Water technology

Prof. Dr. Ala’a Al.Mohammed

 Unit I – WATER TECHNOLOGY
Introduction – importance of water and its sources

Hard water and soft water - definition

Hardness of water – definition, types and its estimation

Boiler feed water – requirements, scale & sludge, priming & foaming,
Caustic embrittlement and Boiler corrosion

Softening / Conditioning Methods – Internal & External methods

Internal conditioning – carbonate, phosphate and calgon conditioning

External conditioning – ion exchange process and zeolite process

Desalination of Brackish water – reverse osmosis

 Unit II – Electrochemistry and Corrosion
Introduction – conductors and their types, non-conductors (insulators)

Cells – types of cells

Redox Reactions – oxidation and reduction

Electrode potential – standard electrode potential, Nernst equation

Electrochemical Series – definition and its applications

Causes of corrosion – definition for corrosion and causes

Effects of corrosion

Types of corrosion – dry (chemical) – oxidation corrosion, corrosion by hydrogen

and liquid-metal corrosion

wet (electrochemical) – galvanic corrosion, differential
aeration corrosion
Factors influencing the rate of corrosion – nature of the metal and
nature of the environment

Corrosion control – a) material selection and design aspects,

b) cathodic protection – sacrificial anodic protection and
impressed current cathodic protectioin
c) by modifying the environment

Protective coatings – paints & metallic coatings – electroplating and

electroless plating
 Unit III – Energy Resources
Introduction – various energy sources

Nuclear fission & nuclear fusion - definition

Nuclear reactor & Breeder reactor

Solar energy conversion & Wind energy

Batteries – definition & types of battery

Alkaline battery & Lead storage cell – construction & working

Nicad battery – construction and working

Lithium battery – advantages and disadvantages

Fuel cells – hydrogen-oxygen fuel cell

 Unit IV – Engineering Materials

Abrasives – definition, properties, classification and applications

Refractories – definition, characteristics, classification & properties

Manufacturing methods of refractories & important refractory bricks

Cement – definition, Portland cement manufacture & special cements

Glasses - types
 Unit V – Fuels and Combustion
Introduction – types of fuels

Coal – analysis of coal, carbonisation, coke and its manufacture

Petroleum – synthetic petrol, Diesel oil, knocking – octane and cetane number

CNG, LPG, Producer gas, Water gas & Bio-diesel

Calorific value – higher and lower calorific values

Stoichiometric calculations of fuel and air ratio

Ignition temperature & explosive range

Flue gas analysis – ORSAT method

UNIT I – WATER TECHNOLOGY
IMPORTANCE OF WATER

Living things are indeed in need of water.

It cleanses our body.

It energizes us every day.

It keeps our body temperature at the right level.

It is one of the essential resources for our health.

Water is essential for the existence of human beings, animals and plants.

Though 80% of the earth’s surface is occupied with water, less than 1%
of water is available for ready use.
 SOURCES OF WATER

Surface water : Rain, Rivers, Lakes and Sea

Ground water: Wells and Springs

 Impurities in water

Dissolved impurities – inorganic salts of Na, K, Ca, Mg, Al, Fe and traces
of other metals as chlorides, sulphates, bicarbonates,

etc.

Dissolved gases – oxygen, nitrogen, CO2, oxides of N and S, NH3, or H2S

Suspended impurities - sand or clay particles, decayed organic substances.

Microbial and biological impurities – pathogenic microorganisms, biological

matter of plant and animal origin.
Surface and ground water are normally used for industrial and domestic purposes.

Hence undesirable impurities should be removed from these water.

Water treatment / water technology - the process of removing all types of

impurities from water and make it suitable for industrial and domestic purposes.
 Quality of water for different uses
Purpose Quality requirements
Drinking Palatable, clear and free from colour, odour,
turbidity and pathogens.
Domestic Soft water producing lather readily.
washing
Textile dyeing Free from colour, turbidity, organic matter, Fe and
Mn.
Boiler feed Free from dissolved salts, suspended impurities, silica
water and dissolved gases.
Drugs and Soft and clear. Free from pathogens, colour, odour
pharmaceutical and suspended impurities.
s
Construction Not too hard, should contain less of chlorides.
Paper industry Free from colour, turbidity, organic matter, Fe, Mn,
silica and alkalinity
Analysis of water

Hardness, alkalinitym, total dissolved solids (TDS), dissolved oxygen (DO),

colour, iron, chloride and turbidity.

