WATER

TREATMENT
 Softening methods
• Two process
• 1. Internal Treatment
• 2. External Treatment
Internal treatment (Sequestration)
• In this process, an ion is prohibited to exhibit
its original character by complexing or
converting into other more soluble salt by
adding appropriate agent.
• An internal treatment is accomplished by
adding a proper chemical to the boiler water
either:
• 1. To precipitate and can remove by blow
down operation
• 2. To convert into dissolved form of water
Phosphate Conditioning
Carbonate conditioning
Calgon conditioning
External treatment of water softening methods

1. Lime soda
a) Batch process
b) continuous process
- Cold lime-soda
- Hot lime-soda
2. Zeolite (permutit) process

3. Ion-exchange and Mixed bed ion-exchange process

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 Lime – Soda Process
a. Reaction of permanent calcium:
Ca2+ + Na2CO3 CaCO3 + 2Na+

b. Reactions of permanent magnesium:

Mg2+ + Ca(OH)2 Ca2+ + Mg(OH)2

Ca2+ + Na2CO3 CaCO3 + 2Na+

c. Reaction of HCO3- (ex-Na2CO3):

2 HCO3- + Ca(OH)2 CaCO3 + H2O + CO32-

d. Reaction of Temporary calcium Ca(HCO3)2 :

Ca(HCO3)2 + Ca(OH)2 2 CaCO3 + 2 H2O

e. Reaction of Temporary Magnesium Mg(HCO3)2 :

Mg(HCO3)2 + 2 Ca(OH)2 2 CaCO3 + 2 H2O + Mg(OH)2

8
 Lime – Soda Process
f. Reaction of CO2:
CO2 + Ca(OH)2 CaCO3 + H2O
g. Reaction of H+:

2 H+ + Ca(OH)2 Ca2+ + 2 H2O

Ca2+ + Na2CO3 CaCO3 + 2 Na+

h. Reactions of coagulants:
i) Reaction of FeSO4:
Fe2+ + Ca(OH)2 Fe(OH)2 + Ca2+
Fe(OH)2 + H2O + O2 2 Fe(OH)3
Ca2+ + Na2CO3 CaCO3 + 2 Na
ii) Reactions of Aluminium sulphate (Al2(SO4)3 :

2 Al3+ + 3 Ca(OH)2 2 Al(OH)3 + 3 Ca2+

3 Ca2+ + 3 Na2CO3 3 CaCO3 + 6 Na+

iii) Reactions of sodium aluminate (NaAlO2):

NaAlO2 + H2O Al(OH)3 + NaOH

A. Lime [Ca(OH)2]requirement :
{
74 Temp. Ca2+ + 2 temp. Mg2+ + Perm(Mg2+ + Al3+ + Fe2+) + CO2 + H+ + HCO3-
100 {
- NaAlO2

{
B. Soda[Na2CO3] requirement : {
100
106 Perm. (Ca2+ + Mg2+ Fe2+ + Al3+) + H+ - HCO3-
10
 Example
1. Calculate the amount of lime and soda required for softening 50,000 liters of hard water
containing Ca(HCO3)2= 81 ppm, Mg(HCO3)2 = 73 ppm, CaCl2 = 222 ppm, MgSO4= 180 ppm,
Na2SO4 = 15 ppm, NaCl = 165 ppm, and Fe2O3 = 25 ppm.
Sol: No hardness is caused by Na2SO4, NaCl, and Fe2O3 (insoluble solid), so they should
not be included in the calculations.

