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The Water The Water By Dr. Rahul Shrivastava

The Water

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The Water. By Dr. Rahul Shrivastava. Water Is one of the abundant commodities in nature, but is also the most misused one. Earth is a blue planet, 71% of our planet is covered by water. But, 97.5% of it is locked in the oceans, which is too saline to drink and other uses. - PowerPoint PPT Presentation

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Page 1: The Water

The WaterThe Water

ByDr. Rahul Shrivastava

Page 2: The Water

2

Water Is one of the abundant commodities in nature, but is also the most misused one

Earth is a blue planet, 71% of our planet is covered by water.

But, 97.5% of it is locked in the oceans, which is too saline to drinkand other uses.

2.4% water is trapped in polar ice caps and giant glaciers, from

which only 1% water is used by human for various development, industrial, agricultural and domestic purposes.

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3

22%

8%

70%

0

10

20

30

40

50

60

70

80

Agriculture Domestic Industry

Water uses

% o

f to

tal

wat

er u

sed

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4

66% of the human body is made up of water.

At just 2% dehydration your performance decreases by around 20%.

We should drink at least 1½ litres of water a day.

66% of the human body is made up of water.

At just 2% dehydration your performance decreases by around 20%.

We should drink at least 1½ litres of water a day.

80% of all illness in developing countries is caused by water related diseases.

90% of wastewater in developing countries is discharged directly into rivers and streams without treatment.

80% of all illness in developing countries is caused by water related diseases.

90% of wastewater in developing countries is discharged directly into rivers and streams without treatment.

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5

Sources of waterSurface Water: (i) Flowing water e.g. rivers and streams (Moorland surface drainage) In general river water contains dissolved minerals from soil such as chlorides, sulphates, bicarbonates of sodium, calcium or magnesium, iron and organics matters derived from decomposition of plants, small particles of sand and rocks in

suspensions. (ii) Still waters e.g. lakes, ponds and reservoirs ( Lowland surface drainage) Lake water has more constant chemical composition.

Underground Water: water from shallow and deep spring and wells

Rain water: It is probably the purest form of natural water

Sea Water: It is probably the most impure form of natural water

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6

Types of Impurities Present in waterDissolved impurities:(a) Inorganic salts e.g. (i) Cations: Ca2+, Mg2+, Na+, K+, Fe+2, Al+3, Zn2+, Cu2+

(ii) Anions: Cl-, SO42-, NO3

-, HCO3-, F-, NO2

-

(b) Gases: CO2, O2, N2, NH3, H2S(c) Organics salts

Suspended impurities:(a) Inorganic e.g. clay and sand(b) Organics e.g. oil globules, vegetable and animal matters

Colloidal impurities:

Clay and finely divided silica colloidal partials of 10-4 – 10-6 mm size

Micro-organisms:

Bacteria, Fungi, algae and other forms of animal and vegetable life

Page 7: The Water

7

Effects of Impurities in natural water

Colour Taste and odour Turbidity and sediments Micro-organisms Dissolved minerals matters (a) hardness (b) Alkalinity (c) Total solids (d) corrosion

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8

Hardness of waterHardness of water is originally defined as the soap consuming

capacity of a water sample. The soap consuming capacity of wateris mainly due to the certain salt of calcium, magnesium and other

heavy metals dissolved in it.

The soap is generally consists of sodium salts of fatty acids such asOleic acid, palmetic acid and stearic acid. Calcium and magnesiumReact with the sodium salts of long chain fatty acid present in the soap to form insoluble scums of calcium and magnesium soaps.

2 C17H35COONa CaCl2 (C17H35COO)2Ca NaCl+ +

(Sodium stearate) (Insoluble)

2 C17H35COONa MgSO4 (C17H35COO)2Mg Na2SO4+ +

(Sodium stearate) (Insoluble)

Other metal ions such as Fe2+, Mn2+, Al3+ also contributing to hardness, but they are present in water only in traces

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9

Temporary hardness (carbonate hardness)Temporary hardness is caused by the presences of dissolved

bicarbonate of calcium and magnesium and other heavy metal ions

Temporary hardness is mostly destroyed by boiling of water. Duringboiling bicarbonate are decomposed in the insoluble carbonate andhydroxide, which are deposited at the bottom of the vessel.

