XU Boosters

Chapter – 1:
Chemistry of “Export Quality D2O”:
pH 6.0 – 8.0
Conductivity, µs/cm <15
Turbidity, NTU <5
Isotopic purity, wt/wt > 99.8 %
Organic matter (KMnO4), ppm 10 (Maximum)
Cl-, ppm < 0.1 (SCC)
Tritium, µ curie/ lit D2O 1 (Maximum)
*Natural abundance of Tritium in water = 2 TU = 14 dpm/lit (Natural abundance of
Tritium in Surface waters vary from 1 TU to 200 TU)

One Tritium Unit (TU) = 3.24 Pico Curie / lit. = 3.24 x 10-12 curie/lit = 7 dpm/lit
1 Bq = 1 disintergrn/sec = 1 dps
1 curie = 3.7 x 1010 Bq = 3.7 x 1010 dps

Tritium @ 2 TU Tritium @ 317142 TU ~

158000 times
GS enrichment
PROCE
Deuterium @ 152 ppm SS ~ 1800 times
Deuterium @ ~15 %
enrichment
18
Further, in DU, O will get enriched from 0.2 atom % to 0.4 atom % (2 times).
Equilibrium time for enrichment in XU:
Total ‘D’ inventory (100 % basis ‘D’)= 6.7 tones ( in all 3 stages)

From initial start up to first drop of product of 15% concentration

No. of stages Single stage Two stages Three stages
Tower Volume 1.0 0.7 (~ 30% 0.6 (40% decrease)
decrease)
‘D’ inventory 1.0 0.12 0.05

From the above table, for fixed annual production, it can be deduced that if D 2O
inventory assumes to be one unit, for a single stage plant,
 For two stage plant, the inventory will be reduced by 1/10th
  For three stage plant, the inventory will be further reduced by 1/20th

With 3 CT packing, 3CT tower inventory reduced by (from 21.13 MT tray holdup to 4.7
MT packing hold up) by 75% (21Te to 4.7 Te) [21 Te. Liq. On trays vs 4.7 Te. On
packing] [out of 6.7 Te D2O 100% inventory 85% will be in 3rd stage, so D2O in 3CT
+3HT = 6.7 x .85 = 5.7 Te of this 5.7 Te, 75% will be in 3CT. so 3CT 100% D 2O holdup
= 5.7 x .75 = 4.275 te, because of packing, inventory reduction = 75%, so 3CT 100%
D2O = 1.1 Te. So ≈ 3Te 100 % D2O in total reduced in system inventory = 6.7-3 = 3.7
Te. So, equilibrium time at 490 Te/hr feed = 3700/(490 x 26 x 24 x 1.1/1000) = 11 days

Inter dependencies of various process parameters:

Separation factor Pressure &

Temp.

Recovery Mass Transfer

No. of Transfer Flow rate Velocity

units
 Separation factor is 30 for low temperature electrolysis of liquid Ammonia.
 Many parameters such as flows, plant volume
Tower and recovery depend directly on
volume
separation factor while the dependence of energy consumption on the separation factor
is indirect.
 There are other process parameters such as Energy
rate of reaction, energy consumption etc.
which often outweigh the advantage offered by high separation factor.
Processes for D2O Enrichment: Two broad categories.
 1. Reversible Processes: Distillation, chemical exchange.
2. Irreversible Processes: Diffusion, thermal diffusion, gravitation, crystallization,
photochemical (laser), adsorption, electrolysis.

Reversible or Equilibrium Process: In reversible or equilibrium process, the

components of a mixture spontaneously approach equilibrium without requiring external
work. They have advantages of using energy efficiently.
If ‘α’ is high, then these separation processes will have
 Low plant volume
 Low energy consumption

Plant volume, operating cost, capital cost is proportional to [1/( α-1)2]

Distillation: It is an equilibrium process

 Simple, ease of operation
 Degree of reversibility is much more than chemical exchange. Since
thermodynamically reversible process, energy requirement is also low
Water, NH3 and CH4 Liquid H2 (Cryogenic
(Distillation) distillation)

‘α’ is low ‘α’ is

satisfactory
CHEMICAL LargeEXCHANGE:
plant volume In chemical exchange process,
Moderatedepending
plant size on the
differences in zero point energies of the exchanging species (D), ‘D’ is transferred from
one chemical species to another.
Low plant volume
High + High degree of
‘α’ reversibility Low energy consumption
DISTILLATION
In a two component system, the separation factor ‘α’ can be defined as the ratio of the
production of deuterium in the phase in which it concentrates to the fraction of ‘D’ in the
depleted phase. ‘D’ almost always concentrates in the liquid phase.

x,y = D/D+H in liq. & vapor.

In case of mixture having two isotope components, such as CH4, CH3O, or H2O, HDO,
which are to be separated by distillation,

When more than two isotope components are present in a mixture which is to be
separated by distillation, such as H2O, HDO & D2O; NH3, NH2D, NHD2 & ND3 etc., the
relation between ‘α’ and vapour pressure becomes more involved. Vapour pressure of
isotopic compounds like HDO, NH2D or NHD2 cannot be measured because of the
difficulty in isolating them in pure form. In such cases, ‘α’ can be approximately
calculated from the ratio of pure isotopic species with the help of geometric mean. For
ex.

In H2O distillation: Boil up rate per unit of product withdrawn is:

In distillation as α 1.0

Min =

For water distillation NMin = 643, Min = 3 x 105

Factors affecting capital & energy costs;
1. The plant volume and plant energy consumption are directly proportional to HETP and
hence HETP should be as small as possible.
2. The eq. time varies with hold-up and hence hold-up per plate should be as small as
possible. In comparing distillation columns, it is often useful to compare them on the
basis of their EFFICIENCY FACTOR, WHICH IS THE RATIO OF THE THROUGHOUT
TO HOLD UP PER PLATE. THIS RATIO RATHER THAN ACTUAL HOLD-UP ITSELF,
DETERMINES THE EQUILIBRIUM TIME.

Eq. Time proportional to 1/eff.factor

α
Eq. Time Proportional to

3. The pressure drop per unit height (dp/dz) which is directly proportional to power
consumption, should be as small as possible. This is more important in the case of water
distillation, which is carried out under vacuum to keep the pressure drop as small as
possible. A lower pressure drop results in lower operating temps., which favor larger
separation factors.
4. A higher vapor velocity reduces column area and thereby plant volume. Vapour velocity
is limited by flooding, High flooding velocities are preferred.
5. The no. of H2 atoms in a molecule also affect the cost. CH4 has four, H2O – 2. So, for the
same production rate of D2O, other conditions being the same, moles of CH4 processed
will be only 50%. Tower dia depends on molar flow rates, so less cost of production.
(vapour flows of CH4 are low because of four atoms of hydrogen).
6. A low latent heat of vaporization in reboiler preferred.
7. Single and the most important parameter which has overwhelming effect on both capital

and operational cost is ‘α’ Both these costs vary as 2

WATER DISTILLATION – H2O, HDO, D2O

Assuming ideal solution, and vapor pr. of HDO = and noting that Equilibrium
const. of self exchange reaction, H2O+D2O 2HDO, is 4.0

α=
α at 50oC = 1.056, α at 100oC = 1.032 α as T
i.e. α
For XF = 0.000150 atom fraction., XD = 0.998 atom fraction.
(Nactual Nmin = 643, (G/F)min = 1,41,000 moles/moles of D2O
For practical plants, Min. steam consumption = 1,41,000 moles/moles of D2O
Disadvantages: 1. Huge steam requirement (2) Eq. time of 3 months (3) Huge plant
volume (4) less recovery. So Uneconomical for enrichment from 0.000150 atom
pressure to 0.998 atom pressure.
But, still distillation is a preferred method from final enrichment. In the high conc. Zone,
energy consumption and equipment size are only a small fraction of those needed in
primary enrichment. Reliability, flexibility & simplicity make water distillation a preferred
choice for final enrichment.
CHEMICAL EXCHANGE
- Hot tower is analogous to the phase converter of Monothermal process
- The hot tower can be though of an analogous to an imperfect reboiler as it provides the
gas to the cold tower at a considerably mall, less than (<18%) (αc - αh)/ Thus the
penaltyRecovery –
= 1phase
for avoiding conversion is a substantial increase in flows and a large
column.(1/However,
) bithermal is attractive because of large energy inputs for mono
thermal.Monothermal, αe=

Bithermal αe =
EQUILIBRIUM CONSTANTS & SEPARATION FACTORS

- Separation factor is equal to the equilibrium constant only if the molecular species taking
part in the exchange reaction contain the same no. of exchangeable atoms. From this
G.S process HDS + H2O = HDOα+effetive = the exchangers molecules [H2S, H2O]
H2S; both
contain the same no. of exchangeable H2 atoms and hence K = α

- In case of NH3 – H2 exchange, NH3+H2O = NH2O + H2 the no. of exchangeable H2atoms

in the exchanging molecules is UNEQUAL, so α K but is obtained by multiplying the

‘K’ by the ratio of exchangeable H2 atoms in the two species α =

- In the case CH3 NH2 + HD = CH3NHD + H2, only amino hydrogens undergo rapid
exchange and methyl hydrogen remain unaffected. So, exchange H2 atoms in CH3NH2
and H2 are equal so, α = K
- We know = , so, α and T At low temp. ln in linear with 1/T, which at
2
higher temp., it varies linearly with 1/T . At very high temp., 1.0

- At low temp. and for low concn. Of D, ln = +C so, if we plot ln vs T, slope = H,

enthalpy of isotope exchange reaction.
SIMULTANEOUS HEAT AND MASS TRANSFER IN HEAT TRANSFER SECTION OF
TOWER

DEHUMIDIFICATION SECTION OF C.T.: (I.E. HTS): Enthalpy from hot gas is

transferred to cold liquid.

Humidification section in H.T. : (i.e. HTS) – Enthalpy transfer occurs from liquid phase to
gas phase.

At Const. L/G

Hg 10000 eq.line
Op.line
Enthalpy ofGas 5000 Humidification (Hot
Tower)
J/mol (liq.
enthalpy gas enthalpy
2500
T/L temp. of liquid oC 150oC
 At Const. L/G
10000 eq.line

Enthalpy of
Gas J/mol

Dehumidification (cold tower)

5000 Optg. Line (gas enthalpy liq.
temp
Hg
2300
150oC
30 TL Temp. of liquid. oC

The humidification and dehumidification operations are illustrated in the above figures
which relate the gas enthalpy and liquid temp.

It can be seen from figs. That during humidification the PINCH EFFECT is IN THE
MIDDLE OF THE HEAT TRANSFER SECTION, where in the DEHUMIDIFICATION, the
PINCH EFFECT IS IN THE ENDS. As a result, the dehumidification operation is able to
extract maximum HEAT UNLIKE THE HUMIDIFICATION SECTION AT A CONSTANT
LIQUID FLOW RATE.
Thats why, in C.T. HTS, approach (H.T top temp – cold tower bottom temp) is <2oC,
whereas the APPROACH IN H.T. 25 – 30oC (H.T. bottom – Booster disch.)

In actual, L/G is not constant in HTS of C.T. and hot tower because of high level of
humidity in gas stream and solubility of gas in liquid phase. So, it’s a curved optg. lines
in humidification and dehumidification sections as shown below:

Hg 10000 eq.line
Optg.line
Enthalpy of 5000
Gas J/ml
Humidification at actual L/G
2000
 30 Liq. Temp. TLoC 150oC

Hg 10000 eq.line
Optg.line
Enthalpy of
Gas J/ml 5000 Dehumidification at
actual L/G
2500
30
TL liq. Temp. oC 150oC
The curved optg. Line, in fact, favours heat transport in H.T. and leads to deterioration of
performance in cold tower.
Reverse M.T. in HTs of Hot Tower:In HTS of hot tower, liquid gets cooled down from
around 140-150 to 70oC. The simultaneous ‘D’ transport indicated that up to a temp. of
91oC, the HTS behaves as extension of MTS. When ‘D’ transfer takes place from liquid
to gas. Below 91oC, M.T. reverses, i.e. ‘D’ transfer taken place from gas phase to liquid
phase. In the fig. below:

‘D’ transport from liq. 18

130oC
18 to gas
Dg Dl
Tray nos.
From bottom DG Dl
In HTS of HT 12
91oC
1
Dg Dl

D 0.78 0.81 1
Dg Dl 700C
X/Xf D’ transport from gas to liquid

Gas
Liquid
In HTS of H.T as liquid travels down, up to around 12th tray (where temp. 91oC), ‘D’
transfer continues to occur from liquid phase to gas phase. Below 12th tray temp. will be
<90oC and M.T. reverses. As a result of this conc. reversal, the ‘D’ recovery from feed
will decrease. A possible modification in the flow sheet, is that waste from H.T may be
drawn from bottom of the MTS, instead of the bottom of HTS, which gives better
recovery. But in this case, the liquid in HTS will be circulating the closed loop, leading to
corrosion problems in S.S. trays.