Conversion to CaCO3 equivalents

Constituent ppm Multiplication factor CaCO3 equivalents
(M.Wt. of CaCO3/
M.Wt. of Constituent)
Ca(HCO3)2 81 100/162 81 x 100/162 = 50 ppm
Mg(HCO3)2 73 100/146 73 x 100/146 = 50 ppm
CaCl2 222 100/111 222 x 100/111 = 200 ppm
MgSO4 180 100/120 180 x 100/120= 150 ppm
Lime required for softening 50,000 L of Water

mg = 10-6 Kg

Soda required for softening 50,000 L of Water

2. Calculate the quantity of lime and soda required for
softening 50,000 litre of water containing the following
salt per litre Ca(HCO3) 2 = 8.1 mg ; Mg(HCO3)2 = 7.5 mg ;
CaSO4 = 13.6 mg ; MgSO4 = 12.0 mg ; MgCl2 = 2.0 mg ; and
NaCl = 4.7 mg. Purity of lime is 85%, soda is 92 %

Solution:
Step 1: Calculate CaCO3 equivalents
Constituent ppm Multiplication factor CaCO3 equivalents
(M.Wt. of CaCO3/
M.Wt. of Constituent)
Ca(HCO3)2 8.1 100/162 8.1 x 100/162 = 5 ppm
Mg(HCO3)2 7.5 100/146 7.5 x 100/146 = 5.13 ppm
CaSO4 13.6 100/136 13.6 x 100/136 = 10 ppm
MgSO4 12.0 100/120 12.0 x 100/120= 10 ppm
MgCl2 2.0 100/95 2.0 x 100/95 = 2.1 ppm
• Step 2:
Lime req per liter=74/100 (Temp.ca +2X
Temp.Mg + Perm. Mg + CO2 + H+)

=74/100 ( 5+ 2 X 5.13 +10 +2.1) X Vol of water

= 1012320 mg = 1.012 Kg
1.012 x100/85 = 1.19 kg

Soda req =106/100(Perm. Ca + Perm. Mg +HCL +H2SO4

-HCO3)
=106/100 (10 +10 +2.1) x vol of water

=Purity
1.171 Cal: x100 /92 = 1.27 kg
100 % (100/100)= C kg
85/100 = C X 100/85
3. Explain with chemical equations and calculate the amount of lime and soda
needed for softening 1,00,000 litres of water containing the following: HCl = 7.3
mg/L, Al2(SO4)3 = 34.2 mg/L ; MgCl2 = 9.5 mg/L ; NaCl = 29.25 mg/L

Purity of lime is 90% and that of soda 98%. 10% of chemicals are to be used in
excess in order to complete the reaction quickly.
Solution:
Calculate CaCO3 equivalents
Constituent ppm Multiplication factor CaCO3 equivalents
(M.Wt. of CaCO3/
M.Wt. of Constituent)

HCl 7.3 100/36.5 7.3 x 100/36.5 = 20 ppm

Al2(SO4)3 34.2 100/342 34.2 x 100/342 = 10 ppm
MgCl2 9.5 100/95 9.5 x 100/95 = 10 ppm
Lime requirement= 74/100[1/2 HCl+ 3/2 Al2(SO4)3+ MgCl2]x
volume of water x100/% 2 H+ + Ca(OH) Ca2+ + 2 H O
2 2

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

purity
= 74/100 (20/2+ 10 X3 + 10)
= 74/100 (10 + 30 + 10 )
= 37 x 1,00,000 x 100/90 mg
= 4.11 Kg
∴Lime required (using 10% excess) = 4.11 x110/100= 4.521 Kg
Soda requirement= 106/100[1/2HCl + 3/2Al2(SO4)3+ MgCl2]x
volume of water x100/%purity
= 106/100(10+ 30 +10) x 1,00,000 x 100/98
= 53 X 1,00,000 X 100/98 mg
= 5.4 Kg
∴Soda required (using 10% excess) = 5.4 x 110/100= 5.94 Kg.
Lime –Soda process equipment

17
Lime –Soda process equipment
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
Advantages of hot lime-soda process:
oThe precipitation reactions are almost
complete
o Reactions takes place faster
o Sludge settles down rapidly; No
coagulant is needed
o Dissolved gases (which may cause
corrosion) are removed
o Viscosity of soft water is lower, hence
filtered easily
o Residual hardness (50 PPM) is low
compared to cold lime-soda process
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 Advantages & disadvantages of lime-soda process:

