LIME-SODA PROCESS

Principle:

• Lime [Ca(OH)2] and soda [Na2CO3] are the reagents used to precipitate the dissolved salts of Ca+2 and
Mg+2 as CaCO3 and Mg(OH)2.

• The precipitated CaCO3 and Mg(OH)2 are filtered off.

• Lime reacts with temporary hardness, CO2, acids, bicarbonates and alums.

• Lime cannot remove the calcium permanent hardness which should be removed by soda.

• The precipitation reactions with lime and soda are very slow.

• Only calculated amounts of lime and soda are to be added. Excess amount of lime & soda causes boiler
troubles like caustic embrittlement.

• Calculation of lime & soda required for the process:

♣ Amount of lime required for softening = 74/100 [temp. hardness of Ca+2 + 2 x temp. hardness of Mg+2
+ permanent hardness of Mg+2 + CO2 + ½ HCl + H2SO4 + ½ NaHCO3 + FeSO4 + {3 x Al2(SO4)3} – ½ NaAlO2]

♣ Amount of soda required for softening = 106/100 [permanent hardness of Ca+2 + permanent hardness
of Mg+2 + ½ HCl + H2SO4 + FeSO4 + {3 x Al2(SO4)3}- ½ NaHCO3]

* All in terms of chemical equivalents of CaCO3.

Treatment with lime:

1. Removal of temporary hardness of Ca+2

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

2. Removal of Temporary hardness of Mg+2

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

3. Removal of Permanent hardness of Mg+2

MgCl2 + Ca(OH)2 Mg(OH)2 + CaCl2 (L+S)

MgSO4 + Ca(OH)2 Mg(OH)2 + CaSO4 (L+S)

Mg(NO3)2 + Ca(OH)2 Mg(OH)2 + Ca(NO3)2 (L+S)

4. Removal of CO2
CO2 + Ca(OH)2 CaCO3 + H2O (L)

5. Removal of acids
2HCl + Ca(OH)2 CaCl2 + 2H2O 1/2(L+S)

H2SO4 + Ca(OH)2 CaSO4 + 2H2O (L+S)

6. Removal of bicarbonates of Na+ and K+
2NaHCO3 + Ca(OH)2 CaCO3 + Na2CO3 + 2H2O (L-S)

7. Removal of alums
FeSO4 + Ca(OH)2 CaSO4 + Fe(OH)2 (L+S)

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

NaAlO2 + 2H2O Al(OH)3 + NaOH (-L)

2NaOH + MgCl2 Mg(OH)2 + 2NaCl

Treatment with soda:

Removal of Permanent hardness of Ca+2

CaCl2 + Na2CO3 CaCO3 + 2NaCl
CaSO4 + Na2CO3 CaCO3 + Na2SO4
Ca(NO3)2 + Na2CO3 CaCO3 + 2NaNO3
 ZEOLITE (OR) PERMUTIT PROCESS

-Zeolites are naturally occurring hydrated sodium aluminosilicate. It general formula is

Na2.Al2O3.xSiO2.yH2O (x=2-10, y=2-6)

- Natural zeolite are green sand and non-porous. The synthetic form of zeolite is known as permitut,
which is porous and possess gel like structure, hence it is generally used for water softening.

-Synthetic zeolite is represented by Na2Ze. Here Na is replaced by Ca2+ and Mg2+ ions present in the
water.

PROCESS

When hard water is passed through a bed of sodium zeolite (Na2Ze), kept in a cylinder, it exchanges its
sodium ion with Ca2+ and Mg2+ ions present in the hard water to form Ca2+ and Mg2+ zeolites. The various
reactions taking place during softening process are

CaCl2 + Na2Ze CaZe + 2NaCl

MgCl2 + Na2Ze MgZe + 2NaCl

Ca(HCO3)2 + Na2Ze CaZe + 2NaHCO3

The softened water is enriched with large amount of sodium salts, which do not cause any hardness, but
cannot be used in boilers.

REGENERATION

After some time zeolite gets exhaust. The exhausted zeolite is again regenerated by treated with 10%
solution of NaCl.
CaZe + 2NaCl Na2Ze + CaCl2

MgZe + 2NaCl Na2Ze + MgCl2

ADVANTAGES

-Water obtained by this process will have only hardness of 1-2 ppm.

-This method is cheap, because the regenerated zeolite can be used again.

-No sludge is formed during this process.

-The equipment used is compact and occupies a small space. It operation is easy.

DISADVANTAGES

-Turbidity water cant be treated, because it blocked the porous of zeolite bed.

-Acidic water cant be treated, because it decomposes the structure of zeolite.

- The softened water contains more dissolved sodium salts like NaHCO3, Na2CO3, etc.

-When such water is boiled in boiler, CO2 and NaOH is produced resulting in boiler corrosion and caustic
embrittlement.