Flow induced vibrations: The operation of high cross flow velocities to obtain
higher h.t.coeffs. can lead to damage due to the induced vibration. Various
mechanisms by which damage can occur are (a) vertex shedding (b) turbulent
buffeting (c) fluid elastic whirling and acoustic excitation. Failures occur when
the frequencies of these flow-induced mechanisms are in resonance with the
natural frequency of tubes. Tube segments with longest unsupported spans,
outer rows, u-bundles nozzle inlet and exist are most prone areas.
Tube segment with the longest unsupported spans, outer rows of u-bundles,
nozzle inlet and exit regions are most prone to such failures. The use of strip
baffle supports on u-bends, reduction of flow rate, redesign with no. of tubes in
window and redesign with different shell type are some methods which have
proved successful in eliminating the damage due to flow induced vibrations.
Effecting increased feed on various parameters:
1. Column Capacity: At 120% of design flows o.p % flooding in H.T. is 90%. Above
90% flooding, excessive entrainment results in drastic drop in tray efficiencies. Plant
processing capacity is limited by the gas handling capacity of the hot towers. No
considerable drop in tray η is observed (calculated drop in η, C.T. 1.6% and HT
13.3%). Fractional entrainment is 0.059 in C.T. & 0.22 in H.T.
2. Trays: Design across M.T. trays in CT/HT is 8304/9620 and for enhanced flows,
observed is 6300/7500 F. Factor 0.284/0.340 as against design. F. factor of
0.279/0.329. No trays damage were observed on towers as seen during MTA.
3. Adequacy of XU gas boosters for enhanced flows: The gas loop pressures are found
to be less than design resulting in lower heat requirement than provides. Trays s
are also less than the design figure. So booster is not a constraint as far as feed
enhance is concerned.
4. Pumps: Installed control valves are of higher CV than sizing requirements and this
aspect offers adequate scope in the system for handling higher flows. Even with
trimmed impellers., we are able to pump enhanced flows. Problems observed in
only with P.T. pumps, both the pumps kept in operating.
5. Heat Exchangers:No Flow Induced vibration(see top) observed.
Design Load: 375 Te/Hr HP, 40 Te/Hr LP, 60MWe (M.P.) + 21 MWe (CPP) = 81
MWe total.
Present : 250 Te/Hr HP, 25 Te/Hr LP, 35 MWe(total), 32 GJ/K D2O
- Over the years of operation, it is seen that optimum L/G is 0.52 in C.T.instead of design
value of 0.497.
- Improvement of on-stream factor by preventive maintenance and condition monitoring
programme of the plant. Stream factor is often >99%.
CORROSION &MATERIALS
OF CONSTRUCTION
ASTM A516 Gr 70 for plates (from vessels, towers)
ASTM A333 for pipes.
Major Corrosion type in H2S – H2O System: Uniform corrosion SCC and blistering.
C.S. gets attacked by aq. Solution of H2S according to the reaction.
Fe + H2S FeS + 2H + FeS + H2
The hydrogen liberated in nascent form combines to form molecular Hydrogen and
FeS forms a protection film. The rate of attack decreases to acceptable limits after
formation of stable protection iron sulfide film.
Type. Mackinwite, Troilite, Marcasiti, pyrrhotita, Pyrita (FeS2),
Mackinwite, Troilite, and Marcasiti: They have a low but inverse solubility in water
with strong temp. dependence. Because of this, they dissolve in water at low temp.
and deposit in sections (iron transport). pyrrhotita, and Pyrita solubility in water is
very less and they don’t depend on temp. for solubility. No inverse solubility.
Initial corrosion product of C.S. is Mackinwite which is not at all protective, and
transforms to Troilite and then to Pyrrhotita and Pyrita, which are protective.
The rate of transformation as influenced significantly by the process condition on pH,
temp, liq. Velocity and concn. Of dissolved iron, p.p. of H2S.
500 hours - Mackinwite (traces) + Pyrita + pyrrhotita (75%)
700 hours - Mackinwite (traces) + Pyrita + pyrrhotita (90%)
1000 hours - Pyrita + pyrrhotita (95%)
The corrosion rates are low only when the Pyrita, Pyrrohotita content of the film is ~
90%. The sulfide film is stable, but whenever there is splash, impingement (or)
turbulent flow, the protection film breaks and a fresh film is prevented from forming.
So, C.S. corrodes rapidly. where such condition exist e.g. sieve trays,H.Ex.tubes,
S.S. is used. This also applies to parts eroded by spray impingement (or) by high
liquid velocity, such as centrifugal pump, throttle valves.Liquid velocity is limited to
<7 ft/sec.
H2 BLISTERING: Some of the nascent, H2 that is formed in the reaction of H2S with
steel, is diffused into the crystalline structure of steel and thus greatly diminishes
the breaking strength.
This nascent hydrogen then returns to the molecular state and builds up in the points
of discontinuity, of this metal. This molecular H2 exerts pressure and blisters will
develop. This is why careful ULTRA SONIC Exmn. Must be made of all the steel
laminates so as to ensure that these are no flows in which H 2 might reside, with
consequent rupture of the metal. C.S. low alloy steel and S.S. must therefore be
suitably heat treated to relieve stresses that may result from fabrication procedures.
If this not done, failure may occur due to H2 embrittlement or to SCC. C.S. are
satisfactory if anneals according to ASTM boiler code. Austenitic S.S. that have
seen cold worked must be quench annealed at 1800 to 2000oF.
BOLTS, made up of low alloy steel – can crack in H2S environment because of SCC.
Both must be heat treated after mechanizing to reduce hardness below a critical
max., stress limited to 40,000 PSI.
MINIMUM THICKNESS HOLES are provide for piping > 3” to ensure that corrosion
of piping does not lead to large release of H2S. These holes about 1/8” in dia are
drilled about half way thro’ the wall from the inside. Loss of metal in the inside of the
pipe with result in a small but detectable leakages thro’ the test holes where
structural strength is still adequate to withstand the operating pressure.
SCC : Both inter granular and trans granular SCC of SS have been observed in H 2S
– H2O system.
Intergranular SCC is encountered when sensitized S.S. are expressed to sulfur oxy
acids which are formed by the interaction of sulfide moisture and oxygen.
Sensitization occurs when Chromium carbide precipitates along the grain boundary
during welding or heat treatment. SS 304, 316 have been known to have failed
when heated to 650 – 760oC with a solution of H2S and air. SS304L resist
sensitization. SS 321, 347 contain carbide stabilisers also resort sensitization.
Trans granular SCC occurs in S.Ss in the presence of H2S, Chlorides and air (O2) at
ambient temp.
PITTING: Pitting corrosion of S.Ss is quite severe in solution containing H 2S,
chlorides and O2, pitting corrosion is fairly low. Mo bearing S.Ss (S.S. 316) have a
better resistance to pitting as compared to SS304.

TRAY HYDRAULICS & FOAMING:

The two major criteria for the design of a tray are (a) STABLE HYDRAULIC
OPERATION and (b) Maximum extraction at design flow condn.
- Hydraulic stability is very crucial to efficient plant performance and has been single
cause for lost production in many G.S. plants.
- For maximum production, liquid and gas flow rates must be maximized.
- Liquid entrainment in the gas is the major factor limiting flow rate in the sieve tray
columns. In normal operation, liquid flows across the trays with minimum weepage
through the holes and minimum entrainment in the ascending gas.
- The tray downcomer should be of sufficient size to allow for essentially, complete
gas/liquid disengagement and to provide a sufficient liquid head to overcome the pr.
drop required to drive the gas thro’ the openings in the tray.
- Stable Foam generation in H2S/H2O system generally increases the rate of entrainment.
- It has been found that reduction of the weir height reduces the entrainment and foam
height and improves the hydraulic stability and thus production is increased. But in
doing so, the tray η decreases. Hence, optimum combination of weir height, hole dia
and total hole area have to be worked out.
FOAMING IN H2S – H2O SYSTEM: In sieve trays. Mixing of gas and liquid occurs
on the tray and the mass transfer occurs across the gas/liquid interface, where area
depends on the bubble size. Such bubbles are in continuous process of foaming
and collapsing.
Efficiency of M.T. is a function of the interfacial area, which in turn is dependent on
froth height. For a fixed tray spacing, there is always an optimum froth height, for
which the tray would have a maximum η. If froth height is lower than optimum, η
would be lowered. On the other hand, if froth height is higher carry over of the liquid
by the gas would increase leading to a decrease in tray η.
Collapse of bubbles in pure water occurs very rapidly, sometimes within
milliseconds. However, impurities, mostly organic, such as mercaptans in gas and
LIGNIN in Feed water may interfere on the above phenomena whereby bubbles
form a stable foam on the top of the tray. This leads to increase in the per tray
and causes carryover of liquid from tray to tray resulting in buildup of liquid in the
down comer. This seriously, limits the capacity of the exchange tower.
THE FROTH HEAIGHT CAN BE MEASURED BY GAMMA RAY ADSORPTION
TECHNIQUES, recently a high speed cinematography technique has been utilized
to measure foam height.
Antifoams used in some plants: Because of foam - column instability – increase in
column pressure drop – which signifies liquid hold up in trays caused by down comer
back up of foams. Silicon based antifoams were used. Antifoams consist of water –
insoluble silicon oil, surface active silica particles and organic emulsifiers – quite
expensive. Also, over a period of time and under hot tower conditions, the organic
emulsifier, present in these antifoams get hydrolised to form fatty acids, which
because of their volatility can accumulate in the process and cause serious fouling
problems in heat exchange and sieve trays.
Feed water purification: Treatment should aim at removing dissolved Fe and reduce
foaming tendency of the feed water.
- The impurities responsible for high foaming in H2S – H2O system have been identified as
naturally occurring organics, such as lignin and fatty acids. These can be removed to a
considerable extent by adsorption on activated charcoal or by treatment with alum.
Treatment with alum is cheap, but results in the formation of colloidal aluminum, which
can promote foaming. The adsorption on activated charcoal is a better process, but
expensive.
- Another impurity which needs attention is the dissolved iron. This causes iron transport
and gross deposition of iron sulfide fouls the trays and heat exchangers.
Quality Control: Stringent quality, control measures are specified by the code –
ASME section VIII Div-2 for process vessels and ANSI B31.3 for piping are
followed. All plate materials are 100% UT done. All butt welds 100% radiography
done.
- Dye Penetrate Test for externel defects.
- All weld joints of C.S and S.S. are stress relieved at appropriate temperatures.
- All forgings UT test hardness RCC22.
How Isotopic Exchange takes place?
When two compounds, each containing a mixture of Hydrogen & ‘D’ atoms are
brought into contact, a shift in H/D ratio between the two compounds may occur.
The isotopic concn. In these compounds differ slightly from each other under
equilibrium conditions. [152 ppm H2O, 64 ppm H2S]. This means that the equilibrium
const. of the reaction is different from the value which it would have iF there was
equal distribution of ‘H’ and ‘D’ between two compounds, exchanging substances.
(i.e. at 30oC if you bring H2S, H2O into contact ‘D’ comes in H2O & H2S is different at
K30 = 2.2, ‘D’ H2O – 152 ppm, D H2S – 64 ppm) If ‘D’ comes is equal in H2O – H2S
then K30 would have been different.
The degree of separation to be achieved is governed by the simple process
separation factor, which can be descended as a ratio of equilibrium constant to the
value which it would have if there were equipartition of ‘H’ & ‘d’ between the two
exchanging substances.
[for eg. Ratio of K30F 2.2 and K30 if ‘D’ comes is same in H2S, H2O].
The equilibrium constant defers from the value corresponding to the equipartition of
isotopes between the two chemical species because of a difference in the internal
vibrational and rotational frequencies of different isotopic molecules.
Vibrational frequencies are altered significantly by isotopic substitution, there is an
appreciable effect in the Zero Point Energy (ZPE). Thus, if the eq. const. is to have
a large value, then not only should the free energy of the exchanging chemical
species be different [ Go = –RT ln K) but the effect of the isotopic mass on the free
energy must also be different in the exchanging compounds. This suggests that in
order to obtain a large separation effect, the element in question should generally
exist in one compound unbonded or with few weak bonds, while in the other
compounds; it should be strongly bonded with as many bonds as possible.
- The ideal situation is when the ZPEs of the isotopic pair (H,D) for one compound (H2O)
are nearly equal, but differ appreciably for the other compounds (H2S). This requirement
implies that the compounds selected for a high separate factor are unlikely to exchange
rapidly. Some of the most important exchange process require the use of catalyst to
make the reaction sufficiently rapid.

- THE CRUCIAL REQUIREMENT THAT THE VIBRATIONAL FREQUENCES SHOULD

BE SUFFICIENTLY ALTERED BY ISOTOPIC SUBSTITUTION, SO AS TO GIVE
WORKABLE SEPARATION FACTOR CANNOT BE MET IN THE CASE OF HEAVY
ELEMENTS U233 . AS A RESULT, CHEMICAL EXCH. PROCESSES HAVE NOT
SUCCEEEDED FOR SEPARATING THE ISOTOPES OF HEAVIER ELEMENTS.

IMPORTANT:
1. Various strategies were adopted for enhancing the production and reduction in energy
consumption by review and re-optimisation of process parameters, increasing the thro
put by SYSTEM ANALYSIS, evaluation of the Hydro dynamics of the system,
performance evaluation of rotary equipment, process intensification.
2. Export to South Korea, China, USA (4.4T, 99.99% wt. Spectra gas ina)
3. Non-nuclear application of ‘D’ – use in medical, life sciences, communication and micro-
electronics, ‘D’ substituted polymers have shown outstanding signal transmission
characteristics with reduced loss of intensity and better transmission efficiency where
‘D’gas Is used. in optical fibers ‘D2’ gas – we are supplying.
4. The performance of HWPM is continuously improving over a period of time with respect
to CAPACITY UTILISATION, SP. ENERGY CONSUMPTION, PRODUCTIVITY,
SAFETY PERFORMANCE, ENVIRONMENT MANAGEMENT ETC.
- Break thro. In maintaining excellent control over O2 in feed water (<10ppb) minimized
the ‘S’ generation, which is used to choke the trays and reduce feed processing
capacity. This has resulted in increased opn. Stream factor. This has also paved the
way for initiating the change over to energy efficient structural packing in place sieve
trays to 3 CT. Reduction of gas loop pressure drop by redesign of flow element and
control valves lead to increase in feed rate. Exchange columns are presently being
operated at 90% flooding velocity as against the design value of 75% resulting in 10-
15% extra production and 8% redn. In energy consumption.
- Energy – 70% of working cost.
- Over a decade entire HWb – 36% redn. In energy – Rs.700 cores.

