U NIT - 5

WATER TECHNOLOGY
Syllabus-
Impurities in water, Turbidity, Hardness of water
Domestic water treatment- Sedimentation, Coagulation -Alum, Poly Aluminium Chloride
Sterilization-Chlorination, Break Point Chlorination, Dechlorination, Ozonization
Industrial Water Treatment-
External treatments - Softening of water by Zeolite proces, Numericals and De-mineralization process,
Internal Treatments- Carbonate, Phosphate & Calgon conditioning
Boiler Troubles - Carry Over,Corrosion ,Caustic Embrittlement, Scale and Sludges - Causes,effect on
Boiler operation and Methods of prevention.
Desalination of sea water- Electrodialysis and Reverse Osmosis process-Principle, Methods and
Advantages

Introduction:
“Water is one of the most abundant commodities in nature, but also the most misused one.”
About 80% of the earth (called as a blue planet) surface is covered by water. But the unfortunate fact of
life is that about 97% of the total water is locked in the oceans, which is too saline to drink and for direct
use for agricultural or industrial purposes. About 80% of the remaining (3%) water is trapped in polar
(glacial, Antarctic) ice caps and huge glaciers, from which icebergs break and slowly melt at sea.
Another 10% is locked in rock crevices & minerals lying as deep as 800 meters below the earth’s crust.
Thus only about 0.3% of the world’s water resources are available for domestic, agricultural and
industrial use.
Water is the most useful commodity. It plays an important role in wide variety of natural processes and
essential for the growth of all animals and plants. It is the basic material needed by almost all industries
and is used as a coolant in power and chemical plants. In industry it is mainly used as feed water in
boilers in the steam generation and hydroelectric power stations. It is also extensively used in industries
like paper, textile, sugar, chemical pharmaceutical and ice manufacturing for their routine operations.
Common Impurities in Water:
Water obtained from different sources is associated with large number of impurities. The impurities
present in water can be broadly classified as follows:
(1) Suspended impurities (3) Colloidal impurities
(2) Dissolved impurities (4) Biological impurities.
The solids present in water can be classified on their size as follows
Dissolved Colloidal Suspended

10-5 10-4 10-3 10-2 10-1 1 10 100 (m)

10-8 10-7 10-6 10-5 10-4 10-3 10-2 0.1 (mm)

1) Suspended Impurities: - These are the dispersion of solid particles in water and can be
removed by filtration or on settling.
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 The suspended impurities include:
(a) Inorganic Impurities: Clay (< 0.002mm), Silt (0.002-0.075mm) and Sand (0.075-0.43mm).
These impurities cause turbidity.
(b) Organic Impurities: Oil globules, vegetable and animal waste. These are responsible for taste,
colour, release of germs and bacteria.
(c) Bacterial Impurities: Bacteria, micro organisms, other forms of animal and vegetable life,
algae protoza. They cause colour, odour and turbidity and some causes diseases.

2) Dissolved Impurities:- Some impurities like atmospheric gases and mineral salts are dissolved
in water, when it moves through air and flows over the rocks, soil etc. Normally the salts like
chlorides, sulphate, nitrate, bicarbonate, fluoride, phosphate, nitrite of sodium, potassium, calcium,
magnesium and traces of zinc exist in raw water. Such types of impurities with their effects are
given as follows:

Nature of Impurity Effect of Impurities on Quality of Water

(a) Minerals:
Carbonate
Causes alkalinity and Hardness
(i) Calcium & Bi-carbonate
Magnesium Chloride
Causes Hardness
Sulphate
Carbonate
Causes alkalinity and Softening
Bi-carbonate
(ii) Sodium
Chloride Causes salty taste
Fluoride Causes teeth and bone problems
(iii) Metals & Lead Causes lead poisoning
Oxide Arsenic Causes arsenic poisoning
Manganese Produces brown or black color in water
Iron Causes taste, red color, hardness and corrosion
(b) Gases:
(i) Oxygen (O2) Corrodes the metals
(ii) Carbon dioxide (CO2) Causes acidity and corrosion of metals
(iii) Hydrogen sulphide(H2S) Causes foul smelling, acidity & corrosion of metals.

3) Colloidal Impurities: - Substances of both organic as well as inorganic origin are present in
water in colloidal state. Colloidal particles have very small size (10–3 mm to 10–6 mm) possessing
normally negative charge.
The inorganic substances like compounds of iron, silicon and aluminium are often present in
water in colloidal state. Similarly, the substances of organic origin like decayed leaves, fungi and
bacteria may also be present in water in colloidal state. Clay particles are negatively charged
particles. Such impurities neither settle down on standing nor can these be removed by filtration.
The colloidal impurities affect performance of boilers. It increases ‘foaming’ tendency of
boiler water. These impurities also disturb the performance of anion exchangers.

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4) Biological Impurities: - Slime growth such as algae, micro-organisms (i.e. bacteria and fungi)
from decayed organic impurities (dead animals and vegetables) are considered as pathogenic (i.e.
disease producing). Such impurities may be present in natural water and these impurities causes
pollution of water by producing harmful disease producing germs. These impurities affect the
efficiency of heat transfer equipment e.g. in air-conditioning. Biological growth can also contribute to
the corrosion of equipment and causes bad odours to the water. Such water is dangerous for
human consumption and health.
Turbidity:Turbidity is the amount of cloudiness in the water. This can vary from a river full of mud
and silt where it would be impossible to see through the water (high turbidity), to a spring water which
appears to be completely clear (low turbid- ity).
High turbidity in drinking water can shield bacteria or other organisms so that chlorine cannot
disinfect the water as effectively. Some organisms found in water with high turbidity can cause
symptoms such as nausea, cramps, and headaches. ... Water that has high turbidity may cause
staining or even clog pipes over time.
Although turbid water is not inherently unhealthy, it can contain particles that should not be
consumed by humans. Some of these problematic particles can include metals or other types of
sediment that can negatively affect human health
The best way to measure turbidity in a wide variety of samples is with a Nephelometer, also known
as a turbidity meter. Turbidity meters utilize a light and photo detector to measure light scatter, and
read out in units of turbidity, such as Nephelometric turbidity units (NTU) or formazin turbidity units
(FTU).The EPA requires us to produce water with a turbidity measuring no higher than 0.3
Nephelometric Turbidity Units (NTU).
Hardness:
1) Hardness is the soap consuming capacity of water. i.e. It is a property of water, which prevents
lathering of soap.
2) Soaps generally consist of sodium salts of long chain fatty acids such as oleic, palmetic, stearic acid.
3) Soap consuming capacity of water is mainly due to the presence of Ca & Mg ions. [Ca2+ & Mg2+].
4) These ions react with the sodium salts of long-chain fatty acids present in the soap to form insoluble
calcium and magnesium soaps, which do not possess any detergent value.

