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Power Plant Chemistry: Power Management Institute Noida
Power Plant Chemistry: Power Management Institute Noida
Power Plant Chemistry: Power Management Institute Noida
POWER PLANT
CHEMISTRY
1. Fundamental Concepts 1
3. Combating Corrosion 69
6. Oil 145
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.
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.
© PMI, NTPC 1
Chemical Calculation
One molecule of Oxygen reacts with two molecules of Sodium Sulphite to form
two molecules of Sodium Sulphate.
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.
© PMI, NTPC 2
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).
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.
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
© PMI, NTPC 3
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
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:
© PMI, NTPC 4
Stage Solution Example
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
© PMI, NTPC 5
more soluble at low temp that an high temp. At higher pressure, it is more soluble
than at low pressures.
Ionization
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
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.
© PMI, NTPC 6
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.)
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.
© PMI, NTPC 7
H2CO3 H++ H2CO3 – (K = 3x10-7)
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.
© PMI, NTPC 8
ionization constant. For example, the ionization of a sodium chloride can
be expressed by the following reaction:
The ionization constant formula for this reaction can be written as follows:
Water
The 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).
© PMI, NTPC 9
(b) Weak Bases
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:
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.
© PMI, NTPC 10
and calcium nitrate,
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
© PMI, NTPC 11
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-)
K1 = --------------------- = 1.8 x 10-16
(H2O)
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:
b) Definition of pH
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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:
1
pH = log --------
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)
© PMI, NTPC 13
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 1 2 3 4 5 6 7 8 9 10 11 12 13
SUBSTANCES SUBSTANCES
CONTRIBUTING CONTRIBUTING OH-
H+ OR LIBERATING OR LIBERATING
H+ FROM WATER OH- FROM WATER
INCREASING H+
------------------------------------------------------------------------------------------------------------
THE PRODUCT OF H+ & OH- CONCENTRATIONS IS A
CONSTANT INCREASING OH-
------------------------------------------------------------------------------------------------------------
© PMI, NTPC 14
d) Measurement of pH
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Table 1 - RANGE OF pH
PH H+ OH-
Moles/liter Moles/liter
-1
Increasingly ) 1 0.1 = 10 10-13
Acid ) 3
Solutions ) 5 10-5 10-9
Neutral ) 7
Increasingly ) 9 10-9 10-5
Basic ) 11
Solutions ) 13 10-13 0.1 10-1
© PMI, NTPC 16
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
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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
© PMI, NTPC 18
c) Using Conductivity to Measure Concentrations
d) Measurement of Conductivity
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conductivity, then, is equal to the conductance (measured at 25OC)
multiplied by the cell constant.
© PMI, NTPC 20
2. Raw Water And Its Softening Process
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
Rain 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.
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.
© PMI, NTPC 22
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
© PMI, NTPC 23
real problem to ensure that this quality is consistently maintained, with regard to
silica.
Impurities
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.
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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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.
Gaseous Impurities
Out of the atmospheric gases found in natural water only Carbon dioxide and
oxygen are the main causes of many corrosion problems.
a) Scale Formation
© PMI, NTPC 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.
© PMI, NTPC 26
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:
The positively charged metallic ion react with negative (OH)- ions to form
the hydroxide 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
© PMI, NTPC 27
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:
© PMI, NTPC 28
RAW WATER
AERATION
COAGULATION
&
CLARIFICATION
ANTHRACITE
FILTER
ACTIVATED CARBON
FILTER
CATION
EXCHANGER
DEGASSER
ANION
EXCHANGER
MIX BED
EXCHANGER
D.M.
WATER
© PMI, NTPC 29
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.
Lime/Soda Softening
© PMI, NTPC 30
1. Ca(HCO3)2 + Ca (OH)2 -----------------> 2Ca CO3 + 2 H2O
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.
© PMI, NTPC 31
magnesium must then be associated with the chloride, sulphate and other
anions present and this is known as the permanent hardness or non-
alkaline hardness.
Note
© PMI, NTPC 32
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
© PMI, NTPC 33
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.
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.
To illustrate the various possibilities in greater detail, following three main types
are more fully described:
© PMI, NTPC 34
(a) Conventional Cold Softener
© PMI, NTPC 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.
© PMI, NTPC 36
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.
© PMI, NTPC 37
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.
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.
© PMI, NTPC 38
Ca (HCO)2 + Ca (OH) 2 --------------------------Æ 2CaCO3 + 2H2O ……………. (5)
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.
1. Compact size.
© PMI, NTPC 40
that some improvement in performance has resulted from the addition of
about 5 ppm of ferrous sulphate to the raw water.
Demineralization
Thus :
© PMI, NTPC 41
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:
a) Cation-Exchange Resins
© PMI, NTPC 42
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:
© PMI, NTPC 43
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 cross-
linking 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 by
copolymerizing methacrylic acid with divinyl benzene directly:
© PMI, NTPC 44
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,
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.
(b) With a primary amine, R ----- NH2; secondary amine basic group
N
----------------- C ----------CH2 are produced
H
© PMI, NTPC 45
R
c) With a secondary amine NH territory amine groups,
R1
R
--------------- C ----------CH2 -------N are produced.
