UNIT - I

WATER TREATMENT
LIME SODA PROCESS
 LIME SODA PROCESS
• PRINCIPLE :- The principle involved in this process
the soluble calcium and magnesium salts in water
are chemically converted into insoluble compounds,
by adding calculated amount of lime [ Ca(OH)2 ] and
• soda[ Na2CO3] .
• Calcium carbonate [ CaCO3] and magnesium
hydroxide [ Mg(OH)2] , so precipitated, are filtered
off.
 Cold Lime –Soda Process

• In this method-calculated amount of chemical

(lime and soda) are mixed with water at room
temperature. The precipitates formed are
finely divided, so they do not settle down
easily and can’t be filtered easily. So it is
essential to add small amounts of Coagulants
(like alum, aluminum sulphate, sodium
acuminate etc.).
 Cold Lime –Soda Process
• Which hydrolyze to flocculent (precipitate),
gelatinous precipitate of aluminum hydroxide
and entraps the fine precipitates.
• Cold L-S process provides water, containing a
residual hardness of 50 to 60 ppm.
 Cold Lime –Soda Process
•  Raw water and calculated amount of chemicals
(lime + soda + coagulant) are fed on top into the
inner vertical circular chamber, fitted with a vertical
rotating shaft varying a number of paddles.
•  As the raw water and chemicals flow down,
there is a vigorous stirring and continuous mixing, so
softening of water takes place.
•  The heavy sludge settles down in the outer
chamber by the time and softened water reaches up.
 Cold Lime –Soda Process
•  The softened water then passes through a
filtering media to ensure complete removal of
sludge.
•  Filtered soft water finally flows out
continuously through the outlet at the top.
•  Sludge settings at the bottom of the outer
chamber are drawn of occasionally.
 Hot Lime –Soda Process

• In this process water is treated with required

chemicals at a temperature of 80 o c to 150 oC.
• Hot L-S process provides water, containing a
residua hardness of 15 –30 ppm. The softener
consists of following three parts-
• Reaction Tank – The tank has three separate inlets
and third for superheated steam. After their entry
they are mixed. The reaction starts and get
completed in the reaction tank.
 Hot Lime –Soda Process

• Conical Sedimentation Tank – from reaction

tank the reactants come in this tank and the
sludge settles down.
• Sand filter – It has layer of lime and coarse
sand which works as filter and makes its
possible to completely remove the sludge
from the softened water.
 Hot Lime –Soda Process

• Processing -
• In Hot L-S process reaction proceeds faster.
• No coagulants are needed because sludge
and precipitates settle easily.
• Some dissolved gases like CO2 also driven
out of the water.
 Hot Lime –Soda Process

• Viscosity of softened water is lower, so

filtration of water becomes much easier.
• The softening capacity of hot process is many
times higher than that of the cold process.
 Advantages of Lime –soda Process

• Lime Soda process is very economical.

