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CHAPTER-1

WATER TREATMENT PLANT


INTRODUCTION

The source of water supply are generally river, ponds, lakes, sea or bore well etc.
Natural water always contains impurities in the form of floating solids, suspended solids,
colloids, dissolved gases, liquids, etc.

In most of the industrial and domestic application, water cannot be used in as


received condition. It requires treatment. Impurities vary with source and depending upon
the end use extent and mode of treatment is decided. In India most of the power plants use
river water. The impurities present in river water can be broadly classified into following
groups:

1. Floating solids
2. Suspended solids
3. Colloids
4. Dissolved solids
5. Dissolved liquids, gases, etc.

In case of thermal power station, most objectionable impurities of water are


dissolved solids, as dissolved solid gives scale or deposition problem. Liquids and gases
are not taken seriously at this Stage. To avoid scaling, deposition and corrosion
problems, modern high-pressure boiler feed make up water needs more or less complete
removal of suspended as well as dissolved solids from water.

REMOVAL OF IMPURITIES

Floating solids are removed before hand at the river intake by screening. Suspended
solids, colloids, organic matters are removed in pretreatment and dissolved solids are
removed in D.M. Plant. So the water treatment plant has two sections. One is pretreatment
and another is post treatment (D.M. Plant) plant.

PRETREATMENT PLANT

Depending upon the impurities present in source water pretreatment plants are
designed. Normally following processes are carried out in pretreatment

(i) Screening
ii) Storage of raw water
(iii) Aeration
(iv) Chlorination
(v) Coagulation and flocculation
(vi) Filtration

In common terms clarification involving coagulation, flocculation followed by filtration


are called pretreatment.

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Of the above processes storage of raw water, aeration and chlorination may or may
not be observed depending upon the requirement. In case of ground water, since it
contains high dissolved solids but very less suspended solids etc it may be directly taken to
the D M Plant after filtration if needed.

SCREENING

Coarse screens are provided at river intake to prevent floating material of fairly large
size entering the works. The steel bar forming the screen are normally quite substantial
(about 25mm Dia) and are spaced about 100 mm apart. They are often placed on slight
inclination from the vertical to facilitate raking. Sometimes the bars are mounted in frames
which are duplicated so that one frame can be lifted for clearing or repair without admitting
unscreened water to the plant. The velocity of water through the screen openings should not
exceed 0.5m/s.

Fine screens are also normally fitted immediately after the coarse screens, the orifices
of which are generally of the order of 6mm. It is now common practice to install one of the
many proprietary forms of mechanical screen (also called traveling water screens), which
are constructed on the endless band or drum principle and cleaned continuously by water
jets which wash the straining away along channels.

RAW WATER STORAGE

In many instances and for various reasons, raw water is stored for appreciable
periods. In all such cases, an improvement in the raw water quality is noticeable purely as a
result of retention of water provided. The storage provided is for 7-15 days of the average
water demand. This is sufficient of to reduce pathogenic bacteria suspended solids and river
algae, while at the same time not long enough to encourage other organisms to develop.

PRE CHLORINATION

This is a practice of injecting chlorine into the raw water soon after it enters the plant,
generally at a dosing rate of 2-5mg/1. This destroys the high bacterial count, but also
oxidizes and precipitates iron and manganese, kills algae, reduces color and slime formation
and generally assists settlement. However, if water is highly turbid the merit of pre
chlorination declines, as chlorine absorbs without compensatory benefit.

AERATION

It is a cheap and valuable means of controlling taste, odor and corrosion but not in all
cases complete control may be achieved. Gases are absorbed or liberated from water until
equilibrium is reached between the natural content of each gas in the atmosphere and its
content in the water. The process is however slow unless the water is agitated or great area
exposed to atmosphere. This is commonly done by splashing the water over trays cascades
to break up the strean1 into countless droplets or by reversing the effect and blowing air
bubbles through the water. Thus, if the water is lacking in dissolved oxygen, it will pick up
oxygen from the air, and its taste will improve. If it has an excess of CO2 or H2S, it will tend
to lose them. Certain volatile substance is liberated by algae growths or decomposing
organic matter, can be released from water by aeration. Iron and manganese in solution are
also oxidized and precipitated out.

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COAGULATION

Coagulation is a process by which small particles in suspension join together to


form larger agglomerate. Fine suspended particles and colloids present in water carry
charges on their surface and most of the common materials assume negative charge.

For agglomeration, fine particles should come in contact with each other or collide
with each other. Since they carry the same charge, they repel each other. They will only
come in contact when they are on a true collision course. In that case, they will join
together to coagulate into large particles and settle down quickly. The rate of this
coagulation depends upon the frequency of collisions. So mixing promotes the effect but
violent agitation will break down the attraction between the particle and retard
coagulation. If enough time is given, stagnant water may coagulate sufficiently to form
particles large enough to settle down, leaving the water largely clear. This auto
coagulation improves the water quality of large reservoir, lakes, etc. The above process is
very slow and in industry we are continuously in need of water, so it is very important to
promote the coagulation process to accelerate sedimentation of the suspended and
colloids particles.

Obvious way of promoting coagulation is to neutralize or reverse the electrical


repulsion effect. In that case, the particles will touch each other or pulled together and
agglomerate. This can be done in two ways

(i) By adding traces of surface-active materials called coagulation aids.


(ii) By introducing fresh particles with positive charge, which is best done by Flocculation
that is by precipitating aluminum or iron hydroxide in water?

COAGULATION AIDS

Coagulation aids of different types are available. They are all long chain molecule
carrying electrically active groups all along the length of the chain.

For example, very effective aids are long chain poly-acryl amides, which carries positive
charge.

Each long chain molecule collapses on to a single suspended particle, where it covers
a sizable area as it settles. The area is then electro positive and attracts and holds the
electro negative surfaces of suspended particles/colloids. This arrested particle may also
have an electro positive patch on it and so on. The aids have very long chains. In shorter
chain molecules, amount: required for the same effect is higher. The amount required for
effective coagulation with the coagulation aids are very small and they are effective in any
type of water. The problems with them are that they are difficult to dissolve, dilute or mix.

Most of the very effective aids (Polyacrylamide as mentioned above) are toxic and
cannot be used in potable water.

A Common nontoxic aid is activated silica, which, is prepared on the site because it is
unstable. Requirement may be more than ten times than that of polyacrylamides. Other
than perfectly controlled preparation and dosing it will leave high polymers of silica in
water (non reactive silica).

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All coagulation aids or big polymers will foul the ion exchanger bed. Other than
effluent treatment or cooling water treatment use of coagulation aids may be avoided as far
as possible.

FLOCCULATION

Ferric and aluminum salts when added in water forms insoluble hydroxides, which
come out as floppy flocs, whose surface carry positive charge. This positive charge flocs
attaches itself with the negative charged particles in water and also attracts and holds
humic acid.

Flocculation is more effective as flocs has large electropositive surface area and also
it greatly increases particle concentration in water, which increases the probability of
collision, proper pH, good mixing, time and presence of nuclei on which precipitate can
form, favors good floc formation.

Aluminium and iron hydroxide gives good flocs normally in slight acidic pH.
(Iron 5-6 pH and Aluminium 6-7 pH)

When alum (Aluminium sulphate is known as alum in TPS) is added in water


aluminium hydroxide floc and sulphuric acid is formed. This acid reduces the pH of the
water.

( Al 2 SO4 ) 3  6 H 2 O  Al (OH ) 3  3H 2 SO4

Normally raw water pH is alkaline. In that water after addition of requited amount of
alum, pH may come down to coagulation pH.

In rainy season when the turbidity is high alum dosing is also high. In that case pH
may fall far below the coagulation pH. Lime Ca (OH) 2 is generally used to increase pH to
the required level.

Ca (OH) 2 has also some coagulation properties and it helps to remove some
temporary hardness.

Iron salts gives best coagulation at low pH. However, it is not so much pH sensitive
as aluminium salts. Hence, with iron salts, coagulation can be done at whole range of pH.
Where the coagulation pH is very narrow, raw Water pH is very high iron slats may better
choice.

Exact chemical condition to give best coagulation can only be ascertained by


systematic trial and error method in the laboratory. The test is called Jar Test, and the
results from the Jar Test are applied in the actual plant.

CLARIFIERS

Clarifiers are structure/system in which water is cleared from most of the suspended
solids with or without addition of coagulant. There are different types of clarifiers.

A conventional type clarifier is shown in Fig.1.

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CONVENTIONAL TYPE CLARIFIER

This has the arrangement of a flash mixer, flocculator and separate compartments.
The water first enters the flash mixer, where it is mixed with the chemicals by means of a
high-speed agitator. Usually several minutes of detention are needed in the chamber. The
mixed water then enters the flocculator chamber, where slowly rotating paddles provide
more gentle agitation, stimulating the growth of the floc, which enmeshes the turbidity,
colour and other suspended matter. About 20 to 60 minutes of retention are allowed in the
flocculator.

The flocculated water then is distributed uniformly to the horizontal flow settling
basin compartment, where the floc and precipitates settle out. A slowly rotating sludge
scraper makes the settled sludge to the centre for discharge to waste, the settled clarified
water flows to the outlet launder at the top, from which it passes to the filters.

The setting basin for the horizontal flow may be a square or rectangular chamber or it
may be a round, vertical tank for radial, inclined flow from the bottom of a central
cylindrical down comer to a peripheral launder. In the latter case, the flocculator may be in
a separate chamber or be inserted in the down comer. The detention time for the settling
varies from 2 to 6 hr. The speed of flow should be kept at less than 1 to 2 ft/min for a good
separation and setting of the precipitates and floc.

A second major category of clarifiers is solid contact unit, available in two basic types:

(i) Slurry re-circulation clarifier


(ii) Sludge blanket clarifier

Both of these combine chemical mixing flocculation and clarification in a single unit.
In the mixing zone of a solids contact clarifier, the solids concentration may be as much
as 100 times that of simple clarifier. The high solids level greatly increases the rate of
chemical destabilization reactions particle growth. Because of this feature, the solids
contact unit is used in limes softening. In the sludge recirculation unit the high floc
values is maintained by recirculation from flocculation zone to the clarification zone.

In the blanket type clarifier, the floc solids are maintained in a fluidized blanket
through which the water must flow. Because of the increased solids, in a solids contact
unit, clarifier size may be reduced. The even distribution of inlet flow and the vertical
flow pattern of this type clarifier provide better performance than standard horizontal
flow clarifier.

HOPPER BOTTOM CLARIFIER

Latest concept of clarifier is hopper bottom clarifier. The tank is usually square in
plan with upper portion having vertical sides and the lower position in the form of an
inverted pyramid with sides at an angle of 60 0 to the horizontal, size of the tank is
governed by the turbidity and volume of the feed water.

Raw water with chemicals is delivered near the bottom of the hopper portion by a
vertical inlet pipe. Velocity of discharge and change in direction of flow creates and
maintains the mild agitation needed for initial flocculation, which continues within the
sludge blanket.

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SLUDGE BLUNKET

The water rises at a steady decreasing velocity at the initial stage up flow velocity
of water is more than the settling velocity (down word) of the suspended particle. Then
at a distance, both velocity equals and we get maximum sludge formation in that area.
This sludge blanket is composed of relatively long particle and they are capable of
maintaining their position. After this sludge blanket is formed subsequent settling of the
smaller particles is quick because when they come in contact with sludge blanket.
Agglomeration is quick due to very easy contact. Sedimentation of the smaller particle
may be said to be taking place on the surface of the larger stationary particles of the
sludge blanket.
The particles that are too heavy to be carried to the sludge blanket fall to the
bottom of the hopper from where they are discharged periodically.

CONTROL OF FLOCCULATION

A variable velocity valve adjustable from the top of the tank is fitted with inlet pipe to
take care exceptional changes of water characteristics or wide variation of flow.

In normal cases, inlet pipe has a fixed diameter out let to give required discharge
velocity. The effect of increases flow through the tank is the expansion of the sludge
blanket until the equilibrium is re-established. The surface of the sludge blanket will rise
but carryover will not occur until the increase in flow is excessive.

COLLECTION OF CLARIFIED WATER

The water coming out of the sludge blanket passes up through straight position of
the tank and is drawn off by a series of collecting troughs. They have notched side and
are provided with adjustable supports to enable them to be set for uniform draw off. This
eliminates chances of short-circuiting.

SLUDGE DISCHARGE.

It is necessary to bleed off a small flow of sludge through concentrating pocket. It


may be a constructed in the concrete or it may be suspended from the top of the tank.

The sludge is drawn from the sludge blanket zone into the pocket and is piped to a
convenient point out side the tank. Amount of the bleed is controlled by an automatic non-
clogging discharge valve controlled by an adjustable timer or by regulation of a continuous
discharge.

The main discharge pipe is periodically used to remove heavier sludge from the bottom of
the tank.

SPECIFICATION OF CLARIFIED WATER

The clarified water should be seen by naked eye without any turbidity. However,
clarified water cannot be completely turbid free as in a continuous process some slip is
always permanent feature and the slip so occur is restricted in the next process known as
filtration. In general, we may assume a clarifier properly designed can take care 98%
turbidity very safely.

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The cautions that are to be observed in operation are:

(i) The mixing of coagulants in proper proportion (to be determined by jar test) and
at proper place.
(ii) The abnormal increase in loading of raw water i.e. sudden openings of
valves and throttling of inlet valves must be avoided.
(iii) The clarifier should not be over flooded.
(iv) The drains are to be operated to flush the muds at fixed interval.
(v) The clarifier should be periodically cleaned on complete shutdown period.

FILTERATION

MECHANICAL FILTERS

Filtration means taking suspended solids out of fluids. The present discussion will restrict
to water treatment only.

The Suspended Solids in Water

Water carry many types of particles, in shapes and sizes, in the water treatment
terminology they are known as 'suspended matter' to cover quite narrow range. Very large
pieces as well as sands and mud are not included in the filtration operation as they have
been removed in other operation. Water, which has been screened and settled, may still
contain suspended matter and also colloids. Colloids are particles so small that they cannot
be seen by simple microscope. The agitation due to the movement of water molecule is
enough to keep them in suspension. The colloids are sometimes defined as particles
between 0.005 and 0.2 microns in diameter. The colloids in water absorb and scatter light
passing through it and therefore cause turbidity. This provides a method for colloid content
Filters are designed to remove colloids from water as well.

Basic Filtration

In its crudest form, filtration is like tea staining. The fluid (water) is passed
through a screen with smaller opening The particles, which are bigger than those,
opening will be held back in the screen. Here screen means a barrier, which has small
holes/pores. Thus a screen can be created in many ways.

Here we may consider following problems:

(i) Suspended matter and water is relatively viscous (in respect of air). This
means that very small holes must be used and any reasonable rate of flow,
through them will raise a high-pressure loss.

(ii) As the filtration process is in progress, the suspended matter slowly blinds
the pores of the Screen resulting greater pressure loss and slowly
stoppage of the process. Deposition of suspended matter on the pores of
the screen is known as formation of filter cake.

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Filterability

If a filter cake is allowed to form, it efficiently form a new screen which has
smaller size than those in original screen. This cake then dictates the size of particle,
which passes through and a much finer filtration results. The phenomenon is called auto
filtration. The small pore size of the cake tend to increase the pressure loss. All the
suspended matter over filter screen may tend to pack closely into one another by virtue
of their shape, or because they slide easily over another. The degree to which they do
these things depends on the pressure. Pressure Loss across the cake, which forces them
one another, tending to compress the cake. A really bad and highly compressible material
is capable of forming an almost impermeable membrane across the screen, through
which a small tickle of extremely clear water flows. The filtration properties of the
suspended matter, which occur in practice, cannot be predicted from the basic properties
of the material of the particle. This can only be done with carefully selected laboratory
materials. There are various tests on 'filterability' in which the water is passed through
standard screens. As per Suss's law, most of the suspended material which we want to
filter has a very poor filterability.

Filter Washing

Compressible material, which squeeze and cling on one another also likely to cling
to screen. The compressible material is troublesome to filter and also problematic to
cleaning the filter media for next cycle. In fact, filter cleaning becomes most problematic
when we deal with compressible material.

Types of Filter

The designer of a filter has a very limited choice. First, he proposes to remove
particles by providing a screen of smaller size than that of the material that has to be
removed. But the material so filtered forms a cake and reduces the pore size, which
increases the pressure on filter media and reduces the rate of filtration. There is no control
over this. The main job towards designing a filter is thus to select proper filter media, with
largest economical screen area.

There are two kinds of simple screen filters:

(a) True screens, such as meshes, sieves, sinters, felts, fibrewound candles or cloth,
held in some device which forces water to flow through. There must be some
form of cleaning.
(b) Disposable screens which are created a fresh for every filter cycle. This class
includes paper filters and cartridge filter, which are used at place where there is
little suspended matter to remove, else filter replacement becomes too costly.
More important in this class are precoat filters. Micro Strainers

The only simple screen, which is widely used in water treatment, is micro-strainer.
This is a cylindrical drum covered with a very fine wire mesh. Raw water flows into the
middle of the drum and out through the mesh by gravity. The drum rotates continuously
and bring the mesh under a high pressure jet which squirts water on to the outside and
dislodges the accumulated matter inside the drum. The smallest particle mesh is 25
microns, so the finest particles cannot be removed by micro strainers, but they are used
up on this by depositing a layer of precoat medium on it.

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Filter pre-coat media is relatively course materials with a good filterability, such as
diatomite or cortain grades of cellulose fiber. They are composed of particles of reasonably
uniform size so that they do not pack into one another and they form filter cake with high
pore volume. Being rigid they do not compress significantly under flow: Before the filter
run begins, a suspension on filter medium is prepared and is pumped into filter. The screen
is so course that some of the precoat media is passes through, but most of it is retained in
the orifices; across which the rigid particle tend to form a bridge. Pre-coat filter offer high
resistance and require repeat filtering for clear water.

The thin layer of precoat becomes filtering screen. As the filter run starts, a layer of
cake is build-up and the filtration becomes deep bed filtering now. If the suspended matter
in the water has a bad filterability some dosing of precoat material in the water up stream
will be helpful. This additional material gives some stiffness to the newly formed cake and
provides less compressability. This practice is called body feed or body dosing. As the cake
builds up, the pressure loss rises. Precoat filters are build up for quite high pressure losses
limited by the cost of the pressure vessels and of pumping rather than by the process itself.

Final pressure losses of two atmosphere or more are normal. The run is brought to an
end at a predetermined limit of pressure drop and layer of cake is washed off. The precoat
medium is therefore a consumable item which raises operating cost.

In backwashing a precoat filter, as soon as any part of filter is clean, water flows
through that portion more than other areas of filter bed. Thus a portion of filter is likely to
be pilled off during backwashing in precoat filters.

Deep Bed Filters

This is a vessel in which filter bed is created from a fine granular medium such as
sand etc. through which water is made to flow. The suspended matter gets caught in the
discontinuities which occur within such a bed. When the bed accumulates lot of solids that
is practicable, the flow of water practically stops and the bed is backwashed for reviving
the filtering capacity.

The design and operation of such a filter is very simple. In practice what happened
in the filter bed is a matter of great investigation however, this can be fairly stated that as
water passes through the granular sand bed, it creates lots of channels mostly vertical,
however, to formation of some horizontal channel cannot be ruled out. The channels
interlink, open out and narrow down at random. A sand filter therefore represents an
infinite number of mini-events of far greater quantity and variety than those in the similar
types filter. In practice, a particle from water arrives at a narrow orifice between sand
grains in which it gets stuck. This would be similar to ordinary straining, and once again it
does not necessarily close off the orifices as a precoat medium dose, and create a new and
smaller series of orifices across which filtering takes place.

Another remarkable advantage of sand bed filter is that it has very low liquid
turbulence and surface at which particles can easily settle down on the surface of the sand.
Where these condition occur, particles are easily likely to settle on top of one another, so
that this type of filtering also leads to local accumulation of suspended matter. Once the
particles have been brought into contact by settling in the some place, electrostatic forces
tend to hold them together. As the medium accumulates filter dirt, the pressure across the
medium increases and thus leads to increase in shear force, which may collapse some of
the bridges which hold mini cakes. This causes upset infiltration, first dirt passes through
the upper bed, then it starts to pass through entire filter media causing filter break
through.

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The deep bed filter differ from another filters as under:

(a) They are capable to filtering very fine solids including colloids.
(b) Fine sand gives finer filtration because the size of the channel is decreased and
because a more area of filtration is achieved.
(c) Because particles tend to accumulate at the same place, it promotes coagulation.
(d) Deepening the bed increases the availability of the filter medium and improves
the quality of filtrate.
(e) At the end of a filter cycle, the rising pressure loss can force accumulated dirt
right through the filter.

Backwashing the Bed

Sand filters are always back washed upwards so that the sand bed expands and
solids so accumulated are released. The theory of backwashing indicates, the maximum fluid
velocity at any point is terminal velocity of solid accumulation at that point. Normally this
velocity is not enough to rip the accumulated material from it. Extra agitation is necessary
for efficient washing usually by air blowing through the bed does the job. In practice, a bed
on backwash should classify, so that the smallest particles end up at the top and the largest
at the bottom. Sand filters are not usually fluidized for complete clarification. Bit by bit,
however, the bed does tend to classify. With a bed of uniform density, the finest particle
ends up at the top. Thus a filter bed may be designed to held different layer of filter media
having different density. The specific gravity and media of filter is described as under:

Material Typical specific gravity


Polystyrene 1.04
Anthracite 1.40
Silica sand 2.65
Gamest 3.83

There are two types of filters mainly:


(a) Up-flow filters
(b) (b) Down -flow filters

These are again termed as "slow" and "rapid" sand filters. The slow filter has
usually a flow rate of 1-2 g/sq ft/h. i.e. rate will be just as 100 litres/sq.m/hr. This
requires very large filter bed or restricted to small amount of water to be handled. Thus
the high capital cost, had made it progressively less economical.

Rapid Sand Filters

This is the present day concept in the filter industry. It consists of a bed of graded sand
typically + 30 mesh to 15 mesh about 0.6 meter in depth. This lies in a bed of graded
gravel in several layers. The gravel sizes vary from 2.5 mm to 25 mm. This filter operates
between 5-10 m3/m2/hr. and capable of removing particles up to 10 micron size from
water containing 100 ppm of suspended load, the capacity can be increased. The filters
are designed to back wash once/twice a day. The back washing water should be filtered
water. Air scoring is done to agitate the filter bed.

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Gravity vs. Pressure filter

The head of water required to push the water through filter media can be supplied
either by gravity or by pressure. These filters are having their own merits and demerits.

Activated Carbon Filter: (AC Filter)

Granular carbon is used as a filter bed through which water is passed. The impurities
that is left behind is extracted methodically. The water, as it progressively losses its
pollutants encounters zones of activated carbon which are less and less saturated and
therefore more and more active.

An A C filter in board has four limitations:

(a) Filteration: This must often be reduced to minimum in order to avoid clogging of the
bed. In addition carbon tends to extract absorbable products from the flow with which it is
contact, causing premature saturation. Thus a sand filter before activated filter will reduce
such problems.

(b) Biological media: The surface of carbon offers ideal conditions bacterial growth. This
phenomenon does assist purification but can also be very dangerous if not properly
controlled (anaerobic fermentation giving off odour, clogging of bed etc.) Catalytic action:
The main function of activated carbon is oxidation of water by free chlorine.
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Cl 2  H 2 O  2 HCl  O2
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The pH has considerable role to play. The de-chlorination property is affected by any
factor that interfaces between carbon and chlorine such as filterable impurities like flock,
algae, etc. Thus, a clean water performs better for activated carbon filter.

Absorption: This is the principle role of the activated carbon. Thus a grate care is taken to
keep the bed active and unaffected.

There are two possible arrangements of AC filter.

Membrane Filters

There are various kinds of membrane filters with organic membranes which have
very fine pores, “Ultra filtration” membranes have pores small enough to remove most kind
of non reactive silica with a pressure across the membrane of less then 5 bars. Ultra
filtration plant is generally installed after DM plant to absorb colloidal silica from DM water.
“Reverse osmosis membranes actually retain not only all large molecules but the rate of flow
across the membrane is small and requires pressures of the order of 50 bars. However
reverse osmosis plant followed by DM plant can produce water of almost ultimate purity and
is very economical in handling brackish water/ sea water or even with a water having total
dissolved salts or more then 500 ppm.

CONVENTIONAL PRETREATMENT PLANT

Fig.1 gives the schematic flow for pretreatment of water generally practiced in TPS.

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D.M. PLANT

Dissolved solids present in water are removed in DM plant by ION exchange process
and for this ION exchange resins are used.

ION EXCHANGE RESINS

Ion exchange resins are synthetic organic polymers. Most commonly used resins are
gel type polystyrene resins which is manufactured by polymerization of Vinyl Benzene
(styrene) and 8-10% Divinyl Benzene (cross-linking to increase stability of the resin).

Ion exchange resin are manufactured in bead form (0.3 mm or 1.2 mm size)
optimum size 0.6 mm. Smaller size would restrict flow and with higher size, retention time
would not be sufficient for proper exchange.

Resins are porous. It contents 45-55% moisture. It swells after absorption of


moisture. Gel type resins, after addition of water, if allowed to dry, it will shrink and if again
water is added, osmotic pressure developed will crack the resins. For this reason, gel type
resins once wet are never allowed to dry.

Cross-linking (in fig. 2a pictorial form of resin is shown) increases stability of resin
but decreases the moisture content and porosity, hence the exchange rate. To strike the
balance in stability and exchange capacity, 8-10% cross-linking is done.

The resin beads are insoluble in water. Functional groups are then attached to each
of the benzene rings to make it chemically active. Depending upon the functional group
attached to resin Matrix, it behaves as cation exchange resin or anion exchange resins.
Acrylic resins / Macro porous / micro porous resins are now also available in market.

Fig.-2a

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CATION EXCHANGE RESIN

Cation exchange resins are nothing but acid and can be simply represented as: R--H+,
where R is resin matrix, completely insoluble in water and only H+ is mobile in water.

Cation resins are of two types. Strong Acid Cation Exchange resins (SAC) and
weak Acid Cation Exchange resins (WAC).

SAC : When the functional group attached to resin matrix is strong acid group it is called
SAC resin.

SAC can split all salts and its performance is not influenced by pH of water.
Operational exchange capacity and regeneration efficiency of SAC is less than WAC.

WAC: When the attached functional group is of weak acid, it is called WAC resin.
WAC can only split weak electrolyte (carbonate and bicarbonate) only.

It performs better with high pH water and with lower pH water its performance decreases
and when pH falls below four, actually regeneration takes place.

Na 2 CO3 H CO H CO
 WAC 2 3  SAC 2 3
NaCl NaCl HCl
Na 2 CO3 H 2 CO3
 SAC 
NaCl HCl

ANION EXCHANGE RESINS

Anion resins can be simply represented as R+- OH- and is nothing but an alkali /
base. OH- is only mobile in water.

Anion exchange resins are of two types: Strong base anion resins (SBA) and
weak base anion resins (WBA).

SBA: When the functional group is strong base it is called SBA resins. SBA
performance is not influenced by water pH and it exchanges with both strong and
weak acids.

WBA: When the functional group attached is weak base it is called WBA. WBA performs
better at low pH and increased pH decreases its performance. When pH is more than
11, actually regeneration takes place.

Operational capacity and Regeneration efficiency of WBA is higher than SBA. WBA can
only react with strong acids:

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HCl HO HO
 WBA  2  SBA  2
H 2 CO3 H 2 CO3 H 2O
H 2 SiO3 H 2 SiO3
Cation effluent
H 2 CO3
H 2 SiO3 HO
Cation Effluent  SBA  2
HCl H 2O

PRINCIPLE OF DEIONISATION

All impurities except dissolved solids are removed in pretreatment plant.


Only dissolved solids are removed in D.M. Plant. Dissolved solids in water dissociates into
ions (as water is a polar solvent and it dissolves electrovalent compounds only). Positive
charged ions are called cations and negative charged ions are termed as anions.

In normal river water most common are salts present are calcium, magnesium and
sodium salts, associated with corresponding equivalent anions like Cl-, SO4-- CO3-- etc.

In solution dissolved solids can be represented as:

Cation Anion
Ca++ HCO3 -,CO3-

Mg 4++ SO4--

Na+ Cl-
--
SiO3

If the above water passes through a cation exchanger, all the cations are exchanged
with H+ of cation exchange resins.

R   H   CaCl 2  R   Ca    HCl
R   H   CaCO3  R   Ca    H 2 CO3

Similarly all cations are exchanged and retained by resin and ultimate product will be
corresponding acids. pH drops around 3.5 and it becomes soft.

Cation Anion
H+ HCO3 – CO3--
SO4 --
Cl-
SiO3--

The above water when passed through an anion exchanger, all anions are
exchanged with OH- of SBA resins and equivalent amount of water is produced.

16
H  Cl   R   OH   R  Cl  H  OH  ( H 2 O)
 
H 2 CO3  R   OH   R  CO3  H  OH  ( H 2 O)

Similarly, all the acids are converted to H 2O. It appears that by passing water
containing salts through a cation and anion exchange resins all ionsiable salts can be
removed. However actual process is a little bit different.

SELECTIVITY OF IONS

Resins have a preference for exchange and it depends on charge and size of the ion.
Triple charge is preferred to double and double is preferred to single charge. Charge being
same preference is given to bigger size ions.

Thus for cation: Ca++>Mg++>Na+>H+

Similarly for anions: HSO-4 >NO-3 >Cl->SiO3=

SODIUM SLIP

When water containing Ca, Mg, Na ions is passed through cation exchanger bed, Ca ions
are retained in 1st layer then Mg and in the last layer Na ions are retained. Ion exchange
reactions are reversible (for regeneration and reuse).

The reaction in the bottom part of the bed is with sodium salt (say NaCl).

R  H  NaCl  R  Na  HCl

Now even at very low concentration of R -Na some back reaction produces NaCl.

R  Na  HCl  R  H  NaCl

Thus, effluent coming out from cation exchanger is not 100% acid but contain a
little amount of Sodium Salt. This is called sodium slip. Increased bed depth reduces this
amount of slip but it can never be reduced to zero. Further, it is not techno-economically
feasible to increase bed depth indefinitely. Hence, some amount of sodium slip is
accepted in design.

The cation effluent containing some sodium when passes through anion exchanger,
acids are converted to water but sodium salts are converted to NaOH.

R  OH  NaCl  R  Cl  NaOH
R  OH  HCl  R  Cl  H 2 O

Therefore, the effluent coming out of anion bed contains NaOH that increases the pH and
conductivity of the anion effluent. Further, similar to Na-slip, silica slip takes place from
anion exchanger.

Thus, water coming out through cation and anion exchanger has high pH/conductivity and
silica and is not as per requirement of H.P. Units.

17
MIXED BED UNITS

After passing water through cation and then through anion exchanger, it is passed
through mixed bed unit. In mixed bed, cation and anion resins are thoroughly mixed and
while water passes through it, as if, it passes through thousands of cation / anion
exchangers 'resulting final effluent of very good quality water. Therefore, minimum
requirements for DM Plant are,

SAC  SBA  MB .

