Ch.

1
Water As Basic Utility -

Prepared By:-
Dhaval N.Yadav
Lecturer (CL-II),
Chemical Engineering Department,
Shri K. J. Polytechnic, Bharuch.
Topics to be Covered
 Types of Water
 Method of Removal of Hardness

 Various methods of Purification of Raw

Water : Screening, Sedimentation,
Coagulation, Sterilization
 Types of Water

Water

Deminer Boiler
Hard Soft alised Feed
Water Water Water
Water
Soft Water
 The water which does not contain any of
the Ca or Mg salt dissolved in it is called
Soft Water.
 It may contain certain salts like Sodium
or Potassium dissolved in it.
 A sample of soft water when used with
soap forms lather.
Hard Water
 Hardness in water is that
“Characteristics which Prevents The
Lathering of Soap.”
 This is because of presence of certain
salts of Calcium, Magnesium and other
Heavy Metals dissolved in water.
Continued…
 A sample of hard water when used with
soap does not produce lather, but on the
other end produces white scum or
precipitate.
 This is formed because of formation of
Insoluble Soaps of Calcium and
Magnesium.
 Sludge
Slimy loose
precipitate called
sludge suspended in
water

Water

Boiler
wall
Sludge is a soft, loose and slimy precipitate formed within the boiler. It
can be easily scrapped off with a wire brush.
It is formed at comparatively colder portions of the boiler and collects
in areas of the system, where the flow rate is slow or at bends.
It is formed by substances which have greater solubility's in hot water
than in cold water, e.g. MgCO3, MgCl2, CaCl2, MgSO4 etc.,

Remedy: Sludges can be removed using wire brush or mild acid

7
 Scale Hard adherent coating on
inner walls of boiler

water

Boiler
wall
Scales are hard substances which sticks very firmly to the
inner surfaces of the boiler wall.
Scales are difficult to remove even with the help of a hammer
and chisel.
Examples: CaSO4, CaCO3, Mg(OH)2
8
Why to worry?
 Hard water does cause Soap Scum,
Clogs Pipes and Clogs Boilers as Lime
Scale.
Types of Hardness

Hardness

Temporary Permanent
or Or
Carbonate Non-Carbonate
 Temporary Hardness
 Dissolved bicarbonate (HCO3-) of Ca, Mg.
 It is mostly destroyed by mere boiling of water, when
bicarbonates are decomposed yielding insoluble
carbonates.
Ca(HCO3)2 Heat CaCO3 + H2O + CO2
Calcium bicarbonate Calcium Carbonate

Mg(HCO3)2 Heat Mg(OH)2 + 2CO2

Magnesium Bicarbonate Magnesium hydroxide

 Calcium/Magnesium Carbonates thus formed being

almost insoluble, are deposited as a scale at the
bottom of vessel, while carbon dioxide escapes out.
 Permanent Hardness
 Presence of Chlorides, Sulfates of Calcium,
Magnesium, Iron and other heavy Non Carbonate
Hardness is due to
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sodium stearate Hardness Calcium stearate
(sodium soap) (Insoluble)

2C17H35COONa + MgSO4 (C17H35COO)2Mg + 2Na2SO4

Sodium stearate Hardness Magnesium stearate
(sodium soap) (Insoluble)

 Cannot be removed by simple boiling it requires the

addition of certain chemicals and process.
 Permanent Hardness
 Presence of Chlorides, Sulfates of Calcium,
Magnesium, Iron and other heavy Non Carbonate
Hardness is due to
2C17H35COONa + CaCl2 (C17H35COO)2Ca + 2NaCl
Sodium stearate Hardness Calcium stearate
(sodium soap) (Insoluble)

2C17H35COONa + MgSO4 (C17H35COO)2Mg + 2Na2SO4

Sodium stearate Hardness Magnesium stearate
(sodium soap) (Insoluble)

 Cannot be removed by simple boiling it requires the

addition of certain chemicals and process.
 Draw backs (or) Disadvantages of Hard Water

Domestic Use Industrial Use

1. Washing 1. Steam generation in Boilers

2. Bathing
The sticky precipitate adheres
3. Drinking on the fabric/cloth and gives
spots and streaks. Fe salts
4. Cooking stain the cloths.

Produces sticky scum on the

bath tub and the body

Bad to the digestive system

and calcium oxalate
formation is possible in
urinary tracts

Requires more fuel and time.

