Water Technology

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 UNIT I
WATER AND ITS TREATMENT
 Water– sources and impurities
 Water quality parameters – Definition and significance of colour,
odour, turbidity, PH, hardness, alkalinity, TDS, COD and BOD,
fluoride and arsenic.
 Municipal water treatment - primary treatment and disinfection (UV,
Ozonztion, break-point chlorination).
 Desalination of brackish water - Reverse Osmosis.
 Boiler troubles (scale and sludge), Boiler corrosion, Caustic
embrittlement, Priming and Foaming.
 Treatment of boiler feed water: Internal treatment (phosphate,
colloidal, sodium aluminate and calgon conditioning)External
treatment – Ion exchange process, zeolite process

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 SOURCES OF WATER

WATER SOURCE

UNDERGROUND
SURFACE WATER WATER

Sea water Spring

water
River water
Well water
Lake water

Rain water
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TYPES OF IMPURITIES IN WATER

Biological impurities

Suspended impurities

Colloidal impurities

Chemical impurities

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 Water Technology
The process of removing all types of impurities
from water and making it fit for domestic or
industrial purposes is called water technology

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Hard Water
Water, which does not produce lather with soap
solution, but produces white precipitate is called hard water,
- due to dissolved Ca and Mg salts

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Soft Water
which produces lather readily with soap solution is
called soft water

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 HARDNESS OF WATER

What is hardness of water ?

It is the property of water which does not produce
lather with soap.

How to detect hardness?

Hardness can be detected in two ways.

1. Hard water + Soap solution ------------ White scum

CaCl2 + C17H35COONa -------------- (C17H35COO)2Ca + 2NaCl

(Sodium stearate)

2. Hard water + Eriochrome Black – T ------- Wine red

colour
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 TYPES OF HARDNESS
HARDNESS

Temporary Hardness Permanent Hardness

Or Or
Carbonate hardness Total Non-carbonate hardness
Or hardness Or
Alkaline hardness Non-Alkaline hardness

Due to the presence of Due to the presence of

carbonates chlorides &
and bicarbonates of Ca Sulphates of Ca & Mg
& Mg

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Temporary / Carbonate / Alkaline Hardness
It is due to the presence of Carbonates and bicarbonates
of Calcium and magnesium salts.

It can be removed by

- boiling the water.

- Adding lime to the water.
CO32- Ca Temporary Hardness
& &
HCO3- Mg

On boiling the bicarbonates are converted to soluble carbonates and

hydroxides which can be easily removed by filtering.
Boiling
Ca(HCO3)2 ------------ CaCO3 + H2O + CO2

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

Lime
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Permanent Hardness/Non-Carbonate hardness/Non-
alkaline hardness

- due to presence of chlorides and sulphates of

Ca and Mg.
- cannot be removed by boiling
- removed by Lime soda and Zeolite Process

CaCl2 + Na2CO3 CaCO3 + 2NaCl

Soda

CaSO4 + Na2Ze CaZe + Na2SO4

Zeolite

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 UNITS OF HARDNESS
PARTS PER MILLION - ppm
- the number of parts of CaCO3 equivalent present in
million parts of water

MILLIGRAM PER LITRE - mg/l

- the number of milligrams of CaCO3 equivalent present in
one litre of water

DEGREE FRENCH - 0 Fr
- the number of parts of CaCO3 equivalent present per
105 parts of water

DEGREE CLARKE - 0 Cl
- the number of grains of CaCO3 equivalent present per
gallon parts of water

1 ppm = 1 mg/l = 0.10 Fr= 0.070Cl

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 Why to express hardness in terms of CaCO3 equivalence?
Because,

Its molecular weight is 100 and its equivalent weight is 50,

which is a whole number easier for calculation.

It is the most insoluble salt that can be precipitated in

water treatment.

Calculating CaCO3 equivalence

Weight of hardness producing salt

CaCO3 equivalence = X 100
Molecular Weight of hardness producing salt

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 Water Quality Parameters
Colour:
Imparted by organic or inorganic material
pale straw through yellowish-brown to dark brown.