Further, H2SO3 produced in SAC can be easily removed at low running cost in a
Degassifier. Thus simplest D.M. plant scheme for High Pressure Unit is

SAC  Degasser  SBA  M .B

D.M.PLANT: From filter water, chlorine is removed before allowing it to enter ion
exchanger. It can be done by: (a) Passing through activated carbon filter which
absorbs chlorine or (b) Dosing calculated amount of sodium sulphite, which reduces
chlorine to chloride ion.

Depending upon the amount of water to be treated and quality of the filter water, different
types of demineralization schemes are made.

(1) Cation Unit Degasser Anion Unit M.B. Unit


(SAC) (SBA)

This is the simplest arrangement. Capital cost less and running cost more.

(2) Cation Unit WBA Degasser SBA MB


(SAC)
Where water requirement is more. Here capital, cost is more than (1). However, running
cost is less.

(3) WAC SAC WBA Degasser SBA MB

Where water contains more carbonate / Bicarbonate and requirement is more.

Capital cost is more than (2) running cost is less than (2). A typical D.M. scheme is shown in
Fig.2b.

18
19
CATION EXCHANGER

Ion exchange vessels are designed for operation of deep beds of resins in
column. It aims to provide water flow in smooth steady piston like motion across the
entire width of the bed. Provisions for resin distribution and support is also important.

Fig.2c shows a typical cation exchanger’s piping arrangement.

Cation exchanger vessel is constructed with steel inside rubber lined. It has 50 to
75% void space to allow free expansion of resin during back wash.

Size of the vessel varies considerably depending upon the quantity of resins
required. Upper limit of the diameter if set by need for uniform flow distribution. For
successful column operation minimum bed depth 30 inches is required to minimize
leakage. Maximum bed depth is restricted to about 60 inches as higher bed depth will
create pumping problem. Hence height of the vessel is set by the resin bed depth. Feed
water flow distribution is regulated by distribution. The lower manifold serves to
distribute the backwash flow and collect treated water evenly for optimum performance.

During operation cation exchange effluent contains some Na (Na slip) which is
ultimately removed in MB Unit. End point of the run is detected by increase in Na
leakage in cation effluent, which also increases the conductivity and pH of the anion
effluent.

REGENERATION

Regeneration of the cation exchanger is done when the sodium leakage increases to
certain pre set value.

The following steps are observed in Regeneration.

(i) Backwash: Backwash is done by up flow of water with air scouring (if arrangement is
available). Purpose of backwash is to loose the bed and remove accumulated suspended
solids, dirt, resin fines, fragments, etc. Otherwise these will lead to channeling at points of
flow break through, poor kinetics and large pressure drops. To allow removal of
accumulated solids without loss of resigns through distributor, free board should be 50-
75% of the resin bed height.

Backwash rate is normally 5-10 5 pm/sq ft and duration is about 10 minutes.

(ii) Acid Injection: After backwash required about of acid is injected at specified
concentration. Contact time is normally 30 min. Two types of acid are used, sulphuric acid
and hydrochloric acid.

When sulphuric acid is used for regeneration; until all Ca is removed, concentration
of acid is restricted to 2% and higher flow rate is maintained to avoid precipitation of
calcium sulphate in the bed. When maximum calcium is removed, the concentration of the
acid is increased to 4.5% to 5% and flow is reduced to normal flow rate. In case of
hydrochloric acid 5% acid is injected with normal flow. Regeneration level is normally 4-5
Ibs/cubic ft of resin.

(iii) After acid injection the bed is rinsed with water, first at slower rate (1 qpm/sqft)
and then at higher rate of 5 to 8 qpm/sq.ft. Volume used is 30-40 gall cubic ft.

20
21
22
WEAK ACID CATION EXCHANGER

For regeneration of weak acid cation exchanger acid strength may be 0.8 to 1 %.

If WAC exists in the stream then normally acid coming out of SAC unit as the time of
its regeneration is passed through the WAC to regenerate it. This is called thorofare
regeneration. See Fig. (2d).

Other steps are similar to SAC regeneration.

ANION EXCHANGER

Constructional features of anion exchanger are similar to cation exchanger unit.

During operation, effluent coming out from anion out let contain some silica as leakage
and NaOH. At the end point of run silica leakage starts increasing and at a preset value
the Unit is taken out of service for regeneration.

Operational capacity of the Anion exchanger depends upon anion load, regenerant level,
SiO2, Anion ratio, quality of treated water, bed depth, performance of cation exchanger,
temperature of the regenerant etc. The Unit is normally designed to have one regeneration
a day.

REGENERATION

The following steps are observed for regeneration of Anion exchange unit.
(i) Backwash: Backwashing is done to loose the bed-and remove resin fines and
fragments (below 50 mesh) Normal backwash rate is 2-4 g pm / sq. ft. for 10 minutes.

(ii) Injection of caustic: 4% caustic at 4 to 8 Ibs/ cubic ft. resin is injected for a contact
time of about 1 hour. For better removal of silica particularly in WBA/SBA combination
higher regenerant level more contact time and higher temperature of the regenerant
(50°C) may be needed.

(iii) Rinse: Slow rinse at 1 qpm/sq ft ,then fast rinse at 5 to 8 g pm/sq ft. for 1 to 1 Y2
hour may be required to bring down the conductivity and silica to the acceptable level.
Volume used is 40-100 gal/cubic ft.

WBA
End point of WBA is detected by increase in the conductivity and lowering of pH.

The Regeneration of WBA need about 1 % NaOH. Therefore regeneration is done for
WBA where SBA outlet caustic is injected to WBA with some modification to avoid silica
precipitation in the WBA Unit (Fig.2e) Other steps are similar to SBA Regn.

MIXED BED

Mixed bed unit gives much better quality of water compared to series of cation and
anion units.

MB unit is designed to take care of expected leakage from preceding cation and
anion bed. Regeneration frequency is normally once in a week. Not more than 30-40% of
the capacity of MB unit is utilized to have better quality of treated water. If the MB is over

23
24
25
26
run, it will be loaded with more ions, Which needs higher regenerant level in the next
regeneration. A typical MB internal is shown in Fig.2f.

It is similar to conventional ion exchanger, a cylindrical steel vessel. Internally


rubber lined containing resin bed above which there is free space to allow expansion of
resin when back washed. In addition to the usual distributors, a mixed bed is fitted with a
central distribution and collection system.

At the time of regeneration the bed is back washed. This expands tl1e resin bed
and allows the heavy cation resin to sink to bottom and lighter anion resin rises to top.
After some time when backwash is stopped, the resins settle without upsetting the
seperation. There is a well-defined interface between the cation and anion resin bed and
that interface is just at the level of central distributor.

Anion resin can be regenerated with caustic and rinsed. Spend caustic solution and
rinse water can be withdrawn through the central distributor.

After this cation resin can be regenerated and rinsed. In that case caustic outlet
will now be acid inlet/ rinse water inlet.

When both the resins are regenerated and rinsed tl1e excess water is drained down to the
surface of the bed and the resins are mixed thoroughly, with the help of air blowing. The air
is 'blown in through bottom distributor and out through the air release at the top. After
proper mixing, the space above the bed is filled from above and unit is put into final rinse.

REGENERATION OF MIXED BED

MB is normally regenerated when the effluent conductivity is more than preset


value of silica is more than 0.02 ppm.

The following steps are observed at the time of regeneration.

(i) Air Scrubbing: Water is drained to top of the resin bed and air scrubbing is done
for 10 min.

(ii) Back Washing: Unit is filled with water and back washing is done at 4-9 qpm I
sq. ft; then the resin is allowed to settle for 10 minutes which separates the anion
and cation resin. (Fig.2g).

(iii) Regeneration of Anion Resin Bed: Regeneration of anion resin bed is done with
4% caustic at 12 1 bs/cubic ft. resins. (Fig.2h).

(iv) Rinse of the Anion Resin Bed: For about an hour until effluent conductivity is
below 10 ms/cm.

(v) Regeneration of Cation Resin Bed: Regeneration of cation resin bed is done with
4% acid at a regeneration level 8-12lbs/cubic ft. (Fig.2i).

(vi) Rinse of the Cation Resin bed till conductivity less than 10 ms/cm (20 minutes).

(vii) Mixing of the Resins: The water is drained down to the surface of the resin bed
and mixing is done by air blowing for about 5 minutes then it is allowed to settle.
Through the site glass proper mixing can be observed. (Fig.2j).

27
(viii) Final Rinse: After mixing the unit is refilled with water and put to final rinse till
the effluent comes to the acceptable limit (approx. 30-50 mins.)

MIXED BED OUTLET WATER QUALITY

Conductivity 0.2 -0.3 micro S/cm

pH 6.8 -7.2

SiO2 Less than 0.02 ppm

28
DEGASSIFIER

After the cation exchanger the effluent is acid and all the bicarbonate present in
water is converted to CO2. This CO2 can be removed in Degasser very cheaply. The capital
cost of a Degasser is very less and running cost also. Other wise this CO2 is to be removed
in anion exchanger. Hence, Degasser actually reduces load in Anion exchanger.

The theory of degasification is mainly based on following gas laws.

DALTON'S LAW

The total pressure exerted by a mixture of several gases is equal to the sum of the
partial pressures of individual gas. Again, according to Charles law the partial pressure of
each gas is determined by the amount of that gas in 1he mixture.

HENRY'S LAW

The solubility of the gas in water is directly proportional to the partial pressure of
that gas in contact with water.

X = P/H,

X = amount of gas dissolved in water, P = Partial pressure of the gas in contact with
water. H=constant at that temperature.

Further solubility of the gases decreases as the temperature of the solvent is


increased. When water reaches it saturation-temperature all the uncombined gases are
theoretically insoluble in it and may be removed. Hence, solubility of a gas may be
decreased to effect more complete from water in several ways.

i. By lowering the partial pressure by inserting another gas in contact with water (De
gasifier).

ii. By decreasing the pressure (cold water deareation).

iii. By lowering the partial pressure by heating the water to boiling point
corresponding to the pressure of the steam introduced (Hot water deareation).

In case of removing CO2 from cation effluent principal is normally adopted.

X=P/H

Where, P=partial pressure of CO2 in atmosphere X=concentration of CO 2 dissolved in


water.

29
Table-2: Henry’s law constant for CO2

Temperature Value of H to give X in ppm CO 2


0 0.30 x 10-3
10 0.43 X 10-3
20 0.58 X 10-3
25 0.67 x 10-3
50 1.16 x 10-3

Dry air contain around 0.03% (300ppm) at atmospheric pressure. It has a partial
pressure 300 x 10-6 ats. At 10oC, according to Henry’s law, this is equilibrium with ppm CO 2
in water. Hence, by bringing water and air in contact, CO 2in water can be reduced to a very
low level. This can be achieved when air and water air brought to near equilibrium, which
is done in a degassifier.

There are different types of degasser. The unit essentially consists of a tower mounted
on a tank to hold 1-2 minutes supply of degassified (decarbonated) water. Degasser
internal packing of wooden slant trays or ceramic raschig rings or ceramic / plastic ball
rings etc. over which water trickles down from a spray pipe (corrosion resistant) at the top.
Filtered air is blown in at the bottom and rises counter current to the downward water.

The spray and packing divide the water into droplets or thin films, exposing new
surfaces to the gas phase. Packing materials also provide agitation am thus allows the
dissolved gases to leave the water readily. Packing also provides adequate detention time
for near approach to equilibrium solubility of the gas in water. The height required for
packing material ~ when the amount of influent CO 2 is higher, when the amount of effluent
CO2 derived is lower and when the water temperature is lower.

Normally degassifier is designed to reduce CO 2 at the level of 5 ppm, operating design


temp. Selected for such CO2 content, is normally above IO°C. If temperature falls below,
the slight increase in CO2 may be taken care by anion exchange unit. By degassifier CO 2
level of water can be very easily reduced to 5 ppm. Problem with degasser is that while
blowing CO2 out it saturates the water with oxygen.

This is undesirable as oxygen finds way into condensate with make up water, which is
more or less free from oxygen.

Though air filter is supposed to take care of any dust or dirt in the air, still it sometime
finds entry into water.

From the oxygen / corrosion point of view cold water deaeration based on
principle (ii) is a better choice though more expensive. Here CO 2 and oxygen level
is reduced and thus make up water does not increase the condensate oxygen
level.

30
COUNTER FLOW REGENERATION (CFR)

In the conventional ion exchanger during service run, water flows from top to bottom
through the resin bed and the regeneration is done in the same direction.
Since like operation, Regeneration is not 100% the bottom part of the bed contains more
ions. During service, when the final treated water leaves the bed it passes through less
regenerated portion of the bed and thus picks up more ions; for example ,in case of cation
exchanger sodium slip will be more.

However, if the regenerant is injected from bottom to top then the bottom portion of
the bed will be better regenerated. During service when treated under leaves the bed it
passes through the better regenerated bottom position and ion pick up is less, say for
cation exchanger R-Na concentration is very less at the bottom position thus Na slip will
be very less. This gives a better quality of water and Regeneration level is also low.

The CFR design has to meet all the requirements of conventional exchangers with some
additional attachments.

The requirements of CFR are as below:

(1) The exchanger should have normal arrangement for down flow service.
(2) Back washing is required time to time to regrade the bed and remove dirt and fines.
For this 50- 100% free expansion space is to be provided.
(3) Resin must be free to shrink and swell during the cycle.

(4) Arrangement is to be made to hold the bed packed and immobile during up flow
regeneration.

Most common design is shown in (Fig.3).

The ion exchange unit is of conventional layout. It consists of a resin bed in a


cylindrical vessel above which there is the usual 50% -100% rising space. The top and
bottom of the unit are fitted with inlet and outlet distributors. In addition to these,
however there is a third -buried collector lying just below the upper level of the resin
bed, and fitted with strainer nozzles or mesh-covered holes through which resin cannot
pass.

These units are run in normal down flow service. When the resin is exhausted,
regenerant is pumped into the bottom distributor and passes upwards through the bed.
At the same time, air or water enters the top distributor and flows through the very
small depth of the bed, which lies above the buried collector. Both the two flows leave
the unit through this buried collector. The up flow of regenerant tends to make the resin
lift and mix, but this tendency is overcome by the force exerted on the bed by the down
flow through the upper layer.

This basic principle has been used in several variations. The liquid which enters the
top distributor during regeneration may be water, (Fig.3a). Or the down flow may be of
spent regenerant (Fig.3b), which avoids the waste of water but needs an expensive
corrosion resisting pump. The most successful variation uses air which avoids the dilution
problem, air blower for air mixing at MB and this blower can double up for the CFR duty at
no extra cost (Fig.3c).

31
32
The resins above the buried collector are never regenerated and play no part in the
ion exchange process. On the contrary, if this totally exhausted resin accidentally get into
the working portion of the bed, it could have a damaging effect on CFR operation. A layer of
inert resin may solve this problem (Fig.3d). The buried collector may be of the header and
1ateral type (Fig.3e) or the collector may be placed outside the bed with long individual
down comers dipping into the bed, each down comer being fitted with a standard nozzle
(Fig.3f).

Any suspended matter contained in the water tends to filter out at the top of the bed
and an upward wash from the buried distributor will remove it. For this at each
regeneration back wash is not needed. But after few regeneration when bed is
backwashed; double regeneration is required.

With sulphuric acid regeneration, the overall outcome is that chemical efficiency can
hardly be improved by CFR. On the other hand, it does make it possible to obtain a very
much lower leakage of cations by HCI. The object of CFR is to keep unwanted ions away
from the bottom of the unit so that the resin with which the treated water last comes into
contact is fully regenerated. In CFR, to avoid ions removed by the spend regenerant being
pushed back to the zones from where they came, the slow rinse must be in the same
direction as the regenerant injection itself. If raw water is used for this, it will deposit fresh
ions just where they are wanted least, which is at the treated water outlet of the bed, and
where they would cause high leakage during the following service. For this, cation
exchanger is rinsed with degassed water and anion exchanger with D.M. Water.

33
FOULING PROBLEMS IN ION-EXCHANGE RESINS

Certain inorganic and organic impurities such as heavy metals, high molecular
organic compounds etc. precipitate on the surface of the bed or absorbed irreversibly by
tile resins cause fouling.

This is characterized by drop in operation exchange capacity or poor treated water


quality or both. Noticeable changes takes place in physical and chemical condition of resins
as well as operating parameters like pH, conductivity, rinse requirements etc.

It is only possible to remove part of the fouling by treatment .100% recovery is not
possible. For this prevention of fouling by proper design, well operated pre-treatment plant
is a better proposal.

Following types of fouling are normally encountered in ion exchangers.

1. Heavy metal fouling


2. Organic fouling
3.Oil fouling
4.CaSO 4 precipitation
5. Silica fouling

HEAVY METAL FOULING

Well water may contain significant quantities of iron, in the form of ferrous
bicarbonate. This salt become insoluble when oxidized in contact with oxygen.

When ion exchange resin absorbs iron, which is converted from soluble to insoluble
form by dissolved oxygen and allowed to accumulate it is difficult to remove. Where HCI is
used as regenerant the problem does not occur as HCI elutes the iron as ferric chloride.
However, with sulphuric acid regeneration cation resin may be fouled, as this acid is less
effective in eluting ferric ion.

Iron fouling can be easily detected by treating, resin sample with HCI acid and then
adding ammonium-thiocyanate. A blood red colour indicates presence of iron fouling which
can be removed by soaking resin in HCI acid. In case of softener, which may not have acid
resistant lining, treatment may be given out of the exchange bed. Resin antifoulant to
remove iron as well as colloidal matters are also available in the market.

However, it is better to remove iron at the pretreatment plant by aeration.

In case of surface water, organic matter may contain iron, which is taken up by anion
exchange resins. Carry over of aluminium due to improper pre-treatment may take place
but aluminium has only one valency form and does not create serious problem.

ORGANIC FOULING

Organic fouling of anion exchanger is due to the irreversible absorption of big


organic molecule mostly humic and fulvic acids. Being acid, they are taken up by anion

34
exchange resin. These big molecules enter through the pores but cannot come out.
Exchange sites are gradually lost. Further, at the time of regeneration carboxylic acid
groups attached to the organic molecule are converted to sodium salt. During operation,
they release NaOH due to hydrolysis.

The fouling is characterized by :

1. Increase rinse (Rinse effluent is coloured from straw yellow to even purple,
depending upon the magnitude of fouling).

2. Decrease in operation capacity.

3. Deterioration of treated water quality, Such as high conductivity or high pH


or premature silica breakthrough.

Resin becomes dark in colour and opaque and some times foul odour comes
out.When organic fouling is suspected, resin sample is collected and laboratory scale
alkaline brine wash is done. Before and after brine wash operating capacity difference will
justify the plant scale treatment. Amount of chemical requirement can also be established
from this.

Anion exchange resin fouled by organic matter is treated with alkaline brine solution
(10% NaCI + 2% NaOH). Before giving alkaline brine treatment, fouled resin is tested for
iron. If iron is present, first iron is removed before alkaline brine wash. Removal of iron is
done by treating the resin (in exhausted form) by 10% HC1 acid.

In alkaline brine wash brine solution with 2%, NaOH at 40-50oC is passed through the
resin bed in exhausted form for an hour. Overnight soaking gives better result. Then after
normal rinse, the bed is regenerated with double quantity of alkali.

Alkaline brine treatment at regular interval is a better choice where water has a
history of fouling.

WBA are seldom fouled by organic matter and they are used to protect SBA from
fouling. From WBA organic matters are easily eluted because functional groups of WBA
(Ammines) have high affinity of OH ion.

Macro porous resin has big pores and is not fouled by organic matters. Macro porous
WBA can be used as a guard against organic fouling of SBA units. In MB, cation and anion
resins are not completely separated. If a small amount of fouled anion resin in cation bed
comes in contact with acid at the time of regeneration, the organic matter is precipitated.
During subsequent service run it re dissolved releasing mineral acid. This results in low pH,
high conductivity of the MB effluent and also drop in capacity
OIL FOULING

If oil contaminant water enters ion exchanger, it will from a film on resin bed
preventing diffusion of ions. Oil fouled resins may be cleaned by non-ionic detergent.

FOULING DUE TO CaSO 4 PRECIPATATION

In sulphuric acid regeneration, insoluble CaSO 4 precipitate may foul the resin. The
precipitation of CaSO4 results due to injection of high concentration of acid, low flow rate
during regeneration or high temperature of the regenerant.

35
This can be removed by backwash with large quantity of water and then soaking with
HCI acid.

Though step up regeneration is followed to avoid CaSO 4 precipitation, there is always


some chance of slow accumulation of CaSO 4 in the bed.

If the unit after some regeneration with H2SO4, is regenerated with HCI, CaSO 4 will
be removed during HCI regeneration and CaSO 4 fouling can be avoided.

SILICA FOULING

Silica fouling is normally observed in WBA. At the time of regeneration the


regeneration after passing through SBA is passed through the WBA (thorofare
regeneration). This regenerant contain high silica and low caustic. When this solution enters
WBA ,silica precipitate out and fouls with WBA resin. To avoid silica fouling, either of the
following steps are observed in thorofare regeneration.

1. Before thorofare regeneration, pass some caustic through WBA


2. Discard the initial high silica discharge from SBA then pass it through WBA.
3. Dilute the SBA outlet caustic and pass it through WBA.

Silica fouling can be removed by treating the WBA resin with 10% caustic solution at
around 45- 50oC.

36
CHAPTER-2

CORROSION

Corrosion can be simply defined as the deterioration of the metal by chemical or el~
chemical reaction with its environment.

M + ENV = CORR. Product

In nature, every thing wants to attain stable state (low energy state). Metals are
normally found as compound. We spend lot of energy to reduce metal ore to pure metal.
Hence, metallic form is higher energy state and less stable than its ore. Therefore, metals
have a tendency to go back to its ore form (corrosion). Higher the energy spend on ore to
get metals, higher will be the tendency of that metal to go back to its ore form by means
of Corrosion.

For example, we spend lot of electrical energy to get aluminium from Alumina.
Therefore, aluminium is very corrosive metal. Aluminium when exposed to atmosphere
immediately oxidized to aluminium oxide. But, fortunately the corrosion product aluminium
oxide forms an impervious protective layer on the base metal which does not allow further
oxygen to came in contact with aluminium and metal is protected by the corrosion product.

The oxide layer formed on the metal surface may be impervious protective (AI, Cr
-oxides ,Fe30 4) or porous un protective (Fe203, FeO, etc.).

CORROSION PROCEEDS WITH CELL FORMATION(ELECTRO CHEMICAL CELL)

If we place Zn rod in a solution containing Zn ion some Zn will go into the solution as
Zn++ leaving behind electrons on the Zn rod Zn rod will have -ve potential. After some time
(-) ve potential will be such that it will balance the driving force for Zn to form Zn++ and
equilibrium will establish. Thereafter there will be no further loss of Zn as Zn ++ ion and it will
remain in the equillibrium. The potential between the metal and the solution of standard
strength of its ions is "standard electrode potential".

(Standard potential of different metals are determined to construct a table of


standard Electrode potential or Electro Motive Force (E.M.F.) Table-3.

37
Table-3

EMF Series
BASE END
Li -3.045 Ni -0.255
Mg -2.37 Mo -O.2
AL -l.66 Sn -0.136
Mn –1.18 Pb -0.126
V -0.876 H2 - 0.000
Zn -0.762 Cu +0.337
Cr -0.74 Ag +0.7990
Fe -0.44 Pt + l.l9
Cd -0.402 Au +1.68
Co -0211

Here in case of Zn it is -O.76. Similarly, if a copper rod is dipped into standard


solution of copper salt it will assume a potential +0 .34. If, these two electrodes are
joined with a low resistance wire (Fig.4a), current will flow from Zn electrode Cu
electrode. This will reduce (-) ve potential of Zn electrode hence Zn will start going into
the solution as Zn++ ion and in Cu electrode since (+) potential will drop, Cu ++ ion from
solution will start taking electron and deposit as copper. Now the process is continuous.
So the loss of Zinc from Zinc electrode will continue (Danniel cell).

Anode: In an electro chemical cell, anode is that electrode where from (+) current
enters the solution or anode is that electrode where chemical oxidation takes place. In
the above cell (Fig.4a) Zn electrode is anode and reaction on Anode is:
Zn Zn++ +2e---------(1)

At anode, loss in metal (corrosion) takes place.

Cathode: Cathode is that electrode where (+) current enters from solution or cathode is
that electrode where chemical reduction takes place.

Here Cu is cathode and cathode reaction is

++
Cu +2e Cu ---------(2)

No loss of metals takes place in cathode (protected).


Amount of current flowing depends upon the potential difference between the two
electrodes and resistance in electrical circuit / solution.

Rate of dissolution of Zinc (corrosion) can be determined from the current flowing
through the circuit by Faraday's Law.

CORROSION CELL
If in the above cell, Cu sulphate solution is replaced by hydrochloric acid. current will flow
and dissolution of Zinc will continue and electrons will be accepted by H+ at cathode
(Fig.4).

38
Anode Cathode

Zn Zn ++ +2e 2H+ +2e- 2H H 2.


------- (3)

If instead of Zn rod we put an iron rod current will flow and reaction will be

At Anode At Cathode
++
Fe Fe +2e- 2 H+ +2e- H2 ---------(4)

Hence iron will act as anode (from E.M.F. table) and corrode. If any of the above half
cell reaction is slowed down then entire reaction rate will be reduced. Now if we want to
control loss of iron (corrosion) we can either, slow down the cathode reaction (cathodic
control) or anode reaction (anodic control) or both (mixed control).
If resistance is increased that will also reduce the corrosion current (resistance
control) i.e. loss of iron. If, in the above cell (Fig.4b) we add NaOH to increase pH of the
electrolyte, then H+ ions will be less. This will reduce the cathode reaction (H+ + e- = H)
rate and ultimately corrosion rate. However, in neutral and alkaline medium it is oxygen,
which takes up electrons to help cathode reaction proceed.
Cathode reaction:
4e- +02 +2H2O 40H- --------------------(5)

Fe++ ion and OH- diffuses through each other and forms Fe(0H) 2 precipitate (corrosion
product). Now if the solution can be de-aerated the cathode reaction (5) rate can be
reduced to control loss of Fe from anode. Maintaining pH and removing oxygen corrosion of
Iron can be controlled cathodically (which is done in power station).

DIFFERENT TYPES OF CORROSION CELL

1. Potential (E) difference can be obtained by

(i) Difference in metals: Bi metallic cell or dissimilar metallic or


galvanic cell as already discussed (Fig.4b).

(ii) Difference in concentration: concentration cell (Fig.4c).

(iii) Difference in Metal composition: Local action cell (Fig. 4c’)

(iv)Difference in temperature: Differential temperature cell.

It is evident that all above situations create difference in E. values i.e.

Eanode ( Ea ) and Ecathode ( Ec) are different.


In a solution of resistance RSOL.

Corrosion current Icor. = (Ec-Ea)/ RSOL

39
40
CORROSION OF SINGLE METAL

It is not necessary to have two dissimilar metals in contact for developing


potential difference. In a single metal one part may act as anode and another part as
cathode due to the difference in composition, Mill scale, solvent composition, cold
working etc. If a metal is 100% homogenous it generally do not corrode in uniform
environment but it is practically not possible to make a perfectly homogenous metal
surface.

In Fig. 4c’ we see a break in mill scale which acts as anode and oxide scale
as cathode (Local cell formation).

Fig.4c’ : Cor: of Steal is HCL at Break in Mill scale

A Local corrosion cell may also develop due to the velocity difference of the
electrolyte. At place where electrolyte velocity is higher, metal ion concentration is lower
than the area where electrolyte speed is low where accumulation of Metal ions results in
higher metal ion concentration. High metal ion concentration area (low speed) will be
cathode.

Fig. 4e: Pitting corrosion

41
Difference in oxygen concentration causes lot of local corrosion where low oxygen
area is anode. Common causes for differential aeration cell attack is the presence of a
deposit at one area of an otherwise freely exposed metal surface.

POLARISATION

Initially corrosion starts with higher rate but gradually corrosion product build up at
anode and cathode and the potentials drift towards each other, slowing down the corrosion
rate. This change in Anode and Cathode potential is called polarization.

Polarization at Cathode is usually more than at anode. Some metals polarize more
than others do. Study of metals polarization tendency is very important for corrosion
control.

EIGHT(8) FORMS OF CRROSION

i) Uniform corrosion
ii) Galvanic corrosion
iii) Crevice Corrosion
iv) Pitting Corrosion
v) Intergrannular Corrosion
vi) Selective Leaching
vii) Erosion Corrosion
viii) Stress Corrosion

The above are most distinguished yet concise classification. Many other types are
there. It is found that conditions may be similar to each other for many common
classifications.

Other than the above Fatigue Corrosion, Fretting Corrosion, Exfoliation, High
Temperature Oxidation are important for power station.

GENERAL CORROSION OR UNIFORM CORROSION

Here anodic and cathodic sites shifts from place to place on the metal surface. When
loss of metals takes place from entire surface it gives uniform corrosion. Normally this is
common in case of non resistance metal like plain carbon steel.

This is the safest form of corrosion and measure can be taken at the design stage
by adding excess thickness as per corrosion rate of that metal in that environment.
Example: High temperature oxidation, Rusting of iron, metal in contact with acid etc.

GALVANIC CORROSION

When two dissimilar metals are in contact galvanic corrosion occurs. The driving
Force for Galvanic corrosion is the potential difference between two metals. Coupling
widely separated metals in the series will give greater potential difference that this
higher corrosion rate.

In galvanic corrosion the metal normally on the top in the table becomes anode
and corrode but this may not be always true.

42
While coupling two dissimilar metals care should be taken that anodic metals
should have higher surface area than that of cathode. A small anode if coupled with
large cathode will give severe corrosion and failure of anode. For example if we have
steel rivets (anodic) on copper-plate (cathode, large) steel rivet will severely corrode,
but if copper rivet is used on steel plate (anode, large) slight corrosion will take place.
While coupling two dissimilar metals contact area up to some extension may be properly
insulated if possible.

PITTING

Pitting is one of the most destructive form of localised corrosion. Normally


resistant metals/alloys or inadequally protected metal gives pitting corrosion (Fig.4e).
When a small anode is surrounded by large cathode pitting corrosion takes place. Metal
loss may be less but penetration is high as loss of metal takes place from a small area-
giving rise, to failure of the equipment. Pits also acts as initiating point of stress
corrosion.

Pitting corrosion may take place when a protection film, layer of corrosion
product breaks down or due to formation differential concentration cell etc. Example
stainless steel if exposed in chloride environment, chloride ion breaks down the
passive film and gives pitting.

CREVICE CORROSION

Crevice corrosion is intense localized corrosion, which occurs in crevice or area,


which is shielded from the bulk environment. This gives rise to the differential,
concentration cell. Since the crevice hinders the diffusion of oxygen, a differential
areation cell is formed. The best way to avoid crevice corrosion is to avoid crevice
(Fig.4f)

Fig.4f: Crevice corrosion

INTER GRANNULAR CORROSION

Inter granular corrosion is localized attack at metal grain boundaries. For example, a
stainless steel improperly heat-treated may have grain boundaries depleted in chromium
thus less resistant. Attack is along the grain boundaries giving inter crystalline crack. Some
high strength aluminium alloys are also prone to inter grannular corrosion.

