Water Technology

 Softening of hard water: Ion-exchange method; Zeolite methods

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 WATER SOFTENING
Ion exchange or deionization or demineralization
process: Ion-exchange resins are widely used in different separation,
purification, and decontamination processes. The most common examples are
water softening and water purification.
Ion-exchange resins are insoluble, cross linked, long chain organic polymer
with micro porous structure and the functional groups attached to the chains are
responsible for the ion exchange properties.

Cation Resin after

exchange Resin treatment

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Resins containing acidic functional groups (-COOH, -SO3H) are capable of
exchanging their H+ ions with other cations which comes in their contacts, known as
a cation exchange resins (RH+).
e.g. styrene-divinyl benzene copolymer, which on sulphonation and carboxylation,
become capable to exchange their hydrogen ions with the cations (Metal ions) in the
water.

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Resins containing basic functional groups (-NR3+OH-) are capable of
exchanging their anions with other anions which comes in their contacts,
known as a Anion exchange resins (ROH-).

They are styrene divinyl benzene or amine-formaldehyde copolymerization

which contains quaternary ammonium or quaternary phosphonium or
tertiary sulphonium groups as an integral part of the resin matrix. These
after treated with dil NaOH becomes capable of exchanging their OH - ions
with anions of water.

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 Process
The hard water is passed first through cation exchange column, which remove
all the cations from it and equivalent amount of hydrogen ions are released
from this column to water:

2RH+ + Ca2+ R2Ca2+ + 2H+

2RH+ + Mg2+ R2Mg2+ + 2H+

After cation exchange column the hard water is passed through anion
exchange resin column, which remove all the anions from it and equivalent
amount of hydroxide ions are released from this column to water :
ROH- + Cl- RCl- + OH-
2ROH- + SO42- R2SO42- + 2OH-

H + + OH- H 2O
Thus, water coming out from the exchange is free from cations as well as
anions.
Ion free water is known as deionized or demineralised water.
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 Ion exchange purifier or softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

Wastages to
Acid solution for sink Alkaline solution for
regeneration of regeneration of resin
Wastages to
resin sink
pump

6 Soft water
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 Regeneration:
Cation exchange column is regenerated by passing a solution of
dil HCl or dil H2SO4. The regeneration can be represented as

R2Ca2+ + 2H+ 2RH + Ca2+

Exhausted anion exchange column is regenerated by passing a

solution of dil. NaOH. The regeneration can be represented
as

R2SO42- + 2OH- 2ROH + SO42-

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Advantages:
Can be used to soften highly acidic or alkaline waters.

It produces water of very low hardness.

Disadvantages:
The equipment is costly

Expensive chemicals are needed

Output of the process is reduced if water contains turbidity.

(turbidity must be below10 ppm)

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 Zeolite (Permutit) method of Softening of
water
Zeolite is a Hydrated Sodium Alumino
Silicate (HSAS), capable of exchanging
reversibly its sodium ions for hardness
producing ions in water.

The general chemical structure of zeolite

is given below Na2O.Al2O3.xSiO2.yH2O (x =
2-10 and y = 2-6)

Micro pores of Zeolite Porous Structure of zeolite

 Porosity or cavity size of synthetic zeolite structures can be
controlled by varying the Si/Al ratio
 Ion-exchange process of zeolite structure is associated with sodium ions
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 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

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Process of softening by Zeolite method
For the purification of water by the zeolite softener, hard water is passed through
the zeolite bed at a specified rate. The hardness causing ions such as Ca 2+, Mg2+
are retained by the zeolite bed as CaZe and MgZe respectively; while the
outgoing water contains sodium salts. The following reactions takes place during
softening process

To remove temporary hardness

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO 3
Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO 3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na 2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na 2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained
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Limitations of Zeolite process
1. If the water is turbid: then the turbidity causing particles clogs the
pores of the Zeolite and making it inactive
2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which
can not be regenerated that easily as both metal ions bind strongly
and irreversibly to the zeolite structure.
3. Any acid present in water (acidic water) should be neutralized with
soda before admitting the water to the plant.

