Softening of water(External treatment)

Zeolite or Permutit Process :

Zeolites are naturally occurring hydrated sodium alumino silicate minerals (like Na2O . Al2O3 . xSiO2
. yH2O where x ═ 2-10 and y ═ 2-6) capable of exchanging reversibly its sodium ions for hardness
producing ions in water.
Zeolites are also known as permutits and in greek it means boiling stone.
A zeolite crystal can be considered to result from the linking of several SiO4 tetrahedron. Each
oxygen atom of the tetrahedron being shared with an adjacent one.
The empirical formula is thus (SiO2)n. However some of the Si4+ ions may be isomorphously
replaced by Al3+ ions and in order to balance the charges an extra positive ion such as Na+ and K+
must also be incorporated for every Al3+ introduced.
The linking of these tetrahedron results in an open structure with cavities. The porous nature of the
structure permits free movement of water molecules and ions.

Structure of a naturally occuring zeolite

 Types of zeolites
1) Natural zeolite
2) Synthetic zeolite
Natural zeolite :
• They are nonporous, amorphous and durable
eg: (a) Thomsonite (Na2O, CaO).Al2O3.2SiO2.2 H2O
(b) Natrolite Na2O, Al2O3.3SiO2.2H2O
(c) Laumontite CaO.Al2O3.4SiO2.4H2O
(d) Harmotome (BaO. K2O).Al2O3.5SiO2.5H2O
(e) Stilbite (Na2O.CaO). Al2O3.6SiO2, 6H2O
(f) Brewsterite (BaO. SrO. CaO).Al2O3.6SiO2.5H2O
(g) Pitlolite (CaO. K2O. Na2O).Al2O3.10SiO2.5H2O
Synthetic zeolite :
• They are porous and posses a gel structure.
• They are prepared by heating together sodium carbonate, alumina and
silica.
Synthetic zeolite posses higher exchange capacity per unit weight as compared
to natural zeolites.
 Process of softening
• For softening of water by zeolite process, hard water is percolated at
specified rate through a bed of zeolite, housed in a cylindrical unit.
• Zeolite holds sodium ion loosely and can be simply represented as Na2Ze
where Ze represents insoluble radical framework.
• The hardness causing ions (Ca 2+ , Mg2+ etc.) are retained by zeolite as CaZe and
MgZe respectively, while the outgoing water contains sodium salts. In the
process the water becomes free from calcium and magnesium ions, the main
hardness causing cations.
• Reactions taking place during the softening process are :
 Regeneration: (Reclaimed zeolite)
• After sometime the zeolite is completely converted into calcium and magnessium zeolites.
• At this time the bed of zeolite ceases to soften water i.e. It gets exhausted.
• At this stage the supply of hard water is stopped and the exhausted zeolite is reclaimed by
treating the bed with a concentrated sodium chloride(brine) solution when the following
reactions takes place
CaZe/MgZe + 2NaCl → Na2Ze + CaCl2/ MgCl2
exhausted zeolite reclaimed zeolite washings

Zeolite softener
Regeneration continued…………

Scheme for softening of water by zeolite process

 Regeneration Continued........

• The washings containing CaCl2 and MgCl2 are led to drain and
regenerated zeolite bed thus obtained is used again for softening purpose.
• Instead of NaCl, NaNO3, KCl, KNO3 etc can also be used for regeneration
but NaCl is mostly used because of its low cost and the product of
regeneration process (CaCl2 and MgCl2) are highly soluble and can be
easily rinsed out from zeolite bed.

• Advantages of zeolite process:

The hardness is almost completely removed by this method.
Equipment is compact and occupies less space.
It is quite clean and rapid process which requires less time for softening.
It automatically adjust itself to waters of different hardness.
For maintenance as well as for operations less skill is needed.
In this process the hardness causing ions are simply exchanged by sodium
ions. There is no precipitate formation and so there is no danger of sludge
formation and after precipitation in later stages of softened water.
 Limitations of zeolite process:
Water with turbidity should not be used as pores of
zeolite gets dogged.
pH of water should not be too high or too low as it
effects zeolite.
Water containingFe+2and Mn+2should be avoided as it
forms their own zeolites which cannot be regenerated
easily.
Hot water should not be used as it dissolves the zeolite.
Acid radicals are not removed by this process.
Water treated by zeolite contains 25% more dissolved
solids as compared to water softened by lime soda
process.
 Comparison between Zeolite process and lime soda process

Zeolite Process Limesoda Process

1) This process produces water of almost 1) This process produces water having
zero hardness hardness of 15 to 60 ppm depending on
whether it is hot process or cold
process.