Advantages of Lime – soda process:

o Economical
o Process improves the corrosion resistance of water
o Mineral content of water is reduced
o pH of water raises thus reducing content of pathogenic bacteria
o No skilled labour is required

Disadvantages of Lime – soda process:

o Huge amount of sludge is formed and its disposal is difficult
o Due to residual hardness, water is not suitable for high pressure
boilers

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 Permutit or Zeolite Process
o Zeolite is hydrated sodium aluminium silicate having a general formula,
Na2OAl2O3.xSiO2.yH2O.
o It exchanges Na+ ions for Ca2+ and Mg2+ ions.
o Common Zeolite is Na2OAl2O3.3SiO2.2H2O known as natrolith.
o Other gluconites, green sand (iron potassium phyllosilicate with
characteristic green colour, a mineral containing Glauconite)etc. are used
for water softening.
o Artificial zeolite used for water softening is Permutit.
o These are porous, glassy particles having higher softening capacity
compared to green sand.
o They are prepared by heating china clay (hydrated aluminium 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)
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 Zeolite process
o Method of softening:

Na2Ze + Ca(HCO3)2 2 NaHCO3 + CaZe

Na2Ze + Mg(HCO3)2 2 NaHCO3 + MgZe
Na2Ze + CaSO4 2 Na2SO4 + CaZe
Na2Ze + CaCl2 2 NaCl + CaZe

o Regeneration of Zeolite:

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

Brine solution

21
Zeolite process equipment diagram
 Zeolite Process

Advantages:
o Residual hardness of water is about 10 ppm only
o Equipment is small and easy to handle
o Time required for softening of water is small
o No sludge formation and the process is clean
o Zeolite can be regenerated easily using brine solution
o Any type of hardness can be removed without any modifications to
the process
Disadvantages:
o Coloured water or water containing suspended impurities cannot be
used without filtration
o Water containing acidic pH cannot be used for softening since acid will
destroy zeolite.

23
 Ion-Exchange Process

o Ion-exchange resins are cross linked long chain polymers with

microporous structure.
o Cation exchange resins will exchange cations with H+.
o Anion exchange resins will exchange anions with OH-.
o Functional groups present are responsible for ion-exchange
properties.
o Acidic functional groups (-COOH, -SO3H etc.) exchange H+ for
cations &
o Basic functional groups (-NH2, =NH etc.) exchange OH- for anions.

24
 Ion-Exchange Process

A. Cation-exchange Resins(RH+):

- Styrene divinyl benzene copolymers

- When sulphonated, capable of exchange H+

25
 Ion Exchange Process
B. Anion-exchange resins (R’OH):
- Styrene divinyl benzene copolymers or amine formaldehyde copolymers with NH 2,
QN+, QP+, QS+, groups.
- On alkali treatment, capable of exchange of OH-

Anion Exchange resin 26

 Ion Exchange Process

The Process of Ion-exchange is:

2 RH+ + Ca2+/Mg2+ R2Ca2+/R2Mg2+ + 2 H+ (Cation exchange)

R’OH- + Cl- R’+ Cl- + OH- (anion exchange)

2 R’OH- + SO42- R’2 SO42- + 2 OH- (anion exchange)

2 R’OH- + CO32- R’2 CO32- + 2 OH- (anion exchange)

Finally,
H+ + OH- H2O

Regeneration of exhausted resins:

Saturated resins are regenerated by treating with strong mineral acid or alkali respectively
R2Ca2+/R2Mg2+ + 2H+ 2 RH+ + Ca2+/Mg2+ (Strong acid)
(washings)
R’2 SO42- + 2 OH- 2 R’OH- + SO42- (Strong base) 27
 Ion-exchange process

