WATER TECHNOLOGY

Water plays an important role in our daily life. 70% of the earth is covered
by water, out of which 97% is in oceans and hence saline (not usable) 2%
is locked as polar ice caps (not available for use) only 1% is available as
surface and ground water (Usable) Though the ground water is clear, it
contains dissolved salts, hence not pure. Surface water contains dissolved
salts, dissolved gases and suspended impurities. Water is an essential
commodity for any engineering industry. The sources for water are of
Stationary or of flowing type. Depending on the source, water may consist
of impurities In soluble or dispersed or suspended form. The impurities in
water impart some Undesirable properties to water and hence render water
ineffective for the particular
Engineering application.

Main sources of water:

1. Surface water- River water,lake water etc.

2. Sea water – It is the most impure water

3. Underground water-shallow and deep springs and wells

Types of impurities:

1. Physical Impurities: Clay, sand oil globules, vegetable and animal

matter.

2. Chemical Impurities:

Dissolved Inorganic salts: Ca2+, Mg2+, Cl-, SO4 2- etc.

Dissolved Gases: CO2, O2, N2,Oxides of nitrogen.

3. Biological impurities: microorganisms like bacteria, fungi etc.

 Characteristics of water- hardness and alkalinity.
Hardness - the property of water which prevents it from lathering. Water
which does not produce lather with soap solution but produces white
precipitate is called hard water and which produces lather readily with soap
solution are called soft water. Temporary Hardness or Carbonate Hardness
(CH) or Alkaline Hardness (AH): This is due to the presence of
bicarbonates of calcium and magnesium. It can be removed by
mere boiling. The bicarbonates are converted into insoluble carbonates and
hydroxides, which can be removed by filtering.

Ca (HCO 3)2 ▬▬▬► CaCO 3 ↓ + H2O + CO2

Mg (HCO3)2 ▬▬▬► Mg(OH) 2 ↓ + 2CO 2

Permanent Hardness or Non-carbonate Hardness (NCH) or Non- alkaline

Hardness

(NAH): This is caused by the presence of chlorides and sulphates of

calcium and
magnesium. It cannot be removed by boiling. It can be removed only by
Chemical or
special treatment.

Units of Hardness :

ppm : 1 part of CaCO 3 equivalent hardness in 10 6 parts of water

mg/ L :1 mg of CaCO 3 equivalent hardness in 1 L of water Weight of 1 L of

water = 1

Kg. = 1000 g = 1000000 mg = 10 6 mg Hence 1 ppm = 1mg / L

Expression of Hardness in terms of CaCO3 Equivalents (Importance of

calcium
Carbonate equivalents). Hardness is expressed in terms of CaCO3
equivalents because
i) it is most insoluble salt obtained in water treatment
ii) ii)Molecular weight is 100(Eq.Wt50)

Alkalinity: The alkalinity of water is its acid neutralizing capacity .It is

attributed to the presence of the following species hydroxide (OH-),
Carbonates CO3 2-and bicarbonates (HCO3_) of alkali or alkaline earth
metals.

BOILER FEED WATER

Water is largely used in boilers (as feed) for the production of steam. The
presence of impurities in water sample renders it hard (and corrosive too in
some cases) and any water sample cannot be used as boiler feed as it may
pose the problems of corrosion, embrittlement of the boiler vessel etc.
Water with some specifications, used in boilers for steam generation is
called boiler feed water.

Requisites of boiler feed water:

(i) It should be free from suspended solids and dissolved corrosive gases
such as CO2, SOx, NOx, halogens, hydrogen halide etc.

(ii) Hardness should be less than 0.1 ppm (iii) alkalinity (soda and caustic
alkalinity values)
Should be in the range 0.1 – 1 ppm ; less than 0.5 ppm alkalinity is
preferable

(iii) It should be free from dissolved salts and oily / soapy matter that
reduces the surface Tension of water. Boiler feed water should be free from
hardness producing substances. If hard water is fed directly into the boiler it
leads to the following boiler troubles which reduce the efficiency of the
boiler.
Disadvantages of using hard water in boiler:
The main destructive effects of using hard water in boilers are
(i) formation of scales and sludge
(ii) boiler corrosion
(iii) caustic embrittlement and
(iv) Priming and foaming.
 (v) Formation of scales and sludge is the main disadvantage of using
hard water in boiler.

BOILER TROUBLES

1. SCALES AND SLUDGES

In boiler, water is converted to steam. During this process, when the
volume of water decreases, a saturation point is reached and all the
dissolved salts precipitate out. Depending on the physical and
chemical nature of the impurity (salt) it may form a loose, slimy, non-
adhering precipitate (Sludge) or hard strongly adhering precipitate
(Scale).

Sludge:
Loose, slimy and non-adhering precipitate due to presence of salts like
MgCl2, Mg SO 4, CaCl2, MgCO3. It forms in colder portions of boilers and
the portion where water flow rate is low.

Disadvantages:
Sludge are poor conductor of heat. Excess of sludge formation decreases
the efficiency of boiler.

