POWER PLANT SIMULATOR TRAINING

INSTITUTE

16
FEED WATER TREATMENT, WATER IMPURITIES AND ITS
EFFECTS, PROBLEMS WITH HIGH PRESSURE BOILERS, And
METHODS OF FEED WATER TREATMENT.

Water, Coal and Oil are the three main raw materials, which are used in any Thermal Power Station for steam
generation. Coal and Oil are used as fuel for generation of steam from water. The purity of this steam should
be of high degree. High purity steam can only be produced from pure water.
Water is usually tasteless, colourless, and odourless in its pure state. It has a property of dissolving many
substances; so many impurities (gases, solids and colour) are found in the usual sources of water. As such the
treatment of water is the primary need for any Industries.

SOURCE OF WATER
Surface water e.g. Rivers, Lakes, and Reservoirs etc.
Dissolve solids in surface water are generally low. Surface water comes from streams, ponds, lakes and
reservoirs. Surface water contains some organic matter and is more readily exposed by Biological
contamination. The composition of surface water undergoes rapid change due to rainfall, domestic &
industrial pollution. The most troublesome impurities in surface water are colloidal matter and insoluble
substances.
Ground Water:- e.g. Tube Wells.
Ground water usually contains large amount of dissolved substances because such water percolates through
rock and soil .Due to this percolating action ground water contain small quantities of suspended matter and
little colour.
The basic objective of water treatment is to treat the available source of water and make it suitable for the
particular end use.
Impurities Present in Water
The impurities present in water may be classified into four categories.
Undissolved or non-ionic.
Dissolved or ionic.
Dissolved gasses.
Micro-organism.
Undissolved or non-ionic impurities cause turbidity and colour. Suspended particles are either floating or
suspended or easily settle-able impurities and vary in particle size. Finely suspended particles are due to
colloidal particles and cause turbidity. Coagulation, sedimentation and filtration are the unit processes for the
removal of suspended solids and turbidity. Colour is due to the decayed vegetables and other matters.
Chlorination, coagulation and filtration through activated carbon remove the colour.
Dissolved or ionic impurities: Dissolved salts are of two kinds, neutral and alkaline. Examples of neutral
salts are NaCl, CaCl2, MgCl2, CaSO4, and MgSO4 etc. Examples of alkaline salts are the bicarbonates of Ca,
Mg, and Na. These salts are dissociated into positively charged cation and negatively charged anion and are
removed in the Demineralised Plant.

Dissolved gasses: Generally CO2, O2, NH3 and H2S are present in water. These gasses are removed by
mechanical and /or chemicals means.
Micro Organism may range from Bacteria to Algae growth, which affects deposits, growth or corrosion in
water supply and cooling water system and are controlled by Biocides.
Raw water available from surface source is treated in a pre-treatment Plant. Firstly, water enters into stilling
chamber where Chlorination is done to remove the organic matter then enter into Parshall flumes
where alum dosing is done. Raw water with alum solution is mixed in flux mixture and enters into
the flocculating zone of the Clariflocculator where coagulation and flocculation occur. The feed
stream comes in intimate contact with chemicals mixture and suspended sludge particles from

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previously treated water. This contact promotes floc growth as smaller particles agglomerates into
larger heavier particles and settles down. Settled sludge is removed continuously along the floor
towards the centre of the unit by means of a slowly rotating scraper which covers the entire floor
area. The accumulated sludge is transferred to the sludge pit at the centre of the unit and is removed
by blow down.
Part of the water enters the clarified water zone and rises towards the effluent collector called launder
through series of orifices. Clarified water so produced is then allowed to pass through gravity sand filter
where residual suspended particles are arrested, then collected in filtered water reservoir.
What is meant by Coagulation?
Coagulation is simply the aggregation of the smaller particles into larger ones, which are big enough to settle
down.The colloidal particles, which are responsible for turbidity in raw water, are electrically charged. The
presence of electrical double layers of the same sign surrounding all the particles results in their mutual
repulsion, so they do not approach sufficiently closely to coalesce. If a small quantity of an electrolyte is
associated with colloidal system, the particles grow in size and are precipitated. The coagulating power of
different electrolytes is not the same. It is almost solely determined by the valency i.e. electric charge of the
ion having a charge opposite to that of the colloids. Al 2 (SO4) 3 of alum has a property due to higher valent
Al+3 ions to neutralise the negative charge of the colloid particles in raw water, which causes the
aglomerisation of the smaller particles of raw water into bigger particles and finally settled down.
The filtered water is almost turbidity free, but having dissolved salts which are removed in
Demineralised Plant. Now the question arises, what is meant by Demineralisation?

Demineralisation is a process in which mineral salts dissolved in water are completely removed. Correctly
says the Cations and Anions of the salts present in minerals are arrested by the Cation & Anion resins by
exchanging H+ and OH- ions
Now, why Demineralisation of water is needed?
If water is a not demineralised then total dissolved solid in water enters into the boiler. The scale forming
elements such as Calcium, Magnesium is very harmful to any boiler, producing hard scale and deposit on the
surface of boiler and tubes. This scale resists the flow path of fluid in the tube and also affects the heat
transfer. As the scale is not uniform in nature, over heating will be occurred in some part of the tube and
finally tube failure will be occurred. Chloride ions also create acid chloride corrosion. High alkalinity will
create caustic embrittlement. To avoid scaling and corrosion, water should be demineralised and deionised.
How water is demineralised?
The filtered water from filter water reservoir first enters through Activated Carbon filter, where residual
chlorine, colour and some organic material are removed. After exhaustion of this Activated Carbon filter,
simple backwashing reactivates them. Activated Carbon filter are nothing but finely powdered peat, wood,
lignite or coal, which have pores for adsorbing the molecules of Gases and Liquid. The carbon atoms at the
internal surface of the activated carbon exert an attraction of the molecules of surrounding gases and liquids,
the so-called Vander walls forces. The strength of these forces is related to the molecular strength of the
surrounding medium.
The schematic diagram of a typical D.M. plant is as follows :

If underground water is the source of water, then one Pressure Sand Filter is necessary before ACF and one
WAC is necessary before SAC to minimise bicarbonate loads on SAC.
Ion-exchange resins are synthetic polymers, insoluble in all solvents, which are capable of, reacting like
acids, bases or salts. The resins however differ from acids, bases or salts.
Only the cations (in cation exchange resins) or anions (in anion exchange resins) are free to take part in
Chemical reactions. Those exchanges in which the anionic parts are able to react are called anion exchanger,
whereas the ones in which cations portions are able to react are called cation exchanger.
The basic polymeric structure or solid support for ion exchange resins is called the matrix. The matrix is a
three dimensional co-polymer on which acidic or basic sites is situated. Those acidic or basic sites are called
functional group or functionality of the ion exchange resins.