2C17H35COONa + Ca/Mg-Cl2/SO4  (C17H35COO)2Ca/Mg + 2 NaCl/SO4

Sodium Soap (soluble) Calcium soap (insoluble)
5) Other metal ions like Fe2+, Mn2+ and Al2+ also react in the same way, thus contributing to hardness,
but generally, these are present in natural waters only in traces.
6) Acids such as carbonic acid can also cause free fatty acid to separate from soap solution and thus
contributes to hardness. C17H35COONa + H2CO3  C17H35COOH + NaHCO3

7) However, in practice, the hardness of a water sample is usually taken as a measure of its Ca2+ and
Mg2+ contents.

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Types of Hardness:
Temporary, Permanent and Total hardness.
1) Temporary (or carbonate or alkaline) hardness: - Temporary hardness is due to the
presence of bicarbonates of calcium and magnesium and the carbonate of iron. Temporary hardness
can be easily removed by mere boiling of water. During boiling of water, bicarbonates are decomposed
to form insoluble carbonates (or hydroxides) which precipitate and CO2 is set free.
Ca(HCO3)2 CaCO3 + H2O + CO2

Mg(HCO3)2 Mg CO3 + H2O + CO2

OR MgCO3+ H2O Mg(OH)2 + CO2

Alkaline hardness is defined as the hardness due to the presence of bicarbonates, carbonates, and
hydroxides of the hardness causing cations. It is also called as carbonate hardness. This is same as
temporary hardness. In raw water, the alkaline hardness is normally due to bicarbonates. However, a
treated water may also contain hardness due to small quantities of CaCO3 and Mg(OH)2 in solution.
The Non-Alkaline hardness is obtained by subtracting the alkaline hardness from the total hardness.
This is also known as non-carbonate hardness.
Alkalinity in most natural waters is due to the presence of carbonate (CO3=), bicarbonate (HCO3-),
and hydroxyl (OH-) anions. However, borates, phosphates, silicates, and other bases also contribute
to alkalinity if present. Most alkalinity in surface water comes from calcium carbonate, CaCO3, being
leached from rocks and soil
Total alkalinity is affected by environmental factors like rain.Acidic sanitizers, addition of sewage,
agriculture water and other product can all change the alkalinity of water.
Higher alkalinity levels in surface water will buffer acid rain and other acid wastes, preventing pH
changes that are harmful to aquatic life. Alkalinity is also in important considering
the treatment of wastewater and drinking water because it influences cleaning processes such as
anaerobic digestion.
2) Permanent (or non-carbonate) hardness: - The permanent hardness is due to the presence of
chlorides, sulfates and nitrates of calcium (Ca2+), and magnesium (Mg2+) in water. Sometimes
permanent hardness is due to the presence of salts of other metal ions like Fe2+, Fe3+, Al3+ and anions
like nitrates and silicates. Unlike temporary hardness, the permanent hardness cannot be removed by
simple physical means like boiling of water, but it requires certain chemical treatment.
Degree of Hardness:
The hardness of water is expressed in terms of parts by weight of equivalent amount of CaCO3. The
choice of CaCO3 is due to its molecular weight equal to 100 (equivalent weight = 50). Moreover, it is the
most insoluble salt that can be precipitated in water treatment.
Wt. of hardness causing substance
x 50
Equivalents of CaCO3
=
Eq. wt. of hardness producing substance

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e.g, 162 parts by weight of Ca(HCO3)2 (or 2 equivalents) would react with the same amount of soap as
100 parts by weight of CaCO3 (or 2 equivalents). Therefore, the weight of Ca(HCO3)2 is multiplied by a
factor 100/162 to get the weight in terms of CaCO3. Following table gives the multiplication factor for
converting various substances causing the hardness of water into equivalents of CaCO3.

Table: Calculation of equivalents of CaCO3

Dissolved Molecular Multiplication
Salt
Ca(HCO3)2 Weight162 Factor100/162
Mg(HCO3)2 146 100/146
CaCO3 100 100/100
MgCO3 84 100/84
CaCl2 111 100/111
MgCl2 95 100/95
CaSO4 136 100/136
MgSO4 120 100/120
Mg(NO3)2 148 100/148
CO2 44 100/44
HCl 36.5 100/(36.5x2)
H2SO4 98 100/98
HCO3– 61 100/(61x2)
Ca2+ 40 100/40
Mg2+ 24 100/24
Al2(SO4)3 342 (100/342) x 3
FeSO4.7H2O 278 100/278
NaAlO2 82 100/(82x2)
Unit of Hardness:
The following are the most common units of hardness:
1) Parts per million (ppm) : It is a unit weight of solute per million unit weights of solution. i.e 1 ppm =
1mg/kg. In dilute solutions (density ~ 1), 1 ppm = 1mg/liter. As hardness is expressed as CaCO3
equivalent, hence hardness causing impurities are first converted in terms of their CaCO3
equivalent and the sum is expressed as parts per million.
2) Equivalents per million (epm): It is a unit chemical equivalent weight of substance per million unit
weight of water. Density of dilute aqueous solutions is almost equal to 1, hence, 1 epm = 1
equivalent weight in mg per litre;
1epm of Mg = 12 ppm of Mg. = 50 ppm of CaCO3 = 42 ppm of MgCO3
3) Grains per imperial gallon (gpg) or Degree Clarke (oCl): In British system, hardness is expressed
as grains (1 grain = 1/7000 lb) per gallon (1gallon = 10 lbs). It is the parts per 70,000 part of the
water. It is also called as degree Clark. i.e It is the weight of CaCO3 equivalent hardness present in
70,000 parts by weight of water. Thus,
1 oCl = 1 parts by weight of CaCO3 equivalent hardness / 70,000 parts by weight of water
On ppm scale: 1 oClark = 1 gpg = 1 parts per 70,000 parts of water
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 = 1x106/70,000 ppm = 14.3 ppm hardness as CaCO3
4) Degree French (oFr): It is the number of parts by weight of CaCO3 equivalent hardness present in
105 parts by weight of water. Thus,
1 oFr = 1 parts by weight of CaCO3 eq. hardness/105 parts by weight of water.
5) Degree Russian ( 1oRussian) : 1 part Ca/106 parts of water.
6) Degree German ( 1oGerman) : 1 part CaO/105 parts of water.