(Insoluble)

Ca(HCO3)2 CaCO3 H2OCO2 ++Heat

(Insoluble)

Mg(HCO3)2 MgCO3 2 CO2+Heat

Permanent hardness (non-carbonate hardness)This is due the presences of chlorides and sulphates of calcium, magnesium, iron and other heavy metal ions.

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10

Hardness is expressed in terms of equivalent of calcium carbonate because it is the most insoluble salt that can be precipitated in water treatment.

Equivalent of CaCO3

Mass of hardness producing substances x 50

Chemical equivalent of hardness producing substances=

Dissolved salt

Molar Mass

Chemical equivalent

Multiplication factor for converting into equivalent

of CaCO3

Ca(HCO3)2 162 81 100/162

Mg(HCO3)2 146 73 100/146

CaSO4 136 68 100/136

CaCl2 111 55.5 100/111

MgSO4 120 60 100/120

MgCl2 95 47.5 100/95

MgCO3 84 42 100/84

Page 11: The Water

11

Calculate the temporary hardness and permanent hardness of a sample of water containing: Mg(HCO3)2 = 7.3 mg/L; Ca(HCO3)2 = 16.2 mg/L; MgCl2 = 9.5 mg/L; CaSO4 = 13.6 mg/L

Molecular weights:Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95; Al2(SO4)3 = 114

Page 12: The Water

12

Calculate the temporary hardness and total hardness of a sample of water containing: Mg(HCO3)2 = 73 mg/L; Ca(HCO3)2 = 162 mg/L; MgCl2 = 95 mg/L; CaSO4 = 136 mg/L

Molecular weights:Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95; Al2(SO4)3 = 114

Page 13: The Water

13

Three samples A, B and C were analyzed for their salts contents:Sample A was found to contain 168 mg of magnesium carbonate per LSample B was found to contain 820 mg of calcium nitrate and 2 mg of silica per LSample C was found to contain 2 g calcium carbonate per 500 ml Determine the hardness in all above three sample in ppm

Molecular weights:Ca(NO3)2 = 164; MgCO3=84; CaCO3= 100

Page 14: The Water

14

Estimation of hardness: Hardness are usually determined by two methods

Soap solution methods:-

soaps gives lather with hard water only after sufficient quantity of soaps is added to precipitate all the hardness causing metal ions present in water

2 C17H35COONa CaCl2 or MgCl2 (C17H35COO)2Ca or Mg NaCl+ +

(Sodium stearate) (Insoluble)

2 C17H35COONa MgSO4 or CaSO4 (C17H35COO)2Mg or Ca Na2SO4+ +

(Sodium stearate) (Insoluble)

After precipitation of all the hardness causing ions present in water, further addition of soap gives lather

Page 15: The Water

15

EDTA Method:-

Hard water+

EBT Indicator

N N

O O

NaO3S

O2N

HH

+10 PH buffer solution

N N

O O

NaO3S

O2N

N N

O O

NaO3S

O2N

Ca/Mg

N CH2 CH2 N

CH2COONa

CH2COOH

NaOOCH2C

HOOCH2C

N CH2 CH2 N

CH2COO

CH2COONa

OOCH2C

NaOOCH2C

M

Page 16: The Water

16

WATER SOFTENING

removal of hardness » Hardness is?...

How is Softening done?...

primarily Ca, Mg, plus Fe, Mn, St, Al

Precipitation of Ca and Mg, orIon exchange of Ca / Mg with ion such as Na

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17

Why bother?

Hardness in 300-500 mg/l as CaCO3

range considered excessive

Even > 150 mg/l may result in consumer objection

60-120 mg/l as CaCO3 is considered a

moderate amount

high soap consumption scaling in heating vessels and pipes

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18

Lime-Soda processIn this process, all the soluble hardness-causing impurities are converted into insoluble precipitates which may removed by setting and filtration .

In the lime soda process, calculated amount of lime Ca(OH)2 and soda Na2CO3 is added in the hard water. The soluble calcium and magnesium salts in water are converted into insoluble compound such as calcium carbonate and magnesium hydroxide which may removed by setting and filtration.

