Slides prepared by Dr. A. Anand Prabu  9444686145; Email: aprabu21@yahoo.

com

Module 2a

1. Water treatment for Industrial purpose

2. External softening methods: Lime Soda process –
Cold and Hot lime-Soda process.
3. Lime-Soda numerical problems
4. Zeolite process
5. Ion-exchange including mixed-bed ion-exchange
processes.
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Water Softening methods

The process of removing the hardness producing substances from the water before it is
passed inside the boiler for steam generation is known as softening of water. In
Industry, 3 main methods are employed for softening of water.
1. Lime soda
(i) Cold lime-soda process (residual hardness: 50 to 60 ppm) and

(ii) Hot lime-soda process (residual hardness: 15 to 30 ppm)

2. Zeolite (permutit process) (residual hardness: up to10 ppm)

3. Ion-exchange (de-ionization or de-mineralization) process
(i) Cation exchange resins (RH+)
(residual hardness: around 2 ppm)
(ii) Anion exchange resins (R’OH-)
(iii) Mixed-bed deionizer (residual hardness: < 1 ppm)

1. Lime-Soda Method
In this method, the soluble Ca2+ and Mg2+ salts in water are chemically
converted into insoluble compounds by adding calculated amount of Lime
[Ca(OH)2] and Soda [Na2CO3]. Magnesium hydroxide [Mg(OH)2] and Calcium
carbonate [CaCO3] are precipitated, which are filtered off.
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Deficiencies in L-S method:

1. The chemical reaction between the salts and the L-S are very slow.
2. The precipitates [Mg(OH)2 and CaCO3] formed are very small (colloidal)
and hence, produce a super-saturated solution.
3. This results in “after-deposition” in the pipes and tubes producing sludges
which eventually cause blockage and corrosion.

How to solve the deficiencies in L-S method?

1. Thorough mixing of L-S with the hard water is carried out.
2. Enough time for the completion of reactions is given.
3. The reaction rate can be increased by using hot L-S method instead of
cold L-S.
4. Accelerators like activated charcoal that adsorb the fine precipitated
particles using physical adsorption technique can be used.
5. Coagulants or flocculants that help in the formation of coarse precipitates
(which can be removed by sedimentation/filtration) are added.
6. Suitable sedimentation chamber is provided before final filtration.
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]
Cold Lime-Soda Process

 Calculated amount of L & S mixed with

water at room temperature with stirring

 precipitate formed are finely divided,

hence do not settle down easily

 It is essential to add small amount of

coagulant {alum, NaAlO2, Al2(SO4)3}

 Coagulant hydrolyze to form gelatinous

ppt. and entraps the fine ppt., silica and
oil, if present in water.

2NaAlO2 + 4H2O  2Al(OH)3 + 2NaOH

Al2(SO4)3 + 3Ca(HCO3)2  2Al(OH)3 +

3CaSO4 + 6CO2
 The softened water passes through a
filtering media (wood fiber) for complete
removal of sludges.
 It provides water with a residual
hardness of 50 to 60 ppm
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]
Hot Lime-Soda Process
 Occurring at 80 to 150 °C close to the
boiling point of the solution
 Reaction proceed faster, softening
capacity is increased many folds
 The precipitate and sludges formed
settle down rapidly; no coagulant
needed
 Dissolved gases (CO2, O2) are driven
out easily; viscosity of the softened
water is low, so filtration of water is
much easier (filtering capacity of
filters is improved)
 Produce water contain the residual
hardness of 15 to 30 ppm
o Hot lime-soda process consists
of three parts:
a) Reaction tank to mix all ingredients
b) Conical sedimentation vessel where
the sludge settles down
c) Sand filter where sludge is
completely removed
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Advantages of Lime – Soda process:

1. Economical operation costs
2. If the process is combined with coagulation + sedimentation, lesser amount
of coagulants shall be needed.
3. Process increases the pH and hence corrosion of the distribution pipes are
reduced.
4. Due to alkaline pH, the amount of pathogenic bacteria in water is also
reduced.
5. Mineral content in water reduced; Fe and Mn ions are also removed from
water.