SSB2 Shutdown: 4.6 MWe, 15 Te/Hr steam, 4 Te (3CT + 3 HT) D 2O (100%)

inventory, 15Te of H2S inventory.
Resource Consideration : Raw Water – 5600 M3/Hr to 1750 M3/hr.
- HWPM contribute lion’s share of HWB’s production.
- 2006 calendar year – Production –120% of rated capacity, which is the best every
production achieved during a MTA year.
- 2006 (1) South Kores – 13 Te., USA – 4.4, 99.0%.
CO2 removal SBA : H2S loss thro’ P.T. for removal of CO2 – 4 kg/hr. Solubility of
CO2 decreases as pH goes down. In purge tower, in order to decrease the solubility
of CO2, its pH should be kept very low. Hence, H2S is lost thro’ PT.
- Redn. Of CO2 improves gas purity, feed process
- Redn. Of H2S loss thro’ PT.
- H2S loss comes down from 11 Te/month to about 5-6 Te/month.
- Neutralisation cost comes down as lime consumption comes down.
- 3R philosophy – Re-use, Recycle, Reduce.
- XU-II MTA completed in a record 62 days because of the professional approach.
2005 – Best Plant Performance Award – 6th time.
- AERB Safety Fire Award.
- Maximum Production thro’ highest utilization of equipment.
- New Intake Well Pump – 280 KW saving.
- SBA
- H2S recovery from sour oil – 2 kg/hr H2S recovery.
- Ch.W. loop hydraulic study, 1500 M3/hr, 40M head – 250 KW.
- Bifurcation of C.W. circuit : 3 existing pumps are for XU, VAR
- 1New pump – 1200 M3/hr for H2S, CAP, DU, N2 – 275 KW
DIVERSIFICATION: Having met its mandates in the core activities i.e. supply of D2O
to Indian PHWRs and having surpassed the demand within the country, HWB
diversified its activities in other field, particularly in Industrial scale production of
other inputs reqd. for Front end as well as back end of Nuclear Fuel Cycle.
Nucelar Fuel Cycle requires a large variety of solvents for fuel reprocessing, actinide
partitioning, separation of fission products, waste management etc.
TALCHER FACILITIES: (1) D2 EHPA (Di-2 ethyl Hexyl phosphoric acid) also known
as TOPS-99 (Talcher Organo Phosphorous Solvent, 99- year in which pilot plant
started yielding)
Note: The ‘Solvents’ or ‘Metal Extractants’ are a class of organic elements,
essentially immiscible or near immiscible with water and have an ability to extract a
desired component (or) group of components from an aqueous solution leaving
behind the undesirable components such a process, employing a solvent to
selectively extract desirable components from an aqueous medium is called a
solvent extraction (SX). These solvents form a crucial input to the Nuclear Fuel
Cycle, both in front and back end.
TALCHER – contd.
1. Tri-n-Butyl Phosphate (TBP) – supplied to NFC – also known as TOPS-03 (started in
2003) – 6OMTPA – TBP is often required to an work horse of full reprocessing
operation.
2. Isotopes for 2nd stage Nuclear Power Programme – B10
Enrichment of B10
10
- Elemental Boron has two stable isotopes, B &11B which occur in nature with
abundance ratio of 1:4.
IMP: BECAUSE OF HIGHER NEUTRON ABSORPTION CROSS SECTION,
BORON ENRICHED in 10B has two important applns – (a) as CONTROL ROD
MATERIAL FOR PFBR (prototype Fast Breeder Reactor) in the form of Boron
Carbide with >65% 10B and (b) FOR DETECTION GRADE appln. In the form of
Boron Tri Fluoride (BTF) at >90% enriched 10B.
Two Processes: (1) Exchange Distillation of Boron Tri-fluoride Ether Complex and
(2) Ion Exchange displacement chromatography of Boric Acid.
- First Process – TALCHER, 2nd – Manuguru.
- TALCHER PILOT Plant was set up – produced considerable quantities of 10B at >90% IP
in the form of Ether Complex, chemically converted to desired form – Evaluated by end
user ECIL and found to be at part with imported material. Structural packing for
distillation column has been selected, facility is at advanced stage of installation.
CAPACITY – 5 kg. per year of B-10 at >90% IP for detector grade application and 50 Kg
per year B-10 at 65% IP for control rod appln. In PFBR.
TALCHER CONTD.
3. Recovery of Rare Material (Uranium) from Secondary sources by Solvent
Extraction:
 The pressing need for augmenting indigenous availability of rare metal (or)
keeping in pace with the PHWR programme, lead to the task of developing of
solvent extraction process from recovery of rare metal for secondary sources like
Wet Process Phosphoric Acid (WPA) Uranium content in WPA – 70-150 ppm
(mg/lit). Having identified TOPS-99 in synergetic combination with TOPS-03
(TBP) as the solvent and WEAK WPA as feed stock, laboratory seal studies were
done. After complete of lab tests, establishing six chemists and generating
necessary eq. and kinetic data, their validation under continuous were done in
mixer settler battery. This bench seal test facility capable of continuous
processing of WPA in the scale of ton/day.
The engg. Data generated by the 3 stage process development facility at Talcher
on the process and equipment performance has provided the design basis for
Technology Demonstration plant being set up at CCF, Trombay.
KOTA facilities: HEWAC - Heavy Water Clean up Facility – details of D2O ….
TUTICORIN: Synthesis of organo phosphoric solvents which play a vital role in
the front end of Nuclear Fuel Cycle.
Optimum of parameters done at lab level campaign, later bench scale campaign
were established with commercial chemical then pilot scale prodn. Was
achieved. The solvents are:
(a) TOPO: Tri Octyl Phosphine Oxide
(b) TAPO: Tri Alkyl Phosphine Oxide
(c) DNPPA : Di Nonyl Phenyl Phosphoric Acid.]
As per literature, DNPPA & TOPO combination has better coefficient of
extraction compared to D2EHPA – TOPO combination for extraction if Uranium
from MGPA (Manufacturer’s Grade Phosphoric Acid, its purity >WPA).
Manuguru: HWPM has taken up production of Na metal and enrichment of B10
isotope for 2nd phase of Nuclear Power Programme:
Na test cell, Elemental Boron Test Cells were operated & data collected.
2. BEP : Plant erection in progress. Ion Chromatographic separation technique.
3. O18 is having appln. In Nuclear Medicine and biochemical research – used as
tracer. Doubling Labeled Water (DLW) having certain cocn. Of ‘D’ and O 18 is
used for measuring Energy Expenditure, total body water content etc.
- Distillation of H2O18 – 99.8% prutiy.
While production of D2O still remains major activity, Diversification in other fields
will provide growth opportunity to the board. HWB’s horizon is widened.
95-99% H2O is bombarded with proton in cyclotron to get F18 (Fluogine). Using
F18, F18 FDG (Fluorine Dextra Glucose is produced by radiochemical synthesis.
F18FDG is injected into patients on intravenous diagnostic pharmaceutical. Thin
PET (Positron Emission Tomography) scan is performed on the patient for
diagnosis if disease in the area of oncology, neurology and cardiology.
PET shows images which show body metabolism and other functions. These
type images cannot be obtained with other scans like CT scan, MCI scan etc.
- 10% H2O18 is also used in medical research for energy expenditure studies. It measures
the amount, food that is being metabolized. Also used in cholesterol research.
At 5 ppm, start survey

H2S level normal

H2S in other than XU-I/II – H2S 5 monitors in the same zone of

No one monitor 50 ppm (or) XU-I H2S 50 ppm or area
2 monitors of different zones in comes
XU-I/II H2S 50 ppm

See lan on-site yes

emergency Scram the affected
tower/ towers
See lan on-site
Leak Identification ½ emergency
hr.
No Yesidentification
Leak
within ½ hr.

Leak U/s or d/s of 1st

Yes iso. valve
No

Rectification
within ½ hr.

No during the
affected set/
equipmt.
No

Scram during the affected tower/towers

Recovery increased from 70% to 84%
Feed processing rate reduced from 246 kg/hr (15%) to 185 kg/hr at 18.5%
Reject concn. Reduced from 5% to 4.5%
‘D’ inventory of DU columns has got reduced from 8000 to 5,300 kg.
Why 5th Column : Product set up is able to handle 185 kg/hr of XU product at 18.5%
concn. And producing 27 kg/hr of 99.9% concentrated product.
With high feed processing rate of XU, the present cascade of XU can not handle the
expected production rate of 30 kg/hr. Even if 100% stream factor for DU is
considers, DU is going to become a bottleneck whenever XU stream factor exceeds
90%. Hence two options considered.
a)Adding up one more section to all four columns: It requires a minimum head room
of about 3.25M . As the present head room available is only 2.7M, it is not possible
to install the added section. Also simultaneous calculation show that addition of one
more section can increase the prodn. Rate to 28.3 kg/hr only and not meeting the
requirement of 30 kg/hr.
b)Adding up one more column: of 1 mt. dia and 14 sections and operating in series
with the available four columns operating parallely., A,B,C,D parallel, E in series, E
reject will go to ‘C’. This arrangement can produce 36.9 kg/hr. If the unit is operated
at 30 kg/hr, which is present requirement, XU product concn. can be reduced below
18.5%, which will not only reduce inventory in XU, but also reduces the net losses.

A,B, D → feed : 6.5 kg/hr 18.5%

Product : 9.7 98.7%
Reject ; 55.3 4.6%
C → Feed 55 (u) + 2.7 (L) from Col.E
↓ ↓
18.5% 58.1%
Product : 10.5 97%
Reject : 47.2 4.5%
Col. E : Feed : 39.6 kg/hr 97%
Product : 36.3 kg/hr 99.9%
Reject : 2.7 kg/hr 58.1%
Packed Column Design:
1. First find the theoretical no. of stages
2. Next selection of packing : normally structured packing is used for very low pr. Drop
applications and for increasing the capacity of an existing column.
3. Column dia/packing size ratio should be greater than 30 for Rasching rings; 15 for
ceramic saddles; 10 for plastic saddles or rings.
4. Assume column dia based on gas flow rate given. Select the type of packing. From
column dia to packing size ratio we will come to know of packing size. For eg. Column
dia = 24”; packing is plastic pall rings so, packing size should be greater than 10, 2”
plastic pall rings will do.
5. Find out Column Dia : is based on vapor velocity. Normally vapor velocity is kept at 80-
85% of flooding velocity; value down to 60% and sometimes used.
Down comer flooding occurs when liquid backs up on a tray because of very small down
comer area. This is not usually a problem. Most worrisome is entrainment flooding,
caused by too much liquid being carried up the column by the vapor steam. A no. of
corrilations and technique exist from finding out flooding velocity; from this, the active
area of the column is calculated so that the actual velocity can be kept to no more than
80-85% of flood; values down to 60% are sometimes used.
Flooding Velocity: A force balance can be made on droplets entrained by the vapor
stream, which leads to entrainment flooding. This balance yields an expression relating
the vapor and liquid densities and a capacity factor (C, units → Velocity units) to the
flooding velocity.

C = capacity fraction, flooding factor etc.

The capacity factor (or) flooding factor depends on droplet dia, drag coeff etc. but is
usually from correlations based on experimental data from distillation tray tests.
Depending on the correlation used, ‘C’ may include the effects of surface tension
tendency to foam and other parameters.
In all ‘C’ (or) ‘F’ factor = f (L,G, L, G, tray spacing, surface tension, tendency for
foam etc.)
Fair Plot forF factor: F factor is functional group based on liquid to vapor mass ratio,

FLV =
From the plot, you will get F factor for non-foaming systems, it is to be corrected for
surface tension.
F (or) C = Cfair [ 0.2 σ = surface tension on n/m

So,

(or) C or F can be calculated for tray towers using the following formula:

C (or) F = 0.2

α, β = const, flow parameter E = 0.5, σ in N/M Con IF 0.2

At = 0.1 to 1.0 in SI units
α = 0.0740 + 0.01173 t = tray spacing,M
β = 0.0304 + 0.015 t = -do-
Use 80 – 85% of flood, velocity.
Vapor velocity V = 0.8 x VFlood [80-85% for non foaming & foaming]

Active area of column = (Area thro’ which gas flows)

‘O’ cannel’s correlation for overall µ of column with feed viscocity and relation
velocity of key of the mixture =
-0.245

= 0.245
should be determined at arithmetic average of column top & bottom towers.
µ drops as increases (M, T, rates on lower)
drops as increase since the mass that must be transferred to obtain eg.
Increased
of packed column = HETP (or) NTSM
For a typical distl/z systems, the resistance to M,T is highest in vapor phase.
EFFECTS OF PHYSICAL & TRANSPORT PROPERIES ON EFFICIENCY OF A
TRAY COLUMN
1. Liquid Viscosity = As D2 (liquid phase diffusivity) and hence tray µ

So, µ D2 ↓ so µ ↓ O’ Connell correlation η = 0.245

2. Relative Volatility α, O’ connell’s correlation

α ,η↓ η = 0.492 / ( )0.245

3. Vapor Diffusivity DG = DG η
Note: As pressure increases, Dh (P DG ) so η ↓
4. Liquid Diffusivity DL : DL η , (P DL ) so, η
DL generally increase with pressure. This will directionally tend to off set the change in
DG (vapor diffusivity). However in most distilln. Systems, the influence of the vapor
diffusivity will dominate the influence if liquid diffusivity.
5. Liquid Surface Tension : Surface tension of liquid was found to have a significant
effect on tray µ thro’ its effect on bubble sizes and interfacial area in froth. In froth
regime, a decrease in alone will cause a resulting increase in η.
↓η in froth regime

Effect of tray design and operation.

 6. Weir Height – With trays operating in froth regime, an increase in Weir Height will
increase efficiency. It was found that the removal of small outlet weir can noticeably
decrease η
7. Flow path length: Increase in flow path length increases η.
8. Liquid vapor maldistribution decreases η
9. Weighing and entrainment decrease η
78000 tonnes of Uranium reserves
5,18,000 tonnes of Thorium – beaches of Orissa and Kerala.