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The mechanism of ion exchange is reversible and ion exchange resin can be converted from one ionic form
to another and reused. The process of converting the ion exchange resin to the desired ionic form at the end
of cycle of its use is known as Regeneration.
Ion exchange resins are broadly classified into four categories.
o Strong acid cation exchange resin
o Weak acid cation exchange resin
o Strong base anion exchange resin
o Weak base anion exchange resin
STRONG ACID CATION EXCHANGE RESIN: These types of resins are the co-polymerised product of
Styrene & Divenyl benzene. The functional groups present in SAC are sulphonic acid group, which have
replaceable H+ ions. The cations of any water exchange their cations with these replaceable H+, producing
acids.
WEAK ACID CATION EXCHANGE RESIN: Weakly acid cation exchange resins consist of Poly-acrylic
acid Divenyl benzene matrix with carboxylic acid functional group. This resin commonly exchanges the
cation part of the bicarbonate salts produces only carbonic acid.
STRONG BASE ANION EXCHANGE RESIN: These types of resin consist of OH - as functional group.
They can replace all the anions present in water with the OH ions.
WEAK BASE ANION EXCHANGE RESIN: These types of resin consist of primary, secondary and
tertiary amino group as functional group. They can only remove the strong acids such as HCl, H 2SO4, HNO3,
but they have no action with carbonic acid and silica. Actually addition reaction of the strong acid with the
primary, secondary and tertiary amino group takes place.
Now let us discuss the reactions takes place in different exchangers.

In STRONG CATION EXCHANGER RESIN if R be denoted resin matrix then

2RH + CaCl2 = R2Ca + 2 HCl

2RH + MgSO4 = R2Mg + H2SO4

For WEAK ACID CATION EXCHANGER, if R1 is the matrix then

R1COOH + Ca (HCO3) = (R1COO)2Ca + H2CO3

For WEAK BASE ANION EXCHANGER :

RNH2 + HCl = RNH2HCl

For STRONG BASE ANION EXCHANGE RESIN :

2R-OH + H2SO4 = R2SO4 + 2 H2O

H2SiO3 +2RN(CH3)3OH = [RN(CH3)3 ]2SiO3 + H2O
R-OH + HCl = RCl + H2O
Mixed beds are nothing but mixed resin. Cations and anions are kept in mixed condition. Slippage from
cation (mainly sodium) and anion (mainly silica) are exchanged with in Mixed Bed resins.

The function of degassifier is to remove the carbonic acid present after cation exchanger. Here water is
allowed to fall on an extended surface and air is blown from the bottom. Carbonic acid breaks into CO 2 and
H2O. This CO2 removes with the air.

After exhaustion of cation resins they are regenerated with acid mainly HCl where both weak cation &
strong cation are present, the effluent acid after strong cation bed is allowed to pass through weak cation bed
for regeneration as only 1% acid is sufficient for regeneration of weak cation.

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After exhaustion of anion resin they are regenerated with caustic soda solution. Where both weak and strong
anion is presents, effluent from strong anion is sufficient for the regeneration of weak anion resins.
Regeneration of Mixed bed is done after separating both the resin by back washing. Then individual cations
and anions are regenerated by acid and caustic soda solution respectively.

Quality of D.M. water is as follows

PH : 6.8 to 7.2
Conductivity : <1.0 s/cm
SiO2 : <0.02 ppm
Boiler Water Treatment
The overall objective in any Power Plant is to maintain operation at the best possible levels of availability,
economy and efficiency.
To attain this objective chemical control of the water and steam is classified into three parts.
Prevention of corrosion in the boiler, steam and feed system.
Prevention of scale and deposit formation on heating surface.
Maintenance of a high level of steam purity.
Scaling impedes heat transfer rate, obstructs the flow of fluid, results in overheating of metal and finally to
its failure. By using demineralised make up water scaling has been eliminated.
Steam of high purity is essential for turbine efficiency and for prevention of its corrosion and erosion with
the modern improved design of the steam separating system of high-pressure boiler proper control of water
treatment, high purity of steam can be ensured.
Corrosion results in decay of metals and is caused by the effect of oxygen and carbon dioxide on ferrous &
nonferrous. Metals of various components of the total steam / water system. Iron and copper oxide, which
emerge from corrosion, get deposited in the boiler causing scale leading to boiler tube failure and reduction
in efficiency of the turbine, condensers, heater and valves. Circulated of pure condensate and D.M. water
make up and by proper conditioning, corrosion of boiler and its auxiliaries may be avoided.
Corrosion:
Corrosion of a metal is an electrochemical phenomenon. When a metal is in contact with water, it has a
tendency to give up positively charged metal ions leaving free electron on the metal. As a result of
accumulation of free electron on the metal atom and the positively charged metal ions on the solution side, an
electric double layer is established arresting the passage of further metal ions in the solution. The equation of
a bivalent metal ion can be expressed as follows.
M = M +2 + 2e
The potential across the double layer is called electrode potential. If the electrons are withdrawn further
dissolution of metal takes place. If the withdrawn of electron are continuous, the dissolution of metal is also
continuous.
Withdrawal of electrons may take place in either of the following :
Electron can interact with H + of the solution, forming initially hydrogen atom and finally hydrogen gas.
H++ e = H
H + H = H2
This type of corrosion is known as Hydrogen evolution type of corrosion.
(b) Electron may interact with dissolved oxygen to form OH
O2 + 2H2O + 4e = 4OH
Fe presents in the system reacts with OH- forming Fe (OH) 2. If additional oxygen is present Fe (OH) 2
+

converted into Fe (OH) 3. This type of corrosion is known as Oxygen absorption type of corrosion.
When CO2 is present in the water carbonic acid will form :
H2O + CO2 = H2CO3
H2CO3 is dissociates as follows :
H2CO3 = H+ + HCO3-
HCO3- = H+ + CO3=
So hydrogen evolution type of corrosion will continue by the H +.