R1
R1
are produced.
© PMI, NTPC 46
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:
In demineralization plants, the cation and anion exchange resins are often
contained in separate to columns or units and the design of these ion-
exchange 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.
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
© PMI, NTPC 47
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.
Fig. No. 6
© PMI, NTPC 48
d) Strong and Weak Resins
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 multi-
stage 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.
© PMI, NTPC 49
The data given in Table illustrates these differences in exchange capacity
and regeneration efficiency.
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 anion-
exchange 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).
© PMI, NTPC 50
Type- I Type – II
CH3 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.
© PMI, NTPC 51
a) Cation Units
b) Anion Units
© PMI, NTPC 52
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
90 1 ½% 2 ½% 3 ½%
Acid Acid Acid
80 ----------------------------------------------------
70
Total hardness % of total
60
50 1½%
Acid
40
30 2 ½% 3 ½% 4 ½%
Acid Acid Acid
20
10
10 20 30 40 50 60 70 80 90
© PMI, NTPC 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.
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.
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
© PMI, NTPC 54
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.
Fig No.: 7
PERMIT MIXED BED.
© PMI, NTPC 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.
The water flow rates acceptable for a mixed bed unit with different
methods of regeneration are given in Table.
© PMI, NTPC 56
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
e) Regeneration Equipment
© PMI, NTPC 57
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.
© PMI, NTPC 58
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:
© PMI, NTPC 59
(b) The degree of de-ionisation required, that is, the quality of the final feed
water.
© PMI, NTPC 60
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.
© PMI, NTPC 61
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 bed’s 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.
© PMI, NTPC 62
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.
2. Setting
© PMI, NTPC 63
3. Regeneration
4. Cation
Anion
5. Rinsing
© PMI, NTPC 64
Volume used
Cation
Anion
Mixed Bed
© PMI, NTPC 65
HCl - 145 Kg. 30% HCl
NaOH - 128 Kg. (100%)
Hcl - 30% - 5%
NaOH - 48% - 6%
Regeneration steps for cation, Anion & Mixed bed exchangers are shown
below with the help of following schematic diagrams.
© PMI, NTPC 66
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
© PMI, NTPC 67
© PMI, NTPC 68
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.
© PMI, NTPC 69
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:
© PMI, NTPC 70
B. The formation of unwanted substances within the circuit. The unwanted
substances depend partly on the type of the boiler.
- 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.
- In the event of a failure, to ascertain the cause after the event with the
help of recorded data.
- Inhibitation of corrosion.
© PMI, NTPC 71
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.
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 initial reaction then proceeds further. The electro chemical reaction can be
summarised.
© PMI, NTPC 72
Corrosion can be stopped by the removal of dissolved oxygen.
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.
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.
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
© PMI, NTPC 73
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
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
© PMI, NTPC 74
stations to seal only their high pressure heaters where the corrosion is most
serious.
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.
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
© PMI, NTPC 75
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.
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:
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.
© PMI, NTPC 76
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.
© PMI, NTPC 77
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.
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
© PMI, NTPC 78
7 ½ Ammonia and 2 ½ 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.
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.
© PMI, NTPC 79
Recommended Feed Water Limits
© PMI, NTPC 80
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.
On load corrosion
Carry over causing superheater and turbine deposits
© PMI, NTPC 81
The chloride impurities and in particular magnesium chloride chemically react
with the water, in a process called hydrolysis to form hydrochloric acid.
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.
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
© PMI, NTPC 82
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.
© PMI, NTPC 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.
© PMI, NTPC 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 (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.
© PMI, NTPC 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.
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.
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
© PMI, NTPC 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.
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.
© PMI, NTPC 88
Condensate polishing
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.
© PMI, NTPC 89
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.
© PMI, NTPC 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.
-----------------------------------------------------------------------------------------------------------
BTPS SSTPP KSTPP RSTPP
MCR NCR MCR NCR MCR NCR MCR NCR
-----------------------------------------------------------------------------------------------------------
Drum press 151 148 152 166 163
2
(kg/cm )
© PMI, NTPC 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/
at 25OC in s/cm) shift
after passing through
cation exchange in H+
form.
