IG/

For restricted Circulation Only

POWER PLANT
CHEMISTRY

Power Management Institute

Noida

CONTENTS
SI. No.

Subject

Page No.

1.

Fundamental Concepts

2.

Raw Water and its Softening Process

21

3.

Combating Corrosion

69

4.

Boiler Water Treatment

81

5.

Coal and its Analysis

98

6.

Oil

145

A. Fuel Oils

145

B. Lubricating Oils

155

C. Insulating Oils

164

7.

Hydraulic Fluids

166

8.

Other Chemical Aspects of Power Plant

167

9.

Model Session Plan

173

1. Fundamental Concepts
Units of Measurement and Concepts
The term concentration refers to the amount of one thing dissolved in another.
For example if we put pound of sugar in-to one gallon of water, the concentration
of sugar in the water in one pound per gallon.
There are other ways to express concentration as well.
Probably the most familiar unit of measurement in Chemistry is percentage,
which states the number of units (or parts) of a constituent in 100 units (or parts)
of a solution. Thus, percent concentration could be thought of as parts per
hundred.
A typical concentration of NaCL (Table Salt) in raw might be only 0.003 parts per
hundred, or 0.003%. This number is so awkward that we use the smallest units:
parts per million or parts per billion (ppb). These units mean weight per million
units of weight of solution or weight per billion units.
In many cases, we use milligrams per liter (mg/1) instead of ppm. In the very
dilute solution employed in water treatment chemistry, it is nearly always safe to
assume that ppm and mg/l means exactly the same thing. This is because 1 liter
of water weighs one million milligrams and so 1 mg/l is 1 ppm. Parts per billion
(ppb) is used to express concentration less than 1 ppm.
1%

10,000 ppm =

10,000,000 ppb

1 ppm

1,000 ppb

0.001%

1 ppb

0.001 ppm

0.0000001%

1 ppm

1 mg/1

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Chemical Calculation
The number of moles of a material is defined as the weight of material to be
reacted divided by the molecular weight of that materials.
Elements combine to form compound in specific, whole number ratios according
to the valency of the elements. Similarly, molecules compound react with each
other in specific whole number ratios according to the weights of combining
molecules. This ratio is determined from examination of the numbers preceding
the molecular formula in the written equation for a chemical reaction. Lets
examine reaction between Oxygen and Sodium sulphite to form Sodium
Sulphate.
2 Na2SO3 + O2------------------ 2 Na2 SO4
Sodium Sulphite + Oxygen ------------------ Sodium Sulphate
One molecule of Oxygen reacts with two molecules of Sodium Sulphite to form
two molecules of Sodium Sulphate.
The Molecular Weight of Sodium Sulphite is 126 (2 Sodium atoms of 23 atomic
Wt + 1 Sulphur atom of 32 atomic Wt + 3 Oxygen atoms of 16 atomic Wt each)
thus
2 x 23 + 1 x 32 + 3 x 16 = 126
The weight of one atom (atomic weight) of oxygen is 16 (rounded off from 15.994
for convenient calculation). The weight of the oxygen molecule (molecular
weight) is 32, then, since it contains two oxygen atoms.

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So, one oxygen molecule, weighing 32, reacts with two molecules of sodium
sulphite, weighing 126 each a total of 252. Thus, we form two molecules of
Sodium Sulphite, weighing 284 (the sum of 32 and 252).
This relationship can be conveniently displayed by writing the molecular weights
above the components of the reaction in the equation.
2Na2SO3 + O2 ------- > 2Na2SO4
252

32

284

It is now clear that it requires 252 parts (gm, pounds, tons, etc.) of sodium
sulphite to react with 32 parts (grams, pounds, tons, etc) of oxygen to make
desired sodium Sulphate.
If the molecular weight is expressed in grams, it is called molecular weight, or
gram mole, for short. Thus, one gram mole of oxygen (32 grams) always reacts
with two gram mole of sodium sulphite (252 gm). Some similar mole ratio is fixed
and is always true for any reaction, so that it is possible to compute the amount
of Chemicals required to participate in that reaction. This ability to compute
chemical requirements and consumption is important to the power plant chemist.
It enables him to know how to compute the amount of chemicals to be added to a
system.
PPM AS CaCO3
In water chemistry, certain mineral constituents are nearly always present and
are of particular interest due to their interaction with each other and due to their
influence on corrosion and deposits problems. These constituents are the
elements that cause hardness (Calcium or magnesium) and the radicals that

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cause alkalinity (hydroxide, carbonate and bicarbonate). Because these minerals

are involved in frequent chemical calculations, it is convenient to employ a
common measurement unit for their concentration in water. In this way, one can
compute their combinations without combining weight calculations & procedures.
We use for this purpose ppm as CaCo3, because CaCo3 (Calcium Carbonate)
includes both hardness (Ca) and alkalinity (CO3) and because its molecular
weight is the round number 100. Once the concentration of all minerals elements,
compounds and radicals is expressed as ppm as CaCo3, the quantities can be
added, subtracted and combined directly.
Solution Characteristics
A solution is a homogenous mixture of two or more substances, whose
concentrations can vary continuously within certain limits (This variability
distinguishes a solution from compound). Defining a solution as a homogenous
(or uniform) mixture means that there are no distinguishable boundaries between
any of the components. (This characteristic also distinguishes a solution, such as
salt dissolved in water an example of heterogeneous mixture, is a combination
of salt and pepper).
In a true solution, the individual particles of the components are no larger than
molecules. Solution may be composed of gases, liquids and solids in any
combination.
The following table gives the nine possible types of solutions and gives an
example of each type:

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Stage

Solution

Example

Gaseous

Gases in gases

Oxygen in Nitrogen (Air)

Liquid in gases

Water in air

Solids in gases

Iodine in air

Gases in liquid

Carbondioxide in water

Liquids in liquids

Alcohol in water

Solids in liquids

Salt in water

Gases in solids

Hydrogen in Steel

Liquid in solids

Mercury in silver

Liquid

Solids

(Amalgam)
Solids in solids

Carbon in iron (Steel)

In water chemistry, the only types of solutions of major concern are solids in
water, gases in water and solids in solids (alloy materials that may corrode in
presence of water).
Solubility
The material that is dissolved is called the Solute, and the material in which it is
dissolved is called solvent. When table salt is dissolved in water, the salt is the
solute and the water is the solvent.
When a solute has been dissolved in a solvent to the extent that no more can be
dissolved, the solution is said to be saturated. The saturation value for a specific
solute in a solvent is called its solubility in that solvent. The solubility of any
solute in water is usually depends on temperature. If the solute is a gas, it is

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more soluble at low temp that an high temp. At higher pressure, it is more soluble
than at low pressures.
Ionization
When compounds dissolve in water, they produce observable changes in some
of the physical properties of the solution, such as increase in conductivity. The
special effect of minerals dissolved in water is caused by the fact that, when
minerals are dissolved in water, they break up partially into particles that are
charged. In case of NaCl, for example the natural way for the compound to split
up into sodium ion (one Na+) and one chlorine Ion (one CL-). The minerals break
up this way because the Sodium (Na) is only loosely attached to Chlorine (CL).
The charged particles formed are called ions. The positively charged ions are
called cations. (One way to remember which is to spell Cation as Ca+ Ion,
replacing the + with a+). The negatively charged ions are called anions.
Ionization Constant
When compounds break up or ionize in solution, they do so only partially.
Different compounds ionize to different degrees and it is important that we should
note that water is slightly ionized. Most of the molecules in water remain as H2O
and do not split or dissociate into cations and anions. We say, therefore that
water has a low dissociation constant. Molecules of compounds which all split
into cations and anions are said to have high dissociation constant.
Water itself is neutral, that is neither an acid nor alkali, because there is an equal
number of hydrogen and hydroxyl ions, each hydrogen ion or acid ion is
balanced or neutralized by the other half of the molecule, which is a hydroxyl ion
or alkali ion.

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Acids
An acid is a substance that ionizes in water to release free hydrogen (H+) ions.
The strength of an acid is determined by how many hydrogen ions it supplies
(that is, its degree of ionization.)
(a)

Strong Acids
Typical examples of strong acids are hydrochloric acid (HCl). Sulphuric
Acid (H2SO4) and Nitric acid (HNO3). In a solution, these acids ionize as
follows:

(b)

HCl

H + CL

(92% ionized)

H2SO4

2H + S04

(60% ionized)

HNO3

H+ + N0-

(92% ionized)

Moderately Strong Acids

Phospheric acid (H3PO4)is only moderately strong and partially ionizes 1%
H3PO4 H+ H2PO-4

(K1 = 7.5x10-3)

Weak Acids
Carbonic acids (H2CO3) is considered a weak acid. Its tendency to supply the
hydrogen is very slight, far less than for acids such as HCL or H2SO4. Even
moderately strong phosphoric acid has an ionization constant of 7.5 x 10-3, which
is 25,000 times greater than the value for the hydrogen ion released from
Carbonic Acid.

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H++ H2CO3 (K = 3x10-7)

H2CO3

The ionization constant is then a measures of the degree of ionization of a

compound in water. The larger the numbers the greater the degree of ionization.
Generally speaking, the acids that readily ionize, HCL and H2SO4 are more
dangerous to handle than the weakly ionized acids, such as H2CO3, Carbonic
acids.
Bases
A base, when dissolved and ionized in water, supplies free hydro xyl (OH-)
ions. As with acids, the strength of bases depends on their ionization constant.
(a)

Strong Bases
Typical strong bases are the hydroxides, sodium hydroxide (NaOH),
commonly called caustic soda; potassium hydroxide (KOH), commonly
called potash; and calcium hydroxide [Ca(OH)2], commonly called lime.
The dissociation reactions and degree of ionization for these strong bases
are as follows:
NaOH

Na+ + OH-

(91% ionized)

KOH

K+ + OH-

(91% ionized)

Ca(OH)2

Ca++ + 20H-

(90% ionized)

This degree of ionization determines the strength, or chemical reactivity, of

that substance in water solution. The degree of ionization (also called
dissociation) can be expressed numerically by a factor called the

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ionization constant. For example, the ionization of a sodium chloride can

be expressed by the following reaction:
NaCl ------------------ Na+ ClThe ionization constant formula for this reaction can be written as follows:
K (NaCl) = ------------------ (Na+) (Cl-)
The symbol stands for the expression of solution concentration in moles
per liter of the compound determines its strength or chemical reactivity, a
highly reactive substance will be highly ionized. If it is highly ionized, the
product of its ionic concentrations will be a large number.
If on the other hand, the dissolved compound is slightly reactive, the
product of its ionic concentrations and its ionization constant will have a
low value.
Useful Physical Chemical Properties
Water
Water is made up of hydrogen atom and oxygen atoms. A molecule of
water is made up of two hydrogen atoms and one oxygen atom. Water
itself is slightly ionized and the water molecule splits up into a cation (H+)
and an anion (OH-).
HOH <==============> H+ + OHThe ion of water are called hydrogen ions (H+) and hydroxyl ion and these
ions are the basis of all acids (hydrogen ion) and alkali (hydroxyl ion).

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(b)

Weak Bases
A typical weak base is ammonium hydroxide (NH4 OH):
NH3 + H2O ---------------------------- NH-4 + OH- (K1 = 1.8x10-5)
Note that ammonia (NH3) is a gas that dissolves in water to form NH4+
and OH-. In this case, you cannot say how much of the NH3 has ionized.
But as you can gather, the K1 is quite small, indicating a low concentration
of the ionized reaction products, NH4 + and OH-.
Again, you most exercise caution when handling all strong bases.

Salts
Acids react with bases and neutralize one another. The reaction products are
water and a compound called a salt. The salt is the compound formed by the
cation (+ ion) of the base and the anion (-ion) of the acid. A typical neutralization
reaction is the one between hydrochloric acid (HCL) and sodium hydroxide
(NaOH) to form the salt, sodium chloride (NaCl). The reaction is written as
follows:
HCL + NaOH ---------------------- Nacl + H2O
Acids + base ----------------------- salt + water
The salt formed by the reaction between a strong base and a strong acid is said
to be neutral. The cations balance the anions, and there is no residue of
hydrogen or hydroxl ions to cause acidity basicity. Other examples of a neutral
salt are potassium sulphate.
2 KOH + H2 SO4 --------------------- K2SO4 + 2 H2O

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and calcium nitrate,

Ca (OH) 2 + 2 HNO3 ----------------- Ca (NO3) 2 + H2O
The salts formed in these reactions are highly ionized, but not as much as the
original acids and bases.
The reaction between a strong base and a weak acid or between a weak base
and a strong acid forms a salt that is not neutral, but has acidic or basic
properties like the stronger of its original components. For instance, the salt
formed by a reaction between sodium hydroxide (strong base) and carbonic acid
(weak acid) is basic. The large quantity of hydrogen from the strong base
overwhelms the smaller quantity of hydrogen from the weaker acid to produce an
excess of hydroxyl ion a basic condition.
Similarly, the salts known as ammonium sulphate (NH4) 2SO4, aluminum sulphate
Al2 (SO4)3, and ferric chloride (FeCl3) all have acidic properties, because they are
formed from weak bases and strong acids. In other words, if any of these salts
are dissolved in water, the resultant solution will be acidic.
In water chemistry, then, we must be alert to the possibility that some salt
solutions may be either acidic or basic and must be properly treated before
disposal.
1.

pH

2.

Alkalinity and Acidity

1.

pH
a)

Ionization of Water

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Soluble acids, bases, and salts all ionize in water. Acids form free
hydrogen ions (H+) bases form free hydroxyl ions (OH-) and salts
produce either H+, or OH- unless they are completely neutral. When
acids and bases react to form salts from the cation of the base and
the anion of the acid, the other halves, H+ and OH-, react to form
water.
H+ + OH- ---------------- H2O (or HOH)
Because water has a small ionization constant, however, the
reaction is reversible to a slight degree. The ionization, or
dissociation, constant for water is:

K1

(H+) (OH-)
--------------------(H2O)

= 1.8 x 10-16

This small dissociation constant can also be expressed as an ion

product:
KW = (H+) (OH-)
In pure water, which is desirable in the power plant, (H+) must equal
or exactly balance (OH-). It has been found that (H+) and (OH-) in
pure water both have the value of 1.0 x 10-7 moles per liter.
Therefore:
KW = (1.0 x 10-7) (1.0 x 10-7) = 1.0 x 10-14
b)

Definition of pH
Adding acids or bases to pure water changes the concentration of

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H+ and OH- ions. Acids increase (H+) to a value greater than 1.0 x
10-7, and bases do the same for (OH-). But, as long as the solution
remains dilute KW is constant at 1.0 x 10-14 of the (H+) (OH-)
product. If this mathematical product is constant, any increase in
either (H+) or (OH-) must be accompanied by a proportional
decrease in the other. Therefore, as an aqueous solution becomes
more acidic, (H+) increases. As the solution becomes more basic,
(H+) decreases. This relationship is used to express relative degree
of acidity or basicity in terms of the hydrogen ion concentration.
This relationship has been given the name pH. It is defined
mathematically in terms of the logarithm of the hydrogen ion
concentration:

pH = log

1
-------H+

You do not need to remember this equation, but whenever you see
log, you should think in terms of powers of ten. For simplicity the pH
can be considered to be the power of the hydrogen ion. For
example, a pH of 5 means a concentration of 1x10-5 moles per liter
of hydrogen ions. A pH of 6 means a concentration of 1x10-6 moles
per liter of hydrogen ions. Thus, a change from a pH of 5 to a pH of
6 is a decrease by a factor of 10 in the hydrogen ion concentration.
c)

Range of pH Values
-

A neutral solution has a pH of 7.

An acid solution has a pH less than 7.

A basic solution has a pH greater than 7.

(The term alkaline is frequently used in place of word basic)

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A change of one pH in either direction is a change by a factor of 10

in the H+ concentration. A solution with a pH of 3, for example, has
10,000 times more (H+) than a solution with a pH of 7. These
concepts are demonstrated in Figure 4A and Table 1. Table 1
includes both the H+ and OH- concentrations associated with
specific pH values. Table 2 indicates the pH of some common
materials and the pH of water in various plant systems. Remember
that the pH scale is only an indicator of the balance between
hydrogen and hydroxyl Ions.
-----------------------------------------------------------------------------------------------------------pH
pH is an indication of the hydrogen ion concentration
hydrogen ion concentration (Grams/Liter)
-----------------------------------------------------------------------------------------------------------10-0 10-1

10-2

10-3

10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-11 10-12 10-13

-----------------------------------------------------------------------------------------------------------0

10

11

12

SUBSTANCES

SUBSTANCES

CONTRIBUTING

CONTRIBUTING OH-

H+ OR LIBERATING

OR LIBERATING

H+ FROM WATER

OH- FROM WATER

13

INCREASING H+
-----------------------------------------------------------------------------------------------------------THE PRODUCT OF H+ & OH- CONCENTRATIONS IS A
CONSTANT INCREASING OH------------------------------------------------------------------------------------------------------------

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d)

Measurement of pH
The pH of a solution can be determine directly by measuring the
voltage developed across a cell composed of two electrodes and
the solution to be tested. The pH meter is a sensitive voltmeter
whose output is calibrated in pH units. One of the two electrodes is
a reference electrode, and the other is an electrode made of a pHsensitive glass. As the H+ concentration of the solution changes, the
voltage developed between the reference electrode and the glass
electrode also changes. The pH meter measures the voltage
developed in pH units.
Since the electrodes are sensitive to temperature, the temperature
of the test solution must be measured, and a compensating dial on
the pH meter must be adjusted. Some pH measuring systems
measure the temperature and adjust the meter automatically.
These automatic systems are generally used for the on-line pH
meters that are installed in plants.
A pH meter is always calibrated with a solution of known pH to
ensure that it operates properly. The solutions used are called
Buffer Solutions, because they maintain constant pH over a range
of concentrations and in the presence of small amounts of acidic or
basic impurities.

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Table 1 - RANGE OF pH
PH

H+

OH-

Moles/liter
Increasingly )

Acid

Solutions

Neutral

Increasingly )

Basic

11

Solutions

13

0.1 = 10

-1

Moles/liter
10-13

10-5

10-9

10-9

10-5

10-13 0.1

10-1

Table 2 - PH OF SOME COMMON MATERIALS

SOLUTION

pH RANGE

Beer

4.0 5.0

Blood

7.3 7.5

Cider

2.9 3.3

Maple Syrup

6.5 7.0

Milk

6.3 6.6

Orange Juice

3.0 4.0

Saliva

6.5 7.5

Soft Drinks

2.0 4.0

Water, Drinking

6.5 8.0

Wine

2.8 3.8
PH OF WATER IN VARIOUS PLANT SYSTEMS

PH

PLANT SYSTEM

Raw Water

Makeup Water

8.8 9.2

Feed Water

9.2 9.5

Boiler Water (phosphate)

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Alkalinity and Acidity

In all the previous discussion, the property of a solution that causes the presence
of free hydroxyl ion has been referred to as basicity or alkalinity. But alkalinity
has a specific meaning in water chemistry,

the ability to neutralize acidity.

Alkalinity is measured in some specific unit of concentration, commonly parts per

million (ppm). Acidity is the ability to neutralize alkalinity and is also measured in
ppm.
Alkalinity and acidity are invariably measured when characterizing the quality of a
water. Knowing these properties helps to predict the behaviour of any water in
service, practically whether it will form scale or be corrosive.
The alkalinity and acidity in natural waters always consists of free carbon dioxide,
carbonate ions, bicarbonate ions, hydroxyl ions, or some combination of these
components. In rare instances raw water will contain some other alkaline or acid
ion as well, but this situation is so unusual that it is generally ignored.
a)

Conductance of Solutions
A solution that conducts electricity is called an electrolyte. Electrolytes are
water solutions of acids, bases, or salts. Electrolytes vary inability to
conduct electricity. The ions in a solution actually carry the electricity
through the solution and different ions have different carrying capacities or
conductances. The hydrogen ion has the greatest conductance, the
hydroxyl ion has about half the conductance of the hydrogen ion, and all
other ions have considerably less conductance.
As the concentration of a solution increases, the conductance of the
solution increases, since there are more ions to carry the electricity.

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Power Plant Chemistry is usually concerned with very dilute solutions in

which there are few ions to carry electricity. Where there are few ions, it is
easier to measure the resistance of solution to electricity. Because
conductance is the ability to conduct an electric current, and resistance is
the inability to conduct an electric current, these two concepts are related
follows:
1
Conductance = ---------------Resistance
Since resistance is commonly expressed in units called ohms, it was
decided to use the unit mho (ohm spelled backwards) for conductance. In
the very dilute solutions of interest in power plant water chemistry,
conductance is so low that we employ units smaller than mhos. For
instance, a common value for the conductance of high pressure boiler
water might be 0.00005 mhos. For this reason, the common unit for
conductance in water chemistry is the micromho, or one millionth of a mho
(10-6 mhos). This unit is abbreviated as mhos.
Conductance values are usually reported at the standard temperature of
25OC. If they are measured at another temperature, it is necessary to
convert our readings to the value in micromhos at 25OC. There are
accepted procedures for doing this.
b)

Specific Conductance, or Conductivity

The conductance of a solution measured at 25OC between two electrodes
that are each 1 cm2 in area and are spread 1 cm apart is called the
specific conductance, or the conductivity of that solution. The units of
conductivity are mohs/cm.

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c)

Using Conductivity to Measure Concentrations

In the past, conductivity measurements were converted into ppm
dissolved solids by using calibration curves developed for each
conductivity measuring device. As a rule of thumb, dissolved solids can be
related to conductivity as follows:
ppm of dissolved solids = 0.7 x conductivity in mhos/cm. This
approximation holds true only for solutions of salts. For solutions of acids,
bases, or salts that are strongly acidic or alkaline, the multiplier will be in
the range of 0.5 to 0.6.
Conductivity measurements are important tools for monitoring quality of
water in power plants because of their relationship to dissolved impurity
concentration. As you know, it is important to know and control the
relatively large amount of total dissolved matter in boiler water. It is also
important to know and control the small dissolved contaminant
concentration in water that must remain very pure (return condensate or
demineralized water). The quantity of dissolved matter can be detected
more simply and quickly by measuring conductivity than by evaporating a
sample to dryness and weighing the residue.

d)

Measurement of Conductivity
As we have seen, conductivity is defined as the conductance of solution
measured at 25OC between two electrodes that are each 1 cm2 in area
and spaced 1 cm apart. Since most conductivity cells in use do not have
electrodes 1 cm2in area, and since the electrode are not spaced 1 cm
apart, the cells are given a cell constant, or correction factor, by the
manufacturer. The cell constant corrects the reading to what it would have
been if the electrodes were 1 cm2 and spaced 1 cm apart. The

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conductivity, then, is equal to the conductance (measured at 25OC)

multiplied by the cell constant.

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2. Raw Water And Its Softening Process

Basic Water Chemistry
Water absolutely pure is not found in nature. As the water vapour condenses in
Air and falls, it absorbs dust, dissolves Oxygen, Carbon dioxide and other gases.
At the ground surface it takes up silt and other inorganic matter. A few bacteria
will have entered the water also.
These impurities, whatever may be the source, always contains impurities either
in solution or in suspension. The determination of these impurities make water
treatment essential.
Sources
Various sources of water can be broadly classified as:
Rain Water
Surface waters (Rivers, Streams, Ponds, Lake and Reservoirs)
Ground water (Springs, Shallow wells & Deep wells)
Quality of Raw Water
The composition of water from different sources varies widely both in the amount
of dissolved salts and in the dissolved gases which it contains. In addition,
surface waters, that is water from rivers and lakes, etc., usually contain
suspended matter and often contain organic matter in solution and in
suspension, derived from either decayed plant material or sewage.