Sources:
1. Organic sources - Algae, tannins, humic compounds,
organic dyes, etc.
2. Inorganic sources - Fe and Mn compounds,
chemicals and inorganic dyes
 Water Quality Parameters
Colour:
Significance:

1. The colours and the materials which produce colour are

objectionable
2. Variation in colour of water serves as index of quality of the
water.
a. Yellowish tinge - 'Cr' and organic matter.
b. Yellowish red - iron.
c. Red-brown - peaty matter

Removal of colour:
coagulation, settling, adsorption and filtration
 Water Quality Parameters
Tastes and Odours
Taste
Taste is the sensation of flavour perceived in the mouth
and throat on contact with a substance.
Odour
Odour is a smell (or) scent caused by one (or) more
volatilized chemical compounds that are generally found in
low concentration.
Sources
Organic sources: Algae and decaying vegetation, etc.
Inorganic sources: Mercaptans, amines and sulphides, etc.
 Water Quality Parameters
Tastes and Odours
Significance
•Disagreeable odours and tastes are objectionable for
various industrial processes
•Most of the odours in natural waters are organic in nature,
except H2S.
•Taste helps we us to decide what to eat and influences
how efficiently we digest these foods
•Senses of smell and taste are vital in identification of
valuable nutrients in the environment.
•Taste enables the evaluation of foods for toxicity.
 Water Quality Parameters
Turbidity:
Turbidity is the reduction of clarity of natural water due to the
presence of finely divided, insoluble impurities suspended in
water.

Sources

Inorganic sources : Clay, silt, silica, ferric hydroxide, calcium

carbonate, sulphur, etc .,

Organic sources : Finely divided vegetable or animal matter, oils,

fats, greases, etc.,
 Water Quality Parameters
Turbidity:
Significance:
•Turbidity affects the taste and odour of drinking water.
•It blocks light to aquatic plants and aquatic organisms.
•Turbidity affects the growth rate of algae.
•It increases water temperature because suspended
particles absorb more heat.
Removal of Turbidity:
Coagulation and filtering
Coagulation and settling
Coagulation, settling and filtering
 Water Quality Parameters
pH:
The hydrogen ion concentration is represented by the pH
value
pH = - log10[ H+]

The pH value ranges from 0-14 as

O < -- -- ->7 < ----- >14
Acidic<- Neutral - >Basic

Significance:
pH determines the solubility
Determines the biological availability
A rise (or) fall in pH can indicate chemical pollution (or)
acid rain
 Water Quality Parameters
Alkalinity:
Alkalinity of water is a measure of its acid-neutralising ability.

Sources :
Hydroxides, carbonates and bicarbonates

Significance:
Very high values of alkalinity are harmful to aquatic organisms.
Alkalinity in boiler feed water causes caustic embrittlement of
pipes.

Removal of Alkalinity:
Alkalinity in water, can be removed by adding limited amount of
HCI.
 Water Quality Parameters
Hardness of water:
characteristics of water, which does not produce lather with soap.

Types of hardness
.Temporary hardness.
due to the presence of bicarbonates of calcium and magnesium. It can be
removed by (i) boiling the water (ii) adding lime to the water.

Permanent hardness.
due to the presence of chlorides and sulphates of calcium and
magnesium. It cannot be removed by boiling the water. But, it can be
removed by (i) Lime-soda process (ii) Zeolite process.

Significance:
Hardness affects the amount of soap that is needed to produce foam.
It forms scale in heat exchange equipments.
Hardness mitigates metal toxicity
 Water Quality Parameters
TDS - TDS stands for Total Dissolved Solids
It is defined as the measure of all inorganic and organic substances
present in water.

Significance
(i) TDS impacts the salinity of water.

(ii) TDS in water must be filtered out before intake.

(iii)Water with TDS level higher than 300 ppm taste salty.

(iv)Water with high level of TDS (> 1200) impacts the color, odour and
taste.

(v) Water with high level of TDS may not be suitable due to excessive
scaling.
 Water Quality Parameters
Biological Oxygen Demand (BOD)
BOD is defined as, "the amount of free oxygen required by
bacteria for the biological oxidation of the organic matter under
aerobic conditions at 20°C for a period of 5 days".

Significance
Indicates the amount of decomposable organic matter in the
sewage.

Enables to determine the degree of pollution.

Lesser the BOD, better is the quality of water.

 Water Quality Parameters
Chemical Oxygen Demand (COD)
COD is defined as, "the measure of amount of oxygen required to
chemically oxidise all the oxidisable impurities present in sewage
using an oxidizing agent like acidified K2Cr2O7".