Ca(HCO3)2 Ca(OH)2 2 CaCO3 2 H2O

Mg(HCO3)2 Mg(OH)2

+ +

2 Ca(OH)2+ CaCO3 H2O+ +

(i) Lime removes the temporary hardness:

(ii) Lime removes the permanent magnesium hardness:

MgCl2 Mg(OH)2Ca(OH)2+ + CaCl2

MgSO4 Mg(OH)2Ca(OH)2+ + CaSO4

Page 19: The Water

19

(iii) Lime removes the dissolved iron and aluminum salts:

FeSO4 Fe(OH)2Ca(OH)2+ + CaSO4

Al2(SO4)3 2 Al(OH)33 Ca(OH)2+ + 3 CaSO4

(iv) Lime removes free mineral acids:

H2O

Ca(OH)2+ +

CaSO43 Ca(OH)2+ +

2 HCl

H2SO4

H2OCaCl2

(v) Lime removes dissolved CO2 and H2S: CaCO3

2 H2O

Ca(OH)2+ +

3 Ca(OH)2+ +

H2OCO2

H2S CaS

(vi) Soda removes all calcium permanent hardness:

CaCO3

+

+ +

+

CaCl2 Na2CO3 NaCl

Na2CO3 CaCO3CaSO4 Na2SO4

Page 20: The Water

20

Now the 100 parts by mass of CaCO3 are equivalent to : (i) 74 part of Ca(OH)2 and (ii) 106 parts of Na2CO3

Lime required for softening:

[ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3

-]

74100

=

Soda required for softening:

[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) - HCO3

-]

106100

=

Page 21: The Water

21

Calculate the amount of lime required for softening 50,000 litre of hard water containing CaCO3=25ppm; MgCO3=144ppm; CaCl2=111ppmMgCl2=95 ppm; Na2SO4= 15 ppm; Fe2O3 = 25 ppm.

Lime required for softening:

[ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3

-]

74100

=

Soda required for softening:

[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) - HCO3

-]

106100

=

Molecular weights:Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95;MgCO3 = 84; CaCl2 = 111

Page 22: The Water

22

Calculate the amount of lime and soda required for softening 50,000 litreof hard water containing Ca(HCO3)2= 8.1 mg; Mg(HCO3)2 = 7.5 mg; CaSO4 = 13.6 mg; MgSO4 = 12.0 mg; MgCl2 = 2.0 mg; NaCl = 4.7 mg.

Molecular weights:Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95

Lime required for softening:

[ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3

-]

74100

=

Soda required for softening:

[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or H2SO4) - HCO3

-]

106100

=

Page 23: The Water

23

Explain with chemical equation and calculate the amount of limeAnd soda needed for softening 1,00,000 litrs of water containing Following:HCL = 7.3 mg/L; Al2(SO4)3 = 34.2 mg/L; MgCl2 = 9.5 mg/L; NaCl = 29.25 mg/LPurity of lime is 90% and that of the soda is 98%.Molecular weights:Ca(HCO3)2 = 162; Mg(HCO3)2=146; CaSO4= 136; MgSO4 = 120; ; MgCl2 = 95; Al2(SO4)3 = 114Lime required for softening:

[ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3

-]

74100

=

Soda required for softening:

[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or H2SO4) - HCO3

-]

106100

=

Page 24: The Water

24

A water sample on analysis gave the following data: Ca2+ = 30 mg/L; Mg2+ = 24 mg/L; CO2 = 24mg/L; K+ = 10 mg/LCalculate the quantities of lime (90%) and soda (94%) required to soften one million litres of water sample.

Lime required for softening:

[ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3

-]

74100

=

Soda required for softening:

[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or H2SO4) - HCO3

-]

106100

=

Page 25: The Water

25

A water sample have the following impurities : Ca2+ = 20ppm; Mg2+ = 18 ppm; HCO3

- = 183 ppm; SO42- = 24 ppm. Calculate

the amount of lime and soda needed for softening.