Fluoride, sulphate, nitrate, nitrite, biochemical oxygen demand (BOD), chemical

oxygen demand (COD) , metal ions – Mn, Pb, As.
 HARD WATER and SOFT WATER
Hard water – does not produce lather with soap solution, but produces
white precipitate.

Soft water – produces lather readily with soap solution.

Hard water Soft water
Disadvantages of using hard water
HARDNESS OF WATER

Hardness – the property or characteristics of water, which does not produce lather
with soap.

Detection of hardness

Hard water does not produce lather with soap solution and produces white scum.

Hard water gives wine red colour with Eriochrome Black-T indicator at pH 9 – 10.
TYPES OF HARDNESS
1.Temporary hardness (or) Carbonate hardness:

- due to the presence of bicarbonates of Ca and Mg.

- removed by boiling the water; adding lime to the water.

2.Permanent hardness (or) Non-carbonate hardness:

- due to the presence of chlorides and sulphates of Ca and Mg.

- removed by i) lime soda process and ii) zeolite process.

Total hardness – the sum of temporary hardness and permanent hardness.

Units of hardness

ppm – the number of parts by weight of CaCO3 equivalent hardness per million
(106) parts of water.

mg/l – the number of milligrams of CaCO3 equivalent hardness per litre of water.

The concentration of hardness producing salts is calculated as

Mass of hardness producing salt x 50

amount of equivalent of CaCO3 = --------------------------------------------------
Chemical equivalent of the hardness
producing substance
Determination of hardness

1.Soap titration method

2.Hohner’s alkali titration method

3.EDTA method
BOILER FEED WATER

In industry one of chief uses of water is generation of steam by boilers.

Boiler feed water – the water fed into the boiler for the production of steam.
Requirements of boiler feed water

It should have zero hardness.

It must be free from dissolved gases like O2, CO2, etc.
It should be free from suspended impurities.
It should be free from dissolved salts and alkalinity.
It should be free from turbidity and oil.
It should be free from hardness causing and scale forming constituents like
Ca and Mg salts.
Boiler troubles (or) Disadvantages of using hard water in boilers

Formation of deposits (scales and sludges).

Priming and foaming (carry over).
Caustic embrittlement.
Boiler corrosion.
 Formation of deposits in boilers and heat exchangers

On continuous evaporation of water in boiler the concentration of soluble

matters increases progressively which leads to the deposition of salts.
SLUDGE – the precipitate is loose and slimy

formed by the substances like MgCl2, MgCO3, MgSO4 and CaCl2.

have greater solubility in hot water than cold water.

SCALE - precipitate forms a hard and adherent coating on the inner walls.

- formed by the substances like Ca(HCO3)2, CaSO4 and Mg(OH)2.

 Comparison of scales and sludges
S. No. Sludge Scale
1. A loose, slimy and non- S hard and adherent
adherent precipitate coating
2. MgCO3, MgCl2, MgSO4 Ca(HCO3)2, CaSO4,
and CaCl2 Mg(OH)2
3. Poor conductors of heat Decreases the efficiency
and decreases the of boiler, crack
efficiency of boiler developed leads to
explosion
4. Prevention:
Using softened water Using HCl, H2SO4
By blow-down operation Internal and external
treatment, by applying
thermal shocks,
scrapers, wire brush,
etc.
 Disadvantages of scales & sludges

1. Wastage of fuels

The heat transfer from boiler to inside water in not efficient

because of the low thermal conductivity of scales.

Overheating is done to provide steady supply of heat to water

which causes wastage of fuel.

