WATER TREATMENT

Contents

• Introduction
• Hardness of Water
• Determination of Hardness
• Water Softening Techniques
• Boiler Feed Water and Boiler Problems
 Introduction
• Water is essential for life
• solvent of great importance
• Water is used for industrial purposes and for municipal supply
• Water is used in for the production of electricity
• Water is also used in chemical plants, paper industries,
pharmaceutical industries, textile industries, steel industries,
food industries as well as in atomic reactors
• used in irrigation for agricultural purposes
• widely used in domestic uses such as drinking, bathing,
washings, sanitary etc.
• Although water is nature’s most wonderful and abundant
compound but only less than 1% of the world’s water resources
is available for ready use.
 Sources of Water

Source of Water

Rain water Surface water Ground water

Rivers, Lakes, Wells, Step

Ponds, water wells, hot water
falls, streams, springs etc.
Sea etc.
Impurities in Water
Dissolved impurities:
(a) Inorganic salts:
Cations: Ca2+, Mg2+, Fe2+, Al3+, Mn2+, Na+, K+, Zn2+, Cu2+, Sr3+ etc.
Anions: HCO3-, Cl-, SO42-, NO3-, CO32-, F- etc.
(b) Organic constituents:
Aldrin, benzene, carbon tetrachloride, chlordane, tetrachlorethane,
trichlorethane, chloroform, lindane, methoxychlor etc.
(c) Gases:
SOx, NOx, CO2, H2S etc.
Suspended impurities: :
(a) Inorganic impurities: Sand, Clay etc
(b) Organic impurities: Oil globules, vegetable and animal matter
(c) Colloidal impurities: Finely divided silica and clay, organic waste products
Microorganism:
Algae, Fungi, bacteria etc.
 Hardness of Water
• Hardness is that characteristics of water by which it can prevent the

formation of lather / foam with soap solution.”

• also defined as the soap consuming capacity of water.

• Presence of certain salts of Ca, Mg and other heavy metal ions like

Al3+, Fe3+ and Mn2+

• Typical reactions of soap with water(CaCl2 and MgCl2) does not

produce lather but for insoluble white scum or precipitate

2C17H35COONa + CaCl2 → (C17H35COO)2Ca↓ + 2NaCl

2C17H35COONa + MgCl2 → (C17H35COO)2Mg↓ + 2NaCl

Types of Water: Hard Water and Soft Water

– Hard Water

• Does not produce lather

• Contains dissolved salts of Ca and Mg

– Soft Water

• Produces lather easily

• Doesn’t contain dissolved Ca and Mg salts in it

Determination of Hardness

Hardness rating Concentration of Calcium

Carbonate (mg/L)
Soft 0-50
Moderately soft 50-100
Slightly hard 100-150
Moderately hard 150-200
Hard 200-300
Very hard >300
Types of Hardness: Temporary hardness and Permanent hardness

• Temporary Hardness
• Presence of dissolved bicarbonates of calcium and magnesium

and other heavy metals

• Removed by mere boiling

Ca(HCO3)2 CaCO3 + H2O + CO2
Mg(HCO3)2 Mg(OH)2 + 2CO2

• Carbonate hardness or alkaline hardness

• Permanent Hardness
• Presence of dissolved chlorides and sulphates of calcium and

magnesium, iron and other heavy metals

• Not removed by boiling but with the help of chemical methods

• Non-Carbonate hardness or non-alkaline hardness

Total Hardness = Temporary hardness + Permanent hardness

• Pseudo-Hardness
• There is one more type of hardness called pseudo hardness which is

also called as fake or false hardenss

• Sea water, brackish water etc. that contain appreciable amounts of

salts of Na+, K+ etc. also doesn’t form lather with soap because of

the common ion effect (Any Sodium or Potassium salt e.g. NaCl,

KCl, K2SO4, Na2SO4 etc.)

• Sodium is not a hardness-causing cation, and so this action which it

exhibits when present in high concentration is termed pseudo-

hardness
Degree of Hardness

It is the parts of calcium carbonate equivalent hardness per a particular

number of parts of water depending upon the unit used

ppm

(106)

◦Cl ◦Fr
Units of
(70000) Hardness (105)

mg/L
Units of Hardness

• Parts per million (ppm):It is the number of parts of

CaCO3 equivalent hardness present in 106 parts of water.