-Water containing Fe, Mn cant be treated, because regeneration is very difficult.

DEMINERALISATION (OR) ION-EXCHANGE PROCESS

This process removes both cations and anions present in the water. The soft water produced by lime-
soda and zeolite process, does not contain hardness causing ions Ca2+ and Mg2+, but it may contain other
ions like Na+ , K+ , SO4 2-, Cl- , etc. On the other hand, demineralized water does not contain both cations
and anions. Thus, a soft water is not demineralized water whereas a demineralized water is soft water.

This process involves the use of ion-exchange resins for softening water. Ion-exchange resins are
insoluble, cross-linked, long chain organic polymers with micro-porous structure. The functional groups
attached to the chains are responsible for the ion-exchanging properties.

There are two types of ion-exchange resins namely:

1. Cation exchange resins

2. Anion exchange resins.
Cation Exchange Resins:

-Resins capable of exchanging the cations from hard water are called cation exchange resins.

-It contains acidic functional groups like – COOH,SO3H or H+ , which can replace their H+ ions with the
cations of hard water.

- It can be represented as RH+ (or) RH2.

-Examples: Sulphonated coals, Sulphonated polystyrene, Phenol formaldehyde resin

Anion Exchange Resins: Resins capable of exchanging the anions from hard water are called anion
exchange resins.

- It contains basic functional groups like -NH2,-NR3 or OH- , which can replace their OH- ions with the
cations of hard water.

- It can be represented as R”OH- (or) R” (OH)2.

- Examples: Methyl ammonium hydroxy styrene, Cross-linked quaternary ammonium salts.

PROCESS

The hard water is passed first through cation exchange column (containing cation exchange resins, RH+).
All the cations such Ca2+, Mg2+, Na+ , K+ , etc. present in hard water are exchanged with H+ ions of the
cation exchange resin. That is, it removes all the cations from hard water and equivalent amount of H+
ions are released from this column to water.

2RH+ + Ca2+ R2Ca2+ + 2H

2RH+ + Mg2+ R2Mg2+ + 2H+

The water leaving the cation exchange column is now passed through anion exchange column
(containing anion exchange resins, R”OH- ). All the anions such as Cl- , SO4 2-, HCO3-, etc. present in the
water are exchanged with OH- ions of anion exchange resins. So that all the anions are removed from
water and equivalent amount of OH- ions are released from this column to water.

R”OH + Cl- R”Cl + OH-

2R”OH + SO4 2- - R2”SO4 2- - + 2 OH-

Ions released from cation and anion exchange columns, combine to produce H2O.

H+ + OH- H2O

Thus, the water coming out of the anion exchange column is completely free from hardness causing
cations and anions. This ion free water is known as demineralized water or deionized water.

REGENERATION: When all the H+ and OH- ions of the ion exchange columns are exhausted, the ion
exchange resins have to be regenerated.

1.The exhausted cation exchange column is regenerated by passing dilute HCl or dilutes H2SO4 through
the column. The washing containing Ca2+, Mg2+, etc. is passed to sink.

R2Ca2+ + 2 H+ 2 RH+ + Ca2+

2.Similarly, the anion exchange column is regenerated by passing dilute NaOH through the column. Then
washing containing SO4 2-, Cl- etc. is passed to sink.

R2”SO42-+ 2 OH- 2 R”OH- + SO4 2-

The regenerated ion exchange resins are then used again.

ADVANTAGES OF ION-EXCHANGE PROCESS:

-This method produces soft water of very low residual hardness.

- Highly acidic and alkaline water can be treated by this process.

-Regeneration of ion-exchange resin is possible.

-Maintenance cost is less.

- No sludge disposal problem arises.

DISADVANTAGES OF ION-EXCHANGE PROCESS:

-Cost of the equipment is high.

- Highly turbid waters cannot be treated. Turbidity should be less than 10 ppm.

- Expensive chemicals are required.

- Water containing turbidity, Fe and Mn cannot be treated, because turbidity reduces the output as it
blocks the pores and Fe and Mn form stable compound with the resin which cannot be regenerated.
 REVERSE OSMOSIS

Principle
Reverse osmosis works by reversing the principle of osmosis. The salt solution is subjected to pressure
and pressed against the semi-permeable membrane. Here, the applied pressure is greater than the
osmotic pressure. Thus, the molecules move from a highly concentrated solution to a less concentrated
solution.
When two solutions of different concentrations are separated by a semi-permeable membrane,
solvent molecules flow from a region of lower concentration (dilute) to higher concentration side. This
process is called Osmosis. The driving force in this phenomenon is called Osmotic pressure.

If a pressure higher than that of osmotic pressure is applied on the concentrated side, solvent
flow reverses. That is the solvent molecules pass from concentrated side to dilute side through the
membrane. This phenomenon is called Reverse Osmosis.