Disadvantages of Lime – soda process:

6. Careful operation and skilled supervision is necessary (If not, the excess L-S
addition will cause an increase in hardness levels in the treated water).
7. Huge amount of sludge is formed and its disposal is difficult
8. Due to residual hardness of at least (minimum) 15 ppm, the treated water is
not suitable for high pressure boilers
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Zeolite or Permutit Process

 Zeolite is hydrated sodium alumino silicate having a general formula,
Na2O.Al2O3.xSiO2.yH2O. (x = 2 to 10 and y = 2 to 6). Also known as
Permutits.
 Reversible exchange of Na+ ions for Ca2+ and Mg2+ ions in water.
 Natural zeolites are non-porous. Ex. Na2O.Al2O3.4SiO2.2H2O known as
natrolite.
 Other gluconites, green sand (iron potassium phyllosilicate with characteristic green color, a
mineral containing glauconite) etc. are used for water softening.

 Synthetic zeolites are porous, possess gel structure, have higher softening
capacity compared to natural zeolites due to their higher exchange
capacity per unit weight.
 Synthetic zeolites are prepared by heating together china clay (hydrated
aluminum silicate), feldspar {(KAlSi3O8-NaAlSi3O8–CaAl2Si2O8) are a group
of rock-forming tectosilicate minerals which make up as much as 60% of
the earth’s crust)} and soda ash (Na2CO3).
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Zeolite process
 Method of softening:

Na2Ze + Ca(HCO3)2 CaZe + 2 NaHCO3

Na2Ze + Mg(HCO3)2 MgZe + 2 NaHCO3
Na2Ze + CaSO4 CaZe + Na2SO4
Na2Ze + CaCl2 CaZe + 2 NaCl
zeolite hardness
 Regeneration of Zeolite using Brine solution:

CaZe (or) MgZe + 2 NaCl Na2Ze + CaCl2 or MgCl2

Exhausted Brine Reclaimed
zeolite zeolite

The washings are led to the drain and the regenerated zeolites are used for
softening purpose again
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Zeolite Process
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]
Zeolite Process
 Limitations of zeolite process:
 If water is turbid, the suspended impurities must be removed (by
coagulation, sedimentation, filtration) before the water is admitted to the
zeolite bed; otherwise the turbid particles will clog the zeolite bed and
make it inactive.
 Water containing large quantities of color ions such as Mn 2+ and Fe2+ must
be removed first because these ions produced Mn-zeolite and Fe-zeolite
which cannot be easily regenerated.
 Mineral acids, if present in the hard water will destroy the zeolite bed, and
hence must be neutralized with soda (Na2CO3) before sending the hard
water to the zeolite softening plant.

 Disadvantages:
 Treated water contains more Na + ions than in the L-S process.
 Replaces only Ca2+ and Mg2+ ions but leaves the acidic ions (HCO - and CO 2-) as such in
3 3
the softened water; HCO3 decompose to produce CO2 which causes corrosion in boilers;
-

CO32- hydrolyze to NaOH to cause caustic embrittlement.

 Advantages:
 Residual hardness of water is about 10 to 15 ppm only.
 Equipment is compact, clean, easy to handle, requires less softening time.
 No impurities, no sludge formation and the process is clean.
 The process automatically adjusts itself to the hardness of incoming water.
 Zeolite can be regenerated easily using brine solution
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