• Milligram per liter: It is the number of milligrams of

CaCO3 equivalent hardness present in one liter of water.

• Clarkes Degree: It is the number of parts of CaCO3

equivalent hardness in 70,000 parts of water.

• French Degree: It is the number of parts of CaCO3

equivalent hardness in 105 parts of water.
 Degree of Hardness
Hardness of water is conveniently expressed in terms of equivalent

amount of CaCO3

• Molecular mass is 100

• Most insoluble salt that can be precipitated in water

treatment

• Most common substance in hardness

Amount of hardness producing subs tan ce

CaCO3 Equivalent = x Molecular weight of CaCO3
Molecular weight of hardness producing subs tan ce

Amount of hardness producing subs tan ce

CaCO3 Equivalent = x Equivalent weight of CaCO3
Equivalent weight of hardness producing subs tan ce
Hardness of water
• Soft water: 0-50 ppm

• Moderately soft water: 50-100 ppm

• Slightly hard water: 100-150 ppm

• Moderately hard water: 150-200 ppm

• Hard water: 200-300 ppm

• Very hard water: 300 ppm and above

 REMOVAL OF HARDNESS BY
ZEOLITE (PERMUTIT) PROCESS

Latin word Permutare = To exchange

Na2O.Al2O3.xSiO2.yH2O
X = 2-10 (5-13); y = 2-6 (3-4)
Natrual Zeolites:
Natrolite: x = 1; y = 1
Thomsonite: x = 3; y = 2
Analcine: x = 4; y = 3
 REMOVAL OF HARDNESS BY
ZEOLITE (PERMUTIT) PROCESS
ZEOLITE PROCESS REACTIONS

REGENERATION OF ZEOLITE
REMOVAL OF HARDNESS BY
ION EXCHANGE RESINS
ION EXCHANGE PROCESS
 ION EXCHANGE PROCESS REACTIONS

REGENERATION OF ION EXCHANGE RESIN

Cold Lime Soda Treatment
Hot Lime Soda Treatment
Lime Soda Process Reactions
 Alkalinity

• Alkalinity is the name given to the

quantitative capacity of water to neutralize
an acid.
• Due to OH−, CO3−2, HCO3− ions

OH− + H+ → H2O
CO3−2 + 2H+ → CO2 + H2O
HCO3− + H+ → CO2 + H2O
 Relation of Phenolphthalein & Methyl Orange readings
with the possibility of alkalinity producing ions

S. NO. Result of Titration OH- ion CO32- ion HCO3- ion

1 P=0 Nil Nil M

2 P=M P or M Nil Nil

3 P=½M Nil 2P Nil

(V1=V2)
4 P>½M 2P-M 2(M-P) Nil
(V1>V2)
5 P<½M Nil 2P M-2P
(V1<V2)
 Desalination of Water

• Brackish water or briny water is water

that has more salinity than fresh water, but
not as much as seawater.
• Dissolve salts like NaCl, KCl etc.
• Fresh water: < 1000 ppm
• Brackish water: 1000-3500 ppm
• Sea water (Saline water): > 3500-5000 ppm
• Brine water: > 5000 ppm
DESALINATION OF BRACKISH WATER BY
ELECTRODIALYSIS PROCESS

Pressure: 5-6 Kg/m2

DESALINATION OF BRACKISH WATER BY
REVERSE OSMOSIS PROCESS (RO)

Pressure: 15-40 Kg/cm2 (Super filtration, Hyper filtration, Ultra filtration)

