Lime soda process

It is the most common and economic water softening method. It is very useful for the treatment of large
volumes of hard water. Addition of lime i.e. Ca(OH)2 and soda ie.Na2CO3 to the hard water precipitates
calcium as the carbonate, and magnesium as its hydroxide. The amounts of the two chemicals required
are easily calculated from the analysis of the water and stoichiometry of the reactions. The lime‐soda
method uses lime, Ca(OH)2 and soda ash, Na2CO3 to precipitate hardness from solution.

In case of Temporary hardness, the following reactions take place:

Ca(HCO3)2 + Ca(OH)2 → 2CaCO3 + 2H2O
Mg(HCO3)2 + Ca(OH)2 → Ca(HCO3)2 + Mg(OH)2
In case of permanent hardness, the following reactions take place:
CaSO4 + Na2CO3→ CaCO3 + Na2SO4
CaCl2 + Na2CO3→ CaCO3 + 2NaCl
MgCl2 + Ca(OH)2 → Mg(OH)2 + CaCl2
MgSO4 + Ca(OH)2 → Mg(OH)2 + CaSO4
• Non-carbonate hardness of Mg is converted into non carbonate hardness Ca, which is removed
by soda.
In case of other impurities, the following reactions take place:
CO2 + Ca(OH)2 → CaCO3 + H2O
2HCl + Ca(OH)2 → CaCl2 + 2H2O
H2SO4 + Ca(OH)2 → CaSO4 + 2H2O
H2S + Ca(OH)2 → CaS + 2H2O
2Na(HCO3)2 + Ca(OH)2 → CaCO3 + Na2CO3 + 2H2O
Ca(NO3)2 + Na2CO3→ CaCO3 + 2NaNO3
Mg(NO3)2 + Ca(OH)2 → Mg(OH)2 + Ca(NO3)2
In case of coagulants, the following reactions take place:
FeSO4 + Ca(OH)2 → Fe(OH)2 + CaSO4
Al2(SO4)3 + 3Ca(OH)2 → 2Al(OH)3 + 3CaSO4
There are two types of lime-soda processes;
1. Cold lime soda process
2. Hot lime soda process.
1. Cold Lime soda process:
• When the chemicals (L Or S) are added to hard water at room temperature, the process
is known as cold lime soda process.
• At room temperature, the precipitates are finely divided and do not settle easily so small
quantity of coagulant is also added to water which help in the formation of coarse
precipitates.
NaAlO2 + 2H2O → NaOH + Al(OH)3
• Use of sodium aluminate as Coagulant also helps in the removal of silica as well as oil
present in the water.
• Cold lime soda process provides water containing a residual hardness of 50-60 ppm.
Process:
• Raw water and calculated quantities of chemicals (lime+soda+coagulant) are fed from
the top into inner vertical circular chamber fitted with a vertical rotating shaft carrying
a number of paddles.
• As the raw water and chemicals flow down, there is vigorous stirring and continuous
mixing whereby softening of water takes place.
• The heavy sludge settles down in the outer chamber by the time softened water reaches
up.
• The softened water then passes through a filtering media (made of wood fibres) to
ensure complete removal of sludge.
• Filtered soft water finally flows out continuously through the outlet at the top and
sludge settling at the bottom of the outer chamber is drawn off occasionally.
2. Hot Lime soda process:
• When the chemicals are added to higher temperature (80ºC to 150ºC) the process is
known as Hot lime soda process.
• Since hot process is operated at a temperature close to the boiling point of the solution,
so
a) The reaction proceeds faster,
b) Softening capacity of hot process is increased,
c) The precipitate and sludge formed settle down rapidly and hence no coagulants are
needed,
d) Much of the dissolved gases (CO2) are driven out,
e) Viscosity of softened water is lower so filtration of water becomes much easier.
• Hot L-S Method is preferred over the Cold L-S Method because in hot lime soda
method at higher temperature the reactions are fast, precipitation is more complete,
settling rate and filtration rates are increased.
• As a result, the precipitate and sludge formed settle rapidly and coagulants are not
required and also chemicals needed are in smaller quantities than that of cold L-S
process.
• Dissolved gases are eliminated from water to a certain extent.
• The softened water recovered from hot L-S process has hardness of about 15 to 30 ppm.