Inter Relation between various units of Hardness.

1 ppm = 1 mg/L = 0.07 oCl = 0.07 gpg = 0.1 oFr = 0.02 epm as CaCO3
1 gpg = 1 oCl = 14.3 ppm = 1.43 oFrench = 0.833 grains/US gallon

Domestic Water Treatment:

Drinking Water:
Water suitable for drinking purposes is called as potable water. It should satisfy the following:
1) Its mineral contents and other parameters should be well within the limit of IS:10500
2) It should be clear and have agreeable taste and no objectionable odour.
3) It should be free from disease-producing microorganisms.
4) It should be reasonably soft. Its hardness should be less than 250 ppm.
5) Its pH should be about 7. (6.5 – 7.5)
6) Its total dissolved solids should be less than 500 ppm
Methods of Domestic Water Treatment:
1. Screening: - “Screening is the process of removing floating materials from water.” The water is
allowed to pass through screens having a large number of holes.
2. Sedimentation: - “Sedimentation is the process of removing suspended impurities by keeping water
undisturbed for sufficient time in large tanks when most of the suspended particles settle down due to
force of gravity.” The clear water can be taken out from the tank with the help of pumps. Settled
suspended impurities at the bottom are called as sludge.
3. Coagulation: - “Coagulation is the process of settling colloidal or fine particles from water by the
addition of certain chemicals known as coagulants.”The clear water can be taken out from the tank with
the help of pumps. Colloidal particles are very small particles possessing negative charge. Due to
similar charge they do not unite to form bigger particles. Therefore, they do not settle down during
sedimentation. Added coagulant neutralizes the charge on the colloidal particles to unite together.
Coagulants: The following coagulants are mostly used:

a) Alum (K2SO4, Al2(SO4)3 .24H2O):

It is the most widely used in water treatment plants.

Al2(SO4)3 + 6H2O 2Al(OH)3 + 3H2SO4
Sulphuric acid formed reacts with bicarbonate and lime added to water during the treatment. The
insoluble aluminum hydroxide forms the floc, which neutralizes, absorbs and entangles the fine

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suspended and colloidal impurities. The floc becomes heavy and settles down due to the gravity. For
best results, the pH of water should be between the range 6.5 to 8.5.
b) Polyaluminium Chloride(PAC):
PAC is one of the most efficient water treatment chemicals utilized today. It is widely used in both
potable water and waste water treatment because it provides high coagulation efficiency and it has the
widest pH and temperature application ranges compared to other water treatment chemicals.
Polyaluminum chloride (PAC) coagulant can be prepare from AlCl3·6H2O and Na2CO3.
PAC is a 'coagulant' chemical added to water to help remove small particles of dirt and contaminants
that can make people sick, and block the water system's filters.
Advantages of Poly aluminum chloride:
1. They are effective over a broader pH range compared to alum and experience shows
that PAC works satisfactorily over a pH range of 5.0 to 8.0.
2. Flocs formed from polyaluminium coagulants tend to settle equally well at low and at
normal water temperatures.
3. Less sludge is produced compared to alum at an equivalent dose.
4. Lower doses are required to give equivalent results to alum.
4] Filtration:
During filtration process, suspended, insoluble, colloidal and some bacterial impurities are removed by
passing water through a sand bed material of proper grain size.

5] Sterilization (Removal of bacteria and micro-organisms)

Water, after passing through screening, sedimentation, coagulation and filtration operations, still may
contain a small amount of pathogenic (disease producing) bacteria, for example (a) Enteric bacteria:
Salmonella shigella, Vibrio, (b) Intestinal Protozoa: Entamoeba histolytica, (c) Schistosomes, (d)
Viruses: Hepatitis, (e) Coliform. Therefore, it is necessary to remove these bacteria and micro-
organisms from water.
“The process of destroying the bacteria and micro-organisms etc. from water is known as disinfection or
sterilization of water.” The disinfection can be carried out by following methods: -
(i) Boiling (ii) Chlorination (iii) Ozonization
(i)Boiling: Sterilization is the boiling of water before using for domestic purposes. Boiling kills the
disease causing germs and bacteria like cholera and typhoid. But this method is useful only for
household purposes.
(ii)Chlorination: Chlorination can be carried out by following methods:
(a) By using Chlorine Gas or concentrated solution of chlorine,
(b) By using Chloramine
(a)By using Chlorine Gas (Cl2): Chlorine can be used directly as a gas or as chlorine water for
sterilization of municipal water supply. It reacts with water to form hypochlorous acid and nascent
oxygen, both of which are powerful germicides.
Cl2 + H2O HOCl + HCl
Hypochlorous acid
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 HOCl HCl + [O]
Nascent Oxygen
However excess of chlorine should be avoided because it produces unpleasant odour, taste and
irritating effect on mucous membrane.
The treated water should not contain more than 2 ppm free chlorine.
Process:
Apparatus used for this purpose is known as chlorinator as shown in figure. It is a high tower having
number of baffle plates. Water and proper quantity of chlorine are introduced at its top. During flow they
get thoroughly mixed. Treated water is taken out from the bottom.
Disadvantages: (i) Excess of chlorine produces unpleasant odor, taste and irritating effect on mucous
membrane
(ii) Tri-halomethanes (THM) are formed.
Raw Water Cl2 gas
Ex. Chloroform, bromo--dichloromethane,
dibromo-chloro-methane and bromoform,
Baffle Plates which are carcinogenic.
(iii) THM, are formed when chlorine
combines with natural organic substances,
such as decaying vegetation.
To tackle this problem, organics should be
removed completely before chlorination.