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Again HCO3- reacts with Fe+2 producing Fe (HCO3) 2, which dissociates into FeCO3 again hydrolysed as Fe
(OH) 2 & CO2.
FeCO3 + H2O = Fe (OH) 2 + CO2
So due to the presence of CO2, hydrogen evolution type corrosion and formation of Fe (OH) 2 will continue.
Treatment of boiler water may be classified into four groups.
1). Precision Control.
2). Co-ordinated Phosphate-PH Control.
3). Congruent Control.
4). Zero Solid / Pure water treatment.
Precision Control: - This method consists in the maintenance of a controlled residual orthophosphate of the
order of 2 to 4 ppm and 15 to 50 ppm of NaOH. pH: 10.8 to11.2. Magnesium Silicate sludge can be
maintained in the fluid stage under high alkaline condition and can be removed by blow down.

As boiler pressure increased with corresponding increase of metal temperature and due to Caustic
embrittlement type of Corrosion, this type of treatment has been rejected.
Co-ordinated Phosphate-pH Control:- Here Phosphate in the range of 15-20 ppm, Zero alkalinity and pH
10.0 to 10.6. are maintained in boiler water. Due to absence of free Caustic Soda, Caustic attack will not
occur. Carryover of Phosphate in steam and Phosphate hideout are the main problem due to high Phosphate
in boiler water. So this Co-ordinated Phosphate pH controls system has been modified into Congruent
Controls System.
Congruent Control System: - Here boiler water is maintained at pH 8.5 to 9.5, zero alkalinity and
phosphate 2 to 4 ppm. It is the modern treatment of any high-pressure boiler. Hideout problem eliminates in
this system due to presence of low phosphate.
Zero Solid Treatment: - Boiler water conditioning without Phosphate and Caustic Soda has been called
Zero Solid Treatment. This type of treatment is also called Volatile treatment. Here Volatiles Chemicals such
as Cyclohexylamine, morpholine and ammonia are used to maintain pH 8.5 to 9.5 and hydrazine is used as
Oxygen Scavenger.
Controls of Dissolved Gasses: - CO2 & O2 enter the system through gland leakage in the Vacuum
portion of returned condensate and also with make up water. They are removed by mechanically and
chemically.

Mechanically they are removed partly by air ejector and partly by deaerator. Due to high vacuum
maintained in the condenser, most of the dissolved gasses remain in the vapour state and are
removed in the air removal section of the air ejector. The rest of gases still remaining, are removed
in the Deaerator. Extracted steam contacts the spray of in coming water, raising its temperature to
boiling point. The partial pressure of the gases in the Vapour phase is decreased than that in the
liquid phase. Venting out of the gases results in further lowering of the partial pressure of the gases.
CO2 reacts with water producing H2CO3, which dissociates in two stages
H2CO3= H + + HCO3-
HCO3- = H+ + CO3-2
At higher pH value 8.8 to 9.1 the dissociation of H 2CO3 increases. The neutralised amine such as Cyclohexyl
amine, Morpholine, Ammonia is used to neutralise the residual H2CO3.
Chemically Oxygen is removed by Hydrazine. The reaction is as follows:
N2H4 + O2 = N2 +2H2O
N2H4 also breaks into Ammonia at high temperature ( 2030C)
3N2H4= 4NH3+ N2.
Trisodium Phosphate hydrolyses as follows:
Na3PO4 +H2O = Na2HPO4 + NaOH
Na2HPO4 + H2O =NaH2PO4 +NaOH

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pH of boiler water is maintained by this liberated NaOH and scale forming elements if ingresses will react
with di-sodium hydrogen Phosphate and sodium di-hydrogen Phosphate producing sludges which are
removed by blow down.
Close monitoring of the boiler water and feed water regarding the concentration of Phosphate, Silica,
Ammonia, Hydrazine, dissolve Oxygen and alkalinity helps any boiler to run smoothly and efficiently.
Turbine may run efficiently with minimum deposition of Silica on Turbine Blade by proper control of steam
purity. Corrosion of condenser tube will be minimum by maintaining Ammonia concentration within limit,
specially for the condenser of Cupro Nickel alloy.
If water treatment of any boiler can be maintained properly outage of the unit will be minimum,
attaining steady generation which is the ultimate objective of any power station

17
TESTING and ANALYSIS OF COAL, OIL & FLUE GASES, HP / LP
DOSING SYSTEM
OIL :

SPECIFICATION :

1. Turbine Oil : Used as lubricating as well as 2. Lubricating Oil -

cooling.
Kinematic Viscosity at 40C 47 to 49.5 CS. Sp. Gr. - 0.88
50C 28 CS
Total acidity 0.2 mg of KOH/gm of oil Flash Point - 201.7C
Sp. Gr - 0.852 Viscosity : 49 at 37.8C
6.8 at 98.9C
Flash point - 200C Acidity - 0.14 mg of KOH/gm of oil
Pour point - 6C Max. Pour Point = - 6.7C
Rust preventive character Negative Moisture - Nil (< 50 ppm)
Foaming character - Nil
Moist - < 50ppm

3. Transformer Oil : 4. LDO :

Sp.Gr. - 0.87
Density at 29.5C 0.89 gm/cm Flash Point 105 C
K. Viscosity - 27 CS at 27C Pour Point = - 11.7C
Flash Point - 140C Acidity - Nil
Pour Point = - 6C K. Viscosity - 10.1 CS at room temp.