Note: Hard water should be first passed through the cation exchanger and then
Anion exchanger to avoid hydroxides of Ca2+ and Mg2+ getting formed
28
29
 Mixed bed ion-exchanger

o Contains intimate mixture of cation and anion exchangers

o Water is in contact for a no. of times with the two exchangers alternatively
Anion exchanger
(low density)

NaOH

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

Backwash
water Comp.
air
Raw water Washings to
Deminaralised
inlet sink30
water
Advantages & Disadvantages of ion-exchange process
o Advantages:
- Can be used for highly acid and highly alkaline water
- Residual hardness of water is as low as 2 ppm.
- Very good for treating water for high pressure boilers

o Disadvantages:
- Expensive equipment and chemicals
- Turbidity of water should be < 10 ppm. Otherwise output will
reduce; turbidity needs to be coagulated before treatment.
- Needs skilled labour

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 Specifications of different materials in drinking water (ICMR and WHO)
S.No. Parameter/Material WHO Standards/ppm ICMR/BIS
Standards/ppm
1 Colour Clear Clear
2 Odour Pleasant Pleasant
3 Turbidity 2.5 2.5
4 pH 6.0 – 8.5 6.0 – 8.5
5 TDS 300 500
6 Total Hardness as CaCO3 200 300

7 Calcium 75 75
8 Chlorides 200 200
9 Sulphates 200 200
10 Fluoride 0.5 1.0
11 Mercury 0.006 0.001
12 Cadmium 0.003 0.01
13 Arsenic 0.01 0.02
14 Chromium as hexavalent 0.01 0.1

15 Lead 0.01 0.01

16 E.Coli No colony Should be present No colony Should be
in 100 mL water present in 100 mL
water
 Water treatment for municipal supply
Removes dirt and other
particles suspended in
water. Alum and other
chemicals are added for
coagulation through floc
Lakes/Reservoirs/
Rivers Storage tanks Coagulation

Multilayer filtration using Heavy particles (floc) settle to

sand, gravel and charcoal the bottom and clear water goes
for filtration
Flocculation &
Filtration Sedimentation Clarification

Calculated amount of
chlorine is added
Storage in
Disinfection closed Supply
containers through
pipelines
Purification of Treatment of water for Municipal Supply
1. Screening
2. Aeration
3. Sedimentation and coagulation
4. Filtration
5. Sterilisation and disinfection
6. Storage and distribution

Flow chart:
Screening
Floating matter in the water can be retained by passing the water through
Screens having a large number of holes

Aeration
Promotes taste and odour by exchange of gases between the water and atmosphere
• to add or increase the content of oxygen in water
• to remove CO2 , H2S and other volatile substance causing bad taste and odor in water
• to remove the impurities like Fe and Mn (which are precipitate as their respective hydroxides)

Sedimentation with Coagulation

Suspended and collodial impurities are separated in a sedimentation tank by gravitation
Fine particles take many hours or days to settle down. Coagulation are added
Salts of aluminium (alum, sodium aluminate) and salts of iron (ferrous sulphate, ferric sulphate,
ferric chloride)
36
Filtration
Removal of collodial and suspended matter (remaining after sedimentation)
and bacteria by passsing the water through filter beds containing fine sand, coarse
sand and gravel Types: Gravity type or pressure type

Sterilization and Disinfection

Harmful bacteria are destroyed to make the water safe for drinking is called disinfection
Chemical used – Disinfectants

Boiling: When the water is boiled for 15 - 20 minutes, the harmful bacteria are killed

Disadvantages:
i. Boiling changes taste of water
ii. It is impractical for large treatment plants
 Removal of micro-organisms

• By adding bleaching powder (hypo-chlorination)

– About 1kg of bleaching powder per 1000 kiloliters of water is mixed

– Produces hypochlorous acid (powerful germicide)