COMPARISION OF DIFFERENT METHODS
Zeolite process Ion exchange process Lime-Soda process
1 Soft water up to 10 ppm 1 Soft water up to 2-5 ppm 1 Cold lime soda: 50-60 ppm
Hot lime soda: 15-30 ppm
2 Larger amount of pseudo 2 No Na salts 2 Lot of insoluble salts
hardness in purified water
3 Initial high cost 3 Initial cost is double than 3 Initial investment is very high
Zeolite
4 Operation expenses is low. 4 Operation expenses is high 4 Operation expense is high as
as costly chemicals are specialized chemicals are
used used
5 Can’t used for acidic water 5 Can be used for acidic or 5 Can be used for any type of
basic water water
6 Space required is less 6 Space required is double 6 A very huge space is required
than the Zeolite process
7 Can be operated under 7 Can be operated under 7 Can be operated under room
pressure pressure temperature (25-30 ◦C) as
well as high temperature (95-
110 ◦C)
8 High TDS 8 Less TDS 8 Very high TDS as well as
chemical mud produced
9 Can’t remove negative ions 9 Remove positive as well as 9 Remove positive ions only
negative ions
10 Less skilled person required 10 Little skilled person required 10 Highly skilled person required
11 No ppt are formed and no 11 No ppt are formed and no 11 Lot of ppt are formed and
slug formation slug formation slug formation
12 Turbid water can’t be 12 Turbid water can’t be 12 Turbid water can also be
purified as it will decrease purified as it will decrease purified
the efficiency the efficiency
13 Other name is Permiutit 13 Other name is 13 Other name is precipitation
process Demineralization process process
 Drinking Water Specification as per
Bureau of Indian Standard (BIS 10500)
BOILER FEED WATER AND
ITS TREATMENTS
Contents
• Boiler Feed water
• Major Problems in Boiler
Sludging & Scaling
Boiler corrosion
Caustic embrittlement
Foaming & priming
Boiler Feed Water
• A boiler is a device for generating steam
• Consists of two main parts:
• Furnace and Boiler proper
Furnace provides heat, usually by burning a
fuel
Boiler proper, a device in which the heat
changes water into steam
• The steam or hot fluid is then recirculated
out of the boiler for use in various
processes in heating applications
 Boiler Feed Water

• Boiler receives feed water in the form of

• Recovered condensed water (return water)
• Fresh water (make up water: purified in varying
degrees or natural water in its raw state)
• Feed-water composition therefore depends
on the quality of the make-up water and the
amount of condensate returned to the boiler.
• Steam which is coming out from the boiler,
contains liquid droplets and gases.
• Water remaining in the liquid form at the
bottom of the boiler picks up all the impurities
from any form of water.
• The impurities must be blown down by the
discharge of water from the boiler to the
drains.
 Boiler Feed Water

• Proper treatment of boiler feed water is an

important part of operating and maintaining a
boiler system.
• As steam is produced, dissolved solids become
concentrated and deposits inside the boiler.
• This leads to poor heat transfer and reduces the
efficiency of the boiler.
• Dissolved gases such as oxygen and carbon
dioxide will react with the metals in the boiler
system and lead to boiler corrosion.
• In order to protect the boiler from these
contaminants, they should be controlled or
removed, through external or internal
treatment
 Problems in Boiler
Sludging & Scaling
• In boiler, water is continuously converted into
steam
• Increasing the concentration of salts.
• Concentrates changes into loose and slimy
precipitates called sludge and
• if these are become hard and adherent, called
scales.
• Scales are hard deposits, which stick very firmly to
the inner surface of the boiler.
• The type of scale will depend upon the chemical
composition of the concentrated water.
Scale due to calcium and magnesium
Scale due to iron oxide
Scale due to copper
Scale due to silica
 Effect of Scale or Sludge Formation
• The thermal conductivity of boiler scale is very
low (similar to insulating brick). The scale acts as
an insulating layer and prevents an efficient
transfer of heat through the tubes to the
circulating water. The reduction in thermal
conductivity means lower boiler efficiency which
in turn leads to overheating and may result in the
softening, bulging or even fracturing of the boiler
tubes.
• Boiler scale can also cause clogging or partial
obstruction of circulating water tubes in a boiler,
which again causes overheating of the tubes.
• It increases the maintenance and operating costs.
• Scales also cause corrosion (serious problems in
boiler operation)
Prevention of Scale or Sludge Formation
External pretreatment of feed water with water
softeners, demineralizers, or reverse osmosis to
remove minerals before enter into boiler
• Scale/sludge is prevented by introducing the kerosene,
colloidal substances such as tannins, lignosulphonates,
polyacrylates, maleic acrylate copolymer, maleic styrene
copolymer, polystyrene sulphonates etc. these colloids
get coated over the scale and forming particles and are
suspended in water which can easily blown-off from the
boiler.
• Internal treatment using chemical conditioning
carbonate conditioning
phosphate conditioning
calgon conditioning
into boiler feedwater to keep the scale forming materials
in dissolved form.
 Carbonate Conditioning Process
• Sodium carbonate is added to boiler water.
• Scales react with it and form insoluble
calcium carbonate
CaSO4 + Na2CO3 → CaCO3↓ + Na2SO4
• Used only for low pressure boilers
• In high pressure boilers the excess of
sodium carbonate get converted into
sodium hydroxide due to hydrolysis and
causes caustic embrittlement
 Calgon Conditioning Process
• Calgon [sodium hexametaphosphate,
[(NaPO3)6] is added to boiler water
• forms the sludge [Na4P6O18]2- and
prevents the scale formation by
forming the soluble complex
compounds
Na2[Na4(PO3)6] → 2Na+ + [Na4P6O18]2-
[Na4P6O18]2- + 2CaSO4 → [Ca2P6O18]2- +
2Na2SO4
 Problems in Boiler
Boiler Corrosion