Nuclear Science
Transmutation: The transmutation of one isotope or element in another (eg. U238 to
U2390 requires an extraordinary type of reagent sub-atom particles. Larger nuclear
weapon programme consume some of these artificial isotopes in tone quantities. Only
one sub-atomic particle is available in the necessary Kg amounts = NEUTRONS
- A 1GW Nuclear reactor will produce 3.75 Kgs. of Neutrons during the course of a year.
This fact that neutrons have no electrical change is very important since it allows them to
easily penetrate the charged electron shells and nucleus of an atom.
- Each fission produces roughly 2.5 neutrons, one of these is required to keep the reaction
going, the others are available for transmuting other materials although some portion of
these are unavoidably captured by materials making up reactor structure.
- An alternative source of neutrons is to use particles accelerators to produce neutrons
without reactors. Recent advances in accelerator technology make it possible to
produce very intense beams of protons relatively efficiently. These protons upon striking
a target material of moderate atomic number with energies of a few hundred Mev, would
knock loose some 50 neutrons each. Expensive, time consuming.
- By neutron transmutation, the isotopes produced – PU (from U238, Tritium (from Lithium-
6), U233 from Th232.
- Pu239 – Rate at which Pu-239 conc. builds up α (Neutron flux) x (U238 concn.). This Pu-
239 is pure. The produced Pu-239 is now exposed to the same flux on U238, so it also
participates in neutrons reactions. The rate of these reaction is proportional to Pu
concn., so the rates are initially very small. Mostly, these reactions are simply fission,
partially off setting, Pu prodn, but also releasing more neutrons for breeding.
- Pu239 has larger fission cross section than U-235, but also has a much larger neutron
absorption (non.fission capture) cross section. Absorption results in the following
reaction:
Pu 239 + n01 → Pu240
 As the concn. Of P=239 grows, so too does the rate of Pu-240 prodn. Pu-240 in turn
breeds Pu-241, which leads to Pu-242. The longer irradiation of the V-238 continues
(either in fuel rods, or in a Pu prodn. Blanket), the lower the % of the most desirable
isotope Pu-239 in the plutonium. similar processes lead to contamination of reactor
produced U-233 as well.
Fission Materials: U-235, Pu-239, U-233.
Only U-235 occurs in nature (0.7% only). Pu-239, U-233 must be produced by
bombarding other isotopes with neutrons.
U-238, Th-232 a fertile – can undergo only fast fission, but can be used for breeding P u-
239 and U-233 respectively.
URANIUM – Natural Uranium U-234 → 0.0454%.
U-235 → 0.7110%, U-238 → 99.2836% (MCM%). U-235 cocn. Is decreasing due to
depletion from ancient fission reactions that took place when U-235 concn. Used to be
3% ,1.9 billion years back. (Oklo reaction – 1.9 billion years old).
- Natural uranium is sufficiently radioactive to expose a photograph plate in an hour or so.
- Avg. concn. Of Uranium in earth’s crust is about 2ppm.
- In sea water, uranium concn. = 150 microgram/M3 or ton. The oceans are estimated to
contain 4.5 x 109 tons of uranium.
- Primary uranium minerals → Uranite, Pitchblend.
- Australia → 27% of world U reserves export as UO2
Despite of pitch blend, the richest uranium ore, are found in Canada, Congo,
US
In solvent extraction process, the uranium ore is removed from acidic ore leach liquors
by extracting with a solvent mixture such as Tri Butyl Phosphate (TBP) in Kerosene. In
modern methods, alkyl phosphoric acids –Di (e-ethyl hexyl) Phosphoric acid (DEPHA)
– and secondary and tertiary alkyl amines are the usual solvents.
U-235: is the only naturally occurring material suitable for NPP fission. Weapons
require U-235 at min. of 80% preferably more than 90%. U-235 has a spontaneous
fission rate of 0.16 fission/sec-kg. A pure mass of U-235 weighing 60 kg. would thus
emit only 9.6 fission/sec.
U-238: Although it can’t be used on a primary fissile material due to the high threshold
energy required for neutrons to cause fission. U-238 is still a very important material. It
is fissioned by fast neutrons. About 40% of fission neutrons and all fission neutrons are
energetic enough to fission U-238.
U-238 has a spontaneous fission rate → 35 times that of
U-235 → 5.51 fissions/sec.kg.
It is raw material for breeding Pu-239, a valuable primary, fissile isotope.
U-233: not found in nature. Bred from Th-232.
PU – PLUTONIUM: Pu239 exists in naturally in trace amounts in Uranium ore (several
parts per quadrillion) Pu-239 is produced by bombarding U-238 with slow neutrons
(breeding). U-238 + n → U239 → NP-239 → Pu 239.
Plutonium has large no. of very peculiar properties:-
 a. It has the lowest thermal conductivity of any metal.
b. It electrical conductivity is lower than any metal exept Mn.
c. It is the most viscous liquid metal known.
d. It undergoes the most extreme and bizarre density changes with temp. of any element.

- The cost of reprocessing reaction fuel to extract Plutonium is more expensive than the
current commercial cost of low enriched Uranium.
- Pu is also used as a smoke detector in Europe. US smoke detectors use Americium due
to shorter half life.
- Plutonium Beryllium alloy is used as lab neutron source.
- Pu-239 can also be produced in special reactor that use highly enriched Uranium or
Plutonium as fuel, but includes a blanket of natural or depleted Uranium for Pu breeding.

Thorium: is abundant in nature. 7.2 ppm in earth’s crust. It is three times more
abundant than Uranium and about equal to lead.
- It occurs in several minerals, the most common being Monazite (3-9% ThO2), Thorite
(Thoric Silicate).
- Thorium Oxide has an extremely high melting point, 3300oC, the highest of all oxides
and higher than the melting points of all but a few substances.
- It is estimated that the potential energy represented by accessible thorium deposits
exceeds that of Uranium and fossil fuels combined by a wide margin.
Fusional Material:
1. Hydrogen Isotopes: Light hydrogen participates in fusion reactions extremely slowly
(thatiswhy the sun is still around) ‘D’ fuses much mere readily.

Two interesting properties of D2O: (a) D2O releases significant amounts of heat upon
mixing with light water and (b) Heavy Water ice is slightly denser than light water.
Hence, it will sink in glass of light water.
Chemical Exchange: It uses the fact that ‘D’ concentrates to varying degree in H2S gas
at different temperatures.
Tritium:- D12 + D12  T12 +n01 + energy  fusion
In isotope reactions,Li6+n01T+He24 ; PHWR’S  250-500 grams T annually.
Basic of CANDU reactor: Heavy Water as moderator. The function of the moderator is
to slow fission neutrons down. The reason is that neutrons coming from fission typically
with a very high K.E – Max. 1 Mev. However, the probability for a neutron to induce
fission is orders of magnitude higher at ‘thermal’ energies (-0.025 ev) than in the range
of 1-2 Mev. Therefore, a modulator is used to slow the fission neutrons down to thermal
energies. To slow the reactor down in a few collusions as possible, the moderator
should have nuclei of mass close to that of a neutron, i.e. it should be a light element.
Mass closest to neutron  hydrogen ‘H’. So, ordinary water is certainly very effective at
slowing neutrons and it is in fact used in light water reactions. However, 1H has a high
absorption cross section of neutrons. Thus, it can slow them down, or it can also
absorb them (making D) and take them out of circulation as agents of further fission.
Other light nuclides → D, C (graphite) and Be (Beryllium). These have a smaller

absorption cross section for neutrons than 1H. ‘D’ has the smallest a. Then D2O is
the moderator with “best Neutron” economy.
3 quantities are important in determining the properties of Moderator:-
1. ⅀s → scattering cross section for neutrons. Larger is better, it means that the nuclide is
efficient at colliding with neutron.
2. ⅀e → the “lethargy decrement” → this is the avg. energy lost by a neutron in a collision
with the nuclide Larger is better, because it means that the neutron is thermalized in
fewer collision.
3. ⅀a → Absorption cross section for neutrons. Smaller is better, because it means that
the nuclide is port at absorbing neutrons.

Modernizing ratio : = MR
Highest MR, the best moderator
No. of collision for 2Mev to M.R
1ev
H2O 16 71
D2O 29 2100 (0.2% H2O as
immunity)
22000 (100% D2O)
He 43 83
Be 69 143
C 91 192
U-238 1730 0.0092

- Reactor production D2O > 99.75 wt. % pure. Light water content CANNOT be more than
0.25 wt%, otherwise the neutron economy could be significantly impaired for
sustainance of chain reaction.
Natural Uranium as Fuel: the neutron economy of D2O is such that natural uranium can
be used as fuel. With light water as modulator, this is not the case: the rate of neutron
absorption is sufficiently high that the reactor cannot go critical with natural uranium
fuel, the uranium must first be enriched in the U-235 isotope to increase the probability
of fission relative to that of absorption.
Fuel → uranium dioxide pellets encased in Zircaloy sheath.
Heavy Water as Coolant: In the pressure tube design, the moderator and coolant are
separated, in contrast to the situation in the pressure vessel design. In principle, this
allows the moderator and coolant to be different. The idea for retaining D2O as the
coolant too is to MAXIMISE THE NEUTRON ECONOMY.
How to find E : We have graphs for co-currents Cowhiter current h.ex. of NTU = UA/CMin
Vs
E (rather E (y-axB) vs NTU) Cmin = (MCp)Min.
1. C. W. → 0.1 KWH/TR
2. Ch.W. System (VCR, 10oC) → 0.7 KW/TR
3. Ch.W. System (VAR) → 0.7 KWH/TR

15 Te/Hr of LP steam, Cons.temp = 85oC, so, enthalpy to = 660 -85 = 580 Kcal/kg
H = 660 kcal/kg Conversion = 860 Kcal/KWH

15 Te/hr =

So, efficiency = = 0.7 KW/TR

Residual Life of Plant :
During the operating life of any plant, components are exposed to influences like
stress, temperature, vibration, fretting, and corrosion. These results in changes of
microstructure and material properties. Managing the operation of plants with a well
designed programme for condition assessment thro’ in-service inspection (ISI) and
using time-tested approach for life prediction, it is possible to extend the life of the plant
condition assessment thro’ ISI and life prediction approaches would enable repair,
upgradation, modernization and replacement of necessary components and extension
of the life of the remaining components and over all plant well beyond the design life.
ISI becomes a necessity to detect any incipient failures, to avoid unplanned plant
outages and for effective life management.
a. Towers, vessels undergo corrosion if there is any damage to the protection film. Hence,
during every MTA, the thickness of the vessel is measured by ultrasonic testing to
assess the extent of corrosion as part of conducting assessment programme.
b. Periodic in-situ metallography is carried out to assess the degradation of microstructure
(conversion of delta ferrite in the cast structure to sigma p…. causing embrittlement).
c. The main inspection techniques employed are visual examination for location of the
cracks and UT for detection of the cracks and for the determination of the depth of the
crack.
d. Eddy current testing of heat exchange tubes. A highly sensitive focused eddy current
probe has been developed to detect extremely fine defects of the order of scratches in
the range of 50-75 microns. Indigenous procedure, codes, and inspection methods have
been developed for assessing the safe operating life of pressure tube bundles the
degrading effects of creep, hydriding and embrittlement.
e. In any Chemical Plant, failure of engg. Components in service is a cause of concern as it
may lead to loss of productivity and raise issues related to safety and reliability.
However, it is a fact that failure give very important information about the mal-functioning
 of the system, changes in material properties/behavior, operational man occurs, design
in compatibilities etc.

Heavy Water Clean up facility : (HEWAC/Kota):

In PHWRs of 235 MW, the tritium concn. Builds up in the D 2O moderator liquid
to a practical eq. conc. Of about 40 Ci/kg, with a typical tritium prodn. Rate of 2.4 k
Ci/Mwe over many years of operation.
Tritium level in moderator should not exceed 3 ci/lit for personal safety and
operational efficiency of D2O moderator coupled with environmental restrictions.
Tritium recovery processes:
a. Catalystic exchange of DTO with O2 gas to produce DT and D2O followed by cryogenic
distillation to separate tritium in concentrated form (>90%).
b. Electrolysis of D2O/DTO to D2/DT and O2 followed by cryogenic distillation to separate
tritium in concn. form (>90%).
Tritium prodn. Processes:
1. Water Distillation: In spite of simplicity, dependability, not competitive because of its low
separate factor ( more plant volume, less recovery
besides handling of tritium in the most hazardous form – liq. DTO (This is as compared
to DT gas since the DAC values for DT in air is always higher than DTO (liq).
2. Electrolysis; High separate factor – 2.0. But not considered because (a) large inventory
(b) direct utilization of energy in costliest form (c) handling of DTO liq – most hazardous
form of ‘T2’.
3. Chemical Exchange followed by cryogenic distillation:Cryogenic distillation procedure is
the one and only process for enrichment of T2 if the desired concn. Of >90% is to be
achieved. Handling of DT gas instead of DTO and that too in a double containment is
safer. In this process, DTO (l) in liquid form is being handled only during chemical
exchange and for less duration compared to the time dealt in other processes. Energy
consumption is not excessive.
New Detriation: Chemical Exchange: This moderator D2O and pure D2 gas are
allowed to counter currently pass thro’ a column having hydrophobic catalyst. This
catalyst used in PLATINISED ACTIVATED CHARCOAL (or) PALLADIUM –
ACTIVIATED CHARCOAL coated with PTFE so as to have hydrophobicity. Earlier,
only platinum (or) palladium activated charcoal was used (without PTFE coating)
and hence this chemical exchange was being carried out at very high temp. and
pressure (200oC, 2.73 kg/cm). As water to the liquid form poisons the catalyst. This
made the process energy intensive, and cumbersome. Later, hydrophobic catalyst
was developed and this is suitable for carrying out chemical exchange at ambient
conditions, it was developed in hall I of BARC.

(l) DTO + D2(g) D2O (l) + DT (g)

Option L/G = 0.2, % of recovery - 90%
 In the plant scale, 3 stage catalytic exch. Columns may be required for achieving the
desired detriation factor.