Using reverse osmosis, pure solvent (water) is separated from salt water. This membrane
filtration is also called Super Filtration or Hyper Filtration.

The membranes consist of very thin film of cellulose acetate and cellulose butyrate. Polymers
like polymethacrylate and polyamide of superior quality are also being used.

Reverse osmosis removes 99% of dissolved salts particles, colloids, bacteria, pyrogens from feed water.
The contaminants are separated by the RO membrane on the basis of size and charge. The smaller the
charge of the contaminant, the more are the chances for it to pass through the RO membrane. For eg.,
sodium and calcium are monovalent and divalent respectively. RO cannot remove gases such as carbon
dioxide from the water because they are not highly ionized.

METHOD: In this process, pressure higher than that of osmotic pressure is applied to sea water so that it
is forced to move through semi permeable membrane to pure water side. The membrane consists of
very thin films of cellulose acetate.

The typical single pass seawater RO system consists of:

1. Intake: To set up RO system an intake pump is needed at the source of the water to be purified.
2. Pre-treatment: This step includes removal of solids, sediments, carbonic acid from the water so as to
protect the membrane. This step also includes dosing of oxidizing biocides like chlorine to kill bacteria.
3. High-pressure pump: The high-pressure pump is required to let the water pass through the membrane.
Pressure for brackish water typically ranges from 225 to 376 psi and in the case of seawater it ranges
from 800-1180 psi.
4. Membrane: In membrane assembly there is a pressure vessel with a membrane, allowing feed water to
be pressed against the membrane.
5. Energy recovery: Energy recovery is used to reduce the energy consumption. Much amount of energy
input of the high-pressure pump can be recovered by efficient energy recovery device.
6. Remineralisation and pH adjustment: Stabilization of desalinated water is done to protect downstream
pipelines and storage, generally by adding lime or caustic soda to prevent corrosion.
7. Disinfection: Reverse osmosis is an effective blockade of pathogens, but post-treatment assures
secondary protection against downstream and membranes problems. To sterilize pathogen which has
bypassed the RO process, disinfection by means of UV lamps can be employed.

ADVANTAGES:
-It removes ionic as well as non-ionic and colloidal impurities.
-Life time of the membrane is high (2 - 3 years) and it can be replaced within few minutes.
- Maintenance cost is less.
-Capital cost is low and operation is simple.
-RO systems are very compact and requires little space.
-This system does not require any chemicals for purifying water.
- The energy requirement of the unit is very less.

DIS-ADVANTAGES

-The System cost will be higher

-The High Pressure Pump is required to extract Clear water from the membrane element.
-RO membranes cannot block chlorine or other chemical contaminants. Similarly they cannot block
bacteria or microns smaller than the size of the pores in the membrane.
-it can significantly reduce these good minerals that can aid in overall heart and muscle health.
 ELECTRODIALYSIS

Principle

Most dissolved salts are positively and negatively charged and they will migrate to an electrode with an
opposite charge. In this method the ions are pulled out of the brackish water, under an electric field.

• Electro Dialysis (ED) is a membrane process, during which ions are transported through semi
permeable membrane, under the influence of an electric potential.
• It is an electrochemical process in which ions migrate through ion-selective semipermeable
membranes as a result of their attraction to two electrically charged electrodes.
• ED is able to remove most of the charged dissolved ions.
• The membranes are cation- or anion-selective, which basically means that either positive ions or
negative ions will flow through it.
• Cation-selective membranes are polyelectrolytes with negatively charged matter, which rejects
negatively charged ions and allows positively charged ions to flow through.
• By placing multiple membranes in a row, which alternately allow positively or negatively
charged ions to flow through, the ions can be removed from wastewater.

METHOD

The cation and anion selective membranes are kept alternatively so that many chambers can be
made through which brackish water passes.

By the passage of direct current to the electrodes, the cation selective membrane repels
negative charged ions, but allows the +ve ions to enter, while the reverse is true for the anion
selective membrane. Therefore, water in one chamber of the cell is desalinated water, while
the salt water concentration increased in the next chamber. Thus, we get alternative streams of
pure water and concentrated brine solution. Hence, this method enhances the efficient
separation. The important uses of the electrodialysis are in treatment of metal plating wastes,
battery manufacturer, glass etching and desalination of effluents.

ADVANTAGES:
• Low pressure requirement
• Long membrane life expectancy
• Minimal scaling and minimum chemical usage
• Because ED removes only ionized species, it is particularly suitable for separating non-
ionised from ionized components.

DISADVANTAGES

• Organic matter, colloids and SiO2 are not removed by ED system.

• Feedwater pre-treatment is necessary to prevent ED stacks fouling.
• Elaborate controls are required, and keeping them at optimum condition can be
difficult.
• Selection of materials of construction for membranes and stack is important to ensure
compatibility with the feed water.