Sterilized Water
Figure Schematic Diagram of Chlorinator

Break – Point Chlorination or (Free Residual Chlorination):

1] It involves addition of sufficient amount of chlorine to oxidize (a) Organic Matter (b)
Reducing Substances (c) free
Bacteria

Free Residual Chlorine

ammonia in raw water,

leaving behind mainly free
Residual Chlorine

A B C D chlorine, which possesses

b d
disinfecting action against
Oxidation of

disease producing
c Break Point (pathogenic) bacteria.
2] When the dosage of
a chlorine is applied to water
Applied Chlorine Dose
Figure Break-Point Chlorination Curve rich in organic compounds or
ammonia the residual chlorine

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gradually increases, the results obtained can be depicted graphically, in which appearance of
the following four stages occurs:

A. Chlorine consumption in oxidizing bacteria.

B. Formation of chloro-organic compounds and chloramines.
C. Destruction of chloro-organic compounds and chloramines.
D. Free residual chlorine begins to appear.

The addition of chlorine at the dip (point ‘c’) is called as “Break–Point Chlorination”. This
indicates the point at which free chlorine begins to appear. Usually, all tastes, odors etc
disappear at break point, resulting in appearance of water free from bad tastes and odors.
Moreover, because of the highly persistent and powerful disinfection possessed by free
available chlorine; any type of pathogenic organisms present in water is destroyed making
disinfection highly efficient.

Advantages of Break–Point Chlorination:

(1) It oxidizes completely organic compounds, ammonia and other reducing compounds.
(2) It removes colour in water due to the presence of organic matters.
(3) It destroys completely (100%) all the diseases producing bacteria.
(4) It removes both odour and taste from water.
(5) It prevents the growth of any weeds in water.

De-Chlorination:
1) Over-chlorination after the break point produces unpleasant taste and odor in water.
2) These objectionable qualities may be removed by filtering the over-chlorinated water
through a bed of activated carbon.
3) Alternatively, a small amount of activated carbon may be added directly to the water and
after allowing a short reaction period, it is then removed by filtration.
4) Over-chlorination can also be nullified by addition of small amount of sulphur dioxide (SO2),
sodium sulphite (Na2SO3), sodium-thiosulphate (Na2S2O3), etc. This is called as De-
chlorination.

SO2 + Cl2 + 2H2O H2SO4 + 2HCl

Na2SO3 + Cl2 + H2O Na2SO4 + 2HCl

2Na2S2O3 + Cl2 Na2S4O6 + 2NaCl

(Sodium tetrathionate)

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(c) By using Chloramine (ClNH2):
Chlorine and ammonia are mixed in the ratio of 2:1 by volume to produce a compound
‘chloramine’. This process is known as ‘chloramination’.
Cl2 + NH3 ClNH2 + HCl
( Chloramine )
Chloramine is a quite stable compound and does not impart any disagreeable smell and bad
taste to water, hence, is considered as better germicidal than chlorine alone.
ClNH2 + H2O HOCl + NH4OH
Hypochlorous acid
HOCl HCl + [O]
Nascent Oxygen

Advantages of Chloramination:
1) Irritating smell due to excess of chlorine is absent.
2) It does not impart bad taste to water.
3) It checks the dissipation of chlorine (by stabilizing chlorine) when water is exposed to
atmosphere especially to sunlight.

The chloramine tablets are used in the army for sterilization of water. Water is collected in
individual bottles in which chloramine tablets are added.
(iii)Ozonization:
This is an effective method of sterilization of water. Ozone (O3) is unstable and it decomposes
into molecular oxygen (O2) and nascent oxygen [O].

O3 O2 + [O]
Nascent Oxygen

The nascent oxygen thus produced is very effective and kills all the germs and bacteria.
In Ozonization, water is allowed to percolate through a tower having perforated partitions as
shown in figure.
Raw Gases
Water Ozone is allowed to enter from
the bottom, which kills the germs

Gravel when it comes in contact with

Bed water. Sterilized water is
Curved Partition
having collected at the bottom of the
Perforations
Ozone tank.
Gas This method is quite expensive
Sterilized and hence is not employed for
Water
Fig: Ozone Sterilizer 10
sterilization of municipal water supply.
Advantages of Ozonization:
1) O3 acts not only as a sterilising agent but also as decolourising and deodorising agent.
2) It improves the taste of water.
3) In excess, it is not harmful, since it is unstable and decomposes into oxygen.
Industrial Water Treatment:
1) Water used for industrial purposes, like steam generation, should be sufficiently pure.
2) It should be free from Ca, Mg and Fe salts. Otherwise troubles like scale and sludge
formation, corrosion occurs in boilers.
Methods of Softening Hard Water
“The process of removing hardness producing salts from water is known as softening
of hard water”.
In industry following methods are mainly used for softening water:
1] Zeolite / Permutit Process
2] Ion-Exchange Process
1] ZEOLITE PROCESS:
The removal of calcium and magnesium by ion exchange using natural or synthetic zeolite is
termed as zeolite process. Chemical structure of sodium zeolite may be represented as:

Na2O.Al2O3.xSiO2.yH2O where x = 2 to 10 and y = 2 to 6

Zeolite is hydrated sodium or potassium 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: -

i) Natural Zeolites: - for example Natrolite Na2O.Al2O3.4SiO2.2H2O.

ii) Synthetic Zeolites: - are porous and possess gel structure. They are prepared by
heating together China clay, Feldspar and Soda ash. Such zeolites possess higher
exchange capacity per unit weight than natural zeolites.

Process :
1) Zeolite softener consists of steel tank, packed with a thick layer of zeolite.