Lime required for softening:

[ Temp. Ca2+ + 2×Temp. Mg2+ + Perm. (Mg2+ + Fe2+ + Al3+) + CO2 + H+ (HCl or H2SO4) + HCO3

-]

74100

=

Soda required for softening:

[ Perm. (Ca2+ + Mg2+ + Fe2+ + Al3+) + H+ (HCl or H2SO4) - HCO3

-]

106100

=

Page 26: The Water

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Cold lime soda process:Calculated quantity of lime and soda are mixed with water at room temperature the precipitates formed are finely divided, so they do not settle down easily. Therefore, It is essential to add small amounts of coagulants (like alum, aluminum sulphate, sodium aluminates etc).

Use of sodium aluminate as coagulant also helps the removal of silica as well as oil if present in water..

NaAlO2 + 2H2O NaOH + Al(OH)3

Al2(SO4)3 + 3Ca(HCO3)2 2Al(OH)3 + 3CaSO4 + 6CO2

Page 27: The Water

27 27

Continuous cold lime soda softener

Hard water feed

Chemicals (soda+lime+coagulant) feed

Softened water

Sedimented sludge (CaCO3, Mg(OH)2

Stirrer paddles

Wood fiber filter

Page 28: The Water

Hot lime soda process: Calculated quantity of lime and soda are mixed with

water at 80 to 1500C.

Advantages of high temperature:

The reaction proceeds faster. Softening capacity is increased. No coagulant needed as the precipitate and sludge formed settle down rapidly.Much of the dissolved gases are driven out of water. Viscosity of soften water is lower, so filtration of water becomes easier. This process produces water of comparatively low residual hardness 15 to 30 ppm.

Page 29: The Water

Continuous Hot Lime Soda Process

Page 30: The Water

Advantages of lime soda process:

It is very economical.

If the process is combined with sedimentation/coagulation lesser amounts of coagulants shall be needed.

The process increases the pH of the treated water thereby corrosion reduced.

In addition to the removal of hardness, the quantities of minerals in the water are reduced.

Due to alkaline nature of treated water amount of pathogenic bacteria in water is considerably reduced.

Page 31: The Water

Disadvantages of lime soda process:

For efficient and economical softening, careful operation and skilled supervision is required.

Disposal of large amount of sludge poses a problem.

This can remove hardness up to 15 ppm which is not good for boilers.

Page 32: The Water

Ion exchange or deionization or demineralization process: Ion-exchange resins are widely used in different separation, purification, and decontamination processes. The most common examples are

water softening and water purification.Ion-exchange resins are insoluble, cross linked, long chain organic polymer with micro porous structure and the functional groups attached to the chains are responsible for the ion exchange properties.

WATER SOFTENING

Cation exchange Resin

Resin after treatment

Page 33: The Water

Resins containing acidic functional groups (-COOH, -SO3H) are capable of exchanging their H+ ions with other cations which comes in their contacts, known as a cation exchange resins (RH+).

e.g. styrene-divinyl benzene copolymer, which on sulphonation and carboxylation, become capable to exchange their hydrogen ions with the cations in the water.

Page 34: The Water

Resins containing basic functional groups (-NR2+OH-) are capable of

exchanging their anions with other anions which comes in their contacts, known as a Anion exchange resins (ROH-).

They are styrene divinyl benzene or amine-formaldehyde copolymerization which contains quaternary ammonium or quaternary phosphonium or tertiary tertiary sulphonium groups as an integral part of the resin matrix. These after treated with dil NaOH becomes capable of exchanging their OH- ions with anions of water.

Page 35: The Water

Process:- The hard water is passed first through cation exchange column, which remove all the cations from it and equivalent amount of hydrogen ions are released from this column to water:

2RH+ + Ca2+ R2Ca2+ + 2H+ 2RH+ + Mg2+ R2Mg2+ + 2H+

After cation exchange column the hard water is passed through anion exchange resin column, which remove all the anions from it and equivalent amount of hydroxide ions are released from this column to water :

ROH- + Cl- RCl- + OH-

2ROH- + SO42- R2SO4

2- + 2OH-

H + + OH- H2OThus water coming out from the exchange is free from cations as well as anions. Ion free water is known as deionized or demineralised water.