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Most waters can be treated to make them suitable for cooling services, the
purpose of any treatment employed being to minimize the risk of fouling or
corrosion of the heat-exchanger surfaces, or corrosion of the associated plant
through which the water passes.
Very pure water containing no more than a scarcely-measurable trace of
dissolved salts is required for boiler feed make-up purposes.
Chemical Composition
The major constituents of all natural waters consist of the salts of sodium,
potassium, calcium and magnesium, together with bicarbonate, carbonate,
sulphate, chloride and nitrate ions. Other constituents present, usually in low
concentrations but which may create special problems, are silica, hydrogen
sulphate, ammonia, organic matter (particularly substances known as fulvic
acids), detergents, phosphates, and dissolved gases. Silica occurs in water in
several different forms some of which escape detection by the normal chemical
test employed (non-reactive silicon), and phosphate can occur as complex
phosphate which escapes detection by the normal test used for orthophosphates,
but there is some evidence to suggest that it can interfere with water-softening
reactions. Sea water contains traces of most of the soluble salts and small
concentrations of nitrates. Ferrus iron and manganese are found in certain
waters.
Calcium bicarbonate, usually included in the temporary hardness or alkaline
hardness, is unstable and on heating breaks down depositing calcium carbonate.
Some calcium and magnesium salts are sparingly soluable so that if the water is
evaporated or concentrated they crystallize out as hard scale.

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The equivalent mineral acidity (E.M.A.) is a measure of the concentration of salts

of strong acids (sulphuric, hydrochloric and nitric acids usually) present in the
water.
Carbon dioxide in the form of carbonates and bicarbonate dissolved in the water
and this is known as free carbon dioxide.
The other salts present in the water create no particular problem but since they
are electrolytes they will, if present in sufficient concentration (for example sea
water), allow galvanic action to take place between dissimilar metals, resulting in
dissolution of the more anodic metals.
Reference has already been made to the fact that ultra-pure water is required for
boiler feed water make-up in a modern generating station. A typical specification
for a new high pressure station may call for the following guaranteed quality.
-----------------------------------------------------------------------------------------------------------Conductivity (before and after passage

Not greater 0.10 micro mho/cm

Through a cation-exchange column in the

(corrected 20OC)

Hydrogen
-----------------------------------------------------------------------------------------------------------Sodium

Not greater than 0.015 ppm.

-----------------------------------------------------------------------------------------------------------Silica (including non-reactive silicon)

Not greater than 0.02 ppm with

95% condence limit

-----------------------------------------------------------------------------------------------------------The quality of the water required is almost that of absolutely pure water which
has a conductivity of 0.056 micromho/cm at 25OC and 0.038 at 18OC and there
is, therefore, little chance for improvement on the quality specified above. The

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real problem to ensure that this quality is consistently maintained, with regard to
silica.
Impurities
The major impurities of water can be classified in the following groups:
1.

2.

Non-ionic and

Silt Mud and

Undissolved

Bacteria

Ionic and Dissolved Impurities-carbonate, bicarbonate, chloride and

sulphate of Ca and Mg.

3.

Gaseous-Oxygen and Carbon dioxide.

Non-ionic Impurities
They are mainly turbidity, silt, mud, dirt and other suspended matter; micro
organism & other organic matter; oil and other corrosion products. It goes without
saying that drinking water and most industrial water supplies should be clear and
organics free.
Ionic and Dissolved Impurities
Any salt which dissolves in water splits into positively charged cations and
negatively charged anion and since these permit the water to conduct electricity
these salts are called electrolytes. Some of the most common cations in water
are: Calcium, Magnesium, Sodium and iron rarely Ammonia and Manganese.
These cations are associated with Anions like Bicarbonate, Carbonate
Hydroxide, Sulphates & Chlorides.

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24

The sum of Cations or total cations always equals the total of Anion.
Quantitatively, these are expressed in parts per million or milligrams/litre. One
part per million equals one ten thousands of one percent (0.0001%). One part
per million means one part in a million parts, for example one ounce in a million
ounces of water or one lb in a million lbs of water.
Dissolved silica is another troublesome impurity, especially in water fed to boilers
at very high temperature & pressure.
Gaseous Impurities
Out of the atmospheric gases found in natural water only Carbon dioxide and
oxygen are the main causes of many corrosion problems.
Various problems caused by the impurities
a)

Scale Formation
The process of deposition of mineral constituents in boiler on metal
surfaces is called scale formation. The primary cause of scale formation is
the fact that the solubilities of scale forming salts decrease with increase
in temp. Consequently, the higher the temp. and pressure of boiler
operation, the more insoluble the encrusting salt become and may tend to
form strong adherent scale on the evaporation surfaces. Amongst the
natural substances found in water are salts of calcium and magnesium,
which may give rise to scale formation. It is this particular salt which give
water its Hardness.
Scale in boiler can be prevented by removing hardness salts from make
up water, so that no calcium and magnesium enter the boiler from this

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25

source and by internal chemical treatment of boiler water to deal with any
trace which may enter the system.

Fig. No. 1
SCALING
Due to earlier mentioned salts in water they get deposited on the tube surfaces,
when water is converted into steam.
This provides over-heating of tubes, less heat transfer and finally leads to tube
leakages.
In modern boiler, all the impurities forming scale is removed before the water
enters the boiler.

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b)

Corrosion
Corrosion is the wasting away of metal in contact with water. Metallic iron
in contact with water goes into solution as ferrous ions liberating negative
charged electrons as per the following reaction:
M -------------- > M+

+ e ..

(1)

The positively charged metallic ion react with negative (OH)- ions to form
the hydroxide as below:
M+ + OH-

-----------------> MOH

(2)

The ferrous hydroxide formed is oxidized to ferric form by the oxygen

present in water in the dissolved state.
The electrons released in the reaction (1) are neutralized by an equivalent
amount of hydrogen ions from water to the neutral state as below:
e

+ H --------------------> H

The neutral H formed in the above reaction reacts with the dissolved
oxygen present in water to form H2 as per the reaction given below:
2H

+1/2 O2 ----------------H20

Hence, for every hydrogen neutralized and converted to water a

corresponding hydroxyl ion combines with the metal to form insoluable
hydroxide ion and the corrosion process continues. It is quite evident that
the oxygen present in water in the dissolved state has considerable effect
in accelerating the rate of corrosion.

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c)

Carry Over
When steam leaves a boiler drum at rapid rate, tiny droplets of boiler
water are carried upward with the steam as the droplets would become
pure steam on further heating in super heaters, dissolved solids which
also go along, are called Carry over. These solids may deposit in the
super heater tubes or on the turbine lades, reducing the

%. Silica is

particular troublesome in this respect because it dissolves in high press

steam and is transported through steam system.
As the Raw Water obtained from intake contains all the impurities
mentioned earlier, it is unfit for is intended, before it can be supplied as
make-up water to a boiler. The process commonly employed to remove
impurities is shown in following block diagram:

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28

RAW WATER
AERATION

COAGULATION
&
CLARIFICATION

ANTHRACITE
FILTER

ACTIVATED CARBON
FILTER

CATION
EXCHANGER

DEGASSER

ANION
EXCHANGER

MIX BED
EXCHANGER

D.M.
WATER

Raw water is fed to cascade aerator. Before aeration, through a mixing T,

lime and chlorine (or Sodium sulphate) are injected to increase pH value
and removal of bacterial infection any in the water.

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After aerator, water is dozed with the required amount of alum.

Suspended particles present in water take a very long time to settle. It is
therefore necessary to device a means to coagulate the very small
particles in to bigger ones with higher settling values. It is achieved by
adding certain chemical known as coagulant, the commonest is Aluminum
Sulphate i.e. Alum.
The coagulant Alum is mixed in raw water in the Flash Mixer. Then it
passes through a settling basin called Clariflocculator.
Water from the Flash Mixer enters into the flocculating zone of the clarifier
through the R.C.C Central shaft opening. The clarifier is fitted with a
rotating bridge driven by a electric motor. Here mechanical flocculation is
done at the tip zone by the motor operated stirrer mounted on the bridge.
Preliminary settlement of flocs takes place in the bottom zone. Water then
enters into the clarifying zone through bottom openings. The sludge in
settling zone and other clarification zone is scrapped towards the central
pit by means of scrappers linked with the rotating bridge. Sludge is then
removed from this pit in the form of 10% slurry through sludge discharge
pipe manually.
The object of water softening is to remove the calcium and magnesium
salts causing scale deposition, particularly in evaporators.
Lime/Soda Softening
In lime soda softening, advantage is taken of the fact that calcium
carbonate and magnesium hydroxide are sparingly soluble in water and
can be precipitated from solution by the following reactions:

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30

1. Ca(HCO3)2 + Ca (OH)2 -----------------> 2Ca CO3 + 2 H2O

2. Ca(SO4)2 + Na2 C03 ---------------------> Ca CO3 + Na2S04
3. Mg(HC03)2 + 2Ca (OH)2 ---------------------> Mg (OH) 2 + 2CaC03 +2H
4 MgCl2 + Ca (OH)2 + Na2 CO3 -------------> Mg (OH) 2 + 2CaC03 +2Na
It can be seen from the above reactions that the precipitating agents are
calcium hydroxide (lime or more correctly hydrated lime, Ca (OH)2, and
sodium carbonate (soda-ash or soda, Na2CO3). These are the reagents
normally used in water softening. But in fact any soluble carbonate or
hydroxide could be used. However in removing temporary hardness, lime
is a particularly suitable reagent since the only soluble product of the
reactions (1) and (3) is water and this therefore results in a reduction of
the T.D.S. of the water.
At 0OC the solubility of calcium carbonate is 15 ppm and magnesium
hydroxide 17 ppm. In the presence of a small excess of carbonate and
hydroxide ions it is usually possible to reduce the combined residual
hardness to below 20 ppm as CaCO3 by cold lime-soda softening, the
normal excess being:
20 ppm hydroxide alkalinity as ppm CaCO3
40 to 60 ppm carbonate alkalinity as ppm CaCO3
In considering the chemical reactions taking place in water softening, it is
assumed that if the calcium and magnesium content is in excess of the
bicarbonate concentration (bi-carbonate alkalinity) then all the bicarbonate
alkinity is associated with calcium and magnesium and in this form is
known as the temporary hardness. The excess of the calcium and

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magnesium must then be associated with the chloride, sulphate and other
anions present and this is known as the permanent hardness or nonalkaline hardness.
Temporary harness or bicarbonate Permanent hardness`
alkalinity
Calcium chloride CaCl2
Calcium Sulphate CaSO4
Calcium bicarbonate Ca (HCO3)2

Calcium nitrate Ca (NO3)2

Magnesium chloride MgCl2

Magnesium

bicarbonate

Mg Magnesium Sulphate MgSO4

(HCO3)2
Magnesium Nitrate Mg(NO3) 2

Note
In water analysis it is normal to report all the main constituents in terms of
the equivalent concentration of calcium carbonate (ppm CaCO3).
At higher temperature the solubilities of both calcium carbonate and
magnesium hydroxide are reduced and it is therefore possible to soften
water to a lower residual hardness, using smaller excesses of hydroxide
and carbonate alkalinities, if some form of heating is employed. As a
corollary to this, poor water softening often occurs in period of low ambient
temperature so that with softeners sited outdoors, improved performance
can often be achieved if heat is available during the winter months.

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The reactions represented by equations (1) to (4) take place fairly rapidly
since they are ionic reactions. However the particles of calcium carbonate
and magnesium hydroxide first formed, will be of near colloidal dimensions
and would pass through the various types of filter employed.
Over a period of time the precipitated material grows into larger crystal by
a process of redissolving and recrystallisation and at normal ambient
temperature in about 4-6 hours crystals of sufficient size and density will
have formed and will sink to the bottom of the reaction vessel.
Use of Coagulants
If the small crystals formed in the early stages of the softening reaction
can be induced to agglomerate into larger particles, the rate of
sedimentation can be increased thus reducing the burden on the filter.
This is achieved in water softening by adding small quantities (usually
about 20 ppm) of the salts of relevant metals such as iron and aluminum.
In the alkaline soft water these precipitate a bulky gelatinous floc of metal
hydroxides which carry a small positive charge. These flocs agglomerated
the calcium carbonate and magnesium hydroxide crystals, partly by pure
physical entanglement and partly because the crystals carry a small
negative charge.
Activated silica and starch are also used, often in conjunction with alum.
Silica in the form of a gel has been found particularly useful on certain
waters, notably those low in magnesium.
More recently organic chemicals having high molecular weights and with
molecules having many ionisable groups, have been used successfully as
coagulants. These chemicals are known as polyelectrolyte and many
different types are available. They have the advantage of being effective

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at a much lower concentration (usually 1 or 2 ppm) but at the present

stage development they are very expensive and are not always as
effective as the conventional coagulants.
To obtain the maximum effect, aluminum sulphate is added to the raw
water after the softening chemicals. Alternatively sodium aluminate may
be used and frequently this is premixed with the lime and soda as a
combined softening charge.
(b)

Effect of Nuclei
If suitable nuclei are present in the water the crystals of calcium carbonate
and magnesium hydroxide will grow preferentially on them, resulting in
more rapid growth of crystals large enough to settle.
Thus the time required for the softening reactions to be complete may be
considerably reduced. The nuclei may be either added materials of
suitable size such as sand, or alternatively the previously precipitated
softening sludge may be recycled. This reduces the time required for
softening to an hour or less, thus enabling the size of the reaction vessel
for a given output to be reduced proportionately.

Types of Lime and Lime/Soda Softeners

To illustrate the various possibilities in greater detail, following three main types
are more fully described:
(a)

Conventional cold lime-soda softener.

(b)

Sludge blanket lime-soda softener.

(c.)

Catalyst lime softener.

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(a)

Conventional Cold Softener

A typical softener of this type is illustrated in Figure-3. In this case it
consists of a tall cylindrical tank made of steel or concrete and a central
cylindrical down comer which terminates at some distance above the
bottom of the outer vessel. This serves as a mixing and reaction
compartment. Raw water and softening chemicals enter at the top of this
compartment and a coagulant, if added separately, enters a short way
down. To ensure adequate mixing a stirrer is often included. The water
flows downwards through the central chamber and then upward through
the outer annular space. As it does so the precipated hardness falls into
the dead space at the both concentrates into sludge and is drawn off
either intermittent or continuously.

CONVENTIONAL LIME/SODA SOFTNER

Fig No.: - 3

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35

In some of the earlier softeners (as illustrated) the upper part of the outer
compartment contained a wood-wool filter through which the outgoing
water passed. In other version filtration is done externally in pressure
(sand or anthracite) filters. For either of these the aim is to produce clear
water before it enters the filter in order to ensure long filter life.
This is achieved partly by the correct choice of coagulants and by
designing the softener to ensure that the flow rate is sufficiently low and
the retention time sufficiently long, so that even under conditions of low
ambient temperature softening is complete.
Addition of softening chemicals: The solubilities of the two chemicals are
very different, sodium carbonate (soda ash having solubility of about 17%
at 20OC whereas calcium hydroxide (lime) will only dissolve to the extent
of less than 0.2% at 0OC and also exhibits retrograde solubility. Therefore,
if the chemicals are added separately, soda ash is added as solution and
lime usually as a suspension. Only in some small softeners lime solution
used and in this case a lime saturator is employed where part of the
incoming raw water passes through a vessel containing powdered lime.
Where the composition of the raw water is fairly constant it is convenient
to feed the two chemicals mixed together in suspension.
Control of the rate of addition of softening chemicals is effected by either
volumetric apportioning gear regulated by the raw water flow or by using
variable stroke metering pumps.
Sludge Blanket Softener
A softener of this type is illustrated diagrammatically in figure-4. It employs
the principle referred to earlier of resuspending a proportion of the

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precipitated sludge in the raw water, providing nuclei on which the freshly
Precipitated hardness can crystalise.

Raw water is first mixed with the softening chemicals and some
precipitated sludge, the mixing and re-entrainment of the sludge being
assisted by the central stirrer. The mixture then flows upwards through the
sludge zone into the central reaction chamber at a rate many times that
employed in conventional softeners, usually about 20 ft/h and at this stage
it is mixed with the added coagulant.
If the flow rate, the rate of addition of chemicals and the rate of sludge
removal are correctly adjusted, the softening reactions should be
completed within the sludge zone, and the precipitated material remains in
this zone so that the sludge level is held constant and the water rising in
the outer chamber is clear.

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The retention time in a sludge blanket softener is usually about l h and this
is particularly useful where adjustment the rate of addition of chemicals
have to be made, since control can be more easily effected and in a
shorter time.
(c.)

CATALYST Softener
The catalyst softener shown in figure-5 is used to remove calcium
temporary harness, lime only being employed. It consists of a conical tank,
which may if required be a completely closed pressurized vessel.
Raw water and lime enter tangentially at the bottom of the tank and in this
way are induced to take a spiral path upward.
The catalyst is usually fine sand and is contained in the bottom part of
the reactor. It is carried upwards by the flow of water and calcium
carbonate grows on its surface. Gradually it increase in size until it can no
longer be carried upward by the water. Periodically the reactor is blown
down from the bottom to remove this grown sand and fresh sand is fed
in at the top to make up for the loss.

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Ca (HCO)2 + Ca (OH) 2 -------------------------- 2CaCO3 + 2H2O . (5)

Mg (HCO3) 2 + Ca (OH) 2 ----------------------- CaCO3 + MgCO3 + 2H2 O (6)
MgCO3 + CaCl2 ---------------------- CaO3 + MgCl2
Since magnesium hydroxide will not grow on sand it will be carried forward and
overload the filter, if one is fitted.
In order to calculate the amount of lime required it is usually assumed that all the
bicarbonates are associated with calcium, the magnesium with the sulphate and
chloride etc. and in order to ensure that magnesium hydroxide is not precipitated,
slightly less than the calculated amount of lime is used. Obviously in computing
chemical reactions of this sort, success depends largely on the concentration of

PMI, NTPC

39

the various constituents present. With a water having a high magnesium content
(above about 40 ppm as CaCO3) some precipitation of magnesium hydroxide is
likely to occur and for this reason the catalyst softener is seldom used for these
waters.
The advantages of the catalyst softeners are
1.

Compact size.

2.

It can be pressurized so that softened water can be fed direct to a filter

without additional pumps.

3.

The precipitated hardness is in a granular form having a low moisture

content (that is, little water is wasted) and which can be easily disposed of.

The disadvantages are

1.

Normally only calcium temporary harness is removed, although it is also

possible to add soda and remove calcium permanent hardness.

2.

Under low-temperature conditions sand growth is very slow with the

result that filters become overloaded by the quantity of calcium carbonate
carried forward to them.

3.

With some water supplies, certain seasonal variations in water

composition adversely affect the performance of the softener. The most
troublesome period occurs in the late Autumn and Winter and it is believed
that the problem is associated with the presence of increased
concentration of organic matter and phosphates in the raw water at these
times of the year. Where this problem has arisen it has often been found

PMI, NTPC

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that some improvement in performance has resulted from the addition of

about 5 ppm of ferrous sulphate to the raw water.
Demineralization
Using synthetic ion-exchange resins similar to those described earlier, it is
possible to remove all of the ionsable salts in a fresh supply and produce a water
at least as pure as that obtained by softening and distillation.
The strongly acidic cation-exchange resins, similar to the synthetic baseexchange resins but in hydrogen form, will exchange hydrogen ions for other
cations. The result is that neutral salts are converted to their corresponding
acids, a process known as salt splitting.
Thus :

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The strongly basic anion-exchange resins, when they are regenerated with
strong bases, such as sodium hydroxide (NaOH), will exchange other anions for
hydroxyl ions (OH)If, therefore, the water after treatment in a cation exchanger is further treated in
an anion exchanger, the salts originally present will be converted to water. Thus:

Synthetic Ion-Exchange Resins

These are organic substances of higher molecular weight made by either
condensing together or polymerizing certain simple molecules. Chemically, the
basic material is similar to many of the so-called plastics in common use today
but it is treated during manufacture to confer ion-Exchange properties.
a)

Cation-Exchange Resins
The first synthetic cation-exchange resins were formed by condensing
tannins or phenols with formaldehyde and sulphonation of (reacting with
sulphuric acid) the resulting resin. It was produced in large masses which
were crushed and screened to yield a granular material of the required
particle size, and materials of this type are still in use.

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Later methods of manufacturing cation-exchange resins which have

improved stability. Particularly towards oxidizing agents involved the
sulphonation of a polymer of styrene known as Polystyrene*, thus:

* Polystyrene is an example of a linear polymer since the basic structure

of its molecule is a long chain of carbon atoms linked together.
If a small amount of divinyl benzene is included in the reaction mixture, a
cross-linked co-polymer is formed which can again be sulphonated to yield
a cation-exchange resin. Thus:

By varying the amount of divinyl benzene, the degree of cross-linking can be

controlled and thus the pore size and the stability of the resins, the more highly
cross-linked resins having similar pore size and being more resistant to
temperature above ambient.
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This copolymerization can be conveniently carried out by suspending the mixed

liquid monomers in water and as they solidify, hard transparent spherical beads
of predetermined sizes are formed which required no further crushing and
screening.
Although the degree of cross-linking can be controlled, the actual sizes of crosslinking will occur in random fashion throughout the polymer chain so that we can
only refer to the average pore size of the resin. By causing the linear polystyrene
type of polymer to undergo self cross-linking, it is claimed that it is possible to
produce a cross-linked polymer having sensibly constant pore size.
The sulphonated resins formed in this way are strongly acidic cation exchangers,
that is they are capable of salt splitting. Weakly acidic cation-exchange resins
can be produced by introducing a carboxylic group (---CO2H) in place of the
sulphonic

group

(----SO3H),

but

they

are

produced

more

easily

copolymerizing methacrylic acid with divinyl benzene directly:

The product is an active ion-exchange material, without further treatment.

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by

b)

Anion-Exchange Resins
If basic groups are introduced into the polystyrene resins instead of the
acidic groups, anion-exchange properties are conferred on the resins. The
basic group may be derived from ammonia or an amine, and in order to
facilitate the introduction of the basic group into the polymer, the later may
first be produced to contain, for example, chloro-methyl groups,

---------------- C ------------- CH2CL. Then, on reaction with ammonia or

an amine,

basic groups are built into the resin structure, and the following summary
of such reactions, the symbols R, R1 and R2 may be chosen from several
subsidiary simple organic group.
(a)

With ammonia, NH3: primary amine basic groups

---------------- C ------------- CH2---N. are produced.

(b)

With a primary amine, R ----- NH2; secondary amine basic group

N
----------------- C ----------CH2

are produced
H

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R
c)

With a secondary amine

NH territory amine groups,

R1

R
--------------- C ----------CH2 -------N

are produced.
R1

d)

With a tertiary amine,

R
NR2, quaternary ammonium salt
R1

--------------C ---------CH2 --------N ---- R1

+ [CL-]

are produced.

The resins containing primary, secondary and tertiary amine groups

behave as weak alkalis and will only exchange, or (more correctly) form,
acid salts, with strong acids, The strong acids. (quaternary ammonium
groups are strongly basic, similar in strength to strong alkalis and will
exchange even weak acid such as carbonic acid and silicic acid or, in
effect, carbon dioxide and silica in water.)