2) For softening of water by zeolite process, hard water is passed through a bed of zeolite,
kept in a cylinder at a specified rate.
3) The hardness causing ions (Ca2+, Mg2+, etc.) are retained by the zeolite as CaZ and MgZ;
while the outgoing water contains sodium salts. Reactions taking place during the
softening process are:-

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 Na2Z + Ca(HCO3)2 CaZ + 2NaHCO3

Na2Z + Mg(HCO3)2 MgZ + 2NaHCO3

Na2Z + CaCl2 CaZ + 2NaCl

Na2Z + CaSO4 CaZ + Na2SO4

Na2Z + MgCl2 MgZ + 2NaCl

Na2Z + MgSO4 MgZ + Na2SO4

(Zeolite) (Hardness) (Exhausted / Used Zeolite)

4) Soft water is collected at the bottom of the tank.

5) Regeneration: - After some time, the zeolite is completely converted into calcium and
magnesium zeolites and it ceases to soften water i.e. it gets exhausted.
6) At this stage, the supply of hard water is stopped and the exhausted zeolite is recharged
by adding a concentrated (10%) solution of NaCl (Brine).

Hard
Water Inlet

Zeolite Bed

Gravel Bed

Injector

To Soft Water
NaCl Solution Sink Outlet
Storage

Fig. Zeolite Softener

CaZ + 2NaCl Na2Z + CaCl2

MgZ + 2NaCl Na2Z + MgCl2
(Exhausted Zeolite) (Brine) Reclaimed Zeolite (Washings)

7) The washings (containing CaCl2 and MgCl2) are led to drain and the regenerated zeolite
bed thus obtained is used again for softening purpose.

Limitations:
1) If the supply of water is turbid, the suspended matter must be removed (by coagulation,
filtration, etc.) before the water is admitted to the zeolite bed; otherwise the turbidity will
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 clog the pores of the zeolite bed, thereby making it inactive.
2) If water contains large quantities of coloured ions such as Mn2+ and Fe2+, they must be
removed first, because these ions produce manganese and iron zeolites, which cannot be
regenerated easily.
3) Mineral acids if present in water reacts with zeolite, which cannot be easily regenerated
and therefore, it must be neutralised with soda, before admitting the water to the zeolites.

Advantages:
1) Hardness of treated water is about 10 ppm i.e hardness is removed almost completely.
2) The equipment used is compact, occupying a small space.
3) No impurities are precipitated, so there is no problem of sludge formation in the treated
water at the later stage.

4) The process automatically adjusts itself for variation in hardness of incoming water.

5) It requires less time for softening, and is a quite clean process.

6) It requires less skill for maintenance as well as operation.

Disadvantages:
(1) The treated water contains more sodium salts than the lime-soda process.
(2) The method only replaces Ca2+ and Mg2+ ions by Na+ ions, but leaves all the acidic ions like
HCO3– and CO32–,.Thus the softened water, contains NaHCO3, Na2CO3, etc. When such
water is used in high pressure boilers for steam generation, NaHCO3, Na2CO3 produce
CO2, which causes corrosion; and NaOH, which causes caustic embrittlement.

(3) High turbidity water cannot be treated efficiently by this method, because fine impurities get
deposited on the zeolite bed, thereby creating problem for its working.

Ion–Exchange Process Or Demineralisation Process Or Deionisation Process:

1) Ion–Exchange Resins are insoluble, cross-linked; long chain organic polymers with micro–
porous structure, and their ‘functional groups’ are responsible for exchange properties.

2) Resins containing acidic functional groups (–COOH, –SO3H, etc.) are capable of
exchanging their H+ ions with other dissolved cations, which comes in their contact.

3) Whereas the resins containing basic functional groups (–NH2, –NR3+, OH–, etc) are capable
of exchanging their OH– with other dissolved anions, when comes in their contact.

4) Ion exchange provides an effective method of demineralisation.

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 Cation Exchange Resin (H2R) is mainly styrene-divinyl benzene copolymers, which on
sulphonation or carboxylation become capable to exchange their hydrogen ions with the
cations in water.

---–CH2–CH–CH2–CH–CH2–CH–CH2–--- ---–CH2––CH–––CH2–––CH–––CH2–––CH––CH2–---

+ + –
SO3H SO3H CH2NMe2+OH CH2NMe2+OH
–

---–CH2–CH–CH2–--- ---–CH2 –––CH–––CH2–---

---–CH2–CH CH–CH2–--- ---–CH2–CH CH–CH2–---

SO3H+ SO3H+ CH2NMe2+OH

– –
CH2NMe2+OH
Hypothetical Structure Acidic or Cation
Exchanger Resin (Sulfonate Form) Figure : - Basic or Anion Exchange Resin (Hydroxide Form)
Anion Exchange Resin (R’(OH)2) is styrene-divinyl benzene copolymers, which contain
amino or quaternary ammonium or quaternary phosphonium or tertiary sulphonium groups as
an integral part of the resin matrix. These, after treatment with dilute NaOH solution become
capable to exchange their OH– anions with water.

Process : -
1) The hard water is passed first through the cation exchange resin column, which removes all
the cations like Ca2+, Mg2+, Na+ etc. from it and equivalent amount of H+ ions are released
from this column to water. Thus,

RH2 + Ca2+ + SO4 2- or 2Cl- RCa + H2SO4 or 2HCl

RH2 + Mg2+ + SO42- or 2Cl- RMg + H2SO4 or 2HCl
RH2 + 2Na+ + SO4 2- or 2Cl- RNa2 + H2SO4 or 2HCl
RH2 + 2Na+ + CO3 2- RNa2 + H2CO3

2) After cation exchange column, the 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. Thus,

R’(OH)2 + H2SO4 R’SO4 + 2 H2O

R’(OH)2 + H2CO3 R’CO3 + 2 H2O

R’(OH)2 + 2HCl R’Cl2 + 2 H2O

3) Thus, the water coming out from the exchanger is free from cations as well as anions. This
water is known as deionised water or demineralised water.

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4) Regeneration: - When capacities of cation and anion exchangers to exchange H+ and OH–
ions respectively are lost, they are then said to be exhausted.