Page 36: The Water

36

Ion exchange purifier or softener

Cation exchange Resin Anion exchange Resin

Gravel bed

Hard water

InjectorInjector

Alkaline solution for regeneration of resin

Soft water

Wastages to sink

Wastages to sink

Acid solution for regeneration of resin

pump

Page 37: The Water

Regeneration:

Cation exchange column is regenerated by passing a solution of dil HCl or dil H2SO4. The regeneration can be represented as

R2Ca2+ + 2H+ 2RH + Ca2+

Exhausted anion exchange column is regenerated by passing a solution of dil. NaOH. The regeneration can be represented as

R2SO42- + 2OH- 2ROH + SO4

2-

Page 38: The Water

Advantages:

Can be used to soften highly acidic or alkaline waters.

It produces water of very low hardness.

Disadvantages:The equipment is costly

Expensive chemicals are needed

Output of the process is reduced if water contains turbidity.(turbidity must be below10 ppm)

Page 39: The Water

39

Zeolite (Permutit) method of Softening of water

Zeolite is a Hydrated Sodium Alumino Silicate (HSAS), capable of exchanging reversibly its sodium ions for hardness producing ions in water.

Porous Structure of zeolite

The general chemical structure of zeolite is given below Na2O.Al2O3.xSiO2.yH2O (x = 2-10 and y = 2-6)

Micro pores of Zeolite

Porosity or cavity size of synthetic zeolite structures can be controlled by varying the Si/Al ratio Ion-exchange process of zeolite structure is associated with sodium ions

Page 40: The Water

40

Zeolite softener

Zeolite bed

Gravel

Hard water in

Injector

NaCl storage

Softened waterTo sink

Hard water spray

Page 41: The Water

41

Process of softening by Zeolite method

For the purification of water by the zeolite softener, hard water is passed through the zeolite bed at a specified rate. The hardness causing ions such as Ca2+, Mg2+ are retained by the zeolite bed as CaZe and MgZe respectively; while the outgoing water contains sodium salts. The following reactions takes place during softening process

Na2Ze + Ca(HCO3)2 CaZe + 2NaHCO3

Na2Ze + Mg(HCO3)2 MgZe + 2NaHCO3

To remove temporary hardness

To remove permanent hardness

Na2Ze + CaCl2 CaZe + 2NaCl

Na2Ze + MgSO4 MgZe + Na2SO4

Regeneration of Zeolite Bed

CaZe (or) MgZe + 2NaCl Na2Ze + CaCl2 (MgSO4)

Washings drained

Regenerated Zeolite

Used Zeolite

10% brine solution

Hardness

water

Page 42: The Water

42

Limitations of Zeolite process1. If the water is turbid ---- then the turbidity causing particles clogs the

pores of the Zeolite and making it inactive

2. The ions such as Mn2+ and Fe2+ forms stable complex Zeolite which can not be regenerated that easily as both metal ions bind strongly and irreversibly to the zeolite structure.

3. Any acid present in water (acidic water) should be neutralized with soda before admitting the water to the plant, since acid will hydrolyze SiO2 forming silicic acid

Advantages of Zeolite process

1. Soft water of 10-15 ppm can be produced by this method

2. The equipment occupies less space

3. No impurities are precipitated, hence no danger of sludge formation in the treated water

4. It does not require more time and more skill

Page 43: The Water

1. Soft water contains more sodium salts than in lime soda process

2. It replaces only Ca2+ and Mg2+ with Na+ but leaves all the other ions like HCO3

- and CO32- in the softened water (then it may form

NaHCO3 and Na2CO3 which releases CO2 when the water is boiled and causes corrosion)

3. It also causes caustic embrittlement when sodium carbonate hydrolyses to give NaOH

Disadvantages of Zeolite process

Page 44: The Water

Scales and Sludges Formation In Boilers: In boilers, water evaporates continuously and the concentrations of the dissolved salts increases progressively. when concentrations of dissolved salts reach saturation point, they form precipitates in form of loose and slimy, it is called sludge. On the other hand, if the precipitate matter form a hard adhering crust/coating on the inner walls of the boiler, it is called scale.

Page 45: The Water

Disadvantages of sludge formation

Sludge’s are poor conductor of heat, so they tend to waste a portion of heat generated.

Sludge’s get entrapped in the scale and both get deposited as scales. Excessive sludge formation, disturbs the working of the boiler. It

settle in the regions of poor water circulation such as pipe connection etc.