The wastage of fuel depends on the thickness and nature of the

scale, which is shown in the table.
Thickness of scale
(mm)
Wasrage of fuel
2. Decrease in efficiency – due to the deposition of scales in the
valves and condensers of the boiler and choke.

3. Boiler explosion

Sometimes due to over heating the thick scales may crack and causes
sudden contact of high heated boiler material with water.

This causes formation of a large amount of steam and high pressure is

developed which may lead to explosion.
 Prevention of scales

Scales can be removed using scraper, wire brush etc. at the initial
stage.

If scales are brittle, they can be removed by thermal shocks.

By using suitable chemicals like dil. acids (for CaCO3 scale), EDTA
(for CaSO4 scale) with which they form suitable complexes.

If the scales are loosely adhering, they can be removed by frequent

blow down operation.
Priming and Foaming

Priming – the small droplets of liquid water associated with steam (wet steam).

Carry over - the droplets of water carry some suspended and dissolved solids.

It is caused by -

a.Improper boiler design

b. Very high water level in the boiler
c. Presence of finely divided particles in the water
d.Sudden increase in boiling rate
e.High steam velocity
 Prevention of priming

Priming can be prevented by

a.Controlling the velocity of steam.

b.Keeping the water level lower.
c.Using good boiler design.
d.Using soft water.

Priming can be minimized by placing a series of baffle plates or spiral baffles

near the steam outlet to facilitate the condensation of water droplets carried
over by the steam .
Foaming – the formation of stable bubbles over the surface of water.

These bubbles are carried over by steam leading to priming.

It is caused by

a.The presence of oil, grease, organic matter or finely divide solids.

b.Substances which decrease the surface tension of water and increase the
viscosity of the film.
Foaming can be prevented by

1.the addition of coagulants such as ferrous sulphate and sodium aluminate.

2. adding antifoaming agents such as castor oil or ployamides.

Caustic embrittlement

A form of corrosion caused by high concentration of NaOH in the boiler feed water.

It is a type of electrochemical corrosion occurs when the concentration of NaOH is

above 100 ppm. It occurs at the stressed parts like bends, joints, rivets, etc.
Caustic embrittlement
 Prevention of caustic embrittlement

Caustic embrittlement can be prevented by

using sodium phosphate as the softening agent instead of Na2CO3.

adding chemicals such as tannin, lignin to the boiler water. They block the
hairline cracks.

adjusting the pH of the feed water carefully between 8 and 9.

Boiler Corrosion

Corrosion in boilers is due to the presence of

dissolved oxygen

dissolved carbon dioxide

dissolved salts like MgCl2

 Dissolved oxygen

Water containing dissolved oxygen when heated in a boiler, free oxygen is

evolved, which corrodes the boiler material.

Dissolved carbon dioxide

When water containing bicarbonates is heated, CO2 is evolved which makes the
water acidic (by forming carbonic acid). This leads to intense local corrosion
called pitting corrosion.
Dissolved MgCl2

Hydrochloric acid, produced from MgCl2, attacks the boiler in a chain-like

reaction producing HCl again and again which corrodes boiler severely.

Corrosion by HCl can be avoided by the addition of alkali to the boiler water.
Prevention of boiler corrosion – chemical method or mechanical method

Chemical method

Removal of dissolved oxygen – sodium sulphite, hydarzine

Removal of dissolved CO2 – NH4OH

Mechanical method – dissolved oxygen and CO2 can be removed mechanically by
The de-aeration method.
Mechanical de-aerator
Softening or Conditioning Methods of Hard Water

It is mandatory to soften water to make it free from hardness producing

substances, suspended impurities and dissolved gases, etc.

Softening or conditioning of water - the process of removing hardness producing

salts from water.

Two methods – External treatment and Internal treatment

Distillation
External Treatment – the removal of hardness producing salts from the water
Before feeding it into the boiler.

Lime-soda process

Zeolite or Permutit process

Demineralisation or Iron exchange process

Zeolite (or) Permutit Process

Hydrated sodium aluminosilicate – Na2O.Al2O3.xSiO2.yH2O; x = 2 – 10, y = 2 – 6

Natrolite – Na2O.Al2O3.3SiO2.2H2O

Natural zeolites are green sand and are usually non-porous.