43
SELECTIVE LEACHING

In selective leaching one element of an alloy has preferential dissolution. Most common
example is dezincification of Brass. If brass (less than 85% copper) is exposed to wet
condition for a long time Zinc may be lost from the brass. Resulting zinc free copper looses
its ductility and strength. A small amount of, Antimony or Arsenic acts as a poison to
dezincification. Another example is graphite corrosion of cast iron (see cooling water).

EROSION CORROSION

When corrosion takes place, rate of corrosion: decreases with time due to polarization
but if erosion also takes place it are ever increasing. For example, an oxide layer is formed
on the S.H. tube surface due to high temperature oxidation and then rate of oxidation
decrease. However, abrasive solids present in flue gas will erode that oxide layer and base
metal will be exposed and again oxide layer will form and this will continue. Combined effect
of erossion and corrosion is more detrimental than any of them. It can be identified by the
grooves, rounded holes etc., which are smooth and have directional pattern.

Erosion corrosion is increased by high fluid velocity turbulence, high solids contents, etc.

CAVITATION

Which is damage due to formation and collapse of bubbles in high velocity turbines,
propellers, etc. is a form of erosion corrosion.

STRESS CORROSION CRACKING

When a metal under stress exposed to a specific corrosive environment for that
metal, it might ultimately fail due to stress corrosion cracking (Fig.4g).

Fig.4g: Stress corrosion cracking

Tensile stress build up at the metal surface under static loading corrosion concentrate the
stresses causing them exceed metal yield point and results in local failure. Further corrosion
takes place and again stress concentration and the crack propagates (either inter granular
or transgrannular) with eventual failure.
Metal Environment

Austenitic stainless steel for SCC chloride


Copper alloys ammonia/oxygen
Mild steel. High caustic (Table-5)

44
CORROSION FATIGUE

When a metal is under cyclic stress, it can undergo infinite cycle of operation if the
stress is under the endurance or fatigue limit. But if it exceeds the endurance limit metal
will fail. This failure is purely mechanical.

In corrosive environment endurance limit or fatigue limit do not exist. Hence, a metal
under cyclic stress if exposed to corrosive environment will definitely fail whatever low
stress may be. This failure is due to corrosion fatigue.

HOW TO COMBAT CORROSION

There are various ways to fight with corrosion. Some of the approaches are listed below:

1. Change the metal, use some suitable resistant alloys but some times it
become expensive and resistant alloy also gives localized corrosion.

2. Use of suitable paints, protective coating etc.

3. Change of design.

4. Change of environment

5. Cathodic protection
Of the above let us consider (4) and (5).

CHANGING THE ENVIRONMENT

This is widely used practical method of controlling corrosion in liquid media. There
are different ways to modify the environment.

Eliminate oxygen: It is already discussed that oxygen accepts electron to continue the
cathodic part of the corrosion reaction. Hence, removal of oxygen will control the
corrosion cathodically. By proper mechanical deaeration and using chemical oxygen
scavengers, oxygen level can be reduced to ppb level. Effect of oxygen on corrosion of
low carbon steel is shown in (Fig.5a).

Fig.-5a

45
REMOVE CO2 : Carbon dioxide in water forms carbonic acid result is lowering of pH
and acid corrosion. Effect of carbon dioxide can be neutralized by suitable volatile
alkaline chemicals like ammonia, morpholene, cyclohexyl ammines, etc.

pH: If pH is not maintained properly it may give severe acid corrosion at low pH (below4.5)
and alkaline corrosion at very high pH (about 13).

For plain carbon steel effect of pH on corrosion is shown in Fig.6a. Stability of the
protective oxide layer on mild steel is pH dependent. Hence, proper pH should be
maintained with suitable alkaline agent to reduce corrosion.

Humidity: Humidity makes the environment conducting. If the environment is dry, it will
offer higher resistance and thus reduce corrosion current. We can solve many corrosion
problems by keeping the environment DRY. Example Dry preservation of Boiler.

REDUCE LIQUID SPEED TEMPERATURE : Any chemical reaction rate is accelerated with
rise in temperature, hence control of temperature helps to reduce corrosion. Higher liquid
velocity has a depolarizing effect and hence increases corrosion. Therefore, corrosion can
be reduced by cutting back the liquid speed (Fig.5b).

Fig,5b : High velocity tends to depolarize metal thus increases corrosion

INHIBITORS: Inhibitors are inorganic or organic compound when added in small amount
in solution retards the corrosion rate by increasing polarization rate at either anode or
cathode or both.

Anodic Inhibitor: (Chromate, Nitrite, Phosphates, etc.) polarize the anode potential
towards cathode and cathodic inhibitor (Arsenic, Nickel salt etc.) polarize the cathode
potential to wards that of anode resulting in lowering of potential differences hence
corrosion rate.

46
Some inhibitors builds up an electrically resistant film on anode or cathode and reduce
corrosion. Effects of anodic & cathodic inhibitor on corrosion are shown in Fig. (5c) to (5f).

Fig.5c : without inhibitor Fig.5d: with Cathodic inhibitor

Fig.5e : Effect of Anodic inhibitor fig.5f: Approaching ideal

47
While using anodic inhibitor care should taken that insufficient amount may lead to
severe localized corrosion

Cathodic Protection: is considered to be the most. effective method to check corrosion of


metals even to the extent of complete protection. All forms of corrosion such as uniform
attack, stress corrosion Cracking (e.g. brass, stainless steel, steel aluminium and
magnesium alloy), corrosion fatigue, intergrannular corrosion (e.g. duralumin, 18.8
stainless steel), dezincification of brass and pitting (steel in soil, stainless steel in sea
water), can be effectively checked or totally stopped by this method.

In principle, cathodic protection consists of supplying direct current to the structure


through an external anode which polarizes cathodic points of the local corrosion cells to a
potential equal to the anode potential. This results in an uniform equipotentiality of the
anodic and cathodic regions all over the surface and the flow of the corrosion current
ceases.(Fig.5g)

Fig.5g : Both electrode same potential –No Corrosion

The metal, therefore, cannot corrode so long as the external current is maintained.
The corresponding polarization diagram is given in Fig.5h where I applied, is the current for
complete protection.

48
Fig.5h

EXTENT OF POLARIZATION NECESSARY

i) If the metal is polarized slightly beyond the open circuit potential of the anode,
the corrosion rate remains zero. Net current to the anode areas is from
electrolyte to metal and hence metal ions cannot enter into solution.

ii) Current used in excess of required does no good, however may do harm to
atmospheric metals and coatings. In practice, therefore, imposed current is
kept close to the theoretical minimum.

iii) Should the applied current falls below that required for complete protection,
some degree of protection is afforded nevertheless.

For example:

(a) If the applied current is (b-e) the corrosion potential is moved from  cor.
to (a) and the corrosion current decreases from I cor. to (a-b). The total
cathodic current (corrosion plus applied current) is (a-e)

(b) The applied current (b-e) is increased, the potential (a) moves to more
active values and the corrosion current (a-b) becomes smaller.

(c) At the limit, when (a) coincides with  A, corrosion current (a-b) becomes
zero and applied current for complete cathodic protection equals Iapplied.

Application of cathodic protection on the entire bare surface of a structure needs


heavy current, and involves high cost. Therefore, cathodic protection is usually applied
as a supplement to a paint coating.

49
There are two ways to cathodically protect the structure. The 1 st method consists
of using a rectifier and insoluble auxiliary anodes. From an external power supply a
direct current is impressed on the system by connecting the negative terminal to the
structure, intended for cathodic protection, and the positive terminal to the insoluble
anodes. A steady flow of current is maintained through the circuit. The magnitude of
current required for cathodic protection depend on the corrosiveness of the environment
and amount of surface to be protected. In the 2nd method anodes of less noble metal are
fixed on the structure, having a galvanic contact with it. These galvanic anodes dissolve
out in the medium to provide the protective direct current and voltage. These are termed
as sacrificial anodes. For medium and low corrosive media and also where the power
supply is not available, the galvanic coupling has more advantages.

The criterion for cathodic protection of steel structures is considered to maintain a


polarization potential – 850 mv with respect to Cu/CuSo 4 reference electrode. For other
metals, potential may be lowered by 100-200 mv from their corroding potential,
depending on the corrosiveness of the environment, for adequate protection. See table 6
and 7. For both the systems, design of the installations plays an important role.
Selection of anode material and their distribution (in case galvanic anode), anode bed
design (in case impressed current system), selection of backfill material, mode of cable
joints, etc. are important.
Pre-survey of the surroundings of the structure including electrical resistivity of
the media, current requirement and characteristics and position of other neighbouring
structures, etc. is essential to avoid various troubles including 'interference effect.
The tendency to provide over-protection to the structure not only uneconomic but
also over protection may results in alkali attack on the metal as well as on the paint
coating.

Magnesium, aluminium, zinc and their alloys are commonly used as sacrificial
anode. For impressed current system known anode materials are scrap iron, Fe3O4
graphite, Duriron, Pb-alloys, Pt. etc. Insoluble anodes with higher current carrying
capacity, better mechanical strength and durability help to reduce cost in maintenance
and provision of protection.

Table-4 Orders of magnitude of current density required fo cathodic protection of steel


Environment Amp/dm2 Amp/sq.ft
Sulphuric acid pickle tank 4.0 35.0
1- Soils 0.0001-.005 0.001-0.05
Moving sea water 0.0003-.0015 0.003-0.015
Air std. water (Hot) 0.0015 0.015
Moving fresh water 0.0005 0.005

Table-5 Potential requirement for cathodic protection


Metals V ref. to Cu-CuSO4
Electrode

Fe -0.91

Cu -0.16

Zn -1.25

Pb -0.59

50
Table-6 Galvanic Series of Commercial Alloys in Sea Water Corroded end

Mg
Zn
AI
Cd
Duralumin (4.5 Cu, -0.5 Mg, 0.6Mn)
Steel of iron
Cast iron
St. steel (13% C)
Ni-resist (high nickal cast iron)
18:8 st. steel
18:8 Molybdenum steel
Lead tin soldier
Lead
Tin
Ni (active)
Inconel (active)
Hastealloy B
Chlorimet 2
Brass
Cu
Bronzes (Cu-Sn)
Cupro-nickel
Monel
Silver Solder
Nickel (passive)
Inconel (passive)
St. steel passive
Hastealloy C
Chlorimet3
Ag
Ti
GrapHite
Gold
Pt
Protected end

51
TABLE 7.

Environments that may cause stress corrosion of metals and alloys

Material Environment Material Environment


Alluminim NaCI-H2O2 solution, NaCI Ordinary NaOH solutions,
Alloys solutions, Sea water, Air, steel NaOH-Na2SiO2 solutions
Water vapor Calcium, ammonium and
sodium nitrate solution ,
mixed acids
(H2SO4+HNO3)HCNsolutions. Acidic H2S
solutions, Sea water, Molten Na-Pb
alloys

Copper Ammonia Vapors and Gold Alloys FeCL3 solutions acetic acid –salt
Alloys solutions Solutions
Amines,
water vapor
Inconel CausticSoda solutions Lead Lead acetate solutions
Stainless Acid Chloride solutions, Such Monel Fused caustic soda, Hydrofluoric acid
steel as MgCI2 and
BaCI2, NaCI, H 2O 2
Solutions, sea water
Magnesium NaCI-K2CrO4 solutions, Nickel Fused caustic soda
Alloys Rural and costal
atmospheres,
Distilled water
Titanium H2S, NaoH-H2S solutions,
alloys condensing stream from
chloride
Red fuming nitric acid, sea
water,N2O4, methanol-HCI

52
CHAPTER-3

INTERNAL CORROSSION

During normal operation, an impervious film of protective oxide layer (magnetite) is


formed on the metal surface, which protects the base metal form internal corrosion. If by
some mechanism, this protective layer is disturbed, giving rise to less adherent porous
laminated oxide layer or cracks in the protective layer, tubes will corrode at faster rate.

Deviation from the recommended chemistry limits, which results in high or low pH
where the protective layer is unstable, promotes failures due to corrosion.

In a running boiler mainly two types of corrosion takes place.

I. Caustic corrosion or Ductile gauging


2. Hydrogen damage

Generally on load corrosion is accelerated by concentration of impurities in water


where partially or fully stagnant conditions exists. Concentration of impurities is caused by
evaporation of water leaving behind the dissolved impurities at this locations. The regions
where such stagnant conditions exist are regions of the tubes where internal surface is
fouled by deposits, imperfect weld penetrations, horizontal tubes, etc.

CAUSTIC CORROSION OR DUCTILE GAUGING

Caustic can get into the boiler in the following ways:

(i) If caustic phosphate treatment is followed.


(ii) Due to condenser tube leakage where CW contains high bicarbonate which breaks up in
boiler producing caustic.
(iii) Faulty make up water.

Normal caustic concentration are not corrosive but under deposit when concentrated
it dissolves Magnetite layer and then steel. The damage progress to failure, when the tube
wall thins to a point, where stress rupture occurs locally. There is no change in the metal
microstructure, it retains ductility. The failure is due to thinning of metals.

HYDROGEN DAMAGE

Hydrogen damage occurs when a low pH boiler water environment is produced from
condenser tube leakage or some other types of system contamination.

This type of corrosion usually occurs beneath a relatively dense deposit. Although
some wastage occurs the tube normally fails by thick edge fracture before the wall
thickness is reduced to the point where stress rupture would occur. Hydrogen produced in
the corrosion reaction diffuses through the metal, causing decarburization and inter
granular micro fissuring of the structure. Brittle fracture occurs along the partially
separated boundaries and in many cases, an entire section is blown out of an affected
tube. .

53
As per laboratory research programme, clean tubes are not susceptible to corrosion even
under high heat transfer conditions unless unusually high concentration of acid or alkali is
present.
Further fouled tubes are not much susceptible to corrosion if proper boiler water treatment
is maintait1ed.

Condenser cooling water is a potential source of contamination of boiler water.


Depending on chemical constituents presents, highly acidic or alkaline materials may be
produced in boiler environment because of condenser tube leakage. Co-ordinate pH/PO 4
control / congurant control program to maintain boiler water pH is best way to combat on
load corrosion.

PITTING CORROSION

Pitting is mainly caused by dissolved oxygen in water. This type of corrosion is


common in economizers. This may also occur in super heaters and other tubular sections
of boilers if proper shut down practices are not observed.

Some important measures to control corrosion:

(i) The storage and construction condition should be proper and thorough
pre operational cleaning of boiler to be carried out.

(ii) Proper preservation of unit during shut down.

(iii) Minimum metal oxide in feed water during start up operation and full
load condition by proper pHlO2 controls. This will reduce amount of
fouling of tube surface.

(iv) Periodic chemical cleaning to remove deposit and keep the tube surface
clean.

(v) Co-ordinated pH phosphate control, to avoid free caustic or low pH


condition in boiler.

(vi) Ammonia concentration to be kept below 0.5ppm to minimize


cupper corrosion.

TURBINE

Main damages found in steam turbines are due to:

(i) Down time and wet end corrosion


(ii) Erosion
(iii) Stress corrosion cracking

 In down time and wet end corrosion, attack is on carbon steel portion due to
presence of water droplets and CO 2. Neutralizing ammine is the remedy. O 2 ingress
should be avoided if unit is not dry.
 Erosion, due to water droplets, solid particles, impinging on blades at high
velocity.

54
Water droplets may present in steam if desuperheating control is not well
maintained. These droplets may cause erosion in H.P. end.

Low or changing load may result in water droplets erosion in LP end, due to
condensation. Remedy: Avoid operating condition to minimize water droplet formation.

STRESS CORROSION CRACKING

The main contaminants that contribute to this type of failure are caustic, chloride
and sulphide. while caustic and chloride are usually presents in deposits as a result of
mechanical carryover from boiler, sulphide can be present in make up water as H 2S and
leave with the steam as a gas or may be formed due to decomposition of Na 2S03 when
used for oxygen scavenging.

In presence of H2S, stress corrosion cracking can occur as H2-embrittlement. Caustic


embrittlement of turbine alloys results from reaction between caustic and grain boundaries
of the steel in an environment of high stress, high temperature and high caustic
concentration leading to an intergrannular type failure.

Chlorides attack stainless steel, one mechanism being pitting which Notches the
metal, resulting in the formation of stress risers. However stress cracking in presence of
chloride without any visible surface defects has also occurred.

Very recently, it is reported that organic carbon can induce stress corrosion cracking
in turbine. As a remedial measure, care should be taken to minimize gross carryover.
However, at present sodium sapphire treatment is more or less discarded. Caustic and
chlorides are also restricted in boiler. Care should be taken during initial start up and
operation with condenser leakage.

Decomposition of cyclohexyl ammine and morpholene at higher temperature may


produce organic carbon. Most of the high-pressure unit now uses ammonia, which does not
give any organic carbon. As a precautionary measure, organic carbon should be monitored
in the cycle.

CORROSION IN COOLING WATER SYSTEM

Various metals and metal alloys are used in construction of cooling water system. The
condenser tubes are normally made of copper alloys. Condenser water boxes pipe works,
Valve bodies etc. are of cast iron or mild steel. Valve and pump internals may be stainless
steel or phosphor bronze.

In normal cooling water, the above materials give good service but with saline or
heavily polluted cooling water, corrosion between dissimitear metals takes place.

CORROSION IN CONDENSOR WATER BOX

Condenser water box is normally made of mild steel or cast iron. Since this is
attached to more cathodic materials, in aggressive cooling water severe corrosion takes
place. In case of cast iron, Fe preferably goes into solution leaving behind graphite. The
structure retains its shape but looses mechanical strength. Selective leaching of Fe from
cast iron is known as graphitic corrosion.

55
In case of mild steel galvanic corrosion also results in loss of metal from condenser
water boxes.

PROTECTION

Condenser water boxes, if allowed to corrode, gives cathodic protection to


condenser tubes. It can be protected by painting or other protective coating. However,
the best method of protection is to give cathodic protection either by Impressed current
or by using suitable sacrificial anode.

CONDENSOR TUBE CORROSION

When copper alloy condensers are exposed to cooling water a very thin protective
oxide film is formed which protects the metal from further corrosion. In very aggressive
water, if the condenser tubes are exposed before formation of this film or if the film is
damaged, then corrosion will occur.

Iron, present in cooling water, assists in formation of a very tough and adherent
protective film. Source of iron may be from corrosion of condenser water box or may be
in cooling water as iron salts. To form a protective film, Ferrous sulphate treatment may
be given to the new condenser tube before exposing to aggressive cooling water. This is
not so much effective in case of Cupro-Nickel alloys.

The attacks, which break down the above protective film are:

(i) Erosion corrosion

(ii) Differential concentration cell formation.

ERROSION CORROSION

Normally occurs in case of once through cooling system where solid particle,
entrained gases present in cooling water, removes the protective film, again, the base
metal is exposed and oxide film is formed which is repeatedly removed. Higher
turbulences, velocity increases this rate of erosion. Hence erosion corrosion, if the
condenser looks like a new one with bright yellow lusture, it is not a good sign. It indicates
that oxide layer has been removed due to erosion.

CORROSION DUE TO CONCENTRATION CELL FORMATION

If the condenser tubes are not clean, if it has deposits (which are porous), under goes
corrosion due to formation of differential aeration cell. The area under deposit is less
oxygen area and hence anode, in comparison to the surrounding metal exposed to cooling
water, which contains more oxygen hence cathode.

In case of very polluted water, which contains no oxygen, sulphide is formed by


bacterial action on the sulphate present in water. This sulphide also corrodes

Condenser tubes. Table 7a gives some common condenser alloy and their specific
properties.

56
Table 7a: Condenser Tube Alloys
70/30 Brass Cu-70 % As inihibit-dezincification
Zn-29.96%
As- 0.04%
Admiralty Brass Cu=70 % Good performance in fresh
Sn-01% unpolluted water
Zn-28.96%
As- 0.04%
Alluminium Brass Cu-76 % Rapid healing of films,
AI-O2 % resistant to impingement

Zn-21.96% attack used less severe


As- 0.04% condition than cupro- nickel
90/10 Cupro-Nickel Cu-87-88% Not so resistant to erosion
Ni-O9-10% 70/30 as cupronickel
Fe- O1-O2%
Mn- 01%
70/30 Cupro Nickel Cu-66 % Resistant to impingement attack
low Fe/Mn Ni-30%
Fe- 01%
Mn-01%
70/30 Cupro Nickel Cu-66% More Resistant to impingement
high Fe/MN Ni-30% attack
Fe-02%
Mn-02%
Stainless steel Cr-18% ,Ni-12%
Mo-2.5% Very resistant to erosion and corrosion
Titatinum Very resistant to erosion and corrosion

From Top to Bottom

1. Heat transfer decreases


2. Corrosion and Erosion resistance increases

3. Cost increases
4. Biological fouling increases

5. Chemical deposition decreases

OVERHEAT FAILURE

57
Tube failure caused by over heating: It has been already discussed that internal
deposits accelerates the corrosion of boiler tubes. Deposits also promote the majority of
tube failure caused by overheating. Failures due to overheating can be classified into two
categories (1) short term overheating and (2) long term overheating.

Short term over heating failure occurs when metal temp. exceeds lower critical
temperature of plain carbon steel (723°C). At this temperature yield strength is low, metal
deform plastically and fails. This failure is characterized by massive swelling, bulging and
wide thin edge rapture, commonly known as fish mouth opening.

Such failure are caused by loss of circulation either because of choking or loss of
water level in drum or flame impingement on the tubes, secondary combustion etc. These
are common in high heat flux areas like water wall. Flame impingement is commonly
caused by damage to burner system. Short term overheating failure in super heater may be
caused due to choking or design defect.

Creep range overheating or long term overheating:

In this case, temperature of overheat falls below 700°C. Depending upon the material
and temperature of over heat actual failure may occur within a few hours to a few years.

Thick rupture edge, extensive scaling, scale cracking parallel to the main burst are
typical visual evidences of this type of over heating.

Long term over heating failures may be caused by a high furnace temperature, partial
chocking of tubes, internal deposits, external deposits etc. This type failure may occur in
super heaters, water wall, re heaters etc.

58
CHAPTER-4

CHEMICAL CONTROLS OF WATER AND STEAM

Main objective of chemical parameter control is to avoid corrosion and deposition


problem in the system. Samples are collected from different places as shown in Fig.6
and tested at regular interval to know the condition of the unit.

In Boiler feeder water some parameters like total solids / conductivity, silica are
controlled to lower the blow down requirement in boilers where as pH, oxygen, Cu-oxide,
Fe-Oxide, etc are controlled to minimize corrosion in feed system. However, Fe and Cu
oxides also give deposition in boiler.

In boiler water, some parameters like total solid, alkalinity and Silica is controlled
to produce required quality of steam whereas pH and phosphate is maintained to
minimize corrosion and deposition in the boiler.

In steam, Silica is controlled to avoid deposition of silica in turbine blade which is


very difficult to remove when deposited in insoluble form, pH is maintained to minimize
corrosion.

In condensate pH is maintained to minimize corrosion, NH 3 is controlled to avoid


stress corrosion cracking of condensers.

The advantage of taking sample from different location is that if some thing goes
wrong it can be easily pinpointed.

For example, say saturated steam conductivity after cation column, which indicates
carry over of water droplets containing more solid which increases the conductivity. If
conductivity of super heated steam is less than saturated steam, it indicates deposition of
solids is taking place in super heater. Similarly, if silica in condensate is less than silica in
steam, it indicates silica deposition in turbine. When silica in condensate is more than in
steam it may be due to condenser tube leakage or make up water contamination or due
to blade washing. In this way, continuous monitoring helps to find the problem as well as
cause for the same. This helps quick remedial measures.

CORROSION AND DEPOSITION CONTROL IN STEAM AND WATER CIRCULATING


SYSTEM

BOILER FEED WATER

Boiler feed water comprises around 95-97% return condensate and 3 to 5% make up
water from D .M. Plant.

59
60
Most of the high Pressure boilers up to 500 MW capacity, so far installed in India,
are all drum type units. This helps us to operate the boilers with margina1 quality of feed
water. Impurities present in feed water concentrate in drum and in the drum, for quality
steam, amount of permissible solids are specified. The total solid in the drum is controlled
by blow down.

The main objectives of feed water chemical control are:

1. To minimize blow down in boiler drum.

2. To minimize corrosion and deposition in the feed system and boiler.


Let us take up the control parameters and discuss:

TOTAL SOLIDS

Basic idea of controlling total solids, to be more specific, total dissolved solids is to
minimize the blow down. Higher TDS in feed water will carry and increase TDS in boiler,
which will lead to foaming, carryover, if not controlled by increased blow down. Blow down
means loss of costly DM water, conditioning chemicals and heat.

Another important factor is that the feed water is used as spray media for
attemperation. With high TDS water, the solid will be carried over with steam and deposit in
the secondary super heater, turbine stop valve etc.

CONDUCTlVITY

Total dissolved solid in feed water or rather in all water can be determined by
measuring conductivity.

Pure water is a bad conductor because its dissociation is very less. Pure water
contains very less ion and so its conductivity is around 0.056 S/cm at 25°C.

When solids dissolve in water they dissociate and number of ions increases which
increase the conductivity of water. Hence, concentration of dissolved solids is proportional
to the conductivity of water.

For feed water type water, 0.5 ppm solid may increase conductivity by 1 S /cm. Other
cases the factor may by 0.6 -0.9 depending upon the impurity of water.
Conductivity is monitored in water/steam etc. to know how much solid is present in
that water/steam.
Since liquids & gases do not give deposition, we are not interested about liquids & gases but
they also give rise to conductivity. As ammonia, hydrazine etc, are dosed in the feed water
they also increases the conductivity.

For this conductivity is measured after passing through a cation exchanger column
which removes ammonia

CO2 present in water also gives conductivity for which necessary correction is required
for ascertaining the actual solid present.

61
SILICA

Silica in feed water is controlled as in boiler we have to maintain specified silica


concentration for steam silica restriction. Higher silica will increase blow down reducing
plant efficiency.

Further, when this feed water is used for attemperation this will increase the silica
level in steam resulting in silica deposition in turbine. For this reason silica in feed water is
kept at minimum.

pH

In feed water, pH is maintained for corrosion control in the feed system. Feed system
comprises of plain carbon steel and some copper alloys.

Steel is protected by formation of an impervious protective layer of Fe 304 on its


surface. This is black in colour and called magnetite. As long as this protective oxide layer
remain intact base metal is protected from corrosion. The stability of this oxide layer is best
around pH 10.5-11. At low pH (acid) and at very high pH this oxide layer get dissolved
exposing the base metal to corrosive environment

Like magnetite, copper alloys are protected by formation of cuprous oxide layer,
which is best stable at pH 8.3-8.6.

To strike a balance, to minimize both steel and copper corrosion the pH is


maintained around 8.2 to 9.2. In case no copper alloy exists it may be kept little bit
higher i.e. 9.2 to 9.5.

OXYGEN

Oxygen in feed water is controlled to minimize corrosion. If oxygen is not present,


most of the corrosion problems are solved. Rate of corrosion increases with increase in
oxygen concentration.

The rate of corrosion of steel decrease with increase in pH and is minimum at 10.5 to
11 pH, but in absence of02 this can be achieved even just at neutral pH (7 above).

Deaerating heaters are designed to reduce oxygen to 5-10 PPb. However,


practically improper operation prevents to achieve that goal. Hence, chemical scavenger is
a must. For high pressure boiler hydrazine is used for this purpose. In low pressure,
sodium sulphite is a better scavenger.

It is not possible to make oxygen level zero but 0.007ppm is for all practical
purposes may be treated as zero.

HYDRAZINE

Hydrazine is used for scavenging oxygen. It has the advantage that it is liquid hence
it does not increase the TDS. Reaction with oxygen produces N2 and water.

62
Fig.6a: Attack on carbon steel by water of varying Degree
of acidity and alkalinity

Fig.6b : Time l Temperature relationship for 90% oxygen removal by hydrazine at 9.5 pH

On decomposition, excess hydrazine gives ammonia. Only draw back of hydrazine is


that it reacts very slowly at low temperature Fig.6b and it is carcinogenic. Prolong contact
with skin may cause skin cancer.

It is advisable to add hydrazine after deaerator to avoid unnecessary loss through


deaerator vent. Since make up water is saturated with oxygen, like ammonia, hydrazine
dosing (LP) is also continuous.

63
HARDNESS

Hardness is restricted to below detectable limit. Calcium/magnesium salt may come


into feed water through condenser tube leakage, condenser tube end leakage or from
improper D.M. water. They may form scales in stage heaters, economizers, evaporative
system in steam generator. Pre boiler corrosion also gives Fe- oxide and Cu- oxide which
also may from deposit in boiler.

IRON AND COPPER

Amount of iron and copper oxide in feed water indicates how much corrosion is taking
place in feed system. Since it is not possible to make pre boiler corrosion nil, aim is to
restrict the corrosion to the acceptable limit.

Fe-oxide and cu-oxide is the major source of deposition in the modem HP boilers.
Further, they contain oxygen which is a potential source of corrosion.

Further if copper deposited it may induce localized corrosion cell giving pitting. Copper
some times sublime and gives deposit in super heater and turbine. By attemperation they
will contaminate steam directly. If the level of iron and cu-'oxide is kept within specified
limit, the detrimental effects can be controlled.

CARBON DIOXIDE

Carbon dioxide is the most important dissolved gas after oxygen to accelerate the
corrosion. Low pH corrosion in steam and return lines are caused by carbonic acid.
Carbonic acid is formed by the reaction of water and carbon dioxide. Carbon dioxide comes
in the system from air in leakage in low pressure region. Other source is condenser tube
leakage. As most of the cooling water contain lot of carbonate and bi- carbonate which
breaks down to CO2 in boiler. This is carried over to after boiler. The direct effect ofH 2CO3
is to reduce condensate pH, leading to generalized loss of metals and grooving of
condensate lines. When CO2 and O2 both present, corrosion rate is very high.

Low pH conditions are controlled by adding volatile alkaline chemical. In high pressure
unit ammonia is used for this.

CHLORIDE

Presence of chloride is harmful as chloride ion can break through any passive
protective layers and induce corrosion. Further, chloride ions induce stress corrosion
cracking to austenic steel.

OIL

Presence of oils gives rise to foaming in boiler. Further, oil forms films on heat
exchanger/ heaters, which impairs the heat transfer.

64
BOILER WATER

Objectives of boiler water chemical control are:

(i) To, prevent scale formation in the system, which impair heat transfer resulting in loss in
efficiency. Further, this also causes over heating and ultimately failure of the tubes.
(ii) To prevent corrosion in the boiler.
(iii) To produce quality steam as specified.

CONTROL OF CORROSION AND SCALE FORMATION

The principle sources of ingress of scale and deposit forming solids in boiler are :

(i) Condenser tube leakage


(ii) Condenser tube end leakage
(Iii) Faulty Demineralization
(iv) Corrosion products from improperly treated feed system.

Contamination from the above sources concentrate in boiler with eventual deposition
of scale forming substances.