5) The exhausted cation exchange column is regenerated by passing a solution of dilute HCl
or H2SO4. The regeneration can be represented as: -

RCa + 2H+ RH2 + Ca2+

RMg + 2H+ RH2 + Mg2+
RNa2 + 2H+ RH2 + 2Na+
(Regenerated Zeolite) (Washings)
Hard
Water Inlet

Cation Ex- Anion Ex-

changer Bed changer Bed

Gravel Bed

Injector Injector
Pump
To To
Sink Sink Soft Water
Acid Re- Outlet
generator Alkaline Re-
Solution generator
The Storage Storage
Figure:- IONEXCHANGE PROCESS or DEMINERALIZATION
exhausted
anion
exchange column is regenerated by passing a solution of dil. NaOH. The regeneration can be
represented as: -

R’SO4 + 2NaOH R’(OH)2 + Na2SO4

R’CO3 + 2NaOH R’(OH)2 + Na2CO3
R’Cl2 + 2NaOH R’(OH)2 + 2NaCl
(Regenerated Zeolite) (Washings)
6) The column is washed with deionised water and washings (Ca2+, Mg2+, Na+ and Cl–, CO32–,
SO42–) are passed to sink or drain. The regenerated resins are then used again.
Advantages:

1) The process can be used to soften highly acidic or alkaline waters.

2) It produces water of very low hardness (<2 ppm), so can be used in high-pressure boilers.

3) It has effective and reliable operation.

4) Cost effective when low -TDS water is treated.

Disadvantages:

1) The equipment is costly and more expensive resins are needed.

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2) If water contains turbidity, then the output of the process is reduced. The turbidity must be below 10
ppm. If it is more, it has to be removed first by coagulation and filtration.

Main applications
• Production of demineralised water for industrial boiler plants.
• Production of ultra-pure water for manufacturing of electronic components.
• Production of ultra-pure water for pharmaceutical and medical applications.
• Production of demineralised water for various industrial applications.
• Demineralised water is commonly used in laboratories and other high-tech applications.
Comparison between Zeolite and Ion-Exchange Process
Characteristics Zeolite Process Ion-Exchange Process
1) Cost of plant and materials lower. much higher.
2) Space occupied by Plant less space. more space.
3) Contents of Na+ in treated water higher no Na+ ions.
4) Hardness of softened water 5 to 10 ppm. < 2 ppm.
5) Removal of cations and anions. only Ca2+, Mg2+ etc. all ions and salts.
6) Question of regeneration. regenerated by 10% NaCl (brine) regenerated by dil.HCl and NaOH.

Boiler Troubles:
Boiler Troubles are classified in to three types 1] Carry Over 2] Boiler Corrosion 3] Scales and Sludge
Carry Over
1) As steam rises from the surface of the boiling water in the boiler it may be associated with small
droplets of water and foam bubbles. Such steam, containing liquid water, is called wet steam.
2) These droplets of water and foam bubbles naturally carry with them some suspended and dissolved
impurities present in the boiler water.
3) This phenomenon of carrying of water by steam along with impurities is called “Carry Over”. This is
mainly due to priming and foaming.

Priming
When a boiler is steaming (i.e. producing steam) rapidly, some fine water droplets in the form of spray
are carried along with the steam. This process of ‘Wet Steam’ formation is called ‘Priming’.

Priming is caused by: - 1) Presence of large amount of dissolved solids 2) High steams velocities.
3) Sudden boiling 4) Improper boiler design 5) Sudden increase in steam rate 6) high water levels in
boiler

Priming can be avoided by: -

(i)Fitting mechanical steam purifiers (ii) Avoiding rapid change in steaming rate (iii) Maintaining low
water levels in boilers (iv) Efficient softening and filtration of the boiler feed water.

Foaming
It is the production of persistent foam or bubbles in boilers, which do not break easily. Foaming is due
to the presence of substances like dissolved solids, suspended impurities which greatly reduce the
surface tension of water in boilers.

Foaming can be avoided by: -

a) Adding anti-foaming agents like castor oil.
b) Removing oil from boiler water by adding compounds like sodium aluminate.

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Priming and Foaming usually occur together. They are objectionable because
1)Dissolved salts in boiler water are carried by wet steam to super heater and turbine blades, where
they get deposited as water evaporates, which may reduce their efficiency.
2)Dissolved salts may enter the parts of machinery, where steam is being used, thereby decreasing the
life of machinery.
3)Actual height of water column cannot be judged properly; thereby making the maintenance of boiler
pressure becomes difficult.

2] Boiler Corrosion:
The most serious problem created by the use of unsuitable water in boiler is corrosion. “Boiler
Corrosion is decay or destruction of boiler material by a chemical or electro-chemical action by its
environment.”
Corrosion in boilers is mainly due to Dissolved Gases , Acidity and Alkalinity of Water.
Dissolved Gases:Dissolved Oxygen
O2 is the most corroding gas in water. Dissolved O2 (about 8 mg/L at room temperature) in water
attacks the boiler material under high temperature to form ferric oxide (rust).

2 Fe + 2H2O + O2 2 Fe(OH)2

2 Fe(OH)2 + ½ O2 Fe2O3.2H2O
(Ferrous hydroxide) (Rust)

Dissolved oxygen can be removed from water by adding calculated quantity of sodium sulphide (Na2S)
or sodium sulphite (Na2SO3) or hydrazine (N2H4). These compounds combine with oxygen as below: -
Na2S + 2O2 Na2SO4
2 Na2SO3 + O2 2Na2SO4
N2H4 + O2 N2 + 2H2O
If sodium sulphide or sodium sulphite is used, the sodium sulphate (Na2SO4) so formed may
decompose giving SO2, particularly in high-pressure boilers. The SO2 enters the steam pipes and
coverts into sulphurous acid (H2SO3). Hence, ‘Hydrazine’ is an ideal chemical for the removal of
dissolved oxygen. It reacts with oxygen, forming nitrogen and water and nitrogen is harmless.
Consequently, hydrazine removes oxygen without increasing the concentration of dissolved salts.
Recently, Azamine 8001–RD (a polyvalent organic compound) is used for degasifying water in
minimum time.
Water Feed Mechanical De-Aeration
Dissolved oxygen can also be removed by
Mechanical De-Aeration i.e. spraying water in a
To Vacuum tower fitted with perforated plates. This tower is
Pump Steam Jacket heated from sides and connected to a vacuum
pump. The high temperature, low pressure and
large exposed surface (provided by perforated
Perforated plates) reduce the dissolved oxygen from water.
Tower Plates

De-Aerated
Water
Figure: Mechanical De-Aeration of Water

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Dissolved Carbon dioxide (CO2)

Dissolved Carbon dioxide (CO2) in water is carbonic acid.