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Acid value - 0.03 mg of KOH/ gm of oil Water Content - <50 ppm

Water content - < 50 ppm Sulpher - 1.56 %
Carbon residue - 1.48%
Gross CV - 10,822 K.Cal/kg/19,481 BTHU /lb
Sediment (Benzene insoluble ) 0.03%

VISCOSITY : Time taken for a specific volume of liquid flowing through a jet of specific dimensions ,
starting with a specified height of the liquid column of the jet. Viscosity decreases with the rise of temp.
Flash point by Pen-sky Martens apparatus Flash point is the minimum temp. at which an oil gives off
sufficient vapour to ignite momentarily on the introduction of a flame of standard dimensions.
Fire Point : It is the temp at which oil vapour starts continuous firing on introduction of flame of std
condition.
Pour Point : It is the temperature at which the oil just fails to flow under specified condition.
Basic requirement of insulating oil in a transformer is to absorb heat from the core and the conductors.
Development of acidity is an indication of insulating oil deterioration by oxidation.
Water content by Dean & Stark Method : 50 CC sample + 50 CC tolune ) Boiled and cooled in a condenser
to find out water content . Water content can also be determined by Karl Fischer Apparatus.
Acid value 10 gm oil +( neutralize 25 CC benzene +25 CC isopropyl alcohol) reflux for 8 to 10 mins and
cooled and titrate against std KOH solution either N/10 or N/50 using para napthol benzoin as indicator
:
56.1 X V X N Mg of KOH /gm of oil
Acidity =
W

Advantage of liquid fuel : (a) High CV (b) Heat value is nearly const. (c) Negligible ash content (d)
Less space required for storage & transit (e) Prompt attainment of desired temperature (f) Simple & quick
extinction of fire when required.
Draw back high cost :
Sulpher and ash of fuel oil : Sulpher is undesirable in FO because its product of combustion are acids which
cause corrosion in ECO, AH & gas ducks. High H 2 in FO and resulting high water vapour content in
product of combustion sulpher in FO does more damage than the same amount of sulpher in coal. Ash is
very low and often not exceeding 0.1% . Oil taken in platinum dish and keep one hr. at 800C.
Oxidation of insulating oil: 100 gm oil at 150C temp is subjected to oxidation under standard condition
and the number of hours required for the sample to absorb 300 mg of oxygen is recorded. Result is T300
absorption time . If the result is below 15 an urgent action is recommended.

Buchholz gas : In under oil arcing and under oil hot metal reaction the main gas evolved is hydrogen
together with acetylene and low boiling point paraffins.

Sl. 5% Amoniacal
5% AgNO3 Solution Inflammability Remarks
No. AgNO3 Solution
1 No reaction No reaction Non-inflammable Air
2 Heavy white curdy ppt. Yellow ppt Inflammable Hydro
carbons
3 Black hot Black ppt -do- Cellulose
solution opaque degradation
Determination of CV of fuel oil (LDO) :

CV of Benzoic Acid - 6319 K. cal/kg

CV of Nicrome wire - 335 K. cal/kg
CV of Thread - 4120 K. cal/kg
CV of H2SO4 - 11 K. cal/kg
CV of HNO3 - 1.43 per 1 ml HNO3

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CV of sulpher of coal = 22 cal/gm

Regnault Pflaundler correction for cooling = nv +KT

(n-1) 1
T= + ( to + tn) - nt
1(t) 2
VII-VI
K=
TII- TI
Net CV = Gross CV (Heat of condensation of any steam resulting from the combustion of H2 of the fuel to
water at room temp).
Some calculations for analysis of coal:
U.H.V= 8900-138 (A+M)
A
Ash (Dry basis ) = X 100
100-M
VM
3) VM(Dry Ash free basis) = X 100
100-A-M
4) FC ( do ) F.C 100
= X
100 A-M
VM-0.1A
5) V.M. (Dry Mineral Matter Free Basis ) = X 100
100-M-1.1A
6) F.C
F.C. ( do ) = X 100
100-M-1.1A
7) V.M. (Dmmf) = 100 FC(Dmmf)
3
8) HGI =105-R(1.16+0.002)-0.4A where A-Ash % ; R=(VM+M) at 60% RH at 40C
M-7.2; A-26.2; VM-27.3 (Calculated HGI = 52)
9) C=0.97F + 0.70 (V-0.1A) 0.6M F-FC
V-VM
10) H= 0.036F + 0.091 (V-0.1A -0.05M A-ASH
11) When moist is > 2.0% Gross CV in Bthu /lb = 154 [ 100 (1.1A+M]-108M where A-Ash; M-
moist.
12) When moisture is >2 CV =85.6 [ 100 (1.1A + M)] -60M K Cal/kg.
When moisture is <2 CV =91.7FC + 75.6(VM-0.1A) 60M K Cal/kg.

13) Grade UHV K. cal /kg

A - > 6200
B - 5600 6200
C - 4940 5600
D - 4200 - 4940
E - 3360 - 4200
F - 2400 - 3360
G - 1300 - 2400
COAL FOR T.P.S.

Fuel is the basic source of energy in any industry.

Solid - Coal /Wood coke / Charcoal
Liquid Petroleum - Petroleum distillates e.g. Gasoline, Kerosene , F.O. etc.
FUELS
Gaseous Natural gases Coal gas, Water gas , Producer gas.

Formation of coal (Basic fuel for power station ) : Plants absorbs CO 2 from atmosphere and under the
influence of sunlight, moisture and other factors convert it into compound of C,H and O that go to make up
the plant structure. Under favourable condition , vegetation is converted into coal. Time, pr, temp and
micro-organisms are the agencies that work for coal formation through millions of years.

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Wood & vegetation slowly transformed into peat - Lignite

(carbon pure coal) 51-59 59-75
Sub-bituminous Bituminous -Carbonaceous Anthracite
75-80 80-91 91-93 93-95
Wood to anthracite a reduction in VM & O content but increase in carbon content. The mineral matter which
finally appears as ash remains unaltered. Spontaneous combustion of coal when exposed in atm. coal
(except anthracite) absorb O2 and develop heat which may give rise to spontaneous combustion. The critical
temperature below which spontaneous combustion cannot start is about 60C when coal reaches its ignition
point and burns into flame.
Prevention : Lumps & fines are packed together and well mixed throughout in a manner which will
ensure least ventilation.
COAL SAMPLING :
ROM-Run of Mines No size -23 to O cm
Large Coal -15 to O cm (upper limit 23 cm)
Small Coal 5 to O cm
wt. of gross sample 350 kg (ROM) -175 kg (large )-75 kg (small)
wt of increments (approx.) 5 kg - 5 kg - 5 kg
No. of increments - 70 - 35 - 15
REDUCTION OF GROSS SAMPLES

Size -23.0 cm Size -15 O cm Size -5.0cm

Min.wt -350 kg Min. wt -175 kg Min.wt -75 kg

Original Original Original

>5 cm > 5 cm - 5 cm
- 5 cm - 5 cm
Mechanically Mechanically

- 12.5 mm
1 2 1 2 By Jaw Crusher
4 3 4 3

175 kg 87.5 kg - 3.35 mm

By Palmac type of mill
-12.5mm

1
2 1 2

-3.35mm 4 3
87.5 kg
Jaw Crusher 4 - 12.5mm (1/2) 2 kg
Palmac type - 3.35 mm (1/8) 1 2
3
of mill
4 3
212 Micron IS SIEVE
1 2

4 3
2 kg 2 KG 1.5 KG

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212 Micron IS SIEVE 212 Micron IS SIEVE

1.5 Kg 1.5 kg

Necessity of coal analysis

Boilers are designed on the following characteristic of coal (1) Proximate analysis (2) Ultimate analysis (3)
Gross CV (4) Hardgrove grindability index (5) Fusion behavior of coal ash.