The different methods of internal treatment of boiler are as below:

(i) Caustic-phosphate treatment


(ii) Co-ordinated pH-PO4 treatment
(iii) Congurant control
(iv) Caustic treatment
(v) All volatile treatment

CAUSTIC PHOSPHATE TREATMENT

Boiler water pH is maintained by caustic and phosphate level is maintained by


addition of any phosphate. Corrosion is controlled by pH control and if hardness comes in
the system calcium/magnesium salts are precipitate as sludge, which can be removed by
blow down.

The main disadvantage of this method is that the caustic may concentrate under
deposits, crevices, bends etc. giving rise to local high concentration of caustic which
dissolves the magnetite layer and steel. Due to thinning of tube surface, the tube fails. This
is called caustic gauging/caustic corrosion.

For this reason this method of control has been discarded as TPS practice.

65
66
CO-ORDINATED pH - PHOSPHATE CONTROL / CONGURANT CON1ROL

Trisodium phosphate is used. Phosphate is a pH buffer in this programe and limits the
localized concentration of caustic.

On hydrolysis Trisodium Phosphate gives sodium hydroxide and disodium Phosphate

Na3P04 <=> NaOH + Na2 HP04

NaOH thus produced helps to maintain pH of the boiler water and Na 2 HPO4 removes
hardness by formation of sludge.

When equimolecular mixture of NaOH and disodium Phosphate is evaporated to


dryness, only trisodium phosphate remains; not disodium phosphate or NaOH. Trisodium
phosphate is least soluble of these three and first precipitates out.

Thus, if NaOH and Na2HP04 are concentrated under deposit, pH never exceeds 12.5.
So caustic corrosion does not take place.

For safe boundary, ratio 2.6:1 is maintained (Congurant control). The restriction
imposed is that sodium to phosphate molar ratio should not exceed 3: 1. If exceeded this
indicates formation of free caustic.

Problem with trisodium phosphate is its very low solubility at higher temperature.
Hence at higher temperature phosphate disappears from the solution, get deposited in
some loops/ bends etc. and when the load is reduced it reappears in the solution. This is
called phosphate hide out.

To maintain pH-PO4 ratio 2.6:1 other than trisodium phosphate another phosphate
like disodium phosphate or monosodium phosphate may be used

CAUSTIC TREATMENT

Since at high-pressure boilers phosphate hide out takes place and this phosphate
gives deposits, in some countries phosphate treatment is discarded. Instead, to ensure
buffering capacity of boiler water they recommend maintaining 2-3 ppm caustic soda in
boiler to maintain alkalinity.

In India since most of the units do not have condensate polishing arrangements,
cooling water contains lot of scaling minerals and has to run the unit with some leakage;
phosphate treatment still is the best option.

VOLATILE TREATMENT

All volatile treatment excludes all nonvolatile salts from boiler water and depends
upon ammonia or other volatile ammines to provide necessary alkalinity. Super critical
boilers use all volatile treatment generally consisting of ammonia and hydrazine as no
solid can be tolerated in super critical once through boiler.

67
PARAMETERS TO CONTROL STEAM QUALITY

Total Solids: Total solid in boiler water is restricted to restrict solids in steam. Solids in
steam, depends on two variables; one is boiler water solid and other is boiler water
pressure. Since whatever solids present in boiler water will have proportional representation
in steam, at a given pressure steam solid will increase with increase in boiler water solid.
Again, with same boiler water solid with increase in pressure steam solid will increase. This
is chemical carryover and cannot be controlled by any mechanical separators. To keep
steam solid under control higher the pressure of the boiler lower is the permissible limit of
solids in Boiler water.

Further dissolved solids, suspended solids and alkalinity give rise to foaming, which
causes carry over and contaminate steam. For this reason solid in Boiler water is
controlled. The limit depends upon design and operating pressure on the unit.

SILICA: Like total solids silica is also controlled to restrict steam silica. With
increase in pressure amount of silica carry over increases and for high pressure boiler this
selective carryover is very high.

The Silica in steam creates two problems erosion and deposition. If there is a gross
mechanical carryover due to inefficient operation of steam purification equipment,
resulting in mechanical entrainment of boiler water in saturated steam, the total silica
content may exceed the solubility product at the operating pressure and super heat
temperature. In this case, silica particle will be present in steam and result in erosion of
turbine blading and steam control valves.

However, modern high pressure unit do not allow such amount of carry over to
cause silica erosion problem. Second problem is the volatilization of silica into steam
carrying through the super heater and depositing in the turbine.

The formation of adherent deposits in steam passages distorts the original shape of
the turbine nozzles and blades. The deposits, frequently rough or un-even at the surface,
increase resistance to flow. Distortion of steam passages alters the steam velocity,
causes pressure drops and reduces efficiency. When the conditions are severe, the
deposit may develop un-evenly and create imbalance of the turbine rotor, causing
vibration and excessive rotor thrust.

Stage pressures in the turbine will indicate progressively higher value and may exceed
the recommended limit. Removal of this deposit needs longer outage and mostly carried out
manually. This results in a high revenue loss.

It is observed that steam can hold 0.02 ppm silica at the lowest pressure to
turbine. Hence, steam silica is controlled below 0.02 ppm to avoid silica depositions in
the turbine.

68
69
At different pressure of boilers and different pH amount of boiler water silica which
gives steam silica 0.02 ppm can be calculated from silica distribution vs pH curve
(Fig.6a) shows pressure V.S. Boiler water silica corresponding to steam silica 0.02
ppm. Boiler Water silica is controlled as per the pressure silica chart (Fig.6a).

BLOW DOWN
Increase in dissolved solids, silica, high alkalinity suspended solids etc. can be controlled by
blow down. Concentrated boiler water is removed by blow down and replaced with feed
water.

% blow down = Quantity of boiler water blow down x 100


Quantity of feed water
Normally, percentage of blow down ranges from 2-5%. In some critical cases where
feed water quality is very poor, this may have much higher value.

The maximum permissible limits of the above solids, silica etc. for each specific system
is usually determined from experience .eg. Two unit of BHEL of 210 MW in the same
station may have upper tolerance limit different.

Blow down may be given intermittently or continuously.

INTERMITTENT BLOW DOWN (IBD)

Intermittent manual blow down is designed to remove any sludge formed in the
boiler. Blow down take off is usually located at the lowest part of the boiler where the
sludge will tend to settle.

Intermittent manual blow down properly controlled lowers the dissolved solids,
suspended solids etc. Most of the boiler system contains intermittent and continuous blow
down system. Bottom blow down is given as per operation schedule and chemical testing.
Frequent short blow down is preferred to in frequent lengthy blow down to optimize control
and economy.

Generally, bottom blow down is recommended at moderate steaming rates and low
combustion rates. Blow down connections on the down comer header should be operated
strictly in accordance with manufacturers recommendations. For circulation problem,
water wall header blow down connections are not blown down while unit is running. They
are operated while the unit is under shut down. Water level is closely monitored during
this blow down.

CONTINUOUS BLOW DOWN (C.B.D.)

Continuous blow down removes concentrated boiler water continuously. It is an


extension of the schedule of frequent short blow down. Setting of the control valve is
adjusted to decrease or increase the blow down depending upon the test results. When
both blow down arrangements are provided IBD is given once in a day for short time to
remove suspended solids. Orientation of CBD take off line is such that it takes maximum
concentrated boiler water. The line also should be located so that boiler feed water and
chemical feed is not get easy entry in it. The sizes of the lines depends upon feed water,
quantity of blow down required, boiler rating etc.

70
Table –8
Recommended quality for water steam and super heated steam for
200/210 MW Unit Feed water (Sample from economizer inlet)
Sl.No. Parameter Limit Frequency of Remarks
Te
st
1 PH at 250C i. 8.8-9.0 Once/shift i. If F.W. Heater are of
ii 9.0-9.2 copper based alloy
ii. If heaters are of steel.
2 Specific conductivity at 250 0.3 Once/shift
C in (us /cm)
after passing
through cation
exchanger in H2
form
3 Total hardness (ppm as B.D.L. -do- B.D.L. (Below Detectable
CaCO3) (limit).. instrument is
available.Check th instrument
calibration in mid week

4 Dissolved oxygen (ppm) 0.007 Once/day If on-line instrument is not


(see note 2) available
Once/week If on-line instrument is
available check
the instrument
calibration in mid
week
5 Residual Hydrazine (ppm) 0.02 Once/shift
6 Silica (ppm) 0.02 Max -do-

7 Chloride (ppm) B.D.L. -do-

8 Total iron (ppm) 0.01 Once/week

9 Oil (ppm) B.D.L. -do-

10 Copper (ppm) 0.005 -do-

71
Table – 9
Boiler water (sample from C.B.D. line)

. Sl.No Parameter Limit Frequency of Remarks


Test
1 PH at – 250 C 9.4-9.7 Once/shift

2 Specific conductivity at 50 -d0-


250C
(us/cm)
3 Total dissolved 25 -do-
solution
(ppm)
4 Phosphate (as ppm 2 t0 5 -do- Any mixture of Na3 PO4 and
PO3-4 ) di or mono sodium
phosphate or
sodium hexa -meta
phosphate can be
used. pH control by
congruent Tech.
5 Total hardness (as B.D.L. -do-
ppm CaCO3
6 Free hydroxide (as B.D.L. -do-
ppm CaCO3 )
by strantium
chloride
method
7 Silica (ppm SiO2) 0.3 Once/shift As per pressure

8 Chloride (ppm) B.D.L. -do-


9 Sodium (ppm) Corresponding
to Na3
PO4
etc.
additi
on

Table-10
Boiler water quality
Drum operating pressure (kg/cm2) 61-100 above 101
Maximum total dissolved solids(ppm) 100 50

Maximum specific electrical 200 100 conductivity


at 25°C (micros/cm)

Residual phosphate (ppm) 15-25 5-10 (Note)

72
pH at 25°C 9.8-10.2 9.4-9.7(Note)

Maximum silica (PPM) To be controlled on the


basis of silica in boiler
water and pressure relationship
to maintain less than 0.02 ppm
in the stearn leaving the drum

Chlorides Not allowed


NOTE: PO4 and pH to be controlled in accordance with congruent phosphate
treatment to prevent the presence of free caustic in boiler water
Table-11
Boiler water limits for two stage drums In the case of two stage drums, the following
limits are recommended for drum operating pressures above 100 kg/cm 2:
Clear Salt
Compartment Compartment
Maximum total dissolved 25 75
solids (ppm)
Specific electrical conductivity 50 150
at 25°C (Micro-moho/cm)
Phosphate residual (ppm} 5-10 15-25
Chlorides Not allowed
Maximum silica ppm (for 60 0.9 27
& 100 MW units)
Maximum silica ppm (for 110) 0.4 12

During condenser tube leakage CW water comes into the system. Ca, Mg present in
CW water will react with phosphate and residual phosphate will be reduced. At the same
time, pH of the boiler water may increase or decrease depending upon the characteristics of
CW.

In case of sea water, pH of the boiler water will decrease and in case of normal
river water, pH may increase due to the formation of NaOH from carbonate/ bicarbonates
of CW. At the time of condenser tube leakage phosphate dosing pump should be started
to maintain higher level of phosphate. Blow down is needed for control of boiler water
solids and removal of sludge.

De-superheating spray should be avoided by permitting reheat temperature to fall and


reducing load. In case of CW water, which decreases pH, unit should not be run if pH
couldn’t be maintained above 8.5 and total solid below limit (Table-12).

CONDENSOR TUBE LEAKAGE DETECTION

If condenser tube leakage occurs, its early detection is essential to take necessary
action to limit impurities in feed water.

Normal method of detecting condenser tube leakage is to monitor conductivity of the


condensate. Increase in the conductivity indicates condenser tube leakage. But, increase

73
may be due to chemical dosing (ammonia/Hydrazine etc.). For this reason conductivity is
measured after action column which removes ammonia/hydrazine. Further the salts are
converted to acid, conductivity is also amplified which helps to confirm the increase.

For a small leakage, as the raw water coming into the hot well are mixed with very high
quantity of condensate effect is very much diluted which makes it difficult to confirm it.
However, in boiler this effect is concentrated. TDS, conductivity, SiO 2 etc. all increases but
phosphate decreases. pH may increase or decrease depending upon the CW.

TABLE – 12
Criteria for operation during condenser leak

Hot well Operational action Boiler water treatment Boiler water control
Concentration
Abnormal (0.5 to Schedule inspection of Total solids less than 100 Immediately start
2.20 ppm) Condenser as soon as ppm, pH- 9.5 to 10.5, PO 4 chemical injection
system load requirement – 15 to 20 ppm pumps to maintain
permits. excess phosphate and
pH conditions. Do not
continue to operate
unit if pH cannot be
maintained above 8.5
or the total solids
below 100 ppm.
Increase blow down to
limit total solids. Avoid
unnecessary use of
desuperheating spray
by permitting reheat
temp. to fall or
reducing load.
Excessive (above 1.Immediately reduce load Total solids less than 100 See above prepare to
2.0 as necessary to permit ppm, PH - 9.5 to 10.5, establish chemical
Ppm) isolation of damage PO4 - 5 to 20 ppm. conditions for wet lay-
condenser. up of boiler unit and
auxiliary equipment
2.Prepare for orderly shut during condenser
down if hot well repair.
concentration can not be
quickly reduced below 2.0
ppm.

Boiler water chloride can be monitored for detection of condenser tube leakage.
Station can have the standard graphs of after action conductivity by mixing varying
percentage of cooling water with condensate to judge the magnitude of mixing.

STEAM

The objective of steam quality control is to prevent corrosion and deposition in super
heater, turbine and condenser. The total solids, silica etc. are controlled to avoid their

74
deposition in the superheater and turbine.

Ideally, purity of steam must be monitored at the turbine inlet i.e. superheated
steam, which not only includes impurities from boiler water as a result of steam solubility
and carryover but also includes those impurities introduced by de-superheat spray. But
sampling of super heat steam is difficult. Saturated steam sampling is not difficult and is
used for steam quality/purity monitoring.

CARRYOVER

STEAM QUALITY AND STEAM PURITY

Amount of moisture in steam after separation and purification in the drum is


defined as steam quality and the amount of solid impurities present as steam purity.

Steam quality and steam purity is mostly affected by carryover. Carryover is the
contaminant that leaves the boiler with steam. Incomplete separation of steam from
steam water mixture in boiler results in carryover.

There may be many factors for incomplete separation. They can be broadly classified
as mechanical carryover and chemical carryover.

MECHANICAL CARRYOVER

Boiler design, insufficient or leaking in separator, high water level, method of firing
and load characteristics are the main reasons for mechanical carryover.

When the bubble of steam leaves the surface of water a very fine water droplets are
formed which can be easily carried over by steam. This type of carryover is called Mist or
Spray carryover. In normal condition this very fine mist accounts for the small impurities
present in steam.

As the amount of carryover increases it indicates failure of drum internals due to


exceeding the velocity limitations of the purification equipments. It begins with full rating
and is characterized by a constant increase with increase in rating. If the rating increases
sufficiently the heavy carryover is similar to priming.

Priming is the most intensified form of mechanical carryover and is characterized by


the entainment of sludge of water in the steam. Under severe condition of priming, steam
may carry more than 50% moisture by weight that represent less than 1 % by volume.

Sudden surge of steam due to a rapid increase in load or a sudden drop in drum
pressure causes priming.

Sudden increase in process steam demand may lower the steam header pressure and
in turn boiler drum pressure, causing rapid expansion of steam in boiler that can raise the
drum water level. As high water level reduces steam space, this causes carryover. Sudden
changes in operation should be avoided as far as possible.

75
Chemical carryover may be due to foaming or selective vapor carryover.

SELECTIVE VAPOURS CARRYOVER

As already discussed selective vapour carryover occurs due to solvent properties of


steam for various impurities present in water. Since they are carried over in vapour phase,
chemical carryover cannot be taken care of by steam purifying equipments. This can be
controlled by controlling boiler water solid impurities.

RETURN CONDENSATE

Feed water mostly contains return condensate; hence, quality of the feed water
depends upon the quality of return condensate. Under normal condition steam and returned
condensate parameters are same. Deviation indicates some problem.

pH in return condensate is maintained by condensation of volatile amines or


ammonia dosed in feed water, which prevents corrosion. Ammonia is restricted below 0.5
ppm to protect condenser tubes from stress corrosion cracking, oxygen level in the
condensate depends upon the air ingress and on make- up percentage.

Table - 13

Steam and S.H. Steam (Samples from drum outlet and main steam line
respectively)

Sl.No. Parameter Limit Frequency of test Remarks


1 PH at 250 C 8.8-9.2 Once/shift
2 Specific conductivity at 0.3 -do- Once/day if on-
250 C (us/cm) (after line instrument
passing through cation is available
exchanger in H2form)
3 Silica (ppm) 0.02(max.) -do-
4 Sodium (ppm) 0.015max. Once /day
5 Ammonia (ppm) 0.5 Once/shift

Table 14

Condensate (sample from condensate extraction pump discharge)

Sl.No. Parameter Limit Frequency of Remarks


test
1 PH at 250 C 8.0-9.2 Once /shift
2 Specific conductivity at 250 C 0.3 -do-
(us/cm) (after passing
through cation exchanger in
H2form)
3 Dissolved oxygen (ppm) 0.02 Once /day
4 Silica (ppm Si02 ) 0.02 (max) -do-
5 Total hardness (ppm CaC03) B.D.L. -do-
6 Free ammonia (ppm) 0.5 -do-

76
7 Chloride (ppm) 0.5 -do-
8 Sodium (ppm) 0.015 Continuous
(max.)

Table:
Make up water

Sl.No. Parameter Limit Frequency of Remarks


test
1 PH at 250 C 6.8-7.2
2 Specific conductivity at 250 0.3
C
(us/cm)
3 Silica (ppm Si02 ) 0.02)
4 Total hardness (ppm B.D.L.
CaC03)
5 Free ammonia (ppm) 0.5 Once /shift
6 Sodium (ppm) 0.015 Once /day

77
CHAPTER-5

CHEMICAL CLEANING

INTRODUCTION

In the earlier period, the pre-commissioning cleaning consisted of an alkali boil out
of the boiler, using caustic soda and tri-sodium phosphate or sometimes sodium carbonate
and subsequent flushing to remove gross contaminants that had entered the system
during construction stages. The cleaning process was aimed at loosening some of the mill
scale thus enabling it to be removed by blow down and the removal of oil and grease used
during construction. As working temperatures and pressures and also physical size and
complexity of the plant increased, it became less tolerant of foreign materials and
operating difficulties causing loss of availability and restricted output has led to the
development of more elaborate cleaning methods, including the use of acids primari1y to
dissolve mill-scales and other metal oxides. This would otherwise impair the heat transfer
as well as induce local corrosion cell.

Present precommissioning cleaning involves removal of loosely attached materials


etc. by water flushing then removal of oil and grease by alkali boil out and finally removal
of mill scales of corrosion products by inhibited acid. This gives a clean steel surface on
which a protective film of magnetite is developed by passivation with NH 3 and hydrazine
that protects the base metal from corrosion onward.

During the above process high pressure flushing removes most of the loose debris
etc. that would otherwise cause physical damage of the plant.

The process of cleaning must also include pre- boiler system as well. This is normally
done by flushing with a hot alkaline solution. A mild acid cleaning may be required if the
nature and quantum of fouling warrants it.

Here we will discuss the cleaning schedule that includes a portion of feed line, entire
evaporative system of the boiler and economizer. Super heater and reheaters are excluded
from this chemical cleaning operation. However super heaters and reheaters are subjected
to steam blowing that ensures total removal of foreign materials present in, them and save
the turbine from physical damages.

REASONS FOR PRE-COMMISSIONING CLEANING

The reasons may be summarized as:

(i) To enable the plant to be commissioned and operated without incurring physical or

78
corrosive damages.

(ii) To eliminate deposits that may not only harm the plant by obstructing heat transfer
or by restricting the flow of steam or water, but may also adversely affect the
operational efficiency.

(iii) To ensure that the operational parameters as specified for the water steam cycle are
achieved as soon as possible after commissioning.

In general, cleaning agents suitable for removing grease etc. are likely to be
totally ineffective in removing metallic films such as mill-scale incrustations due to
corrosion, or adherent scale laid down by water and steam. Oil, grease must be removed
at the early stage of cleaning programme, mainly because these will interfere with
subsequent cleaning processes.

The miscellaneous debris usually present in the boiler at the end of the construction
stages, such as dust, cement, lagging, sand, welding material, welding flux and mill scale
etc. must be removed physically and by chemical cleaning. Many of these contaminants
cannot be completely dissolved in the cleaning process, but it is possible to attack the
material that is bonding them to the metal surface and so enable them to be removed
during subsequent flushing or at least to move to an accessible part of the plant, where
they can be manually removed.

Failure to remove this type of material will lead in the early stage of commissioning
blockage of strainers and valves, drain lines and other parts having small clearances.
Mechanical damages may also be caused by the impingement of debris carried by high
velocity steam or water, particularly in turbines and pumps.

. Apart from the physical aspects of debris, which have to be removed from the
plant, there is a need to remove the debris from the chemical viewpoint. For example,
silica, calcium, magnesium and aluminium are present in sand, cement dust and lagging
if not removed, these can lead to the formation of scale.

STAGES OF CLEANING PROCESS OF BOILER

(i) Flushing cold and hot


(a) Re-heaters (b) Superheaters ( c) Boiler evaporative system

(ii) Alkali boil out of boiler evaporative system


(iii) Acid cleaning of boiler evaporative system

(iv) Flushing of boiler evaporative system after acid


washing and rinsing with ammoniated citric acid
(v) Passivation stage-I and stage-II

Before taking up the stages in detail we shall discuss certain aspects involving the above
processes.

SOME ASPECTS OF ACID CLEANING

(a) Temperature: Like most chemical reactions, the rate of attack by acid on iron oxide
increases with temperature, but in practice, the maximum temperature is limited by the

79
fact that the effectiveness of corrosion inhibitors decreases with increasing temperature. In
general, a temperature of around 90°C is used for citric acid and approximately 65°C-70°C
for hydrochloric acid.

(b) Strength of Acid: The strength of acid is expected to vary according to the amounts
of oxides and other acid soluble debris to be removed. However, the effectiveness of
inhibition is also affected by the acid strength and this together with economic
consideration has led to the general use of hydrochloric acid at an initial strength of 5%-
6% w/w and citric acid 2%-4% w/w. Quantity of acid sometimes has to be increased or
even acid at a higher strength need be used if the strength of the circulating acid solution
becomes unduly depleted due to heavy amount of debries, as time limit of acid circulation
is normally limited .

(c) "Soaking" and "Circulation" Techniques: At present for acid cleaning pumped
circulation is employed. Static soaking have the disadvantages that the acid adjacent to
the surface becomes depleted in strength leading to incomplete and unequal cleaning,
patches of detached material fall at the bottom blocking the drains and representative
sample of acid solution being not available it is not possible to exercise chemical control of
the process.

On the other hand circulation process eleminates these, expect that, if circu1ation
velocity is not carefully controlled, the inhibitor becomes less effective.

(d) Pumps: Only centrifugal pumps should be used for pumping the acid solution
because the damage that may result from pocketing and compressing of solution and
liberated hydrogen in reciprocating pumps. Pumps normally used in power station
operation are not to be used for acid circulation as these will be damaged by acid
action and the pump components should be of special material to resist acid action.

The pump pressure-heads should be at least 50% more than the static head of
solution against which it is to work. As the same pumps are used for water flushing and
final passivation where high velocities are needed the capacity of the pumps should be
sufficient so that the required velocities are available inside the system.

(e) Choice of Acids : In order to remove the firmly attached scale and debries which
remain after the alkali boil out, various acids are used each of which is accompanied
with advantages and disadvantages. The main considerations which lead to the
selection of one particular acid are :

(i) Efficiency and speed of dissolution of metal oxides

(ii) Availability and cost of the acid

(iii) The degree of safety with which it can be used, with respect to the personnel and
plant.

Among mineral (inorganic) acids, hydrochloric acid, sulphuric acid and pHospHoric
acid and among organic acids, citric acid, formic acid and EDT A are used.

SULPHURIC ACID

It is the cheapest and is effective. It has disadvantages the strong acid (95%)
liberates a large amount of heat when mixed with water and this poses difficulty in

80
dilution for preparing required strength of acid solution quickly.

Further disadvantage of sulphuric acid is that the attack by dilute solution on


steel cannot be inhibited as effectively as for other mineral acid.

PHOSPHORIC ACID

. The use of pHospHoric acid was largely based on the assumption that it would
confer some degree of passivation on the newly cleaned surfaces by formation of a
surface film of insoluble iron pHospHate. However, it has the risk that insoluble iron
pHospHate would rapidly be removed from boiler surfaces under operating condition
and be Carried over with steam. Further it has a low solution capacity and also it has
high cost.

HYDROCHLORIC ACID

Among inorganic acids, the choice is almost invariably hydrochloric acid which is
a comparatively, cheap acid. The required strength of solution poses no problem and
has high solution capacity. The disadvantages is that in austenitic steel it produces.
Stress-corrosion cracks because of chloride ion attack resulting from the combined
effect of residual stress within the metal associated with corrosive action.

ORGANIC ACID

The organic acids are in varying degree less effective than the inorganic acids, but
have the important ; advantage of being associated with a negligible risk of causing
corrosion on alloy steel. This property is advantages by reducing the dependence on
highly effective inhibitors to prevent corrosion of the cleaned metals. Among organic
acids the one most commonly used is citric acid.

Solubility of iron oxide in citric acid is increased by adding some ammonia which
forms ammonium dihydrogen citrate, a complex salt of sufficiently high solubility. For this
reason citric acid is now commonly ammoniated to a pH of3.5-4.0, which corresponds to
the formation of ammonium dihydrogen citrate.

The following table shows the capacities of some cleaning solutions to hold iron in
solution.

Capacities of cleaning agents for dissolving iron oxides given in table 15.

Table-15
Table from CEGB publication

Cleaning solution Solution capacity (Ibs Fe3O4 /gal


soln)
5 % hydrochloric acid 0.33
3% pHospHoric acid 0.008
19% pHospHoric acid 0.05
3% ammoniumdihydrogencitrate
(pH-3.54.0) 0.072

81
EFFECT OF FLUORIDES

The addition of fluorides, either as ammonium bi-fluoride or sodium fluoride to


hydrochloric acid for precommisioning cleaning has often been made on the assumption
that it would assist in dissolving siliceous material.
Spinner of VGB has shown that the rate of solution of silica in a mixture of 6.5% HCI and
2.0% HF at 25°C is so slow that dissolution of siliceous material in practical acid cleaning is
inappreciable. However, though its use may not be beneficial for dissolving siliceous
material, it certainly increases the solubility of mill-scale.

FLUSHING WITH WATER (COLD AND HOT)

For the removal of dirt, loose solid material and solid material that might have found
way in side the boiler system, the system is washed (flushed) with water first at the
ordinary temperature and then with water at a temperature of 80°C-85°C. Heating further
loosens, dissolves and detaches the foreign materials. The drum internals are removed for
the process.

(a) Flushing of Reheater : The first series of flushing operations are carried out on the
reheater. De mineralized water is used at a high velocity for this purpose. The water
velocity initially kept less and gradually increased in the range from 0.2 m/sec. to 1.5
m/sec.

The flushing DM water is pumped into "Cold reheat line, passes through; primary' and
'secondary' reheaters and finally passes out through the 'hot reheat' pipe work to waste.
The flushing period lasts for 15-20 minutes each stage, which may be required to be
repeated until the clarity and conductivity measured at inlet and outlet are comparable. (In
practical field it is not possible to have same values as advocated theoretically). Normally
the process should be considered as complete when the conductivity of outlet water is 25-
30 micro-moho/cm.

The process is repeated with water at temperature 80°C-85°C. In case pre-


commissioning acid washing (using citric acid-ammonia) is not intended by the suppliers of
the plant, the reheater should be filled with DM water containing 100 ppm hydrazine and
0.1% NH3/w/w isolated and banked till the steam blowing or purging process is
contemplated.

(b) Flushing of boiler and Super Heaters: Next operation is flushing the boiler through
economizer, to drum and from drum to waste through down comers and water walls.

This flushing is considered complete when the out water is visibly clear. The boiler is then
drained and emptied.

For flushing of boiler and superheater it must be remembered that flush


water to enter from super heater to drum and not vice versa. This point is important
as flush water entering super heater from drum i.e. through the circuit economizer and
drum may carry debris into the super heater with it. It is very difficult to flush such debris
out from super heaters, particularly the pendent superheaters.

The superheater is back flushed into the empty boiler through the circuit i.e. from
main steam pipe, radiant and convection platen superheater, front wall radiant superheater,

82
primary superheater to drum and from drum to waste. Flushing repeated with DM water at
80-85oC.

Finally, the boiler circuit i.e. from drum through water walls and down comers is
flushed once more to remove any debris transferred from superheater to drum.

Ammonia and hydrazine are then added to superheater and boiler with DM water
(0.1%NH3 and 100ppm N2H4) re circulated and drained to waste.

Flushing water velocity for superheaters is in the range of 0.5 m/sec to 1.5 m/sec.

ALKALI BOIL OUT

The alkali boil out of boiler is carried out at elevated temperature to remove any
grease or oil from the surfaces, which could not only lead to operational difficulties but
would certainly reduce the efficiency of the acid cleaning solutions by preventing them from
coming in contact with the surface.

Additionally the alkali will loosen and remove some of the metal oxides which will be
present and will thus enable the acid cleaning more efficiently, since the acid strength will
not be depleted quickly being used up by these metal oxides.

PREPARATION

Alkali boil out is carried at 40 kg/cm 2 pressure. Pre boiler system cleaning should be
completed. Entire feed system including feed pump should be available, boiler should be
ready for regular firing operation.

All boiler instruments, leads and sampling line should be isolated except drum
sampling and direct reading level gauge glass (better use temporary guage glass). Drum
blow down lines, bottom drain valves, chemical feed lines etc. should be free from
chocking, if condensate system is not ready, arrangements for feeding DM water to the
deareater is to be made.

PROCEDURE

Boiler is filled with DM water and drained. The process repeated to clear the drain.
Then the boiler is filled up to bottom level with DM Water. Trisodium phosphate and sodium
carbonate (optional) solution prepared outside is charged into the boiler through manhole
cover in batches. Final strength 1000 ppm phosphate and 500 ppm carbonate.

Manhole door closed properly and the boiler is lit up, the pressure is increased slowly
to 40 kg/cm2. Drum level is maintained at normal working level. The pressure is held at 40
kg/cm2 for 2 hours. Samples are taken for analysis.

Then fire is killed and blow down is provided by operating low point drains in
sequence, each for 30 sec. After blow down normal drum level is restored, boiler is lighted
up and pressure is raised to 40 kg/cm 2 and held for 2 hours. Samples are drawn for
analysis of pH, alkalinity, oil and phosphate. Again, fire is killed and low point sequential
blow down for 30 sec is given. This process is repeated for 8 to 9 times or till the oil content
is nill (less than 0.5 ppm).

83
If chemical concentration falls below half of the initial concentration, excess
chemicals are injected to restore initial concentration.