Detriation factor =

Mod.D2O DT to catalyst
counter
DTO(5 ci/lit) 1.5ppm Pt activated
charcoal (or) Coated with
( =0.6) PTFE Pd
activated charcoal
2M hydrophobic catalyst

D2
Drier (L/G = 0.2)
D2O 0.5ci/lit
(0.15 ppm)
De-oxo catalyst

O2 tower

D2 gas
Electrolyte
Test set up for Detritiation
cell

D2O
T mci/lit Inlet T mci/lit Outlet Detriation factor % recovery
5420 960 5.65 82
4005 532 7.59 86
2060 200 10.3 90
Cryogenic Distillation: radioactivity + flammable gases → H2, O2& T2. All are austenitic
S.S. as it is the most suitable material for cryogenic conditions and also for TRITIUM
Embrittlement.
Helium refrigeration unit for providing cooling medium in the condensers. Turbo
molecular pumps for pulling high vacuum between double containment of cold box
where houses distillation columns .Cold box is double walled vessel made of S.S. This
double containment also helps in preventing any radioactivity release to the
environment. All are welded joints.Min. 240 theoretical stages are required for enriching
tritium which is in ppm range to >90%. It is carried out in 3 stage cascade. Tower
internals → structured packing made of S.S.
>90% concentrated tritium is drawn off from bottom of column and would be
immobilized in the matrix of metal tritide which is compact, safe and stable at normal
temps. The T2 gas can be recovered at any firm by heating, the metal tritide, the
reaction being reversible.
The OPTG parameters of distillation columns.

1.2 ata – 1.5 ata, 25oK – 27oK

H2 to catalyst…..
25oK
DTO DT gas 1.2
atn He

He

Pt-C-PTFEcold box
2
Feed Hydrophobi =1.2
c catalyst (I/T)
Catalyst bed
Mod D2O D2 gas 1.5 atn

27oK
Detriated D2OExch.column
He T2

Distillation column (3rd stage)

D2O Processes:
H2 – H2O bithermal 19 Sp.Energy
Amine – H2 11 Sp. Energy
HT → 40oC → thermal decomposition potassium methyl chloride catalyst at >40oC
CT → 60oC → Basis reaction proceeds with sufficient speed.
Amine H2 = It is several times faster than NH3-H2 exchange because of lower activation
energy – Methylamine – H2 process has high separation factor ( c = 8.02, h = 3.46)
– THE HIGHEST OF ALL known feasible exchange processes, faster rates and hence it
has high recovery and need much smaller intra tower flows. So, energy requirement is
the lowest of all the processes considered for commercial exploitation. recovery = 85%.
Disadvantage: The processes chemistry of amine – H2 exch. Is much more complex
than that for NH3-H2 system and hence the operational problems are enormous. The
decomposition products have very low solubility in amine and might deposit all over the
equipment leading to very serious clogging problems.
H2-H2O: C.T ( =3.8) →30oC, H.T ( = 2.4) →200oC Ho2O(l) + HD(g) ⇌ HDO(l)
+ H2(g) 30
Over all separation factor of bithermal H2-H2O with CT atC30oC, HT at 200oC is 1.9. A
high operating pressure is required to restrict water to liquid
200ophase
C in hot tower condns.
(200 C) and to increase thro’ put. So the catalyst chosen should withstand these
o

temps. And pressures. Hydrophobic catalyst → PE – C – PTFE (Platinum activated

charcoal coated with PTFE (Poly tetra fluoro ethyli…) [0.1:0.9:99 = Pt : C: PTFE].
At high pressures [ 7 kg/cm2g] water enters the pores of the catalyst and making it
inactive. So, the catalyst in the present form is not suitable for appln. At higher
pressures. Efforts are being made to suitably modify the procedure for making catalyst
so as to control the porosity.

Uranium Extractions: uranium ore pitchblends, Uraninite, uranium ore typically

contain a small amount of uranium bearing minerals, so initial extraction &
concentration steps are reqd. physical separation steps (gravity, floatation,
electrostation etc.) are not useful for uranium. HYDROMETALLURGICAL extraction
(as Leaching) is the useful first step in ore processing.
Acid leaching procedure for uranium extraction: The pitchblend ore is broken up and
roasted to dehydrate it, remove carbonaceous materials, oxidises sulfur compounds
to sulfates and oxidises any other reductant that may interfere in the subsequent
leaching operations.
It is then mixed up with H2SO4,and HNO3 acids. Uranium dissolves to from uranyl
sulfate UO2SO4, radium and other metals in pitchblende are precipitated as sulfates.
Then NaOH is added, Uranium is pptd. as Sodium diuranate, Na2U2O7 6H2O, known
as YELLOW CAKE.

Up to now, steps:
roast +H2SO4
Pitchblends To remove, H2O, carbonceas UO2SO4
broke …….. to +HN
down to pieces ixidizing SO4 O3 Yellow cake, +NaO
H
Na2U2O7.6H2O
 These classical methods of extracting uranium from its ore are now supplemented in
current practice by such procedures as (SX) Solvent Extractions, Ion Exchange and
Volatility methods.
In solvent extraction processes, the uranium ore is removed from acidic ore leach-
liquors by extracting with a solvent mixture such as Tributyl phosphate in kerosene.
In modern industrial ore extraction methods, alkyl phosphoric acids – eg. Di (2-ethyl
hexyl) phosphoric acid (D2EHPA) – and secondary and tertiary alkyl amines are the
usual solvents.
As a general rule, SX is preferred over Ion-Exchange methods for acidic leachates
containing more than one gram per liter.
URANIUM, meeting nuclear-grade specifications is usually obtained from yellow
cake thro’ an additional solvent extraction step using the TBP SX process. First, the
yellow cake is dissolved in HNO3 to prepare a feed solution. Uranium is then
selectively, extracted from this acid feed by TBP diluted with kerosene or some other
suitable hydrocarbon mixture. Finally, uranium is stripped from the TBP extract into
acidified water to yield a highly purified uranyl nitrate.
This uranyl nitrate is calcined to form UO3, which is reduced in furnaces under a H2
atmosphere to UO2. This UO2 is converted to UF4 with anhydrous HF.
TB
Yellow Cake (Na2U2O7.6H2O + P
HNO3 Extraction calcinatio
→ Uranyl Nitrate
UO3 Kerosene n
+H H2 atoms
(Uranium Tetra Flouride) UF4 UO2F
Reduction in
UF4 is then reduced with Mg at 1300oC in a ‘bomb’ (steel container refractory
furnace lined) –
Exothermic reaction – called Thirmite reaction (process – Thermite process). UF4 + Mg
→ MgF2 + U. MgF2 slag separates and floats on the top. While this bomb is cooled to
30oC, Uranium metal ingot (or) ‘button’ is obtained, which despite its H 2 content is the
best quality uranium metal available commercially – rolled into fuel shapes for Nuclear
Reactors.
In Nutshell:
Pitchblends Drying toHremove
2SO4 H 2O NaO UO 2SO4
Or
Na2U2O7.6H2O yellow cake (sodium HNO H
S→ SO4 - -
Diurante)
roating 3

Dissolved
Na2U2O7.6H2O yellow cake Extraction calcination
feed solution
Uranyl Nitrate HNO3 TBP +
coo reduction Kerosene
U U + MgF2 HF UF4 Redn.in furnace UO2
UO3 l Mg, 1300oC Anhydrous In H2 atoms
Thinitereaction HF
exothermic
To Nuclear reactors
Slag ,floats ,filter
BEP :– 3 stage cascade. I stage – 2 streams, each having six columns, 10B gets
enriched from 20% to 33%, Second stage is having six columns, 33% 10B to 49% 10B.
3rd stage – small in size (dia, ht is the same as 1st, 2nd stage) – six columns – 49% 10B
to 65% 10B
BEP & EBP: IGCAR
Natural abundance of B10 = 20% atom B11 = 80% atom, 10B is used in control rods
because of its high neutron absorption cross section & high temp. stability.
Thermal neutron absorption cross section B10 = 3850 barn, B11 = 0.005 barn
Natural Boron = 752 barn.
Among chemical exchange, distillation, in exchange chromatography, gaseous
diffusion, gas centrifuge and loser isotope separation process only industrially viable
methods are distillation and Ion Exchange Chromatography.
- In the process of distillation, DME-BF3 complex is distilled in a packed distillation column
operating under vacuum and the conditions of total/partial reflux. The preferential
exchange affinity of B10 in the liquid phase is taken advantage of and the complex
gradually enriched in B10 in the reboiler. Cascading has been done to get desired concn.
At desired rate. But the distillation process has many disadvantages like flammability
and corrosive nature of the feed material (BF3-DME complex), requirement of vacuum,
and uninterrupted power supply. On the otherhand, due to flexibility of operation in Ion-
Exchange chromatography has been set up.
- Ion Exchange: An SBA strong base type IV resin is first converted to hydroxyl form.
After thorough washing with DM water, it is loaded with natural borate ions either as
boric acid (or) any of its complexes. The process of displacement chromatography is
used for enrichment of B10 and displaced with strong (HCl) acid. Borate band is moved
from one column to the other in a battery of IE columns. During the borate band
movement, the rear end of the borate band is enriched in B10 isotope due to its higher
exchange affinity compared to B11 isotope. The exhausted resin in chloride form is then
regenerated to OH – form and put back in service to facilitate continuous band
movement.
- Eq. time for BEP by distillation = 100 days.
- Eq time for BEP = 18 months
- Eq. time for 18O = 24 months.
The product is eluted out of the band as enriched boric acid solution. After achieving
the desired enrichment, the front end of the band is connected to reject column and
the rear (enriched) end of the band is transferred to product drum. An equivalent
amount of boric acid is introduced into the band, at the location of matching isotopic
conc’s to achieve the desired length of borate band. These operations are repeated
at the end of every batch.
NaOH – regenerant for resin bed
HCl – for movement of band.
220 kg/Anu of 65% B10 EBP Elemental Boron Plant ; Fee: Boric Acid.
Three steps are involved:
1. Conversion of Boric Acid to KBF4 (Potassium fluoroborate) and precipitation of KBF4:-
The enriched boric acid powder (65% B10) will be dissolved in HF and cooled to 5oC in a
reactor vessel. KOH will be added. Mixture is subjected to gentle stirring to settling.
 H3BO3 (S) + HF (L) → HBF3 (L) + H2O (L)
HBF3 (L) + KOH (L) → KBF4 (S) + H2O (L)

Solution of KBF4 in water is gelatinous having µ of 500 centipoise. It is filtered to filter

out KBF4, this KBF4 is washed with acitone/alchohol. It is then dried under vacuum to
reduce moisture level to <1%.

2. Electro winning: Mixture of Salts: 18% KBF4 + 70% KCl + 12% KF. This mixture is dried
at room temp. by evacuation and Argon flushing. Then it is subjected to degassing at
250oC with vacuum up to 10-3 torr to moisture level of 0.02%. Further salt is subjected to
drying at 300oC to remove moisture to ppm level. Then the whole charge is melted in a
furnace at 800-850oC to eliminate dissolved gases and volatile matter and to
homogenize the mixture. Then it is cooled and charged to electrolytic cell.
Boron Analysis: TIMS – Thermal Ionisation Mass Spectrometer
ICPMS – Inductively Coupled Plasma Mass Spectrometer
The cell holds the charge in graphite crucible. Cell has MS cathode and graphite
anode. Pre-electrolysis is done by maintaining cell voltage at 1.2 to 1.5v. This is done
to remove gaseous impurities present in the molten salt, evolving at graphite electrode.
This voltage is slowly increased from 1.5 v to 4.5v with current density of 0.3 to 0.5
amp/cm2. The duration of electrolysis depends on the boron content of electrolyte.
Approx. 9 gr/hr. of boron will be deposited on MS Cathode.
Reactions in the cells:
KBF4 → KF + BF3
BF3 → B(cathode) + 3/2 F2
3/2 F2 + KCl → KF + 3/2 Cl2 (anode)
Boron is electro deposited at cathode and Cl2 is liberated at the anode. This Cl2 gas
liberated at the anode is removed continuously by purging with high purity, Argon. Cl 2 is
absorbed in water using absorber
Finally the charge will be stripped once the boron contact in the mass falls below
100ppm (current drops from 70 amp initially to 40-50 amps). This KF rich spent
electrolyte is recycled after recovery of Boron by using Boron selective anion resin to
reduce boron losses. The tripped boron in resin will be recovered in the form of Hydro
fluoroboric (HBF4) acid by eluting with HCl. This HBF4 is converted to potassium fluoro
borate KBF4 by treating with KOH. This KBF4 formed is recycled for further processing
after moisture removed.
Purification: This elemental boron collected on cathode surface is washed using hot DM
water at 60oC and is collected from cathode by gentle scrapping. Collected boron
powder will have iron impurity ingresses for cathode. This product is subjected to
recycled leaching with HCl at 80-100oC for removal of iron. This iron free boron powder
is filtered, DM water washed, dried with methanol/acetone, further vacuum dried. Final
Boron powder is collected under Argon blanketing.
 compressor s CORROSION & MATERIALS OF CONSTRUCTION

 ASTM A516 Gr 70 for plates (from vessels, towers)

 ASTM A333 for pipes.

Major Corrosion type in H2S – H2O System: Uniform corrosion, SCC and blistering.

Carbon Steel gets attacked by aq. Solution of H2S according to the reaction:

Fe + H2S FeS + 2H + FeS + H2

The hydrogen liberated in nascent form combines to form molecular Hydrogen and FeS forms a
protection film. The rate of attack decreases to acceptable limits after formation of stable
protection iron sulfide film.

Iron sulfide film type: Mackinwite, Troilite, Marcasiti, pyrrhotite, Pyrite (FeS2),

Mackinwite, Troilite, and Marcasiti: They have a low but inverse solubility in water with strong
temp. dependence. Solubility α (1 / Temperature)

Because of this, they dissolve in water at low temp. and deposit in hot sections (iron transport).

Pyrrhotite and Pyrite solubility in water is very less and they also don’t depend on temperature.

Carbon steel corrosion mechanism with H2S:

Initial corrosion product of C.S. is Mackinwite (FeS0.83) which is not at all protective, and
transforms to Troilite (FeS) and then to Pyrrhotite (Fe0.8S) and Pyrite (FeS2), which are
protective films.

The rate of transformation is influenced significantly by the process conditions like pH,
temperature, liquid velocity and concentration of dissolved iron, ppm of H2S.

500 hours - Mackinwite (traces) + Pyrite + pyrrhotite (75%)

700 hours - Mackinwite (traces) + Pyrite + pyrrhotite (90%)
1000 hours - Pyrite + pyrrhotite (95%)

The corrosion rates are low only, when the Pyrite & Pyrrohotite content of the film is stable. But
whenever there is splash, impingement (or) turbulent flow, the protection film breaks and a fresh
film is prevented from forming. So, Carbon steel corrodes rapidly. Where such above conditions
exist, Ex. Sieve trays, heat exchanger tubes, S.S. is used. This also applies to parts eroded by
spray impingement (or) by high liquid velocity, such as centrifugal pump, throttle valves liquid
velocity is limited to <7 ft/sec.