Permutit – artificial zeolite, porous.

Sodium zeolite – Na2Ze which exchange Na+ ions with the hardness producing
ions like Ca2+, Mg2+ in water.
Process
The sodium salts formed in the above reactions remain dissolved in the softened
water and do not impart any hardness.
Regeneration

Sodium zeolite gets exhausted due to its conversion into Ca and Mg zeolites.

Regeneration is done by percolating 10% brine solution through the exhausted

zeolite. The Ca and Mg zeolites are converted back into sodium zeolite.
Advantages of the process

Water obtained by this process will have a residual hardness between

7 and 15 ppm

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

This process does not produce any sludge and hence a clean process.

The equipment is compact and occupies less space.

Disadvantages of the process

The process exchanges only calcium and magnesium ions with sodium ions and
hence the softened water contain more sodium and also more of dissolved salts.

It does not remove the acidic ions such as bicarbonate and carbonate and remain
as sodium salts contributing to the alkalinity and causes boiler corrosion.

The water containing turbidity and suspended impurities cannot be treated by this
method because turbidity clogs the pores of the zeolite bed.

The process cannot tolerate acidity or alkalinity as the zeolite disintegrates.

The process is not very efficient for treating water containing large quantities of
Fe2+ and Mn2+ ions as these ions convert sodium zeolite into their respective zeolites
which are difficult to be regenerated.
Demineralization or Ion Exchange Process

This process removes almost all the ions present in water.

Soft water does not contain hardness producing Ca2+ and Mg2+ ions but it may
contain other ions like Na+, K+, Cl-, SO42-.

Every soft water is not demineralized water whereas every demineralized water
is soft water.

Ion exchangers are resins with a long chain, cross-linked, insoluble organic
polymers with a microporous structure. The functional groups attached to the
chains are responsible for the ion exchanging properties.
The following two types of resins are used for demineralization process:

Cation exchange resins and Anion exchange resins

Cation exchange resins – possess acidic group such as –COOH or –SO3H groups.
Cations in hard water are exchanged with H+ ions of this resins. This resin may be
represented as RH2.

examples: sulphonated coal, sulphonated polystyrene

Anion exchange resins – possess basic groups such as OH- or NH2- group. Anions
in hard water are exchanged with –OH ions of this resins. It may be represented as
R’(OH)2.

examples – cross-linked quaternary ammonium salts, urea-formaldehyde resin.

 A strongly acidic sulphonated
polystyrene cation exchange resin
A strongly basic quaternary ammonium
anion exchange resin
 Process

Demineralization or Ion Exchange Process

Hard water is first passed through the cation exchange resin. The cations like
Na+, K+, Ca2+, Mg2+, etc. in hard water get exchanged with H+ ions of the resin.

The water coming out from this column is acidic in nature.

The water is then passed through the anion exchange resin which exchanges the
anions like Cl-, SO42-, HCO3- with OH- ions of the resin.

The water coming out from this column is completely free from both cations and
anions. H+ and OH- ions combine to produce water molecule.

The water coming out from the second column is neutral and is free from all ions.
It is known as deionised or demineralised water.
Regeneration of resins

The exhausted cation exchange resin is regenerated by percolating a dilute HCl

solution through it.

The exhausted anion exchange resin is regenerated by percolating dilute NaOH

solution through it.
Advantages

The hardness of water can be reduced to about 2 ppm and hence it is suitable for
use in high pressure boilers.

Highly acidic or highly alkaline water can be softened by using this process.

Limitations

The resin used in the process are quite expensive.

If water contains turbidity, the efficiency of the process is reduced.