When test results show no further repetition is required, the boiler is allowed to cool
down. And at 2-3 kg/cm 2 pressure the entire system is drained through all the bottom
drains, keeping the vent open. After draining, the unit is flushed with D.M. water repeatedly
until drain sample free from phosphate. The final rinse is given at elevated pressure and
temperature (2 kg/cm2) to help removal of the loosely bonded substances.

ACID CLEANING

Preparations for acid cleaning: Erection of temporary piping, valves, fittings, solution
tank etc. should be completed and hydraulically tested. The scheme of temporary piping
etc. are shown in fig.

Drum internals are removed. The super heaters are isolated by plugging the
connecting tubes to the superheater from drum inside. Then the super heater is back filled
with ammonia and hydrazine solution in D.M. water (200 ppmN 2H4 /pH-10) and kept under
a positive pressure of 4 to 5 kg/cm2.

PROCESS

The system is filled with D.M. water and circulation is established. 3 to 4 kg/cm 2
drum pressure is maintained, temperature is raised to 60-65°C by addition of steam.
Steam is cut off, required quantity of inhibitor is added (0.1 % to 0.15% v/v) and
circulation continued for uniform distribution.

Calculated amount of ammonium bi fluoride (0.5 w/v) is added slowly keeping


circulation for dissolving and having an uniform concentration.

Hydrochloric acid is then added slowly taking care that at pump discharge,
concentration never exceeds 6% (every 10 minutes samples). The charging of the acid is
completed within a period of 1-11/2 hours and 4-5% acid strength in circulation solution.

After completion of acid addition, samples are collected from pump discharge and
return line, every 15/20 minutes and tested for acid strength and iron. When the acid
strength and iron content reach more or less constant value (three consecutive reading) the
acid circulation is stopped and the system is drained under N 2 cover. The spend acid is
drained to the Neutralization pit.

N2 CAPPING

N 2 capping is applied to protect freshly prepared surface of steel from oxidation. A


number of nitrogen cylinders of suitable capacity are connected to a bus, which is
connected to the drum air vents through a stop valve and non-return valve. Nitrogen
capping is to be done during each dumping after acid pickling.

The stop valve in the nitrogen line and the air vent valve near the drum are kept open
and other air vent valves on the drum are kept closed. As the dumping starts, nitrogen
enters through non-return valve into the system and offers protection. When the system is
completely drained and filled with nitrogen the stop valve in the nitrogen line is closed. The
pressure of the nitrogen is to be maintained slightly above atmospheric pressure (0.5 to 1.0
gauge). When the system is filled for next operation, the nitrogen is vented out. The non-

84
return valve in the nitrogen line near the drum prevents entry of water or chemical solution
to the nitrogen piping.

Nitrogen Capping to be Stopped after First Stage Passivation

D.M. Water Rinse: When the draining is over system is filled with D.M. water,
heated to 45-50°C and circulation continued for an hour. The discharge and return line
samples are checked for acid strength and iron. When the value is almost constant the
system is drained under N2 cover.

85
CITRIC ACID RINSE: The system is filled with D.M. Water 2% (w/v) citric acid. Circulation
is established and temperature is raised to 60°C. Now ammonia is added slowly to increase
the pH to 3.5 to 4. Circulation continued until the uniform concentration of citric acid and
iron is obtained. Then the system is drained under N 2 cover, filled in with D .M. Water and
circulation continued keeping 2 to 3 kg/cm2 drum pressure. It is drained under N2 cover
when discharge and return line sample attains same iron. This is repeated until iron
concentration falls below 25ppm and acidity almost nil.

1st STAGE PASSIVATION

The system is filled with D.M. Water and circulation established. Temperature is raised
to 90- 95°C, required quantity of hydrazine and ammonia are added (200ppm hydrazine,
pH-10). Circulation continued. Hourly samples are collected and tested for pH and
hydrazine. If required chemicals are added to maintain the above concentration and pH.

After 20 hours, the system is drained hot. The effluents is neutralized with bleaching
powder. The vents and drum holes are opened, the drum is inspected and sediments if any
in drum or header are cleaned.

IInd STAGE PASSIVATION

The super heater plugs, safety valves, down comer orifice plates are removed. Drum
internals are manually cleaned and refitted.

All provisional equipments and piping are dismantled and original fittings, mountings
are installed back, and boiler is made ready for normal operation.

The boiler is filled up to the normal operating level with 200ppm hydrazine and
ammonia to raise the pH to 10 by chemical dosing pump.

The boiler is then lighted up. Pressure is raised to 40 kg/cm 2 and maintained for 24
hours. Ammonia and hydrazine is injected into feed water to keep residual hydrazine of
25ppm.

After 24 hours, the boiler is boxed up and allowed to cool. At about 1 to 2 ata
pressure, the superheater vents are opened and at about 80°C (Drum temperature),
system is drained to neutralization pit. The 2nd stage passivation ends the chemical
cleaning.

SOME IMPORTANT MEASURES TO BE TAKEN BEFORE AND DURING CHEMICAL


CLEANING

86
1. All temporary pipelines to be hydraulically tested and water circulated by the acid
circulation pumps at maximum flow and pressure. Seepages / leakages to be
thoroughly checked and eliminated.

2. All bands and tees, etc, where maximum turbulence occurs are more prone to
leakages. These points should be wrapped with rubber sheets. This will restrict acid
spillage over wide area in case of leakage at these points.

3. Though arrangement for venting hydrogen is made, there is every likely hood of
accumulation of hydrogen gas at some place. Hence, no fire should be allowed in the
area. 'No smoking' boards to be displayed and welding work in the area to be
suspended during the process.

4. Provisions should be made for the following emergencies: Alternate arrangement for
power and lighting should be made if one source of power supply fails, so that
forcible draining of acid solution from the boiler in case of failure can be made.

5. Temporary piping should be laid over ground for easy inspection for leakages and
repair and should not be near or over equipment.

DISPOSAL OF SPENT CHEMICALS

Nearly all the chemicals used for chemical cleaning of boiler and pre boiler system are
toxic, corrosive and potentially harmful to human beings and animals.

The discharge to drains, sewage works, to the river or to lake will cause damage to
the flora and fauna of natural waters. The limits of pollution must be followed before these
can be discharged to rivers, etc. The point of discharge of these effluents need also to be
decided so that these do not get short circuited to the intake of C W or raw water.

Generally in most cases, it may be possible to with hold the chemical effluents into a
holding tank. Here the effluents can be stored and then released at a slow rate of
discharge so that when mixed with other waste water, no damage to sewers or drains
occur and also pollution level is kept below the limit.

Also effluents can be neutralized by the acid and alkali wash discharge. Hydrazine
and ammonia may be stored there for natural oxidation.

The tank should of course be of sufficient capacity to hold all the waste effluent
and should be cordoned off by fencing with danger board display. However, only display of
danger boards may not be enough as illiterate people due to ignorance and others not fully
aware of the extent of danger, may ignore it. It is better to post personnel also to
warn the people.

87
CHAPTER-6

STATOR COOLING WATER


INTRODUCTION

In big turbo-generators where a huge mass of metal is used as that of a stator core,
the steel used for laminations always tend to be of low eddy current and hystresis loss.
Still the rise in temperature is there and system has to be cooled.

In smaller turbo-generators, the cooling is by air circulation. Later, for bigger units
hydrogen cooling system came in the field because hydrogen has some advantages.

The transition from direct hydrogen to direct liquid cooled turbo-generator stator winding
is the next step due to two main reasons. Firstly, as the ratings of the generators
increased, more space had to be provided in the conductors for the passage of the
necessary quantity of cooling gas.

Secondly, Mechanical limitation on rotor diameter made it necessary to increase the


physical size by extending core length, and to force hydrogen through very long circuits
required high pressure heads.

Water as coolant superceded hydrogen not only because of the liquid’s superior heat
transfer capacity but also because the viscosity of pure water is very small and it is possible
to maintain flow in small tubes without building up dangerously high pressure heads.

STATOR WATER COOLING SYSTEM

The direct liquid cooling in India is at present is limited to stator winding only. Direct
liquid cooling for rotors will have one draw back, leak proof connection from the outside
header to the rotating rotor. Another problem may be high centrifugal force that will be
developed in the rotor body due to the weight of the cooling water, if it is required to be
rotated at that high revolution.

In 200/210 MW unit normally the stator has windings having two parallel paths. Each
coil side consists of glass insulated solid and hollow rectangular conductors with cooling
water passing through the hollow conductors. Ring type water headers, made of copper
are provided separately for cooling water (D.M. water) inlet and outlet of the stator
winding on the turbine side. The headers are supported on insulators and isolated from
stator body. Individual conductor bars are provided with water inlet and water outlet
connections made of taflon Hose.

The complete water path assembly is hydraulically and pneumatically tested for
water-tightness and any blockage in the flow paths of the coolant.

88
DESCRIPTION OF EQUIPMENTS

A closed loop stator water cooling system is designed to maintain a constant rate of
flow of cooling water to the stator winding at a specified range of inlet temperature by
providing pumps and coolers.

1. EXPANSION TANK

The D .M. Water from the D .M. Plant is pumped directly to an overhead tank in the
turbine house. The tank is hermetically sealed and a vacuum is maintained above the water
surface in the tank by connecting it to the outlet water box of the condenser cooling water.
The level controlled by a float control valve device in the tank. Electrical signa1ling device is
provided to give 'high' and 'low' level alarm. An additional ejector is connected to the tank,
actuated by service water. The vacuum in the tank is maintained at 250 mm to 300 mm of
mercury column for vacuum deaeration. Complete material of construction of the tank and
pipeline is stainless steel.

2. CIRCULATNG PUMPS

Circulation of the cooling water is maintained by any of the two 100% duty circulating
pumps. One pump is working as the "working" and the other as "stand by". The pumps are
electrically inter-locked between each other in such a manner as to start the stand by pump
in the event of drop in the pressure of the circulating coolant water below the specified
value of in case of tripping of the pump in service. Isolating valves have been provided in
the lines so that either pump can be taken out of the system without disturbing the cooling
water circulation in the system.

3. WATER COOLERS

The stator cooling water coming out from the winding has a higher temperature. The
water is cooled by two 100% duty water coolers, one as "working" and the other as "stand
by". The stator water passes through the outer surface and the secondary cooling water,
which is also D.M. water, from the bearing cooling water system for cooling the bearings of
pumps of feed and condensate system, flows through the tubes made of copper.
Thermometers are provided at the inlet and outlet points to note the temperatures of the
inlet and outlet water.

4. STRAINERS

Mechanical strainers are provided to catch any solid impurities for accidental passing
out of resin from the stator po1ishing units due to any damage in the strainer nozzles
during SPU in service.

5. MAGNETIC FILTERS

Magnetic filters of permanent magnet are provided at the inlet of the water to the
stator winding in the header. There are two such filters and one is put into service, the
other is kept as stand by and they are used alternately for cleaning.

6. SECONDARY COOLING SYSTEM

89
The cooling water required for the cooler the stator cooling water is from the bearing
water-cooling system. The BCW for the pumps and the feed and condensate system is also
circulated in a closed loop system and is also D M Water so that the chances of
contamination of the stator cooling water is minimized even in case of a tube leakage. This
cooling D .M. water is pumped to the over- head tank provided for in the same scheme. The
tubes here are of copper with a copper strainer.

7. STATOR POLISHING UNITS

These are conventional mixed bed exchangers using strongly acidic cation and
strongly basic anion exchanger resins. They are cylindrical, vertical M S Shells lined inside
with protective lining like rubber, PVC etc. The resin bed in the case of polishing units has
to perform duel function of filtering out any particulate form of metal, generally Copper, as
also to exchange the copper in ionic form. The cation and anion resins are in equal volume.
The unit has acid and alkali distributor and collector headers, strainer nozzle plates, rinse
and backwash water inlet and drain arrangement, air inlet and air vents.

The polishing Unit is placed on the same floor with the inlet header to avoid pressure
head in the resin bed. For easy mobility, the unit is mounted on wheeled trolleys. When the
resin is exhausted, as shown by the increase in conductivity and/or copper content, this is
transported to the WT plant where it is regenerated. There is a pH meter and a conductivity
meter at the SPU outlet to keep a check on the quality of the effluent. The copper content is
checked in the laboratory.

MEASURING, AND ANNUNCIATION SCHEME

i) Stator Water Flow Indicator and Recorder:


There are three flow instruments provided and the scheme is so designed that there
will be indication of low flow and if two out of the three instruments indicate flow
below the specified limit, the set will trip.

ii) Specific Resistivity Instruments:


In order to measure the purity of the stator cooling water in terms of specific
resistance, three specific resistance meters are provided at the inlet of the windings.
If the specific resistance falls to 75K ohm/cm., as recorded by two out of the three
instruments, the set will trip.

iii) Temperature Detectors


The temperatures of the inlet water to the stator winding and that of the outlet water
from the winding are monitored.

ANNUNCIATION SCHEME

Some of the important annunciations provided are:

(i) Expansion tank water level High -1200 mm ,Low -850 mm Emergency -500 mm

90
(ii) Temperature of cooling water to stator winding inlet high -41°C

(iii) Temperature of cooling water at the outlet of winding -high -85°C

iv) Cooling water flow rate to stator winding low -18 M3/hr

v) Stator cooling water specific resistivity at inlet -Nominal -200 K.ohm/cm


Low - 75 K.ohm/cm

WORKING SCHEME OF STATOR COOLING WATER (CLOSED LOOP CIRCULATION)

For cooling the stator winding, D M Water from the WTDM plant is supplied to the
expansion tank through a pipeline having a non-corrosive lining or - HDP pipe by a pump.
The tapping may be taken from the common delivery header of the D M transfer pump or a
separate pump of sufficient head and capacity is used. The inlet to expansion tank is
controlled by a float controlled valve and pipe of about 6 mm dia, low dia pipe at the actual
inlet is to control the flow uniformly and slowly so that the deaeration is more effective.

A vacuum of 250 mm to 300 mm of mercury column is maintained in the expansion


tank above the water surface for vacuum deaeration, i.e. removal of dissolved oxygen and
carbon dioxide as these dissolved gases cause corrosion in the conductor metal.

Out let from the tank is from the bottom and connected to the suction header of the
cooling water circulation pumps, two in numbers. The delivery of the pumps is connected
to a common delivery header. From the header the water goes to either of the coolers
where the water is cooled. The piping are so arranged that these coolers can be bypassed
or either or both can be put into service.

From the cooler the water goes to the stator water polishing unit where the
particulate and ionic impurities, mainly copper is removed.

There are pH meter and conductivity meter on the outlet of the SPU to check the
purity of water. Here also there is piping and valve arrangements so that the SPU can be
completely by-passed or full or partial quantity of the water can be passed through the
SPU and remaining required quantity goes directly to the ring inlet header of the stator
winding through a by pass line. There are mechanical filters in the ring header for filtering
the water.

A magnetic filter to remove iron particles, if present, after the mechanical filter,
attaches the iron particles. The water passes through the hollow conductors of the stator
winding for cooling and comes out through the outlet header, then goes back to the
expansion tank and kept in the circulation. The make-up is given to the expansion tank.

The stator cooling water while absorbing heat from the windings rises in temperature.
This is cooled in a second set of coolers, two in numbers. One is in service and the other as
stand-by. This water is drawn from the bearing cooling water system D M water and is
also in a closed loop.

This secondary cooling water is again cooled by a third set of coolers where ordinary
filtered service water is used as a coolant.

91
Table-16 Some technical particulars for cooling water to stator winding

1. Nominal gauge pressure at inlet to winding 3  0.5kg

2 Nominal cooling water inlet temperature to winding 4O  5°c

3. Flow rate of stator cooling water 25 3 m3/hr

4. Nominal r specific resistivity 200 K.ohm/cm

5. Minimum specific resistivity 75K.ohm/crn

6. Nominal ternperature of cooling water to stator winding water cooler 33°c

7. Nominal flow rate for cooling water to stator cooling water 95 m 3/hr

8. Maximum temperature of stator cooling water at winding outlet 85°c

9. pH of inlet water to stator winding nearly neutral to mild alkaline

10. Conductivity Not more than 5 micro mho/cm


i.e. 200K.ohm cm resistivity
preferable value 3 micro mho/cm

11. Dissolved carbon dioxide Practically nil

12.Dissolved oxygen At pH 7 not more than


10 micro grams/Iit. ie. 0.01ppm
at pH 8 not more than .02ppm

13. Total iron content Not more than 0.05ppm

14. Chlorides Nil

15. Optimum copper content Desirable .05ppm but


not more than 0.15ppm

92
STATOR WATER COOLING SYSTEM WITHOUT MIXED BED POLISHING UNIT

Stator water cooling system without M.B. Polishing units are also in use. Scheme of that is
shown in Fig.8.

93
CHAPTER-7

COOLING WATER

Corrosion, scale deposition and fouling is major problem encountered in cooling


water system.
The objectives of cooling water treatment are:
I) Prevention of scale deposition on heat exchange surface.
2) Prevention of organic and slime growth on heat exchange surface.
3) Prevention of mud deposition on heat exchange surface.
4) Control of organic growths is intake culvert.
5) Minimizing corrosion through out the cooling water system.

TYPES OF COOLING SYSTEM

Three types of cooling water system is in use today.


I) Once Through system
2) Closed Recirculating System
3) Open Recirculating System

ONCE THROUGH COOLING SYSTEM

If plentiful water is available, cooling water passes through the heat exchangers only
once.

In once through system due to less contact time and some tendency of CaCO 3 to
remain in super saturated condition in clean tube surface, chances of deposition of CaCO 3
scale is less.

Further, due to the huge amount of water involved no treatment is given in once
through cooling water except chlorination.

CLOSED RECIRCULATING SYSTEM

Cooling water in closed recirculating system is completely within the system pipes and
heat exchangers. The heat absorbed from the plant process is generally dissipated by air-
cooling.

Loss from the system is very less and little make up is required, hence concentration
of salt in the water is very less.

As such in closed recirculating system, deposition /scale formation is not a problem.


Major problem may be corrosion, which can be easily controlled by use of suitable
corrosion inhibitor.

94
OPEN RECIRCULATION SYSTEM

The open recirculating system is often used in large thermal power station. The
problems of deposit formation, corrosion and microbiological organism occur here in
greater degrees than other two systems due to following reasons:

1) Higher water temperature enhances corrosion and deposit formation.


2) Cooling tower is a huge scrubber, introducing microorganism, dust, dirt etc. in
circulating water which increase fouling and corrosion,
3) Make up water brings more scale forming and corrosion forming salts.
4) Water is exposed to air allowing continued presence of oxygen, which is responsible
for corrosion.

WATER LOSSES IN RECIRCULATION

1) Evaporation loss
2) Windage loss
3) Bleed off
Evaporation Loss: (E) is approx. 1 % of the water circulated per 10°F drop in temperature.
When water evaporates off it leaves behind all the salts hence increases total solid
concentration.
Windage Loss (W): Small droplets of water carried away by wind. Since it carried salts along
with it, windage loss actually have dilution effect in salt concentration of cooling water.

Table-17

Approximately windage loss

Spray pond 1%-5%


Cooling pond 3%-1%
Cooling tower 1 % -3%
(mech. Drought)

Bleed off (B) necessary to control maximum solid in cooling water: bleed off also gives
dilution effect.

CYCLE OF CONCENTRATION

Depending up on the E, W and B a certain amount of solid build up occurs in the


system. This can be presented by cycle of concentration.

Cycle of concentration = Concentration of a stable compound say chloride in recirculating


water / Concentration of the same stable compounds (say chloride) in
make up water

In a new tower, cycle of concentration can be determined as below

95
%E
C= +1
%B+%W

All losses are expressed as percentage of recirculating water:

With the help of the graph (Fig.9a) assuming fixed value of E and W as per design by
varying B, a desired cycle of concentration can be held. Say E = 1 %, W = 1 %, 0.8% bleed
off is required to maintain cycle of concentration 1.5.

Fig.9a Fig.9b : Expected pH of cooling tower water

The entire thrust of cooling water treatment is to reduce the effect of deposits,
corrosion and biological attack on the most important constituent of the cooling system: the
heat exchanger. For economically efficient heat transfer to be maintained at a maximum
level, heat exchangers must remain clean. To minimize product leaks and the consequent
need for maintenance shutdowns, the continuing integrity of the heat -exchanger metal
must be ensured. Thus, the primary objective of cooling-water treatment is to protect the
exchanger tubing, where all heat extraction takes place. The secondary treatment target is
the distribution line, followed by the remaining system components.

96
SCALE FORMATION

Scale on a heat-exchange surface presents the most serious barrier to the transfer of
heat through the surface. It occurs when soluble salts are precipitated and deposited from
cooling water. The rate of formation depends mainly on: (1) Temperature (2) Alkalinity or
acidity and (3) the amount of scale-forming material in the water.

Scales occurring most frequently in cooling-water system are listed in Table-18.

Table -18
Scale occurrence in cooling water systems
Most common Less frequent
Calcium carbonate Iron oxide
Calcium sulfate Zinc phosphate*
Calcium phosphate Calcium fluoride
Magnesium silicate Iron carbonate
Silica (SiO2)

* From corrosion-control treatment chemicals

They form in the following situations :

When water temperature increases as it passes through a heat exchanger, causing a


decrease in the solubility of dissolved materials such as calcium sulphate, calcium
phosphate and calcium carbonate. These deposits usually occur first in the cooling-system
heat exchangers, where the temperature is the highest and solubility is lowest.

When the bicarbonate alkalinity and calcium hardness of circulating water increases.

When water becomes oversaturated with silica or any other scale- forming compound.

Calcium Carbonate is by far the most common scale forming agent in cooling-water
systems. It normally results from the breakdown of calcium bicarbonate, a naturally
occurring soluble salt. The degree of scaling depends primarily on the levels of calcium
hardness and bicarbonate alkalinity in the cooling water. The rate of calcium bicarbonate
breakdown increases with pH and temperature.

We can analytically measure the mineral levels and related conditions to determine
fairly accurately whether calcium carbonate scale will form or not. In addition to the cited
parameters, its formation depends upon the total dissolved solids, the pH and temperature
of the water.

A prediction of formation is done by determining one of the three scaling indices: the
Langelier (or saturation) index, the Ryznar (or stability) index and the Puckorius (or
modified stability) index. To determine any of these, the pH of saturation (PHs) for calcium
carbonate is first calculated using values of the parameters mentioned above. This
calculation, which is quite complex, has been simplified by the development of monographs
and slide rules, available from most chemical-treatment suppliers. In general, calculation
of pHs for calcium carbonate results in a value between 5 and 11. Depending on the index
sought, the next step is to use this value in one of the formulas given in Table-19.

The Langelier index (LSI) will produce either a positive or a negative value, indicating

97
either that calcium carbonate scale will form (+) or that it will not form (-) under the
conditions being evaluated. The Ryznar (RSI) and Pukorius (SI) indices always produce
positive values. Table-20 is a guide to the scaling potential of a particular water using all
the indices.

Other than CaCO3, CaSO4, Calcium phosphate, magnesium silicate etc also forms
scales if solubility exceeds.

Table -19
Calcium carbonate indicators

Langelier (Saturation) Index:


LSI = pH act -pHs + indicates scaling tendency
-or 0 indicates non-scaling
Ryznar(stability) index:
RSI = 2pHS –pHact > 6 indicates scaling tendency
< 6 indicates non-scaling
Puckorius (modified stability) index:
PSI = 2pHs -pHe* > 6 indicates scaling tendency
< 6 indicates non-scaling

* pHe is the equilibrium pH, based on total alkalinity

Table -20
Scaling severity keyed to index

LSI1 RSI2 Condition


3.0 3.0 Extremely severe scaling
2.0 4.0 Very severe
1.0 5.0 Severe
0.5 5.5 Moderate
0.2 5.8 Slight
0.0 6.0 Stable water3
-0.2 6.5 No scaling, very slight
tendency to dissolve scale
-0.5 7.0 No scaling, slight
tendency to dissolve scale
-1.0 8.0 No scaling, moderate
tendency to dissolve scale
-2.0 9.0 No scaling, strong
tendency to dissolve scale
-3.0 10.0 No scaling, very strong
tendency to dissolve scale

1 Langelier Saturation Index


2. Ryznar Stability Index

98
3. No scaling or tendency to dissolve scab

PREVENTION OF SCALE FORMATION

Factors affecting scale formation:


i) High alkalinity
ii) High Ca content
iii) High Ph
iv) High temperature
v) High dissolved solids

By influencing above factors scale fom1ation may be controlled.

There are three basic methods for preventing scale formation of Ca scale in cooling
water system:

1) Remove the calcium hardness or scaling salts from make up water.

2) Keep the scale forming constituents in solution.

3) Allow the impurity to precipitate as a removable sludge rather than as a hard


deposit.

1. REMOVAL OF CALCIUM HARDNESS OR SCALING SALTS FROM MAKE UP WATER

The make up is treated either by lime-soda process, base exchange or reverse


osmosis. The power station using soft water as make up water has little problem of scale
formation. Only care is to be taken for cycle of concentration other wise silicate may be
increased giving silica deposit.

2. KEEPING THE SCALE FORMING AGENTS IN SOLUTION

The solubilizing chemical mostly use today are polymeric organics or organic
phosphorous compounds. Poly acrylates of lower molecular weight (1000) are most
effective in CaCO3 and CaSO4 scale control. They are stable over change of temperature and
pH; most often 3- 5ppm active poly acrylates in cooling water is enough to keep Ca scale
from forming.

Very high dose (100ppm) may result in Ca- polyacrylate scale. It has a limit in
preventing CaCO3 scale, which is at 4.5 PSI. It is consumed by biocides or strong cations.
It is non-toxic.

ORGANO-PHOSPHORUS COMPOUNDS

99
Two types of organo phosphorus chemicals are used phosphates and phosphate
esters. Propionates are most commonly used in Ca scale control. They are even effective in
high pH/high salt concentration.

Two types of propionates are in use:

1) AMP (amino-methylene phosphoric acid)

2) HEDP (l-hydroxy-ethylidine-l, l-diphosphonic acid)

They are similar in reaction but differ in stability. AMP reacts with Cl 2 and destroyed.
Decomposition product orthophosphate gives CaPO 4 ,FePO4 scale. HEDP is stable in normal
Cl2 level encountered, 3-5ppm HEDP / AMP in circulating water permits PSI of 4 without
scaling.

AMP/HEDP are weak chelating agents and attack Fe and Cu. Cu-corrosion inhibitors
must be used when pHospHonates and phosphate esters are used in scale control.

Other solubilizing agents are in-organic polyphosphates viz hexa met phosphate. Very
low dosage can keep scale and iron oxide deposit from forming scale. However,
polyphosphates degrades to orthophosphate form that do not have solubilizing properties:

CRYSTAL MODIFIERS
.
Two different classes of chemical are used as crystal modifiers. These are polymaleic acids and sulfonated
polystyrenes. Both are synthetically produced and water soluble. 0.5 to 5 ppm is required in most severe cases.
Normally 0.5 to 2 ppm is sufficient.

Crystal modifying chemicals acts on the scale forming salt to produce sludge. Sludge can be allowed to
settle out in an accessible region such as cooling tower basin or it can be treated to keep it fluidized until removed
externally either by blow down or by side stream filtration.

Treated water should appear turbid to indicate that crystal modifiers are working. By
any of the above approaches for controlling chemical deposition or scale formation, scaling
in the heat exchangers can be kept at minimum

If scaling occurs, mostly it is calcium carbonate, which can be easily removed by


cleaning with 2% H CI with suitable inhibitor.

BIOLOGICAL DEPOSITION

Cooling water contains different micro organisms. They tends to grow and multiply on
the warm heat exchanger surface giving an organic deposition which also impair the heat
transfer.

To control organic growth on heat exchanger surface most of the power station
practice chlorination. The chlorine is added in cooling water by means of a chlorinator.

Chlorine is a costly oxidizing agent. For economic dosing, instead of adding to bulk
cooling water, chlorine may be added to the water when it enters the heat exchanger.
Amount of chlorine added must ensure a small chlorine residual after passing through heat
exchanger and this should be below enough to have no adverse effect on cooling tower

100
wood.

The chlorine demand of a cooling water can be determined by dosing known amount
of chlorine to the water and measuring the residual chlorine after a time interval equal to
the time taken by water to pass through the heat exchanger. For organic control chlorine
bas lot of advantages (comparative performance is shown in Table-21).

Table –21

BIOLOGICAL DEPOSIT
Effectiveness and characteristics of biocides against fouling organisms:
Sl.No Micro biocide Bacteria Iron Corrosive Fungus Algae
Slime depositing
forming
1 Chlorine +++ +++ 0 + +++
2 Quaternary +++ +++ ++ + +
ammonium salts
3 Organo-tin plus +++ +++ +++ ++ +++
quaternaries
4 Methylene Bis +++ ++ ++ + +
thiocyenate

5 Isothiazolones +++ +++ ++ ++ +++


6 Coper salts + + 0 + +++
7 Bromine Organics +++ +++ ++ 0 +
8 Organo-sulfur +++ ++ ++ ++ 0

1. Oxidizing, dangerous to handle, corrosive to metals less effective at high pH.


2. Foams, cationic, most effective at high pH.
3. Foams, cationic, most effective at high pH.
4. Not effective at pH above 7.5,nonionic.
5. Dangerous to handle, losses effectiveness above pH 7.5, nonionic.
6. May cause copper plating.
7. Hydrolyzes, must be fed directly form drum.
8. Toxic effluent, reduces chromate, anionic.

+++ Excellent, ++ Very good, + Slight, 0 None

Only draw back is that with increase in pH of the cooling water efficiency of
chlorination decreases and above 8.8 to 9.0 pH chlorine has very little effect on organic
control.

101
CHAPTER-8

PRESERVATION OF STEM AND WATER CIRCUIT


OF GENERATING PLANT DURING IDLE TIME
During operation, the plant is provided with adequate protection against any
corrosion damage but damage can occur in offload plant that has not been stored
properly.

Corrosion of steam/water circuits frequently occur in off load plant because of


retained water that causes severe localized attack. To minimize this it is essential to
store plant following standard procedure.

DIFFERENT APPROACHES TO PRESERVATION

Corrosion of the steam/water circuit at ambient temperature is the result of oxidation


of metal by combined effect of water, oxygen and lowering of pH from absorption of CO 2 and
S02' The preservation approaches are to counter one/more of the above factor.

1. Exclude moisture DRY preservation

2. Exclude oxygen Nitrogen preservation,

3. Use suitable chemical to Wet preservation


raise the pH and exclude O2

PRESERVATION SITUATION

Plant to be preserved may be divided into four categories:

1. New plant in course of erection, which is subject to hydraulic testing prior to completion
or subject to delay between initial commissioning and regular service.

2. Plant, which is undergoing overhaul or repair.

In the above two cases plants may have to be drained at some period for repair or
errection.

3. Plant, which is laid off for long period.

May be stored in variety of conditions but storage empty and dry would be better.

4. Plant which is temporarily taken out of service and required to return to service at
short notice.

102
Should be stored full and have sufficient water available for quick return to service.

PRESERVATION PROCEDURE

Any preservation technique depends on the facilities available, environmental restriction


and cost effectiveness.