Prevention of sludge formation: By using well softened water By frequently ‘blow-down operation’, i.e., drawing off a portion of

the concentrated water.

Page 46: The Water

Scales are hard deposit, which stick very firmly to the inner surface of boiler. Scales are very difficult to remove. Formation of scales may be due to

(1) Decomposition of calcium bicarbonate:

Ca(HCO3)2 → CaCO3 + H2O + CO2

Scale composed mainly from calcium carbonate is soft and is the main cause of scale formation in low pressure boiler. But in the high pressure boiler calcium carbonate is soluble.

CaCO3 + H2O → Ca(OH) 2 (soluble) + CO2(In high-pressure boilers)

(In low-pressure boilers)

(2) Deposition of Calcium Sulphate:

Solubility of calcium sulphate in water decrease with rise of temperature. Hence CaSO4 gets precipitated as hard scale on the heated portions of the boiler.

Page 47: The Water

(3) Hydrolysis of magnesium salts:

Dissolved Mg salts undergo hydrolysis forming magnesium hydroxide precipitate, which forms a soft type of scale

MgCl2 +2H2O → Mg(OH)2 + 2HCl (Scale)

(4) Presence of silica:

SiO2 even present in small quantities, deposits as calcium silicate

(CaSiO3) and /or magnesium silicate (MgSiO3). These deposits stick on

the inner side of the boiler surface and are very difficult to remove.

Page 48: The Water

Wastage of fuel: Scales have a low thermal conductivity, so that rate of heat transfer from boiler to inside water is greatly decreased

Lowering of boiler safety: Due to scale formation, over heating of boiler is done, which causes distortion of boiler tube.

Decrease in efficiency: Scales may deposit in the valve and condensers of the boiler and choke them partially.

Danger of explosion: When thick scales crack, the water comes suddenly in contact with over heated iron plates.

Disadvantages of scale formation

Removal of scales With the help of scraper or piece of wood or wire brush.By giving thermal shocks, if they are brittle. By dissolving them by adding chemicals, (5-10% HCl, EDTA) if they are adherent and hard. By frequent blow-down operation, if the scales are loosely adhering.

Page 49: The Water

Prevention of scales formation (1) External Treatment: Includes efficient ‘softening of water’

(i.e., removing hardness-producing constituents of water)

(2) Internal Treatment: Accomplished by adding a proper chemical to the boiler water either:

Internal treatment:

In this process, an ion is prohibited to exhibit its original character by complexing or converted into other more soluble salt by adding

appropriate reagent.

An internal treatment is accomplished by adding a proper chemical to water either:(a)To precipitate the scale forming impurities in the form of sludge, which can be removed.(b)To convert them into compounds, which will stay in dissolved form in water and thus do not cause any harm.

Page 50: The Water

Trisodium phosphate is most suitable for treatment when alkalinity is low

Disodium phosphate is used when the water alkalinity is sufficient.

Monosodium phosphate is used when the alkalinity of boiler water is too high.

The choice of salt depends upon the alkalinity of the boiled water because calcium cannot be precipitated below a pH 9.5.

Important Internal Treatments are:

Phosphate conditioning:Scale formation can be avoided by adding sodium phosphate which reacts with hardness of water forming non-adherent and easily removable soft sludge of calcium and magnesium phosphate.

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

Page 51: The Water

Calgon conditioning:

Its involve in adding calgon (Sodium hexa-meta phosphate (NaPO3)6 to boiler water. It prevents the scale and sludge formation by forming soluble complex compound with CaSO4.

Na2[Na4(PO3)6] 2Na+ + [Na4P6O18]2-

2CaSO4 + [Na4P6O18]2- [Ca2P6O18]2- + 2Na2SO4

soluble complex ion

Page 52: The Water

(i) Colloidal conditioning: Scale formation can be avoided by adding organic substances like kerosene, tannin, agar-agar (a gel) etc., which get coated on over the scale forming precipitate, thereby, yielding non-sticky and loose deposits.

(ii) Carbonate Conditioning: In low pressure boilers, scale-formation can be avoided by adding sodium carbonate to boiler water.