CO2 + H2O H2CO3 (Carbonic acid)
CO2 is also released inside the boiler, if water containing bicarbonates is used for steam generation.

Ca(HCO3)2 CaCO3 + H2O + CO2

Mg(HCO3)2 MgCO3 + H2O + CO2

Such Dissolved CO2 from air and from the decomposition of bicarbonates produces carbonic acid
(H2CO3), which slowly attacks the metal of boiler causing corrosion.

Dissolved CO2 can be removed by:

1) Mechanical De-Aeration along with oxygen
2) Adding calculated quantity of ammonia.
2NH4OH + CO2 (NH4)2CO3 + H2O

DISSOLVED SALTS
If water used for steam generation contains dissolved magnesium salts (like MgCl2) they liberate acids
on hydrolysis.
MgCl2 + H2O Mg(OH)2 + 2HCl
The liberated acid reacts with boiler like a chain reaction, producing HCl again and again.
Fe++ + 2HCl FeCl2 + H2
FeCl2 + 2H2O Fe(OH)2 + 2HCl
Hence, the presence of even small amount of MgCl2 will cause corrosion of boiler to a large extent.
Corrosion by acids can be avoided by adding alkaline salts or even ammonia.
Acidity and Alkalinity of Water:
Caustic Embrittlement:
1) Caustic Embrittlement is a boiler corrosion, caused due to use of highly alkaline water in the boiler
2) After treatment process, free Na2CO3 is usually present in small amount in the softened water.
3) In high-pressure boilers, Na2CO3 decomposes to give NaOH and CO2 and this makes the boiler
water ‘Caustic’.
Na2CO3 + H2O 2NaOH + CO2
4) The NaOH containing water flows into the hair cracks, present in the boiler, by capillary action. Here
water evaporates and the dissolved caustic soda attacks the surrounding area, thereby dissolving iron
of boiler as sodium ferroate.
5) This is called as caustic embrittlement, and weakens boiler parts, particularly stressed parts (like
bends, joints, rivets, etc.), causing even failure of the boiler.
3 Fe + 4OH– Fe3O4 + 4H+
Caustic Embrittlement can be avoided

(i) By using sodium phosphate as softening reagent, instead of sodium carbonate;

(ii) By adding tannin or lignin to boiler water, since these blocks the hair cracks, thereby preventing
infiltration of caustic soda solutions in these cracks.

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 (iii) It has been observed that caustic cracking can be prevented, if Na2SO4 is added to boiler water in
some particular ratio.
3]Scales and Sludges:

1) In boilers, water evaporates continuously and the concentration of the dissolved salts increases
progressively.
2) When their concentration reach saturation point, they form precipitates on inner walls of the boiler.
3) If the precipitation forms loose & slimy particles, it is called as ‘Sludge’.

Boiler Walls Hard adherent

Loose Precipitates coating on inner walls
suspended in water WATER
of boilers (Scale)
(Sludge)

HEAT HEAT
FIG. SCALES AND SLUDGES IN BOILERS
4) If the precipitated matter forms a hard, adherent crust/coating on the inner walls of the boiler, it is
called ‘Scale’.
Sludge:
Sludge is a formation of soft, loose & slimy precipitate. Sludge is easily removed.It is formed at
comparatively low temperature portions of the boilers and collects in areas of the system where the flow
rate is slow or at bends.Sludge is formed by substances like MgCO3, Mg(OH)2, Ca(CO)3, Ca(OH)2, etc.
Causes of Sludge Formation:
Hydrolysis of Magnesium Salts:
Dissolved magnesium salts undergo hydrolysis (at high temperature inside the boiler) forming
magnesium hydroxide precipitate, which forms a soft type of sludge.

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

(Sludge)
Decomposition of Calcium Bicarbonate:
Forms insoluble CaCO3, which get precipitated as sludge.

Ca(HCO3)2 CaCO3 + H2O + CO2

(Sludge)
Disadvantages of Sludge Formation:
i) Sludge is poor conductors of heat, so they tend to waste a portion of heat generated.
ii) If Sludge is formed along with Scale, then former gets entrapped in the later and both get deposited
as Scale.
iii) Excessive sludge formation disturbs the working of the boiler. It settles in the regions of water
circulation such as pipe connection, plug opening, gauge-glass connection, thereby causing even
chocking of the pipes.

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Prevention of Sludge Formation:
a) By using well softened water.
b) By frequently carrying ‘Blow Off / Blow Down Operation’ i.e. drawing off a portion of the
concentrated water which includes sludge.
Scales:
Scale are hard deposits, which stick very firmly to the inner surfaces of the boiler.Scales are difficult to
remove, even with the help of hammer and chisel.Scales are the main source of boiler troubles.

Causes of Scale Formation:

Decomposition of Calcium Sulphate:
i) The solubility of calcium sulphate in water decreases with rise of temperature.
ii) Thus, solubility of CaSO4 is 3,200 ppm at 15 OC and it reduces to 55 ppm at 230 OC and 27
ppm at 320 OC. In other words, CaSO4 is soluble in cold water but almost completely
insoluble in super heated water.
iii) Consequently, CaSO4 gets precipitated as hard scale on the heated portions of the boilers.
This is the main cause of scales in the high-pressure boilers.
iv) Calcium sulphate scale is quite adherent and difficult to remove, even with the help of
hammer and chisel.
Presence of Silica (SiO2):
i) Silica even present in small quantities, deposits as calcium silicate (CaSiO3) and or
magnesium silicate (MgSiO3).
ii) These deposits stick very firmly on the inner side of the boiler surface and are very difficult
to remove.
iii)One important source of silica in water is the sand filter.
Disadvantages of Scale Formation:
1) Wastage of Fuel: Scale has a low
Thickness of Scale (mm) Wastage of Fuel (%)
0.325 10 % thermal conductivity, so rate of
0.625 15% heat transfer from boiler to inside
1.25 50%
2.5 80% water is greatly decreased. In
order to provide a steady supply of
heat to water, excessive or over heating is done and this causes increase in fuel
consumption. The wastage of fuel depends upon the thickness and the nature of scale.

