1.
0 Water Softening
Soft water is a desirable prerequisite for all textile wet processes. Modern synthetic detergents do
not form precipitates in hard water containing calcium and magnesium ions so a certain degree
of hardness is tolerable provided that other dyes and chemicals are not seriously affected by this.
In general, however, if a mill is in a region where the water is hard, a softening pretreatment is
essential for at least part of the water used. The objective of this is simply to reduce the
concentration of the alkaline earth metals to a level at which the water has the desired quality. In
many cases, the softening process may reduce the calcium and magnesium ion concentrations to
zero.
The principles involved in different methods that are usually adopted for the removal of hardness
are briefly described below.
i) Addition of sufficient quantity of soap.
ii) Boiling
iii) Clark process
iv) Lime – soda process
v) Ion exchange process
1.1 Treatment with soap
The simplest way in principle to get soft water is the addition of sufficient quantity of soap. The
stearate ions derived from the added sufficient quantity of soap precipitate all the objectionable
calcium and magnesium ions leaving the excess soap to carry on its detergent actions. This
process is not economically feasible, as because, soap is a costly material in comparison to other
materials used in other methods.
1.2 Boiling
Boiling is another way of softening water. But in this method, only the bicarbonates of calcium
and magnesium can be removed. The soluble bicarbonates of calcium and magnesium
decompose on boiling and are precipitated as insoluble carbonates and hydroxides respectively,
which are settled down and filtered off.
Ca(HCO3)2 → CaCO3 ↓ + CO2 + H2O
Mg(HCO3)2 → MgCO3 + CO2 + H2O
MgCO3 + 2H2O → Mg(OH)2 ↓ + CO2
Boiling is not, however, practical for large scale softening.
1.3 Clark Process
In this process a calculated amount of lime is added. Lime converts bicarbonates of calcium and
magnesium into calcium carbonate and magnesium hydroxide respectively. These are easily
removed by filtration. The lime treatment of water can be represented as –
CaO + H2O → Ca(OH)2
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 → MgCO3 + CaCO3 ↓ + 2H2O
MgCO3 + Ca(OH)2 → Mg(OH)2 ↓ + CaCO3 ↓
In the clark process, lime is added as suspension or as milk of lime. In this process the
bicarbonate hardness reduces to 0.7 – 1.0 ppm.
1.4 Lime-soda process
In this process, the above discussed lime treatment is followed by the addition of soda ash. Lime
removes the bicarbonate of calcium and magnesium by converting them into insoluble carbonate
and hydroxide respectively. The other salts such as chloride, sulphate are removed by soda and
lime by converting them into insoluble calcium carbonate and magnesium hydroxide
respectively as shown below.
Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 ↓ + 2H2O
Mg(HCO3)2 + Ca(OH)2 → MgCO3 + CaCO3 ↓ + 2H2O
MgCO3 + Ca(OH)2 → Mg(OH)2 ↓ + CaCO3 ↓
CaCl2 + Na2CO3 → CaCO3 ↓ + 2NaCl
CaSO4 + Na2CO3 → CaCO3 ↓ + Na2SO4
MgCl2 + Na2CO3 + Ca(OH)2 → Mg(OH)2 ↓ + CaCO3 ↓ + 2NaCl
MgSO4 + Na2CO3 + Ca(OH)2 → Mg(OH)2 ↓ + CaCO3 ↓ + Na2SO4
The old lime-soda process is now obsolete but was very useful for the treatment of large volumes
of hard water. Since calcium carbonate and magnesium hydroxide are not completely insoluble,
the water obtained has a residual hardness of not less than 20 ppm CaCO3. A major problem of
this type of process is the disposal of the sludge of precipitated calcium carbonate and
magnesium hydroxide.
There are two important types of softeners which are commonly used for softening water by
lime-soda process, theses are
i) Intermittents (Batch wise /Discontinuous) type and
ii) Continuous type
Figure: Intermittent water softener
Figure: Continuous water softener
1.4.1 Modified Soda-Lime Process
For certain advantage such as the higher solubility of Barium salts than sodium salts, soda ash is
replaced by barium carbonate.
1.5 Ion exchange methods
A zeolite is a naturally occurring inorganic insoluble mineral of the sodium aluminosilicate type.
When hard water passes through a bed of small particles of such a mineral, an ion exchange
reaction takes place. As more and more alkaline earth metal ions are retained by the zeolite, its
exchange capacity gradually decreases. Regeneration of the sodium salt of the zeolite involves
passing a concentrated solution of NaCl through the zeolite. The calcium and magnesium ions
are displaced and leave with the solution. After rinsing with water to eliminate the excess salt,
the zeolite is ready for another cycle of softening.