H2 Blistering: Some of the nascent, H2 that is formed in the reaction of H2S with steel, is
diffused into the crystalline structure of steel and thus greatly diminishes the breaking strength.
 This nascent hydrogen then returns to the molecular state and builds up in the points of
discontinuity of the metal. This molecular H2 exerts pressure and blisters will develop. This is
why careful Ultra Sound examination must be made of all the steel laminates. So as to ensure
that there are no flaws in which H2 might reside, this consequently ruptures the metal. C.S, Low
alloy steel and S.S. must therefore be suitably heat treated to relieve stresses that may result from
fabrication procedures. If this is not done, failure may occur due to H2 embrittlement or to SCC.
Carbon Steels are satisfactory if anneals according to ASTM boiler code.
Austenitic S.S. that have been cold worked must quench anneals at 1800 to 2000oF.
BOLTS, made up of low alloy steel – can crack in H2S environment because of SCC. Both must
be heat treated after mechanizing to reduce hardness below a critical max., strength limited to
40,000 PSI.
MINIMUM THICKNESS HOLES are to be provided for piping > 3” to ensure that corrosion of
piping does not lead to large release of H2S. These holes about 1/8” in diameter are drilled about
half way thro’ the wall from the inside. Loss of metal in the inside of the pipe which result in a
small but detectable leakages thro’ the test holes where structural strength is still adequate to
withstand the operating pressure.

Stress Corrosion Cracking: Both inter-granular & trans-granular SCC of SS are observed in H2S
– H2O system.

Intergranular SCC is encountered when sensitized S.S. are exposed to sulfuric acid which is
formed by the interaction of sulfide moisture and oxygen. Sensitization occurs when Chromium
carbide precipitates along the grain boundary during welding or heat treatment. SS 304, 316
have been known to have failed when heated to 650 – 760oC with a solution of H2S and air.
SS304 –L resist sensitization. SS 321, 347 contain carbide stabilisers also resort sensitization.
Trans granular SCC occurs in S.S in the presence of H2S, Chlorides and air (O2) at ambient
temp.

PITTING: Pitting corrosion of S.S is quite severe in solution containing H2S, chlorides and O2.
Mo bearing S.S (S.S. 316) have a better resistance to pitting as compared to SS304.

FILM FORMATION
Several different phases of Iron Sulfide form as a result of interaction between aqueous
H2S solution solutions and carbon steel. Many of these phases have been identified in G.S.
HWP scales and pm CARBON STEEL COUPONS exposed to similar conditions:
Phase Formula Crystalline Structure
S
Mackinawite FeS(1-x) Fe(1+x) Tetragonal (X=0.2)
Cubic Iron Sulfide FeS Cubic
TRIOLITE FeS Hexagonal
PYRRHOTITE Fe(1-x)S X = 0.2 Hexagonal and Monoclinic
Greigite Fe3S4 Cubic (Spinel)
Marcasite FeS2 Orthorhombic
Pyrite FeS2 Cubic

The dissolution products of Iron Sulphide that form as corrosion products of carbon steel
in G.S plants are transported from lower to higher temperature zones of the heat exchangers and
XU towers, where a subsequent deposition in some critical areas results in a loss of production.
Therefore, it seemed desirable to study the role of the solubility and dissolution rate of different
Iron Sulphides in such transport.
The majority of values of Fes solubility at 20oC are in the range of 10-5 to 10-4 mol/kg.
Most often seen phases in G.S. plant are … Mackinawite FeS(1-x),Troilite FeS and Pyrite
FeS2.
IMPORTANT FACTS & FIGURES:
TOTAL AREA = 6880 m2
Film = 300 gr/m2
01. Film formation is done at 120 – 130oC at H2S partial pressure of 1.0 kg/cm2g. Approximately, it
takes 500 hours for STABLE FILM FORMATION.

02. AT HIGH FLUID VELOCITY → MACKINAWITE FeS(1-x); Triolite FeS are formed.

03. AT LOW VELOCITYIES AND STAGNATION → PYRRHOTITE FeS; PYRITE FES2 are formed.

04. ONCE PROTECTIVE FILM IS FORMED, FURTHER CORROSION DEPENDS ON HS- thin film to metal
and Fe+ + ions reaching from metal to aqueous Solution through the film.

05. PRESENCE OF INERTS DURING FILM FORMATION MAY INCREASE THE POROSITY OF THE FILM
Formed AND INCREASE CORROSION RATE (Transfer of HS- and Fe+ + ions.

06. LOW temperature and GAS PHASE ARE NOT FAVOURABLE FOR FILM FORMATION (Adherent film
formation).

07. PROCESS CONDITIONS INCLUDE Dissolved IRON CONTENT, LIUQID VELOCITY, P H and
temperature were found to influence the rate of transportation of iron from one place to
another.

08. For a very stable and adherent Sulphide film formation on the C.S. in H2S-H2O system, the
composition of the Sulphidefilm should be about 90% of pyrrite and PYRRHOTITE.

SOLUBILITY:
(SOLUBILITY OF MACKINAWITE and Triolite) ↓
as pH and Temperature
a. Mackinawite(FeS(1-x)):

Among all the Iron Sulphides, the solubility of Mackinawite is the HIGHEST.

At 25oC and 0.1 MPa H2Spressure, the observed values of solubility range from 0.2 x 10-3 mol/kg.

The solubility of Mackinawite at temperature >25oC could not be accurately determined due to
its rapid trans. Mackinawite has a negative temperature coefficient of solubility. All the values
measured at T=120oC were in the range of 10-5 – 10-6 mol/kg, obviously lower than those
measured at 25oC. Hence, solubility of FeS(1 –x ) ↓ as temperature .
 b. TRIOLITE (FeS): Solubility of FeS decreases with increased temperatures. Solubility ↓ as T
(Hence 130oC maint.)

c. Pyrrhotite:- (monoclinic): As triolite, for phyrrhotite also, the concentration Of dissolved Fe+ +
is affected only slightly by H2S pressure. The solubility decreases at higher temperatures. But
the difference between the value at 25oC and that at 120oC is only a factor of two (4.0 x 10-6
mol/kg and 2.0 x 10-6 respectively). The solubility of monoclinic pyrrhotite is lower than that of
troilite by about a factor of two at the corresponding temperatures.

d. Pyrrhotite (hexagonal): The solubility of hexagonal pyrrhotite was found to be (1.5 1.0) x 10-6
mol/kg at 25oC and 1.8 MPa H2S pressure. When the temperature was raised to 120oC, the Fe+ +
concentrationdid not change significantly. However, when the temperature was lowered back
to 25oC, the dissolved Iron concentrationdecreased, and decreased further on subsequent
heating. The explanation for these observations may be the conversion of hexagonal pyrrhotite
to pyrite phase during heating.

Advantages of Stages:

Single Stage Two Stage Three Stage

1. Relative total volume → 1 0.7 0.6

2. Relative process inventory → 1 0.12 0.05

If any problem comes in the plant, this calls for plant shutdown. On the other hand, if
staging is done, we can isolate the affected section and keep the other sections in operation.
(i.e. operational convenience).
 35
30
Corrosion 25
Rate MPY20
15
5

100 200 500 700 900 1000

Exposure period hours.

e) PYRITE (FeS2): The solubility of PYRITE was very low and at the limit of capability of Fe+ +
detection. Also no noticeable change (in solubility) was observed in the dissolved iron
concentration values at 1.8 MPa and 0.1 MPa H2S pressures.
The solubility values at different temperatures were almost constant.
2. EFFECT OF pH and phosphate on solubility:
a. Effect of added acid or base:
The dissolved Fe+ + concentrationdiffer significantly with the pH
SOLUBILITY OF IRON SULFIDES ↓ pH .
The solubility of Iron Sulfides decrease with increasing pH. TRIOLITE has the sharpest
decrease with increasing pH, followed by Mackinawite and Pyrrhotite.
For e.g. an increase in pH from 3.5 to 4.0 reduces the dissolved Iron concentration by a
factor of 10 for triolite 5 for Mackinawite and 2 to 3 for Pyrrhotite respectively at 25oC
and 0.1 MPa H2S pressure.
For Pyrite, the observed effect of pH is least.
There are two possible explanations: (1) The solubility of Pyrite does not change with pH
or (2) the solubility is below the detection limit.
b. Effect of added Phosphate: At 0.1 MPa H2S pressure with 10 g/gr Phosphate added to the
system, the dissolved iron concentrations from Pyrrhotite to Pyrite do not change as compared
with the values when no phosphate is present.
But there was a slight decrease in the solubility of triolite (<10%) but this decrease is
accounted for by the slight rise in the PH (<0.1)of the system with added phosphate.
Therefore, addn. of phosphate does not affect the solubility of iron sulfides under conditions
similar to those in G.S. process.
B

FLARE
H2S after burning in flare will get converted to SO2. SO2 is also lethal. It may also
explode.
But there is one advantage. By burning H2S, because of its velocity at the tip of nozzle,
we can achieve some height (126 m + Height achieved with velocity head) and also, because of
high temperatures, at the tip, the dispersion of gases will be very high. Because of these two
factors (1 → height, (2) → dispersion), we can avoid settling of H2S or SO2 at the ground level
and also we can reduce the GLC (ground level concentration).
 How do you design a flare: For the design of flare, we will take Maximum dumping into
consideration. Depending on the velocity of dump, nozzle diametermeter will be fixed by LPG
and height will be fixed by the Gaussian dispersion formula using the explosive limits of H2S.
What is Gaussian dispersion formula?
EXPLOSION LIMITS
LEL UEL Auto Ignition TLV TWA
H2S 4.3% 46% in air 262oC 10 ppm
SO2 2 ppm
LPG 1.6% 9.5% in air 800oF
NH3 16% 25% in air 1204oF 25 ppm
H2 4% 74.2% in air 1035oF
Cl2 1 ppm
CO→ 12.5% 74.2% o
1128 F 50 ppm
CO2→ 5000 ppm
SO2→ 2 ppm
NaOH→ 2 mg/M3
Cao 5 mg/M3
Freon 0.01 ppm

LPG Flare tip temp = 1980oC (Max.)

Freon → TLV – 0.01 ppm
Freezing point of H2S: -
Latent heat of evaporation: 132 Cal/Gram
Water Treatment

Hydrogen bonding. Bond angle = 105o

Because of Hydrogen bonding, bond energy is very high. Energy required to rupture the
hydrogen bond and liberate a molecule of H2O to form vapour is much greater than for other
common compounds. Hence, the water vapor-steam has high energy content. Also, water
release more heat upon freezing than do the other compounds. Because of Hydrogen bonding,
the freezing of water is unusual compared to other liquids. Hydrogen bond produces a crystal
arrangement that causes ice to expand beyond its original liquid volume so that ice density is less
than that of the liquid and ice floats.
Water has high surface tension because of Hydrogen bonding. Because of the high surface
tension, a needle with density about 7 times that of water, can be made float on the water.
Water molecules in contact with a crystal, orient themselves to neutralize the attractive forces
between ions in the crystal structure. The liberated ions are then hydrated by these water
molecules preventing them from recombining and recrystalizing.
Relation between Total Dissolved Solids and Conductivity:
As salts or other ionizing materials dissolve in water, electrical conductivity develops. Thus
conductivity of naturally occurring water provides a measure of their dissolve mineral content
TDS of water can be estimated from its specific conductance. The conversion factor is:

1.55 s conductance per mg per litre of TDS. CONDUCTIVITY: 1.55 X

OsmosisTDSand inReverse
MG/LIT Osmosis: If two aqueous solutions are separated by a membrane, water
will pass from the more dilute into the more concentration one. This important process controls
the performance of all living cells. This is called Osmotic flow of water and the process,
osmosis.
It (Osmosis) explain the effectiveness of food preservation by salting; the salt creates a strong
solution, disrupting the cells of organism that might cause food spoilage, or the water inside their
bodies leaves in an attempt dilute the external salt solution ,, there by killing them.
In specially designed membrane cells, the osmotic flow of water across the membrane can be
reversed by applying a sufficiently high pressure to the more concentrationentrate solution. This
process of reverse osmosis is a practical one for Desalination of Water.
CHELATION AND SEQUESTRATION OR THRESHOLD TREATMENT: (to prevent
deposits of CaCO3 scales, silt, and other scales)
A great important concentrationept to water chemistry is the process of CHELATION
A chelating agent is a molecule-usually organic-which is soluble in water and can undergo
reactions with metal ions to hold them in solution thus preventing scale formation.
So, chelation is analogous to Ion exchange, with the difference being the solubility of the
exchange material i.e. in chelation, the exchange material is very (highly) soluble in water as a
large molecule, whereas in Ion exchange, the exchange material is insoluble in water and is a
large solid particle.
The chemical equation for chelation is similar to that for Ion exchange. For e.g. Common
chelant is the Sodium salt of Ethylene Diametermine Tetra acetic Acid (EDTA).
Added to water, this chelant reacts with CALCIUM IONS to keep them in solution, preventing
the formation of CaCO3 scale:
Ca2+ + Na4EDTA → CaNa2EDTA + 2Na+
NOTE: There are a number of Natural Organic Materials in water which have chelating ability,
such as humic acid and lignin (=Natural chelants). Because of their chelatic ability, some
organic materials interfere with certain water softening processes (in Ion exchange, for e.g.).
Because of these organic materials deposition on the ion exchange resin, bed performance will
come down.
COOLING WATER TREATMENT PLANT:
NOW,
A variety SEQUESTRATION ALSO CALLED
of phosphate compounds THRESHOLD
called polyphosphates are used in this process to PREVENT
TREATMENT
FORMATION OF IRON, MANGANESE AND CaCO3 DEPOSITS.
How to get Poly Phosphate and why to use polyphosphate? Condensed phosphates are produced
by dehydration of one or more ortho phosphates (PO43-) compounds. If monosodium phosphate
is used, the condensed product is sodium meta phosphate
NaH2PO4 – H2O = NaPO4
The condensed phosphates form chains containing P-O-P group. Proper selection of raw
materials can produce long chains, called POLYPHOSPHATES. THE POLYPHOSPHATES
ARE CORROSION INHIBITORS, ANTISCALANT, ANTIFOULANTS or defoulants. Hence,
very useful.
These polyphosphates have strong electrostatic charges which resist hydration (reversion) to
original orthophosphate.
NOTE: Many bacteria like fungi are capable of Dehydration of orthophosphate to
polyphosphates.
THE MOST COMMONLY USED PRODUCT IS CALLED HEXA META PHOSPHATE
(NaPO3)6
Water containing a high concentration of CALCIUM that is in a condition to PRECIPITATE,
treated with ONLY 0.5 mg/L of Polyphosphate, can be kept from depositing CaCO3 scale. Thus
the amount of Polyphosphate required for effective SCALE CONTROL IS FAR LESS THAN
THAT required for softening on stoichiometric basis, hence the name THRESHOLD
TREATMENT.
POLYPHOSPHATES CAN ALSO HOLD Fe and Mn in SOLUTION (sequestration) in an
involvement where they would otherwise precipitate e.g. In presence of OXYGEN or
CHLORINE at a pH over 8.0. From this it is clear that Fe and Mn precipitate in presence of O 2
and also in presence of Cl2 at a pH over 8.0. If polyphosphate are present they will hold them in
solution and prevent precipitation.
OTHER properties of polyphosphates are also useful in water treatment. When CaCO3
precipitates in the presence of poly phosphate, the usual CALCITE CRYSTAL form is
deposited, and the scale structure is WEAK.
Also Because, POLY PHOSPHATES ARE STRONGLY CHARGED, POLY PHOSPHATE,
ADSORB ON SILT PARTICLES and help to keep them from settling because the individual
particles repel one another.
(Adsorption here means, Adhesion of a larger of molecules or colloidal particles to the surface of
a solid which is usually porous).
THUS, POLYPHOSPHATE, also prevent silt to settle on the exchange surfaces.
EFFECT OF pH, TEMPERATURE, PRESENCE OF OXIDES OF Heavy Metals including Iron
on POLY PHOSPHATES
The value of POLYPHOSPHATE is destroyed if this reverts to ORTHOPHOSPHATES
SOLUTIONS OF GLASSY (Non crystalline) Poly Phosphates REMAIN STABLE FOR
MONTHS. But in water system, they may be reverted to orthophosphates by:
1. Low pH

2. High temperatures.

3. Presence of Oxides of certain heavy metals including IRON.

NTOE:
1. Hardness: is the solution in water of both calcium and magnesium as cations, independent of
the nature of the anions present. Expressed in terms of CaCO3.

2. M-alkalinity (methyl orange alkalinity) exists when pH is below 4.2 – 4.0, P-alkalinity exists when
pH is over a range of 8.2 – 8.0

Source of Alkalinity and hardness:- Alkalinity of water is caused by dissolved bicarbonate

(HCO3-) salts.
Sources of Alkalinity and Hardness: The following equation show how water containing CO2
from the atmosphere and from respiration of soil organisms, dissolve Mg and Ca from a
common mineral, DOLOMITE (CaCO3, MgCO3) to produce HARDNESS AND
ALKALINITY:
H2O + CO2 + MgCO3 → Mg(HCO3)2 Mg2+ + 2(HCO3-)
H2O + CO2 + CaCO3 → Ca(HCO3)2 Ca2+ + 2(HCO3-)
Hardness of sea water is more? Why?
Higher the mineral content of water, higher the conduction. The higher the conductivity (the
more the corrosion), the less completely ionized are the minerals dissolved in water, as ions
are packed more closely together and collide more frequently. This decreases the activity
coefficient or freedom, increasing the solubility of CaCO3, MgCO3 and other slightly soluble
materials.
As a result, CaCO3 is more soluble in seal water than in fresh water under equal condition of
pH, temp, alkalinity.
TURBIDITY: Solid matters occur in waters as suspended solids and colloidal matter.
“The solids remaining with supernatant water above the settled matter are fine and called
TURBIDITY.
Turbidity is measured in NTU (Nephelometric Turbidity Units) and JTU (Jackson Turbidity
Units).
Turbidity standards 100 NTU = 40 JTU i.e. 1 NTU =
0.4 JTU
100 NTU = 40 JTU. This is from 325 Mesh diametertomaceous earth
JTU is measured with a transmitted light beam
NTU is measured by a light scattering.
Silica form hard scale on H.T. exchanger surface. SMALL turbid particles are negatively
changed. If these are neutralized, the particles are coagulated.
ORGANICS in water: Known as Lignin and Tannin → present in water as colloidal
suspension in water. Many organic compounds are soluble in water. There are several tests
to find out the organics. But is it difficult to distinguish between them.
Some of Tests for Organics in water:
1. B.O.D: Biochemical Oxygen Demand. It measures the ability of common bacteria to digest
organic matter. It is measured by depletion of Oxygen. This measures the BIODEGRADABLE
ORGANIC MATTER. Expressed as O2.

2. C.O.D: chemical oxygen demand: Measures the ability hot chromic acid solution to oxidize
organic matter. It measures both biodegradable and non-biodegradable organic matter.
Expressed as O2.

3. Color: It is a rough measure of Tannin, Lignin and other humic matter in surface waters –
Expressed in APHA Units, related to platinum standard.

4. IDOD: Immediameterte Dissolved O2 Demand: Measures the presence of strong reducing matter
in water. Expressed as O2.

5. T.O.C: Total Organic Carbon. Measures the CO2 produced from organics when water sample is
atomized into a consumption chamber. Reported as ‘C’.

SOME PROBLEMS, CAUSED BY WATER IMPURITIES

1. HARDNESS: (Ca, Mg)

a. Process Water:- Industries effected = all

How affected: - Scale and deposits.

b. Boiler Water:- Deposits = Major problem (very much effecting heat transfer coefficient)

Corrosion = ------------, other = ---------------

 c. Cooling Water:- Deposits = Major problem

Corrosion = ------------, other = ---------------

2. ALKALINITY:

a. Process Water :- Industries affected – Paper, Textile, Beverages

How affected: - Destroys acid, reagent, dyes, alum and flavour

b. Boiler Water :- Deposits = --------------

Corrosion = MAJOR problem (in steam condensate)

Others = ------------

c. Cooling Water:- Deposits = MAJOR problem

Corrosion = ---------, others = ---------------------------

3. Dissolved Solids:

a. Process Water: - Industries affected – Electronics, Utilities.

How affected: - Adds to the cost of making high-purity water

b. Boiler Water :- Deposits= ----------- Corrosion = NIL

Others = High blow down and thereby loss of heat

c. Cooling Water:- Deposits = ---------, Corrosion = Contributes

Others = High blow down and thereby loss of heat

4. SUSPENDED SOLIDS:

a. Process Water – Industries affected = all

How affected = Deposits, wear

b. Boiler Water – Deposits = Major problem

Corrosion = --------------Others = --------------------

c. Cooling Water – Deposits = MAJOR problem

Corrosion = ---------------, Others = ----------------------

5. DISSOLVED OXYGEN:
 a. Process Water – Industries affected = All

How affected = MAJOR CAUSE OF CORROSION.

b. Boiler Water – Deposits = --------------

Corrosion = MAJOR PROBLEM, Others = -------------------

c. Cooling Water – Deposits =

Corrosion = MAJOR PROBLEM, Others = -----------------

6. CO2 (in deep well water system)

a. Process Water – Industries affected = All

How affected = It may flash at well pump and cause scaling.

b. Boiler Water – Deposits = NIL

Corrosion: MAJOR PROBLEM (in steam condensate); Others = ----------------

c. Cooling Water – Deposits = -------------, Corrosion = -----------------------

Others = affects pH.

7. IRON AND Mn:-

a. Process Water – Industries affected = All

How affected = Deposits and discoloration

Paper and textile – stains fibers

b. Boiler Water – Deposits = MAJOR PROBLEMS

Corrosion = --------------- Others = ---------------------

c. Cooling Water – Deposits = MAJOR PROBLEMS

Corrosion = NIL, Others = ------------------

8. ORGANIC MATTER:
 a. Process Water – Industries affected = Food, Beverages, All

How affected: Tastes and odors, food for bacteria, fouls ion-exchange resins.

b. Boiler Water – Deposits = -------------- Corrosion: ------------------

Others = May cause foaming.

c. Cooling Water – Deposits = ------------------- Corrosion = ---------------------

Others = May cause foaming.

9. SILICA:

a. Process Water : Industries effected = ---------------

How affected = -----------------

b. Boiler Water – Deposits = Contribute to the problem

Corrosion = ----------------, Others = Major problem in steam turbine.

c. Cooling water = Deposits = Contribute to problem

Corrosion = ----------------- Others = ------------------------

10. MICRO ORGANISMS:

a. Process Water : Industries effected : All

How affected = Produces slimes and odors.

b. Boiler Water = Deposits = ---------------, Corrosion: -------------, Others = -----------

c. Cooling Water : Deposits = MAJOR PROBLEM

Corrosion = -----------------Others = -----------------

IMPURITIES CONTROL:
Process used for removal Chemical used
1. HARDNESS a. Precipitation Lime, Soda ash, Caustic,
Phosphate
b. Ion exchange Salt, Acid
2. ALKALINITY a. Precipitation Lime, Gypsum
b. Ion exchange Salt, Acid
c. Neutralization Acid
 3. CO2 a. Precipitation Lime
b. Ion exchange Caustic
c. Neutralization Lime, Caustic
d. Degasification None
4. Dissolved Solids a. Reverse Osmosis None
b. Reduction by removal of
separate components
adding to dissolved solid
5. Suspended Solids a. Coagulation, Alum, Aluminate, coagulant aids
flocculation,
Sedimentation
6. Iron and Mn a. Oxidation And filtration Chlorine, Lime
b. Precipitation Lime, Chlorine, Air
c. Ion exchange Salt, Acid
7. Silica a. Precipitation Iron, Salt, Magnesium
b. Ion exchange Caustic
8. Organic Matter a. Clarification Alum, Aluminate
b. Oxidation Chlorine
c. Adsorption Activated carbon
9. Oxygen a. Regasification None
b. Reduction Sulfite, Hydrazine
10. Microorganisms a. Clarification Various, coagulant, coagulant aid
b. Sterilization Chlorine, Sterilants, heat

SOLUBLE MATERIAL IN WATER SUPPLIES:

Class 1:- Primary Constituents – generally over 5 mg/l or 5 ppm
Bicarbonate Mg Na
Ca Organic Matter Sulfate
Chloride Silica Total dissolved solids.
 Class 2:- Secondary Constituents – generally over 0.1 mg/l or 0.1 ppm

Ammonia Iron Potassium

Borate Nitrate Strontium
Fluoride
Class 3:- Tertiary Constituents – Generally 0.01 mg/l
Al Cu Phosphate
Arsenic Pb Zn
Ba Li
Br - Mn
Class 4:- Trace Constituents – Generally 0.01 mg/l
Antimony Co Tin
Cd Hg Titanium
Class5:- Transient Constituents
Acidity – Alkalinity, Biological cycle, Fe2+, SO2, SO32-
Non Soluble Constituents in water supplies:
Class 1: Solids: - floating, settleable, suspended
Cass 2: Microbial Organisms:
Algae, Bacteria, Fungi, Viruses
BICARBONATE: (HCO3-) is the principal ALKALINE constituent of almost all water supplies,
generally in the range of 5 to 500 mg/l.
By Mon cho, alkalinity enters water through industrial and domestic detergents.
Cl- concentration in sea water = 30,000 ppm
Cl- concentration in fresh water supplies = 10 to 100 ppm
Mg Hardness of water is usually about 1/3rd of the total hardness
Ca hardness of water is usually about 2/3rd of the total hardness
(TH = 1/3 Mg + 2/3 Ca)
PC – 1, 2
Capacity = 3750 m3/hr. each
Hold up = 9376 m3 each
Detention time= 2 ½ hrs. Each
Bridge speed = 4.5 m/min.
Flash Mixer:
Capacity = 1733 m3/hr.
Retention time = 47 sec.
CLF – 1, 2, 3
Capacity = 1733 m3/hr. each
Retention time = 30 min. flocculation
= 152 min. clarifying
FB – 1 to 14 (12 + 1 + 1)
Capacity = 400 m3/hr.
Rate of filtration= 100 liters/sq.m/min
Filtration area = 67.2 m2
Normal P = 300 MMWG
Max. P = 1800 MMWG
COAGULATION AND FLOCCULATION
Turbid raw water contains suspended matter – both settleable solids, particles large enough to
settle quiescently and dispersed solids, particles which won’t readily settle.
A significant portion of these non-settleable solids may be colloidal. Each particle is stabilized
by negative electro charges on its surface, causing it to repel neighboring particles, just as
magnetic poles repel each other. Since this prevents these charged particles from combining to
form larger masses, called flocs, they do not settle.
Coagulation is the de-stabilization of these colloids by neutralizing the forces that keep them
apart. This is generally accomplished by adding chemical coagulant and applying mixing
energy.
Aluminium salts, iron salts or polyelectrolyte are the chemicals usually used.
The figure below shows how these chemicals reduce the electric charges on colloidal surfaces
allowing the colloidal particles to agglomerate into flocs. These initially small flocs join,
creating larger, settleable agglomerates. THE DESTABLISATION (I.E. CHARGE
NEUTRALISATION) IS COAGULATION. THE FLOC – BUILDING STAGE IS
FLOCCULATION.

Effective valves
Colloid
+-+-
+ ++
+--
+

(a) (b)

a) Coagulation: The addition of coagulant neutralizes charges by collapsing the ‘cloud’ surrounding
the colloids there by favoring agglomeration.

b) Flocculation: The bridging of the flocculates and agglomerated colloidal particles form settleable
particles.