2) Lowering of Boiler Safety: Due to scale formation over heating of boiler is to be done in order to
maintain a constant supply of steam. The overheating of boiler tube makes the boiler material softer
and weaker and this causes distortion of boiler tube and makes the boiler unsafe to bear the
pressure of the steam, especially in high-pressure boilers.
3) Decrease in Efficiency: Scales may sometimes get deposited in valves & condensers of the boiler
and choke them partially; this decreases the efficiency of the boiler.
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4)Danger of Explosion: When thick scales crack, due to uneven expansion, the water comes
suddenly in contact with overheated iron plates. This causes formation of a large amount of steam
suddenly. So sudden high pressure is developed, which may even cause explosion of the boiler.
Removal of Scales:
1) With the help of scraper or piece of wood or wire brush, if they are loosely adhering,
2) By giving thermal shocks (i.e., heating the boiler and then suddenly cooling with water),
3) Dissolving them by adding chemicals, if they are adherent and hard. Thus, calcium carbonate
scales can be dissolved by using 5–10% HCl. Calcium sulphate scales can be dissolved by adding
EDTA, with which they form soluble complexes.
4) By frequent blow-down operation, if the scales are loosely adhering.
Prevention of Scale Formation:
1) External Treatment:
It includes efficient ‘softening of water’ i.e. removing hardness producing constituents of water by
Zeolite and Ion-Exchange Processes.
2) Internal Treatment or (Sequestration):
In this process (also called as ‘Sequestration’), an ion is prohibited to exhibit its original character by
complexing or converting it into other more soluble salt by adding appropriate reagent. In this proper
chemicals are added to the boiler water either: -
(a) To precipitate the scale forming impurities in the form of sludge, which can be removed by ‘Blow-
Down’ operation, or
(b) To convert them into compounds, this will remain in dissolved form in water and thus do not
cause any harm.
Note: - All the Internal Treatment Methods are, generally followed by ‘Blow down Operation’ so that
accumulated sludge is removed.
Important Internal Conditioning/Treatment Methods are: -
i) Phosphate Conditioning:
In high-pressure boilers, scale formation can be avoided by adding sodium phosphate, which forms
non-adherent and easily removable, soft sludge of calcium and magnesium phosphates, which can be
removed by blow down operations.

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

The main phosphates employed are: (a) NaH2PO4, Sodium dihydrogen phosphate (acidic) (b)
Na2HPO4, disodium hydrogen phosphate (weakly alkaline), Na3PO4, trisodium phosphate (alkaline).
Note: - The choice of salt depends upon the alkalinity of boiler feed water. Calcium cannot be
precipitated properly below a pH of (9.5 – 10.5), hence, trisodium phosphate is most suitable for
treatment, when the alkalinity is sufficient, then disodium phosphate is more preferred. But if the
alkalinity of boiler water is too high and requires to be reduced, then monosodium phosphate, being
acidic in nature, is preferred.
ii) Carbonate Conditioning:In low-pressure boilers, scale formation can be avoided by adding sodium
carbonate to boiler water, when CaSO4 is converted into calcium carbonate.
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 CaSO4 + Na2CO3 CaCO3 + Na2SO4
This avoids the deposition of CaSO4 as scale and calcium is precipitated as loose sludge of CaCO3,
which can be removed by blow down operation.
iii) Calgon Conditioning:
Calgon conditioning involves addition of calgon (Sodium hexa meta phosphate) [Na6(PO3)6] to boiler
water. It prevents the scale and sludge formation by forming soluble complex compound with CaSO4.
Na2[Na4(PO3)6] 2Na+ + [Na4P6O18]2–
Calgon
2 CaSO4 + [Na4P6O18]2– [Ca2P6O18]2– + 2Na2SO4
(Soluble Complex Ion)
Desalination of sea water:
Two types of membrane processes are used in sea water treatment -
1) Electrodialysis membrane process
2) Pressure membrane process -Reverse Osmosis(RO)

1) Electrodialysis membrane process:

Electrodialysis membrane process comprise of sheet like barriers made up of high-capacity,highly
cross-linked ion exchange resins that allow passage of ions but not of water. These are of two types
Cation exchange membrane which allows only cation to pass through it and Anion exchange
membrane which allows only anion to pass through it.
In Electrodialysis setup Cation and Anion exchange membranes are installed alternatively in the tank.
After passing electric current cation and anions are attracted towards appositely charged electrodes. As
shown in figure,water in the compartment 1 and 3 become almost free of all the ionic impurities and it
can be withdrawn as the product water. Almost all the cationic and anionic impurities get concentrated
in the middle compartment no 2 and the concentrated solution is removed as waste. Compartment 1
and 3 are called diluting compartments while compartment no.2 is called concentrating compartment.

2) Reverse Osmosis(RO):
A Bag of semipermeable membrane is placed in a bigger container full of pure water. The membrane
bag contains a solution of Sucrose. Due to the osmotic pressure of the solution,water from outside is
22
suck into the bag through the membrane. This causes the solution level in the bag to rise,as indicated
by the height π shown in the figure. The height π is the measure of osmotic pressure .Now,if sufficient
pressure is applied to the tip of the tube in excess of that of osmotic pressure,the height π will be
suppressed and the flow of water through the membrane will be reversed ( the water inside the bag will
flow outside the bag into the container).This process is called Reverse Osmosis.
The percentage removal of a solute from water is depend on - functional group in the membrane,
nature of membrane surface, size of solute molecule, molecular weight of solute, degree of dissociation
of the solute molecule.

---------PDF COPY BY DR.MANISH M.JACHAK,ASST.PROF,SVPCET,NAGPUR

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