• Destructive attack or decay of boiler

material or metal by chemical or
electrochemical reaction with its
environment
• Main responsible for corrosion in boiler:
Dissolved Oxygen
Dissolved Carbon dioxide
Acids from dissolved salts
 Boiler
Corrosion

Dissolved oxygen (D.O)

• Water usually contains about 8 ml D.O/L at
room temperature
• D.O in water and presence of high
temperature attacks boiler material
2Fe + 2H2O + O2 → 2Fe(OH)2 ↓
4Fe(OH)2 ↓ + O2 → 2[Fe2O3.2H2O] ↓
Ferrous hydroxide (Rust)
 Boiler
Corrosion
Removal of Dissolved oxygen
(D.O)
• By mechanical deaeration
• Chemically, oxygen is removed by adding
oxygen scavenger or absorbing chemicals in a
calculating amount such as sodium sulphite or
hydrazine or sodium sulphide
If only small quantities of oxygen is present, the
addition of sodium sulphite is practical , in large
quantities causes foaming
Hydrazine is used in large utility boilers to remove
dissolved oxygen but not recommended for heating
boilers because it must be closely controlled because
of explosive nature of hydrazine and if used excess,
it decomposes to produce ammonia which again
cause corrosion
 Boiler
Corrosion

Dissolved carbon dioxide

• Carbon dioxide in presence of water forms
carbonic acid (H2CO3)
CO2 + H2O → H2CO3
• Carbon dioxide is also released inside the
boiler, if water used for steam generation
contains bicarbonates
Mg(HCO)3 → MgCO3 + H2O + CO2
• Slow corrosive effect on the boiler material
 Boiler
Corrosion
Removal of Dissolved Carbon
Dioxide

• By adding calculated quantity of ammonia

2NH4OH + CO2 → (NH4)2CO3 + H2O

• By mechanical deaeration process, reduces CO2

concentration to 5-10 ppm
 Boiler
Corrosion

Acids from dissolved salts

• Water containing dissolved magnesium
salts liberate acids on hydrolysis

MgCl2 + 2H2O → Mg(OH)2 ↓ +2HCl

• The liberated acids reacts with iron (of the

boiler) producing HCl again and again
 Problems in Boiler
Caustic Embrittlement

• Caustic embrittlement is a type of boiler

corrosion caused by using highly alkaline
water in the boiler.
• During softening process by lime-soda
processes, free sodium carbonate is
present
• sodium carbonate decomposes to give
carbon-dioxide and sodium hydroxide
(caustic)
Na2CO3 + H2O → 2NaOH + CO2
 Caustic embrittlement

• sodium hydroxide containing water flows into

the minute hair-line cracks by capillary action
• water evaporated and the dissolved caustic
soda concentration increases gradually
• caustic soda attacks the surrounding area,
thereby dissolving iron of boiler as sodium
ferrate
• This causes embrittlement of boiler parts
 Caustic
embrittlement
Prevention of Caustic
Embrittlement
• By using sodium phosphate as softening
agent instead of sodium carbonate