Significance
Measures both the biologically oxidisable and biologically inert
organic matter.

Used to monitor water treatment plant efficiency.

COD is used to measure pollutants in water.

It provides an index to assess the effect of discharged waste water.

 Water Quality Parameters
Fluoride
Found in ground water as a result of dissolution from geologic formulations.
Sources
Fluoride containing minerals
Contaminated domestic sewage, run-off from agricultural lands.

Significance
Optimum permissible fluoride concentration in water 0.7 to 1.2 mg/lit.
Low fluoride concentration – causes dental caries in children
High fluoride concentration - Causes fluorosis

Removal
Precipitation using Aluminium salts
Using strongly basic anion exchange resin
Adsorption on activated carbon
 Water Quality Parameters
Arsenic
It is a metallic element that forms poisonous compounds.

Source:
Natural deposits
Runoff

Significance:

Long-term intake leads to arsenic poisoning with cancer of skin,

bladder, kidney

Produces diabetes, hypertension and reproductive disorders

Children may be at greater risk of illness.

 Municipal water treatment
Domestic supply of water involves the following
stages in the purification processes
 Primary Treatment
Screening
Process of removing the floating materials
Screen - retains the floating materials
 Primary Treatment
Aeration
Process of mixing water with air
Remove gases, bad taste, odour, ferrous and
manganous salts.
 Primary Treatment
Sedimentation
•Process of removing suspended impurities
•Water is allowed to stand undisturbed for 2-6
hours - suspended particles settle down
 Primary Treatment
Coagulation
Finely divided particles are removed
Alum Al2(SO4)3
- form a gelatinous precipitate of Al(OH)3
- entraps the finely divided colloidal impurities
 Primary Treatment
Filtration
Process of removing bacteria, colour, taste, odour and
suspended particles.
 Disinfection
The process of removing harmful bacteria

By Using Ozone
Ozone is a powerful disinfectant

It breaks down to give nascent oxygen which is a

powerful oxidizing agent and kills bacteria.
O3 O2 + [O]
 Disinfection
By using ultraviolet (UV) radiations

UV rays are produced by passing electric current

through mercury vapour lamp

Useful for sterilizing water in swimming pool

 Disinfection
3. By chlorination
The process of adding chlorine to water

(a) By adding chlorine gas

Chlorine gas can be bubbled in the water

(b) By adding chloramine

When chlorine and ammonia are mixed in the ratio
2:1 chloramine is formed which is a better disinfectant
than chlorine.
Cl2 + NH3 ClNH2 + HCl
 Disinfection
(c) By adding bleaching powder
When bleaching powder is added to water, it
produces hypochlorous acid which is a
powerful germicide.

CaOCl2 + H2O Ca(OH)2 + Cl2

Cl2 + H2O HCl + HOCl

HOCl + Bacterias Bacterias are killed

 Break Point Chlorination
Water contains Bacteria, Organic impurities, Reducing
substances and Free ammonia.
 Break Point Chlorination
Chlorine is applied in the form of gas
applied chlorine is used to kill the bacteria and oxidizing the
reducing substances and there is no residual chlorine.
applied chlorine increase results in increase of residual
chlorine.
Further chlorination results in oxidation of chloramines

Break point chlorination is the point at which the combined

residual chlorine decreases to a minimum point where
oxidation of chloramines and other impurities complete and
free residual chlorine begins to appear.

The break point chlorination eliminates bacterias, reducing

substances, organic substances
Desalination - Reverse Osmosis

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What is desalination?
Process of removing common salt from the water and to make it
fit for drinking or usable for industrial purposes is called
desalination.
Brackish water - Water containing dissolved salts with a peculiar salty taste.
Example: Sea water

Desalination of Brackish water can be done by,

Distillation method
Multi stage evaporators
Electro-dialysis
Reverse Osmosis
Freezing

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 Methods of desalination of Brackish water

Distillation method

- Sea water is boiled and evaporated in giant stills.

- Water vapour is collected and condensed into fresh drinkable

water.

Multi stage evaporators

- Repeated heating, evaporation and condensation of sea water.

Electro-dialysis

- is a method in which ions are pulled out of the salt water

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 Water is classified into three types based
on the dissolved salts.