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Anion exchange materials are regenerated with alkalis. The weakly basic
resins are usually regenerated with sodium carbonate (soda ash or soda)
but almost any alkali will serve. The regeneration reaction is represented
by the following equation:

2R.HCL

+ Na2CO2 ----------------- 2R + 2 NaCL + H2O+CO2

Resin acid complex

Free base

(exhausted resin)

resin

The strongly basic resins require a strong alkali, such as sodium

hydroxide (caustic soda) for regeneration, since the process involves the
exchange of anions for hydroxyl ions, thus:

R.CL

+ NaOH ---------------- R.OH + NaCL

Exhausted resin

Regenerated resin in

In chloride form

hydroxyl form

In demineralization plants, the cation and anion exchange resins are often
contained in separate to columns or units and the design of these ionexchange units is similar to that of the base-exchanger unit. The complete
demineralization plant contains one or more of each of the two types of
units, the water passing through them in series.

c)

Mixed Bed Exchange Units

The mixed bed unit is single column or unit containing both cation and
anion exchange resins intimately mixed together. When water is passed
through such as unit it comes into contact alternately with grains of cation
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and anion resin, so that the water is subject to an almost infinite number of
demineralization stages. In operation it behaves like a large number of
two-stage demineralisers in series, with the result that it will produce a
final water which is neutral and has a very low residual dissolved solids
content.
The conditions existing inside the mixed bed unit at different stages of
operation and regeneration are illustrated in figure-6. During normal
service, its mode of operation is similar to other ion-exchange units, in that
water enters the top of the unit and leaves at the bottom.

MIXED BED ION EXCHANGE UNIT OPERATION & REGENERATION

Fig. No. 6

In order to regenerate the two different resins, it is necessary to have a

more complex pipe-work and internals arrangement than for the single
resin units.

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d)

Strong and Weak Resins

A brief description of the chemical structure of ion-exchange resins has
been given and some of the basic aspects of the use in the
demineralization of water have been mentioned.
It is clear from the discussion so far that there is a wide variety of resins
having different chemical structures, but in practice only a relatively small
number find use in water treatment. The four major groups of resins,
strong cation, weak cation, strong anion and weak anion exchange resins
fairly clearly defined by their different ion-exchange properties but within
each group, suitable changes in chemical and physical characteristics can
yield a resin tailor-made for a particular ion-exchange application.
Weak resins have only a limited capability for ion exchange since strong
resins will perform all of the functions of weak resins, there would appear
to be little point in using them. However, in commercial operation it is
possible to reduce the cost of demineralising water by employing a
combination of two types of resin. In general it may be said that weak
resin have a higher exchange capacity than strong resins and hence for a
fixed output of treated water between regenerations, smaller volume of
weak resin will be required; also weak resins can be regenerated with a
smaller excess of chemicals. The higher exchange capacity helps to
reduce the capital cost of the demineralization plant and the better
regeneration efficiency helps to minimize running costs, so that by
employing combinations of weak and strong resin-exchange units (a multistage plant) the overall cost is kept to a minimum using the strong resin
units to perform only those functions which can not be performed by weak
resin units.

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The data given in Table illustrates these differences in exchange capacity

and regeneration efficiency.
Resin Exchange Capacity and Regeneration Efficiency
Type of resin

Approximate

Approximate

Regeneration

Exchange capacity

efficiency %

Kgr CaCO3/ft3

Strong cation

60

42

Weak cation

90

76

Strong anion

30

28

Weak anion

60

40

Weak resins are regenerated with more dilute regenerates than are strong
resins, thus in a multi stage demineralization plant the spent regenerate
from the strong exchange resin unit can often be used to regenerate the
weak resin unit; this is an additional way of reducing operation costs and
is known as series regeneration. For example, cost of the strong resin unit
is regenerated with 2% sulphuric acid, the spent regenerate leaving the
unit will still contain about 1% sulphuric acid. Weak cation resins are
usually regenerated with 0.8% to 1% acid so that the spent regenerate
from the strong resion can be diluted slightly and used to regenerate a
weak cation resin, if one is used.
Within the broad classification of strong and weak resins, the strong anionexchange resins are further sub-divided into two types, known as Type-I
and Type-II. Both have quaternary ammonium active groups, but in Type-I
the groups (CnH2r+1) such as methyl (-----CH3) and ethyl (------C2H5),
whereas in the type-II resins one of type groups is an alcohol group such
as ethanol (-----C2H4OH).

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Type- I

Type II
CH3

----- N ----------- CH3

CH3

------N --------------CH3

CH3

CH3

Both are strongly basic resins, that is they are capable of salt splitting
neutral salts, but Type-II is slightly less basic and has a higher
regeneration efficiency than Type-I. Type II resins are not as efficient at
removing silica from water and suffer more degradation at higher
temperatures than Type-I, but where silica removal and temperature are
not a problem, it is more efficient to use Type-II.

Regeneration

The process of regeneration for all ion-exchange units is similar and follows the
description given for base-exchange softners. The resin is first back flushed,
which removes any suspended matter filtered out of the raw water during
operation, and also causes the resin to increase in appear volume.

Next the regenerant is admitted above the resin and flows downward through the
bed. Finally the bed is rinsed again by downward flow to remove excess
regnerant, the rinse water being run to waste until the quality is satisfactory unit
to be returned to service.

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a)

Cation Units

Sulphuric acid is usually used to regenerate cation-exchange resins as it

is the cheapest acid commercially available. Since calcium sulphate,
which may be formed as the resin is regenerated has a low solubility
(about 0.2%) and may otherwise be precipitated on the resin, it is usually
necessary to keep the strength of the sulphuric acid below 2%. For raw
waters with very low calcium content, sulphuric acid strength up to 5%
may be used. Table gives the maximum concentration of sulphuric acid
recommended for the regeneration of the strong cation-exchange resin,
Zeo-Karb 225.

In demineralization plants, the strong cation-exchange resins are normally

regenerated with about 2% sulphuric acid but with weak resins a high level
of regeneration can be achieved with more dilute acid and strengths of
0.8% to 1% are frequently used for these resins.

Hydrochloric acid may be used at almost any strength because there is no

risk of precipitation. Strengths of up to 15% have been employed, but 2%
to 4% is most common.

b)

Anion Units

Weak basic anion-exchange resins can be regenerated with weak alkalis

such as sodium carbonate. The regeneration process is in essence the
neutralization of an acid and not true ion exchange, since it involves the
conversion of the resin-acid complex to the free-base resin. Other alkalis
which are used include sodium hydroxide and ammonia solution. Sodium

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carbonate and sodium hydroxide are usually used as 4% solutions, but

satisfactory regeneration can be achieved with more dilute solutions. If
sodium hydroxide is used as the regenerant, the same solution can be
employed to regenerate a strongly basic resin and a weak basic resin in
series.

Table
Maximum Strength of Sulphuric Acid for Regeneration
90

1 %
2 %
3 %
Acid
Acid
Acid
----------------------------------------------------

Total hardness % of total

80
70
60
50

1%
Acid

40
30

2 %
Acid

3 %
Acid

4 %
Acid

20
10
10

20

30

40

50

60

70

80

90

(% of Total Hardness (all as CaCO3)

Strongly basic anion-exchange resins require a strong alkali to regenerate
them to the hydroxyl (OH-) form and 4% sodium hydroxide solution is
normally used.

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53

c)

Mixed Bed Units

In regenerating the mixed bed, the first state is to separate the two resins
into two discrete zones. Fortunately the resins employed have different
densities, so that the initial backwashing causes the resins to separate
into two layers, the lighter anion resin being at the top.
To facilitate regeneration of the resins a central combined collector and
distributor is provided at the interface of the two layers. Caustic soda is
introduced at the top and the spent regenerant runs to waste from the
central collector. The rinse water follows the same path.
Acid is then introduced at the central distributor, passes down through the
cation resin and is run to waste from the bottom of the unit. This is
followed by rinsing as for the anion resin. Finally the two resins are again
intimately mixed by passing low-pressure air upwards through the unit and
after a final rinse it is again ready for service.
The efficiency of regeneration in a mixed bed is never as high as in
separate units, since separation of the two resins is never quite complete
and there will always be some interference at the interface. For this
reason a mixed bed unit requires more resin than two separate units and
the running cost is higher but as mentioned earlier it can produce almost
complete de-ionisation of the input water.
d)

Resin Transport Regeneration

In water treatment demineralization plants, the water flow rate through the
resin bed, the depth of resin and the size of the resin granules employed,
are mainly determined by the kinetics of the ion-exchange reactions. The
design parameter chosen ensure that, with a raw water having a T.D.S. of

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perhaps several hundred ppm, virtually complete demineralization results.

A water treatment plant for a 2000 MW station will have a through put of
about 45,000 gal/h and units to handle this through-put with perhaps two
complete demineralization streams operating in parallel can be designed
to acceptable dimensions.
Mixed bed units, or sometimes cation-exchange units are also used to
remove traces of contaminants (metal corrosion products silica and
cooling water leaks) from feed water particularly in feed systems
associated with once-through boilers. This is one method of condensate
polishing. The condensate polishing ion-exchange units form an integral
part of the feed system and may have to handle from 25% to 100% of the
full feed water flow.

Fig No.: 7
PERMIT MIXED BED.

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55

For a 500 MW unit this will mean treating between 80,000 and 320,000
gal/h and with the flow rates normally used in ion exchange, would require
a number of ion-exchange units operating in parallel:
These condensate polishing units have only to remove traces (less than 1
ppm) of contaminants from the feed water and reduce the concentration of
these contaminants to an acceptable level. From this aspect, therefore,
much higher water flow rates through the resin bed are acceptable and
hence fewer units are required. With normally designed units, particularly
with mixed beds, the laterals and distributors necessary for regeneration
of the resin impose a serious resistance to water flow, but they must be
sufficiently robust to withstand the pressure acting on them. These
engineering considerations impose an upper limit on flow rate which is
below that imposed by ion-exchange kinetics.
To achieve even higher flow rates, it has been necessary to simplify the
internal design of the units so as to minimize resistance to water flow and
with these simplified units regeneration in situ is no longer possible.
Regeneration of the exhausted resin is therefore carried out in a separate
unit of normal design, to which the resin is transferred hydraulically. This
process is known as resin transport regeneration.
The water flow rates acceptable for a mixed bed unit with different
methods of regeneration are given in Table.

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Acceptable Water flow Rate for A Mixed Bed Unit with Differing Methods of
Regeneration
-----------------------------------------------------------------------------------------------------------Mixed Bed Units

Flow Rate gal/F

-----------------------------------------------------------------------------------------------------------1.

Make up water treatment plant

4 to 7

2.

Condensate polishing with in situ regeneration

upto 25

3.

Condensate polishing with External regeneration

upto 60

-----------------------------------------------------------------------------------------------------------The use of resin transport regeneration in condensate polishing units has

an additional advantage in that there is no longer a risk of strong
regeneration accidentally contaminating the feed system.
e)

Regeneration Equipment
The principal reagents used for regeneration ion-exchange resins are
sodium hydroxide, sulphuric acid and sometime hydrochloric acid. Caustic
soda used in other kinds of water treatment is normally purchased in solid
form

(anhydrous

flakes)

but

for

the

large

quantities

used

in

demineralization plants it is usually more convenient to purchase it as a

46% solution liquid caustic soda.
Sulphuric acid is purchased as a 96% solution and at this strength it can
be safely stored in mild steel vessels.
Hydrochloric acid is supplied as a 28% to 32% solution the lower strength
being normally supplied during summer months in order to reduce the

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nuisance due to hydrochloric acid vapour. It is very corrosive towards mild

steel and all steel surfaces must be protected with a suitable lining as
rubber.
The storage tanks are surrounded by bund walls, which is formed in
collecting tank sized to contain the whole contents of the storage vessel,
in the event of a major leak developing. Storage tanks are lagged proved
with means of heating to ensure that the chemicals do not freeze during
periods of low ambient temperature. Of the three principal regenerants
mentioned, only liquid caustic soda and sulphuric acid are at all likely to
give trouble by freezing at winter temperatures, and figures show freezing
points at various concentrations of these chemicals.

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Using these liquid regenerants, the regeneration equipment employed is

illustrated in figure-9. It consists of a closed measuring tank into which the
concentrated regenerant is drawn from the bulk storage tank by suction.
The measured quantity of regenerant is then run into tank to obtain a
suitable strength. Finally the regenerant is further continuously diluted to
the required strength and introduced into the unit to be regenerated by
means of water ejectors. Whenever possible, the use of pumps to handle
regnerant chemicals is avoided, because it is considered safer to avoid
the pressurization of these potentially dangerous liquids.

Demineralisation Processes
The type of demineralization process chosen for a power station will depend on
four main factors:
(a)

The quality of the raw water

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(b)

The degree of de-ionisation required, that is, the quality of the final feed
water.

(c)

The capital cost

(d)

The running cost

Although a large number of different processes is possible, the nine

schemes illustrated in Figure represent some that are commonly in use in
power stations. Schemes 1 to 4 will produce demineralised water suitable
for low-or medium pressure plant (up to say 600/in2) and will have low
dissolved solids content, low carbon dioxide and silica less than 0.1 ppm.
At the level of regeneration normally employed, up to 2 ppm of salts,
particularly sodium salts may pass completely through the cation units
without being exchanged. In the strongly basic anion-exchange units the

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anions will be exchanged for hydroxyl ions so that the final treated water
will contain a few ppm of sodium hydroxide and will therefore be alkaline.
Schemes 5 to 9 are used, where virtually de-ionised water is required, that
is water having the following characteristics:
T.D.S. less than 0.5 ppm.
Conductivity less than 0.5 micromho/cm.
Silica less than 0.05 ppm.
For modern high-pressure stations, a plant based on scheme 6 will
commonly be used.

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Back Washing
Usually done after every service cycle, is one of the most important operations.
Although feed water pre-treatment is designed to remove vast majority of
suspended solids and colloids, trace quantities invariably pass into the ion
exchange units. Resin fines and fragments also require removal suspended and
colloidal matter are likely to accumulate at the beds upper surface, and possible
on the bed surfaces throughout the bed. Film of this type will lead to channeling
at points of flow break-through, poor kinetics and large pressure drops.
Proper back washing involves expansion of the bed, so each resin article is in the
motion. Sufficient flow rate must be available for this purpose.
Typical Back Wash Flow Rates
2-4 gpm/ft2

For anions

5-10 gpm/ft2

For cations

Duration

Usually 10 minutes

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Cation
Back Wash flow rate -

40M3/hr (1/2 of the normal flow rate).

Duration

5 Minutes

Type of Water

Filtered Water

Anion
Back Wash flow rate -

20M3/hr (1/3 of the normal flow rate).

Duration

5 Minutes

Type of Water

Filtered Water

Mixed Bed
Mixed bed differs from that of the single resin bed primarily with regard to the
regeneration step. The key to the process is back wash, which serves to classing
the two resin components the lighter anion resin forming at the top, the heavier
cation resins remains at the bottom; when done properly, a clear and level
interfacing is formed between two layers. An interface collector is incorporated at
this point.
Back Wash flow rate -

18M3/hr

Duration

3 Minutes

Type of Water

D.M. Water

2.

Setting
Before regenerating, the bed is allowed to settle to its original volume to
provide compactness necessary for proper chemical contacting.

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3.

Regeneration
Dilute acid is applied to Cation exchangers and caustic to the anion
exchangers. HCl is the usual acid choice, with concentration ranging from
2-10% Resin quantity 7400 Lit/Unit.

4.

Cation
Type of Resin

10 NAC C242

Capacity per regent

1080 M3

Period between regeneration

18 Hrs.

Regenerant Qty

1931 Kg. (30% HCl)

Final Con

5% W/V

Anion
For regenerating anion exchange resin, caustic usually is applied as 5%
solution.

5.

Resin

IONAC A 440

Qty of Resin

6630 Lit/Unit

Reagent

NaOH

100% NaOH reqd./regeneration -

465 Kg.

Final Conc. Of NaOH

5%

Rinsing
Rinse water of likely quality is used to remove regenerant when process is
completed-first at slow rate and then at fast rate.

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Volume used
For cation

30-40 gallon/ft3

For anion

40-400 gallon/ft3

Type of water

Filtered Water

Slow rinse rate

19.5 M3/m.

Duration

15 mts.

Fast rinse rate

65 M3/hr.

Duration

35 mts.

Type of water

Degassed Water

Slow rinse rate

15 M3/hr.

Duration

20 mts.

Fast rinse rate

65 M3/hr.

Duration

50 mts.

Final value after rinsing silica

0.5 ppm.

Conductivity

Less than 20 mho/Cm

Regeneration quantity

1050 lit.

Anion

1050 lit.

Capacity per regeneration

7560 M3

Period between regeneration

126 hrs.

Cation

Anion

Mixed Bed

Qty. for regenerant

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65

HCl

145 Kg.

30% HCl

NaOH

128 Kg.

(100%)

Final Conc.

16 Kg. 100% NaOH

Dilution Tank

Final conc.

Hcl

30%

5%

NaOH

48%

6%

Regeneration steps for cation, Anion & Mixed bed exchangers are shown
below with the help of following schematic diagrams.

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Mixed Bed Blower

(Plant Technical Data)
-----------------------------------------------------------------------------------------------------------Nos. off -2

Suction capacity 228M3/hr.

Nos. operating 1

Discharge pressure 0.5 Kg/CM2.

-----------------------------------------------------------------------------------------------------------Blower Details

Motor Details

-----------------------------------------------------------------------------------------------------------Type/Stage Single

KP/KW

10/75

Construction ----------------

RPM

1500 Syn.

Material

Construction

Hor. Foot

C.I. IS219 Gr.

20 Alloy Steel

mounted

Make

Kay Engg. Works

Frame size

132 M

Model

65

Make

Siemens

----------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------Accessories

Instruments

Pressure Gauge

-----------------------------------------------------------------------------------------------------------1)

Suction strainer

Type

Burdon

2)

Silencer

Location

Delivery

Nos. (Tag)

1047: 1048

Range

0-1 Kg/CM2

------------------------------------------------------------------------------------------------------------

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 PMI, NTPC

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3. Combating Corrosion
Introduction
The trend in India is now for higher pressure and higher capacity boiler in power
Generation. Number of 200 & 500 MW units have been commissioned in India
and very soon 660 MW units are going to be commissioned.
The operation of these units under such high pressure and temperature demands
much higher standards of steam and feed water purity. The problem of
maintaining the quality of feed and Boiler water can be well understood by the
following example:
If one ppm of dissolved solids enters in each 1,000,000 lb. of feed water, one
pound of dissolved material enters the boiler each hour. Since 999,000 of that
water is removed as steam (pure water vapour), one pound of solids is left
behind in the boiler in each hour of operation.
Obviously, if we continue to operate in this way, the solid content of the boiler
water would keep on increasing.

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Let us study steam-water cycle. The feed water is made up of condensate and
make up water. It is essential to have good water treatment plant. Consumption
of make up water used per unit generated is a good index of the state of
maintainability of plant and should be closely monitored:
Various constituents in water in accordance with the trouble, they create are
classified as:
1.

Corrosive substance.

2.

Scale forming substance.

3.

Foam forming substances.

In past, the water chemistry was not given due consideration. Higher operation
reliability and hence maximum availability can be achieved by close and regular
monitoring of water/steam circuit. Two possibilities to be considered are:
A.

The penetration of unwanted substances into steam/water circuit.

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B.

The formation of unwanted substances within the circuit. The unwanted

substances depend partly on the type of the boiler.

Main Aims of Monitoring the Steam/Water Ckt.

-

To keep track of the performance of individual part of the plant and hence
the plant as a whole in order to verify that specified values are maintained.

Prevention of failure by early diagnosis.

To achieve a high standard of reliability and maximum plant availability.

In the event of a failure, to ascertain the cause after the event with the
help of recorded data.

Plant availability is the function of the quality of working medium viz.

Water/Steam. The analysis of water/steam is of importance due to following
reasons:
-

Inhibitation of corrosion.

Prevention of deposits on boiler tubes, superheater tubes and turbine

blade.

Ability of condenser material.

The choice of parameters to be monitored, depends on the ground of operation

safety and plant reliability.

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Importance of Individual Parameter:

(Dissolved oxygen & Hydrazine measurement in feed water).
Corrosive substances are in the form of dissolved gases such as carbon dioxide
and oxygen are dissolved in the feed water by operation and unavoidable contact
with atmosphere.
Solubility of oxygen decreases with an increase in water temperature, the most
common method of removal is the deaeration of water.
Dissolved oxygen hastens corrosion by a number of reactions depending on
conditions.
The following is a typical type presentation of an important phase of iron-water
corrosion accelerated by oxygen under alkaline or neutral conditions. Iron in
contact with water exerts a certain solution pressure and sets up the anodic half
reaction.
Fe ----------------- Fe2 2C
This ceases after a certain potential is reached. However oxygen can react with
water to give OH ion at the cathode.
O2 + 2H2 O + 4e ------------------ 4 OH
The Fe-2 + OH ---------------- Fe (OH)2
The initial reaction then proceeds further. The electro chemical reaction can be
summarised.
2Fe + O2 + H2O ----------------- Fe (OH) 2

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Corrosion can be stopped by the removal of dissolved oxygen.

Deaeration in the condenser
Steam entering the condenser contains air and incondensable gases mainly due
to in-leakage at parts of the system operating below atmospheric pressure.
Make-up water, vents and drains to the condenser are other sources of
incondensable gases which must be removed for the condenser to function.
The primary duty of the condenser is to condense the exhaust steam leaving the
LP turbine, by passing it over the condenser tubes which are cooled by CW. As
the steam is condensed it undergoes a massive reduction in specific volume and
a vacuum is created. In condensing the steam the condenser also acts as a
deaerator liberating incondensable gases. Unless these gases are removed they
will blanket the condenser tubes and progressively impede the heat transfer
process, which in turn will result in a deteriorating vacuum.
Air extraction equipment is installed to continuously remove these gases. Makeup water, in the form of a spray, is fed into the condenser steam space above the
water level and the fine droplets expose a greater surface area to the vaccum
resulting in more efficient deaeration. With good condenser deaeration the
condensate will have dissolved oxygen content of less than 0.015 mg Kg-1
If any air leaks are present in the condensate pipe work or at the extraction pump
glands, the dissolved oxygen content will increase and it is important that this
part of the system is also maintained in an airtight condition.
Deaeraton in the Deaerator and LP Direct contact Heaters
Oxygen is least soluble in water at boiling point and the function of the deaerator
and LP Direct contact Heaters is to raise the feed water temperature by mixing

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with bled steam.