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl

Germs + HOCl Germs are killed

Disadvantage

Introduces Calcium in water, thereby making it more hard

excess of it gives a bad taste and smell to treated water

38
• Chlorination
– Chlorine either gas or in concentrated solution form produces hypochlorous
acid, which is a powerful germicide

Cl2 + H2O HCl + HOCl

Germs + HOCl Germs are killed

• Factors affecting efficiency of chlorine

– Number of micro-organism destroyed by chlorine per unit time is proportional
to the number of micro-organism alive.
– The rate of reaction with enzymes increases with temperature
– pH values between 5-6.5, less contact time is enough

• Advantage
– (i) Effective and economical (ii) used low as well as high temp (iii) most ideal
• Disadvantage
– (i) should not exceed 0.1 – 0.2 ppm (ii) less effective in higher pH values (iii)
excess chlorine produces unpleasant taste and odour.
39
 Break point chlorination or free-residual chlorination

Involves addition of sufficient amount of chlorine to oxidize organic matters,

reducing substances, free ammonia leaving behind free chlorine to kill bacteria.
•Removes color of water – no organic matter
•Removes odour and taste from the water

The addition of chlorine at the dip or break is called break-point chlorination 40

Chloramine (ClNH2)
Chlorine is not stable in water. Hence it is sometimes mixed with ammonia in the
ratio 2:1 by volume to form stable compond called chloramines.

Cl2 + NH3 ClNH2 + HCl

(Chloroamine)

ClNH2 + H2O HOCl + NH3

(Disinfectant)
HOCl inactivates the enzymes responsible for Bacteria and are killed

Disinfection by ozone
Ozone is an unstable isotope of oxygen. It contains three atoms of oxygen and
one easily breaks away. This produces nascent oxygen which is a powerful
Disinfectant. It does not produce any taste of adour

Electric
3O2 Discharge 2O3

O3 O2 + [O ]
.
Nascent oxygen
Domestic water purification system
Candles
 Activated Carbon Filtration
• Activated carbon filters are generally used in the process of
removing organic compounds and/or extracting free chlorine from
water.
• Coconut shells and coal (anthracite or bituminous) are both
organic sources of activated carbon.

(SiO2)
Working Mechanism in the fabrication of Activated Carbon
• Carbon forms when an organic source is burned in an environment without
oxygen. This process leaves only about 30% of the organic mass intact, driving
off heavy organic molecules.

• Prior to being used for water treatment, the organic mass must then be
"activated by either Steam Activation (800°C-1000°C) or Chemical Activation (a
powerful dehydrating agent like phosphoric acid (P2O5) or zinc chloride (ZnCl2)."

• The process of activation opens up the carbon’s massive number of pores and
further drives off unwanted molecules. The open pores are what allow the
carbon to capture contaminants, through adsorption. 

• The rate of adsorption for a surface area of a just one pound (0.45
kg) of Activated Carbon is equal to 60-150 acres!
 Candle Filtration
The Candle Filters are, like all pressure filters, operating on a batch cycle and may
be seen in process lines handling titanium dioxide, flue gas, brine clarification, red
mud, china clay, fine chemicals and many other applications that require efficient
low moisture cake filtration or high degree of polishing.

The Candle Filter consists of three

major components:
• The vessel
• The filtering elements
• The cake discharge mechanism
• Candle Filters are very well suited for
handling flammable, toxic and
corrosive materials. 
Ceramic candle filters are simple devices made out of clay
and used to  filter drinking water in order to removes turbidity,
suspended materials and pathogens.
Removal takes place by physical process such as mechanical trapping and
adsorption on the ceramic candles, which have micro-scale pores.
 Candle Filtration
• Advantages
• Excellent cake discharge.
• Adapts readily to slurry thickening.
• Minimum floor space.
• Mechanically simple since there are no complex sealing
glands or bearings.
• Disadvantages
• High headroom is required for dismantling the filtering
elements.
• The emptying of the vessel in between cake filtration, washing
and drying requires close monitoring of the pressure inside
the vessel to ensure that the cake holds on to the candles.
 Disinfection Methods
Disinfection methods used for disinfecting water for
drinking purpose are