Certains food don’t cook soft
and also gives unpleasant
taste
14
 External Water Treatment
Methods
E
 The widely used methods are:
x
t
Lime Soda Process
e
r
Zeolite (or Permutit Process)
n
a
Ion Exchange Process
l
Phosphate Process (Conditioning)
Internal
Treatment
Lime Soda Process
Principle:
It is a process in which Lime (Ca(OH)2)
and Soda (Na2CO3) are added to the
hard water to convert the Soluble Ca
and Mg Salts to insoluble compounds by
a chemical reaction.
The CaCO3 and Mg(OH)2 so
precipitated are filtered off and removed
easily.
LS Process Continued….
 It is one of the most oldest process used
for water softening.
 Because of technology advancement it is
now no more used.
 It is further classified as
Cold LS Process
Hot LS Process
LS Process Working
Step-1:
 In this process a calculated quantity of Ca(OH)2 (lime) and Na2CO3
(soda) are mixed with water at room temperature and added to
the hard water. The following reactions takes place depending on
the nature of hardness

If it is permanent hardness and due to calcium salt

Ca2+ + Na2CO3 CaCO3 + 2Na+ (soda)
Slimy Suspended Precipitate

If it is due to Magnesium salt

Mg2+ + Ca(OH)2 Mg(OH)2 + Ca2+ (lime)
Slimy Suspended Precipitate
LS Process Working
If it is Temporary hardness and due to calcium salt
Ca(HCO3)2 + Ca(OH)2 2CaCO3 + 2H2O
Slimy suspended precipitate

If it is due to Magnesium salt

Mg(HCO3)2 + 2Ca(OH)2 2CaCO3 + Mg(OH)2 + 2H2O
Slimy suspended precipitates
LS Process Working
Step-2:
 The precipitates CaCO3 and Mg(OH)2 are very fine and
forms sludge like precipitates in the boiler water and
are difficult to remove because it does not settle easily
making it difficult to filter. Finally reduces the efficiency
of the boiler.
 Therefore, it is essential to add small amount of
Coagulant (such as Alum, Aluminium Sulfate,
Sodium Aluminate etc) which hydrolyses to
flocculent precipitate of Al(OH)3 which entraps the fine
precipitates.
Step-2:
 When coagulants are added flocculation takes place
followed by the formation of flocculants.
NaAlO2 + 2H2O NaOH + Al(OH)3
Coagulant Flocculent- Gelatinous
precipitate which
entraps the fine
precipitates of CaCO3
and Mg(OH)2

Al2(SO4)3 + 3 Ca(HCO3)2 2Al(OH)3 + CaSO4 + CO2

Aluminium Hard water Flocculent- Gelatinous
sulfate sample precipitate which
entraps the fine
precipitates of CaCO3
and Mg(OH)2

The Al(OH)3 formed by the addition of coagulants initiates

the process of flocculation and entraps the fine precipitates
and becomes heavy. The heavier flocs thus settles at the
bottom and filtered off easily.
 Continuous cold lime soda softener

Chemicals
Hard water
(soda+lime+
feed
coagulant)
feed
Softened
water
Wood fiber
filter

Stirrer
paddles

Sedimented sludge (CaCO3,

Mg(OH)2

22
Hot LS Process
 In this process a calculated quantity of Ca(OH)2
(lime) and Na2CO3 (soda) are mixed with hot
water at a temperature range of 80 to 150oC
and added to the hard water.
 It consists of :
Reaction tank: water, chemicals and steam are
mixed
Conical sedimentation tank : sludge settles down
Sand filter : complete removal of sludge from the
softwater is ensured
 Continuous Hot Lime soda Process

Hard water feed

Super heated steam

Chemicals feed (lime and
soda)

Reaction tank
Soft water

Conical sedimentation
tank

Precipitated sludge
(CaCO3, Mg(OH)2 Sludge
outlet

Filtered soft
water

24
Advantages & Disadvantages
Advantages
1. It is very economical compared to other
methods
2. Iron and manganese salts are also removed by
this process
3. It increases the pH of the softened water hence
corrosion is minimized also pathogenic bacteria
Disadvantages
1. Disposal of large amount of sludge (insoluble
precipitates) poses a problem
2. This can remove hardness to the extent of
15ppm which is not good for boilers
Zeolite (or Permutit Process)
 Zeolites are micro porous, alumino silicate
minerals commonly used as commercial Adsorbents
and catalyst.
 The term zeolite was originally coined in 1756
by Swedish mineralogist Axel Fredrik Cronstedt, who
observed that upon rapidly heating the
material STILBITE, it produced large amounts of
steam from water that had been adsorbed by the
material. Based on this, he called the material zeolite,
from the Greek ζέω (zéō), meaning "to boil" and λίθος
(líthos), meaning "stone"
 Zeolite (or Permutit Process)
• Zeolite is a Hydrated Sodium Alumino
Silicate, 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)
•Why synthetic zeolite is better than natural
zeolite for the softening of water?
Ans: Natural zeolites are non-porous
Micro pores of Zeolite Porous Structure of zeolite

27
 Zeolite softener

Hard water in

Hard water spray

Zeolite bed
Gravel

Injector

Softened water
NaCl storage To
sink

28
 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 Ca2+, 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 + 2NaHCO3 Scale formation