The feed water is finely divided by sprays and readily releases its oxygen which,
together with other non-condensible gases, are vented to atmosphere or to the
condenser. An efficient Deaerator can reduce the concentration of dissolved
oxygen in the feed water to less than 0.005 mg kg-1.
Operation Aspects
Mechanical deaeration alone cannot maintain the oxygen or carbon dioxide
concentrations at acceptable levels in the feed water of a modern plant.
Generating units which operate on a two shift basis are very prone to corrosion
from dissolved oxygen and carbon dioxide. When the unit is offload, the water in
the system cools down and tends to absorb air. Also, air fills the steam spaces as
the vacuum is broken and contaminates the water.
As a result, when the unit is started-up, the feed water reserve in the system has
a high concentration of dissolved oxygen and carbon dioxide making ideal
conditions for corrosion. This can be minimized by keeping the deaerator water
at boiling temperature using the off-load deaerator heaters.
Feed heaters with 70/80 cupro/nickel tubes suffer particularly from corrosion due
to oxygen with regular two shift operation of the unit. This is known as exfoliation
because the corrosion products on the tubes form as thin layers of oxide which
flake off as the temperature changes. Exfoliation is much less pronounced when
90/10 cupro/nickel tubes are installed in the system.
Filling the system with nitrogen, to keep the air out, as the vacuum is broken has
also been used with varying success. However, the difficulty of excluding all the
oxygen from such large space and the cost of nitrogen, has led some power

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stations to seal only their high pressure heaters where the corrosion is most
serious.
Chemical Removal of Oxygen
Corrosion by oxygen and carbon dioxide in the feed lines and economizer can
cause small amounts of corrosion debris to be carried into the boiler and be
deposited on the tube surfaces. These deposits than act as potential areas for
further corrosion. In the control of corrosion certain chemicals are added to the
feed water to remove or neutralize gases that have entered the system and
escaped mechanical deaeration.
Originally oxygen was removed from feed and boiler waters by adding sodium
Sulphite (Na2SO3) in the form of white crystals or Powder. This chemical has now
been superceded because, whilst removing oxygen, it increases the total
dissolved solids in the water.
2Na2SO3 +

02 ------------------------- > 2 Na2SO4

SODIUM

OXYGEN

SODIUM SULPHATE

SULPHITE
Modern practice is to use hydrazine (N2H4) and it reacts as follows:
N2H4 +

O2 ------------------------ > N2 +

HYDRAZINE

OXYGEN

NITROGEN WATER

(Liquid)

(gas)

(Gas)

2H2O
(Liquid)

From the above chemical equation we can see that no solids are produced, in
fact the product nitrogen and water are completely harmless. Hydrazine,
therefore, is the ideal chemical for removing oxygen and its only disadvantage is

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that it is expensive. Hydrazine, is a toxic substance and the approved protective

clothing must be worn when it is handled.
Any surplus hydrazine that remains after removing the oxygen will decompose to
give ammonia (an alkaline gas) and nitrogen.
3N2H4 ----------------------- > 4NH3 +

N2

HYDRAZINE

AMMONIA

NITROGEN

(Liquid)

(gas)

(gas)

The significance of the ammonia and the fact that it is alkaline will be shown
when the neutralization of carbon dioxide is studied. GOM72* recommends that
for trouble free running the maximum concentrations of dissolved oxygen in
water are as follows:
Extraction pump discharge

0.015 mgkg-1

Economizer inlet

0.005 mgkg-1

Neutralization of carbon dioxide

When acids and alkalis were discussed earlier in the lesson, we noted that
carbon dioxide was an acidic gas and could form carbonic acid with water. We
also saw that acids could be neutralized by alkalis.
Carbon dioxide is an acidic impurity in feed water, and its corrosive nature can be
minimized by neutralizing it with an alkali such as ammonia.
2NH3

+ CO2

+ H2O ---------------- >(NH4) 2CO3

AMMONIA

CARBON

WATER

DIOXIDE

AMMONIUM CARBONATE
(Neutral)

(Acidic)

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Compounds called amines which decompose to give ammonia can also be used
to neutralize carbon dioxide. They are known as neutralizing amines and can,
under certain circumstances be more efficient than ammonia.
Cyclohexvlamine and morpholin are examples of neutralizing amines but are now
rarely used because in most cases there is no advantage compared to ammonia
and they are more expensive.
To summarise, feed water is dosed with sufficient hydrazine remove oxygen, any
surplus will also produce ammonia and neutralize the carbon dioxide present. If
the ammonia is insufficient then additional ammonia is introduced to maintaining
pH of between 8.8 and 9.2 in the feed water.
Monitoring and Analysis of Feed Water
We have so far examined the preparation of purified and conditioned water
acceptable as boiler feed. However contamination can still occur through system
defects. Thus an essential part of the control of corrosion and scale formate is
continuous monitoring of the quality of the condensate, feed water and boiler
water, to ensure the water throughout the system contains the correct amount of
treatment chemical and the minimum of corrosive impurities.
The important instruments include, dissolved oxygen recorder on-line pH meters,
ammonia analysers, conductivity meters and sodium monitors. Concentrations of
elements such as iron, copper and nickel (often referred to as crude) are also
measured in modern plant to indicate the rate of corrosion of the system. These
instruments are often on-line and known as auto-analysers.
If hydrazine is added to feed water primarily to remove oxygen it is possible that
enough will remain to neutralize the carbon di-oxide also present in water. If the

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hydrazine does not provide enough ammonia, more is added by chemist, after
water has been analysed by the chemist.
It is a very important point to remember that feed water should be dozed with
hydrazine (if necessary ammonia as well) to prevent any attack by acidic carbon
dioxide & others.
In most boiler systems, the pH is maintained on the alkaline side, by adding
chemicals, at about 8.8 to 9.5, this prevents acidic attack on the system tubes
and pipes, so that pH measurement is very critical.
It is normal practice to use copper alloy tubes in the condenser and L.P. Heaters
and Carbon steel in H.P. Heaters. The carbon steel required a mildly alkaline pH
of about 9.5 while non-ferrous materials last longer between pH of about 8.8
9.0. Thus for system with both ferrous and non-ferrous materials, a compromise
pH of 9.2 is usually recommended. A close control of pH is essential to avoid
acidic attack on ferrous components or alkaline attack on non-ferrous
components. However, if stainless steel (rather than carbon steel) tubes are used
in Feed water Heaters, as experience has shown operation can be at pH
compatible with copper base alloys.
Following table gives the relationship of NH3 content water and its corresponding
pH.
NH3 (ppm)

pH

0.08

8.5

0.10

8.6

0.17

8.8

0.28

9.0

0.50

9.2

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7 Ammonia and 2 Hydrazine are mixed with water in two solution

preparation cum feed tanks. Weak ammonia hydrazine solution are pumped to
feed water suction line through hydrazine dosing pump (2 Nos.) These Candy K
pumps are metering pumps of an accurate variable strokes positive displacement
type which are capable of meeting a wide variety of pumping requirements.
Rotation of the stoke adjusting but varies the delivery setting of pump and this
can be carried out with pump operating or at rest.
Hydrazine dosing is required to be done continuously. Quantity is to be adjusted
as advised by the chemist. pH meter installed at various places, give indication a
steady predetermined value, the chemist is assured that the correct amount of
chemicals are added to the system to maintain optimum alkali condition.
By measuring the concentration of metals in water such as iron, copper and
nickel, an indication is contained of corresponding products coming from plant
manufacturers from these metals.
Filling amines are sometimes used in feed water treatment. They are
octadecylamine and other decylamines. When added to feed water, form a thin
protective skin on the metal surfaces of feed waters. The metal is then protected
from attack, not only from carbon dioxide, but from all corrosive gases; because
the film is very thin, it does not have an adverse effect on heat transfer. Filming
amines are therefore very useful in the protection of feed system, although they
nothing to remove corrosive gases from water.
The following are the recommended feed water quality for H.P. Drum type
boilers.

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Recommended Feed Water Limits

Drum pressure kg/CM2 (g)

61-100

101 & above

Hardness

Nil

Nil

pH at 20OC (Copper Alloy

8.8-9.2

8.8-9.2

PH at 25OC (*)

9.0-9.4

0.0-9.4

Oxygen max mm ppm

0.007

0.007

Total iron maximum ppm

0.01

0.01

Total copper maximum ppm

0.01

0.005

Total CO2

Nil

Nil

Total silica

0.02

0.02

Hydrazine residual ppm

0.01-0.02

0.01-0.02

Oil

Nil

Nil

preboiler system)

* (Not copper alloy preboiler system).

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4. Boiler Water Treatment

The solid impurities that are likely to enter a boiler can originate from one or more
different sources.
1.

Condenser leak

2.

Faulty demineralization

3.

Corrosion products from an improperly treated feed system

In all cases the solid impurities that enter the boilers water probably contain
calcium and magnesium hardness salt. Chlorides and another compound, silica
or silicon dioxide (SiO2) which we have not yet mentioned.
Condenser leaks
Evaporator Carry-over
Faulty demineralization
Contamination of the clean drains
Recovery system
Corrosion products from the feed system
In all cases, except the latter, the impurities that enter the boiler water probably
contain calcium and magnesium hardness salts, chlorides and silica.
When discussing the hardness of water earlier, we mentioned that scale on a
boiler tube would seriously affect the heat transfer properties and possibly lead to
failure by over-heating. The impurities mentioned above will have detrimental
effects other than scale formation and these are:
On load corrosion
Carry over causing superheater and turbine deposits
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The chloride impurities and in particular magnesium chloride chemically react

with the water, in a process called hydrolysis to form hydrochloric acid.
MgCl2

Magnesium

H2O ------------------ >2 HCl

+ MgO

Water

Hydrochloric

Magnesium

Acid

Oxide

Chloride

Acids are undesirable in boiler water because they attack the metal surfaces.
This attack is known as acidic chloride corrosion. To combat this acid attack the
boiler water is kept in a slightly alkaline condition (pH of 9-10) by dosing with
sodium hydroxide (NaOH). This alkali will neutralize any acid produced by
hydrolysis of chlorides. In recent years it has been found that sodium hydroxide
itself can concentrate in the boiler and cause caustic corrosion. A fine balance is
therefore necessary to prevent on the one hand acidic corrosion and on the other
caustic corrosion.
Acidic chloride corrosion is often accompanied by hydrogen embrittlement. When
an acid attacks metal hydrogen gas is produced and in a boiler the hydrogen
reacts with the carbon in the boiler steel weakening the structure and producing
methane as a by-product.
2H2

Hydrogen

C < ================== > CH4

Carbon

Methane

In steel
Eventually the hydrogen diffuses through the steel below the corrosion pit and a
brittle fracture occurs.
Acidic chloride and caustic corrosion are usually referred to as on load corrosion
because the very dilute solutions of chemicals and impurities in boiler waters can
reach dangerously high concentrations whilst on load. This effect usually takes

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place in areas of high heat transfer which are subject to poor circulation in the
water circuit. Such areas are usually found at horizontal or inclined surfaces or at
flow disturbances such as bends or welds. In these areas are usually found at
horizontal or inclined surfaces or at flow disturbance such as bends or welds. In
these areas, the tube surface is folded by porous deposits of iron and copper
oxides carried forward from the feed system. These deposits prevent mixing and
wick boiling takes place because the liquid is felt to the surface through the
small pores in the deposit similar in action to a wick. Steam escapes through
their larger lose leaving the salts behind enabling them to concentrate.
A similar effect occurs at boiling surfaces containing a narrow crevices in which
the solution can concentrate. Crevices may be found at poor welds or

at

tube/tube plate joints. Although the addition of chemicals can neutralize the
effects of impurities it is not necessarily the complete answer. For example,
should a condenser leak occur there will be a massive rise in impurities in the
boiler feed water. Adding chemicals will help to alleviate the condition but it must
be accompanied by blow down to prevent an increase in dissolved salts in the
boiler water which would cause carry over. When these measures can no longer
contain the concentrations within the limits given in GOM 72 for the particular
plant then the defective condenser must be isolated (or the unit taken out of
service) and repairs carried out.
Control of carry-over to superheater and turbine deposits
When water is converted to steam in a boiler, a small proportion of any impurities
in the water will be carried forward with the steam and deposited in the
superheater or on the turbine blades by one of two mechanisms. These are:
a)

Physical carry-over whereby small droplets of impure water escape

through the steam scrubbers.

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83

b)

Some impurities become more soluble and are carried forward as the
saturation temperature of the steam increase with pressure.

Therefore on modern high pressure plant even with well designed drum internals
and good operation it is imperative that the dissolved solids content of the water
is as low as possible. Even very small deposits of sodium hydroxide and sodium
chloride cause stress corrosion in austenitic steels in superheater and may lead
to failure off the tubes.
Silica Control
One of the soluble impurities carried forward in the steam is silica (SiO2). Silica
is more soluble in steam than other impurities and when it deposits on turbine
blades it is extremely difficult to remove. This effect is so pronounced that special
precautions have to be taken. Fig. shows these plotted against different boiler
pressures. These limits are controlled (a) by preventing dust particularly pfa,
entering parts of the unit when opened up during survey or inspection and (b)
monitoring and controlling silica at the outlet from the demineralization plant.
Should the silica limits to reach they must be reduced by lowering the boiler
pressure and blowing down.

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84

Austenitic (stainless) steels contain a higher percentage of chromium (ie., about

18%) than ferritic steels used elsewhere in the boiler. They are used in the high
temperature zones because they have a longer life.
Tri Sodium Phosphate Treatment
Tri Sodium phosphate (Na3PO4) often called TSP, is added to the water of many
boilers, mainly low pressure below 62 bar (900lb/in) to combat the effects of
scale forming calcium or magnesium salts, although most calcium and
magnesium salt form hard scales. Therefore by the addition of TSP the salts are
converted into calcium and magnesium phosphates and soft sludges are
produced which can be removed by blow down.
3CaSO4

+ 2NA3PO4

Hardness

Trisodium Phosphate

---------------- >

Ca3 (PO) 3

+ Na3SO4

Soft Sludge Sodium

Sulphate

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85

Another useful property of trisodium phosphate is that it produces small

quantities of sodium hydroxide (NaOH) which helps to control the alkalinity of the
boiler water. Also disodium phosphate is formed and is available to produce
phosphate sludge.

Na3PO4 +

H2O =========== >

NaOH +

Na2HpO4

Trisodium

water

Sodium

disodium phosphate

Hydroxide
Therefore the alkalinity mentioned under sodium hydroxide treatment above, can
be achieved and maintained by using trisodium phosphate. This is the reason
that many countries use TSP in higher pressure boilers. It acts as a reserve to
correct a rise in acidity without the necessity to add sodium hydroxide with the
associated dangers of caustic corrosion. The main drawback of TSP is its
comparatively low solubility which means it is much more prone to concentration
effects than sodium hydroxide a term used to describe the phenomenon whereby
the TSP disappears from the water whilst the boiler is steaming, only to re PMI, NTPC

86

appear as the load is reduced. This is attributed to the fact that the TSP
concentrates in various sites on the inside surfaces of the tubes and solid
deposits form. Eventually all the TSP is deposited. As the rate of evaporation is
reduced during de-loading the TSP redissolves in the water.
Recommended Boiler Water Limits
-----------------------------------------------------------------------------------------------------------Drum Pressure Kg/cm2 (g)

61-100

100-above

-----------------------------------------------------------------------------------------------------------1.

Total dissolved solids

Not more than 100

Not more than 100

-----------------------------------------------------------------------------------------------------------2.

Phosphate residual ppm

15-20

5-10 ppm

-----------------------------------------------------------------------------------------------------------3.

pH

9.8-10.2

9.4-9.7

-----------------------------------------------------------------------------------------------------------4.

Silica-To be controlled on the basis of silica in steam in the range of 0.02

pm leaving the drum.

Treatment for Once-through and Supercritical Boilers

The requirements for boiler water quality control differ in these boiler compared
to drum type boilers and includes:
1)

In a drum boiler the quality of the water can be monitored and the
concentrations of impurities can be controlled by adding chemicals and
blowing down to waste. Once-through and supercritical boilers do not
have a drum, so boiler water sampling and control is not possible and the
only option is to analyse and control the feed water at the boiler inlet.

2)

In drum boilers the tube wall surfaces are usually wet. If dry spots occur
then high concentrations of salts will form at the periphery. In a once

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87

through boiler there will be regions where dry and wet walls exist by
design. Thus the feed water to such boilers must be of exceptionally high
quality.
3)

Concentrations of normally safe materials in sub-critical boilers must be

eliminated in the once through boiler with no blow down everything
entering will either deposit or pass out with the steam to the turbine.

In case of the supercritical boiler, the problems of feed water treatment are
accentuated by the fact that at critical pressure the solubility of dissolved salts is
the same in the steam as in the water. There is no physical separation and
impurities in the water may again pass through with the steam to be deposited in
the superheater and on the turbine blades.
If deposition occurs, it can result in an increased pressure drop across the boiler.
This will reduce output efficiency and affect heat transfer necessitating shut down
to chemically clean the plant.
Also solutions of other, possibly corrosive, materials will concentrate and corrode
the boiler. If these are carried forward to the turbine they can deposit and lead to
loss of efficiency or possibly cause cracking of the special alloy steels used in
turbine rotors.
For once-through boilers only volatile additives can be used for feed water
dosing. These are normally ammonia and hydrazine. This is known as zero
solids treatment or all volatile treatments (AVT). In order to achieve the high
quality feed water required for once through boilers, it is necessary to polish the
whole of the condensate continuously. This is particularly important at sea water
stations where the ingress of salt from condenser leakage would cause rapid
boiler corrosion.

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Condensate polishing
Unit make up water is typically between 1 and

3% of the maximum boiler

evaporation capacity. The feed and condensate systems contain such a vast
quantity of water that if contamination occurred the make-up water would do little
to correct the impurity of the feed water.
When a turbine is started up, contamination of the feed water can occur if
corrosion products are carried forward. The contaminant can be both suspended
and soluble. To remove contaminants during start up, a method adopted to dump
the condensate after the extraction pump. The disadvantages of this method are
the waste of condensate and the time limit imposed by the amount of clean water
reserve available in the de-aerator. Once the de-aerator water is used, dumping
has to cease although there may still be some impurities in the condensate
system.
Some of the earlier condensate polishing units incorporated a filter to remove
crud but the filter proved to be unnecessary since the mixed bed resin was
equally capable of performing this duty. The filter was omitted on subsequent
polishing units which were therefore called naked mixed beds.
Condenser Leak Detection
If a leakage of CW into the condensate occurs it is essential that an immediate
indication is given so that the necessary action is taken to limit the unwanted
impurities entering feed system.
The normal method of detecting condenser leaks is to monitor the conductivity of
the condensate.

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Conductivity as a measurement is proportional to resistance equivalent to

reciprocal megohms/cm or dionic units and the units are expressed in
microsiemens/cm.
Pure water has a low conductivity because only a few of the H2 molecules of
water dissociate into cations and anions. Condensate should give an indication
of less than 0.3 microsiemens/cm. On the other hand salt water will give a
conductivity indication of about 50000 microsiemens/cm.
The conductivity cell used to measure water purity consists of two electrodes
immersed in the water. The standard cell electrodes are each 1 cm square
placed 1 cm apart to give conductivity units in mocrosiemen/cm. The current is
conducted between the electrodes by the ions of the salts in the water. The more
ions that are present the higher the conductivity indication.
The cell normally contains three ring-like electrodes equally spaced within an
epoxy resin moulding which is accurately made so that the conductivity of a
precise volume of solution is measured. Condition through the solution takes
place between the central electrode and the two outer electrodes which are
connected in parallel and act as one.
Conductivity is increased not only by unwanted impurities but also by dosing
chemicals and a false reading of the level of contamination would be given if the
conductivity cell was used alone. Thus the cation exchange resin column as well
as amplifying the conductivity indication is essential to remove dosing chemicals
such as ammonia and hydrazine allowing the true level of contamination to be
measured.
The most recent method of condenser leak detection is to measure the
concentration of sodium in the condensate which is as much as 100 times more

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90

sensitive than conductivity test. Sodium can be detected and measured at much
lower levels than would be indicated by a conductivity meter.

Recommended Limits for Water Steam and Super Heated Steam for 200/210
MW Sets of N.T.P.C.
Suppliers: B.H.E.L. and Bredo Thermo Meccanica (ANSALDO)
----------------------------------------------------------------------------------------------------------BTPS
MCR

NCR

SSTPP
MCR

NCR

KSTPP
MCR

NCR

RSTPP
MCR NCR

----------------------------------------------------------------------------------------------------------Drum press

151

148

152

166

163

137

136

138

155

154

342

340

342

349

348

540

535

535

540

540

(kg/cm )
S.H. Steam

157

Press (kg/cm2)
Sat Steam
O

Temp. ( C)
S.H. Steam

540

Temp. (OC)
-----------------------------------------------------------------------------------------------------------

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91

(A)

Feed Water (Sample from Economiser Inlet)

----------------------------------------------------------------------------------------------------------S.No. Characteristic
Limit
Freq. of
Remarks
Test
---------------------------------------------------------------------------------------------------------1
2
3 4
5
----------------------------------------------------------------------------------------------------------1.
pH at 25OC
i. 8.8-9.0
once/
i. If F.W. Heaters
ii. 9.0-9.2
shift
are of copper
based alloy
(See note 1)
ii. If heater are of
steel
2.
Specific conductivity
0.3
once/
shift
at 25OC in s/cm)
after passing through
cation exchange in H+
form.
3.
Total Hardness
B.D.L.
once/
B.D.L.Below Detectshift
able Limit
(ppm as CaCO3)
4.
Dissolved Oxygen
0.007
once/
If in line instrument
ppm
(see note 2)
day
is not available
Once/
If in-line instrument
Week
is available.
Checkt he Instrument
Calibration in mid
Week.
5.
Residual Hydrazine
0.02
Once/
(ppm)
shift
6.
Silica (ppm)
0.02
Once
max.
shift
7.
Chloride (ppm)
B.D.L.
Once/
shift
8.
Total Iron (ppm)
0.01
Once/week
9.
Oil (ppm)
B.D.L.
Once/week
10.
Copper (ppm)
0.005
Once/week
------------------------------------------------------------------------------------------------------------

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92

(B)
Boiler Water (Sample from C.B.D. Line)
----------------------------------------------------------------------------------------------------------S.No. Characteristic
Limit
Freq. of
Remarks
Test
----------------------------------------------------------------------------------------------------------1
2
3
4
5
-----------------------------------------------------------------------------------------------------------1.
pH at 25OC
9.0-9.5
Once/
shift
2.
Specific conductivity
25
Once
at 25 OC ( s/cm)
shift
3.
Total Dissolved solution 5
Once
(ppm)
shift
34.
Phosphate (as ppm PO4 2-4
Once/
Any or mixture of
shift
tri, di or Mono
sodium phosphate
sodium Hexaphosphate can be
used. pH control
by concurrent
Tech.)
5.
Total hardness
B.D.L.
Once/
(as ppm CaCO3)
shift
6.
Free hydroxide
B.D.L.
Once
(as ppm CaCO3)
shift
by stremtium
chloride method
0.4 (BTPS)
Once/
7.
Silica (ppm SiO2)
shift
0.4 (SSTPP) Once
shift
0.25 (KSTPP
RSTPP) Once/
Shift
8.
Chloride (ppm)
B.D.L.
Once/
shift
9.
Sodium (ppm)
Correspond
Once/day
ing to Na3PO4
etc. addition

PMI, NTPC

93

(C)

Steam & S.H. Steam (Samples from drum outlet & main steam line

respectively)
-----------------------------------------------------------------------------------------------------------1

-----------------------------------------------------------------------------------------------------------1.

pH at 25OC

9.0-9.2

Once/
shift

2.

Specific Conductivity

0.3

at 25 C (us/cm)

Once/

Once/day if in-line

shift

instrument is
available.

(after passing through

cation exchange in
H+ form)
3.

Silica (ppm)

0.02 (Max.)

Once/
shift

4.

Total Iron (ppm)

0.01

Once/week

5.

Copper (ppm)

0.001

Once/week

6.

Sodium (ppm)

0.015 Max.

Once/day

7.

Ammonia (ppm)

0.5

Once/
shift

------------------------------------------------------------------------------------------------------------

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94

(D)

Return Condensate (Sample from Condensate Extraction pump

discharge)
-----------------------------------------------------------------------------------------------------------1

-----------------------------------------------------------------------------------------------------------1.

pH at 25OC

9.0-9.2

Once/
shift

2.

Specific conductivity

0.3

at 25 C ( s/cm)

Once/
shift

(After passing through

cation Exchanger in
H+ form)
3.

Dissolved Oxygen

0.02

Once/day

(ppm)
4.

Silica (ppm SiO2)

0.02 Max.

Once/day

5.

Total Hardness

B.D.L.

Once/day

(ppm CaCO3)
6.

Free Ammonia (ppm)

0.5

Once/day

7.

Chloride (ppm)

B.D.L.

Once/day

8.

Total Iron (ppm)

0.01

Once/week

9.

Copper (ppm)

0.001

Once/week

10.

