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Unit 1-Water Technology

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Unit 1-Water Technology

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r0761808
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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ENGINEERING CHEMISTRY – I

Subject Code : CY3151


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 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.
What is breakpoint chlorination?

Breakpoint chlorination is the point where


chlorine levels exceed the oxidant demand,
and the water begins to build a residual of
free available chlorine (FAC). Theoretically,
exceeding the “breakpoint” prevents
increased levels of disinfectant byproducts
(like chloramines).
. When you first add chlorine to water, it
immediately begins to oxidize metals like iron
and manganese, which reduce chlorine. This
initial reaction wipes out a certain portion of
chlorine, which is why nothing shows up on
the graph until point (A). As more chlorine is
added to water, it reacts on contact with
other contaminants—not just germs, but
non-living organics and nitrogen compounds
too—which create byproducts. Organics are
carbon-based, and get oxidized by chlorine,
further reducing it.
• chloramines first contribute to the total
chlorine levels because they help with
disinfection. This, however, reaches a
threshold where chlorine turns on
chloramines, indicated at point (B). In other
words, chlorine oxidizes all contaminants,
which includes chloramines after point (B) on
the graph. That's why the total chlorine level
drops with the addition of more free chlorine
(the X axis on the graph).
• The downward trend on the graph shows
chlorine starting to "win the fight" against
contaminants until it oxidizes all but the
combined chlorine residual. This level of
chlorine residual is shown on the graph
at point (C).
• If chlorine cannot overcome the oxidant
demand, your water's chlorine demand rises,
and the ORP drops. This would look like a
more prolonged downward trend toward
breakpoint, because breakpoint would be at a
much higher dose of chlorine. When the
chlorine can meet the oxidant demand, the
water has reached breakpoint chlorination.
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 color, 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
CALCIUM CORBONATE
EQUIVALENT HARDNESS
Determination Hardness by EDTA
Method
Estimation of Hardness by EDTA Method
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.
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.
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.
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.
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 S hard and adherent
non-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.
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 Ion 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.
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.
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.


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.
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
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
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

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