Fresh water -- <1000 ppm

Brackish water -- >1000 and < 35,000
ppm
Sea water -- > 35,000 ppm

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 Reverse Osmosis
What is Osmosis?

When two solutions of different concentrations are

separated by a semi-permeable membrane, the flow of
solvent from the side of dilute solution side to
concentrated solution side takes place and is called as
osmosis and the pressure which drives is called osmotic
pressure.

Through Semi-permeable
Solvent from membrane Solvent to
Dilute Side Concentrated Side

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What is Reverse Osmosis?
If osmotic pressure is applied on the higher concentration side, the solvent
flow will be from concentrated solution side to the dilute side through the semi-
permeable membrane is called as reverse osmosis.

Osmotic pressure
Through Semi-permeable
membrane
Solvent from Solvent to
Concentration Side Dilute Side

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Thus in reverse osmosis Pure Solvent (water) is separated from
contaminates, rather than removing contaminants from water.

Also called “Super-filtration” or “Hyper-filtration”

Pressure of the order 15 to 40 Kg cm-2

Membrane consists of thin films of cellulose acetate, polymethacrylate

and polyamide polymers.

Advantages:

1. all ionic & non-ionic, collodial & high mol.wt organic matters are
removed
2. Maintenance cost is less- replacement of membrane.
3. Replaced in 2 mins, providing uninterrupted water supply.
4. Simple, low capital cost, operating cost, high reliability.

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Boiler Feed Water

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 What is boiler feed water/ Boiler troubles?

The water supplied into boiler for the production of

steam.
Boiler feed water should be free from,

- Turbidity
- Dissolved gases
- Oil
- Alkali
- Hardness creating substances

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 Disadvantages of using hard water in boilers

If the raw water is supplied directly to the boilers, the

following troubles may arise;

- Scale and sludge formation

- Priming and foaming – Carry over

- Caustic embrittlement - Inter-crystalline cracking

- Boiler corrosion

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 Sludge formation
Formation of loose and slimy precipitate after saturation point.
Sludge are formed by substances like
- MgCl2, MgCO3, MgSO4 and CaCl2

-Greater solubility in hot water than in cold water

- sludges formed generally at colder part and get collected at
places where the flow rate is slow.

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 Disadvantages of Sludge formation

- Poor conductor of heat

- Wastes some amount of heat energy

- Disturbs the working of the boiler like poor water circulation,

choking of pipes ,etc.,
Prevention of Sludge formation

- Using softened water

- Frequent removal of the

concentrated water by blow down operation

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 Scale formation
Precipitation in the form of hard adhering layer on the inner walls of the
boiler.
Scales are formed by substances like
- Ca(HCO3)2, CaSO4, CaCO3, Mg(OH)2,etc.,

Formed due to,

1. Decomposition of CaCO3
2. Formation of CaSO4 precipitate
3. Hydrolysis of magnesium salts
4. Presence of small quantity of SiO2

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 Disadvantages of scale formation

- Wastage of fuel

- Poor thermal conductors

- Act as heat insulator

- Danger of explosion

Removal of scales
- Using Scrapper / wire brush
- By thermal shocks
- Adding suitable chemicals like some dilute
acids
- By blow down operation

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 Difference between Scale & Sludge formation

Boiler Sludge Boiler Scale

Loose, slimy and non-adherent Hard adherent coating

precipitate

Due to MgCl2, MgCO3, MgSO4 and Ca(HCO3)2, CaSO4, CaCO3, Mg(OH)2,etc.,

CaCl2

Poor conductors of heat Act as thermal insulators

Can be prevented by using softened Prevented by adding HCl, H2SO4 etc

water.

Removed by blow down operation. Removed by external and internal

treatment.
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 Priming
It is the process of production of wet steam.
Causes

- High steam velocity

- Very high water level in boiler
- Sudden boiling of water
- Very poor boiler design

Prevention

- controlling the velocity of steam

- keeping the water level lower

- good boiler design

- using treated water

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 Foaming
It is the process of formation of stable bubbles above the
surface of water.

Causes

- presence of oils, which lowers the surface tension of water

- clay or organic matter in water
- finely divided particles of sludge

Prevention

- adding antifoaming chemicals like castor oil

- removing oil from boiler water by adding clarifying agents

such as aluminium hydroxide or sodium aluminate.