Sodium (ppm)

0.015

Continuous
(Max.)

------------------------------------------------------------------------------------------------------------

PMI, NTPC

95

(E)

Ejector Drip

-----------------------------------------------------------------------------------------------------------1

-----------------------------------------------------------------------------------------------------------1.

pH at 25OC

9.5-10

Once/day

If pH is more than
10 or if Ammonia
is more than 10
ppm then reject
the ejector drip.

Ammonia (ppm)

10

Total Hardness
(ppm CaCO3)

B.D.L.

-----------------------------------------------------------------------------------------------------------(F)

Make Up Water:

-----------------------------------------------------------------------------------------------------------1

-----------------------------------------------------------------------------------------------------------1.

pH at 25OC

6.8-7.2

Testing
frequency to

2.

Specific conductivity
O

at 25 C (us/cm)

0.2

be for WTP of

0.1 for

KSTPP as

KSTPP

per operational
Requirement of W.T.P.

3.

Silica (ppm SiO2)

0.02

It is design
fig. for WTP
of KSTPP

4.

Sodium

0.005

5.

Total Hardness

B.D.L.

(ppm CaCO3)
------------------------------------------------------------------------------------------------------------

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96

(G)

Generator Stator Cooling Water:

-----------------------------------------------------------------------------------------------------------1

-----------------------------------------------------------------------------------------------------------1.

pH at 25OC

7.0-7.2

Once/day

2.

Specific Conductivity

1.0 Max.

Once/day

at 25OC (us/cm)

This value S.O.

(stator polise unit
in service S.P.U.

3.

Copper (ppm)

0.005

Once/week should always be

in service. Lime
Conductivity
Monitor must be
Installed. It should
Be after passing
Through cation
column.

-----------------------------------------------------------------------------------------------------------Notes:
1.

To raise pH from the pH brought about by Hydrazine to the desired value,

use Morpholine, Cyclophexylamine or Ammonia. Thumb rule is:
Use Morpholine for low make-up rate (2%) Use Cyclohexymine for
medium make up rate (2-5%)
Use Ammonia for high make up rate (75%).

2.

If unit has tripped, open deaerator vent to the maximum opening. After the
temperature and pressure of the unit have stabilized, check D.O. and then
get the deaerator vent adjusted, till the designed value of D.O. from
Deaerator outlet is obtained. Thumb rule is that if height of steam jet from
Deaerator vent is 1 feet then it should be possible to adjust this.

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5. Coal And Its Analysis

What is Coal
Coal may be defined as that part of the earths crust which has been formed as a
result of the accumulation of decayed plant remains million of years ago, and its
subsequent consolidation over the years by a complex series of chemical and
physical changes.
Today Coal is known to be a complex mixture of the degradation products of
these plant remains and their associated mineral matter, and its properties vary
considerably according to location, geological, bacterial, heat and pressure
influences and chemical change. As these parameters all vary in their intensities,
the final coal substances consequently also varies, to produce a large range of
coals of differing characteristics. The term coal covers a wide variety of materials
ranging from Lignite on one hand to Anthracite on the other.
Formation Theories
There are two main theories by which vegetable matter for the formation of Coal
was accumulated. The first one considers that the deposits accumulated through
the vegetable matter of the swamps, falling where it grew and is called In-Situ
Theory. While second is Drift or transportation theory considers down streams
and deposited in large shallow lakes or hug delta at the river mouth.
Indian Coals including Coals from Singrauli Coal field, have formulation on Drift
theory.
The great of seams of presence of dirt bands in many seams are attributed to
formation of Indian Coals by Drift Theory.
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98

Coal Resources & Demand Pattern

Coal Production is expected to go up to about 400 mte by 2000-2001 AD. The
total reserves as assessed by GSI in 1978 are about 85,000 mts (upto 600 mtrs
depth) of which share of non cooking Coal is about 68,000 mte. Coal is npm
renewable source of energy which not only has to be conserved but utilized
properly.
Coal is perhaps the most versatile fuel. Power, Steel & Railways are the bulk
consumers and consume about 60% of the total production and such a trend is
expected to remain till turn of the century.
The Table -I gives the consumption pattern (actual) for 1977-78 and forecast for
1982-83, 1992-93, and for 2000-2001. the balance 40% of Coal production is
utilized by very large number of small consumers such as cement, paper,
fertilizer, textiles, brick burnings etc.
Analysis of Coal demand pattern as indicated in Table-I shows the major single
consumer with the rapid rate of demand would be the power section. With this
identification of Coal demand pattern to avoid vagaries of rail transportation from
different sources., the concept of pit head thermal power plant was mooted.
For this purpose, Singrauli Coal field has been identified as the most potential
area where Coal and Water is available up to the generation capacity of 20,000
MW within the region.

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Classification of Coal
Dr. Seylers Classification
In an attempt to predict the properties of Coals, from analytical data, Seyler,
using dry mineral matter-free percentage of carbon and hydrogen as the main
parameters, plotted the positions of all known Coals in a graphical form.
Seyler gave each class of Coal a distinctive name based on its rank (the rank of
Coal being a function of its Carbon content calculated on the pure Coal basis)
and named five main classes.
Seylers Coal Classification
-----------------------------------------------------------------------------------------------------------Sl. No.

Class

% Carbon in Coal

-----------------------------------------------------------------------------------------------------------1.

Lignitour

75 84

2.

Bituminour

84 91

3.

Carbonaeous & Semi-Anthracite

91 92.5

4.

Anthracite

over 92.5

-----------------------------------------------------------------------------------------------------------Dr. Seylers Fuels Chart

Seylers Fuels Chart may be used to calculate any two unknown of the quantities
Carbons, hydrogen, volatile matter & calorific value when the other two are
known.

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THE SEYLER CLASSIFICATION OF COAL MAIN

FEATURES DMMF BASIS
For example, if the calorific value and volatile matter are known, the carbon and
hydrogen contents can be read off the charts at the intersection of the
appropriate calorific value line (isocal) and volatile matter line (isoval) provided
the coal falls within the coal band. For dull coals or coals outside the band, a
correction is made to the volatile matter figure which is reduced by 0.5% for
every 10% of durian (the dark grey, hard fraction of coal which contains much of
inorganic matter) estimated to be present.

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101

The intersection of the corrected isovol with the isolcal is then found. Seylers
chart can be used for checking boiler efficiency, but this is outside the scope of
this manual.
Coal Sampling
Any Management requires to know for its power stations the quality:
a.

of coal paid for when delivered.

b.

of coal consumed during a given period.

Any Generating Unit is paying for cost and transportation of coal, it is important,
therefore, to monitor the quality of deliveries to ensure that value for money is
obtained. In addition, knowledge of the quality of coals enables fuel supply officer
to plan the supply of coal to individual station in accordance with their technical
needs in the most economical way.
Secondly the performance of plant is frequently measured using coal test results
so that any deviation from standard may be detected and steps taken to restore
efficiency.
Since it is not possible to check every piece of coal in a consignment, laboratory
tests are carried out on a sample which is taken crushed and reduced to
represent the bulk of coal from which it was drawn.
These processes are scientifically specified and must be rightly observed in
practice, for the final test sample to be dependably representative of the
consignment. If the sample does not represent the bulk accurately, no reliable
test results can be obtained.

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102

The most satisfactory way of obtaining a representative sample is from a falling

stream of coal as near as possible to the station reception point. This can be
taken as the coal leaves the reception hopper or as it falls from the first conveyor.
Even sampling from a conveyor is difficult because, as the belt travels along, the
vibration tends to move the bigger pieces of coal towards the edges. Big piece of
coal often have a different ash content than smaller fine coal. Therefore, to obtain
representative sample the increments must be taken from all parts across the
width of the coal stream.
By sampling in correct manner the result obtained will very close to the average
for the whole train. Few stations have automatic coal sampling equipment fitted
at reception hoppers and conveyor belts. An automatic sampler obtains and
increment coal at regular time interval from the coal stream and passes it to a
crusher where the larger pieces are reduced in size. All the increments are
collected together to form the gross sample.
Treatment of gross sampleA correctly taken gross sample contains the same proportion of big pieces, small
pieces, shale, slate, dirt, and poor coal as there was in the original delivery. This
gross sample is too big to be analysed, so it is reduced to a few gms. These few
gms, however, must still contain the same proportion of all the different
constituents as the gross sample and to achieve this it is further crushed and
reduced.
Analysis and Testing of Coal
Proximate Analysis
This is defined as the analysis of coal expressed in terms of moisture in the
analysis sample volatile matter, ash and fixed carbon. Ash is the residue

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103

remaining when coal is incinerated to constant weight under standard condition.

Volatile matter is the loss of weight (other than that due to moisture) that occurs
when coal is carbonized to a coke under standard condition. The test is an
arbitrary one: if conditions are changed the result will be different. Volatile matter
is not, therefore, an entry contained in the coal which can be extracted and
measured like water and in consequence it is not strictly correct to speak of
volatile mater content. Fixed carbon is a calculated figure.
Fixed carbon = 100-(moisture + volatile + ash) all expressed as per cent on the
same basis. Its purpose is to measure the coke residue (except ash) from the
volatile matter determination; like volatile matter it is not a substance contained in
coal. Since the two figures are the expressions of one determination, chemists
are tending to omit reporting fixed carbon.
Moisture Content
Moisture exists in all coals in three forms:
a)

Free moisture: Surface moisture, also present on apparently dry coals,

which is dried off when coal is exposed to the air without heating.

b)

Inherent moisture: the moisture retained in the pores of the coal

substances when free moisture has evaporated.

c)

Water of hydration: This is the water of constitution chemically bound to

the shales. Such water is driven off by heating to 105-110OC as are free
moisture and inherent moisture.

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104

Air dry moisture is a term used to describe that part of the total moisture retained
in the 72 mesh analysis sample, after it has been exposed to the laboratory
atmosphere and has attained approximate equilibrium with it.
This is necessary so that there should be no change in the condition of the
sample either during weighing of a portion for test or whilst the sample is
standing between the tests. It is not possible to handle the sample in the bone
dry condition because finely ground coal will pick up moisture rapidly; on the
other hand the presence of free during weighing but during preparation of the
sample. In amount, the air dry moisture is similar to the inherent moisture.
Total moisture is the sum of free and inherent moisture. It is an inert constituent
of coal and it reduces the calorific value it costs as much as coal to transport and
its latent heat of evaporation is burned, contributes to flue gas losses.
Free Moisture
All coals contain some free moisture. Its origin may be underground mine water,
water infused into coal seams and sprays used for dust suppression, washing
process or exposure to rain. Free moisture is the proportion which is evaporated
on bringing a sample into equilibrium with the ambient air. Free moisture is
determined, as percentage from the loss in weight of a 10-30 lb. sample after
exposure to freely circulating air at not more than 15OC above ambient
temperature for 16-24 hours. The sample is spread out into trays about 1 deep
and if very wet the drying time may be extended beyond 24 hrs.
Inherent Moisture
When total moisture is determined on coal, the water in a 2 lb. sample is
distilled off with toluene (6 pt 110OC) and the amount of condensed water
collected in the receiver during 6-8 hrs is noted. An alternative method suitable

PMI, NTPC

105

for high rank coal only is to measure the loss in weight when a 2 lb. sample is
heated in an oven at 105-110O for 5-6 hours in a slow air current.
Mineral Matter and Ash
Mineral matter may occur either intimately mixed with the coal substances or as
bands between coal seams. In the latter case partial separation of the mineral
matter and coal occurs on taking and much of the impurity may be removed by
dry or wet cleaning processes. Mineral mater once burnt becomes the ash. Ash
is of three types:
i)

Inherent ash that ash content which cannot be reduced by any method of
cleaning. It may be thought of as the mineral constituents of the vegetable
matter from which the coal was derived plus the silt on which it grew.
Inherent ash is usually constant for a given coal seam and range from %
to nearly 20%.

ii)

Associated ash present in the coal seam as bands, lenticles and parting.
One form of middling consist of such minerals matter, which has not been
split off the coal lumps during mining.

iii)

Adventitious Ash not present in the seam, but introduced from floor and
roof during cutting, as a result of deliberate policy. Or because geological
weaknesses dictate its removal to ensure a safe working roof.
Adventitious ash may be fire clay or carbonaceous shallow from the clay
deposited in shallow water when coal was laid down.

The determination of ash has, to a lesser degree, the empirical nature of

determination of volatile matter and has to be carried out under standard
conditions if reproducible and comparable results are to be obtained. Two
methods are described. In the first a single muffle furnace is used: a known

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106

weight of coal (1-2 g) is heated in air to 500OC in 30 min; the temperature is then
raised to 815OC in a further 60-90 min. The sample is heated to constant weight.
In the second two muffle furnaces are required. The sample is heated in one kept
at 500 OC for 30 min.; the dish is then transformed to the other kept at 815 OC
and is heated to constant weight. The second is preferable in laboratories which
are required to test a large number of samples. In each case the furnace must be
well ventilated to minimize the fixation of oxides of sulphur. Following table
shows the most common constituents of ash.
Table
-----------------------------------------------------------------------------------------------------------Element

Mixture of compound in

Amount of compound

Which element appears

present in ash

-----------------------------------------------------------------------------------------------------------Silicon

Silica or Silicates

Aluminum

In combination with Silicon

Iron

Pyrites or marcasite

Calcium

50-90%

(in combination with silicon)

0.20%

Calcium Carbonate

0.20%

Sulphate & Silicate

Magnesium Magnesium Carbonate & Silicate

0.20%

Sodium &

Sodium & Potassium

0.5%

Potassium

chlorides, Carbonates & Silicates

------------------------------------------------------------------------------------------------------------

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Traces of other elements such as titanium, manganese, sulphur, phosphorus,

chlorine, germanium, and nickel also occur.
Volatile Matter
Volatile matter is defined as the percentage loss in weight when 1 gm. of coal is
heated under controlled conditions for seven minutes at 925OC in a crucible from
which air is excluded. An allowance is made for any moisture in the coal which
would also be driven off at this temperature. The loss in weight is caused by
distillation of gas. The percentage of volatile matter on the probable behaviour of
a coal properties and characteristics such as flame length, rate of combustion,
ignitability (the ease with which a coal will ignite) and calorific value can be
calculated Bituminous coals have a volatile content of between 20% to 30%
whilst anthracites have less than 20%.
Calorific Value
The calorific value is the basic standard of any fuel; it is a measure of its heating
power and is the primary factor in coal pricing.
Calorific Value is the number heat unit liberated per unit weight of fuel when
completely burned in oxygen. In Britain and the U.S., it is measured in British
Thermal Units per pound (Btu/lb); the metric equivalent may be calories per gm.
(Cal/GM or Kilo calories per kilogram these are numerically equivalent. The
relationship between these two systems is simple:
Cal/gm x 1.8 = Btu/lb.
It is worth noting here that the calorific value of liquid fuels is occasionally stated
in Btu per gallon; for gaseous fuels the unit is usually Byu per cubic foot.

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It is necessary to distinguish between four calorific values viz:

1.

Gross calorific value at constant volume.

2.

Net calorific value at constant volume.

3.

Gross calorific value at constant pressure.

4.

Net calorific value at constant pressure.

The laboratory bomb calorimeter determination is the first of these gross at

constant volume the others may be calculated from it if the composition of the
fuel is known. The word gross signifies that the latent heat of evaporation of the
water present in the fuel plus that formed during combustion, is recovered by
condensing the products, net signifies that the latent heat is lost, the water
being discharged as vapour. For a typical coal (low rank, having 10% moisture
and 4% hydrogen) with gross calorific value 10.500 Btu/lb the net calorific value
will be 10,050 Btu/lb.
It will be realized that this latent heat of evaporation is not recoverable under the
boiler operating conditions and this has led to the practice of continental
manufacturers report that boiler efficiencies are based on the lower or net
calorific value.
The efficiencies are some higher than the figures based on the higher or gross
calorific value, which is normal for British and American installations, and this
should be borne in mind when comparing reported performance.
Combustion of Coal in open space differ from that in a boiler; the first is the
content volume, the other at nearly constant pressure.
When the products of combustion are allowed to expand at constant pressure,
work is done and the gross calorific value at constant pressure is higher than the
bomb determined calorific value, by the heat equivalent of this work. The

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correction on this account is about 12 Btu/lb for coal and, being less than the
uncertainty of sampling and analysis normally neglected.
There are a number of formulae whereby the calorific value be calculated to a
fairly close approximation. It is necessary to know the ultimate analysis but as
this is rarely available, it is simpler and more reliable to carry out where a direct
determination, can not be made.
The calorific value of the pure coal substance (that is dry and free from all
mineral matter) is virtually constant for the coal from any given seam in one
locality. Once its value has been established, it may be used with the total
moisture and ash content, to calculate the calorific value of any consignment
from the same seam.
This approach has some advantage for the routine monitoring coal deliveries.
The time and money employed in carrying a number of determinations of
moisture and ash contents and calculating the calorific value, provides much
more useful information about trends and average quality in the long run, than
the same effort devoted to fewer direct determinations of calorific value in a
bomb calorimeter.
In the short term, and for checking, there is no alternative to the standard
procedure of bomb calorimetry.
A small quantity of the sample is burnt in compressed oxygen inside a stainless
steel cylinder, or bomb which is immersed in water contained in a cylindrical
calorimeter vessel. This vessel with its contents is situated inside a larger vessel
of which the hollow cylindrical walls are filled with water to form the jacket and
which has the purpose of minimizing the heat liberated on igniting the same by
an electrical fuse, is calculated form the temperature of the calorimeter water
which is accurately measured before,

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during and after the rise in temperature resulting from combustion. The heat
liberated is of course, essentially equal to the temperature rise multiplied by the
effective heat capacity of water equivalent of the instrument.
Procedure
1 gm of the sample ground to pass a 72-mesh-sieve, is accurately weighed into
the crucible which is then placed in the ring support attached to one of the
electrodes, and a length of 44. s.w.g. platinum wire is fastened to the electrodes,
just above the top of the crucible, so that the wire is taut. A short piece of sowing
cotton is tied to the centre of the wire and positioned so that a part of the cotton
measured into the lower part of the bomb which is then assembled with the cap
carrying the electrodes and sample and the whole is charged slowly with pure
oxygen to a pressure 30 atm (4401 lb/in2). It is important that the original air in
the bomb is not displaced when charging with oxygen. The trace of nitrogen is

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required as a catalyst to promote oxidation of sulphite (SO3-----) to sulphite (SO4-----).

Next the calorimeter vessel is partially filled with a measured quantity of water
(preferable distilled), sufficient to cover the upper surface of the bomb cap, and
the vessel is then located centrally inside the water jacket. The bomb is placed
inside the calorimeter vessel, electrical connections to the electrode terminals are
made and the stirrer, calorimeter thermometer, and covers are placed in position.
The temperature of the water in the calorimeter vessel is adjusted at the
commencement of the procedure so that, when assembly is complete, it is about
1.5OC below that of the jacket.
The calorimeter thermometer conforming to B.S. 791 is of mercury-in-glass,
graduated in 0.01OC and is read with the aid of a magnifying viewer to 0.001 OC.
The stirrer is operated throughout the determination and after 10 min of stirring,
the calorimeter thermometer is read at intervals of 1 min for 5 min, during which
time there should be a uniform gentle rise in temperature. The charge is then
ignited by momentarily connecting the electrode leads to a 6 to 12 V source of
about 50W rating. Readings are continued without interruption at 1 min intervals,
as the calorimeter water temperature rises to a maximum at 1 min intervals, as
the calorimeter water temperature rises to a maximum which usually occurs 5 to
7 min after ignition, having risen by approximately 2.5 OC. Readings are ended
after a further five or six observations during which a uniform fall in temperature
should occur.
The bomb is then removed from the calorimeter. Pressure is released slowly and
the bomb is dismantled. It can then be inspected for any sooty deposits on the
internal parts and in the absence of such deposits, combustion is regarded as
having been satisfactory. The inner surfaces of the bomb and the internal fittings
are carefully washed with distilled water into a beaker, for the subsequent

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determination of the corrections for nitric and sulphuric acids as mentioned

below.
As a safety precaution the firing key should be operated from a position at some
distance away from the calorimeter.
Corrections
A number of corrections must be applied for arriving at the calorific value, as
follows:
Temperature corrections
A cooling correction is calculated as shown in B.5/1016: part 5, to allow
for heat transfer between calorimeter vessel and its environment during
the rise in temperature, and a further correction is made for errors in the
thermometer. Calorimeter thermometers should be sent for test at the
National Physical Laboratory regularlyat 3-5 year interval usuallyand
the thermometer correction is obtained from the test certificate which at
the point of calibration by the N.P.L. is accurate to +200.002 OC.
Fixed corrections
These are necessitated by heat released by the fuse wire and combustion
of cotton, and are kept to a constant amount, about 20 cal., for every
determination.
Nitric acid and sulphuric acid corrections
Some of the nitrogen in the sample and air enclosed in the bomb is
oxidized to nitric acid with the evolution of heat (about 10 cal) whereas this
reaction does not occur perceptibly in boiler furnaces. Additionally, sulphur
in the sample is oxidized to sulphiric acid in the bomb liberating more heat
than it would be in a boiler where practically all the sulphur is converted to

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sulphur dioxide. The correction here is usually between 15 to 60 cal/gm of

coal depending on its sulphur content, and is either calculated (together
with the nitric acid) from analysis of the bomb washings, or from the
sulphur content of the sample, where this has been separately
determined.
Mean effective heat capacity of the instrument
In order to complete the calculation of the calorific value, it is necessary to know
what weight of water and metal (in terms of an equivalent weight of water) has
absorbed the heat evolved during combustion in the bomb. This is obtained
periodically as the mean of five determinations carried out as has been described
but substituting 1.2 gm of dry benzoic acid in place of the sample. The benzoic
acid, which is a crystalline organic substance containing only carbon, hydrogen
and oxygen is specially purified for this purpose and is obtainable as thermo
chemical standard having a calorific value certified by the N.P.L. which value is
close to 6319 cal/gm or 11,374 Btu/lb.
Calculation of the result
To summarise the calculation, we have

CV =

(Tc x H) Cf-Cs-Cn
----------------------------g

where CV is the calorific value in calories per gram. Tc the temperature rise in
degrees C of calorimeter water corrected for colling and thermometer errors.
H

the mean effective heat capacity in calories per degree C,

Cf

the correction in calories,

Cs

the correction for sulphuric acid in calories,

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Cn

the correction for nitric acid in calories,

the weight of sample in grams.

When determining the effective heat capacity the certified calorific value of
benzoic acid is taken as a standard, the temperature rise and corrections are
calculated and a measured weight of benzoic acid is used; the effective heat
capacity can thus be evaluated from the formula:

H=

(CV X g) + Cf + Cn
---------------------------Tc

Having determined the mean effective heat capacity, the calorific value of coal or
other fuel can be calculated and the final result cal/gm, is converted to Btu/lb on
multiplying by the factor 1.8. the difference between duplicates determined in one
laboratory should not exceed 50 Btu/lb and the difference between the means of
duplicate determinations from different laboratories should not exceed 120 Btu/lb.
An experienced operator usually expects to obtain duplicate results within 20
Btu/lb.
Adiabatic Bomb Calorimeter
In the determination of calorific value using the static calorimeter, the magnitude
and accuracy of the cooling correct depend on the temperature difference
between the calorimeter water and the jacket, and it is not always convenient to
compute this so as to produce small cooling correction particular when several
determinations are to be made in one day. Further the calculation of the cooling
correction takes time as does the need to read temperatures carefully at 1 min
intervals during 15 to 20 min. For these reasons the adiabatic bomb calorimeter
which eliminates the cooling correction, was developed commercially 12 to 15
years ago and has replaced static type ring in modern stations.

