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Water Softening Industry

Importance of water in chemical and allied industry:
1. Due to high polarity and high value of dielectric constant (8.1) (It is the capacity of a solvent to
weaken forces of attraction between electrical charges of the charge particles immersed in solution)
water is used as a universal solvent.
2. Water is an associated molecule. Association in water is due to hydrogen bonding. Due to this
property, water possesses high value of boiling point (100oC) as well as freezing point (0oC).
Therefore, water can be used as reaction medium over a very long range of temperature.
3. Water possesses a high value of specific heat (1cal/g oC). It possesses high heat of fusion which is
80cal/g and it possesses high value of latent heat of vaporization (540cal/g). High value reported
above makes water an excellent heat exchange material. It can therefore be used for cooling
purposes in the form of liquid water and for heating purposes in the form of steam.
4. Water has high value of surface tension and the surface tension is found to increase with lowering of
temperature and it can therefore be used as an emulsifying agent for preparation of emulsion at low
temperature.
5. Water possesses a high value of viscosity (1 centipoise) and viscosity decreases with increase in
temperature. Water can therefore be used for preparation of those emulsions which are used at
high temperature.
6. Water containing chlorides, sulphates, bicarbonates and carbonates of calcium and magnesium is
called hard water and the water used in industry for steam making purpose should not contain any
hardness in it.
7. If water contains any hardness, a scale formation takes place inside the tube of boiler.
8. The heat conductivity of scale is much less than the heat conductivity of metals used as material of
construction of the pipes of boiler.
9. The conductivity of CaCO3 is 1/17th of iron. CaSO4 has 1/48th of conductivity of iron. Due to less
conductivity less heat transfer occurs.
10. Because of formation of scale, there will be temperature drop across the scale.
𝑄𝐿
11. An empirical relationship 𝑇 = 𝐾
in the context of temperature drop has been developed where:
 T = temperature in F.
o

 Q = the co-efficient of heat transfer in Btu/ft2 hr.

 L = thickness of scale in ft.
 K = the thermal co-efficient of conductivity in Btu/ft2 hr.
12. Because of temperature drop, fuel consumption is increased. Loss of fuel consumption against
thickness of scale has been found as:
Thickness of scale Loss of fuel
1/32 inches 9%
1/16 inches 12-16%
1/8 inches 20%
1/4 inches 40-60%
1/2 inches 150%
13. If there is no scale inside the boiler tubes then temperature on heating is about 150oC. This
temperature becomes 350oC if there is a scale of 1/2 inches thickness on the water side of boiler

1st Semester (Evening) Chemical Process Industries (I) Prof. Dr. Asghar Butt
By: Hamood Ahmad
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tube. This increase in temperature can cause distortion in the shape of tube which can end up with
bursting of tube.
14. The water used in industry therefore must be softened before raising of steam.
15. Various methods of the removal of hardness are present:
 Precipitation/Chemical method:
It involves two techniques:
i. Cold soda lime process.
ii. Hot soda lime process.
 Ion exchange process:
It involves two techniques:
i. Zeolite method.
ii. Ion exchange resin
 Reverse Osmosis

Comparison between cold and hot soda lime process:

HOT SODA LIME PROCESS COLD SODA LIME PROCESS
1. It is carried out at 96-98oC It is carried out at room temperature
2. The unit is upright vertical column made of The unit is upright vertical column made of cast
cast iron or plain iron steel. iron or plain iron steel.
3. The softening agents are Na2CO3, Ca(OH)2 The softening agents are Ca(OH)2, Na2CO3
4. Water to be softened is introduced The water to be softened and softening agent are
through a heater at top and inlet of introduced tangentially into the unit at its bottom.
chemical is also at the top.
5. Since reaction is carried out at about the CO2 and O2 contained in the raw water are not
boiling point of water therefore CO2 and removed.
O2 both are removed.
6. There are no corrosion problems. Presence of O2 and CO2 in water can be a cause of
corrosion in the tubes of boiler.
7. The precipitated compound is collected at The precipitated compound gets settled on the
the bottom in the form of sludge. surface of packing placed in the unit and there is
no sludge formation.
8. There is no packing. The unit is packed with calcite of the particle size
of 0.3-0.6 mm
9. Since the reaction is carried at 98oC Coagulant such as alum is needed for
coagulants are not needed. sedimentation of suspended impurity.
10. Silica present in water is adsorbed over the Any silica SiO2 present in water remains there.
surface of Mg(OH)2 at 96-98oC.
11. The residual hardness in water is less than Residual hardness in softened water is normally
35ppm and in some cases it is between 17- between 50-60ppm and in some cases it is about
35ppm. 35ppm