• It removes not only hardness causing salts but also
minerals.
• Due to alkaline nature of treated water,
pathogenic bacteria’s in water are reduced.
• Iron and manganese are also removed.
• Treated water is alkaline and therefore less
corrosive.
 Disadvantages of Lime –soda Process
• For efficient and economical softening,
careful operation and skilled supervision is
required.
• Disposal of large amounts of sludge poses
a problem.
• This can remove hardness only upto 15 ppm,
which is not good for boilers.
 Numerical (Lime-Soda)
Q.1 A water sample contains 84 mg/l CaSO4 and
50 mg/l Mg(HCO3)2. Find out the temporary
hardness and the amount of lime and soda
required.
 Numerical (Lime-Soda)
• Q2 – A sample of water was analysed and
found to contain temporary magnisium
hardness 25 mg/l; permanent magnisium
chloride hardness =15 mg/l; permanent
calcium sulphate hardness =20 mg/l and SiO2
=300 mg/l.
Calculate the lime soda required for 30,000 litre
of hard water.
 Numerical (Lime-Soda)
Q3. A sample of water contains the following
impurities:
• Mg(HCO3)4 =73 mg/l
• CaCl2=222mg/l
• MgSO4=120 mg/l
• FeSO4.7H2O=69.5mg
• Calculate the amount of lime and soda
required per litre of water.
 Numerical (Lime-Soda)
Q.4 Calculate the amounts of lime (91% pure)
and soda (97.2%pure) required for softening
one million litre of water containing:
• Ca(HCO3)2= 30.5ppm
• Mg(HCO3)2=35.5ppm
• CaSO4 = 240.0 ppm
• CaCl2 =25.0 ppm
Also calculate the temporary and permanent hardness
of water sample.
 Numerical (Lime-Soda)
Q.5 A turbid hard water using FeSO4. 7H2O as
coagulant at the rate of 278 ppm, give the
following results on analysis:
Ca(HCO3)2= 162ppm; CaSO4= 136 ppm
Mg(HCO3)2= 146 ppm; CaCl2 =111 ppm
MgSO4= 120 ppm; MgCl2= 95 ppm.
Calculate lime and soda needed for softening 1,00,000
litres of the water sample.
 Lime-Soda Numerical
Q6 Explain with equations and calculates the
quantity of quick lime and soda ash required
to soften 10,000 litre of water containing :
i) 219 ppm of magnisium bicarbonate and 234
ppm of sodium chloride
ii)36 ppm of Mg2+ and 18.3 ppm of HCO3-
iii)1.5 ppm of the free acids, 144 ppm of
sulphate ions and 71 ppm of chloride ions.
 Zeolite Process
Or
Permutit Process
• The word zeolite is derived from Greek word –
Zein + lithos means
“Boiling Stones”
• Chemical structure of sodium zeolite may be
represented by-

Na2O.Al2O3.XSiO2.YH2O

Where x = 2-10 & y = 2 - 6

• Zeolite is hydrated sodium alumino silicate.

• Capable of exchanging reversibly its sodium ions

for hardness- producing ions in water.
• Zeolites are also known as permutits.

• Zeolites are of two types-

• Natural zeolites
• Synthetic zeolites
• Natural zeolite-
They are non porous.

EX.- Natural Zeolites

• Synthetic zeolite-
They are porous.
• Process- hard water is percolated at a
specified rate through a bed of zeolite, kept in
a cylinder.

• Hardness causing ions are retained by the

zeolite as CaZe & MgZe, while outgoing water
contains sodium salts.
• Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3

• Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

• Na2Ze + CaCl2 CaZe +2NaCl

• Na2Ze + MgCl2 MgZe + 2NaCl

 Regeneration
• When the zeolite bed is exhausted, it can be
regenerated & reused.

• Exhausted zeolite is reclaimed by treating the

bed with a brine (10%NaCl) solution.
CaZe + 2NaCl Na2Ze + CaCl2
Exhausted Brine Reclaimed Zeolite washings
zeolite
• The washings are ready to drain & the
regenerated zeolite bed thus-obtained as used
again for softening purpose.
• Water containing Fe2+ & Mn2+ ions should be
avoided because Fe2+ will form their zeolite
which can’t be easily regenerated.

• Mineral acids if present in water destroy the

zeolite bed.
 Limitations
• Water with turbidity should not be used as
pores of zeolite get clogged.

• PH of water should not be too high or too low

as its effects zeolites.

• Hot water can’t be used as it dissolves zeolite.

 Advantages
• Hardness is completely removed.

• Equipment used is compact & occupies less

space.

• There is no danger of sludge formation.

• It is quit clean method.

• It requires less time for softening.

Zeolite process Lime-soda process
Water with ~ zero hardness Water with 15 to 50 ppm
is produced. hardness is produced.

Capital cost is higher . Capital cost is lower.