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The innovations of the adiabatic calorimeter are in the provision of the means to
change the jacket temperature rapidly particularly to increase it, and this is done
by installing electric heaters in the jacket through which the water is circulated.
The uppermost cover of the calorimeter is also made in hollow form and the
jacket water is passed through this in turn. Sensitive thermometers are placed,
one in the calorimeter water and one in the jacket and these control the jacket
heaters via a bridge circuit and relay so that as the calorimeter water temperature
rises the jacket water is heated rapidly to the same temperature.
In this way there is a negligible heat transfer between the calorimeter and the
jacket and it is only necessary to read the temperature accurately just before
firing (when initial equilibrium has been reached) and again at a convenient time
calculation of the result is the same as has just been described modified only by
deleting the cooling correction.
Although at present the accuracy of an adiabatic calorimeter is not significantly
greater than that of a properly controlled static instrument, it takes less time and
is potentially simpler to operate. For these reasons although they are costlier and
more complex instruments, adiabatic calorimeters have been widely adopted.
Sulphur
The determination of sulphur is part of the ultimate analysis of coal (g.v.) but is
discussed separately because of its special importance in pricing, as well as
technically, sulphur in coal is found in three combinations:
i)

Sulphate sulphur (negligible)

ii)

Organic sulphur (0.8% average)

iii)

Pyritic sulphur (0.8% average)

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Organic sulphur tends to be relatively constant but pyritic sulphur varies widely.
Sulphate sulphur exists as small quantities of ferrous sulphur (FeSO4. 2 H2O).
They are found as thin plates in partings of the coal where the solution has
evaporated.
Organic sulphur is combined with the carbon and nitrogen to form the coal
substance. In consequence it is not removable by cleaning.
Pyrities (also known as marcasite) is ferrous sulphide (FeS). It occurs as massive
nodules and lenticles, as brassy bands and as finely dispersed particles. The
first form is easily removed by the various coal cleaning methods. Pyrities more
closely associated with the coal is removable only with considerable loss of
saleable carbonaceous material or vend.
Methods are available for assessing the amount of each of the forms of sulphur
but usually they are not important for power station purposes. Total sulphur may
be determined in the bomb-washings from the determination of calorific value;
this is a simple procedure and is usually adopted since the result is required for
the calorific value calculation. If total sulphur has to be determined, and the
number of samples is not large, the Eschka or bomb method is used: large
numbers of determinations are more conveniently carried out by the high
temperature (tube) method.
In the Eschka method 1 gm coal is burned by heating in a crucible with a mixture
of magnesium oxide and sodium carbonate. This alkaline mixture retains all the
sulphur as soluble sulphates which are determined by the standard chemical
method of precipitation as barium sulphate which is finally dried and weighed.
The high-temperature (tube) method requires costly equipment which can be
made largely automatic and needs little special training to operate. The

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justification for its use depends on the number of sulphur determinations to be

carried out, or on results being required more rapidly than can be provided by the
other methods. The coal sample (0.5 gm mixed with alumina) in a small
refractory beat is pushed into a tube kept at 1350OC through which passes a
rapid current of oxygen. The sulphur oxides formed are absorbed as the oxygen
from the tube is bubbled through hydrogen perioxide, which converts them wholly
to sulphuric acid. The acid is measured by titration with standard alkali solution, a
correction being applied for chlorine carried forward by the oxygen. (This is also
a method for the estimation of chlorine (g.v.)
Mention should also be made that sulphur can be determined by the oxygen
flask technique. In this method, 1/30 gm of coal wrapped in paper is burned in a
glass flask filled with oxygen at atmospheric pressure. The flask contains
hydrogen peroxide solution to dissolve and oxidize the sulphur gases to sulphuric
acid. This is estimated by titration with standard barium per chlorate solution with
a special indicator. Research at March wood Engineering Laboratories has
shown that the accuracy of the method is almost as good as the classical
methods and because of its simplicity it may usefully be applied to the routine
determination of sulphur in coal.
Chlorine
Chlorine has been regarded as a significant constituent of coal since about 1939
when a correlation between chlorine content of the coal and the degree of gasside boiler fouling resulting was observed. This aspect is discussed, with ash and
sulphur contents, in a later section.
Chlorine occurs almost entirely as sodium chloride and potassium chloride.
These salts drive from the shallow seas which covered the coal measures in a
later geological period. Although the chlorides can in part be dissolved out by
repeated water washing, some will always remain in the coal. In practice the

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washing processes used in coal preparation do not significantly reduce the

chloride content, partly because of insufficient residence time, but also because
the washery water is largely recycled and tends to reach a state of equilibrium,
where the wash clean water to rinse the washed coal or to dilute the wash water
and in any case surplus washery water must be expensively cleaned to a rigid
standard before disposal.
The methods available for estimation resemble those described for sulphur
namely the Eschka and high temperature methods and for routine analyses the
oxygen flask method has much to recommend it. The finish in all cases is by a
volumetric titration.
The Ultimate Analysis of Coal

Strictly the ultimate analysis of coal is the determination of the elements of which
its molecules are compounded and as such would include elements like chlorine,
phosphorous, etc; for fuel technology purposes the term is defined as the
analysis of coal in terms of its carbon, hydrogen, nitrogen and sulphur contents.
Oxygen is usually taken as being 100 minus the sum of the former constituents,
expressed as percentages. As such it includes the errors of estimation of the
other elements and a direct method is being developed.
The ultimate analysis is of great scientific interest and has important practical
application in combustion calculations and heat balances as already stated, the
C.V. can be calculated to a fairly close approximation from the ultimate analysis.
Until recently elemental analysis by the classical Liebig method required high skill
and experience and it was time-consuming. Accordingly for heat balance
purposes, the ultimate analysis was frequently calculated from analyses which
are on record for the particular seam or coal rank. More recently the hightemperature tube method, cutting down the combustion time from 2h to 9 min

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and introducing other time saving modifications has been developed. In spite of
those improvements the determination of carbon and hydrogen is not a simple
operation and there is an intensive search for a rapid method based on
instruments which will always yield reliable results so far none proposed has
been found wholly acceptable.
Carbon and Hydrogen

Two standard method are available for combustion at 800OC (classical Liebig)
and at 1350 OC (Sheffield high temperature). In both methods the calculated
result is total carbon that is it includes carbon from coal as well as from any
carbonates present and a correction is needed at a later stage. In each the
hydrogen is converted to water which is absorbed and weighed together with the
water present, as moisture in the coal and as water of hydrogen in the associated
mineral matter. In this case corrections have to be applied for these interfering
factors.

(a)

In the low-temperature method. 3 gm of coal is burned in a slow stream of

oxygen in a heated tube 50 in long. Capable of close temperature control
in zones. The tube is packed so that the products of combustion pass
through a plug of copper oxide 18 in long kept at 800 OC and then
successively over a lead chromate plug (4 in long) and then a 1-in roll of
silver gauze, both kept at 600 OC. the copper oxide ensures that all the
carbon is converted to carbon dioxide and all the hydrogen to water. Oxide
of sulphur are removed by the lead chromate and chlorine by the silver
gauze.
The products of combustion carried by the stream of oxygen pass through
in absorption train consisting of tubes which are packed with an absorbing
substance.

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Water is first removed by magnesium perchlorite and measured by the

increase in weight. Traces of nitrogen dioxide which would lead to
erroneous results for carbon are then removed by manganese dioxide.
Finally carbon dioxide is absorbed by soda-asbestos; again the increase
in weight of the absorption tube measures the carbon dioxide evolved.
(b)

The high-temperature method differs from the Liebig methods in having a

shorter unpacked tube (only 26 in long) using a rapid stream of oxygen
and operating at 1350 OC. At this temperature both sulphur and chlorine
are trapped by a roll of silver gauze; nitrogen dioxide is not formed under
these conditions and no special precautions are therefore necessary. The
assessments of water and carbon dioxide produced can be as in the low
temperature method or can be attempted by automatic instruments if
speed is a necessary factor.

Nitrogen
Nitrogen in coal is an inert substance which takes n part in combustion
processes. It may be estimated by the Kjeldahl method of heating the coal with
concentrated sulphuric acid to destroy the organic material; the presence of a
catalyst (selenium mercuric sulphate vanadium pentaoxide) ensures that all the
nitrogen is rapidly converted to ammonium sulphate. When cool excess sodium
hydroxide is added to free the ammonia which may then be steam distilled and
collected for estimation in the condensate by titration with standard acid solution.
The estimation may be carried out with appropriate difference in detail 1 gm
(macro method) or 0.1 gm (semi-micro method) of coal. In practice because of
the shorter times of digestion (1/2h as against 2 h) and the smaller scale of the
apparatus nearly all laboratories use the semi-micro method.

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Moisture
Moisture estimation has not been attended by the same degree of success as
the estimation of mineral matter; however a brief description of some of the
methods tried is given in the following paragraphs.
Moisture in cereals may be indicated satisfactorily by the change in capacitance
of two plates when grain with a varying moisture flows between them but the
difference in particle behavior between grain and coal introduces uncertainties
greater than, are acceptable.
Attempts have been made to produce on automatic chemist which would take a
known weight of coal dry it rapidly by flash-evaporation under low pressure whilst
it is exposed to high energy infrared heating and then reweigh it.
A more successful methods is to measure the attenuation of a microwave radio
signal when it is transmitted through the coal sample. The weakening depends
on the hydrogen-oxygen bonds in the molecule of water but since there are a
number of other bonds of a similar nature in the coal the response is not as clear
as could be wished.
However more recently reports have been received of an instrument for which an
accuracy of + 1% for total moisture contents in the range 3-25% has been
claimed for all ranks of coal and a wide range of mineral matter. This instrument
uses nuclear magnetic response (NMP) to estimate the hydrogen in coal
substance).
NMR depends on the absorption of energy by the nucleus of an atom, when it is
subjected to electromagnetic radiation whose frequency is related to the nuclear
structure and to a strong magnetic field the strength of which can be varied

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slowly. A recorder plots a derivative of the absorption and field strength so that
water content may be read off directly.
As with other instrumental techniques there are the plant scale problems of
taking and handling a representative coal sample.
Other Tests on Coal
Bulk Density
The measurement of the bulk density of coal in small heaps and in wagons in a
fairely simple matter. It is much more difficult when the coal is a large stock-pile
of compacted coal
Bulk density of coal in a wagon is the ratio of net weight to the volume calculated
from the wagons dimensions and the level coal surface.
The same principles apply when using a special bin or box. It must be noted,
however, that when dealing with smaller volume the effect of voids between the
walls and coal lumps introduce error, the smaller the box the large the error.
It is not possible to measure the bulk density of coal in stock piles by these
methods, since the sample when extracted has a large volume than the coal in
situ. Accordingly the technique is reversed. A coal sample is dug out and
weighed: the volume it occupied is assessed by lining the hole with polythene
sheeting and measuring the volume of sand or water needed to fill it.
A further difficulty has to be considered. It is argued that surface results are not
typical of the density at lower levels. To avoid this, it has been proposed that an
auger be used to extract a coal sample which can be weighed; the volume it

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occur is calculated from the cylinder that is represented by the inserted length of
the auger.
In the last two or three years attempts have been made to adapt the Gamma ray
back scatter method to this determination. A tube is driven into the pile and an
emitter and detector are lowered to various depths at which readings on an
indicator are taken. The method is not only subject to instrument error as in the
ash determination but there is the practical difficulty of driving a tube into
compacted coal, without bending ita bend can prevent the instrument from
reaching the required depth. Claimed to have an accuracy of + 5% when used
with care, and +3% after experience has been gained with particular coals
packed by particular methods.
Grindability
75% of coal consumed in our boilers is pulverized for firing. It is desirable to
know how the properties of the coal and mineral matter effect the grinding
process, how easily the fuel can be reduced to the required fineness and what
power is needed to do this. A variety of tests have been proposed; each has its
merits and defects and an international group is now studying them.
The best tester for grindability is the hardgrove machine which is a miniature
ring-ball type pulveriser. The grindability index from this machine was originally
based on the increase in surface area produced on the coal particles but
because its measurement was tedious a simplified procedure was introduced.
A 50-gm sample passing a No. 16 U.S. sieve and retained on a No. 30 U.s. sieve
(0.0469 in and 0.0232 in respectively) is ground for 60 revolutions with 64 lb
loading on the ball ring. The amount of coal now passing No. 200 U.s. sieve
(0.0029) is weighed (W). Although this can be used directly as a measure of the
ease with which the coal was ground in order to retain comparability with the

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original Index based on surface area. It is transformed by the formula Hardgrove

Index = 13+6.9 W.
The Hardgrove Index so calculated can range from over 100 for easily ground
coals down to rather less than 50 for coals which are more difficult. This broad
relationship also holds for other properties associated with rank, such as volatile
matter carbon, etc.
This particular method of test has been criticized because (a) during preparation
for the test some 50% of the sample is sieved out leaving a test portion which
may not be properly representative (b) only part of the sample is taken to the final
ground state and (c) the fines are not removed as they are produced.
Ash From Coal
The colour of coal ash varies from almost pure white to a dark chocolate colour
depending mainly on the iron content. Its fusibility varies widely according to its
chemical composition. Ash containing much iron from a highly pyretic coal, forms
the readily fusible ferrous silicate which is a common source of clinker in
furnaces.
The simplest coal ash consist of the refractory clay kaolin, composed only of
alumina and silica to which may be added as the composition increases in
complexity lime and oxides of iron in varying preparations. With increase of lime
and iron contents the fusion point of ash falls significantly.
Quality Parameters: Singrauli Coals
There are three major coal seams in this coalfield i.e. Purewa, Tura and Kota.
Purewa seam is split into two parts in kanor areas of the coalfield. The bottom
most kota seam is thin and is not being envisaged to be mined at this stage. The

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coalfield is divided into 11 blocks. Table enclosed gives in general the quality
parameters and thinness of various seams in Jhingurda, Bina, Dudhichua,
Jayant, Nigahi, Almori and Mohar blocks.
In this coalfield the quality of coal seams is varying both vertically and
horizontally, as consequence of this, there is general improvement in coal quality
from East to West Composite Tura seam coal with characteristics can be used
mainly for power generation. Purewa seam in the entire coalfield is only suitable
for power generations. Since large scale open cast mines are being
contemplated in this coalfield selective mining would also be mined out. The
combined coal quality parameters for each of the mining blocks make the coal
suitable mainly for power generation only.
Since the quality of coal supplied to the power stations has direct bearing on the
performance and availability of equipment in the thermal power station this
aspect has to be gone into more details, before design. Inferior and inconsistent
quality of coal creates a number of problems in design, operation and
maintenance of thermal power station compared to better and consistent coal
quality. The coal quality can be improved or consistent coal supplies can be
ensured by resorting the coal beneficiation experience as beneficiation of noncoking coals in India is limited. The wet beneficiation or coal washing as it is
normally called is very costly. In addition to cost of washing which itself is quite
high, the moisture contents in washed coal are increased substantially. Also for
the present there is no utility of rejects coming after such coal washing. These
rejects are likely to catch fire. In addition to wastage of this energy, it would also
create an environmental problems. The studies are being conducted for finding a
suitable method of coal beneficiation in totality wherein the so called rejects also
find a favourable use and the whole process of beneficiation becomes technoeconomically viable.

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However, till the time a suitable solution is available power houses would have to
tolerate fluctuations in coal qualities which are more or less inherent in the mining
system.
Quality parameters of Jayant Mine linked to Singrauli STPP:
The coal quality parameters of Jayant mine linked to Singrauli STPP are
indicated in Table enclosed.
As regards coal supplies from Jayant mine linked to Singrauli STPP is concerned
NTPC is better placed compared to other power houses as coal for the first 10 to
12 years would be only supplied from Turra seam of Jayant project. The quality
parameters of the same as indicated by CCL are given here.
Coal Characteristics of Singrauli Coalfield
Proximate Analysis on 60% RH at 40OC
-----------------------------------------------------------------------------------------------------------Excluding Dirt bands
Included Dirt bands
SEAM
------------------------------------------------------------------------Moisture
Ash
V.M.
Ash%
GCV Kcal/Kg
%
%
%
-----------------------------------------------------------------------------------------------------------Turra
7
15
25.4
18
5050
10-24.5
to
to
to
to
to
9
23.7
31
39.9
5810
-----------------------------------------------------------------------------------------------------------Purewa Top 7.5
22.3
28
39.1
4760
5.04 to 10.93 to
to
to
to
to
8.7
25
30
49
5045
-----------------------------------------------------------------------------------------------------------Purewa Bottom6.2
19.8
28.6
26.5
4950
7.69 to 12.7 to
to
to
to
to
8.2
24.3
31.5
40
5275
-----------------------------------------------------------------------------------------------------------Kota
7.4
19
29
26
5035
5m
to
to
to
to
23
30
35
5380

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-----------------------------------------------------------------------------------------------------------Jhingurda
8
25
28.3
33
4185
To
to
to
to
to
9
30.5
29.0
46.4
4500
Hard grove index
Initial Deformation
Temp.O
Hemi Spherical
pointO
Flow temp.O

45 to 50
1180 to 1200
over 1400
over 1400

Proximate Analysis on 60% RH and 40O C

-----------------------------------------------------------------------------------------------------------excluding dirt
bands
Including
Dirt bands PhosphoSEAM
Moisture% Ash% V.M.%
Ash%
rous all
-----------------------------------------------------------------------------------------------------------Turra Seam 6-9
16.9- 28.6
*18.1 - 24.0 *5245-5480 0.14
25.9
31.7
*20.1 - 35.2 *4167-5513
(calculated)
Purewa
5.4-10.6
22.2- 29.0*30.8-44.7 *3700-4400 0.01

Purewa Top 5.3-7.66

30.0

32.7

24.4-

24.0

45.6

30.2

*32.9-49.6

*3300-4200 0.01

-----------------------------------------------------------------------------------------------------------* Including bands upto 1 meter.

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Ultimate Analysis (Pure Coal Basis)

-----------------------------------------------------------------------------------------------------------Characteristics

Unit

Purewa

Purewa Bottom

Top Seam

Seam

Turra seam

-----------------------------------------------------------------------------------------------------------Volatile Matter

40.6-43.8

42.5-45.9

38.1-41.6

Carbon

79.2-82.0

79.6-81.1

79.4-81.5

Hydrogen

4.8-5.0

4.9-1.6

4.5-4.8

Nitrogen

1.7

1.5-1.6

1.4-1.7

Sulphur

0.6-1.6

11.8-13.1

11.6-13.9

Oxygen

10.9-12.6

11.8-13.1

11.6-13.9

Calorific Value

Kcal/

7505-7720

7650-7760

7490-7715

Kg
-----------------------------------------------------------------------------------------------------------Ash Characterisitcs
-----------------------------------------------------------------------------------------------------------Ash Characteristics

Unit

Purewa

Purewa Bottom

Turra

Top seam

seam

seam

-----------------------------------------------------------------------------------------------------------Silica (SiO2)

60.9

64.6

56.66

Alumina (Al 2O3)

24.8

24.8

27.46

Iron Oxide (Fe 2O3)

7.7

5.1

6.40

1.9

1.5

1.95

0.5

0.5

1.10

0.9

0.9

1.81

Titania (TiO2)
Phospheric (P 2O5)
Anhydride
Lime (CaO)

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Magnesia (MgO)

1.0

0.8

0.95

Sulphuric Anhydride

0.2

0.1

0.27

2.1

1.7

3.40

(SO2)
Alkalis
(By difference)
-----------------------------------------------------------------------------------------------------------Hard Grove Index

50-64

Initial Deformation

1190-1400

TempOC
Hemishpherical

Over 1400

PointOC
Flow Temperature OC

Over 1400

Seam Thikcness

On 60% RH basis

In mts.

Excluding Including
Dirt.

Direct Bands

-----------------------------------------------------------------------------------------------------------Turra

14-21

7-9

17-24-5700- 0.2-0.5

20-3

4400-4900

Combustion
Combustion can be defined as that rapid chemical union with oxygen of an
element whose exothermic heat of reaction is sufficiently great and whose rate of
reaction is sufficiently fast that useful quantities of heat are liberated at elevated
temperature.
For thermal power generation in India, two types of fuels i.e. Coal & Fuel oils are
being used and therefore, our discussion would be limited to combustion of coal
& fuel oil in Boilers.

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Coal is proximately analysed into the following:

a)

Moisture

b)

Volatile Matter

c)

Fixed carbon

d)

Ash

Quality wise gradation of coal is done on the basis of Moisture + ash content.
The more they are, inferior the coal will be and lesser will be its calorific value
and so the price. Fixed carbon & volatiles are the combustible portion of coal and
give out heat when they combine with oxygen. Before combination can take
place the atoms of oxygen & fuel must mix well together, and be in a highly
agitated state in an atmosphere higher than the ignition temperature.
Therefore to obtain good & efficient combustion following conditions must be
fulfilled.
1.

Thorough mixing of fuel and air in proportions which will ensure complete
combustion i.e. there should be turbulence in furnace.

2.

Exposure of fuel particles to oxygen throughout a period time sufficient for

their combustion i.e. certain time is required for complete combustion.

3.

Combustion zone should maintain temperature above ignition temperature

i.e. sufficient temperature is required for combustion to take place.

Thus there are three Ts which are essential requisites for efficient combustion
and therefore fuel combustion equipments & furnaces are designed to ensure
these conditions.

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When a coal is subjected to combustion conditions it first absorbs heat necessary

for volatilization of the hydrocarbons. This includes both sensible heat & latent
heat necessary to vaporize any moisture in the coal. After the distillation of
volatiles is complete the remainder is coke a mixture of fixed carbon and ash. It is
the hydrocarbons which must be carefully handled to obtain freedom from smoke
and incomplete combustion. Hence a major function of any furnace or burner
installation is the proper mixing of air with this distilled volatile matter and holding
it at ignition temperature sufficiently long to obtain complete combustion.
The fixed carbon burns in a somewhat complicated way, the nature of which may
be expressed most simply by saying that the manner of carbon combustion is an
incomplete oxidation to carbon monoxide which itself is a fuel. The carbon
monoxide will then be oxidized to carbondioxide provided enough oxygen is
mixed with it, and it remains hot enough to continue combustion. During
combustion each small piece of incandescent carbon becomes blanketed with
either carbon dioxide or carbon monoxide and unless this gas blank can be
continuously scrubbed off so as to expose a fresh surface the combustion will
stop. Continuous combustion is accomplished in stokers and on grates by
moving the air past a fuel bed at high velocity by draft pressure.
The process of Combustion
The combustion is a chemical process which takes place in accordance with
natural law. By applying these laws the theoretical quantities of air required to
burn a given fuel can be determined when the fuel analysis is known. The air
quantity used in a furnace, expressed as percentage of excess above theoretical
requirement, can be determined from the flue gas analysis.
When oxygen and the combustible elements or compound in a fuel are mixed in
definite proportions at an eleouted temperature under ideal conditions, they will

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combine completely. This shows that a given combustible element or compound

requires a definite amount of oxygen for complete combustion. If additional
oxygen is supplied the excess will not enter into the reaction but will pass through
furnace, unchanged. On the other hand, if there is deficiency of oxygen, the
combustible material will remain unburned. Briefly, the law of combining weight
tells us that the elements and compounds combine in definite proportions which
are in simple ratio to their atomic or molecular weights. In practice the oxygen
supplied for combustion is obtained from the atmosphere. The atmospheric air is
a mechanical mixture of gases which for practical purpose may be considered as
being composed of the following:
Element

Percentage

Percentage Weight

Volume
Oxygen

20.91

23.15

Nitrogen

79.09

76.95

Only the oxygen enters into chemical combination with the fuel. The Nitrogen
passes through the combustion chamber and reduces the maximum temperature
attained by the products of combustion.
In order to supply 1 lb. of oxygen to a furnace it is necessary to introduce:
1
---------------0.2315

= 4.32 lb. of air

Since one lb. of carbon requires 2.67 lb. of oxygen one must supply.
4.32 x 2.67 = 11.53 lb. of air/lb of carbon.
The burning of carbon in oxygen to form carbondioxide can be represented by
the chemical equation.