• By adding tannin or lignin to boiler water

• By adding sodium sulphate to boiler water,

blocks hair cracks in the boiler

• By adjusting the pH of boiler water to 8.0–

8.5
 Problems in Boiler
Priming and Foaming
Priming
• When a boiler is producing steam very
rapidly some particles of the water carried
along with the steam. This process of ‘Wet
Steam’ formation is called priming.
• It is caused by:
• presence of large amount of dissolved solids
such as alkali sulphate and chlorides
• sudden boiling
• improper boiler design
• sudden increase in steam-production rate
 Primin
g

Disadvantage of Priming

• Reduces the efficiency of boiler

• Decrease the life of the machinery part

• maintenance cost increases

• Can’t judge the water level in boiler

 Primin
g

Prevention of Priming
• By improving the designing of boiler
• By addition fitting of mechanical steam
purifiers
• By maintaining low water level in the
boilers.
• By using soft water.
• By decreasing the amount of dissolved
salts present in the feed-water.
 Problems in Boiler
Foaming

• Foaming is the persistent formation of

bubbles or foam in the boiler
• which do not break easily.
• It is due to the presence of oily substances
in water.
• These oily substances reduce the surface
tension of water in boiler
 Disadvantage of Foaming

• Actual height of the water column cannot

be judge.
• Dissolved salts in water carried by the wet
steam may damage the machinery parts
especially turbine blades.
• Boiler pressure cannot be maintained
 Prevention of Foaming

• By the addition of anti-foaming agents

such as castor oil, Gallic acid, tannic acid
etc.

• By adding compounds like sodium

aluminate for removing oil from boiler
water.
Differentiate between Sludge & Scale
Sludge Scale
1 Due to heating, the salt containing 1 When these precipitates becomes
water will get concentrated and hard and adherent called scales.
changes into loose and slimy
precipitates called sludge.
2 Sludge is not harmful for boiler. 2 Scales is harmful for boiler.
3 Sludge can be removed from the 3 Scale can be removed by either
bottom of the boiler time to time. external or internal treatment or
hammering.
4 Sludge doesn’t cause clogging 4 Scale causes clogging and
and corrosion. corrosion.
5 Sludge increases the discarding 5 Scale increases the maintenance
cost of waste. and operation cost.
Differentiate between Priming & Foaming

Priming Foaming
1 When boiler is producing steam very 1 Foaming is the persistent formation of
rapidly some particles of the water bubbles or foam in the boiler.
carried along with the steam. This
process of “Wet Steam” formation is
called priming.
2 Priming is caused by dissolved salts, 2 Foaming is caused by the presence of
high steam velocity, sudden heating, oily substances in water.
improper design etc.
3 Priming can be prevented by 3 Foaming can be prevented by
improving the boiler design, adding addition of anti-foaming agents such
mechanical purifier, maintaining low as castor oil, Gallic acid, Tannic acid,
water level and decreasing the salt sodium aluminate etc.
concentration.
4 Priming reduces the boiler efficiency, 4 Foaming reduces the boiler efficiency
life of machinery parts. and damages machinery parts.
5 Due to priming one can’t judge the 5 Due to foaming boiler pressure can’t
water level properly. be maintained and water level also
can’t be judged.
 Determination of Hardness
• By complexometric titration

• Permanent hardness is usually determined by titrating it

with a standard solution of EDTA by using Eriochrome

Black-T

• The EDTA is a complexing, or chelating agent used to

capture the metal ions

• This causes the water to become softened, but the metal ions

are not removed from the water

• EDTA simply binds the metal ions to it very tightly.

 Determination of Hardness

(1) Metal + Indicator Metal-Indicator complex

Ca++ + EBT (blue dye) Ca-EBT complex

(Unstable wine red color)

(2) Metal-Indicator complex + EDTA Metal-EDTA complex

+ Indicator

Ca-EBT + EDTA Ca-EDTA + EBT (blue dye)

(Unstable wine red complex) (Stable colorless complex)
Determination of Hardness