# Lime-Soda method Permutit Method

1. Residual water hardness: 15 to 60 ppm Residual water hardness: about 10 ppm
2. Treated water contains lesser amount of Treated water contains large amount of Na + ions
Na+ ions than in original water than in original water
3. Capital cost is lower Cost of plant and material is higher
4. Operational cost is higher Operational cost is lower
5. No such limitations Cannot be used for treating acid water because
the zeolite material undergoes disintegration
6. Plant occupies more space The plant occupies less space
7. No such limitations Raw water containing suspended impurities block
the pores of the permutit and the zeolite bed
loses its exchange capacity
8. Cannot operate under pressure Can operate under pressure, fully automatic
9. Involves difficulties in settling, No settling, coagulation, filtration or formation of
coagulation, filtration and removal of sludges / precipitation
precipitates
10 To be tested for frequent changes in Water analysis tests only the hardness of treated
. water hardness, control and adjustment water
of reagents
11 Treated water contains lesser dissolved Treated water contains more dissolved solids
. solids but more precipitated solids
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Ion-Exchange Process
o Ion-exchange resins are insoluble, cross-linked, long chain polymers with
micro-porous structure
o Functional groups present are responsible for ion-exchange properties
o Acidic functional groups (-COO-H+, -SO3-H+) exchange H+ for cations &
o Basic functional groups (-NH3+OH-) exchange OH- for anions.
A. Cation-exchange Resins(RH+):
- Styrene/divinyl benzene
copolymers on sulphonation or
carboxylation becomes capable
of exchanging their H+ ions with
the cations in the water.
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

B. Anion-exchange resins (R’OH-):

- are styrene/divinyl benzene copolymers or amine-formaldehyde copolymers
containing amino -NH2, quaternary ammonium -QN+, quaternary phosphonium
-QP+, or tertiary sulphonium -QS+ groups as an integral part of the resin matrix.

- On alkali (dil. NaOH) treatment, they become capable of exchanging their

OH- with the anions in the water.

CH2NMe3OH- CH2NMe3OH-
+
+

CH2NMe3OH- CH2NMe3OH-
+ +
Ion-Exchange Process
Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

At cation exchange column: The hard water is first passed through cation exchange
column, which removes all the cations like Ca2+, Mg2+, etc and an equivalent amount of
H+ ions are released from this column to water.
2 RH+ + Ca2+/Mg2+ R2Ca2+/R2Mg2+ + 2 H+

At anion exchange column: Removes all anions like SO42-, Cl-, etc present in the
water; an equivalent amount of OH- ions are released from this column into the water.
R’OH- + Cl- R’ + Cl- + OH-

2 R’OH- + SO42- R’2 SO42- + 2 OH-

2 R’OH- + CO32- R’2 CO32- + 2 OH-

Finally,
H+ + OH-  H2O (de-ionized water)

Regeneration: When the capacity of the ion exchange resins to

exchange H+ and OH- ions are lost, they are said to be exhausted.

R2Ca2+/R2Mg2+ + 2H+ (dil. HCl or H2SO4) 2 RH+ + Ca2+/Mg2+ (cation)

(washings)
R’2 SO42- + 2 OH- (dil. NaOH) 2 R’OH- + SO42- (anion)
The regenerated ion exchange resins can be (washings)
used again.
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

2-
regeneration
 Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

Ion-exchange process
Raw hard water

Advantages
• The process can be used to soften highly acidic or alkaline water
• It produces water of very low hardness (2 ppm)
• Good for use in high-pressure boiler
Disadvantages
• The equipment is costly and more expensive chemicals are needed
• If the turbidity of water is >10 ppm, then the output of the process is reduced

Important Note: Hard water should be first passed through the Cation exchanger and
then Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed.
Mixed bed ion-exchanger
Slides prepared by Dr. A. Anand Prabu  9444686145; Email: [email protected]

o Contains essentially of a single cylinder containing an intimate mixture of cation exchanger and
anion exchanger.
o Hard raw water gets in contact with the mixed bed ion-exchanger and the out-going water
contains < 1 ppm of dissolved salts.
Raw water inlet
Anion exchanger
(low density)
NaOH

Mixed
Mixed ionizer Exhausted
ionizer
bed mixed
bed ionizer bed
H2SO4
Cation exchanger
(higher density)

Backwash
water Comp.
Demineralized water air Washings to sink

Regeneration: When the resins are exhausted, the mixed-bed is backwashed using
compressed air. The lighter anion exchanger gets displaced to the top and the heavier cation
exchanger stays below.
Anion and cation exchanger were regenerated using NaOH and H 2SO4 respectively.