2) The cost of the plant and the Zeolite are 2) The capital cost is lower.
higher. Hence the capital cost is higher.
3) The exhausted Zeolite bed can be 3) The chemicals needed viz., lime, soda,
regenerated with brine which is very and coagulant are consumed in the
cheap. Hence the operating cost is process. Hence the operating cost is
lesser. higher.
4)The plant is compact and occupies less 4)The plant occupies more space. The size
space. The size of the plant depends on of the plant depends on the amount of
the hardness of water being treated. water being handled.
5) Cannot be used for hot water, acidic 5) The process is free from such
waters, and waters having turbidity and limitations
suspended impurities.
 Comparison Continued………
6. This process can operate under pressure 6. This process cannot be operated under
and can be designed for fully automatic pressure.
operation.

7. This process does not involve a number of 7. This process involves all the problems
operations such as settling, coagulation, associated with settling, coagulation
filtration. and filtration.

8. Water treated with the Zeolite process contains 8. Treated water contains lesser percentage
larger amounts of sodium salts and greater percentage of dissolved solids and lesser quantities
of dissolved salts than the raw water since Ca2+ (eq. of sodium salts.
wt. 20) and Mg2+ (eq. wt. 12) are replaced by Na+
(eq. wt. 23)
9. This process adjusts itself to waters of 9. Reagent doses must be adjusted for waters
different hardness. of different hardness.

10. Salts causing temporary hardness are 10. Temporary hardness is completely removed in the
converted to NaHCO3 which will be form
present in the softened water. Such of
insoluble CaCO3 and Mg(OH)2. a water
creates problems when used as feed
water in boilers.

11. No problems of after precipitation. 11. There may be problems of after precipitation
in distribution systems and even in
boilers when used as boiler feed water.
 Numerical problems based on zeolite process
Example 1: An exhausted Zeolite softener was regenerated by passing 150 litres of NaCl solution,
having a strength of 150 g/l of NaCl. How many litres of hard water sample, having
hardness of 600 ppm can be softened, using this softener?

Solution : Hardness is expressed in terms of equivalents of CaCO3 as ppm.

Step I :Find the total amount of NaCl used for regeneration of zeolite
Amount of NaCl used for regeneration of zeolite = 150 g NaCl in 1 litre solution
1 litre of NaCl solution contains 150 g of NaCl
Therefore, 150 litres solution contains = 150 x 150g = 22500 g of NaCl
= 22,500 x 1000 = 22500000 mg Na Cl

Step II : Covert the amount of NaCl into CaCO3 form

Quantity of NaCl in terms of CaCo3 equivalent hardness =
1 mole CaCO3 = 2 Moles of NaCl (2Na+ = Ca2+ )
100mg of CaCo3 = 2x 58.5 = 117 mg of NaCl
? = 22500000 mg of NaCl
= 22500000 x 100 (CaCO3 equivalent hardness)
117
= 19230750 mg CaCO3 eq. hardness.
Step III : Calculate the total quantity of water softened
Given that 1 litre of hard water contains 600 ppm hardness ≡ 600 mg of CaCO3 = 0.6 g
ofCaCO3
? Litre of water = 19230750 mg of CaCO3
= 19230750 / 600
= 32051.25 litres
 Numerical continued…………
Example 2 : A zeolite bed is exhausted by softening 3500 litres of water sample requires10 litres
of 15% NaCl solution for regeneration. Calculate the hardness of water sample.

Solution : Hardness is expressed in terms of equivalents of CaCO3 as parts per million.

Step 1 : Find the total amount of NaCl used for regeneration of zeolite
Amount of NaCl used for regeneration = 15%=15 g NaCl in 100g solution.
OR 150g NaCl in 1000ml solution= 15%
1 Litre NaCl solution contains 150 g NaCl
Therefore, 10 litres solution contains = 10 x 150g =1500 g of NaCl= 1500000mg of NaCl

Step II : Convert the amount of NaCl into CaCO3 form

Molecular weight of CaCO3 = 100 and that of NaCl = 58.5
Quantity of NaCl in terms of CaCO3 equivalent hardness =
1 mole of CaCO3 = 2 Moles of NaCl (2Na+ = Ca2+ )
100mg CaCO3 = 2x 58.5 = 117mg of NaCl
? = 1500000 mg of NaCl
= 1500000 x 100 (CaCO3 equivalent hardness)
117 (twice NaCl Molecular weight)
= 1500000 x 0.8547 = 1282050 mg of CaCO3 equivalent hardness.

Step III : Calculate the hardness of water softened

Quantity of NaCl used = Hardness of water
Hardness of 3500 litres of water = 1282050 mg CaCO3 eq. hardness
Therefore hardness of 1 litre water = 1282050/ 3500 = 366.3 mg/lit.