Water containing Fe and Mn cannot be treated because they form stable product
with the resins.
Differences between zeolite and demineralization processes
S. No. Zeolite Process Demineralization process
1. Only cations are exchanged. Both cations and anions are
exchanged.
2. Since acidic water decomposes Acidic water can be treaated.
the zeolite it cannot be treated.
3. Treated water contains more Water treated by this process
dissolved salts which causes contains no dissolved salts and
priming, foaming and caustic no priming or foaming is
embrittlement in boilers caused.
4. Disadvantages Disadvantages
Water with Fe, Mn and Water with Fe, Mn and
turbidity cannot be treated. turbidity cannot be treated.
Internal Treatment or Internal Conditioning

It involves adding chemicals directly to the water in the boilers for removing
dangerous scale forming salts.

This method is used to convert scale ro sludge which can be removed by

blow-down operation.
The following are the internal conditioning methods

Carbonate conditioning
Phosphate conditioning
Calgon conditioning
Colloidal conditioning
EDTA conditioning
 Carbonate conditioning

Scale formation can be avoided by adding Na2CO3 to the boiler water.

It is used only in low pressure boilers.

The scale forming salt like CaSO4 is converted into CaCO3, which can be
removed easily.
Phosphate conditioning

Scale formation can be avoided by adding sodium phosphate.

It is used in high pressure boilers.

The phosphate reacts with calcium and magnesium salts to give soft
sludges of calcium and magnesium phosphates.
Generally 3 types of phosphates are employed

Trisodium phosphate – Na3PO4 (too alkaline) : used for too acidic water.

Disodium hydrogen phosphate – Na2HPO4 (weakly alkaline) : used for

weakly acidic water.

Monosodium dihydrogen phosphate – NaH2PO4 (acidic) : used for

alkaline water.
Calgon conditioning

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

This interacts with calcium ions forming a highly soluble complex and thus
prevents the precipitation of scale forming salt.

The complex Na2[Ca2(PO)3]6 is soluble in water and there is no problem of sludge

disposal. So calgon conditioning is better than phosphate conditioning.
Colloidal conditioning

The colloidal conditioning agents are kerosene, agar-agar, gelatin, glue, etc.

They are used in low pressure boilers.

The colloidal substance convert scale forming substances like CaCO3, CaSO4
into a sludge which can be removed by blow-down operation.
Desalination or Desalting

Desalination – the process of removal of dissolved salts (NaCl) from water.

Brackish water – water containing high concentration of dissolved salts.

Water quality is usually graded as

Fresh water : less than 100 mg/l of dissolved salts

Brackish water : 1000 – 35000 mg/l of dissolved salts

Sea water : greater than 35000 mg/l of dissolved salts.

The following techniques are carried out for desalination of sea water
and brackish water

Reverse osmosis

Electrodialysis

Distillation
Reverse osmosis

Osmosis – when two solutions of different concentrations are separated by a

semi-permeable membrane, solvent flows from a region of lower concentration
to a region of higher concentration. This process is a natural process.
The reverse osmosis process is also known as super-filtration or hyper filtration.

Semi-permeable membranes (having pores in the range of 0.0001 - 0.001μm in

diameter) used are

Cellulose acetate

Polyimide sulphone

Cellulose butyrate
Osmotic pressure - the excess pressure applied on the concentrated solution side
to prevent osmosis.

This natural process can be reversed by applying a pressure higher than the
osmotic pressure of the order 15 – 40 kg/cm2 on the high concentrated side.

The solvent flow is reversed ie. solvent flows from higher concentrated side to
lower concentrated side. This process is called reverse osmosis.
Advantages

The water obtained by this process is used for high pressure boilers

Due to low capital and operating cost and high reliability this process is
used for converting sea water into drinking water.

The life time of the membrane is high and it can be replaced within a short time.

It also removes ionic, non-ionic and colloidal impurities.

Water Purifier – RO & UV
Semi-permeable membrane Filters
 International Standards for water

- Depends on purpose
- Standards Set By:
1. WHO- World Health Organization
2. USPHD- United States Health Service
3. ICMR- Indian Council of Medical Research

Water should be free from

4. Turbidity, Colour
5. Taste, Odour
6. Microbes
7. Toxicity (Organic and Inorganic Metals)