DRY PRESERVATION: The most cost effective technique of preservation is complete Dry
out. This is the best method of preservation for long period. Normally it is very difficult to
ensure complete dry out and any moisture retained will condense and cause severe
localized corrosion.

N2 PRESERVATION: The plant which will remain unopened during outage can be
completely filled with N2 gas and a little over pressure is maintained to prevent O2 ingress.
The problem with N2 Preservation is that if there is any leakage then that has to be
repaired.

N2 being odourless, colourless and chemically inactive gas; it is very difficult to


detect N2 leakage.

WET PRESERVATION: The plant item is completely filled with D.M water containing
200ppm hydrazine and ammonia is added to raise the pH to 10. Chloride should be below
2ppm. Sample may be collected and checked periodically and if needed, added with
chemicals.

At the time of return to service, it is better to drain the water and fill with fresh DM
water and add chemicals for normal operation.

If due to shortage of water it has to be brought back to the service using storage
solution, all drains and condensate should be put to waste until the ammonia in steam and
water fells below 1ppm.
N2 BLANKETING : Wet storage combined with N2 is particularly useful for boiler
and associated pipe work for short period. Plant is cooled and when the pressure is
atmospheric, selected air cocks attached to N 2 supply are opened and instead of air; N 2 is
admitted. N2 takes the steam space, thus O 2 is not allowed inside. The water present in
plant is for normal operation. Thus, rapid return to service is achieved by venting out N 2.

NEW DEVELOPMENT

Injection of NH3 gas.

The problem of dry preservation is incomplete dryness. When dry preservation is


done with NH3 injection in such a quantity that this NH 3 will dissolve in retained water and
raise its PH. Localized corrosion due to retained moisture/water is minimized.
The consumption of NH3 is about 9-10% of that needed for wet preservation.
In case of N2 preservation, leakage detection is a difficult, but if N 2 preservation is
done with NH3 injection, leakage can be easily detected and sealed.

103
CHAPTER-9

COAL FOR THERMAL POWER STATION

India is blessed with a very good reserve of Non-coking coal. Non-coking bituminous
coal is normally the basic fuel used for thermal power generation in our country. 60% of the
total power generated in India is them1al power and this scenario will continue until next
century.

In view of the National policy of conservation of resources large utility station have to
use inferior quality of coal with ash percentage as high as 40%.

COAL SAMPLING

To achieve economy of individual plant and to ascertain the efficiency of generating


equipments, representative coal sampling is of prime interest. Further coal prices are fixed as
per the gradation of coal hence if proper vigilance is not given in detecting the quality of coal
received, consumer may suffer a substantial loss. Hence, continuous monitoring of coal
quality is essential.

Coal is very very heterogeneous substance; each part of coal differs from other part.
Nationalization of collieries and introduction of modem equipments for coal mining and
loading has resulted into variation of coal qualities even from single mine.
.
Since it is not possible to check each piece of coal in a consignment, collection of
representative sample is essential.
To collect representative- sample from heterogeneous substance like coal is not an easy
task. Sample can be collected either mechanically or manually. In India sample is collected
manually. At a time amount of coal collected is called increment. More the number of
increments collected from different places more will be the accuracy. In power station,  1 %
accuracy is accepted.

Indian Standard Institute has laid down some specific sampling procedure, which is
obligatory to both the supplier and consumer. Otherwise, both the parties may mutually
adopt some method based on the I.S.I. specifications of sampling. In general sampling of raw
coal is carried out at the unloading point i.e at the consumers end in the coal yard during
unloading from wagons or trucks. Number of samples and quantity of samples depend upon
the quantity of coal received. For each consignment, separate samples are to be collected
and for each consignment of 250 tones, one sample is recommended.

Samples are collected in increments during the motion of unloading. The number and
the quantity of the increments shall be governed by the variability of quality and the size of
the coal and on the accuracy required thereof. The standard practice is to collect 350 kg

104
samples for 250 tones of coal received in increments of 7 kg. 25% of the wagons received
should be arbitrarily selected for sampling.

TABLE-22

Number of gross sample and Number of increment.

For wagon ROM Coal Coal large Coal small

0-9” 2-6” 0-2”

1 Weight of gross sample 350 Kg. 175 Kg. 75 Kg.

2 Weight of increment 7 Kg. 7 Kg. 5 Kg.

3 Number of increment 50 25 15

For conveyers

1 Weight of gross sample 350 Kg. 175 Kg. 75 Kg.

2 Weight of increment 5 Kg. 5 Kg. 5 Kg.

3 Number of increment 70 35 15

Either the bulk of 350 kg sample, so collected are well mixed and reduced by
mechanical sample dividers or by hand methods using shovel by coning etc. The gross
sample is reduced to 50 kg in stages. The 50 kg mass is crushed to 1/8" size and again
reduced by coning and quartering in stages to get a final sample of about 2 kg. About 1 kg
sample from the 50 kg mass whose average size should be below 1/2" should be separated
and sent for determination of gross moisture content. 1 kg of the 1/8" size sample is
divided into two parts, one will be preserved and the other part is to be finally powdered
(72 mesh) in Raymond Mill. The finely powdered sample is to be used for analysis.

For calculating the efficiency of the plant, average sample of coal used daily by the
individual boilers are collected from the hoppers before discharge to the Mills. Some early
designers kept provisions for collecting samples from inside the bunkers, but the method is
now discontinued for many disadvantage cropped up during collection of samples from
bunkers.

Samples of pulverized fuel are also collected to determine the fineness of coal
pulverized to calculate the mill efficiency and to ascertain the burner performance.

ANALYSIS OF COAL SAMPLES

105
The boilers are designed on the basis of the following characteristic of coal:

1. Proximate analysis
2. Ultimate analysis
3 .Gross calorific value
4. Hardgrove Grindability Index
5. Fusion behavior of ash of the coal.

On commercial point of view, the price of coal are now based on the useful heat
value which is directly determined by using an emperical formula taking into consideration
ash and moisture content of the coal. But for plant performance and to plan procurement
of desired quality of coal in accordance to boiler design, the characteristic of coal as
described above 1 to 5 should have to be made known by way of regular sampling and
analysis of the coal received. Before finalization of new tender also, the above properties of
the incoming coal to be supplied by the supplier is to be analyzed first.

1. PROXIMATE ANALYSIS

The proximate analysis of coal means determination of the Moisture content, Ash
content, Volatile matter content and fixed carbon content. The proximate analysis is carried
out at an equilibrated condition. The coal has a characteristic to carry different moisture at
different temperature and humidity condition. Hence, if a high moisture coal is preserved
and analyzed under different temperature and humidity condition it will give different
results for moisture, ash and volatile matter.

Hence, a coal sample is first equilibrated at a temperature of 40°C and 60% relative
humidity, keeping it in a humidifier chamber for 48 hrs. To get a reproducible and correct
result this equilibrated condition is to be achieved before carrying out the proximate
analysis. The equilibrated condition stated above is also termed as air-dried condition at
60% RH, 40°C.

(a) Moisture: Owing to its nature, origin and occurrence coal is always associated
with moisture. It is customary to differentiate between inherent and external
moisture. When a wet coal is exposed to atmosphere the external moisture
evaporates, but the apparently dry coal still contains some moisture, which can only
be removed by heating it above 100°C. The inherent or air -dried moisture is
related to the nature of the coal. The inherent moisture content predicts the
maturity of the coal.

One gram of the equilibrated sample is accurately weighed in a moisture dish


made of glass and the corresponding loss in weight of the sample on heating it to
105°C for one hour is noted. The loss in weight represents the moisture content of
the coal. When the moisture of a coal sample will be talked about, it is its inherent
moisture content. In case of lignite, this method cannot be applied, as lignite starts
decomposing at a temperature below 100°C. Dean and stark apparatus is used for
determination of moisture content of lignite. Moisturized coal unnecessarily increases
the freight charge; in boiler, it increases the furnace volume leading to the higher
sensitive heat loss. Further, this moisture takes latent heat from the boiler, which
cannot be recovered, as flue gas exit temperature has to be kept above dew point to
avoid cold end corrosion. For this reason moisture in the boiler is restricted by
drying the coal during pulverization.

(b) Ash and Mineral Matters: Coal contains inorganic mineral substances, which are

106
converted into ash by chemical reactions during combustion. Ash and mineral
matters are therefore not identical.

Depending upon the nature of source, the mineral matter in coals is classified as
inherent and extraneous. The inorganic substances of the original vegetable substances are
responsible for the inherent mineral matters. But the extraneous mineral matter is either
due to the substances, which got associated with the decaying vegetable materials during
its conversion into coal r due to the rocks and dirt getting mixed during mining, handling
etc. It can however by partly removed from the coal by mechanical method i.e. by washing
the coal. However, the inherent mineral matter is associated with the coal molecules and
cannot be separated by mechanical means.

The mineral matter does not contribute to the calorific value of coal. On the contrary,
it creates many difficulties in the efficient utilization of coal. High ash content of coal
creates laborious problem of removing and handling of ash. Ash may seriously restrict the
passage of air and lower the rate of combustion. So careful determination of ash content is
necessary to ascertain the quality of the coal and to predict the magnitude of the above
problems.

The ash content of coal is determined by burning accurately weighed, one gram of
coal at a constant temperature of 800  20°C for one hour in a furnace. The residue left
after turning all the carbon matter gives the ash content of the coal. The mineral matter of
Indian coals is calculated by using the simplified "Parr" formula.

Mineral matter = 1.1 A (A=% of ash in the coal)

(c) Volatile Matter: Volatile matter in coal also comes into consideration while selecting
coal for use in boilers. The flame size depends on the volatile matter content of the coal.
Coals of very low volatile matter although have a good calorific value are disadvantageous
as a pulverized fuel. Volatile matter represents the volatile substances present in the coal
and the gaseous products of thermal decomposition of coal. V.M. also consist part of the
mineral matter, which escapes into the gaseous or vaporous state while heating.

Volatile matter of coal is determined in the laboratory by accurately weighing one


gram of coal in a specially designed crucible and heating it in a furnace at a temperature of
900  20°c for exactly seven minutes. The loss in weight gives the volatile matter content
of the coal.

Volatile matter is very important for power station coal. In boiler, it is the volatile
matter, which first catches fire, burns with flame and gives support in burning the char
(fixed carbon). Normally V.M. is around 20-30%. Low volatile matter means we have to
give oil support to sustain combustion for which for coal containing V.M. less than 19 %:
compensation is given while calculating useful heat value.

Further, flame length increase with decrease in volatile matter as char takes longer
time for combustion and in front fire boiler chances of striking the opposite tube banks are
there. In case of very high V.M. coal it will burn very quickly means length will be short.
Some time this may affect the nozzles.

Volatile matter also dictates the fineness required for proper combustion. Lower the
V.M. in coal higher is the fineness required for proper combustion. V.M. - 20- 30%, 68-
70% pass through 200 mesh where as below 20% VM, 80% pass is required.

107
(d) Fixed Carbon: Fixed carbon of coal is calculated by using the formula:

Fixed carbon = 100-(Ash% + VM% +Moist%)

2. ULTIMATE ANALYSIS

The ultimate analysis is carried out to determine the percent of carbon, hydrogen,
nitrogen, sulphur and oxygen of the coal to ascertain the composition of the coal.

In a specially designed furnace, coal sample is burnt in an atmosphere of oxygen. The


carbon and hydrogen are oxidized to carbon dioxide and water, which, can be measured by
absorbing them in suitable reagents. From the weight of carbon dioxide and water
produced, corresponding quantity of carbon and hydrogen present in the sample is
calculated. The sulphur and nitrogen content are separately measured by suitable
analytical methods. Oxygen content is then calculated by difference.

Carbon and hydrogen content of coal can also be calculated from its proximate analysis by
using the following formula:

C=0.97 F + 0.70 (V-0.1A) -0.6M


H=0.036F + 0.091 (V-0.1A)-0.05M

Where F, V, A and M represent fixed carbon, volatile matter, Ash and


moisture percent on air dried basis.

Table-23 below shows carbon and hydrogen content derived from ultimate analysis and that by calculation using
the above formula.

TABLE-23

Proximate Analysis By Ultimate By Formula


Analysis
M A VM FC Carbon Hydrogen Carbon Hydrogen
0.9 23.8 18.3 57 65.03 3.64 65.89 3.46
1.0 25.5 14.3 59.2 64.14 3.13 65.05 3.15
1.2 13.8 18.1 66.9 75.98 4.09 75.88 3.87
0.9 32.8 12.5 53.8 58.14 2.96 58.10 2.73

Ultimate analysis predicts that whether the coal is weathered/oxidized or not. A


weathered coal will be deficient in carbon and hydrogen but richer with oxygen
resulting in low calorific value. Proximate analysis may not show any wide difference
between a normal coal and a weathered coal.

By ultimate analysis we can calculate the theoretical air for combustion. Also, we
can calculate gross and net calorific values of coal. This also gives an idea of amount
of SO2 and NOx formation both of which are pollutant gas.

A part of SO2 is further converted to SO 3. Amount of SO3 in flue gas depends upon the
amount of SO2 produced by burning sulphur in coal. Dew point of the flue gas increases
with increase in SO3 that means more sensitive heat loss. SO 2 /NO2, Cl2 etc. improves the

108
performance of E.S.P. by lowering the ash resistivity. However, in Indian coal amount of
sulphur present is very low (below 1 %) except in Assam coal.

CALORIFIC VALUE

This is the basic property of the fuel indicating the quantity of heat evolved by its
complete combustion calorific value of coal may be considered as a single vitally significant
parameter for characterising a power plant coal. In fact, design of boiler is based on gross
calorific value of coal. Gross calorific value is employed to find out

a) Thermal efficiency of a combustor.


b) Coal equivalent of any fuel for operational and commercial purpose.
c) Coal consumption per KWH. Thus, it is a quality control parameter.
d) Useful heat value of coal, which has been accepted as an index of price fixation of high
moisture coal.

In the laboratory the gross calorific value are determined at constant volume in a
Bomb calorimeter. Coal powder is briquetted with approximately 1 gm of coal and taken
into the bomb with pure oxygen at a pressure of25 kg/cm 2 and dipped into the
calorimetric vessel. The coal is fired electrically by external control arrangements. The
heat liberated by the coal is absorbed by the calorimeter and the total heat gained is
calculated by conventional procedures.

Gross calorific value (Q) can be calculated theoretically by using approximate


analysis.

For low moisture coal 1.8 Q = 165 F.C + 136 (V -1.1A)-1 08M Kcal/kg.

For high moisture coal


1.8 Q = 154 (100-1.1A-M)-108 M Kcal/kg

Table -24
High moisture coal : calorifIc value from proximate analysis

Prox. Analysis Determined CV Calculated CV


M A

5.9 24.7 5195 5370


5.7 36.6 4215 4221
5.4 19.4 5380 5473

The coal pricing board has fixed up an arbitrary formula for fixing the prices of
high moisture cool, which is popularly known at present as the formula to determine the
useful heat value, but it has no technical basis whatsoever.

Hu=8900-138 (A+M) Kcal/kg


where A and M represents Ash and Moisture percent at 60% R.H. at 40°C

In case of VM below 19

109
Hu=8900-138(A+M)-150(19- VM) Kcal/kg

HARDGROVE GRINDABILITY INDEX (HGI)

HGI of coal indicates its easiness towards pulverization. It is also related to the power
consumption for pulverization of coal. Therefore, the life and efficiency of the coal mill
depends on the HGI of coal.

It measures the increase of surface produced by the application of standard amount


of work and express the result as Hardgrove Grindibility Index (G), which ranges between
20 and 100 for most of the coals.

G= 13 +6.93 W

Where W= grams of coal passing through 200 mesh sieve after 50 gm of coal of size
16-30 mesh are ground in a standard mill for 60 revolution. A high value of G represents
soft or easily grindable coal. The average hard grove index of Indian coal used in power
stations ranges between 50-60. A formula based on statistical regression may be used to
calculate HGI from the proximate analysis of coal.

HGI = 105-R( 1.16 + 0.002R)-0.4A

Where A= Ash%. R=(VM+M)

Table- 25 below shows the variation and results based on above formula
and that of determined value.

Table- 25

Sample Proximate Analysis HGI


No.

M A VM Calculated Determined

1 1.6 50.2 18.6 60 58

2 7.2 26.2 27.3 52 53

3 1.4 45 18.8 63 57

4 8.3 19.8 30.6 49 43

5 1.5 38.2 18.6 65 65

6 6.7 32.8 26.5 52 52

H.G.I. is normally 45-55. Lower HGI means difficulty in coal pulverization. Very high HGI is
also not wanted, as it will start giving fines right from the mines. Coal [mess are very

110
difficult in handling particularly in rainy season as it forms a very sticky mass. Further very
high HGI coal with high V.M, risk of fire during storage is also very high.

Fusion behaviour of coal ash

ASH FUSION TEMPERATURE :

When heated, coal ash does not melt sharply at any temperature but begin to
soften at a much lower temperature than that at which it melts and flows. This fusion
behavior is due to the mineral matters associated with coal. During combustion of coal,
the associated mineral matters are exposed to thermal environment. The minerals under
the thermal environment undergo thermal break down into oxides followed by chemical
reactions among its various components.

Depending on the temperature of the thermal environment, the atmospheric


condition. (Reducing or oxidizing), the time of heating and the composition of mineral
matters of the coal, the final product may be sintered ash, partially fused mass/clinker or
molten matter/slag. With the combustion of carbonaceous matter of the coal, the ash
components after its primary decomposition starts solid -solid reaction which is followed
by a series of binary reactions in the solid phase to form either a low melting
components or to form a strongly bonded components without melting. At higher
temperature the solid mass start melting and a liquid phase is formed that dissolves in it
more solid mass to form ultimately a homogeneous melt

This stage-wise deformation of ash can be experimentally observed by Leitz


heating microscope in the laboratory. Specimen of ash in a cylindrical shape is heated
under a chosen atmospheric condition (generally in a reducing atmosphere) and the
changes in the shape of the ash is noted through the microscope and photographed.
Three distinct temperatures can be identified as (1) Initial deformation temperature (2)
Hemispherical temperature and (3) Flow temperature. At the initial deformation
temperature, the ash starts its primary decomposition and the ash starts deformation
(solid-solid phase). At the hemispherical temperature liquid solid phase reaction occurs.
A part of the solid mass on melting dissolves in it the rest part of the solid, forming a
homogeneous melt. The homogeneous high viscous melt gives a hemispherical shape
to the cylindrical ash specimen. On heating further the viscosity of the homogeneous
melt falls to such a degree, so that the melt tends to flow. This temperature is termed
flow temperature.

In practice, much significance is attributed to hemispherical temperature, as this


is related to clinkering/ agglomeration of the coal ash at boiler operating condition in
dry bottom furnace. In case of slag tap furnace, the knowledge of flow temperature is
essential. In India, boilers are designed as dry bottom because most of the Indian coals
are refractory in nature.

111
CHEMICAL COMPOSITION AND ASH FUSION BEHAVIOUR

The chemical composition of ash is responsible for the fusion characteristic of the
ash. The major components of ash are SiO 2, Al203, Fe2O3 and CaO. The minor components
are MgO, TiO2, P2O5, Na2O and K2O besides traces of other impurities (See Fig. 10a).

Higher alumina content (Al2O3) and silica makes the ash refractory in nature,
while lime (CaO), magnesia (MgO), iron oxide (Fe 203) and alkali oxides (Na2O and K2O)
have a fluxing effect and lower the ash fusion temperatures. Most of the Indian non-
coking coal ashes have hemispherical temperature above 1400°C and are of refractory
in nature. Based on fusion behavior, coal is classified as

a) Refractory i.e. H.T. above 1400°C


b) Medium refractory i.e. H. T. between 1350 -1400°C
c) Fusible i.e. H.T. below 1350°C

On the basis of chemical composition ash fusion behavior are classified by an Index
R as

R = Refractory Components = SiO2 + A1203


Fluxing Components Fe203 + CaO + MgO + Alkalies
R -Low -coal is clinkering in nature
. High -coal is refractory in nature
The chemical composition of coal ashes can also be used to have an idea about
the hemispherical temperature of the ash by using the molar index(Rm).

Rm = 3.33 SiO2 + 1.97 A1203.

2.5 Fe203 + 3.57 CaO + 5 MgO + 3.22 (Na20 + K20)

H.T. = 1030 + 73.3 Rm(°C)

In case of lignite coal the above formula does not hold good. Therefore, it is
evident that a lot of information can be available from the composition or chemical
analysis of coal ash. The analysis of coal ash is carried out by either of the following
methods.

i) Chemical methods -Conventional process .


ii) Chemical methods -using instrumental techniques for some of the constituents
iii) Modern instrumental methods -it includes atomic absorption spectro photometry
Spectro photometry, X-ray fluorescence etc.

FOULING AND SLAGGING

Fouling and slagging tendency of the coal can be measured from the composition of
the ash. Slagging is the deposition formed on heat exchange surface in the radiation zone
and fouling is the deposition formed in the convection zone. Slagging tendency can be
determined as below:

112
Fe2O3  CaO MgO Fe203+CaO+MgO+Na2O+K2O
Rs = xS
SiO2+Al2O3 + +TiO2

Oxides are % wt in ash . S , % wt in dry coal.

Slagging Index Stagging Category

less than 0.6 Low


0.6-2.0 Medium

2.0-2.6 High
above 2.5 very high

Determination of fouling Index :

Fe203+CaO+MgO+Na2O+K2O
Rf = x Na2O
Al2O3 + SiO2 + TO2

Fouling Index Fouling Category


Less than 0.2 Low

0.2-0.5 Medium

0.5-1 High
above 1 Severe

ABRASION

The quantity ash creates problems like dilution effect in combustion increase cost
against transport,. increase size of storage handling etc. It also increases the disposal
problem. Other than quantity, quality of the ash/mineral matter present may also create
severe problem. The abrasiveness of the coal has major effect on the wear of the
components of coal mill and other coal handling equipments. Further after combustion the
Fly ash also contains abrasive particle that leads to erosion –corrosion failure of super of
etc. Ash content of our coal is very high. The bulk of the ash from pulverized firing is
made up of spherical glossy particles. Much of the erosion is limited because they are
small size and spherical shape.

113
Fig.10(a) Fig. 10 (b)

Erosion is mainly caused by unfused quartz particle. If the ratio Of SiO 2: AI2O3 is 1.6:
1; they form a stachiometric alumino silicate. But if the ratio is more than 1.6 : 1, free silica
is there. Out of this -quartz is very hard’ irregular in shape and size and causes most of the
erosion problems. In our coal ash, this ratio is above two, which indicates that our coal ash
is highly abrasive in nature.

Since wear rate increase with increase in velocity (20% increase in velocity will double
the wear rate), our flue gas velocity is restricted to minimize erosion problems.

BOILER DESIGN ASPECTS IN VIEW OF THE ASH CHARACTERISTIC

The quantity and the characteristic of the incombustible matter i.e. the coal ash
influence the design aspects of the boilers. The quantity of ash decide the means for its
removal and the ash characteristic controls the materials for construction of the boilers
and the temperature at which the combustion products pass over the convection heating
surfaces without deposition of it in a fused state of the incombustible ash particles. So ash

114
fusion temperature is an important parameter in designing a boiler.

The fly ash quantity passing through the boiler accessories increases with ash
percentage. Indian coals ashes are very abrasive in nature. Therefore the gas velocity
carrying the ashes should be kept low to minimize erosion due to abrasion. However, low
gas velocity reduces heat transfer co-efficient and naturally large super heaters,
economizers are designed for boilers using Indian coals.

The size of the furnace heating surfaces is to be made to that extent to ensure that
combustion gases are cooled below the initial deformation temperature of coal ash before
leaving the furnace so that the ash is kept dry and does not stick to the heating surfaces,
restricting heat transfer and increasing resistance to the normal flow of the combustible
gases. The slagging is confined to radiant heating surfaces of the boilers but it can also
occur in convection surfaces if the exit gas temperature is too high to cause melting of the
carrying ash in coals with low ash. Coals with low fusion temperature, has the tendency of
slag formation. The ash fusion temperature is higher in oxidizing atmosphere than
reducing atmosphere. Therefore, at any instance it a slagging tendency is evident feeding
of additional excess air may help to avert the situation. If the coal ash shows any sort of
fouling or depositing tendency, the shoot blowing system should be altered or designed
accordingly.

Now it is thought to reduce the abrasive material percentage in coal ash by


adopting mechanical cleaning process -washing the coals before use. Studies are now
being carried out in this respect particularly in view of cost factor vis-à-vis total life and
functioning of the plant. Free silica or quartz present in the coal ash, if extraneous in
nature, can be minimized by mechanical washing of the coals.

Table-26
Typical chemical composition of coal ash used at power stations in India

Si02 55 -65% Cao 2 -6%


AI2O 18 –30% MgO 0.5 -3%
Fe2O3 6 -15% TiO 1 - 2%
P2O5 0.2 –1.5% Alkali oxides 0.5 –3%

115
CHAPTER-10

COMBUSTION

Combustion is a rapid chemical reaction which takes place when a combustible


element of fuel, combines with oxygen and gives off heat. During combustion, an atom of
combustible (carbon, sulphur, hydrogen) in fuel and one or more atoms of oxygen
combine to give their respective oxides.

The supply of oxygen for combustion comes from the atmosphere, which contains

21 % O2 and 79% N2 by volume (trace gases may be omitted)


23.2% O2 and 76.8% N2 by weight.

The nitrogen plays no useful part in combustion process. In fact, it enters the boiler
at an ambient condition and leaves the boiler at a very high temperature hence carries
away heat to the boiler stack.

Before efficient combustion can take place, several basic requirements must be
fulfilled.

a) The combustible must be supplied with the correct amount of oxygen.

b) The combustible must be at or above its ignition temperature.

c) There must be sufficient turbulence to promote thorough mixing of the combustible


and the oxygen.

d) Sufficient time must be allowed for the reaction to take place.

There are three major requirements referred as the 'Three Ts' of combustion

(1) Time (2) Temperature (3) Turbulence '

THEORETICAL AIR FOR COMBUSTION

Theoretical air may be defined as the quantity of air that actually takes part in
combustion process. Since the chemical reaction between oxygen and the combustible
substance are in accordance with strict specific laws, the combustible will combine with the
exact amount of oxygen the laws specify, and any additional oxygen that is supplied will

116
appear in the flue gas as free oxygen. The theoretical amount of air can be calculated if the
weight and chemical formulae of the combustible substances are known.

The quantity of oxygen required for combustion can be precisely calculated as below
and then the quantity of air required can be calculated.

COMBUSTION OF CARBON

C + O2= CO2 + Heat (33940 KJ/Kg)

12 gms + 32 gms = 44 gms

Therefore 12 gms carbon + 32 gms oxygen = 44gms of CO2

or 1 gm Carbon + 2.67 gms oxygen = 3.67 gms CO2.

As the oxygen required is taken from atmosphere which contains 23.2% O 2 by weight.
Hence to supply 2.67 grams of Oxygen amount of air required will be

2.67x100 = 11.5gms.
23.2

The product of combustion will be 3.67 gms CO2 and 8.83 gms N2 (11.5 - 2.67).

If insufficient oxygen is supplied, incomplete combustion will take place and


carbon will bum to carbon monoxide.

2C + O2 = 2CO + Heat (10120 KJ/Kg)


24 gms + 32 gms = 56 gms
1 gm+ 1.33 gms=2.33 gms
To supply 1.33 gms of oxygen amount of air required:

1.33xl00 = 5.75gms
23.2 gms
The product of combustion will be 2.33 gms CO and 4.42 gms N2.

There is a reduction (about two third) in heat released between burning carbon
to carbon dioxide and carbon to carbon monoxide.

Loss of heat (33940 -10120) = 23820 KJ/Kg .

COMBUSTION OF HYDROGEN

2H2 + O2 = 2H2O + Heat (142679 KJ/Kg)

4gm + 32gm = 36gm

1 gm+ 8 gm=9 gm

The amount of air required =

117
8 x 100
= 34.48gms

23.2

The products of combustion will be 9 gm of water vapors and 26.48 gm of nitrogen.

COMBUSTION OF SULPHUR

S + O2 = SO2 + Heat (9141 KJ/Kg)


32 + 32 = 64
1 gm+ 1 gm=2gms
To supply 1 gm of oxygen amount of air required = 1 x 100 = 4.31 gm
23.2

The product of combustion will be 2 gm SO2 and 3.33 gmN2.

Some fuels contain oxygen and this oxygen is able to combine with the
combustibles in exactly the same way that oxygen in the air combines, for this reason,
due allowance should be made for the oxygen in fuel and the figure subtracted from the
calculated requirement.

Simple formula to calculate the amount of air required from ultimate analysis of coal,
is as below:

The air required = 100 (8/3 C +8(H-O/8) +S


23.2

Where C,H,O & S are the amount of Carbon, Hydrogen, Oxygen and

Sulphur present in the fuel.

EXCESS AIR

The combustion calculation as explained show the theoretical amount of air required
for perfect combustion. In practice, perfect combustion cannot be achieved if fuel is burnt
with theoretical amount of air only, because for the reaction to take place efficiently, the
molecules of oxygen must be in actual physical contact with the atoms of the combustible.
It becomes impossible because air contains almost four times the amount of nitrogen
molecules that hinder the physical contact between the combustible and the oxygen,
simultaneously non combustible matters present in coal, products of combustion CO 2,SO2
and H2O etc. also plays the same role.

This problem is alleviated by supplying an amount of air in excess to the theoretically


required for perfect combustion. The quantity of excess air supplied is a compromise
between heat lost due to incomplete combustion and the heat carried away by excess air to
the stack.

EXCESS AIR LOSSES

There are three main losses influenced significantly by the excess air.

118
1. Unburnt gas loss

2. Dry flue gas loss

3. Combustible in ash loss

UNBURNT GAS LOSS

This loss is mainly the result of burning carbon to carbon monoxide instead of to
carbon dioxide, when carbon bums to carbon monoxide one third of the potential heat of
the carbon is released, obviously an abundant supply of oxygen i.e. more air will quickly
reduce this loss to zero (Fig. 11a).

Fig.11 (a) Fig. 11 (b)

DRY FLUE GAS LOSS

A further loss of heat is due to the dry flue gas, generally referred as stack loss. With
the admission of excess air, this loss goes on increasing (Fig.11 b).

COMBUSTIBLE IN ASH LOSS

This loss in high when there is little or no excess air, because mixing of combustible
and oxygen is very poor. On introduction of excess air, this loss is reduced to minimum not
to zero, because the loss depends upon two factors when burning coal. First the air/coal
mixture must be correct and secondly it depends upon fineness of the coal incase of p.f
firing (Fig. 11c).

119
Fig.11(c) Fig.11(d)

COMBINED HEAT LOSS

If the above three losses are added, the result will be as shown in Fig. 11 d. The loss
gets less as excess air is added, reaches a minimum value and then as still more excess
air is added. Thus there is one and only one quantity of excess air, which will give the
lowest loss for the combustion of a particular fuel. Expressing in other way, there is only
one value of excess air, which will give the maximum efficiency. The value depends upon
quality of fuel Used and type of firing.