Advantages of Zeolite process

1. Soft water of 10-15 ppm can be produced by this method

2. The equipment occupies less space
3. No impurities are precipitated, hence no danger of sludge formation
in the treated water
4. It does not require more time and more skill
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Disadvantages of Zeolite process

1. Soft water contains more sodium salts than in lime soda process
2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions
like HCO3- and CO32- in the softened water (then it may form
NaHCO3 and Na2CO3 which releases CO2 when the water is boiled
and causes corrosion)
3. It also causes caustic embrittlement when sodium carbonate
hydrolyses to give NaOH

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 Water Technology

 Softening of hard water: internal treatment by phosphate, calgon condition

and colloid conditioning

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 Internal treatment

In this process, an ion is prohibited to exhibit its original character by

complexing or converted into other more soluble salt by adding appropriate
reagent.

An internal treatment is accomplished by adding a proper chemical to water

either:
(a) To precipitate the scale forming impurities in the form of sludge, which
can be removed.
(b) To convert them into compounds, which will stay in dissolved form in
water and thus do not cause any harm.

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 Important Internal Treatments are:

Phosphate conditioning:
Scale formation can be avoided by adding sodium phosphate which reacts
with hardness of water forming non-adherent and easily removable soft
sludge of calcium and magnesium phosphate.

3CaCl2 + 2Na3PO4 Ca3 (PO4)2 + 6NaCl

 Trisodium phosphate is most suitable for treatment when alkalinity is low

 Disodium phosphate is used when the water alkalinity is sufficient.
 Monosodium phosphate is used when the alkalinity of boiler water is
too high.

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Calgon conditioning:

Its involve in adding Calgon (Sodium hexa-meta phosphate (NaPO3)6 to boiler

water. It prevents the scale and sludge formation by forming soluble complex
compound with CaSO4.

[Na6(PO3)6] 2Na + + [Na4P6O18]2-

2CaSO4 + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

soluble complex ion

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Colloidal conditioning:

Scale formation can be avoided by adding organic substances like kerosene,

tannin, agar-agar (a gel) etc., which get coated on over the scale forming

precipitate, thereby, yielding non-sticky and loose deposits.

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Q1. Calculate the quantities of lime and soda required for treatment of 125,000
litres of water with the following composition:

Answer:

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Q2. A sample of hard water was only passed through a column of cation
exchange resin. What will be the pH of water sample after the above treatment?
Justify your answer and write the chemical reaction involved.

Answer:

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Q3. A standard hardwater was prepared by mixing 410 mg Ca(NO3)2 and
equimolar (having the same amount of moles) amount of CaCl2. The total
volume of the solution is 500 mL. Calculate the hardness of the solution in ppm
unit. (Molecular weights of Ca(NO3)2= 164; CaCl2=111 and CaCO3= 100)

Answer:

Ca(NO3)2= 410 mg/164 = 2.5×10-3 mol;

CaCl2=2.5×10-3 mol
Total = 5×10-3 mol
CaCO3= 5×10-3 mol ×100 g= 0.5 g in 500 mL or 1000mg in 1000 mL
1000 ppm

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Q4. 50,000-liter neutral hard water was passed through column containing
organic insoluble material. The analysis of treated water showed pH 3. Calculate
the hardness of the water.

Answer:

pH = 3, 1×10-3 molar H+ solution.

1 mole H+ ion = 50 g CaCO3
1×10-3 mole H+ ion = 50 mg CaCO3

Hardness = 50 ppm

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Q5. A zeolite softener was exhausted and regenerated by passing 100 litres of
NaCl solution of strength 585 g/l. Calculate the total hardness of the water
sample in ppm, if the zeolite softener can soften 1000 litres of water before
regeneration.

Answer:

585 g NaCl = 585 x 103 mg NaCl in 1L water

100 L NaCl solution contains = 585 x 105 mg NaCl
CaCO3 equivalent = [(585 x 105) x 50]/58.5 = 50 x 106 mg

50 x 106 mg CaCO3 in 1000 L of water = 50000 mg/L or ppm

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