Coal specifications

Desired Boiler Design

M -< 8.0% M - 12 %
A - < 30.0% A - 37%
VM - > 26.0% VM 22%
FC - > 35.0% FC - 35%
CV - > 4445 K. cal /kg CV - 4110 K. cal /kg

ANALYSIS OF COAL

1. Proximate analysis of coal PA of coal means determination of inherent moist, ash, VM and fixed carbon
expressed in % by weight. First coal sample is equilibrated at temp. 40C and 60% relative humidity
keeping in a humidifier chamber for 72 hours. The analysis results is termed as air dried condition at
60% RH and 40C .
(a) I.M. 2 gm powdered coal (75 micron size ) heated at 110 2C for 1 hour
and loss in wt is expressed as %
(b) Ash Non-combustible residue left after complete combustion of coal. It is
mainly composed of oxides of Si,Al,Ca, Mn,Fe, Na & K.

2 gm coal heated at 450C first for an hour to drive out sulpher as SO 2 and finally at 815 10C for
an hour and wt is expressed as % .

Mineral matter - It is classified as inherent and extraneous. Inherent - Inorganic substances of the
original vegetable substances are responsible for inherent mineral matter. Extraneous Either due to
substances which got associated with the decaying veg. materials during conversion into coal OR due to
rocks and dirt getting mixed during mining.

Mineral matter - 1.1A (A - % of ash in coal)

(c) V.M. Hydrocarbons and other gases resulting from distillation and decomposition.
1 gm coal heated at 900C for exactly 7 mins and loss in wt is expressed as % -% of IM of coal .
(d) F.C. 100 (%M + % A + % V.M)
(e) Free Moisture : 1.0 kg coal (1/2 size) dried at room temp for 24 hours and loss in wt expressed as % is
x.
Moisture at 105C : 5 gm coal (1/8 size) dried at 105C for an hour and loss in wt expressed as % is Y.
So, total Moisture : (x+y) xy /100. %
2. Ultimate Analysis : Determination of carbon, Hydrogen, Sulpher Nitrogen and Oxygen in % is known as
ultimate analysis of coal C & H 2 are oxidized to CO2 & H2O which can be measured by absorbing them
in suitable reagent. From wt of CO2 & H2O corresponding quantity of carbon & Hydrogen is
calculated. Sulpher & Nitrogen can be measured by using suitable methods. Oxygen is calculated by
difference. Typical results : M-7.0; Ash -14.7; C-68-0; H2 - 4.1; S-0.3; N2 1.9; O2-4.0.

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3. Gross CV : Gross CV at const. volume is determined in Bomb calorimeter. One gm powdered coal is
taken in Bom cal. with oxygen at pr. 30 Kg/cm. The coal is fired electrically and heat value is
calculated.
4. Hard grove Grindability Index : The average HGI of Indian coal used in TPS is between 50 to 60. High
value of HGI represent soft coal. HGI of coal indicates its easiness towards pulverization . It also related
to power consumption for pulverization. The life and efficiency of mill depends on the HGI of coal .
HGI = 13+6.93 W where W is the wt in gms of coal passing through 200 mesh sieve after 50 gms of coal
size 16-30 mesh are ground in a standard mill for 60 revolutions at a weight of 64 lbs.

4 (A) Fineness of coal : Design -70% Passing through 200 Mesh

Mesh Retained for 25 gms Retained for 100 gms % passing through
50 0.68 2.72 97.3
100 1.20 4.80 92.5
200 6.85 27.40 65.1

4 (B) Combustible of ash : 2 gms heated at 800c for an hour and loss in weight is calculated in % .
5. Fusion behavior of coal ash :
When heated ash did not melt sharply at any temp. but began to soften at lower temp. than that at
which it melts or flow. This fusion behavior is due to mineral matter associated with coal. The
stage wise deformation of ash in a cylindrical shape can be determined by Leith Heating
Microscope generally in a reducing atmosphere and the change of shape was noted. Tmp. can be
identified as (i) Initial deformation temp (ii) Hemispherical temp & (iii) Flow temp. The fusion
character of ash is responsible for two components one is SiO 2 , Al2O3 , Fe2 O3 & Cao (major) and
other is Mgo,TiO2 , P2O5 , Na2 O & K2O (minor)
Higher alumina (Al2 O3 and silica (Si O2 ) makes the ash refractory in nature while lime
(Cao),magnesia (Mgo), iron oxide (Fe2 O3 ) and alkali oxides (Na2 O & K2 O) have a fluxing
effect and lower ash fusion temp. Most of the Indian coal ashes have hemispherical temp. above
1400C and refractory in nature. On the basis of fusion behavior coal is classified as (a)
Refractory H.T. above -1400C (b) Medium refractory HT 1350 -1400C & (c) Fusible
H.T. below 1350C
6. ANALYSIS OF FLUE GAS :
Efficient combustion is dependent upon the correct supply of air. In practice perfect combustion
cannot be achieved if fuel is burnt with theoretical amount of air only. This problem is avoided by
supplying an amount of air in excess to the theoretically required air for perfect combustion. Flue
gas contain CO2,O2 & CO. For determination of the gases ORSAT GAS ANALYSER is used .
In this apparatus gas sample is taken into a bladder and passes through 3 nos. of absorption
bottles containing the following chemicals and % of CO2, O2 & CO is calculated .
Bottle -1 50% KOH solution for absorption of CO2
Bottle -2 Alkaline pyrogallol solution for absorption of O 2
Bottle - 3 - Alkaline cuprous chloride solution for absorption of CO.