CaSO4 +Na2CO3 → CaCO3 + Na2SO4

Page 53: The Water

(v) Treatment with sodium aluminate (NaAlO2): sodium aluminate gets hydrolyzed yielding NaOH and a gelatinous of aluminum hydroxide

NaAlO2 + 2H2O → NaOH + Al[OH]3

Sod.meta-aluminate (Gelatinous ppt.)

Theses sodium hydroxide precipitates some magenisium MgCl2 + 2NaOH → Mg(OH) 2 + 2NaCl

The flocculent precipitate of Mg(OH)2 and Al[OH] 3 produced inside the boiler, entraps finely suspended and colloidal impurities, including oil drops and silica.

(vi) Electrical conditioning: Sealed glass bulbs, containing Hg connected to a battery, are set rotating in the boiler. when water boils, mercury bulbs emit electrical discharges which prevents scale forming particles to adhere/stick together to form scale.

(vii) Radioactive conditioning: Tablets (radioactive salts) are placed inside the boiler water. Energy radiations emitted by these salts prevent scale formation

Page 54: The Water

Priming and Foaming PrimingWhen a boiler is steaming rapidly, some particles of the liquid water are

carried along-with steam. this process of wet steam is called Priming.

Reasons for Priming: The presence of large amount of dissolved solids High steam velocities Sudden boiling Improper boiler design Sudden increase in steam- production rate.

Priming can be avoided by Fitting mechanical steam purifiers. Avoiding rapid change in steaming rate. Maintaining low water levels in boilers. Efficient softening and filtration of the boiler-feed water.

Page 55: The Water

Foaming: Production of persistent foam or bubbles in boilers. This is due to presence of substances (oils) which reduce the surface tension of water.

Priming and foaming usually occur together. They are objectionable because Efficiency reduces as dissolved salts in boiler water get deposited on super-heater and turbine blades, as water evaporates. Life of the machinery may decrease as dissolved salts may enter the parts of other machinery. Maintenance of the boiler pressure becomes difficult, as actual height of the water column cannot be judged properly.

Foaming can be avoided by Adding anti-foaming chemicals like castor oil. Removing oil from boiler water by adding compounds like sodium aluminate

Page 56: The Water

BOILER CORROSION

Decay of boiler material due to chemical or electro-chemical attack by its environment. Main reasons for boiler corrosion are:

(i) Dissolved oxygen: Dissolved oxygen in water, in presence of prevailing high temperature, attacks boiler material:

2Fe+2H2O + O2 2Fe(OH)2 ↓

4Fe(OH)2 + O2 2[Fe2O3.2H2O] ↓

(Ferrous hydroxide) (Rust)

Removal of dissolved oxygen:

(i) Adding calculated quantity of sodium sulphite or hydrazine

2Na2SO3 + O2 → 2Na2SO4

N2H4 + O2 → N2 + 2H2O

Na2S +2O2 → Na2SO4

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2. By mechanical deaeration

Deaerated water

Water feed

Perforated plate

Steam jacket

To vacuumO2

It comprises of a tall stainless tower with different layers capped with baffles to facilitate multiple equilibration. The entire chamber is vacuumized and also maintained at high tempt using perforated heating plates on the walls.

Principle: High tempt and low pressure favors lower solubility of gases in water (Henry’s law)

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(ii) Dissolved carbon dioxide (carbonic acid):

CO2+H2O → H2CO3

CO2 has a slow corrosive effect on the boiler material. Carbon dioxide is also released inside the boiler.

Mg(HCO3)2 → MgCO3 + H2O + CO2

Removal of CO2

By adding calculated quantity of ammonia.

2NH4OH + CO2→ (NH4)2CO3 + H2O

By mechanical-aeration process along with oxygen.

(iii) Acids from dissolved salts: Water containing dissolved magnesium salts liberate acids on hydrolysis.

MgCl2+2H2O→ Mg (OH) 2↓ + 2HCl

acid reacts with iron (of the boiler) in chain-like reactions producing HCl

Fe +2HCl→ FeCl2 +H2↑

FeCl2 +2H2O→ Fe (OH) 2↓ + 2HCl

Consequently, presence of even a small amount of MgCl2 will cause corrosion of iron to a large extent.

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(ii) By mechanical de-aeration water is sprayed in a perforated plate-fitted tower, heated from sides and connected to vacuum pump.