Operation cost lower Operation cost is higher

because exhausted zeolite is because lime & soda are
regenerated. consumed.
Plantis compact & Plant occupies more space.
occupies less space.
Process is free from any
Can not be used for hot such limitations.
water, acidic or turbid water.

No problem of sludge There may be problem after

formation. precipitation.
Salt causing temporary Temporary hardness is
hardness are converted into completely removed in the
NaHCO3 which is present in form of insoluble CaCO3 &
soft water. Mg(OH)2.

Itdoes not involve any This involves all problems

secondary operation like associated with setting
Salt, lime, coagulation & filter
coagulation,filtration.
 Questions
• Draw neat and labeled diagram of Zeolite
process.

• Write short note on Regeneration of zeolite.

• Write differences in lime-soda & zeolite

process.
 Ion exchange
or
De - ionization process
1.

Numerical (zeolite)
The hardness of 10,000 litres of a sample of water was
removed by passing it through a zeolite softener . The
zeolite softener then required 200 litres of sodium
chloride solution containing 150gm/litre of NaCl for
regeneration. Find the hardness of water sample.
Numerical( Zeolite)
• An exhausted zeolite softener was
regenerated by passing 200 litres of NaCl
soln., having a strength of 0.2 gm/l of NaCl.
Find the total volume of water that can be
softened by this zeolite softener, if the
hardness of water is 350 clark.
 ION EXCHANGE METHOD

• Cation Exchange Resin

• Anion Exchange Resin
• Regeneration
• Advantage
• Disadvantage
• Questions
 Ion exchange resins
• Water insoluble
• Cross linked
• Micro porous
• Long chain organic polymer
• High ion exchanging property
• the functional groups attached to the chains
are responsible for the ion exchange.
• Resins containing acidic functional groups
(-COOH, -SO3H).are capable of exchanging
their H+ ions with other cations.
Cation Exchange Resin

+
H H +
_

Sulphonate form
H++ + H +
H
 Cation exchange resins (RH ) +

• Are mainly styrene divinyl benzene co-

polymers.

• Which on sulphonation or carboxylation

become capable to exchange their hydrogen
ions with the cations in the water.
 Anion exchange resins (R’OH-)
• Are styrene divinyl benzene or amine
formaldehyde co-polymers.
• Which contain amino groups as an integral
part of the resin.
• These after treatment with dil NaOH solution
become capable to exchange their OH- anions
with other anions of water.
Anion Exchange Resin

OH-

OH- OH-
ION- EXCHANGE METHOD
 Process
• The hard water is first pass through cation
exchange column, which removes all the cations
like Ca 2+,Mg 2+ etc.

• And equivalent amount of H+ ions are released

from this column.
• 2RH+ + Ca2+ R2Ca2+ + H+

• 2RH+ + Mg2+ R2Mg2+ + H+

• The hard water is now passed into the anion
exchange column.

• Which removes all the anions like SO42-,Cl- .

• Equivalent amount of OH- ions are released from

this column.
• R’OH- + Cl- R’Cl- + OH-

• 2R’OH- + SO42- R2’SO42- + 2OH-

• H + & OH- ions get combined to produce water
molecule.

• H+ + OH- H2O
• Thus , the water coming out from the
exchanger is free from cations as well as
anions .

• Ion free water is known as De- ionized water

or De- mineralized water.
 Regeneration

• After long use resins are exhausted.

 •The exhausted cation exchange
column is regenerated by passing a
solution of dil HCl or dil H2SO4.

• R2Ca2+ +2H+ 2RH+ + Ca2+ (washing)

• The exhausted anion exchange column is
regenerated by passing a solution of dil NaOH.

• R2SO42- + 2OH- 2ROH- + SO42-(washing)

 Advantages
• The process can be used to soften highly
acidic or alkaline water.

• It produces water of very low hardness

(~2ppm).
 Disadvantages
• The equipment is costly & more expensive
chemicals are needed.