18
CHEMICAL CLEANING
INTRODUCTION:

During fabrication of boiler tubing, drums, heaters, varying degree of heat treatment and Hot work are
employed which results in the development of a coating of iron oxide known as mill scale The thickness of
this oxide layer is dependent upon the temperatures condition and length of time to which steel is exposed
.The shop and field welds are produced by bringing local surfaces up to fusion temperature where rapid
oxidation can occur. During period of erection, the boiler may be exposed in part or as a whole to numerous
environments capable of producing ordinary atmospheric rust. In all such processes the oxides formed may

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be eroded or re deposited in critical areas causing local overheating and associated corrosion problems. To
prevent such types of problem, pre commissioning cleaning is suggested for high-pressure boiler.

The performance of a steam generating system depends largely on the transfer of heat between two fluids
separated by a metallic wall. The thermal conductivity of the metal plays the sole role in such heat transfer
system. In thermo gravimetric process of system, it is observed that deposition of metallic oxides as well as
non metallic oxides on the heat transfer surfaces affects the thermal conductivity of the partition wall and this
also reduces the efficiency but also causes corrosion or over heating of the surfaces of the metallic wall
leading to the rupture of the tubes. To prevent these types of problem post commissioning cleaning is
recommended.

So the objective of chemical cleaning is to commission and operate the plant with the internal surfaces of the
water system circuit free from all foreign matters such as metal oxides, oils, Greases, dirt and to establish a
suitable basis for the protective magnetic film on the boiler internal surfaces.

One way to decide the timings of the post commissioning cleaning is to cut out a few tubes from the highest
heat in put zone and measure the thickness of the scales. If the thickness of the scales is O-15 microns
average, the boiler is said to be cleaned. If the thickness is 16-40 microns average, the boiler is said to be
moderately cleaned. If the thickness of the scale reaches above 40 microns the boiler is said to be dirty and
post-commissioning cleaning is to be performed.

CHOICE OF ACIDS IN CHEMICAL CLEANING :

Numerous acids have been used, including the inorganic acids such as hydrochloric acid, sulphuric
acid, phosphoric acid and the organic acids such as citric acid, sulphamic acid and ethylene diamine
tetra acetic acid (E.D.T.A). Formic hydroxyl acetic acid may also be used.

The selection of the cleaning solvent for a specific cleaning job is primarily based on two facts.
Metal oxide de solution capacity of the solvent.
Protection of metals to be cleaned.
From experience it is found that 5% hydrochloric acid, 3% mono ammonium citrate are best solvent for acid
cleaning of boiler and its auxiliaries. HCl is the most efficient commercially available acid for the removal of
iron oxide, while ammoniacal citric acid is less efficient. Ammoniacal citric acid is recommended when a
small amount of corrosion product needs to be removed or when austenitic steel tubes or non-ferrous alloys
are present. There is also less risk of damages to the parent metal when citric acid is used.

HCl is recommended for post commissioning cleaning of drum type boiler particularly those associated with
feed system containing nickel alloys. HCl is also recommended for pre-commissioning cleaning. If boiler
contains austenitic components HCl should not be considered as a cleaning solvent for both pre & post
commissioning cleaning.
Addition of fluorides to HCl & citric acid slightly increase the rate of dissolution of iron oxide although it
does not improve the saturation solubility of iron. Fluoride improves appreciably the solubility of siliceous
materials.

PURPOSE OF CHEMICAL CLEANING

1) To remove deposits including iron oxides and debris from boiler, this would otherwise restrict flow
and efficient heat transfer.
2) To ensure the boiler to be commissioned and operated without any physical or corrosive damage.
3) To achieve water chemistry standards as early as possible after commissioning.
4) To make the boiler ready for generating steam of utmost purity during operation.
5) To get a uniform protective magnetite coating over cleaned surface.

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PROCEDURE FOR PRECOMMISSIONING CHEMICAL CLEANING OF BOILER

In most recent pre commissioning chemical cleaning of drum type boiler plant, the super heater and re
heater have been omitted from chemical cleaning process. Since their cleanliness has indicated that this
stage was unnecessary. Another reason for exclusion of super heater and re heater was the complexity
of the plant involved and difficulty of ensuring that all cleaning solution was removed from non-
drainable parts.

The following steps are to be done during chemical cleaning.

1) Cold water flushing.
2) Hot water flushing.
3) Alkali boil out.
4) Pickling.
5) First stage passivation.
6) Second stage passivation.
7)
COLD AND HOT WATER FLUSHING
Removal of debris by physical cleaning process such as flushing will be used irrespective of whether
chemical cleaning is necessary or not.
The following steps are to be taken.
1) Fill the boiler with cold water.
2) Re circulate.
3) Drain.
4) Repeat steps (1),(2),(3) till clear water is observed.
For hot water flushing same process is to be done.
ALKALI BOIL OUT
PURPOSE
1) To remove loose mass including iron oxides and debris from the boiler leaving minimum quantity of
oxides for acid digestion in acid cleaning operation.
2} To make the boiler free from oil, grease and any preservative organic coating so the chemicals can
Come in contact with boiler internal surface during acid cleaning.
3) To create fine cracks in internal scale by thermal shocks during blow-down, so the acids may enter
into the cracks and come in contact inside the scale/ iron oxide and can be removed easily.
Alkali boil-out is carried out by lighting up the boiler and raising the pressure to 40 Kg/Cm 2
With the chemicals like tri-sodium phosphate( 1000 ppm) and di-sodium phosphate(500 ppm). This
highly alkaline solution acts as a detergent to loose/disperse the deposit and emulsifies oil/grease in
water, which are removed by intermittent blow-down.
PROCEDURE
1)
Fill the boiler with D.M. water up to the bottom most part of drum gauge-glass.
2)
Mix required quantity of chemicals in the mixing drum and transfer it to the boiler drum through
manhole and after completion of water taking and chemical taking close the manhole door.
3)
Light up the boiler and slowly raise the pressure to 5 Kg/Cm 2 and hold the pressure for few hours for
refractory dry out.
4)
Raise the pressure to 40 Kg/ Cm2 and hold at this pressure for 4 hours for effective digestion of the
Chemicals.
5)
Stop firing and open low point drain one by one at a time for one-minute duration. Ensure that drum
level does not go out sight during blow-down.
6)
Collect water sample from drum and low point drain after blow-down and analyse pH, Phosphate
and oil content.
7)
Again light up the boiler and raise the pressure to 40 Kg/Cm 2. maintains this pressure for 2 Hrs
Repeat blow-down as before. Repeat the procedure keeping 2 Hrs intervals between two blow-down.
8)
Chemicals may be required to add if the phosphate concentration is less, becomes half than initial
concentration.