Prevention and removal:

By using softened water and performing frequent blow down operation.

Scale:
Hard, adherent coating due to presence of salts like Mg(HCO3)2,Mg(OH)2,
Ca(HCO3)2, CaSO4
.

Disadvantages:
The scale formation in boilers, poses a variety of problems, such as
wastage of fuel, overheating of the boiler leading to explosion etc.
 1. Wastage of fuel: Scales are poor conductors (almost insulators) of
heat and result in a low heat transfer rates. To maintain steady heat
supply to water, greater heat energy has to be supplied. This results
in over-heating of the boiler and also increased fuel consumption.
The extent of fuel wastage depends on the thickness and nature of
the scale, as evidenced from the following table:
Scale 0.325 0.625 1.5 2.5
thickness
(mm)
Fuel wastage 10 15 50 80
(%)

2. Decrease in efficiency: Scales, if deposited in the boiler components

such as valves, condensers etc., choke in fluid paths and hence lead
to decreased efficiency of the boiler.

3. Lowering of boiler safety: Scale formation demands over-heating of

the boiler for maintaining a constant supply of steam. The over-
heating of the boiler tubes renders the boiler material softer and
weaker and hence the boiler becomes unsafe at high steam
pressures.
4. Danger of explosion: when scales undergo cracking, water comes in
Contact with overheated boiler plates suddenly. This results in
sudden formation of large amount of steam and hence the development of
high pressure of steam, which may cause the boiler explosion.

Prevention and removal

i) By dissolving in acids like HCl, H2SO4
ii) By applying external and internal treatment.
iii) Removed by scrapping, wire brushes etc.

PRIMING & FOAMING

Priming: When steam is produced rapidly in boilers the steam velocity

suddenly increases and some droplets of liquid water are carried along with
steam. Steam containing droplets of liquid water is called wet steam . The
process of wet steam formation is called Priming.

Priming is caused by
Presence of large amount of dissolved solids.
High steam velocity.
Sudden boiling.
Improper boiler design.
Priming can be prevented by
Using treated water.
Controlling the velocity of steam.
Fitting mechanical steam purifiers.
Maintaining low water level.
Good boiler design.

Foaming: Oil or any other polymeric substance present in boiler feed

water, reduces surface tension of water forming bubbles which do not
break easily in boilers giving a foam appearance. This process is called
foaming.

Foaming is caused by
Presence of oil & grease.
Presence of finely divided sludge particles.
Foaming can be prevented by adding coagulants like sodium aluminate,
ferrous sulphate etc.

Caustic embrittlement:

Caustic embrittlement means intercrystalline cracking of boiler metal. Boiler

water usually contains a small proportion of Na2CO3. In high pressure
boilers this undergoes decomposition to give NaOH. This NaOH flows into
the minute hair cracks and crevices, usually present on the boiler material,
by capillary action and dissolves the surrounding area of iron as sodium
ferroate. This causes brittlement of boiler parts, particularly stressed parts
like bends, joints, rivets, etc., causing even failure of the boiler.

Na2CO3 + H2O ----→ 2 NaOH + CO2

Fe + 2 NaOH -----→ Na 2FeO2 + H2 ↑
Caustic embrittlement can be prevented by
i) using sodium phosphate as softening agent instead of sodium
carbonate.
ii) by adding tannin, lignin to the boiler water, which blocks the cracks.
BOILER CORROSION:

Boiler corrosion is decay of boiler material by chemical or electrochemical

attack of its environment. Boiler corrosion is due to presence of
Dissolved oxygen
Dissolved carbon dioxide
Dissolved salts like magnesium chloride

1. Dissolved oxygen : When water containing dissolved oxygen is fed into

boilers the
following reaction occurs corroding the boiler material (rust formation)

2Fe + 2H2O + O2 ▬▬► 2Fe(OH) 2 ↓

4Fe(OH)2 + O2 ▬▬► 2 [ Fe 2O3. 2H2O]
D. O. oxygen can be reduced
i) By adding hydrazine / sodium sulphite

N2H4 + O2 ▬▬► N2 + 2H2O

2Na2SO3 + O 2 ▬▬► 2Na2SO4
ii) By mechanical deaeration method.

2. Dissolved carbon dioxide: When water containing bicarbonates is

heated, carbon dioxide is evolved which makes the water acidic. This is
detrimental to the metal. It leads to corrosion called of boiler material.

Ca(HCO3)2 ▬▬► CaCO 3 + H2O + CO2 :

CO2 + H2O ▬▬► H 2CO3

Prevention methods for removing dissolved carbon dioxide:

By treatment with ammonium hydroxide:

2NH4OH + CO 2 ▬▬► (NH4)2CO3 + H2O

Can be removed by mechanical deaeration method along with oxygen.