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 Caustic Embrittlement / Inter-Crystalline cracking

A type of boiler corrosion caused by using highly alkaline water

in the boiler.
Causes
STEP I
In high pressure boilers, small amounts of Na2CO3 present in the
water undergo decomposition to give NaOH.

Na2CO3 + H2O ------- 2NaOH + CO2

STEP II
NaOH formed flows into minute hair like cracks in the boiler by
capillary action.

STEP III
As water evaporates, its concentration increases and dissolve the
iron and forms sodium ferroate.
Fe + 2NaOH -------- Na2FeO2 + H2

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 Caustic Embrittlement / Inter-Crystalline cracking

Prevention

1) Using sodium phosphate as softening agent instead of

sodium carbonate.

2) Adding tannin or lignin to boiler water to block the hair

cracks

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 Boiler Corrosion

Due to the presence of

a) Dissolved oxygen
b) Dissolved Carbon di oxide
c) Dissolved salts

Dissolved Oxygen
DO attacks boiler material and forms rust.

4Fe + 2H2O + O2 ----- 4Fe(OH)3

2Fe2O3 .2H2O
Rust

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 Removal of Dissolved Oxygen

- Chemical method - By adding oxygen scavengers

- By Mechanical deaeration

Chemical method

By adding oxygen scavengers

By adding Sodium sulphite

2Na2SO3 + O2 ------- 2Na2SO4

By adding hydrazine
N2H4 + O2 ----- N2 + 2H2O

Mechanical Deaeration
Water flows through a tower fitted with perforated plates.
Tower is heated and connected to a vacuum pump.
High temperature and low pressure reduces the amount of DO in
water. 62
 Dissolved CO2
Carbon dioxide gas is also produced from the decomposition of
bicarbonate salts present in water.

Dissolved carbon dioxide in water produces carbonic acid, which

is acidic and corrosive in nature.

Removal of CO2

- Chemical method - By adding ammonium hydroxide

- By Mechanical de-aeration

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 Dissolved Salts

MgCl2 and CaCl2 undergo hydrolysis at higher temperature to

give HCl which corrodes the boiler.

MgCl2 + 2H2O ------ Mg(OH)2 + 2HCl

Fe + HCl ------ FeCl2 + H2

FeCl2 + 2H2O ------ Fe(OH)2 + 2HCl

2Fe(OH)2 + O2 ------- [ Fe2O3.2H2O ]

Acids cause corrosion to boilers – avoided by addition of NaOH

to boiler water.

HCl + NaOH ---------- NaCl + H2O

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 Requirement of boiler feed water

BOILER TROUBLE REQUIREMENT

Scale and Sludge Zero hardness
formation

Priming and Foaming Absence of suspended impurities

& dissolved salts

Caustic embrittlement Absence of Alkalinity – NaOH &

KOH

Boiler Corrosion Absence of dissolved CO2, O2 and

salts

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Softening
Methods

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 Methods of softening

External Conditioning Internal Conditioning

/ Sequestration

- Lime soda process

- Carbonate conditioning
- Zeolite process
- Calgon conditioning
- Demineralization / Ion exchange
/ Deionization - Phosphate conditioning
- Colloidal conditioning
- Electrical Conditioning
- Radioactive conditioning

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 INTERNAL TREATMENT

Traces of impurities present in boiler feed water are removed by

adding certain chemicals inside the boiler is called internal conditioning.

The chemicals used for this purpose are called as boiler compounds.

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Phosphate conditioning

In high pressure boilers, scale formation is avoided by adding

sodium phosphate.

It reacts with calcium and magnesium to form non-adherent soft

sludge of calcium and magnesium phosphates.

Sludge is removed by blow down operation.

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

The phosphates used are,

a) Tri sodium phosphate – Na3PO4 – for alkaline water

b) Disodium hydrogen phosphate – Na2HPO4 – for weakly alkaline water

c) Sodium dihydrogen phosphate – NaH2PO4 – for acidic water

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Calgon conditioning
Calgon is sodium hexa meta phosphate Na2[Na4(PO3)6]

2CaSO4 + Na2[Na4(PO3)6] Na2[Ca2(PO3)6] + 2Na2SO4

Soluble complex

No Sludge disposal problem in Calgon conditioning.