• If water contain turbidity ,then the output of

the process is reduced.
 QUESTIONS
(1) What is the formula of zeolite ?

(2)What is brine ?

(3) How mineral acid destroy

the zeolite bed ?
 Questions
• Explain demineralization process of water
softening.

• Write down the names of polymers used.

• Draw neat diagram of process.

 Carbonate Conditioning
• It can be done in low – pressure boilers.
• Scale formation can be avoided by adding-
Na2CO3

• Calcium sulphate is converted into calcium carbonate.

CaSO4 + Na2CO3 CaCO3 + Na2SO4
 BOILER PROBLEMS

• Scale
• Sludge
• Priming
• Foaming
• Carry Over
• Caustic Embrittlement
• Boiler Corrosion
 Sludge and Scale formation in boiler

• In boilers water evaporates.

• Concentration of dissolved salts increases.

• At saturation point dissolved salts (ppt) thrown out

in to inner walls of boilers.
 Sludge and Scale
Precipitation

• If ppt is loose, slimy,soft If ppt is hard, adhering

Sludge Scale
 Sludge
• Sludge is a soft, loose, slimy precipitates formed within
the boiler.

• Sludge can easily be scrapped off with the help of wire

brush.

• Sludge generally forms colder portions of boilers .

• Ex. MgCl2, MgCO3,CaCl2, MgSO4.(insoluble)

 Disadvantages of sludge
• They waste the amount of heat.

• They disturbs the boiler’s working.

• They causes choking of pipes connections ,

plug opening.

• They also attach with scale & make strong

precipitation.
 Prevention of sludge
• By using well softened water.

• By blow down operation .

 scale
• Scale are hard deposits.

• They attach inner walls of boilers.

• Scales are difficult to remove.

• They cann’t remove even with help of

hammer & chiesl.
 Scales may be formed due to-

1) Decomposition of calcium bicarbonate-

• Ca(HCO3)2 CaCO + H O + CO2
Soft3Scale 2

• CaCO3 forms in low pressure boilers .

• But in high pressure boilers , CaCO3 is soluble

CaCO3 + H20 Ca(OH)2 + CO2

Soluble
• 2) Deposition of calcium sulphate-
• The solubility of calcium sulphate in water decreases
with increase in temperature.

• CaSO4 is soluble in cold water.

• But completely insoluble in super heated water.

• CaSO4 is a hard scale formed in hotter part.
3) Hydrolysis of magnesium salts-
Mg salts on hydrolysis get precipitate in Mg(OH)2.

MgCl2 + 2H2O Mg(OH)2 + 2HCl

Soft Scale
4) Presence of silica-
Small quantity of SiO2 creates –
(CaSiO3) Calcium silicate.
(MgSiO3) Magnesium silicate.
 Disadvantages of scale
• Wastage of fuel.

• Lowering of boiler safety.

• Decrease in efficiency.

• Danger of explosion.
 Removal of scales
• Scales can be removed by scraper, wire brush.

• By giving thermal shocks.

• By blow down operation.

• By adding chemicals like EDTA.

 Difference
Sludge are loose, slimy,soft ppt. Scales are hard ppt.

They can easily removed. They can’t easily removed.

Formed by substances like- Formed by substances like-

CaCl2, MgCl2, MgSO4, MgCO3. CaSO4,Mg(OH)2.

They forms in colder portions of They forms in hotter portions

boiler. of Boiler.

They are less dangerous. They are more dangerous.

Can be removed by blow down Can’t be removed by blow down

Operation. Operation.
 Priming
• When a boiler is steaming rapidly , some
particles of the liquid water are carried along
with steam.

• This process of wet steam formation is called

Priming.
 Priming is caused by
• The presence of large amount of dissolved solids.

• High steam velocities.

• Sudden boiling .

• Improper boiler design.

• Sudden increase in steam production rate.

 Foaming
• Foaming is the production of persistent foam
or bubbles in boilers.