120
FLUE GAS ANALYSIS

Efficient combustion is dependent upon the correct supply of air. It is necessary to


supply excess air to ensure that combustion is complete, but the ideal amo1mt is quite
critical, too much lead will to an increase in the stack loss and too little will lead to
incomplete combustion.

In the past, it was common practice to do this by measuring the carbon dioxide
content of the flue gas. It will be appreciated that the CO 2 content is a measure of the
excess air, but the CO2 indication has several limitations:

(i) It is not a direct measure of excess air because of the effect of presence of
hydrogen and sulphur in the fuel.

(ii) As the excess air is reduced, the CO 2 % increases until it reaches maximum.
Further reduction of excess air results in decreasing CO 2 %. This may be
interpreted that the excess air has increased

If instead of CO2 an indication of O2 is provided then the relationship between excess


air and percentage oxygen in the flue gas is almost constant. Oxygen analyzer is ideal for
use in boiler automatic control schemes for 'oxygen trim' control. On-line oxygen analysis
utilizes the principle of paramagnetic susceptibility of oxygen, because in flue gas mixture O 2
is the only gas which is paramagnetic in nature.

The recent oxygen analyzer gaining popularity is 'In-situ' zerconia probe system. Still
O2 measurement also is not so reliable for efficient combustion monitoring, because % O2
in flue gas measurement is affect by boiler load change, Air in leakage, fuel type and
burner conditions etc.

The most reliable measuring parameter is CO in flue gas, for efficient combustion the
value of which should be within 100-250ppm, the measurement is based upon the principle
that all hetro atomic gases absorb infrared radiation between 2.5 to 12 micrometer
wavelengths. This measurement is not significantly affected by boiler load change, air
Ingress and fuel type.

ORSAT APPARATUS

The equipment used by chemist for determining the CO 2 % along with other
flue gas components like O2 and CO is ORSAT apparatus.

In this apparatus a sample gas is drawn by means of a hand pump. The


apparatus, shown in Fig.11e consists of a water- cooled measuring cylinder and three
absorption bottles containing chemicals, namely

Bottle I : containing KOH solution to absorb CO2

Bottle 2 : containing an alkaline pyrogallol solution


to absorb O2
Bottle 3 : containing alkaline cuprous chloride solution to absorb CO.

After passing the sample through the individual bottles the sample is brought
to the measuring jar which shows the amount of the gas component absorbed by the
chemical and thus determining the volume percentages of CO2,,O2 and CO.

121
Fig-11e

122
CHAPTER-11

OILS

FUEL OIL

In Thermal Power Station, fuel oils play vital role. It is used for initial light up of
the boilers, as an auxiliary support to compensate the problem of coal flow and
essentially at the time of lean period. The lighting up burners besides initial lighting up
the boilers, are also used to provide effective ignition of the coal associated with the
P.F. burners and to stabilize the coal flames. The burners can provide enough heat to
Carry on boiling out operation of the boilers at initial start up period. It can provide 10
to 15 percent of the optimum load. At lean period or when it is desired to run the boilers
at off load condition, load -carrying burners are used. These are similar to lighting up
burners but of higher capacity to provide approximately 25 percent of boiler MCR.

Various grades and quality of fuel oils are used depending on the nature of
requirements. Products of petroleum origin classified as fuel oils/furnace oils, light diesel
oils, high speed diesel oils etc. are generally used in the power stations.

METHODS AND REASONS FOR OIL SAMPLING

Consumption of huge quantity of oils as fuels in power station necessitates its


proper sampling and testing thereof. Prices are fixed on the quantity of fuel oils.
Identification and storing of different grades of oils are also necessary for testing them
under specific conditions and purposes. Increasing scarcity and expanding demand and
considering its high price, the efficient use of the oil is thought of so seriously. Hence, it
is very essential to be aware of the properties that influence the way the liquid can be
handled; it can be stored, transferred and burnt. Proper representative sampling
followed by careful analysis can only predict those properties accurately.

Sampling of the oil is to be carried out very carefully and by the specified methods,
as incorrect sampling invalidates all the tests ultimately done in the laboratory. Sample
must not contain any adventitious material or be altered during the sampling procedure
by evaporation or oxidation. Appropriate sampling equipments should be used to sample
from cans, drums, road tanker, rail tanker, storage tank etc. Sampling equipments and
container must be chemically cleaned. Precautions for the probability of fire hazards
should also be taken. Sampling is done by any of the three methods -weighted can
method, tube sampling or in- line sampling.

WEIGHTED CAN METHOD

A can 1 -2 pint capacity (1 pint -app. 500 ml) and suitably weighed and fitted with a
long chord attached to a stopper in its neck in such a way that the stopper can be jerked
out at any desired level. The can is clipped in the oil tank at different levels -upper, middle
and bottom from where can full of samples are drawn in intervals. The upper middle and
lower depths are I / 6th, 1/2 and 5/6th depth of the tank. Samples drawn in succession
are composite to one, mixed to form the final sample.

123
TUBE SAMPLING

A long metallic tube fitted with a sliding valve at one end, which can be opened or
closed by a long handle from the other and is used for this purpose. The pipe is dipped into
the oil tank and on opening and by subsequent closing the valve oil is drawn in the tube
from different depth at intervals, in the same method as is followed in weighted can
method.

IN-LINE SAMPLING

It is automatic sampling device during the transfer of oil from the delivery tankers to
storage tanks. A 11/2" pipe is projected in the delivery line internally to one third of the line
diameter. The inner end is bent at 90 o to face the flow of oil stream and a sampling cock is
fitted outside. For more accurate sampling micro-pump is used to draw sample continuously
during the whole period of discharge.

TESTING OF FUEL OILS

Composition: The average composition of liquid fuels of petroleum origin varies within
every close range as follows :

Carbon -83 to 87% Hydrogen -11 to 14%

SulpHur -0.5 to 3% Nitrogen -0.1 %

Oxygen -2 to 3%

In spite of their close resemblance in chemical composition the properties that make
them suitable for burning varies widely. No single test is possible to classify and evaluate
them. Power engineers are mainly concerned with those properties, which influence proper
and efficient burning of the oils in burners, the way the fuel can be handled and stored.

Those properties includes -viscosity, specific gravity, volatility, flash point, gross
calorific value, sediment content, residual carbon etc.

VISCOSITY

Viscosity is one of the main characteristics to classify the oil. This test is necessary as
a routine to classify the correct grade of the oil and to ascertain the temperature of the
preheat to maintain proper viscosity for easy flow of the oil and its vaporization there of.
Viscosity is a measure of their resistance to flow. The absolute or dynamic viscosity,
influence significantly the case of handling, transport and nature of storage. It has a direct
bearing on the perfection of atomization of the oil and its combustion efficiency.

Dynamic viscosity - Resistance to flow of the liquid

Kinematic viscosity -Resistance to gravity flow

Viscosity of oils is measured by using a specially designed apparatus called


viscorietor. The principle that follows in this measurement of viscosity is to measure the

124
1jme required to flow a fixed volume of oil through a fixed at a definite temperature.
Different types of standard viscometers are Engler, Red Wood No.I, Red Wood No. II,
Saybolts Universal, Saybolts furol. The results are expressed in number of seconds required
to flow of the oil through the type of viscometer used. Kinematic viscosity is directly
measured by using U- tube viscometer. Unit of Kinematic viscosity is stoke.

1 stoke = 1 cm2/sec

The viscosity of fuel oils falls with the rise of temperature and above the temperature
of 120°c the viscosity is almost constant. So, for perfect and uniform atomization the oil
should be preheated to a temperature of 120°c before atomization.

The maximum viscosity for easy atomization in conventional burners is

25 centistokes or 100 sec. in Red Wood No.I. For easy pumping through usual
pipeline, maximum limit of viscosity is 1,200 centistokes or 486 secs in Red Wood No. II.

Viscometer Conversion Factors

1 Centistoke = 0.131o Engler = 4.08 secs in R.W.I


= 0.408 Sec in R. W. II
= 4.57 Saybolts Universal
= 0.457 Saybolts furel

At very high pressure the viscosity of oils increase very considerably. At a


pressure of 70 kg/cm2, the increase is about 15%. Most oils begin to solidify at a pressure
of 3,500 kg/cm2.

SPECIFIC GRAVITY

Its main use is in the calculation involving weights and volume of the oil. Higher
specific gravity indicates higher concentration of carbon in relation to hydrogen. Hence,
heavier oils have lower gross calorific value on weight basis.

The specific gravity of the oil is measured by using hydrometers, relative density
bottles or vastphal balance. For quick determination, hydrometers of suitable range are
most commonly used. Specific gravity of oils also gives an idea of the heat value of the oil
by using a simple formula
C (Heat value / calorific value)
= 12400 -2100 d2, d is the density of the oil

FLASH POINT

The flash point of an oil is defined by the minimum temperature at which on oil give
off sufficient vapor to form an inflammable mixture with air, as shown by the momentary
flame (flash) when an external source of fire is brought in contact with the oil vapor.
Determination of flash point of an oil is essential for safe storage of the oil and precautions
of fire hazards during preheating. Fuel oils having flash point about 66°c are regarded as
safe. Flash point also is considered as an indirect measure of the volatility of the oil. Two
types of apparatus are used for determination of the flash point of an oil depending upon its
flash point temperature. Flashpoint of oils below 50°c is measured in Abolts apparatus and

125
that above 50°c in Pansky Marten apparatus. The flash point of oil depends also on the
atmospheric pressure.

GROSS CALORIFIC VALUE

As the ultimate analysis of oils shows that the composition of an oil varies within a
short range, so naturally the gross calorific value also varies within a narrow range of 1
0,000 to 11,300 Kcal/kg. The lighter the oil, the higher its calorific value. The petroleum
oils are enriched in hydrogen (11.5 to 15%) hence the net calorific value is less than the
gross calorific value by as much as 620- 720 Kcal/kg.

The calorific value of fuel oils is determined in bomb calorimeter. However, for plant
practices, the empirical formula is also widely used for ascertaining the heat giving capacity
of the oil for ready reference. The calorific value as determined by using the empirical
formula varies within the range of () 250 Kcal/kg of the determined value in bomb
calorimeter.

PROBLEM OF BURNING FUEL OILS

Oil is easy to burn and being more homogenous than the coal its properties does not
vary within a short time. Advantages of burning fuel oils over coal are heat exchange
surface remaining clean for a longer period, require smaller margin of excess air, problem
of smoke and dust disposal is minimum.

The combustion of fuel oils takes place in vapour phase and so the oil should be sent
in the furnace so that vaporization is rapid and continuous. The oil should be atomized to
the fullest possible extent to achieve maximum efficiency.

Three types of conventional atomizer burners are used by different designers, they
are ( a) pressure jets (b) Rotary atomizer and (c) Blast atomizer.

Sticking and Clogging of oil burners are experienced after some days use resulting in
complete stoppage of oil flow through the burner nozzle. A hard sticky mass almost
looking like a coke is found to deposit at nozzle mouth for not maintaining the ideal
operational permit. Those may happen for various reasons -failure of oil strainer, cracking
of the oil inside the burner due to excessive heating of the burners, high viscosity of the
oil etc.

During the start up period i.e. at cold boiler condition, atomization may not at first
be easy, so carry over of oil droplets causes, accumulation of un burnt oil in air heaters
may subsequently cause serious fire hazards. Poor combustion may happen at the initial
start up period and to minimize this problem, oil of lighter fraction which atomizes more
easily at low temperature should be used for lighting up the boilers.

CARBON RESIDUE

Oil containing intolerable limit of residual carbon content causes burning problem
during oil firing. Even on maintaining the best possible atomization condition, the part of
the residual carbon of the oil do not take part in the oxidation reaction at the burner
temperature and it deposits at the burner tip causing choking of the burner. Sometimes,
for not maintaining proper operational conditions, the burner ends are heated to such a
temperature that the oil gets cracked. Due to this unusual cracking deposition of carbon

126
and its subsequent transformation of a hard sticky mass (coke) results in burner failure.
Residual carbon content of oil is measured by Ramsbottom apparatus or Conardson
apparatus.

HIGH TEMPERATURE FOULING AND CORROSION

Fuel oils contains both sodium and vanadium. These metallic compounds during
combustion of the fuel converts into oxides and sulphates. These compound melt at a
temperature range of 5800 to 1000°c. These compounds are soft sticky mass and highly
corrosive in its molten state. Corrosion of superheater tubes is caused by these corrosive
masses, besides fouling of the sticky mass on boiler surface.

LOW TEMPERATURE FOULING AND CORROSION

Sulphur present in the oil on combustion produces sulphur dioxide, a small portion
of which is converted to sulphur trioxide. The flue gas passing through the boiler
progressively gets cooled and condensation of moisture occurs. The trioxide of sulphur
also condenses as sulphuric acid which is highly corrosive. Corrosion of ferrous metal to
its sulphate and accumulation of corrosion products causes fouling along with ash and
unburnt carbon. Using of oil of low sulphur content and controlling the dew point
temperature of effluent gases, this problem can be minimized.

Table-27
INDIAN STANDARD SPECIFICATIONS FOR FUEL OILS USED IN POWER STATION

Characteristics Grade

Low viscous Medium viscous

Flash Point °c (min) 66 66

Kinematic viscosity in 80 125

centistoke at 50°C (Max)

Water content % by vol. (Max) 1.0 1.

Ash % by wt. (Max) 0.1 0.1

Sulphur % by wt. (Max) 3.5 4.0

Sediment % by wt (Max) 0.25 0.25

Acidity, Inorganic Nil Nil

LUBRICATING OIL

A wide range of products is covered by lubricants. It is a substance which reduces


the friction between two surfaces which are sliding one over the other. Any moving
parts, revolving in high speed should be kept in definite relationship with other parts.
Intimate contact between surface moving relative to each other, is minimized by
introduction of an oil film between and adhering to the surfaces. The oil films offer
resistance to '" shearing” when relative motion of the surfaces occurs. Beside

127
minimizing the friction, lubricating oils remove heat from the bearings.

Lubrication occurs in the following three ways:

a) Complete fluid lubrication


b) Boundary lubrication
c) Extreme pressure lubrication

Due to increase in the size of turbines and generators, resulting in higher specific
loadings of bearings and peripheral speed of journals, the duty the oil is required to
perform is becoming increasingly arduous. It has to withstand continuous thermal
cycling and variable degree of contamination by solid particles, sludge, water, hydrogen
and air. It is expected to readily release such contaminate and retain its lubricating
properties over a long period. New oils are chosen with a 20 to 30 years life for machine
ranging from 30 to 200 MW. Various factors substantially affect oil life and apart from
those mentioned above the following are of importance

a) Oil make up rate


b) Bulk oil temperature
c) Hot spot temperature
d) Total oil volume

Average oil make up rate is known to the order of ten percent per annum. But it varies
between the ranges of 5 to 25 percent per annum under various plant conditions. The make
up is made to keep the average oil quality to the minimum desired value.

In order to be reasonably sure the oil is being maintained in a satisfactory condition it


is necessary to monitor the selected properties of the oil. The following tests are to be
carried out for monitoring of the oil:

Viscosity, flash point, total acidity, oxidation characteristic, demulsification number,


foaming tendency, foam stability, anti-rust.

VISCOSITY

Viscosity is the measure of resistance to flow. Classification of different viscosity


standards and its measurement procedure is discussed in previous notes on 'Fuel Oil'. In
lubrication purpose the knowledge of viscosity is related to its characteristic change
depending on temperature. As the viscosity of oil falls with the rise of temperature, its
very purpose will fail if it is subjected to a wide variation of temperature. The extent of
this variation of viscosity for a given temperature fluctuation is not same for all types of
oil. Oils containing high parafinic components tend to resist alteration in the viscosity
with temperature change while oil containing high napthonic components shows large
dependence on temperature. Hence, for selecting and studying the lubricating properties
of the oil its viscosity index is to be known.

Viscosity Index: Viscosity temperature relationship of lubricating oil is denoted as the


viscosity index and this index is expressed by a number on an arbitrary scale.

128
Viscosity Index (V.I.) = L-H x 100
L-H
L,H and U are the viscosities (in seconds) of a oil of zero V.I., 100 V.I., and that of the given
oil at 100oF.

FLASH POINT

Flash point of the turbine lubricating oil should be always well above its optimum
operating temperature. As flash point indicates the volatility of the oil, hence increase in
flash point temperature of the used turbine lubricating oil gives an indication of its
degradation.

TOTAL ACIDITY

Increase in total acidity indicates degrading of the oil by oxidation, contamination etc.
during its long use. Oil containing total acidity beyond the tolerable limit should never be
used, as it will corrode the metal surface causing serious damage to the moving parts. The
total acidity of the oil is determined by extracting both organic and inorganic acid by alcohol
and titrating with standard solution. It is expressed as mg of KOH consumed per gm of oil.

Total Acidity after Oxidation:


This test gives an indication of the tendency of the oil to oxidize. To 100gm of the oil sample
some catalyst is added and it is subjected to a temperature of 11O°C for 90 hours. Then he
sample is tested for total acidity and these should not exceed 0.2 mg of KOH per gm of oil.

OXIDATION STABILITY

Formation of sludge by oxidation of the oil at hot spots e.g. in bearing housing,
seals, gears, piston and also during normal operating system is dependent on the
oxidation stability of the oil. The oxidation stability gradually decreases in service due
to the catalytic effect of dissolved metals, principally copper and iron and also due to
the depletion of anti-oxidant added in the oil.

As the oxidation stability decreases, it will eventually reach to a stage when small
volume of the oil will be oxidized to the sludging state in several areas of the system.
This sludging may occur without increasing the acid value, so the determination of the
oxidation stability of the oil is essential at suitable intervals.

Five grams of the oil are oxidized at atmospheric pressure under an atmosphere
of oxygen at 150°C without adding any catalyst and the time taken by the oil to
absorb 15 ml of oxygen is recorded. This is commonly referred to T 300 ml (i.e. the
time for 100 gm of oil to absorb 300 ml of oxygen).

DEMULSIBILITY

The exposure of warm oil to air and its admixture with water tend to form an
emulsion. Emulsification is accelerated by any churning action of the oil and water
mixture. Steam blowing from a gland will get into the bearing housing, where it
condenses; water vapour in atmosphere condenses on various parts of the turbine
when it is shut down and some of it ultimately gets into the oil wells, another potent
causes is a leaky oil cooler. Emulsification reduces the value of the oil as a lubricant
and often causes stoppage in the system due to leakage formation.

129
When oil is merely allowed to lie in a drain tank or settling tank the amount of
separation, which will take place in a given time will depend on the demulsibility of the
oil. In any case, a high degree of demulsibility is desirable in turbine oil.

Demulsibility characteristic of an oil is determined by the demulsification number.


It is the number of seconds required for an oil to separate when 20 m1 of the oil is
emulsified with steam at about 90°C. The time of separation of the emulsion is noted by
allowing the oil to separate at a constant temp. of 94 °C.

ANTI-RUST PROPERTIES

There are three environments in a lubricating system which require anti-rust


protection. They are :

a) fluid flow areas


b) areas covered by static droplets or pools of water
c) areas of ferrous material above the oil surface; i.e. the upper parts of
Pedestal, drain pipes and tanks.

Table-28 : Characteristics of steam turbine lubricating oil


Characteristic Light Medium Heavy Extra Heavy

Viscosity in contistoke at 98.9°c 4.7-5.4 5.5-6.4 6.5-8.1 8.2-


10.5

Viscosity Index (min) 80 80 80 80

Inorganic acidity mg ofKOH gm of oil Nil nil nil nil


Total acidity after oxidation, mg of KOH/gm
of oil (max.) 0.2 0.2 0.2 0.2

Flash point (min.) 165°c 165°c 165°c 165°c


Pour point (max.) -3°c -3°c -3°c - 3°c
Rusting – -------------------shall pass ----------------------------
Demulsification number in seconds (max) 300 300 300 300
Corrosion (copper strip)

Foaming. volume in ml of foam after 10 minutes, foam collapse(max),


a) Sequence 2 25 25 25 25
b) Sequence 3 300 300 300 300

Anti-rust additives added in lubricating oil are depleted by performing its normal
function, by removal with water and by removal with wear and corrosion debris. Polluted
water, particularly alkaline water removes anti-rust additives more rapidly than
condensate.

Anti-rust properties of the lubricating oil is tested in intervals. The method involved
stirring a Inixt1noe of 300 ml of the oil with 30 ml of salt water at a temperature of 60°C
with cylindrical steel test specimen completing immersed therein. After 24 hrs contact with
the oil-water mixture, the specimen is examined to determine whether it has rusted or not.

130
DETERMINATION OF FOAMING CHARACTERISTIC

The oil sample of a temperature of 93°c is blown with air at a constant rate for 5
minutes then allowed to settle for 10 minutes. The volume of foam is measured at the end
of this period. The test is repeated after collapsing the foam at 24°c. The comparative study
of the volume of foam formed under these two sequences given an idea of foaming
characteristic of the oil.

INSULATING OIL

In powerhouse practice, bulk quantity of mineral oils (petroleum origin) are used in
transformers, switch gears etc. The consignment of the oil stated as transformer oil does
a dual function in the transformer and switchgears as coolant and as insulator.

Transformer cooling is more difficult than rotating machine, as it has no rotating


parts to induce a ventilating draught. For small transformer of capacity up to 20 KW, the
external surface is sufficient to enable the heat produced to be dissipated by radiation.
However, for larger size transformers, the transformer is placed in a tank of oil. For
providing as large a cooling surface as possible by (a) corrugating the sides of the tank or
(b) using a boiler plate tank provided with external tubes. For still larger one, instead of
using a considerable large tank, small tanks with a worm tube immersed in the oil,
through which cooling water is circulated are used The following cooling systems are in
vogue:-

tank with external tubes, water cooling and air blast cooling.

The oil besides cooling the heat generated, serves the purpose of very good
insulation by increasing the insulation strength. Even from safety point of view, due to
damage or decomposition of the insulating material of the transformer, the oil enables
enough insulation to impart any damage of the equipment or life. As such the oil used in
transformer or switchgears an insulation oil should be of certain specification and quality
to suit the purpose.

TFSTS
For monitoring quality of transformer insulating oils the following tests should be
performed periodically -Total acidity, oxidation stability, viscosity, flash point, copper
discolouration, free water and electric strength.

If at any instant any gas formation is evident by the response of Buchholz gas pressure
relay, the gas must be analysed to detect the nature of the gas and to find out the reason
for such gas formation. The testing of the gas will give an idea whether the gas formation
has resulted due to cracking of the oil due to overheating / momentary spark caused inside
the transformer or due to cellulose degradation.

HYDRAULIC FLUIDS

There are three types of hydraulic fluids :

1) Mineral oil Hydraulic Fluids: These are minerals in origin, soluble in water to give
emulsions. They are cheap, used where not many moving parts are involved. If
leakage is there, it may cause fire hazards at elevated temperature.

2) Water / Glycol Fluids: They contain water so reasonably fire resistant, where more

131
oiliness required it is better than mineral oil. At elevated temperature, water tends to
evaporate and it becomes thick and sticky. Water can be added to restore the original
condition. These are costlier than mineral oil.

3) Synthetic Hydraulic Fluid: They are synthetic products. Such as chlorinated hydro-
carbons and phosphate esters. These are highly resistant to fire and are used where
high temperatures are encountered. These are however very costly.

All the above fluids have a tendency to attack seals or similar parts in hydraulic
system.

Table –29 IS Specification for new insulating oil

Characteristics Requirement
1. Appearance Oil should be clear, transparent
and free from suspended
matter or sediments

2 Density at 29.5°c max. 0.89 gm/cubic centimeter


3. Kinemetic viscosity 27 CST
at 27°c ( min)
4. Interfacial tension at 27°c min 0.04 N!m
5. Flash point, pensky 140°c
Marten (closed) min.
6. Pour point, max. -6°c
7. Neutralization value
(a) Total acidity max. 0.03 mg KOH/gI
(b) Inorganic acidity/ alkalinity nil
8. Corrosive sulphur Non corrosive
9. Electric strength (break down voltage)
(a) New unfiltered oil 30 KV (rms)
(b) After filtration 6OKV( rms)
10. Dielectric dissipation 0.002 max.
11. Specific resistance
(a) at 90°c 35x 10 12 ohm cm
(b) at 27°c, min 1500x 10 12ohm cm
12. Oxidation stability
(a) Neutralization value after oxidation 0.40 mg KOH/G
(b) Total sludge after oxidation max. 0.10 % by wt.
13. Aging characteristics after accelerated aging
(open beaker method with copper catalyst)
(a) Specific resistance
(i) at 27°C min. 2.5x 10 12ohm.cm
(ii) at 90°C min. 0.20 x 10 12ohm.cm
(b) Dielectric dissipa- 0.20
tion factor at 90°C max.
(c) Total acidity max. 0.05 mg KOH/gm
(d) Total sludge value 0.05 % by wt.
14. Presence of oxidation inhibitor Nil
(.05% max. is treated as nil)
15. Water content, max. 50 ppm

132
16. S.K. Value, max. 4-8 %

BUCHHOLZ GAS ANALYSIS

Almost every type of fault inside a running transformer can be judged by the
generation of gas in it. By this, primary indication of any fault developing in a
transformer can be judged and serious damage to this costly electrical gear can be
avoided. The Buchholz gas pressure relay is the device used for gas detection and
automatic isolation of the transformer. It is fitted to the highest point in the
transformer in the connection pipe to the conservator and is initially full of oil. If gas is
generated it accumulates and a float to sink which activates an alarm. If an abnormal
generation of gas occurs, a flap valve is displaced which causes the relay to
immediately isolate the transformer from service.

As soon as a transformer is taken out of service, following by a gas signal,


following information should immediately be sought concerning the nature of fault

a) Past history
b) Rate of gas generation (frequency)
c) Analysis of the gas so generated.
This will clear the doubt whether the accumulated gas is only an air or some internal fault
has occurred.

2.ANALYSIS OF GAS

The accumulated gas is anaIysed in-situ, as its collection is avoided in most of the
cases, so that during collection no air in-filtration do occur. For the analysis, a simple
device, containing two compartments or two small vesse1s through which gas is passed
simultaneously is used.

(a) First vesse1 contain a solution of aqueous silver nitrate (AgNO 3). The gas after
bubbling through this solution passes in to the second compartment.

(b) The second vessel contains a solution of ammonical silver nitrate, both made up
in distilled water. The residual exist gas after bubbling through second vessel is
tested for its inflammability. The interpretation of is made as under:

133
Table-30

Solution No.1 Solution No.2 5% Exit gas Fault


5% AgNO3 ammonia inflammability

a No reaction No reaction Non inflammable No fault

b Heavy, white Yellow precipitate Inflammable Air under oil arcing or


curdy precipitate under oil hot metal

c Black precipitate Black sooty Inflammable Cellulose degradation


Precipitate,
solution opaque

CHEMICAL REACTIONS INVOLVED INABOVE CASES

In under-oil arcing of under oil hot metal reactions, the main gas evolved is
hydrogen, together with acetylene and lighter paraffins. The gaseous ingredient that is
responsible for colour changing is acetylene. Acetylene with silver Nitrate, forms silver
acetylide in solution No.1, a complex of silver nitrate and silver acetylide is first formed
and subsequently changed to silver acetylide. In solution No.2 silver acetylide is formed
directly, but only after reaction in No.1 is completed.

Caution.. The silver acetylide explodes violently on heating, hence the container should be
cleaned after the test is over.

INSULATION BREAKDOWN

This is a case of cellulose degradation, when carbon dioxide (CO 2,) carbon monoxide
(CO2) and methane (CH4) are generally formed. Carbon monoxide reduces the silver
nitrate to black metallic silver.

The sign of inflammability of exit gas indicate the presence of acetyline, carbon
-monoxide and methane.

As soon as Buchholz signal is indicated, the analysis of gas should be carried out
immediately as acetyline gets into oil and precipitation takes place in either of the
solutions, but the exit gas will be inflammable as carbon monoxide has very less
solubility on oil.

134
APPARATUS

The apparatus of Buchholz gas analysis is very simple in design. As described


above, it contains two tubes with an arrangement for passing of gas.

The gas inlet is connected with a perfect leak proof adopter (Brass or gun metal
make) which after screwing on the gas release valve of the transformer; the valve is
opened for passing of the gas

Fig.I2

135
CHAPTER-12

CORROSION AND DEPOSITS- FIRE SIDE

Inorganic matter is fossil fuels, coal and oil, is responsible for troubles in furnaces.
Coal is the worst of offender with roughly 35-45% ash. Residual fuel oil generally contains
less than 0.1% ash, but its ash contents are generally more aggressive than those in coal.
Both fuels lead to serious problems in external corrosion and deposits as these inorganic
materials accumulate on heat receiving surfaces. Such deposits of ash upset heat transfer
coefficient at the normal flow patterns of flue gases, but the main trouble is that rapid metal
wastage can occur beneath deposits, forcing unscheduled outages for replacement of wall
tubes or super-heater elements. In gas turbines, combustor problems are not so severe, but
deposits on turbine blading can be disastrous.

Deposits are objectionable in themselves as thermal insulators or flow obstructers,


but corrosive- conditions, accompanying deposits that cause the greatest concern.

A typical result of metal wastage of super-heaters and re-heaters has been the trend
towards lower steam temperature in boiler furnaces. There was a trend for higher steam
temperatures after 1931 and on an average steam temperature increased by 8 0 C per year
during the period 1931-55; most boilers being designed in 1960 for 566 0C steam. In 1960,
design steam temperature begins to drop with power boilers being built for 566 0 C and more
for 5380 C. Since 1968, the steam temperature in all new units has been limited to 538 0 C.
The reason for this is shown in table 31.Hence, with minimum trouble between 538 and 543 0
C, boiler practice has tended to stabilize at these levels.

Table : 31 – Forced outages caused by super-heaters in Drum-Type units during 1964.


0
Steam Temperature C Forced outages (Per unit)
482 – 513 1.5
538 – 543 0.6
560 – 571 1.4
593 – 649 1.9

Replacing corroded wall tubes or super-heater elements can be costly, but the loss of
availability during an unscheduled outages of a large steam generator through a tube failure
can be expensive indeed. This is the main reason why so much attention has been paid to
investigating the causes of corrosion and deposits, and to seeking corrective measures.

OCCURRENCE OF INORGANIC MATTER IN FUELS:

The nature of non-combustibles in coal is quite different from that of the non-
combustibles in residual fuel oil. In the case of coal, usually only a small part of the
inorganic matter was part of the original growing plant; the remainder was deposited with
the plant material while coalification was taking place. In fuel oil, the major impurities are
complex organic compounds originating in the life forms that became petroleum, plus
inorganic material unavoidability included during transportation and refining.

136
COAL ASH :

Inherent mineral matter in coal, consists of the elements originally present in


growing plants, such as iron, calcium and magnesium, phosphorous, potassium and sulphur.
Extraneous mineral matter making up the remainder of the coal ash, is from sediment
washed into the coal bed, or inorganic solids collected from percolating ground water. Most
of this ash comes from four main groups-shale, clay, sulphur and carbonates. Usually 95%
of the ash exists as Kaolinite, pyrites and calcite. Following combustion, these mineral forms
convert to complex silicates, to un-reacted oxides, and to partially or wholly sintered glasses
of indeterminate chemical structure depending upon the temperature to which they were
heated and are reported as the oxides. Table 32 shows the usual range of composition of
coal ash.