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9)
Continue the activity for 24 Hrs until oil concentration becomes less than 5 ppm.
10)
Stop firing and allow the boiler to cool at boiler pressure of 2 Kg/Cm 2 and hot drain.
11)
Back flush super-heater and fill the boiler drum and replenish the boiler till phosphate ppm becomes
nil and conductivity of super heater tube samples become 10 s/Cm2
12)
Open the manhole and remove manually if any sediment found.
CHEMISTRY BEHIND ALKALI BOIL OUT
Alkali reacts with siliceous materials to form soluble silicates.
2 NaOH + SiO2 = Na2SiO3 + H2O
Alkali reacts with organic oils to make emulsions for removing the same from the wall of the tubes. The
emulsification is enhanced by the presence of surface active agents like Teepols, detergents etc. Excess
caustic may cause caustic embrittlement for the steel body of tubes forming ferrites e.g.
2NaOH + Fe = Na2FeO2 + H2
PICKLING
1) Fill the boiler with D.M. water
2) Raise the temperature to 700C
3) Add Rodine and circulate for 30 minutes.
4) Add HCl to raise the concentration of the solution 5% and 0.5% Ammonium bi-fluoride and
ammonia to maintain the pH at 3 to 4 and re circulate. Strength of the acid should be measured at the
interval of 15 minutes in both supply line and return line. Total transfer of acid should be done within
2 Hrs and the strength of the acid should not exceed over 6%
5) Analyse the samples in both supply and return line for iron concentration and acid strength.
6) Stop circulation when three consecutive samples show same value of acid and iron concentration or
duration of acid cleaning is 6 Hrs. whichever is earlier.
7) Drain the system under nitrogen capping. Neutralise the spent solution with soda-ash in neutralising
pit.
D.M. WATER RINSE
1) Fill the system with D.M. Water. Circulate, analyse the samples from both points for iron
concentration and acid after circulation for one hour.
2) Drain the system under nitrogen capping.
N.B Neutralise the effluent with soda ash.
CITRIC ACID RINSE :-
1) Fill the system with D.M. Water. Raise the temperature to 60 0C.
2) Add 0.2% citric acid and liquor ammonia to make pH 3.5 to 4.0
3) Circulate for 2 Hrs.
4) Analyse the samples for pH and iron concentration.
5) Drain under nitrogen capping when the value stabilises.
N.B.- Neutralise the effluent with soda ash.
D.M. WATER RINSE:-
Fill the system with D.M.Water. Recirculate and drain. Replenish simultaneously till iron concentration
becomes less than 50 ppm and acidity nil. Drain the total system under nitrogen capping.
NEUTRALISATION:-
1) Fill the system with D.M.Water, add 0.1% Di-sodium Phosphate and 0.2% Tri-sodium
Phosphate in the mixing tank and circulate for 1 hour and stop the pump.
2) Light up the boiler and raise the temperature to 80 to 85 0C and stop firing.
3) Re circulate for three hours; if temperature drops down, temperature may be increased by
lighting up after stopping the pump.
4) Hot-Drain the system with drums vents opened to atmosphere.
FIRST STAGE PASSIVATION:-
Purpose:- To create the uniform layer of protective magnetite on the freshly treated surface. Actually a
coating of FeO(OH) is produced, which is temporary and stands for 10 to 15 days. So within fortnight
second stage passivation is to be done.
PROCEEDURE:-

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1) Fill the system with D.M. Water, light up the boiler and raise the temperature to 80 to85 0C.stop firing.
2) Re circulate.
3) Add required quantity of Hydrazine Hydrate( 200 ppm) and Ammonia to maintain the pH at 10.
4) Circulate for 20 Hrs. if the temperature drops down then it can be raised by lighting up after stopping
pumps
5) Add Hydrazine if Hydrazine concentration comes down below 100 ppm & add ammonia if pH is less
than 10.
6) Drain the system with vents open to atmosphere.
7) Open the drum manhole doors. Inspect inside the magnetic coating and remove debris if any.
N.B.:-Neutralise the effluent with bleaching powder.
SECOND STAGE PASSIVATION
Purpose: -To produce a stable coating of protective magnetite
Procedure:-
1) Fill the deaerator with D M water; add required quantity of Hydrazine to get 200 ppm
and ammonia to make pH 10.
2) Run the boiler feed pump, re circulate for one hour & start filling boiler .
3) Once drum level becomes normal light up the boiler.
4) Raise the pressure to 40 Kg/Cm2 and maintain for 24 Hours.
5) During this period make up water should be dosed with Hydrazine and ammonia through
L .P. chemical dosing system to ensure a minimum of 25 ppm of Hydrazine and pH 10 in eed
water.
6) Box up the boiler after killing fire & allow the boiler to cool naturally.
7) Open the vents at pressure at 2Kg/Cm2 and drain the boiler.

N.B: - the effluent water should be neutralised with bleaching powder.

CHEMISTRY BEHIND ACID CLEANING

HCl reacts with non uniform coated mill scale ( magnetite,Fe 3O4),Ferric oxide( Fe2O3) and negligible with
metal surface in properly controlled condition.
FeO + 2HCl = FeCl 2 + H2O
Fe3O4 + HCl
Fe2O3 + 6 HCl = 2FeCl3 + 3 H2O

Fe + 2FeCl3 = 3FeCl2
Fe + 2HCl =FeCl2 + H2
Since HCl has a detoriating tendency to attack metal surface so its direct use is not recommended.