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C + O2 = CO2
12 + 32

= 44

or molecular weight = 12 + 32 = 44
By referring to the above equation we find that 1 lb. of carbon produces 3.67 lbs
of carbon dioxide. Therefore, the total products of combustion formed by burning
1 lbs. of carbon with amount of air are 8.86 lbs. of Nitrogen and 3.67 lbs of
carbon dioxide.
In a similar manner, it can be shown that 1 lb. of Hydrogen requires 34.56 lb. of
air for complete combustion. The resulting products of combustion are 9 lbs. of
water and 26.65 lbs. of Nitrogen, for 1 lb of sulphur 4.32 lbs. of air will be
required with evolution of 3.32 lbs. of nitrogen and 2 lbs. of sulphur dioxide. This
can be given in a tabular form.
Theoretical quantities Involved in Combustion of Fuel all Expressed in
Lb/Lb of Fuel
Constituents

Required

Resulting Quantities

O2

Air

CO2

N2

H2O

SO2

Carbon (C.)

2.67

11.53

3.67

8.86

--

--

Hydrogen (H)

8.00

34.56

--

26.56

9.0

--

Sulphur (S)

1.00

4.32

--

3.32

--

2.0

When quantities expressed in percentage by weight of carbon, hydrogen, sulphur

and oxygen in a fuel are known the theoretical quantities of air can be
determined by the following formula.
Lb of air required/Lb of fuel = 11.53C + 34.56 (H - 1/8 0) + 4.325 S

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In practice it is necessary and economical to supply more air than the theoretical
amount in order to obtain complete combustion. The air supplied to a combustion
process in an amount above the theoretical values is known as excess air. To
exercise control over combustion it is necessary to determine the amount of
excess air. This may be accomplished by chemical analysis of flue gas. The flue
gas analysis is effective in determining the amount of air supplied for combustion
as indicated in the above table. This table shows how the amount of excess air
used in the combustion process indicated either by the percentage of carbon
dioxide or oxygen in the flue gases. When a single fuel is burned the
carbondioxide content of flue gas provides a satisfactory index of excess air
being used. This can be explained by the fact that with the combustion of 1 lb. of
carbon 3.67 lb. of carbondioxide is product.
When a relatively large amount of air is used, the fixed amount of CO2 will be
diluted and the percentage correspondingly lowered. Conversely if only a small
amount of excess air is used, their will be less dilution and the percentage of CO2
will be relatively high. For a given percentage of excess air fuels with higher
carbon hydrogen ratio will have a higher percentage of CO2 in the flue gas than
fuels with lower percentage of excess air, the flue gas from a coal fired furnace
will have a higher percentage of carbon dioxide than when fuel oil is burned.
The percentage of oxygen provided an adequate measurement of excess air
when either single or multiple fuels are being used. The oxygen in flue gas
represents that portion which entered but did not combine with the combustible
elements in the fuel. This oxygen in the flue gas and the Nitrogen with which it
was mixed are the excess air. The theoretical oxygen and air requirement are
approximately proportional to the heat content of the fuel even with variation into
the Carbon-Hydrogen ratio. For a given percentage of oxygen the excess air is
approximately the same for either coal or fuel oil.
Table for the corresponding percentage of excess air, carbon dioxide and oxygen
for Bituminous coal and fuel oil is as follows:

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Kind of fuel
Bituminous

Fuel Oil

Ingradient

% excess air
O

20

40

CO2

18.6

15.5

13.2

O2

3.5

6.0

CO2

15.5

12.6

10.6

O2

3.7

6.4

The excess air in percentage of the theoretical requirements can be calculated

by the following formula

Percentage of excess air

O2 - CO
----------------------- X 100
0.263N2 + CO-O2

However when there is no carbon monoxide present the formula become.

Percentage of excess air

O2
----------------------- X 100
0.263N2 - O2

General specification For Coal and Fuel Oil to be Used

Coal Indian Bituminous
Fixed carbon

28%

Volatile

30%

Moisture

12%

Ash

30%

Grindability

55 HGI

Heating Valve

4500 Kcal/Kg.

Size of Coal

25 mm

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Performance Data
For a proper combustion control the recommended O2% (Dry Volume) CO2%
(Dry Volume) and excess air are as follows:

a)

Oxygen in gas at economiser

MCR

NCR 200 MW

3.84

3.84

15.77

15.77

22.0

22.0

outlet (by dry volume%)

b)

Carbondioxide in gas at economiser

outlet (dry volme) %

c)

Excess air in gas at economiser outlet %

General Layout Furnace with No. Types of Burners

FF

Flame Detector Coal

F
EF

Flame Detector Oil

E
DE

Flame Detector Coal

E
CD

Flame Detector Oil

C
BC

Flame Detector Oil

B
AB

Flame Detector Oil

A
AA

Flame Detector Coal

1.

Coal burners

A, B, C, D, E & F 6 nos. X 4 = 24 Nos.

Oil burners

AB, CD, EF 3 Nos. x 4 = 12 Nos.

3.

Auxiliary air dampers

AA, BC, DE, & EF 4 Nos. x 4= 16 Nos.

4.

Flame Detector Oil

3 x4 =

12 Nos.

5.

Flame Detector Coal

4 x4 =

16 Nos.

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137

6.

IFM Ignitor (by BHEL)

3 x4

= 12 Nos.

7.

HFA Ignitor

3 x4

= 12 Nos.

Therefore four sets of 13 elevations at four corners of furnace, each set consists
of 6 Nos. of coal burners, 3 Nos. oil-burners four nos. of auxiliary air dampers, 3
nos. of flue detector oil, four nos. of flame detector coal and 3 nos. of ignitors.
Hot flue gas from the furnace passes through platen super heater and
economizer to two nos. of Air heaters A and B. From air heater it goes to
electrostatic precipitator where dust is arrested. From ESP the flue gas goes to
the chimney through ID fans.
On Line Recorder for %O2 in Flue Gas
There are provisions for analysis of %O2 in flue gas probe type oxygen analyzer.
Two such on line analyses are there before airpreheater A and B. Model 218
probe type oxygen analyzer are used to measure the net concentrator of oxygen
in the process. Oxygen remaining after oil and fuel are oxidized. This performs
the task without the use of sampling system.
Cross Check of Flue Gas Quantity by Laboratory
In order to cross check the oxygen and carbon dioxide percentage in flue gas,
there are sample pockets before the air heaters. Sampling of flue gas is done by
sucking the gas either by sunction pump of suction bellows after proper filteration
of dust particles. Flue gas after collection can be analysed by the following
methods:

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i)

Lloyd Gas Analysers

This is a portable precision apparatus for the determination of oxygen and
carbon dioxide in flue gas. It is self compensating for temperature and
pressure changes and results are obtained directly from the 10 ml burette.
The main part of the apparatus is in one piece of glass and has a special
five way stop cock through which the samples are introduced passed to
the absorbents and finally expelled. The containing liquid is mercury.

ii)

Orsat Gas Analyser

This apparatus consists of a graduated burette of 10 ml capacity one end
of which is connected to a reservoir containing acidified brine solution with
few drops of methyloxange. The other end is connected to the sample and
absorption pipettes by means of a three way stop cock. The absorption
pipettes contain the absorbents for oxygen and carbon dioxide. A known
volume of sample is drawn from a bladder to the burette through the three
way stop cock and the sample is first passed into one absorption pipette
containing 40% KOH by raising the reservoir and again taken back to the
burette by lowering the reservoir. In the process CO2 is absorbed and the
volume of the gas is noted down difference between the initial volume and
final volume of the gas is noted down difference between the initial volume
and final volume gives CO2%. For the determination of O2% residual
sample is passed into another pipettle containing alkaline pyro gallol when
O2 is absorbed. The difference in the volumes of sample after absorbing
CO2 and the volume absorbing O2 gives the % of O2 in the sample.
Regents
a)

Potassium Hydroxide solution for CO2. Dissolve 40 gms of KOH in

100 ml of distilled water.

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b)

Alkaline pyrogallon solution for O2.

Dissolve 15 grams of pyrogallon in 25 ml of water and add the
solution to 15 ml of 30% KOH solution.
Determination of Carbon Monoxide
Sometimes it may be required to know the percentage of carbon
monoxide in the flue gas. For this purpose one more absorption
pipettes for oxygen and carbon dioxide, containing Ammonical
Cuprous Chloride solution as an absorbent.
Preparation of Ammonical Cuprous Chloride Solution
Add 75 gms of white cuprous chloride to 15 grams of ammonium
chloride in 80 ml of water and then add sufficient concentrated.
Ammonium Hydroxide solution until the solution is complete. A
large excess of Ammonia is avoided. This solution should be kept
in contact with copper gauge.

Effect of Fuel Quality on Combustion

Moisture
If the moisture content in coal is high, trouble starts right from mill. Hot primary air
supplied to mills has two purposes. First to dry up the coal so that grinding is
proper and second to carry coal dust to burners. If coal is not dry higher particles
will be formed by sticking together of finer particles and air will not be able to
carry them freely and efficiently. As a result of this mill will start getting overloaded and consequently milling capacity will be reduced and so the load on the
boiler will be reduced. Also fuel/air mixture temperature will be low and so the
evolution of volatiles. They will retard the combustion process. If efforts are made
to take the same output from mills, more hot air has to be supplied to dry up the
coal sufficiently and to carry the coal to burners. This will cause excess air to

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boiler and will lengthen the flame and affect the combustion. Also there will be
heat loss due to excess air.
In stoker fired boilers, if the moisture of coal is very high, it will become difficult to
maintain position of ignition line and grate spead will have to be reduced to
maintain its position and so the output. But some amount of moisture should be
maintained in coal for stoker fired boiler. This moisture is entrapped in the pores
of coal and when gets heated up, becomes steam and cracks the coal lumps and
thus helps in achieving better air fuel contact and so the combustion.
Volatiles
After removed of moisture from coal,

distillation process takes place

commencing from about 325OC and completing at 965 OC in which hydrocarbons

are released. These hydrocarbons, being in gaseous form get readily ignited and
supply instant heat for further combustion of coke.
Since in P.F. Boilers, coal in powder form gets ignited readily, volatiles do not
have as important part to play as in case of stoker fired boilers. If coal is low in
volatile content, bright and steady flame is not obtained in P.F. boilers. On the
contrary, high volatile coals produce bright and consistent flame.
In stoker fired boilers, since coal is in lump form, it does not get ignited easily and
here volatiles play an important role in combustion. The Hydrocarbons evolved
from coal are burnt above the grate near from arch with the help of secondary air.
Heat provided by combustion of volatiles promotes combustion of coke laying on
grate.

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Ash
Although ash has nothing to do with the combustion directly but on the whole it
affects performance of the boiler very much. Moisture Ash content forms the
basis of gradation of coal i.e. higher ash means reduction in combustible
percentage and so lower the calorific value. High ash content coal causes
increased wear and tear of mills, piping and ducts. If the boiler has been
designed for high ash coals, it will take care of the poor quality of coal while
maintaining furnace stability and load. But if a boiler has been designed for
superior coal low in ash content, feeding of inferior coal will definitely affect the
furnace stability and rate of heat release may not be sufficient to complete the
combustion with the furnace. It may either cause after fires in super heater zone
or wastage of combustibles.
Coal Fineness
Furnace

is always designed for burning a particular size of coal so that its

combustion may be complete by the time it leaves furnace. Therefore, if coarser

coal dust is fed, combustion will not be complete in furnace and after fires may
take place. This will also reduce the output and efficiency of the boiler. Coarse
particles may also fall down to the lower zones of the furnace and may get
entrapped in the slag resulting in loss of combustibles. If coal fineness is
increased by changing classifier vane position, even the particle of correct size
may not pass through classifier and come back to mill for further grinding thus
reducing the milling capacity.
Coal Sizing
While coal fineness affect the performance of P.F. Boilers, so the coal sizing
affects performance of stoker fire boilers. If the coal size is more, surface contact
of air and combustibles will be less and so combustion will not be quick. This

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may result in passing of unburnt coal into ash hopper and will go as waste. On
the other hand if more fine size are fed, they may not only obstruct the small
gaps in the grate which allow air to come into furnace but fuel bed itself become
so uniform (not porous) that it may offer great resistance to flow of air, through it.
Consequently, insufficient air will be available for combustion and combustibles
may go as a waste in ash hopper.
Some Important Points of Combustion Control
i)

A 20OC rise in flue gas exit temp. results in 1% boiler efficiency down
which costs approximately Rs. 6 lakh in additional coal cost for a 120 MW
set.

ii)

1%O2 variation in flue gas causes 0.25% variation boiler efficiency.

iii)

High excess air operations, furnace slagging or inadvertent up tilt of

burners can result in high steam temp. at different stages. Continued
operations under these conditions are conductive to tube failure. Analysis
and comparison of data with normal operating condition may help solving
these problems.

iv)

High input of fuel and consequently air with some streaming conditions
raises outlet steam temp. particularly in the conductive zones. Super
heater outlet steam temp. therefore needs to be closely watched to ensure
that the metal temp. does not exceed the allowable limit. Limiting the load
on this basis will mitigate problems of tube failure.

v)

Unduly high steam side pressure drop, denotes blacking of few coils or
deposition in the super heat tubes.

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vi)

An increase in the radiant super heater outlet temp. for the same steaming
conditions indicates slagging of the furnace. The soot blowing regime
should then the suitably attended.

vii)

Air leakage in the system may result into high O2 content and high ID
amperage.

viii)

Burner tips wearing will lead to oil pressure drop, poor atomisation and
soot formation on air heater.

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6. Oils
(A) Fuel Oil
In India fuel oil fired boilers are not being used because of acute shortage of oil
and for being very expensive. Totally oil fired boilers are generally employed
where oil is available in abundance or if power station is located near refinery.
Here oil is being used in boilers only at the time of starting or for stabilizing flame
if the combustion of coal is not proper due to its bad quality or very high moisture
content. Therefore, our subject of discussion will not concern totally oil fired
boilers, but will be limited to coal fired boilers in which oil is used for
starting/flame stabilization purpose.
Oils used in power plant generation are nearly always by products of petroleum.
Crude petroleum oil contains mainly carbon and hydrogen alongwith some small
amounts of oxygen, Nitrogen and Sulphur. This crude oil is seldom used in
original form. Approximate chemical composition of petroleum and its derivatives
is carbon 85% & Hydrogen 15%. Many fuels are produced from crude oil by
distillation and cracking, which is decomposition under condition of high
temperature and pressure.
In power station following fuel oils are being used:
a)

Light diesel oil (LDO),

b)

High Speed Diesel Oil (HSD)

c)

Furnace Oil (FO, &

d)

Low Sulphur Heavy Stock (LSHS)

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LDO and HSD are low viscosity and low flash point oils and can flow easily even
at low temperatures. These oils are comparatively costly and have other
important applications, such as HSD is used in automobiles and diesel
locomotives etc. Both these oils can be used without heating and can be
automotives etc. Both these oils can be used without heating and can be
atomized by compressed air or by mechanical means i.e. passing it through
spray/nozzle at high pressure. Their calorific value is near about 10720 KC al/kg.
These oils are, therefore, ideal for starting the boiler from cold when no other
source of steam is available for atomization.
Furnace oil, as its name suggests, is the most commonly used oil for limited
power generation purpose as mentioned above. Furnace oils are available as low
viscosity, medium viscosity and high viscosity types. These oils have definitely
much higher viscosity than LDO or HSD. Although they are in fluid state even in
winters but cannot easily be handled or used at that temperature. Particularly
medium and high viscosity F.Os required heating at the time of unloading and
pumping. Even while using, oil has to be preheated to about 110OC to make it
free flowing. Due to low viscosity, it can be atomized by compressed air or
mechanically. But better atomization is obtained with steam.
Since generally steam is used for its atomization, F.O. can not be used when
boiler is cold and no other source of steam is available. It is comparatively
cheapter than HSD/LDO but not very cheap. Its calorific value is approximate
10270 kcals/kg.
LSHS is very thick constituent of petroleum. It is highly viscous. It has to be
intensively heated even for unloading from tankers. It is so viscous that it almost
solidifies in winters and becomes coal tar like substance. It is, of course,
cheapter than F.O.

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Oil Combustion Equipment i.e. Oil Burners or Guns

The main purpose of oil gun is to atomize oil in very fine droplets (almost like a
gas). As mentioned above there are three methods of oil atomization viz (a) by
compressed air (b) by mechanical means (c) by steam. Accordingly, basically
three types of guns are used although different manufacturers have designed
them differently. Now a days oil guns are located in the centre of coal burners
and can either be fitted manually when required or can be made to remain
permanently in position with compressed air operated retract mechanism. Air for
oil combustion is supplied through a concentric (to oil gun) pipe from the
secondary air system.
At the tip of this pipe, vanes are provided, which give the air rotary turbulent
motion which helps in proper mixing of air and atomized oil. In older P.F. boilers
with long flame burners, steam atomization oil guns were provided from side
walls i.e. at right angle to burner flame.
Compressed air atomization
Oil is brought to the oil gun tip from central portion and compressed air is
supplied through the annular space of the gun. At the tip, gun assembly is
comprised of an eddy plant or mixing plate having small holes in the central
portion for oil and several holes near the periphery of mixing plate i.e. facing the
annular space, for air. Some of the outer holes are connected to inner holes with
slots for allowing mixing of compressed air with oil. Over this plate comes the
spray plate which is dome shaped and is provided with holes. Both mixing plate
and spray plate are tightened together to oil gun with the help of nozzle cap.
Oil is supplied at a pressure higher than air pressure by about 1-1.5 kg/cm2.
Maintenance of this pressure differential is most essential for proper atomization.

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If the air pressure is less than oil pressure, oil will enter into air passage. Air
atomization is done generally in light oils.
Steam atomization
The arrangement of steam atomization guns is exactly same except steam is
used in place of air and size of holes in mixing plate and spray plate are large to
allow more quantity of oils to be burnt. Steam atomization is used in furnace oil or
still heavier oils. Due to heat of the steam oil viscosity is reduced and oil
becomes free flowing. Since even in coal fired boilers about 20% of initial load is
taken with oil firing, arrangement is provided for controlling the pressure and
quantity of oil flowing through the burner to control boiler output. Due to variable
oil pressure, atomizing steam has also to be supplied at variable pressure so that
steam pressure is maintained about 1-1.5 Kg/cm2 lesser than oil pressure. Steam
consumption is very small (of the order of 1% of boiler output).
Mechanical Atomization
Mechanical atomization is achieved by forcing the oil under pressure through a
sprayer plate and orifice. The oil flows at high pressure in the central tube of oil
gun and is discharged through tangential slots in the spray plate swirling
chamber. This gives jet a swirling motion. Now oil passes through an orifice to
create a hollow conical shaped spray. In this system oil pressure has to be
maintained high about 16 kg/cm2-20 Kg/cm2.
Note
If atomization is not proper, droplets can be carried over under the suction of ID
fan and can deposit on air heater tubes or plates. This deposit can catch fire if air
heaters are not regularly soot blown.

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148

Further oil has high sulphur content, which on combustion turns into SO2 & SO3.
SO3 raises the due point of flue gases and condensation may take place even at
higher temperature in economizer and in heater zones.
Due to condensation of SO3 and moisture formed because of combustion of
Hydrogen of coal, Sulphuric acid is formed. This acid attacks economizer tubes
and air heaters heating surfaces and corrodes them.
Fuel Oil
Following typical Heavy Fuel Oil has been specified for the use in our boilers1.

Standard

IS 1593/1971
Grades LV -MV HV

2.

Flash Point

66OC (Minimum)

3.

Viscosity (Max.)

80-120-370 CST at 50OC

4.

Gross Heating Value

10270 Kcal/kg.

(Typical)
5.

Total Sulphur (Max.)

3.5-4-4.5% by weight

6.

A.P.I. gravity

12 Sp. Gravity 0.986 at 15OC

A coal fired unit contains oil burners having capacity of 15 to 20%.

The functions are:
a)

to provide necessary ignition energy to light off coal burners.

b)

to stabilize the coal flame at low boiler/burner loads.

c)

as a safe and reliable heat input source during light up of boiler.

Following characteristics of fuel oil is considered while selecting-

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Specific Gravity
Ratio of weights of equal volumes of oil and water at 60OF.
In other words specific gravity tells us nothing more than what would be the
weight of given volume of oil.
Viscosity
This is one of the most important factor while selecting oil for burning in boiler.
Viscosity is measured in terms of time in seconds taken for a standard volume of
oil to flow through a standard orifice at specified pressure and temperature.
This is measured in centistokes (CST), Redwood No. 1, say bolt Universal,
Engler cct. Usually all these units are convertible.
Calorific Value
These are heat content of measured quantity of oil. These are expressed in
Kcal/kg or B.T.U./lb.
Flash Point
This is the temperature at which when tested under specified conditions, oil gives
out vapour which will just ignite if comes into contact with a flame. This
determines the storage conditions of oil.
Pour Point
This is the temperature to which when cooled, the oil stops flowing.

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This may be due to crystallization of wax or due to increase in viscosity. The pour
point determines the handling methods of oil.
Sulphur Content
High sulphur content in oil causes low temperature corrosion of AH elements.
At high temperature it burns as
S + O2 ----------- > SO2
With water at lower temperature zones like AH and sometimes economizers it
forms sulphurous acid
H2O + SO ------------ > H2 SO2
This acid is highly corrosive to the metal over which it is deposited.
Methods of Fuel Oil & Lube Oil Analysis
Water % by Dean & Stark (for Petroleum and its product) IS: P-40 ZP-74.
Apparatus
Burner graduated glass trap; suitable condenser (straight condenser with a
length 400 mm and suitable joint) Round bottom flask with suitable joint (250
mm).

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Solvent
The oil sample is thoroughly mixed. Weight 10 gm material directly into the
round bottom flask and add 100 ml solvent. Assemble the components of the
apparatus. Circulate cold water through the jacket of the condenser.
Apply heat to the round bottom flask, adjusting the rate of boiling so that
condensed distillate discharges from the condenser at the rate of 2 to 3 drops per
second. Continue distillation until no water is visible in any part of apparatus
constant for 5 minutes.
When the evolution of water is complete, allow the trap and contents to cool to
room temperature, dislodge any drops of water adhering to the side of the trap
with a glass rod or other suitable means and transfer them to the water layer.
Read the volume of the water in trap.
Calculation
Water Percentage =

Volume of water in trap X 100

---------------------------------------Mass (or volume) of sample

VISCOSITY INDEX

D2270/P56

---------------------------

-----------------

It is the variation of viscosity with temperature, it determines whether the oil

changes its viscosity with temperature or not and if it changes, then the extent to
which it changes is the rate of change of viscosity with temperature. Viscosity
index also measures the paraffinity of an oil as the paraffins have lower rate of
change of viscosity with temperature. This is determined by determining viscosity
at different temperatures.

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L
U
V.I. = ---------------------L
H
L

X 100 (a) V.I. =

L
U
----------------------- X 100
D

Kinematic Viscosity @ 37.8OC of an oil of O viscosity index having

the same viscosity @98.9 OC as the oil whose viscosity index is to
be calculated.