- Ultrafiltration
- UV treatment
- Ozonolysis
- Reverse Osmosis
 Water purification by Filtration process

The green arrow indicates that the particle is small enough to pass through
the filter, whereas the deflected orange arrow indicates that the filter blocks
the particle from passing through the filter.
 Different filtration processes
A. Ultrafiltration:

o An ultrafiltration filter has a pore size around 0.01 micron.

o A microfiltration filter has a pore size around 0.1 micron, so when water undergoes microfiltration, many
microorganisms are removed, but viruses remain in the water. Ultrafiltration would remove these larger
particles, and may remove some viruses.
o Neither microfiltration nor ultrafiltration can remove dissolved substances unless they are first adsorbed
(with activated carbon) or coagulated (with alum or iron salts).

B. Nanofiltration
o A nanofiltration filter has a pore size around 0.001 micron.
o Nanofiltration removes most organic molecules, nearly all viruses, most of the natural organic matter and
a range of salts.
o Nanofiltration removes divalent ions, which make water hard, so nanofiltration is often used to
soften hard water.

C. Reverse osmosis
o Reverse osmosis filters have a pore size around 0.0001 micron.
o After water passes through a reverse osmosis filter, it is essentially pure water. In addition to removing all
organic molecules and viruses, reverse osmosis also removes most minerals that are present in the water.
o Reverse osmosis removes monovalent ions, which means that it desalinates the water.
Reverse Osmosis
oWhen two solutions of unequal concentrations are
separated by a Semipermeable membrane, solvent will
flow from lower conc. to higher conc. due to osmotic
pressure

oThis phenomenon can be reversed by making the

solvent to flow in the opposite direction by applying
hydrostatic pressure on the concentrated side (Reverse
Osmosis)

oIn reverse osmosis, pressure of 15-40 kg/cm 2 is

applied on the contaminated water compartment.

oThe water gets forced through the semipermeable

membrane leaving behind the dissolved solids.

oThus water is separated from the contaminants rather

than removing contaminants from water.

oBoth ionic and non-ionic impurities as well as colloidal

impurities are left behind.

oThis process is also called as “Super-filtration” or

“Hyper-filtration”
 Advantages of Reverse Osmosis

o Advantage is in removing ionic, non-ionic, colloidal and high molecular

wt. organic matter.

o It removes colloidal silica (which is not removed during demineralisation)

o Cost is only the replacement cost of membranes (life is 2 years)

o Membrane replacement is fast and hence uninterrupted water supply can

be ensured

o Because of the above reasons this process is being adopted for

converting sea water into potable water and for high pressure boilers.

o It can be used as desalination process for removing salt from sea water.

54
 Desalination of brackish water

o Water containing dissolved salts with a peculiar salty (brackish) taste is brackish water
o The process of removing common salt from water is desalination

o Electrodialysis consists of a large container with two membrane separators, one

permeable to positive ions and the other permeable to negative ions.

o In the outer compartments anode and cathode are arranged to pass DC Voltage.

o When DC voltage/current is passed through the cell, Na+ will move towards cathode
and Cl- will move towards anode through the membrane.

o Hence, the concentration of salt decreases in the middle compartment and increases
in the side compartments.

o Water from the middle compartment is collected and this water is desalinated water.

55
 Electrodialysis diagram

For efficient separation, ion-selective membranes are used which selectively allow
cations or anions to pass through them.
56
Electrodialysis cell

o Electrodialysis cell consists of

Large number of pairs of
rigid Plastic membranes.

o Saline water at a pressure of

5-6 kg/cm2 is passed
through the membrane pairs.

o DC current is applied
perpendicular to the direction
of water flow.

Advantages are:

1. Unit is compact and

installation is economical

2. Best suited if electricity is

available.
57