CHEMISTRY BEHIND PASSIVATION

By passivation the steel body of the steam and water circuits got covered with a continuous coherent
corrosion resistant micro film of magnetite at its surface. Magnetite is the stable oxide formed on steel in air
at high temperature. But it is unstable below 1500 0C, changing slowly into ferric oxide. A comparable change
takes place more rapidly in the presence of moist air at atmospheric temperature giving rise to rust which of
course has no protective value.
4Fe + 3O2 = 2Fe2O3
6Fe2O3 + N2H4 = 4Fe3O4 + N2 + 2H2O
( Magnetite)

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So hydrazine is used in passivation for producing a thin film of magnetite.

CHEMISTRY BEHIND ACID CLEANING IF CITRIC ACID IS USED:

Citric Acid is a tribasic acid having three carboxylic groups. The formula of the acid is
H2C-COOH

HOC-COOH

H2C-COOH
In presence of ammonia ( pH 3 to 4) citric acid form mono ammonium hydrogen Citrate which is soluble in
nature.
H2C-COONH4

HOC-COOH

H2C-COOH
Mono-ammonium Hydrogen Citrate
Fe2O3 + 2H3Citrate = 2 FeCitrate + 3 H2O ( In acid solution )
Fe3O4 + 3NH4H2Citrate = NH4FeCitrate + 2NH4 ( FeCitrate-OH ) + 2H2O
(Ferrous Iron Chelate) (Ferric Iron Chelate)

POST COMMISSIONING CLEANING OF BOILER

After commissioning of the boiler the scale consists mainly the oxides of iron, copper and nickel. Here oil
and grease, other debris like sand, cement is absent. So post commissioning cleaning is to some extent
different from pre commissioning cleaning. Before post commissioning cleaning, the super heater should be
filled with D.M. water containing hydrazine and ammonia to form a water plug and back flushing should be
carried out periodically. A constant head over flow device should be filled to the drum.

PROCEDURE:-
1) a) Fill the boiler with D.M.water
b) Raise the temperature to 900C
c) Add 1% citric acid, 0.5% KBrO3
d) Add ammonia to raise the pH 10
e) Recirculate until concentration of copper is constant.
f) Drain the boiler and back flush the super heater with D.M.water containing hydrazine and ammonia.

2) a) Fill the boiler with D.M.water

b) Raise the temperature to 900C
c) Add 3% citric acid, 0.5% ammonium bi-floride and rodine.
d) Re circulate(normally 6 to 8 hrs) until iron and copper concentration are constant.

3) Drain the boiler and rinse with D.M.water

4) A second stage of copper removal shall be carried out after draining the solution from t he iron removal
stage by repeating the process employed in the initial copper removal stage.
5) Drain the boiler and thoroughly back flush the super heater with D.M.water containing
Hydrazine and ammonia. Rinse the unit to remove dirty solution.
6) Refill the boiler with D.M.water and raise the temperature to 60 0C and add citric acid
sodium nitrite and add ammonia to raise the pH above 9.0 . Re-circulate for 6 hrs for first stage
passivation. Rinse the unit to remove cleaning solution.

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7) Refil the boiler with D.M.water add 200 ppm hydrazine and ammonia to raise the pH 10. Raise the
pressure to 40 Kg/Cm2 and maintain for at least 24 hrs. No further addition of hydrazine to the boiler is
required to maintain a reserve in the boiler water since this has been shown to be unnecessary. However
200 ppm hydrazine and sufficient ammonia added to the make up water to raise the pH 10 to react with
dissolved O2. On completion of the passivation process the boiler shall be blown empty at the highest
possible pressure but in any even not less than 3 Kg/Cm2.
Notes: -
a) Since oil and siliceous materials are generally absent so alkali boil out is not necessary for post
commissioning cleaning.
b) If the boiler surfaces are heavily fouled with metal oxide and austenitic components are absent .Then HCl
may be used to replace citric acid. In this case the solution used in stage 2c should be 5% HCl. The solution
should initially be circulated at 750C and continued until iron pick up is constant.
c) Experienced shows that the temperature will not have fallen below 60 0C when cleaning has been
completed.
CHEMISTRY BEHIND POST COMMISSIONING CLEANING
KBrO3 is used with citric acid ammonia combination to oxidise copper ( in mild condition) and
other transitional metal.
Fe3O4 = FeO + Fe2O3
Fe2O3 + 2H3 citrate = 2Fe citrate + 3H2O( in acid soln)
KBrO3
2FeO + (O) Fe2O3
Fe3O4 + 3 NH4H2Citrate = NH4Fe Citrate + 2NH4( Fe citrateOH) Ferrous Iron Chelate Ferric Iron Chelate
KBrO3
Cu + (O) Cu +
KBrO3
+
Cu + ( O ) Cu+2
Cu+2 + NH4H2Citrate = NH4CuCitrate ( Cupro ammonium citrate )

STEAM BLOWING: Target plates by solids in the steam is judged by experienced observers to be
minimal. Steam blowing of the super heater, re-heater and associated pipe work is used to remove foreign
materials, debris. These substances are mainly metal fragments and metal oxide. Such materials entering the
turbine during the early operational life could seriously reduce the efficiency of the machine by damage and
roughening of the turbine blades.
Steam blowing procedure is conducted in two stages. First the super heater and main steam pipes are blown
through to the turbine main steam chest to which is fitted temporary discharge pipe work to atmosphere.
Following this the circuit is rearranged, replacing the discharge connection at the steam chest with a
temporary connection to the cold re-heat pipes and discharging to atmosphere from the turbine reheat
intercept steam chest. Thus in the second stage, steam flows in term through the super heater main steam
pipes, cold reheat pipes, reheater and hot reheat pipes.
The boiler is filled with D.M. water containing only ammonia and hydrazine maintained at 50 ppm both to
normal working level. Pressure is raised to 40 Kg/Cm 2 .The main stop valves are opened as rapidly as
possible. The pressure is allowed to fall to 20 Kg/Cm 2 when the stop valves are closed and duration of steam
flow may vary from 3 to 4 minutes.
During the release of pressure, the boiler is subjected to quite several thermal shock and pressure change and
these must be controlled to avoid undue stress developing, especially in the drum.
This procedure of pressure raising and steam blowing is repeated numerous times for each of the two circuits
and the effect of each blow is observed on Target plates of polished mild steel or aluminium which are
securely fixed to intercept the discharged steam at short range from the point of discharge. A new plate is
used for each blow and the sequence of blows is terminated when no damage is found on the target plate.

*** *** ***

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