Process:
It contains essentially three parts
• A reaction tank in which water, chemical and steam are thoroughly mixed.
• A conical sedimentation vessel in which sludge settle down.
 • A sand filter which ensures complete removal of sludge from the softened water.
Advantages of lime-soda process:
• It is very economical process.
• Less amount of coagulants are required.
• Certain quantity of minerals is reduced from water.
• The level of carbon dioxide can also be reduced using hot L-S Process.
• Fe and Mn are also removed from the water.
• The process increases the PH value of the treated water thereby corrosion of the distribution
pipes is reduced.
Disadvantages of lime-soda process:
• Sludge disposal is problem.
• This can remove hardness only up to 15 ppm, which is not good for boilers.
• Careful operations and skilled supervision are required for economical and efficient softening
Precautions to be followed during lime-soda process:
• Only calculated amounts of lime and soda must be added. Excess of lime-soda causes boiler
troubles like corrosion and caustic embrittlement.
• The chemical reactions of lime and soda are slow and the precipitates CaCO3 and Mg(OH)2 are
very fine.
• Proper time must be given for the reactions of softening process to complete, because all the
reactions of the process are slow.
Numerical:
 Zeolite method
• Zeolite is micro-porous inorganic mineral.
• For odour removal and the softening of hard water generally sodium zeolites are used.
• It is capable of exchanging its sodium ions with hardness causing cations reversibly.
• It is hydrated sodium alumino silicates and its chemical formula is Na 2O.
Al2O3.xSiO2.yH2O here x may be 2-10 and y may be 2-6.
Zeolites are of two types natural and synthetic.
The natural zeolites are generally non or less porous while synthetic zeolites are more porous,
glassy, gelatinous and have higher softening capacity than natural zeolites.
Zeolites are
• characteristically soft to moderately hard,
• light in density,
• insoluble in water but can act as base exchangers in contact with water containing cations.
Hence these can remove Ca2+ and Mg2+ ions from water when hard water is passed through
it.
Zeolite process for water softening:
When Ca2+ and Mg2+ ions containing hard water is passed through a bed of sodium zeolite, the
sodium ions are replaced by the calcium and magnesium ions.
Na2Ze + Ca(HCO3)2 → 2NaHCO3 + CaZe
Na2Ze + Mg(HCO3)2 → 2NaHCO3 + MgZe
Na2Ze + CaSO4 → Na2SO4 + CaZe
Na2Ze + Mg SO4 → Na2SO4 + MgZe
Na2Ze + CaCl2 → 2NaCl + CaZe
Na2Ze + MgCl2 → 2NaCl + MgZe
Na2Ze + Fe(HCO3)2 → 2NaHCO3 + FeZe
Na2Ze + Mn(HCO3)2 → 2NaHCO3 + MnZe
When all sodium ions are replaced by calcium and magnesium ions, the zeolite becomes inactive.
Then the zeolite needs to be regenerated. zeolite can be easily regenerated by passing brine solution
(10% NaCl) through the bed of inactivated zeolite. The following reactions are taken place and
form Na2Ze.
CaZe + 2NaCl → Na2Ze + CaCl2
MgZe + 2NaCl → Na2Ze + MgCl2
Merits of Zeolite Process:
• Used equipment is compact.
• It removes the hardness upto 10 ppm.
• The process automatically adjusts itself for variation in hardness of incoming water.
 • This process does not involve any type of precipitation, thus, no problem of sludge formation
occurs.

Demerits of Zeolite Process:

• The outgoing water (treated water) contains more sodium salts.
• This method only replaces Ca+2 and Mg+2 ions by Na+ ions.
• High turbidity water cannot be softened efficiently by zeolite process.

•
 Ion exchange/deionization/demineralization
• Ion exchange resins are insoluble, cross linked, long chain organic polymers with a micro
porous structure and the functional groups attached to the chains are responsible for ion
exchanging properties.
• Resins containing acidic functional groups (-COOH, -SO3H) are capable of exchanging their
cations; those containing basic functional groups (-NH2=NH-) as HCl are capable of
exchanging their anions with other anions, which comes in their contact.
The ion exchange resins may be classified as:
• Cation Exchange Resins (RH+): are mainly styrene-divinyl benzene co-polymers which on
sulphonation or carboxylation become capable to exchange their H+ ions with cations in the
water.
• Anion Exchange Resins (R’OH-): are styrene-divinyl benzene and amine formaldehyde
copolymers which contain amino or quaternary ammonium or quaternary phosphonium or
tertiary sulphonium groups as an integral part of resin matrix. These, after treatment with dil
NaOH solution, become capable to exchange their OH- anions with anions in water.
Process
Raw water is first passed through cation exchanger and the removal of cations take place like Ca +2,
Mg+2 etc takes place and equivalent amount of H+ ions are released from this column to water. Thus,
2RH+ + Ca+2 → R2Ca+2 + 2H+
2RH+ +Mg+2 → R2Mg+2 + 2H+
After cation exchange column the hard water is passed through anion exchange column, which removes
all the anions like chlorides, bicarbonates, and sulphates (SO42-, Cl-)etc present in the water and
equivalent amount of OH- ions are released from this column to water.
R’OH- + Cl- → R’Cl- + OH-
2 R’OH- + SO42- → R’SO42- + 2OH-
2 R’OH- + CO32-→ R’CO32- + 2OH-
H+ and OH- ions (released from cation exchange and anion exchange columns respectively) get
combined to produce water molecule.
H+ + OH- → H2O
Thus, water coming out from the exchanger is free from cations as well as anions. Ion-free water is
known as deionized or demineralized water. Thus, water of zero hardness is obtained.

Regeneration:
• After the deionization of certain amount of raw water, the cation and anion exchangers will be
exhausted.
 • Regeneration of cation exchanger is carried out by passing dil. HCl or H2SO4 solution into the
bed.
R2Ca+2 + 2H+ → 2RH+ + Ca+2 (washing)
The column is washed with deionized water and the washings (Ca+2, Mg+2 and Cl- or SO42-) is
passed to sink or drain.
• The exhausted anion exchange column is regenerated by passing a solution of dil. NaOH.
R2 SO42- + 2OH- → 2R’OH- + SO42- (washing)
The column is washed with deionized water and washings containing Na+ and SO42- or Cl- ions
is passed to sink or drain.
The regenerated ion exchange resins are then used again.

Advantages:
• Highly acidic or alkaline water samples can be purified by this process.
• The hardness possessed by the deionised water is 2ppm.
• The deionised water is most suitable for high pressure boilers.
• If the output water is passed through de-gasifier, then the gaseous impurities like O2, CO2 also
get expelled,
Disadvantages:
• The ion exchanging resins are expensive hence the cost of purification is high. The equipment
is costly and more expensive chemicals are needed.
• If water contains turbidity, the output of the process is reduced. The turbidity must be below
10ppm; else it has to be removed by coagulation and filtration.
• It can be operated only small-scale purification of water.