Zeolite method of softening of water:

Zeolites are basically hydrated sodium silicates (Na2O.Al2O3.xSiO2.yH2O). When hard water containing
Ca+2/Mg+2 ion is passed through the bed of zeolite, the following reaction takes place:

Na2.Al2O3.xSiO3.yH2O + Ca+2 CaOAl2O3.xSiO2.yH2O + 2Na+

1st Semester (Evening) Chemical Process Industries (I) Prof. Dr. Asghar Butt
By: Hamood Ahmad
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Advantages of Zeolite process:

1. In this method, the hardness is completely removed.
2. It operates at all temperatures.
3. It is more compact and occupies less floor area.
4. It automatically adjusts itself with the amount of hardness.
5. It can be on line and it operates under whatever pressure water is fed into. Hence no additional
pumping is needed.
6. The exhausted zeolite can be regenerated time and again.
7. In this process, no sludge is formed.

Limitations of Zeolite Process:

1. Water to be softened by this method should not be turbid.
2. The suspended impurities get settled or deposit over the surface of bed of zeolite and clog/chock the
bed of zeolite.
3. The water to be softened by this method should not have high acidity or high alkalinity. Highly acidic
or alkaline water can damage/decrease the activity of zeolite. Water to be softened should have pH
almost equal to 7.
4. Water used for softening by zeolite method should not contain Fe+2 or Mn+2. These ions damage the
Na-zeolite permanently.
5. Water passed through zeolite bed must not be hot. Hot water can solubilize to some extent the Na-
Zeolites. It also causes swelling of the granules.
6. Water containing temporary hardness when passed through zeolite bed forms imminent quantity of
NaHCO3. Water containing NaHCO3 if used for steam refining purpose can cause steel embrittlement
due to following reaction:
NaHCO3  Na+OH- +CO2
7. When hard water is passed through the bed of zeolite, the amount of total dissolved solid gets
increased.

Water Softening using Ion-exchange Resins:

General features and chemistry of ion-exchange process:
1. This process is a reversible ion exchange process which takes place between:
a) Stationery phase of an ion-exchange resin
b) External mobile phase of water (contains ions to be removed).
2. The stationery phase is an insoluble polymeric matrix (casting).
3. The polymeric matrix is permeable.
4. The polymeric material is impregnated with fixed charged group and mobile ions carrying charge
opposite to fixed group.
5. If a fixed charge group is negatively charged then the mobile counter ion shall carry a positive
charge, and this type of resin is called as cation exchange resin. If the fix charge group is positively
charged then the mobile counter ion is negatively charged. This type of resin is called anionic
exchange resin.
6. In the cation exchange resin, the fixed charge group is commonly:
i. –COOH ion
ii. –O- ion
iii. –SO3-2 ion
1st Semester (Evening) Chemical Process Industries (I) Prof. Dr. Asghar Butt
By: Hamood Ahmad
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And the cations always are H+ ions.

7. In anion exchange resin the fixed groups are monovalent and are with positive charge –NR3 and P+
and mobile charges are always OH- ions.
8. When water passes over the surface of cation exchange resin the hydrogen ion gets neutralize and
ultimately water becomes neutral.
9. The cation exchange resins are regenerated with use of acid. The anionic exchange resins are
regenerated with the use of NH4OH.

Characteristics of the ion-exchange resin:

1. The ion-exchange resin used in the softening process should be non-toxic.
2. It must not possess such colour which can discolour being softened. The resin should have high
surface area.
3. It should have high ion exchange capacity.
4. It must not get swelled up when kept in contact with water for sufficient long time.
5. The resin must have mechanical strength.
6. They should have reasonably high density to resist hydraulic flow.
7. The resin should be available at competitive price.
8. The resin should be capable of getting regenerated.

Preparation of a typical anion or cation resin:

Preparation of Cation Exchange Resin:
Cation exchange resin is prepared by co-polymerization of following compound:

Preparation of Anion Exchange Resin:

It is formed by co-polymerization of substituted styrene and divinyl benzene.

NOTE: ERRORS AND OMISSIONS ARE EXPECTED

1st Semester (Evening) Chemical Process Industries (I) Prof. Dr. Asghar Butt
By: Hamood Ahmad