Kin viscosity A 37.8 OC of the oil whose viscosity index is to be

calculated.

Kin. Viscosity A 37.8 OC of an oil of 100 viscosity index having the

same viscosity A98.9 OC as the oil whose viscosity index is to be
calculated.

Calculation
1.

Determine the viscosity in centistokes of the oil A37.8 OC and 98.9 OC.

2.

With the help of Lable obtain the value of L and D.

Example
Given Kin. Viscosity A 37.8 OC

82.50 C.St.

Given Kin. Viscosity A 98.9 OC

9.100 C.St

From table L

138.18

From table D

60.44

Substituting in equation (2)

138.18 82.5 X 100

---------------------------60.44

92.1

V.I.
3.

Viscosity Index Book by ASTM: Sec. chart viscosity A 37.8 OC and 98.9
O

C.

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Oxidation Characteristics of Inhibited Steam Turbine Oil

In this method the oil sample is reacted with Oxygen in presence of water and an
iron copper catalyst at 95

C. Test continues until the measured total acid

number of the oil is 2.0 mg/KOH or above. The number of test hours required for
oil to reach 2.0 mg/KOH is the oxidation life time.

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(B) Lubricating Oils

If surface are separated by a fluid, the friction between them is considerably
reduced and lubricating oil is normally used for this purpose. Good lubrication
aims at retaining the oil film between the moving surfaces. Friction produces heat
and so a lubricating oil is not only required to prevent the surfaces from coming
into direct contact, but also to dissipate the heat from the parts being lubricated.
In the case of turbine plant the heat transmitted along the shafts from the steam
cylinders also has to be removed and this is another requirement of the
lubricating oil.
Before mineral oils were developed in the middle of the last century lubricants
were mostly fats such as tallow, castor oil and olive oil obtained from animals,
fish and plants.
The fatty materials, although reducing friction initially, formed gums and sticky
deposits. As machinery developed, these lubricants were gradually replaced by
mineral oils obtained from petroleum. It is essential that a lubricating oil allows
trouble free operation of the plant in which it is used. Deterioration of the oil
inhibitors may cause rusting in oilways with debris being carried forward into
journals and bearings. Shafts can be attacked by acids formed in the oil, or the
lubricating properties of the oil can be impaired by emulsification which may
result in damage to shafts and bearings. Regular examination of an oil can
indicate its rate of deterioration. Thus the sampling and analysis of lubricating oils
ensures that they are satisfactory for continued service. If an oil beings to
deteriorate, it can be either changed or reconditioned (sometime at site) at a time
suited to the operation of the plant, rather than waiting until deterioration makes
the oil change essential at an inconvenient time.

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Lubricating Oil Requirements for Turbine and Large Rotating Plant

Turbine oil maintenance and examination is covered by generation operation
under 84 (CP) which lays down the recommended tests to be carried out and the
intervals between testing. This applies to all oxidation and rust inhibited oils in
recirculation lubricating system of large plant e.g. feed pumps, gas turbine
generators. The oil supplier is chosen from a limited number of oil companies
which have been approved of both the CE GB and the plant manufacturer.
Changes to the specification of the oil are first examined by the Central Electricity
Research Laboratories (CERL) and these must comply with British Standard BS
489 and also with the CEGS standard 20722.
Sampling of Lubricating Oils
Lubricating oils are delivered to CEGB power stations by tanker or in 205 liter (45
gallon) steel drums. The weighted sampling bottle (Fig. 11.2) is used to sample
the lubricating oil in tankers and storage tanks. Oil contained in a steel drum is
sampled by using a clean, dry, tube, called a thief. The tube is dipped into the oil
and by placing a finger or thumb over the open end a sample is withdrawn and
put into a sample bottle.
Properties of Lubrication Oils
The increase in the size of turbines and generators has resulted in higher
loadings of bearings and higher peripheral speeds of journals and the duty the oil
is required to perform has become increasingly arduous. It has to withstand
continuous thermal cycling and possible contamination by solid particles, sludge,
water hydrogen and air.

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It is expected to readily release such contaminants and retain its lubricating and
other properties over very long periods. New oils are expected to last 20 to 30
years.
A lubricating oil may deteriorate for several reasons. It can:
1.

Increase or decrease in viscosity

2.

Oxidise

3.

Become contaminated with water

4.

Lose its rust inhibitor

5.

Foam

6.

Emulisity

7.

Become Acidic

8.

Become contaminated by dirt or metallic particles

Any of the above may cause damage to any lubricated part of the plant. The
tests carried out are designed to pinpoint the type of deterioration and cause so
that remedial action can be taken. In a nuclear station lubricating oils used in gas
circulators and drives in the vicinity of a reactor can become irradiated and so
deteriorate. Lubricating oils are manufactured specifically for these applications
and only oils resistant to damage by radiation, should be used.
1.

Viscosity
If the viscosity decreases the oil film between the moving surfaces could
become so thin that the surfaces actually touch each other. A shaft would
then rub directly on its bearing causing damage from abrasion and
overheating. If the oil viscosity increases, the thickening oil makes it more
difficult for a shaft to revolve in a bearing i.e. the friction is increased. Thus
it is important that lubricating oil is kept within its design temperatures.

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Variations in viscosity can occur by thickening of the oil with age or by

mixing with an oil of different viscosity. Therefore viscosity measurement
is most important
The viscosity of a lubricating oil can be measured in a Redwood
viscometer or more usually in a U tube viscometer immersed in a bath at a
constant temperature.
The U tube viscometer is filled to the mark A with the oil under test. The
tube is placed in the water bath which is at 40OC until the oil and tube
have reached that temperature. Oil is then drawn up into the right hand leg
above mark B by applying suction to the open end E. the suction is
removed and the oil allowed to fall through the capillary F. A stopwatch is
used to record the time taken for the oil to drop from mark B to mark C.
The viscosity of the oil is calculated from the time recorded and expressed
in centistokes (CST) as the kinematic viscosity at 40 OC. Some figures for
viscosities of lubricating oils are given in table.
These are taken from British Standard 489 which the CEGB uses for all
mineral oil lubricants.
Table
Lubricating oil viscosities
--------------------------------------------------------------------------------------------------Grade
Grade Number
Viscosity in centistokes at 40 OC
--------------------------------------------------------------------------------------------------Minimum
Maximum
----------------------------Light
32
28.8
35.2
Medium
46
41.4
50.6
Heavy
68
61.2
74.8
Extra
100
90.0
110.0
---------------------------------------------------------------------------------------------------

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The viscosity of all oils does not alter by the same amounts for the
equivalent temperature change. If the viscosity of an oil remains fairly
constant when its temperature is altered it is said to have a high viscosity
index. On the other hand the viscosity of an oil within low viscosity index
changes appreciably as the temperature is altered. It is desirable to use
an oil with a high viscosity index in a pump or motor that is used only now
and again i.e. it is subject to temperature changes between running and
stopping periods. However, a pump or motor that runs continuously and
so remains at a rarely steady temperature, can be lubricated with an oil
having a low viscosity index.
2.

Oxidation Stability
An oil becomes oxidised when the various compounds which make up the
oil combine with oxygen. The compound formed as a result of this
oxidation are usually fairly thick and sludge-like in quality. As well as
increasing the viscosity of an oil sludges can block small bore pipes and
orifices in a lubricating system and so their formation should be avoided. If
metal or rust particles occur in an oil the rate of oxidation is increased.
Additives called oxidation inhibitors are added to lubricating oils to
stabilize them against oxidation. These inhibitors passivate any metals
present in the oil and so make them ineffective. As an oil becomes
oxidised its acidity increases. It is better to anticipate any oxidation that
might occur rather than wait until the acidity has increased or sludges
have formed. Oxidation stability tests are carried out on CEGB steam
turbine oils at six monthly intervals to provide advance warning of this type
of deterioration.

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3.

Water Contamination
Water in steam turbine oils usually comes from the turbine glands,
although it could come from a leak in an oil cooler. Sea or river water is
often used for lubricating oil cooling. An oil cooler leak may result in the
sea or river water entering the oil system which can cause the oil to
deteriorate by forming rust and other corrosion products, by forming
emulsions with the oil, and by forming other chemical compounds which
cause sediments in the oil. A steam turbine oil in good condition will
contain between 100 and 200 mg. of water and will appear clear. If the oil
appears cloudy, the level of water contamination should be measured by
boiling a known volume of the oil with a solvent in a flask known as the
Dean and Stark apparatus. Droplets of condensed water vapour fall into
the graduated tube and the volume of water is read directly as a
percentage.

4.

Rust Inhibition
Many oils have inhibitors added to prevent rust formation. Rust can block
pipes, choke filters and score bearings. An anti-rust test is applied to an oil
to determine its ability to resist the formation of rust. The results of the test
are reported as absent, light, moderate or severe. An oil which has
produced rusting, even if only light, fails the test. If this occurs further rust
inhibitors are added, usually supplied by the oil company.

5.

Emulsions
When water is churned up with an oil, initially it turns cloudy and then
begins to cream forming an emulsion. If the oil does not demulsify, i.e. the
emulsion persists and the water and oil do not separate, it is said to have
poor demulsification characteristics. Good oils, however, do demulsify,

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and the speed with which an emulsion breaks up is known as the

demulsification number.
An oxidized oil forms emulsions much more easily than a new oil. Rust,
metallic particles and dirt not only accelerate oxidation but also accelerate
the formation of emulsions. Lubricating properties of an oil can be
impaired by emulsions rupturing the bearing oil film and blocking small
passages in the lubricating system.
6.

Foams
Foams are produced by large amounts of air becoming constrained in an
oil. Additives and inhibitors added to the oil to suppress other effects may
cause foam formation to increase. Anti-foam agents are added to
lubricating oils, although it is critical to limit these to a maximum 0.003%
otherwise foaming may be increased.

7.

Acidity
After a lubricating oil has been in service for sometime it tends to oxidize
into acids. Acids are obviously undesirable because they cause corrosion
of metals in the pipework, bearing and other parts of the lubricating
system. The oxidation stability test gives advance warning of this type of
deterioration, nevertheless lubricating oil acidities are measured since
small amounts of acid can be tolerated.
Oil acidities are measured at monthly intervals whilst oxidation stability is
measured only every six months because the acidity test takes less time
to perform. In pumps and motors where small volumes of lubricating oil

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are involved, it is often more economical to determine acidity in preference

to oxidation stability.
Oil acidities are measured by neutralizing the acidity with an alkali, usually
potassium hydroxide, in a known weight of oil. The acidity is then
expressed as milligrams of potassium hydroxide per gram of oil (mg
KOH/g oil).
8.

Contamination by Dirt and Metallic Particles

These insoluble contaminants cause rust, accelerate oxidation, increase
the acidity and increase the formation of emulsions. The contaminants
should be removed by the filters, centrifuges or oil purifiers in the turbine
lubrication system. In other large rotating plants such as pumps and
motors similar safeguards may not be installed so the contaminants
remain in the oil and can cause deterioration.
The test carried out measures the total amount of insoluble organic or
inorganic material in oil. The organic material is generally caused by
degradation of the oil and the inorganic material comes from wearing or
corrosion of the metal parts of the lubrication system.
100 gm of the oil to be tested is diluted with 300 cm3 of reptane solvent
and left for two hours. The mixture is filtered through a fine glass mesh
which is weighed before and after the filtration.
The filtrate, the liquid which passes through the filter, is rejected. The
residue, the material which remains on the filter, consists of organic and
inorganic material. Chloroform acetone and alcohol are then poured
successively over the residue, to dissolve all the organic materials. The
glass filter is weighed again and the amount of inorganic material can be

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determined. The organic and inorganic material in the oil is then

expressed as a percentage.
Other Properties

Lubricating oils are also analysed for various other properties to check their
quality. These are mentioned briefly.
Appearance

A great deal of information on the quality of an oil can be obtained by visual

inspection. For example, the British Standard 489 states that steam turbine oils
shall be clean and free from water, suspended material, dirt, sediment and other
impurities. If an oil sample in a clear glass bottle is held up to the light, all these
impurities can be seen. Even small traces of water will make the oil appear
cloudy.
Flash Point

This is determined on a lubricating oil in exactly the same way as we described

earlier for a fuel oil. The minimum accented flash point, determined on a panskymartins apparatus, for a steam turbine oil is 166OC and any value lower than this
indicates contamination.

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(C) Insulating Oils

Oil is a better insulator of electricity than air. Switchgear, circuit breakers and
transformers operating at high voltages can be made more compact if filled with
oil, rather than relaying on an air gap to prevent arcing or flash-over between
contacts. Oil in transformers is also used as a coolant to transmit heat from the
windings to the cooling surfaces where it is dissipated. In this aspect insulating oil
is similar to lubricating oil, which is used as a coolant as well as a lubricant. Oil
used as an insulator has to be very pure; impurities in oil act as a conductors (in
the same way as impurities in water) and the chemist often has to test the oil and
analyse any impurities to discover from where they are coming, what is causing
them and how to cure the problem.
Insulating oils are very vulnerable to oxidation because of the heat and electric
arcing that is liable to occur in transformers and switchgear. As we saw with
lubricating oils, oxidation is accompanied by an increase in acidity, corrosion
products and sedimentation. These impurities and water which may leak into an
insulating oil or be formed by condensation, are the main causes of oils losing
their insulating properties.
The voltage at which an insulating oil causes to act as in insulator (its breakdown
voltage) is called the dielectric strength of the oil. This is sometimes measured by
the chemist in his laboratory but in many power stations this test is carried out by
the Electrical Department personnel. The other analysis that a chemist performs
on insulating oils are flash point, acidity, viscosity (which are determined as for
lubricating oils) and moisture content. The minimum flash point for an insulating
oil should be 146.1OC if British Standard BS 184 used by CEGB is to be adhered
to. A lower flash point can indicate that combustible gases formed by severe
electric arcing and oil decomposition in a transformer, have dissolved in the oil.

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These gases include hydrogen, acetylene, and methane. In some power stations
the individual gases are tested for, by using a gas chromatograph as already
described under natural gas analysis. Acidity should be below 0.2 mg/KOH/g oil
as in the case of lubricating oils.
The viscosity of an insulating oil should be below 37 centistokes at 21OC so that
the oil can move freely within a transformer. Convection currents will then be able
to carry the hot oil from the core to the cooling surfaces. This test is not
performed regularly, as viscosity is very rarely a cause of insulating oils
becoming ineffective.
The presence of moisture in an insulating oil is indicated by the simple but
sensitive crackle test. To carry out the test about 30mm (1 in) oil are poured
into a clean dry test tube. The tube is then heated until the oil boils. If the oil
contains any moisture an unmistakable cracking occurs. A similar sound is heard
when damp chipped potatoes are thrown into boiling fact in a chip pan. Amounts
of water as low as 30 ppm can be detected by the crackle test.
Moisture and other impurities such as dirt, sediment and corrosion products can
be removed from an insulating oil by filtering the oil in a special filter press. The
press is connected to the transformer and the oil circulated through the filter until
all the impurities have been removed. The advantage of this method is that the
oil does not have to be withdrawn from the transformer and later filtered in a
separate operation.

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7. Hydraulic Fluids
Mineral Oil Hydraulic Fluids
These fluids, in being of mineral origin, are similar to the oils used for lubrication
or insulation. They are soluble in water, forming emulsions and are used where
not many moving parts are involved. Mineral oil hydraulic fluids are cheap, but if
leaks occur in the hydraulic system, these fluids present a definite fire hazard,
particularly at elevated temperature.
Water/Glycol hydraulic fluids
These fluids are better than mineral oils where greater oiliness is required. As
they contain water, they are also reasonable fire resistant. At elevated
temperatures, however, the water tends to evaporate and the fluids become
thicker and sticky. A check on the viscosity of a water/glycol hydraulic fluid will
show if the quality has deteriorated and if necessary, water can be added to
restore the fluid to its original consistency. These fluids are more expensive than
the soluble mineral hydraulic oils.
Synthetic Hydraulic Fluids
Included in these man-made products are hydraulic fluids with chemical names
such as chlorinated hydrocarbons and phosphate esters. These have a high
resistance to fire and so are used in boiler dampers and other systems where
high temperatures are encountered.
Unfortunately, synthetic hydraulic fluid cost about eight times as much as mineral
oil hydraulic fluids and the synthetic fluids also tend to attack sea or other similar
parts in a hydraulic system.
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8. Other Chemical Aspect Of Power Plant

The chemist in a power station is responsible for certain items of plant and the
qualities of materials in addition to these which we have mentioned in the
preceding sections of this lesion. We shall only outline these now, because they
are mentioned in greater detail elsewhere in the course.
Stator Coolant
Certain designs of generator stators employ water as a coolant. We have already
explained that water with dissolved impurities is a good conductor of electricity.
Impure water, therefore, could not be used with any degree of safety to cool a
stator and so stator coolant water is demineralized. The demineralization process
is exactly the same as described earlier in the lesson and the chemist must
ensure that the water is always the best possible quality.
Circulating Water
The water used to cool condensers in both conventional and nuclear power
stations is usually drawn from a river, an estuary or the sea. Cooling towers may
be installed if the volume of available flowing water is inadequate to supply the
cooling needs of the power station.
The circulating water from any of the three sources mentioned above will contain
certain organism (pieces of plant or animal matter) which could adhere to the
insides of tubes in condensers, oil coolers and other heat exchangers in a power
station. Much of this matter is removed mechanically by screens fitted into the
circulating water system but the tiny organisms pass through the screens. Once
inside the system the organisms could grow in the warm temperatures of the
heat exchangers and this could seriously affect the efficiency of the cooling.
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The chemist takes many samples of the cooling water in the early stages of the
running of a power station and decides on the best method of dealing with the
organisms in the water. Chlorine is usually added to the cooling water to kill the
organisms, and the chemist will decide how much and how often the chlorine
should be added.
He regularly samples and tests the cooling water of an operating power station to
ensure that sufficient, but not too much, chlorine is being added to maintain the
system in a clean condition.
In estuarine power stations mud or sand may tend to build up in cooling systems.
The mud may contain organisms. Corrosion can occur under mud or other
deposits and erosion (wearing away by rubbing) can be caused by sand.
Mechanical aids are commonly installed to remove these deposits, but at some
power stations the chemist is responsible for removing the mud by chemical
means.

predetermined

amount

of

chemical

compound

called

polyelectrolyte is added to the circulating water.

Polyelectrolytes do not split up to give equal number of cations and anions as do
salts which undergo normal ionization. A polyelectrolyte is charged either entirely
positively or entirely negatively. Mud particles are usually charged negatively
and, as they all have the same charge, they repel each other and settle slowly as
very many fine particles which eventually build up into heavy deposits. The
addition of a polyelectrolyte (in this case a positively charged polyelectrolyte)
attracts the mud and neutralizes the mud particles. The mud particles, which are
now neutral and no longer repel each other, come together and form flocculent
masses. These remain in suspension and travel with the cooling water, instead of
precipitating in the cooling water system. The chemical treatment using a
polyelectrolyte is expensive and has met with varying success.

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Condenser Scaling
Another problem encountered by stations using river water particularly with
cooling tower has been scaling of the condenser tubes.
Previously some stations suffered from calcium carbonate scaling which was
easily controlled. In recent years however, the picture has changed and many
stations are suffering from calcium phosphate scaling.
The change in composition of the scale is due entirely to a change in the river
composition.
A number of potential remedies are being explored. These include the use of
proprietary chemical additives, pH control, ultrasonic, mechanical solutions e.g.
Taprogge and chemical cleaning.
At present most stations are carrying out chemical cleaning as necessary and
some stations use pH control by adding concentrated sulphuric acid to the
circulating water.
Flue Gas Analysis
Most conventional power stations have automatic analysers installed in the boiler
flue gas outlets to measure the concentration of carbon dioxide or carbon
monoxide or oxygen, so that the efficiency of combustion in the furnace can be
assessed. From time to time these automatic analysers are checked either by the
efficiency of engineer or the chemist. The concentration of these gases can be
measured either on a gas chromatograph (as explained in the natural gas
section) or by using a cheaper portable piece of equipment called an orsat
Apparatus.

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The concentration of sulphur dioxide in the flue gas can also be measured
automatically and most oil-fired stations have sulphur dioxide meters installed in
the outlets from their furnaces.
Stator Polishing Unit
Introduction
Stator winding cooling is carried out by passing DM Water from expansion tank.
This tank is kept at a vacuum of 250-300 mm of Mercury. Due to low pressure
existing, the DM water is stripped of dissolved oxygen and CO2. These dissolved
gases are highly corrosive and objectionable to the conductor metal.
Stator Water cooling is a closed loop system designed to maintain a constant
flow of cooling water to the Stator Winding at a specified range of inlet
temperatures with the aid of pump and coolers.
Description of the Unit
1.

Stator polishing unit is a conventional mixed bed exchangers using

strongly acidic cation and strongly basic anion exchange resins. These are
cylindrical, vertical MS shall rubber lined from inside and containing equal
volume of cation and anion resins. Functionally these polishing units
remove ionic impurities & also act as filters to remove any particulate
matter. At the end of the service run which is indicated by high
conductivity or increase in copper content of effluent water, resin bed is
regenerated by using hydrochloric acid and sodium hydroxide, for easy
mobility. The unit is trolley mounted so that regeneration is carried out in
WTP building. This is done to avoid handling of acids and alkalis in turbine
hall.

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Associated Equipments
The DM Water from DM Plant is pumped directly in a hermetically sealed
tank where vacuum of 250-300 is maintained. The vacuum is maintained
by connecting the tank to the outlet of water box of condenser cooling
water. An additional ejector is also provided to the tank. The material of
construction of the tank and associated pipelines is stainless steel.
Water Coolers
The

Stator cooling water coming out from the winding has a high

temperature. The water is cooled by two 100% duty water coolers. The
stator water passes through the outer surface and the secondary cooling
water (it may be DM Water, or clarified water) passes through the tubes.
The entire system includes other equipments such as circulating Pump,
Strainers, magnetic filters etc.
Instrumentation
i)

Flow Indicators & Recorders

Flow measuring instruments are provided. At specified low flow the
unit trips.

ii)

Specific Resistively Instruments

The purity of stator cooling water is monitored by these instruments
and at low resistively the unit trips.

iii)

Temperature Measuring Instruments

The temperature of the inlet water to the stator winding and that of
the outlet water from the windings is monitored.

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TYPICAL DATA OF SPU

(Figures given are nominal)
1.

D.M. Water required for cooling

25 M3/hr

2.

Pressure at inlet to winding

4.0 kg/cm2

3.

Quantity of water per coolers

110 25 M3/hr

4.

Pressure drop of water through coolers

0.8 kg/cm2

5.

Cooling Water inlet temperature to winding

40OC 45OC

6.

Specific Resistivity

200 K. ohm/cm

7.

pH of inlet water to stator winding

6.5 7.5

8.

Dissolved Carbon dioxide

Nil

9.

Dissolved Oxygen

less than 0.2 ppm

10.

Total Iron content

0.02 ppm max

11.

Chlorides

Nil

12.

Copper content

0.02 ppm max.

PMI, NTPC

172

9. Model Session Plan

POWER PLANT CHEMISTRY

DAY

1.

DURATION : WEEK

SESSION

SESSION

I & II

III & IV

Various impurities in water & Water

need for Water treatment.

treatment

process

&

Regeneration of ion exchange

beds.

2.

Boiler

water

treatment

for Sampling and analysis of coal,

conventional & once thro boilers.

ash, fuel oil, lub. Oil, Hydraulic

fluids and flue gas.

3.

Mechanical
treatment

and
for

deaeration

combating corrosion

PMI, NTPC

Chemical Condenser Leak detection and

& chemical treatment. Sampling &
analysis of H2 & its purity control.

173