2. Dissolved MgCl2: Acids produced from salts that are dissolved in

water are mainly responsible for the corrosion of boilers. Salts like
magnesium and calcium chloride undergo hydrolysis at high
temperature to give HCl, which corrodes the boiler. Presence of HCl
is more damaging due to chain reaction.
 MgCl2 + 2H2O ▬▬► Mg(OH)2 ↓ + 2HCl
Fe+ 2HCl ▬▬► FeCl2 + H2↑
FeCl 2 + 2H2O ▬▬► Fe(OH)2 ↓ + 2HCl

MgCl2 can be removed by

i) internal conditioning and
ii) external conditioning
EXTERNAL CONDITIONING:
Three types of external conditioning methods in use are
(i) Lime-soda process
(ii) Permutit or zeolite process and
(iii) Demineralization process.
The first process is based the precipitation of hardness causing ions by
the addition of soda (Na2CO3) and lime (Ca(OH)2) whereas the second
and third process is based ion exchange mechanism (ion exchange
process). An ion exchange process may be defined as a reversible
exchange of ions between a liquid phase and a solid phase. Materials
capable of exchanging cations are called cation exchangers and those
which are capable of exchanging anions are called anion exchangers.
Both anion and cation exchangers are used in water treatment.

NATURAL AND SYNTHETIC ZEOLITE PROCESS

Internal conditioning is treating the water after feeding into the boiler. An
internal treatment is accompanied by adding a proper chemical to the boiler
water either
a) toprecipitate the scale forming impurities in the form of sludges removed
by blow down
operation. Or
b )to convert them into compounds which will stay in dissolved form
without causing harm to boiler.
 Carbonate conditioning:
Scale forming salts like CaSO4 present in the water adheres more strongly
This can be prevented by precipitating Ca as CaCO3 which gives rise to a
loosely adhering scale , by adding Na2CO3.
CaSO4 + Na2CO3 ▬▬► CaCO3 ↓ + Na2SO4
Disadvantage / Limitation:
1. Applicable only for low pressure boiler
2.Causes caustic
embrittlement and corrosion in high pressure boilers as the unreacted
Na2CO3 will beconverted to NaOH and CO2.
  Phosphate Conditioning:
In high-pressure boilers, scale formation can be avoided by the addition of
sodium phosphate to the water sample. Here, calcium (and also
magnesium) ions (responsible for hardness) are precipitated as their
phosphates (sludges) and can be removed easily by filtration. Three types
of phosphates – mono, di and trisodium phosphates are employed in
phosphate conditioning. The advantages of phosphate conditioning over
carbonate conditioning are
(i) it can be applied to high-pressure boilers and
(ii) it can be used for softening / conditioning acidic, neutral or alkaline
water sample.
Ca2+ + 2 Na3PO4 → Ca3(PO4)2 ↓
If acidic water is to be conditioned, trisodium phosphate can be used. For
neutral and alkaline water samples disodium phosphate and monosodium
phosphate can be used respectively.
 Calgon conditioning:
It is the process of addition of calgon or sodium hexametaphosphate to
boiler feed water. The calcium ions (responsible for scale / sludge
formation) are complexed by calgon to form a soluble complex and hence
prevented from their scale forming action.
Ca2+ + Na2[Na4(PO3)6] → Na2[Ca2(PO3)6] + 2 Na+
This phenomenon of complexing of the ions is called sequestration. Calgon
is the sequestering agent used. The other internal conditioning agents used
are ethylenediamine tetracetic acid (EDTA) and sodium aluminate
(NaAlO2). EDTA functions by sequestration phenomenon whereas sodium
aluminate functions by precipitation phenomenon.
 Colloidal conditioning:
In low pressure boilers scale formation can be avoided by adding organic
substances like kerosene, tannin, agar-agar etc. They get coated over the
scale forming precipitates, converting into loose deposits which can be
easily removed

o Desalination:
Water sample is of three types namely fresh water, brackish
water and sea water depending upon the total dissolved salt (TDS) content.
A water sample is said to be saline if it has much of dissolved salt content.
Desalination is the process of removal of salinity – dissolved content from
awater sample. Four methods of desalination are distillation, freezing,
reverse osmosis and electrodialysis.
 Reverse Osomosis (RO):
Principle: Osmosis can be defined as the phenomenon of spontaneous
flow of solvent molecules from dilute solution side to concentrated solution
side, when they are separated by a semi-permeable membrane. The
driving force for this phenomenon is called osmotic pressure. If a
hydrostatic pressure in excess of osmotic pressure is applied on the
concentrated solution side, the direction of solvent flow can be reversed i.e
higher concentration to lower concentration and the process is called
reverse osmosis.
The dilute solution can be re replaced by fresh water to get fresh water
effectively from impure or sea water. Thus in Reverse Osmosis (RO), the
solvent / water is separated from the contaminants (solution).

The membranes used are cellulose acetate,Polymetha acrylate

,polyamide, poly
Sulphone etc.
Pressure of 15- 40 Kg/cm2 is usually applied.
Advantages:
1. The life time of the membrane is high.
2. Membrane can be replaced within short time.
3. It removes all types of impurities
4. Water obtained by this process is used for high pressure boilers
5. Process is used for converting sea water into drinking water.