When hard water is passed through a bed consisting of zeolites, which are synthetic material
systems composed of complex sodium, aluminium and silicate salts (Na2Z), the calcium and
magnesium ions are exchanged. The displacing reactions
For temporary hardness are:
Ca(HCO3)3 + Na2Z → CaZ + 2NaHCO3
Mg(HCO3)3 + Na2Z → MgZ + 2NaHCO3
For permanent hardness the reactions are:
CaSO4 + Na2Z → CaZ + Na2SO4
MgSO4 + Na2Z → MgZ + Na2SO4
The process is reversible and the bed (Na2Z) can be regenerated by passing concentrated salt
solution. This method of water softening yields a very soft water (0.5-1º hardness).
CaZ + 2NaC1 → CaC12 + Na2Z
Discuss with figures the water softening and regeneration processes using synthetic zeolite. 4
Describe with figures the processes of water softening and regeneration using permutit. 3
Figure: Water softening by zeolite
Figure: Processes for water softening and regeneration using a cation exchanger
The newer synthetic polymer ion exchangers are much more versatile than the zeolites and are
widely used for water softening and demineralisation. Their ion-exchange capacity is greater
than that of zeolite. They are often called ion exchange resins. Many are based on polystyrene
that has been partly crosslinked by incorporation of a small amount of divinylbenzene (2–10%).
These have the appearance of fine white sand. Sulphonation of some of the benzene rings,
mainly on the bead surfaces, provides anionic sites suitable for cation exchange. Since a
sulphonic acid is comparable in strength to a mineral acid, these are called strong acid
exchangers. They may absorb cations and release hydrogen ions, or, in the form of their sodium
salts, exchange sodium ions for other cations in the water.
Figure: Chemical structures of cation and anion exchangers based on cross-linked polystyrene
The weak acid cation exchangers are usually polymers containing carboxylic acid groups, such
as vinyl polymers containing acrylic acid (ethenoic acid) units. These are used in the form of
their sodium salts. They do not exchange hydrogen ions for cations below pH 5 since the free
carboxylic acid groups are barely dissociated at low pH values.
Other types of ion exchange resins are available for anion exchange. These may be of the strong
basic type, containing quaternary ammonium hydroxide groups, or weakly basic with protonated
secondary amino groups. Either type will have associated counter anions that exchange with
anions in the solution in contact with the resin. The weakly basic types have ammonium ion
groups that can lose a proton in contact with an alkaline solution and therefore are ineffective
above pH 10. The ion exchange processes are again reversible so resin regeneration simply
involves treatment with a concentrated solution of a salt containing the appropriate anion.
Therefore, a strongly basic quaternary ammonium ion resin is regenerated using NaOH solution,
and a secondary amine type with NaCl or HCl solution.
A cation exchange synthetic resin may be defined as a high molecular weight, cross – linked
polymer containing sulphonic, carboxylic, phenolic etc. groups as integral parts of the resin and
equivalent amount of cation. An anionic exchange synthetic resin may be defned as a high
molecular weight cross linked polymer containing amine or quaternary ammonium groups as
integral parts.
The two most important properties of an ion exchanger are its capacity and its selectivity. The
capacity is the number of ions that a given mass of resin is capable of binding by exchange,
normally expressed in milliequivalents per gram of dry or of wet resin. The selectivity of the
resin determines how strongly it binds a given ion and therefore its ease of exchange. Clearly, for
water softening a cation exchange resin should have a higher selectivity for Ca2+ and Mg2+ than
for H+ or Na+.
Water can be totally demineralised by firstly exchanging all cations using a strongly acid form of
a cation exchanger. Thus, a solution of salts M+X– becomes a solution of acid H+X–, the M+
ions being retained by the resin. Subsequent percolation through a packing of a strongly basic
form of an anion exchanger absorbs the X– ions and liberates HO– ions into the water. These
then neutralize the H+ ions from the first step. The result is retention of all anions and cations
and the neutralisation of H+ and HO– to form water. Thus, the water has been demineralised.
discuss on the synthetic ionic exchangers used for water demineralization. State the chemical reactions involved in
softening of water by their salts. 3
It may, however, still contain organic material and dissolved carbon dioxide from the reaction of
carbonate and bicarbonate with the acid from the resin. A thorough aeration eliminates the
carbon dioxide.
Demineralisation is important for water fed to very high pressure boilers. The use of ion
exchange resins for water treatment is relatively simple. The resin is packed into a column
containing water and treatment simply involves flowing water up or down the column. The
capacity of the resin and the ionic content of the water determine when regeneration will be
required. One problem with beds of ion exchangers is the retention in the column of suspended
matter and living organisms in the water. Countercurrent rinsing and occasional treatment with a
bactericide minimise these problems. For removal of both cations and anions (demineralisation),
two columns in series are used, the first for strong acid exchange and the second for strong base
exchange. It is even possible to mix anion and cation exchangers in the same bed. If the different
types of particles have different densities, they can be separated by sedimentation in a counter
flow of water, regenerated separately, and then re-mixed.