Calgon conditioning is better than phosphate conditioning

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Sodium aluminate conditioning

 sodium aluminate gets hydrolysed and yields sodium

hydroxide and aluminium hydroxide precipitate

NaAlO2 + 2H2O -------- > NaOH + Al(OH)2 (ppt.)

NaOH reacts with Mg ion in hard water to form Mg(OH)2

precipitate

MgCl2 + 2NaOH ---------- > 2NaCl + Mg(OH)2 (ppt.)

Precipitated hydroxides are removed by blow down operation

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What is demineralization?

It is a method based on ion exchange property of the polymeric resins,

used for treating hard water.

What is ion exchange resin?

Resins are insoluble, cross-linked, long chain organic polymers with

micro porous structure and functional groups attached to the chains
which are responsible for the ion exchange properties.

Types of Resins
 Cation exchange resin

 Anion exchange resin

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 Types of Resins
Cation exchange resins

- Resins with acidic functional groups like COOH, SO3H, etc.,

- capable of exchanging their H+ ions with other cations
like Na+, Ca2+, Mg2+, etc

- Represented as RH2
- Example: Sulphonated Coals and Polystyrene

Anion exchange resins

- Resins with basic functional groups like NH3OH, etc.,

- capable of exchanging OH- ions with other anions like Cl-, SO42-, HCO3-

- Represented as R(OH)2

- Example: quaternary ammonium groups and Urea Formaldehyde resin

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RH2 + CaCl2 ------- RCa + 2HCl R’(OH)2 + 2HCl ---------- > R’ Cl2 + 2H2O

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Process
In Cation exchange resin
- Hard water passed through a cation exchange column.

- Cations like Ca2+, Mg2+, Na+, etc get absorbed on the resin.

-H+ ions are released.

RH2 + CaCl2 ------- RCa + 2HCl

In Anion exchange resin

- Water free from cations is passed through second column containing
anion exchange resin.

- Anions like Cl-, SO42-, HCO3-, CO32- are exchanged.

- OH- ions are released.

R’(OH)2 + 2HCl ---------- > R’ Cl2 + 2H2O

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 Regeneration of resins

Regeneration of Cation exchange resins

Done by passing a solution of dilute HCl or H2SO4

RCa + 2HCl RH2 + CaCl2

Regeneration of anion exchange resins

Done by passing a solution of dilute NaOH

R’Cl2 + 2NaOH R’ (OH)2 + 2NaCl

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 Advantages
 Highly acidic or alkaline water can be treated.
 Hardness present in the treated water is low - suitable in high
pressure boilers.
Disadvantages
 Turbid water can be treated.
 Water with Iron and Manganese cannot be treated.
 Equipment is costly.
 Chemicals are expensive.
 Regeneration is difficult.

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Zeolite Process or Premutit
Process
- Zeolite is porous and gel like structure
- naturally occurring hydrated sodium alumina
silicate, Na2O.Al2O3.xSiO2.yH2O
- represented by Na2Z
- sodium ions loosely held in Na2Z are replaced
by Ca2+ and Mg2+ ions present in the water

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Process:

When hard water is passed through bed of sodium

Zeolite , it exchanges its sodium ions with Ca 2+ and
Mg 2+ ions, to form calcium and magnesium zeolites.

Ca(HCO3)2 + Na2Ze ---- CaZe + 2NaHCO3

CaSO4 + Na2Ze ----- > CaZe + Na2SO4

CaCl2 + Na2Ze ------ > CaZe + 2NaCl

The softened water is enriched with large amount of

sodium salts, which do not cause any hardness, but
cannot be used in boilers.

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Regeneration:
The exhausted zeolite is again regenerated by treating
with 10% solution of NaCl.

CaZe + 2NaCl ---------- > Na2Ze + CaCl2

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Advantages:

1. Hardness is less, 1 -2 ppm

2. Cheap method
3. No sludge formation
4. The equipment is compact and occupy less space
5. Operation is easy

Disadvantages:

1. Turbid water cannot be treated, it blocks the pores.

2. Acidic water cannot be treated, it decomposes the Zeolite.
3. Water containing Fe, Mn cannot be treated, because
regeneration is very difficult.
4. Not suitable for softening brackish water, because it
contains more sodium ions.

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