• Such bubbles do not break easily.

• Foaming is due to substances like Oils in

water.
• Foams Reduce the surface tension
 Disadvantages of priming & foaming

• Dissolved salts are carried out by wet steam.

(Carry Over)

• Dissolved salts enters in machinery parts.

• They reduces the boilers efficiency.

 Priming can be avoided by
• By fitting steam purifiers.

• Avoiding rapid change in steaming rate.

• By maintaining water level in boilers.

 foaming can be avoided by
• By adding anti-foaming chemicals.

• Removing oil from boiler water by adding

coagulants.
 Boiler corrosion

• It is a decay of boiler material by chemical or

electro chemical attack of its environment .
 REASONS OF CORROSION
1) By dissolved Oxygen
2) By dissolved carbon dioxide
3) By acids of dissolved salt
 1)Dissolved oxygen
• 2Fe + 2H2O + O2 2Fe(OH)2

RUST

• 4Fe(OH) + O
FERROUS HYDROXIDE
2 2 2Fe2O3.2H2O
 REMOVAL
• By adding sodium sulphite
2Na2SO3 + O2 2Na2SO4

• By adding hydrazine
N2H4 + O2 N2 + 2H2O

• By adding sodium sulphide

Na2S + 2O2 Na2SO4
 2) DISSOLVED CO2
• CO2 + H2O H2CO3
Carbonic acid

• It has slow corrosive property.

• CO2 is also released in boiler by

Mg(HCO3)2 MgCO3 +H2O + CO2
 Removal of CO2
• By adding ammonia

2NH4OH + CO2 (NH4)2CO3 + H2O

 3) By acids of dissolved salts
• MgCl2 + 2H2O Mg(OH)2 + 2HCl

• This HCl reacts with boiler material

Fe + 2HCl FeCl2 + H2
FeCl2+ 2H2O Fe(OH)2 + 2HCl
2Fe(OH)2 + O2 Fe2O3.H2O
 DISADVANTAGES OF CORROSION

a) Shortening of boiler life

b) Leakage of joints and bents
c) Increased cost of repairs and
maintenance
d) Safety problem of boiler
 Caustic Embrittlement

• Boiler material become brittle due to

alkalinity.
 Caustic embrittlement
• It is a type of boiler corrosion.

• It is due to highly alkaline water.

• Na2CO3 ( soda) creates problems in boilers.

• In high pressure boiler Na2CO3 decomposes-

Na2CO3 + H2O 2NaOH + CO2

 CONCENTRATION CELL

Iron at + Concentrated Dilute -Iron at

rivets, NaOH NaOH Plane
Bends, Solution Solution Surfaces.
Joints.
• NaOH makes water caustic.

• NaOH containing water flows into minute hair

cracks.

• Water evaporates & concentration of

dissolved salts increases.

• So embrittlement takes place.

• Embrittlement arise due to setting up of a
Concentration Cell.

• Iron surrounded by dilute NaOH acts as a

Cathode.

• Iron surrounded by con. NaOH acts as a

Anode.
• Sodium hydroxide + iron of boiler
• Sodium Ferroate( Na2FeO2)
• 3 Na2FeO2 + 4 H2O -- 6 NaOH + Fe3O4+ H2
• Further dissolution of iron due to-
1.NaOH regenerate
2.Precipitation of Fe3O4
•
Prevention
By adding sodium phosphate.

• By adding lignin, tannin.

• By adding sodium sulphate.

• Na2SO4 also blocks hair cracks if Na2SO4 is

added in this ratio-
• Na2SO4 Con.
NaOH Con. Is kept as 1:1,2:1 and 3:1in
boilers at pressure up to
10,20,30atmospheres.
 Question

• Give brief note on caustic embrittlement.