Table- 32 : Usual Range of Ash composition :

Component Percentage
SiO2 20-60
Al2O3 10-35
TiO2 0.5-2.5
Fe2O3 5-35
CaO 1-20
MgO 0.3-4
Na2O + K2O 1-4
SO3 0.1-12

Sulphur in an objectionable constituent in coal for reasons aside from air pollution
considerations. It causes a great many problems in boiler furnaces, mainly because it leads
to SO3 and complex sulphates directly involved in corrosion. Coals contain varying amounts
of sulphur, usually not exceeding 4%..

Sulphur exists in coal in three forms : pyrite, organic and as sulphates. Sulphate
sulphur content is usually negligible. In low sulphur coal (S<1.0%), the sulphur present as
pyrites is generally less than 20% of the total sulphur ; whereas in high sulphur coals, the
pyretic and organic sulphur, being a part of the coal substance cannot be removed by usual
washing.

Chlorine is frequently blamed for corrosion with English coals in which it occurs upto
1.0%. Less than 0.3% chlorine in coal does not cause problems through corrosion and
deposits.

Phosphorous, which occurs upto 1% as P 205 in coal ash was a frequent source of
deposit when coal was burned on grates. With pulverized coal firing, highly reducing
conditions do not occur as in fuel beds, and thus phosphorous does not cause fouling.

Oil Ash :

The major impurity in oil causing trouble through corrosion and deposits is
vanadium. The other elements in residual fuel oil contributing most to corrosion are sodium
and sulphur.

137
Table-33 gives a typical range of composition of these objectionable constituents.
Although such residual fuels are suited to boiler furnaces, they are much too dirty for gas
turbines where fuel call for a maximum of 1 ppm vanadium, 2 ppm sodium and potassium, 1
ppm calcium and 1 ppm lead with not more than 20 ppm.

Table-33: Major constituents of Residual fuel oil


Constituent Residual fuel oil (ppm) Oil ash %
Vanadium 0-500 as V 0-40 as V2O5
Sodium 2-300 as Na 0.1-30 as Na2O
Sulphur 1000-40000 as S 0.1-40 as SO3

As the oil ash is low melting, it must be adhering to tube walls during the starting
up operation when the residual fuel oil is used. Later, this deposit of oil ash may create
trouble by facilitating ash particles to collect on it when the boiler is on coal.

MELTING CHARACTERISTICS
With roughly 100 times more ash than fuel oil, coal poses much more serious
problems with slagging and interference with heat transfer than does oil ash. On the
other hand, the low melting characteristics of oil ash can lead to special problems with
the formation of liquid films of the vanadates on tube surfaces.

Coal Ash – In slag tap pulverized coal fired boiler furnaces the viscosity of the coal ash must
be low to assure satisfactory removal of the slag, in dry bottom furnaces, wall deposits are
made up largely of sticky particles that cover the tubes in irregular patterns.

The fusion test does not give any exact correlation between softening
temperature and extent of clinkering. It only divides coal ash into broad categories of
fusibility-low fusion, 1000-12000C, moderate fusion, 1200-14000C; and high fusion 1400-
16500C.

Oil Ash : Unlike the silicate glasses characterizing melted coal ash, a series of chemical
compounds usually are formed from the residue left when fuel oil is burned. Generally, these
compounds involve vanadium, sodium and sulphur. The melting points of some of the
compounds are given in Table34.

Table 34 : Melting points of compounds formed when residual fuel oil is burned

0
Melting Point C
Material
Sulphates Na2S 207 399
Na2SO4-K2So4/solid solution 832
Na2SO4 885
K2SO4 1077
Complex alkali metal sulphates K3 Fe(SO4)3 619
Na3 Fe(SO4)3 624
NaFe(SO4)2 690
KFe(SO4)2 694
Vanadium compounds 5Na2O.V 204.11V2O5 578
2Na2O, V 205 619
Na2O, V 205 530
Na2O, V 204.5 V 205 658
V 205 674
V 204 and V 203 1970

138
of the sulphates only Na2S2O7 melts at a temperature low enough to be molten on the wall
tubes of boiler furnaces, and hence corrosive. But it dissociates in air or in flue gas to lose
SO3 at its melting point and thus eliminates it as a causative factor in corrosion at the high
metal temperature of super-heaters. But at the lower temperature of wall tubes particularly
beneath deposits where high SO3 concentrations can exit, the pyrosulphates can contribute
significantly to metal wastage. Both Na2SO4 and K2SO4 melt at temperature high enough to
cause any problems directly in boiler furnaces, but they lead to difficulties in gas turbines.
Enough alkalies and sulphur are present in all residual fuel oil to allow for the formation of
these complexes in objectionable amounts.

Since super-heater metal temperatures can be as high as 650 0C, it is evident why
the vandates are so trouble-some. With the exception of V2O4 and V2O3, all of the
vandates are potentially trouble-some, particularly in gas turbines.

External Corrosion :

Loss of metal occurs throughout boilers on surfaces exposed under the proper
conditions to combustion products. Generally, metal wastage of furnace wall tubes, super-
heaters and re-heaters is termed “high temperature corrosion” because the metal
temperature is greater than 3250C. In air heaters where the metal temperature approaches
the dew point of the flue gas, usually about 1500C, “low temperature corrosion” takes place.

High temperature corrosion :


Coal fired boiler furnaces :
Examination of the corroded tubes showed the presence of a tightly adherent porcelain like
coating on the tube beneath the overlying deposit of slag. This coating with a greenish-blue
to pale-blue colour, was moderately soluble in water, giving a solution with a pH as low as
3.0. The coating material was identified as an alkali-iron-trisulphate, principally K 3 Fe(SO4)3,
with Na3 Fe(SO4)3 also present. This corrosion can occur at moderate wall temperatures
(3700C orso) and also at super heat metal temperatures (650 0C). Super-heater alloys are
selected to be oxidation resistant at this temperature, even in the presence of SO 2 ; but the
presence of alkalies and appreciable amounts of SO3, a liquid films of K3 Fe(SO4)3 and Na3
Fe(SO4)3 can cause catastrophic failure.

Mechanism : A normal oxide (Fe 2O3) forms on the tube metal surface and is covered with
alkali sulphates K2SO4 and Na2SO4) from the furnace atmosphere. Particles of ash adhere to
this alkali layer and accumulate to produce a gradually thickening layer of ash. As the ash
layer becomes thicker, the thermal gradient through it increases and the exposed outer
layer melts. Increased temperature within the deposits leads to dissociation of sulphates to
release SO3, which migrates to the cooler oxide covered metal surface. This SO 3 reacts with
alkali sulphates and iron oxide surface, thereby dissolving the protective film of Fe 2O3 and
occurs normally with load change, the layer spells off and the tube metal again oxidizes to
re establish its normal protective oxide film. This re-oxidation causes irreversible loss of
metal. The reactions are :

K2O + SO2 + O2 K2SO4 (furnace atmosphere)


MSO4 MO + SO3 (Dissociation)
3 K2SO4 + 3 SO3 + Fe2O3 2 K3Fe(SO4)3
4 Fe + 3O2 2 Fe2O3 (on metal surface)

Oil fired systems : Because alkalies and sulphur occur in residual fuel oil as well as in coal,
alkali iron trisulphates also cause special problems. The sodium vandates cause worse
corrosion than V2O5.

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For gas turbines, maximum corrosion can be expected when the V 2O5/ (V2O5 +
Na2SO4) ratio falls between 0.78 and 0.85. For boiler furnaces, which of the sodium
vandates is formed is relatively important, Na2O. V2O5 , being the most corrosive, with
Na2O.6 V2O5 slightly less troublesome. Na2O. V2O5 causes least trouble. It is postulated that
vandates must be distorting the normal crystal lattice of the protective oxide film on the
metal and molten vandates dissolving this protective film.

Low temperature corrosion : Corrosion of air heaters has been responsible mainly for
keeping stack gas temperatures above 1630C. At lower temperatures the dew point of the
flue gas is reached and a liquid film of sulphuric acid forms on the metal surfaces of the air
heater, greatly hastening metal failure. Chlorides in the fuel, converted to hydrochloric acid
during combustion, add to this problem.

Glass coated air pre-heater elements have been used with good success to resist
acid films, but the cost is generally considered excessive and the scheme has not caught on
widely. The most obvious method of preventing low temperature corrosions is to design the
air heater so that the metal temperature never drops below the dew point of the flue gas.

Formation of SO3 : Flame formation is inadequate to yield troublesome amounts of SO 3 as


far as high temperature corrosion is concerned. Depending on oxidation of SO 2 by oxygen
atoms present in a flame the amount of SO 3 so formed is generally only 1 % of the amount
of SO2. Hence, in a combustion system with 2500 ppm SO2 in the flue gas the SO3 level will
be 25 to 35 ppm. This is ample to form sulphates such as K 2SO4 but it does not account for
the higher concentrations of SO3 to form K3 Fe(SO4)3.

Homogeneous catalysis contributes little to SO 3 in flue gas. High concentrations of


SO3 required to form alkali iron trisulphates are the result of heterogeneous catalysis.

It has been demonstrated that beneath the deposit gas velocities are low,
approaching stagnation, SO3 concentration can be 30 times or more greater than in the
bulk, rapidly moving, gas stream. Thus, enough SO3 is available to permit the formation of
the alkali iron trisulphates. Thus it can be concluded that conditions beneath deposit can be
quite different from these in the bulk flue gas and that an environment is provided beneath
deposits in which corrosion can be rapid.

Dew point of SO3 : Condensation of sulphuric acid causes serious low temperature corrosion
problems if the flue gas is coaled below its dew point. The dew point of flue gas depends
upon on the quantity of moisture and SO3 present in it. It is observed in case of flue gas that
the variation in dew point with moisture is insignificant. However, very small amounts of SO 3
elevate the dew point appreciably as is evident from Table-V.

0
SO3 in flue gas Dew point C
ppm
0.1 104
1.0 120
10 135
100 155
1000 190

Actual determination of dew point is carried out by measuring the concentration


of SO3 in flue gas. When a hot flue gas is passed through asprial glass condenser maintained
at 80O C, SO3 is separated from SO2 by condensation. Washing out this condensate and
titrating the washings gives the SO3 content directly. Care must be taken to maintain
sampling lines hotter than 8500C to prevent any possible condensation of SO 3 before
reaching the spiral collector.

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Decrease in heat transfer caused by slag accumulation of Furnace wall tube :
Deposits interfere in heat transfer. Within 24 hrs. the layer of slag accumulating on the tube
may decrease heat transfer to one-fourth of its initial value.

Fouling is considered to be any form of ash deposit that retards heat transfer or obstructs
the flow of gases through the unit. Grossley has classified the forms of fouling as :

1. Fused slag deposits occurring principally on surfaces exposed to radiant heat


transfer, such on the furnace walls and the first few rows of boiler or super-heater
tubes.
2. High temperature bonded deposits occurring on convection heating surfaces in
regions of moderately high gas temperature, principally in the super-heater.
3. Low temperature deposits occurring on convection heating surface of economizer and
air heater.

Fused Slag Deposits : The formation of a slag deposit is caused mainly by physical transport
of fused or partially fused particles entrained by the gas stream. When particles strike the
wall or tube surface, they are chilled and solidified. Strength of attachment is influenced by
the temperature and physical characteristics of the slag. As the slag continues to
accumulate, the spaces fill and stranger anchorage develops against the corrugated contour
of the wall. Coverage of this type may shed from large areas if cooled abruptly by change of
load or separated by other causes. Beyond the slagging zone, the tendency to form fused
deposits is diminished by progressive cooling of the ash. These deposits are found mostly in
slag tap furnaces.

As distinguished from slag deposits, a related type known as “birnest” or “re-


fused” deposit has been described, which may develop at the tube bank entrance where
temperatures are in the transition range between liquid and solid condition of the ash. The
mechanism of formation is attributed to a surface stickiness of particles that causes them to
adhere to one another without complete fusion. The formation increases in strength by
sintering processes.
Accumulation of wall deposits delays cooling with a resultant increase in the temperature of
the gases delivered to the super-heater. This tends to raise final steam temperature and
also causes deposits to advance into cooler portions of the furnace.

Because of the necessity of maintaining superheat within a close range, it is


important to limit the extent of ash coverage and to provide separate means of steam
temperature control to compensate for variations. Difficulties from fouling, by fused slag
deposits although inherent with many coals, can usually be avoided by use of “on-line”
cleaning equipment.

High temperature Bonded Deposits :


This type of deposits occur under some conditions in the super-heater or re-heater at a
critical range of temperature appreciably below the fusion temperature of the ash. Such
deposits are particularly troublesome because they obstruct gas flow and are difficult to
remove from the closely spaced tubes. They may also cause corrosion of tubes operating at
metals temperatures above 6000C.

Characteristic formations comprise a relatively thin inner layer of distinctive


composition and appearance and an outer layer having the composition of the normal fly
ash. The inner layer, which is tightly attached to the tube surface, frequently shows
evidence that a liquid phase existed at operating temperatures. The outer layer of semi-
used or sintered fly ash forms the main bulk of deposit and may become quite massive.

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Several types of bonded deposit have been identified and are refereed to as the
alkali, calcium, phosphate cr. Silica types according to the principal bounding agent,
although they may exist in combination. All appear to involve volatilization of elements from
the ash and selective deposition upon or in the vicinity of tube surface, thereby producing
local concentrations several times greater than their normal proportion in the ash.

Alkali-bonded Deposits : Alkali bonded deposits are probably the most prevalent and widely
recognized type--the nominally white inner layer, which is largely water soluble, is found to
be rich in sodium and potassium and usually contains sulphates in excess of the alkali
normal equivalent- a factor attributed to pyrosulphate or a complex sulphate forms involving
iron and aluminium.

Sintered Deposits : Accumulation of ash to form massive deposits depends largely upon
adherence of particle to particle. When this adherence is weak, only thin layers of ash
accumulates before fracture occurs. When particle to particle adherence is strong, ash
continues to buildup into thick layers. Furthermore, such deposits may be so resistant to
fracture that normal blowing operations may not remove the accumulated ash from tube
surface.

The sintering characteristics depend upon chemical composition of ash, the time-
temperature history during combustion the temperature and the time during which the ash
particles are in contact with each other on a heat receiving surface. Many of the initial
chemical reactions between solids occur in the flame where high turbulence ensures
frequent collisions between particles while they are at a temperature where reaction is
capture of other particles by the liquid droplet, and the eventual formation of a particle large
enough to be caught by a surface through inertial impaction. Furthermore, a liquid phase is
more likely to ensure adherence to a solid phase.
Some particles such as SiO 2 although not molten, may have a highly viscous
surface even at a temperature as low as 1100 0C. Many refractory particles sinter well below
their melting point for instance, Al 2O3 can be sintered at 1800 0C even though its melting
point in 20150C. Even at temperatures down to about 640 0C, sintering can occur to bind
loose ash particles into a moderately strong mass. This sintering leads to many of the
deposits found when the gas temperature is below 11000C.

Table 35CHARACTERISTICS OF DEPOSITS

Alkali
Slag Matrix

Type
Outer Inner Outer
Inner
SiO2 33.2 44.5 15.8 41.4
Al2O3 16.5 17.3 9.0 16.8
CaO 23.7 22.7 11.8 24.3
MgO 5.6 6.8 3.9 7.4
(Na, K)O2 0.7 1.0 0.8 0.5
SO3 8.5 3.4 5.9 3.4
Al2O3 5.6 0.2 9.0 2.6
Form Furnace
Tube wall PH 3.3 2.8
Solubility mg 3.0 5.0
100 ml

Remedial Measures :

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Additives : Additives are useful in cil-fired boilers where the ash loading of the file gas is
low. Generally based on magnesia, corrosion controlling additives function in two ways :

1. By neutralizing SO3 through forming MgSO4 and


2. by covering super-heater surfaces with a layer of MgO to prevent the catalysis
formation of large amounts of SO3.

When burning coal, the dust loading in the flue gas is so high that such additives
are impractical. However, air pollution control systems where pulverized lime-stone or
dolomite is added to the boiler furnace to capture SO 2 are expected to prevent external
corrosion. In such systems, the quantity of stone added is based on the sulphur content of
the fuel-because SO3 is more reactive towards CaO and MgO compared with SO 2, it is likely
that no SO3 will exist and corrosion will cease. There is some indication that the
accumulation of massive deposits of CaSO4 on super-heater surfaces may pose new
problems.

Low excess air :

A revolutionary approach has been taken toward eliminating the formation of SO 3 in


boiler furnaces fired with oil by limiting the excess air to an absolute minimum. By carefully
metering fuel oil to each burner and properly adjusting air shutters, excess oxygen could be
lowered to as little as 0.1% before incomplete combustion become troublesome. By
operating at these low levels of excess air, the boilers could be operated with residual fuel
oil for more than 3 years (30,000 hr.) without any corrosion and with no manual cleaning
being required even in large boiler plants. Precise metering of fuel and air to each burner
has proven to be less troublesome than had been expected earlier, and in some instances,
with high furnace turbulence, ordinary controls have been observed that SO 3 largely is
eliminated, irrespective of the amount of sulphur in the fuel, when the products of
combustion contain no more than 0.2% oxygen. At this level the dew point of the flue has
can be as low as 540C when the dew point for the moisture in the flue gas is 410C.

The benefits resulting from the use of low excess air include, in addition to a decrease
in SO3, a limitation on the oxidation of vanadium. Low excess air leads to the formation of
V2O5 and V2O4, with melting points much higher than that of V 2O5. These reduced forms of
vanadium are less objectionable from the stand point of corrosion. Opinion at present is that
corrosion and deposits when burning residual fuel oil can be essentially eliminated by
operating with low excess air.

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CHAPTER-13

CHEMICALS & SAFETY

INTRODUCTION

Many chemical substances are used in the electricity supply industry, few are
inherently safe but many can be used with safety providing that simple precautions are
taken. Contact with some chemical substances may have an immediate effect with others it
may take long time.

The precautions that should be taken in the use and handling of many of the
chemicals in common use in the Generating Stations are discussed here. The relative
infrequency of ill effects from the use of chemical substance makes it all the more necessary
that users or those in direct controls of employee handling chemicals, are aware of the
hazards associated with the substances being used and of the precautions that should be
taken to prevent injury. No chemical substance should ever be used unless careful
consideration has been given to the possibility of injury to the user and until detailed
instructions have been issued on storages, handling, use and disposal and on any
precautions that should be taken. The instructions should be reviewed from time to time to
see that they are up to date and that they are being carefully carried out.

Particular care is necessary where substances have a threshold limit value (T.L.V)
below 200 parts per million. T.L.V. s are to be updated annually.

GENERAL PRINCIPLES- STORAGE, HANDLING, DISPOSAL

i) A knowledgeable and responsible person should provide written instructions on the


storage, issue and methods of handling of all chemicals including chemicals such as solvent,
degreasing agents etc that are not normally the responsibility of the chemical department.
This means that no chemical substance should be taken on to station premises without the
knowledge and approval of the chemist.

ii) The storage facilities should be defined, bearing in mind the need for heating, lighting,
ventilation, the possibility of fire risk and of chemical reactions between substances.
Adequate storage or spillage facilities should be provided. Care must be taken to avoid
wherever possible the storage of similar containers with different contents in the
same room or area of stores.

iii) Identification: Before any chemical is accepted for storage or use it must be identified.
Containers should always be checked to ensure they are adequately labeled and that all
necessary labels- including safety instruction – are legible and securely attached.

iv) All persons to handle chemicals must be informed of any hazards and be instructed
correct methods including methods of withdrawal from bulk supply containers, method of
transport from one location to another, on personal protection if necessary. All subsidiary
containers should be carefully labeled. Basic remedial first aid measures should be given to
handlers in case accidental spillage occurs.

v) The detail of any chemical reaction that is expected or may take place should be
known, as should the nature of the products of reaction.

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vi) Information should be obtained on the toxic effects, if any, of the chemical substance
or of any products or residues that may occur. In assessing the likelihood of toxic effects
particular attention should be paid to the circumstances under which the material is to be
used.

All personal working with a chemical substance should be aware of the precautions
that should be taken and the necessary handling and personal protection equipment should
be readily available. If any serious hazards are associated with the use of a particular
chemical substance, adequate supervision is necessary to ensure all essential precautions
are taken.

The method of disposal of used chemical, waste products; residues and empty
containers should be clearly defined and made known to those concerned. Used containers
should be checked to ensure they are completely empty, returnable containers should be
stored separately until collected, non returnable containers should be decontaminated if
necessary and disposed of in accordance with the instructions.

Spillage of many chemicals may create a potential hazard eg hydrazine, nitric acid,
concentrated sulphuric acid etc. Detailed instructions should be drawn up on how spillages
should be dealt with.

CATAGORIES OF CHEMICAL HAZZARD

Chemical hazards can be broadly classified into three categories:-


i) Corrosive – acids, alkalis and many of the chemicals used in water treatment,
boiler and condenser cleaning are corrosive.The main hazard is often from
splashing but fumes may arise causing irritation or toxic affects.

ii) Flammable – petrol, some solvents and degreasing agents, fuels, oils, paints,
etc.. Flammable materials should be kept in a separate bricks store labeled
“Highly Inflammable store –No smoking –No naked lights”. Many Flammable
materials give rise to toxic fumes at room temperature or if heated, and the
possibility of the accumulation of flammable, explosive, or toxic fumes should not
be overlooked. Many dusts are flammable and can form explosive mixtures with
air. A coal dusts –air mixture in the correct proportion is highly explosive.

iii) Poisonous –most chemicals are poisonous (toxic) to a greater or lesser extent.

EFECTS OF CHEMICAL SUBSTANCE ON THE BODY

Broadly speaking chemical substances can affect the body in two ways, either
externally when the effect will be on the skin or eyes or internally when internal organs will
be affected.

(i) EXTERNAL EFFECTS:

SKIN - Contact between a chemical substance and the skin may result in immediate
damage and –for example mineral acids and caustic alkalis always cause severs damage if
not removed at once. On the other hand many chemicals only cause injury after longer or
repeated contact, e.g. solvent, mild alkaline cleansing agent, mineral oil and paraffin. Here
the skin gradually becomes irritated by the chemical or less commonly becomes sensitized
to it.

145
The susceptibility of the skin varies considerably from person to person. It is
impossible to say which skin will breakdown readily or which will withstand and precautions
must be taken on the assumption that anybody may be susceptible.
Dust, mist, fumes and vapours are just as likely to cause trouble as liquid contact and it
may be necessary to protect exposed skin elsewhere as well as hands and forearms.

Solvent and other cleansing agents for the removal of grease are equally effective in
removing the natural protective fat from the skin and exposure may be followed by signs of
skin irritation and damage such as excessive dryness, redness, cracking, itching or the
development of rash. In many cases this can be prevented by care full attention to normal
skin hygiene and by keeping contact to a minimum. Frequent or prolonged contact should
be avoided by the use of suitable protective clothing.

If signs of skin irritation occur, the person should be removed from contact and referred for
medical opinion.

EYES- Damage to the eyes as a result of chemical contamination is a frequent industrial


accident. The damaging effect of acids and alkalis is well known, but many other
substances may cause injury and whenever there is a risk of a splash entering the
eyes, goggles should be worn. Dusts, mists, fumes, and vapours also may cause injury
and if such exposure is likely the appropriate eye protective should be worn.

It is possible to transfer contamination from the hands to the eyes. If a chemical


contaminates the hands, they should be thoroughly washed before touching the face.

If any chemical enters the eyes, the affected eye should be immediately and
thoroughly irrigated in accordance with the instructions. After through irrigation the victim
should be referred to a hospital /general practitioner, if occupational First Aide is not
available.

ii) INTERNAL EFFECTS

Chemicals gain access to the body in three ways –


-By inhalation as gas, vapour, fume mist or dust,
-By ingestion through the mouth as a liquid or solid
-By absorption through the skin .
In industry inhalation is the most common cause of poisoning. Cases due to skin absorption
are less common and ingestion is relatively rare as an accidental cause of poisoning.

If chemical substance is present in the air that is being breathed it will gain access to
the body. Whether or not this causes any ill effect depends on the nature of the chemical,
the amount absorbed and to some extent on the physical characteristics. For example
carbon monoxide is present in very small quantities in the air at all times and cause no ill
effect, larger concentrations however, rapidly cause serious and often fatal illness. Some
chemicals are irritating to the lungs and upper respiratory tract and to the internal surfaces
of the lungs (examples chlorine),others do not cause local irritation but pass through the
lungs into the blood stream causing an effect to internal organs –this may comes on quickly
or may develop slowly ,only becoming obvious after serious and sometimes permanent
damage has occurred (examples: lead, mercury, carbon-tetrachloride ,benzene). Some
dusts are deposited locally in the lungs causing irritation of the lung tissue and here again
damage only becomes obvious after many years exposure (examples: asbestos, silica –
containing dust).

146
It is obvious that chemicals may effect the body in a variety of ways and to ensure
safety, each must be considered individually, from the point of view of its toxicology, the the
circumstances in which it is going to be used and the precautions that ,should be taken to
avoid ill effects. For example, many organic solvents can be used with safety in relatively
small quantities in the open shop, but become dangerous if used under badly ventilated
conditions.

Personal handling chemicals should not be allowed to smoke or partake of food or drink, in
the working area.

SOME PROCESS PRODUCING TOXIC MATERIALS

WELDING
When welding toxic fumes may be produced either from the material being heated or from
the flux. Good ventilation is necessary.
COAL
Finely divided coal particles moving on one another can produce carbon monoxide.
ELECTRIC ARCING
Electric arcs may produce ozone and oxide of nitrogen from air which can be hazardous in
confined spaces or may break down into more toxic material e.g. SF6 switchgear.

GENERAL PRINCIPALES OF PROTECTION OF PERSONNEL

INFORMATION
Detailed knowledge of the hazards associated with the use of a chemical must be given
to all persons handling it.

ENCLOSURE
Whenever possible the use of an enclosed process should be considered. Where total
enclosure is not possible using closed methods of handling especially where small
quantities of material have to be taken from a bulk supply may reduce hazards.

LOCAL EXHAUST VENTILATION

Many dusts, fumes etc can be adequately controlled by local exhaust ventilation.
Design of an effective system requires expert knowledge to ensure adequate control of
the hazards.

It is not wise to rely on general ventilation for the control of potentially toxic
materials.

SUBSTITUTION

Wherever possible a dangerous chemical should be replaced by one of lower


toxicity. In many instances it is possible to find an equally effective agent, which has little
or no toxic effect.

REMOTE HANDLING

Personal contamination should be avoided as far as possible. In some cases this


may be by the use of protective clothing but in many instances a system of work can be
devised which is equally effective in preventing contact with the chemical.

147
PROTECTIVE CLOTHING

The unnecessary use of protective clothing should be avoided as far as possible, but
it may be the only way of avoiding contact. Personnel should be trained in the care
and use of protective clothing and supervision is usually necessary to see that it
is kept in good order and used properly.

RESPIRATORY PROTECTION

The correct type of respiratory protection should be used. This varies from simple
approved dust masks to self-contained breathing apparatus. Training in the correct use
of respiratory protection is absolutely essential.

ENVIRONMENTAL HYGENE

Contamination of the working environment should be avoided as far as possible.


Spillages should be cleaned up promptly taking of whatever precautions may be necessary.
In some instances protection of the environment by the use of trays, plastic sheeting or
impervious paper may be helpful.

PERSONAL HYGIENE

Personnel hygiene is particularly useful in preventing skin trouble. A clean method of


working associated with the proper care of the skin will often reduce skin trouble. Care of
the skin implies, through washing, the use of appropriate barrier creams, skin cleansers,
with minimal contact during work.

Environmental legislation on Hazardous Chemicals

Under the Environmental Protection Act’ 1986 Manufacture, storage and Import of
Hazardous Chemical Rules (amendment) 2000 have been made.

 The rules specify certain quantities of certain hazardous chemicals, which need to be
handled, stored in appropriate manner. List of such chemicals raised to 684 now.

 A person to be identified who will be responsible for the safety on site.

 Safe guard such as offsite as well as onsite emergency plans are to be made. Clear
labeling of hazardous chemical container with Name, address, physical chemical and tox
logical data.
 Material safety data sheet (MSDS) are to be prepared and maintained in prescribed format
MSDS should be appropriate for the chemicals and based on technical information, like
physical-chemical properties and details of the chemical storage, compatibility with other
chemicals, environmental impact and hazard of disposal, etc.
 Company is obliged to inform all likely affected persons of hazard and Safety.
 For manufacture, storage and import of hazardous chemicals Company has to get
authorization.

Hazardous Waste (Management and Handling) Rules, 1989 as amended is 2000.


Under EPA this rules have been made.

148
 Any industry generating hazardous waste and having facility for collection,
reception, transport, storage and disposal will have to get authorization
from SPCB. Which shall be renewed for 5 years on the basis of steps taken
to reduce (wherever possible) waste generation, recycle or reuse.

 Any operator for collection, treatment, storage, transport and disposal of hazardous
waste will have to get authorization from State Pollution Control Board.

 The waste should be properly labeled and packaged prior to transport.

 Transportation as per color Manifest system along with Form-10 regarding measures
to be taken in emergency situation.

 Occupier, transporter and operator shall be responsible to reinstate or restore the


damages caused to the environment due to improper handling, storage & disposal of
hazardous waste.

 Disposal site to be identified by the occupier after preliminary assessment and inform
SPCB.

 Disposal facility design and layout to be approved by SPCB.

 SPCB should allocate dumping site. The site should be monitored for ground and
water pollution .A complete inventory is to be maintained by SPCB on the location of
sites, types and qualities of waste-stored.

 There is a ban on import of hazardous waste for dumping in the country.

 Hazardous wastes stored by any Company must be declared in the prescribed format
and submitted to SPCB. The ground and ground water condition monitoring
where storage has been done is one a requirement of the format.

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CONTENTS

CHAPTER-1 WATER TREATMENT 01

CHAPTER-2 CORROSION 37

CHAPTER-3 INTERNAL CORROSION 53

CHAPTER-4 CHEMICAL CONTROL OF


WATER AND STEAM 59

CHAPTER- 5 CHEMICAL CLEANING 78

CHAPTER-6 STATOR COOLING WATER 88

CHAPTER-7 COOLING WATER 94

CHAPTER-8 PRESERVATION OF STEAM AND


WATER CIRCUIT DURING IDLE TIME 102

CHAPTER-9 COAL FOR THERMAL POWER STATION 104

CHAPTER-10 COMBUSTION 116

CHAPTER-11 OILS 123

CHAPTER-12 CORROSION AND DEPOSITS FIRE SIDE 144

CHAPTER-13 CHEMICALS AND SAFETY 157

ACKNOWLEDGEMENT

Publication of CEGB, BHEL, ION EXCHANGE, THERMAX, DUEPLAN, IOC,


CFRI & lecture notes of eminent guest faculty were of great help in
preparation of this Manual.
The author extends his sincere thanks to all of them

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