Hardness

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove permanent hardness water

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)

Used 10% brine Regenerated Washings

Zeolite solution Zeolite drained

29
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, since acid will hydrolyze SiO2 forming silicic acid

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

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 embitterment when sodium carbonate hydrolyses to give NaOH
30
 Ion-Exchange/ Deionization/ Demineralization
Process

ION EXCHANGE RESINS are

insoluble, cross linked, long chain organic
polymers with a microporous structure,
and the functional groups attached to the
chain is responsible for the “ion-
exchange” properties.
Cation Resin after
exchange Resin treatment
31
 The resins containing acidic functional groups (-
COOH, -SO3H etc) are capable of exchanging their H+
ions with other cations, which comes in their contact;
whereas those containing basic functional groups ( -NH2,
=NH as hydrochlorides) are capable of exchanging their
anions with other ions, which comes in their contact.
 Based on the above fact the resins are classified into two
types
Cation Exchange Resin (Rh+) – Strongly acidic (SO3-
H+) and weakly acidic (COO-H+) cation exchange resins
Anion Exchange resin (ROH-) – Strongly basic
(R4N+OH-) and weakly basic (RNH2+OH-) anion exchange
resins
Structure
 The Cation Exchange Resins are mainly Styrene
Divinyl Benzene Copolymers which on Sulponation
or Carboxylation become capable to exchange their
hydrogen ions with the cations in water.
 The Anion Exchange Resins are mainly Styrene
Divinyl Benzene or Amine Formaldehyde
Copolymers which conatin amino or quaternary
ammonium or quaternary phosponium or tertiary
sulphonium group as integral part of resin matrix. These
after treatment with dilute NaOH solution, becomes
capable to exchange their OH- anions with anions in
water.
Structure of Resin
Cation exchange resin Anion exchange resin

R = CH3

34
 Ion exchange purifier or softener

Hard
water

Gravel
Cation exchange Resin Anion exchange Resin bed

Injector
Injector

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

Soft water
35
Process Description
Step-1 (Passing through Cation Exchange Resin)
 The hard water is passed through cation exchange
column which removes all the cations like Ca+2, Mg+2
etc from it and equivalent amount of H+ ions are
released from this column into water.
2RH+ + Ca2+ (hard water) R2Ca2+ + 2 H+
2RH+ + Mg2+ (hard water) R2Mg2+ + 2 H+
Continued…
Step-2 (Passing through Anion Exchange Resin)
 The hard water is passed through anion exchange
column, which removes all the anions like SO42-, Cl- etc.
present in the water and equivalent amount of OH- ions
are released from this column to water.
2ROH- + SO42- (hard water) R2SO42+ + 2 OH-
2ROH- + Cl- (hard water) R2Cl- + 2 OH-

 H+ and OH- ions released combine to produce water

molecule.
H+ + OH- H 2O
 Regeneration
Regeneration of Cation Exchange Resin
R2Ca2+ + 2H+ (dil. HCl (or) H2SO4) 2 RH+ + Ca2+ (CaCl2, washings)

The column is washed with deionised water and washing (Ca+2 ,

Mg+2 and SO4-2 or Cl- ions) is passed to sink or drain.
Regeneration of Cation Exchange Resin
R2SO42- + 2OH- (dil. NaOH) 2 ROH- + SO42- (Na2SO4, washings)

The column is washed with deionised water and washing (Na+ and
SO4-2 or Cl- ions) is passed to sink or drain.
Advantages & Disadvantages
Advantages
 It is used to soften highly acidic or highly alkaline
waters.
 It provides water of very low hardness (nearly 2ppm).

Disadvantages
 Equipment is costly.
 Expensive chemicals are required.
 It water is turbid then the output (soft water) is
reduced.Turbidity of raw water must be below 10 ppm.
 Phosphate Treatment
 The zeolite and ion-exchange process removes most of the
Ca and Mg from water. The traces of these impurities in
water may cause scale formation in boiler.
 In high pressure boiler, scale formation can be avoided by
addition of phosphate to boiling water. The soluble
phosphates are:
Disodium hydrogen phosphate : Na2HPO4
Sodium dihydrogen phosphate : Na2H2PO4
Trisodium phosphate : Na3PO4
Sodium ortho phosphate : Na2P2O7
 Phosphate Treatment
 These sodium phosphate reacts with calcium and
magnesium impurities to convert them to their insoluble
phosphate as Ca(PO4)2 which are deposited and removed
as sludge.
 This avoids scale formation.

3 CaSO4 + 2Na3PO4 → Ca3(PO4)2 + 3Na2SO4

3 CaCO3 + 2Na2PO4 → Ca3(PO4)2 + Na2CO3