• INTERNAL TREATMENT
 INTERNAL TREATMENT

• Colloidal Conditioning
• Phosphate Conditioning
• Carbonate Conditioning
• Calgon Conditioning
• Treatment with NaAlO2.
 Colloidal Conditioning
• In lower pressure boiler by adding organic
substance like – kerosene, tannin, agar – agar.

• It get coated over the scale .

• So scale become non sticky, loose.

• Easy to remove by blow down operation.

 Phosphate Conditioning
• It is carried out in high pressure boiler.

• Sodium phosphate is added for removal of scale.

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

• Calcium & magnisum phosphate is loose , non
sticky , non adherent.

• Easy to remove by blow down operation.

 Main Phosphates are
• NaH2PO4 - Sodium dihydrogen phosphate
(acidic)

• Na2HPO4 - Disodium hydrogen phosphate

(weak alkali)

• Na3PO4 - Trisodium phospate (alkaline)

 Carbonate Conditioning
• It is carried out in low pressure boiler.

• scale formation can be avoided by adding sodium

carbonate.

CaSO4 + Na2CO3 CaCO3 + Na2SO4

• So deposition of CaSO4 will not take place

& loose sludge of CaCO3 is formed.

• Which can removed by blow down operation.

 Calgon Conditioning
• By adding calgon (Sodium hexa meta phosphate )
(NaPO3)6 in boiler water.

• It forms soluble complex with Ca2+ ion.

• Na2Na4(PO3)6 2Na++ Na4P6O18 2-

Calgon

2CaSO4 + Na4P6O18 2- Ca2P6O18 2-+2Na2SO4

Soluble complex ion
 Treatment with NaAlO2
• NaAlO2 + 2H2O NaOH + Al(OH)3

• MgCl2 + 2 NaOH Mg(OH)2 + 2NaCl

• The ppt of Al(OH)3 & Mg(OH)2 entraps

finely suspended & colloidal impurities with oil
particles.
 Question

• Write down internal treatment of water

softening process.
• Alkalinity
 Definition
• Total content of those substance of water which
increased the concentration of OH-
ions upon dissociation called alkalinity.

• It is presence of OH- , HCO3- CO3--etc.

• Types of alkalinity -
• 1) caustic alkalinity (due to OH-, CO3 --)

• 2) temporary alkalinity (due to HCO3 -)

• Determination is based on following reactions

• OH- + H+ H2O
P
• CO32- + H+ HCO3 _ M

• HCO3 - + H+ H2O + CO2

• The titration with water sample and acid with phenolpthalein end – point marks the
completion of reaction (1) and (2) only.

• The titration with water sample and acid with methyl orage end – point marks
the completion of reaction (1) (2) and (3)
• P = OH - and ½ CO3 2-

• M = OH- CO32- HCO3 -

 Table

Alkalinity - -- -
OH CO3 HCO3
(ppm) (ppm) (ppm)
P=O NIL NIL M
P=.5M NIL 2P NIL
P<.5M NIL 2P (M-2P)
P>.5M (2P-M) 2(M-P) NIL
P=M P=M NIL NIL
 Situations
• OH- Only
• CO3 2- Only
• HCO3 2- Only
• OH- and CO3 2- together
• CO3 2- and HCO32- together
• The possibility of OH- and HCO3 – together is ruled
out because –

• They combine to form CO3 2- ions.

• OH - + HCO3 - CO3 2- + H2O

• Thus OH- and HCO3 – ions can not exist together.

 QUESTIONS
1)What is alkalinity ?

2) Which combination is ruled out & why ?

Boiler Feed Water
 Composition of Boiler feed water
1) Hardness below 0.2 ppm
2) Caustic alkalinity 0.15 to 0.45 ppm
3) Soda alkalinity 0.45 to 1 ppm
4) Excess soda ash 0.3 to 0.55 ppm
• excess of impurities in boiler feed water gives
boiler problems.
 Boiler corrosion

sludge scale

Boiler problems

priming foaming

Caustic embrittlement
 Question

• Write short note on boiler feed water.