions when hard water is passes through a bed of zeolites. The
zeolite can be regenerated by passing a concentrated solution of sodium chloride through
the bed. The chemical reactions involved are

CaSO4
Na2CO3
+ MgSO4 Ca
Na2SO4
Na2Al(SiO3)2 CaCO3 Al(SiO3)2 +
2NaCl
(Zeolite) MgCO3 Mg
etc.
CaCl2

Regeneration:

Ca + CaCl2
Na2Al(SiO3)2
Al(SiO3)2 2NaCl +
(Regenerated Zeolite)
Mg MgCl2

Advantages
1. In this process, the sludge is not formed hence problem of sludge disposal does not
arise
2. It can be operated easily and no skilled supervision required
3. The hardness of water reduces to zero and hence used for boiler and texile industries
4. The process is economical where salt is cheaply available
5. The load on Zeolite can be reduced by combining it with lime or aeration process

Disadvantages
1. The Zeolite process cannot be used for turbid or acidic water
2. The Zeolite process is unsuitable for water containing Iron and Manganese
3. The Zeolite should be operated carefully to avoid injury or damage to the equipment

3
Exercise: Calculate the quantity of zeolite required to soften 2.27ML of water of 572
ppm to 286 ppm hardness. The interval between successive regeneration is 3
hours and the capacity of exchanger is 27.46 x 106 mg/m3.

Soln.: Quantity of hard water to be softened in 3 hours = 2.27 x 10 6 x 3/24 = 283750

L
Reduction in hardness = (572 286) ppm = 286 mg/L
Total hardness to be removed = 283750 x 286 = 81152500 mg
So, Total quantity of zeolite required = 81152500/27.46 x 106 = 2.955 2.96
m3.

Demineralization
Both cations and anions are removed by resins similar to zeolites in two columns by ion
exchange method; however, the exchanged ions must not contribute dissolved solids to
the effluent. This is accomplished by exchanging hydrogen for the dissolved cations and
hydroxide for the dissolved anions. The two then combine in equal amounts to form
water (H2O), leaving no residual and not affecting the pH. The resins may be regenerated
with acids and bases, respectively. This process is used in industries to get distilled water
or quality water.

Processes of demineralization

Hydrogen zeolite (available under the name Zeo-karb catex and organolite) exchange all
cations for hydrogen.

(HCO )
CO
Ca Ca
3 2 3
+
Mg Mg
H2 X H2 + X
Cl2 NO
Cl22 NO2
Fe Fe
SO4 SO4

Cation Exchange Process

CO3 CO3
HH2ClO + NaOH + Na Cl2
2
2

SO4
SO4

Anion Exchange Process

mg/L
equiv/ L =
4
 Equivalence weight
molecular weight
Equivalence weight =
valence (Mass +ve or ve charge that results from dissolution)

Ex Conuert 116 mg/L of NaCl to equiv/liter unit. [NaCl]=116mg/L

molecular weights : NaCl = 23 + 35 =58 gr/ mole NaCl Na+ + Cl -

Na Cl

58 gr / mole
Equivalence weight : = 58 gr/equiv
1

116 mg/L x 10-3 x g/mg

[NaCl] equiv/liter = = 2 10-3 eq / liters = 2 meq/liters
58 g/equiv

Ex convert 200 mg/L of CaCO3 to equivl / liter units [CaCO3].

molecular weight = CaCO3 = 40 + 12 + 3 (16) = 100 gr/mole

ca carbon oxygen CaCO3 Ca2+ + CO2-3

100 gr/mole
equivalence weight : = 50 gr/eq
2

200 mg/liter 10-3

[CaCO3] equiv/liters = = 4 10-3 eq/ liter = 4 meq/liter
50 gr/eq