3. Total Hardness B.D.L. once/ B.D.L.Below Detect-
(ppm as CaCO3) shift able Limit
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
------------------------------------------------------------------------------------------------------------
© PMI, NTPC 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
3-
4. Phosphate (as ppm PO4 2-4 Once/ Any or mixture of
shift tri, di or Mono
sodium phosphate
sodium Hexa-
phosphate 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
7. Silica (ppm SiO2) 0.4 (BTPS) Once/
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 2 3 4 5
------------------------------------------------------------------------------------------------------------
1. pH at 25OC 9.0-9.2 Once/
shift
2. Specific Conductivity 0.3 Once/ Once/day if in-line
O
at 25 C (us/cm) 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
------------------------------------------------------------------------------------------------------------
© PMI, NTPC 94
(D) Return Condensate (Sample from Condensate Extraction pump
discharge)
------------------------------------------------------------------------------------------------------------
1 2 3 4 5
------------------------------------------------------------------------------------------------------------
1. pH at 25OC 9.0-9.2 Once/
shift
2. Specific conductivity 0.3 Once/
O
at 25 C ( s/cm) 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 2 3 4 5
------------------------------------------------------------------------------------------------------------
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 2 3 4 5
------------------------------------------------------------------------------------------------------------
1. pH at 25OC 6.8-7.2 Testing
frequency to
2. Specific conductivity 0.2 be for WTP of
O
at 25 C (us/cm) 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)
------------------------------------------------------------------------------------------------------------
© PMI, NTPC 96
(G) Generator Stator Cooling Water:
------------------------------------------------------------------------------------------------------------
1 2 3 4 5
------------------------------------------------------------------------------------------------------------
1. pH at 25OC 7.0-7.2 Once/day
2. Specific Conductivity 1.0 Max. Once/day This value S.O.
at 25OC (us/cm) (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.
© PMI, NTPC 97
5. Coal And It’s Analysis
What is Coal
Coal may be defined as that part of the earth’s 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.
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.
© PMI, NTPC 98
Coal Resources & Demand Pattern
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.
© PMI, NTPC 99
Classification of Coal
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.
Seyler’s 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.
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.
Coal Sampling
Any Management requires to know for its power stations the quality:
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.
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.
A 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.
Proximate Analysis
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
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
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 ½%
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.
Table
------------------------------------------------------------------------------------------------------------
Element Mixture of compound in Amount of compound
Which element appears present in ash
------------------------------------------------------------------------------------------------------------
Silicon Silica or Silicates 50-90%
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:
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.
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.
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.
Procedure
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 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
As a safety precaution the firing key should be operated from a position at some
distance away from the calorimeter.
Corrections
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 regularly—at 3-5 year interval usually—and
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.
(Tc x H) – Cf-Cs-Cn
CV = -----------------------------
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.
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:
(CV X g) + Cf + Cn
H= ----------------------------
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.
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.
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.
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:
Organic sulphur is combined with the carbon and nitrogen to form the coal
substance. In consequence it is not removable by cleaning.
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.
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 gas-
side boiler fouling resulting was observed. This aspect is discussed, with ash and
sulphur contents, in a later section.
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.
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 high-
temperature tube method, cutting down the combustion time from 2h to 9 min
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.
(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
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.
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.
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).
As with other instrumental techniques there are the plant –scale problems of
taking and handling a representative coal sample.
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
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 it—a 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
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
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.
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.
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
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 non-
coking 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 techno-
economically viable.
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.
------------------------------------------------------------------------------------------------------------
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
Ash Characterisitcs
------------------------------------------------------------------------------------------------------------
Ash Characteristics Unit Purewa Purewa Bottom Turra
Top seam seam seam
------------------------------------------------------------------------------------------------------------
Silica (SiO2) % 60.9 64.6 56.66
Anhydride
(SO2)
(By difference)
------------------------------------------------------------------------------------------------------------
Hard Grove Index 50-64
TempOC
PointOC
Combustion
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.
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.
1. Thorough mixing of fuel and air in proportions which will ensure complete
combustion i.e. there should be turbulence in furnace.
Thus there are three Ts which are essential requisites for efficient combustion
and therefore fuel combustion equipments & furnaces are designed to ensure
these conditions.
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.
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
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.
1
---------------- = 4.32 lb. of air
0.2315
Since one lb. of carbon requires 2.67 lb. of oxygen one must supply.
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.
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:
O2 - ½ CO
Percentage of excess air - ----------------------- X 100
0.263N2 + ½ CO-O2
O2
Percentage of excess air - ----------------------- X 100
0.263N2 - O2
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.
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.
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:
Regents
a) Potassium Hydroxide solution for CO2. Dissolve 40 gms of KOH in
100 ml of distilled water.
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 over-
loaded 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
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
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.
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
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.
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.
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.
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.
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.O’s 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.
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.
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.
Steam atomization
Mechanical Atomization
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.
Fuel Oil
Following typical Heavy Fuel Oil has been specified for the use in our boilers-
1. 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
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.
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.
Sulphur Content
Water % by Dean & Stark (for Petroleum and its product) IS: P-40 ZP-74.
Apparatus
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
Volume of water in trap X 100
Water Percentage = ----------------------------------------
Mass (or volume) of sample
Calculation
1. Determine the viscosity in centistokes of the oil A37.8 OC and 98.9 OC.
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
V.I. = 92.1
3. Viscosity Index Book by ASTM: Sec. chart viscosity A 37.8 OC and 98.9
O
C.
In this method the oil sample is reacted with Oxygen in presence of water and an
O
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.
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.
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.
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.
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.
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
---------------------------------------------------------------------------------------------------
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.
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,
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
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 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).
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
Other Properties
Lubricating oils are also analysed for various other properties to check their
quality. These are mentioned briefly.
Appearance
Flash Point
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.
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.
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.
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.
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.
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
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.
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. A predetermined amount of a chemical compound called a
polyelectrolyte is added to the circulating water.
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.
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.
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.
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