Coagulation:-
Zeta Potential: is the measurement of force surrounding the colloidal particles. It is a
measure of strength of the particle charge.
In a pH range of 5-8, Zeta Potential ranges from -14 to -30 mv. The more negative the number,
the storage the particle charge. As zeta potential diminishes, the particles can approach one
another more closely, increasing the likelihood of corrosion.
In a conventional clarification system at a pH of 6 to 8, coagulants provide the +ve charges to
reduce the zeta potential.
Coagulation occurs usually at a zeta potential which is still slightly –ve, so complete charge
neutralization is not required. If too much coagulant is added, the particles surface will become
+vely charged (i.e. a +ve zeta potential) and the particle will be redispersed.
 Zeta potential can be found out using certain instruments but Jar test method is the best method
of coagulant selection.
FLOCCULATION:- The floc formed by the agglomeration of several colloids may not be large
enough to settle or dewater at desired rate. A flocculent gathers together floc particles in a net,
bridging from one surface to another and binding the individual particles into a large
agglomerates.
ALUM, Iron Salts, and high M.W. polymers are common flocculants.
Flocculation is promoted by SLOW MIXING. Wheel brings the flocs gently together. Too high
a velocity tears them apart.
CONSTRAINTS BETWEEN COAGULATION & FLOCCULATION:
Variable Conditions Coagulation Flocculation
1. Nature of solids Numerous, fine particulates Scattered, large gels
2. Type of chemical applied Low Mol. Wt. change High mol.wt. particle bind
neutralization
3. Energy requirement RAPID mixing SLOW mixing
4. Velocity of gradient High Low
between particles

Particle 1
V1 = 2.25 ft/sec
0.01 V = 0.25
ft Particle 2 ft/sec
V2 = 2.5 ft/sec

VG factor (shear rate) = =

G-Factor = in sec-1
P = Power input for mixing ft lb/sec (watts)
V = Volume in process ft3 (M3)
= Viscosity (lb) (sec)/ft2
Recommended G factor for most coagulation units = 900 sec-1 for a 30 sec mixing time
established by bench test.
Recommended G factor for flocculation = 50 for cold water to 200 for hot water
COAGULATION AND FLOCCULATION CHEMICALS:
METAL COAGULANTS (Alum and Iron Salts) have been most widely used in water
clarification (THESE PRODUCTS FUNCTION BOTH AS COAGULANTS AND
FLOCCULANTS.
When added to water, they form +vely charged species in the typical pH range for clarification,
about 6-7. This hydrolysis reaction produces insoluble gelatinous Aluminum or ferric hydroxide.
Al2(SO4)3 + 6H2O 2Al(OH)3 ↓ + 3H2SO4
FeCl3 + 3H2O Fe (OH)3 ↓ + 3HCl
The byproducts are Hydroxide Precipitate and Mineral acids, the latter (acids) react with
Alkalinity in the water, reducing pH and producing 2nd byproduct, CO2. Sometimes, the gaseous
CO2 by-product interferes with the coagulation process by coming out of solution, absorbing on
the hydrous precipitate, and causing floc floatation rather than settling.
Hence, Poly aluminium chloride, (wide use in Japan) avoids the problem of alkalinity reduction.
When this material hydrolyzes, the flocs formed incorporates the Cl- ion into the floc structure so
it is not available to produce acid, reduce alkalinity and form byproduct CO2.
METAL COAGULANTS ARE PARTICULARLY SESITIVE TO pH and ALKALINITY. If
pH is not in the proper range, clarification is poor, and Iron or Aluminum may be ………. (lost
in binding)
1. Filtered Water Quality:

P – Alkalinity = NIL
M – Alkalinity = 200 ppm CaCO3
SiO2 = 16.5 ppm
T = < 1NTU
pH = 7.5 to 8.5
2. DM Water Quality:

Dissolved CO2 = <5ppm

T = < 1NTU

SiO2 = 16.5 ppm

TH = NIL

THE LOWER THE COAGULANT DOSAGE the more sensitive the floc is to pH changes (see
fig. below)

Solid line →
20 mg/l alum
Residual
Turbidity Split line →
40JTU
mg/l alum
Dots line →
60 mg/l alum

6.0 7.0
8.0almost constant, but the pH range becomes less restrictive as coagulant
The optimum pH remain
dosage increases.
POLY ELECTROLYTES: are large water-soluble organic molecules made up of small building
blocks called Monomers, repeated in long chain. They usually incorporate in this structure, ion
exchange which give the molecule on ionic change. Those having the charge are cations and
these with a –ve charge are anionic.
These molecules react with colloidal material in the water by neutralizing charge or by bridging
(tying together) individual particles to form a visible, insoluble precipitate floc.
These materials can also be produced with ionic charge, these are called nonionic polymers.
Although they are not, strictly speaking, polyelectrolytes, nonionic polymers exhibit many of the
same flocculating preps. in solution, and are generally considered as rate of poly family.
The cationic poly electrolytes are either poly arrives or quaternary arrives. In water poly arrive
hydrolysis as follow
R R
NH + H2O → NH H+ + OH-
R R
Because of hydrolysis to yield OH-, at high pH, the reaction shifts to left, and the polymer
becomes NONIONIC.
Tertiary polyamine
Coagulant charge quaternary
polymer
(Exchange capacity)
pH

In contrast, the quaternary polymers are bent slightly affected by pH (see graph above)
remaining +ve charged over a broad pH range.
The ANIONIC POLYMER INCORPORATE A CARBOXYL group (-COOH) in their structure.
These ionize in the following manner.
R – COOH R – COO- + H+
+
The H ion forces the reaction to left, so anionics become nonionic at LOW pH.
High M.W. nonionic polymers are effective flocculants in many streams because of their ability
to attract and hold colloidal particles at polar sites on the molecule.
LES SLUDGE IS GENERATED BY ORGANIC POLYMER THAN BY INORGANIC SALT
(ALUM ETC.), SINCE THESE DO NOT ADD WEIGHT OTHER or CHEMICALLY
COMBINE WITH OTHER IONS IN THE WATER TO FORM A PRECIPITATE. ALSO
ORGANIC POLYMERS DO NOT AFFECT THE pH OF THE WATER AND GENERALLY
DO NOT REQUIRE pH ADJUSTMENT FOR EFFECTIVE USE.
So as a general rule, CATIONICS ARE DESIGNED TO WORK AT LOW pH AND
ANIONICS AT HIGH pH.
NONIONICS AND QUATERNERIES ARE ONLY SLIGHTLY INFLUENCE BY pH
But it should not be understood that CATIONICS do not work at high pH and anionics at low
pH. They may produce good results at low or high pH.
ORGANIC POLYMERS USED IN WATER TREATMENT ARE OF TWO MAJOR TYPES,
COAGULANTS AND FLOCCULANTS.
COAGULANTS are +vely charged (CATIONIC only) molecular of RELATIVELY LOW Mol.
Wt. These are not effective flocculants. FLOCCULANT polymers have much higher mol. Wt.
providing long bridges between small flocs to enhance particle growth. FLOCCULANTS ARE
EITHER CATIONIC, ANIONIC OR NONIONIC.
 ION EXCHANGE
Ion Exchange removes unwanted ionsation from a raw water by transferring them to a solid
material, called ion exchanger, which accepts them while giving back an equivalent No. of a
desirable species stored on the ion exchanger skeleton.
The ion exchange has a limited capacity for storage of ions on its skeleton, called its
EXCHANGE CAPACITY.
The earliest Ion exchangers were inorganic sodium alumino silicates, some of which were
manufactured synthetically and other made by processing Natural greensand, which is a miner
called ZEOLITE, into more stable higher capacity forms. Even though these zeolites have only
limited use for water treatment, the name has persisted, and even synthetic organic ion
exchangers are after called zeolites.
Typical ion exchangers are in the form of beads, having an approximate size of 20 to 50 mesh
(0.8 to 0.3 mm)
Ion Exchange beads can be considered as SOLID SOLUTIONS. Chemist normally express
solution concentration in terms of Normality. 1 N solution contains 1 g. eq. of electrolyte per
liter of a solution.
The TYPICAL CATION EXCHANGERS HAS A NORMALITY OF APPROX. 2.0 and the
TYPICAL STRONG BASE ANION EXCHANGER has a NORMALITY OF APPROX. 1.3.
SAC NORMALITY = 2.0, WAC = 2.8 N (60 K/L)
CAPACITY is also expressed as Milli eq./Milliliter, which is same as Normality; mill eq./dry
gram, and kg/ft3.
The factor for conversion of NORMALITY to Kg/ft3 is 22 so that a cation exchange having a
normality of 2.0 has an exchange capacity of 44 kg/ft3.
Using normality as a basis for expressing the exchange capacity of an ion exchange material and
also for expressing the concentration of electrolytes in water, it is very easy to use the clan’s
expression.
VxNx = VwNw where
Vx : Vol. of exchange material
Nx : Normality of the exchanger
Vw : Vol. of water processed per cycle
Nw : Normality of exchangeable electrolytes in the water
Eg. If water having a total electrolyte content of 200 meq/L. as CaCO3 has a hardness of 150 m
eq./L, the normality of exchangeable electrolytes of this water is to be softened is 150/50 or 3 m
eq./L or 0.003 N. If this is softened through a CATION exchanger with a normality of 2.0, then
the

Theoretical Volumetric ratio = = = = = = 667 volumes of water per vol. of

bed.
See the graph below:

Resin Normality in m eq./L

2000
1000 2.0 N resin
M3 water process/
Volumetric ratio,

M3 exchanger
500
200
100
50 1.0W resin
20
10
100 200 300 400 500
Cw = concentration of exchangeable ion in water, meq. /L as CaCO3
(Cw/50 = solution concentration = Meq/L)

Volumetric ratio =
Most commercial ion exchangers are synthetic plastic material such as COPOLYMERS of
STYRENE AND DIVINYL BENZENE.
To produce CATION exchangers, the plastic is reacted with H2SO4. SULFONIC groups attach to
each Nucleus in the skeleton to provide an exchange site. This produces a strong electrolyte, for
which a typical reaction with cations in water is shown below:-
Na+ + R.SO3.H → R.SO3.Na + H+
The resin structure is represented by R.
The usual convention omits showing the action group –SO3.H and simply uses the total
exchanger molecule, which may be shown as Z or X. The above equation is then written as:
2Na+ + H2 X → Na2 X + 2H+
X being considered a divalent cation exchange unit.
This is known as Hydrogen cycle operation. Other examples of cation exchange include the
following:
Hardness removal, with Na – form exchanger, Na2X
Ca2+ + Na2X → CaX + 2Na+
This is known as Sodium cycle operation.
Iron removal: Fe2+ + Na2X → FeX + 2Na+
Change in Ionic distribution during cation exchange – H cycle, with downward flow of acid
(concentrationurrent reagent)
0% 1w%
TOP CO2+ Ca2+
H+ + Ca2+
H + Flow flowflow H
Na+ Na +
Ca 2+ 2+ Na+
Ca
Bottom H+ + H+
New Resin- At exhaustion After Backwash After regn with Na
acid after rinsing at
exhaustion H+ H+ Na+
H-form

A more realistic example Which illustrates an ion exchange property CALLED SELECTIVITY
is Hydrogen cycle processing of a typical water containing a variety of ions.

Ca2+ CaX
Mg2+ MgX
Fe2+ + H2X FeX + 2H+
 2Na+ Na2X
+
2NH4 (NH4)2X
If this ion exchange process continues to exhaustion, the first ions to appear in the effluent will
be NH4+ and Na+ and if the exhausted bed is then analyzed, the distribution of ions would be are
shown in above figure.
This is due to the SELECTIVITY or preference of the cation exchanger for certain ions over
other.
General Order of Selectivity in water below low mg/L TDS
Cations Anions
Fe3+ CrO42-
Al3+ SO42-
Pb2+ SO32-
2+
Ba HPO42-
Sv2+ CNS-
2+
Cd CNO-
Zn2+ NO3-
Cv i.e. at exhaustion Li will leak this first NO2-
2+ +

then Na+, then NH4+ etc.

Fe2+ Br- (hence, at exhaustion F- will leak thro first
then OH- then, HSiO3 then HCO3- then Cw-
etc.)
2+
Mn Cl-
2+
Ca CN-
Mg2+ HCO3-
K+ HSio3-
+
NH4 OH-
Na+ F-
+
H
Li+

In general SELECTIVITY IS AFFECTED by

1. Ionic valence 3>2 > 1

2. Atomic No. Ba > Sr > Ca > Mg in Group II A

3. Hydrated ionic radius: The larger the radius, the lower the selectivity and exchange capacity.

OTHER CATION EXCHANGERS: Another, resin of increasing importance is a resin having

the CARBOXYL GROUP ( - COOH, with the Hydrogen ion exchangeable) as the exhaust site.
This is called WEAK CATION EXCHANGER.
Why Na2SO3 dosing of feed water to DM Plant?
1. Free chlorine degrades the resin used in the ion exchange units

2. If FRC enters the feed water going to XUs, it will lead to sulphur deposition problem as Nacent
O2 reacts with H2S to precepitate the sulphur.

PRACTICAL ION EXCHANGE:

In the commercial application of ion exchange to water treatment, there are four important
principles:
1. (a) A Unit is operated to a predetermined leakage level, where it is considered to be exhausted.

(b) The unit is then regenerated first by upflow cleaning (back washing) and then by chemical
elution, down flow;

(c) The resin bed is then rinsed down flow. Because both water and regenerant flow in the same
direction, the water leaking the unit is in contact with the resin having the highest level of
contaminating ions, so quality and efficiency both suffer (see the figs. (Na+ slip will be there)

2. Because of the cyclic operation with cocurrent flow of water and regenerant, chemical
utilization in regenerating ion exchange resin is usually poor. This drawback is most pronounced
with STRONG Resins – Sulfuric type cation exchangers and quaternary Amine anion exchangers.

ACID efficiency for hydrogen exchange using – Sulfonic-type resin and H2SO4 for regeneration
and caustic efficiency for regeneration of strong base anion resin are very poor, about 20 to 40%
only.

However, Weak Cation resins (Carboxylic type) and Weak anion resin (amine type) can be
operated at close to 100% chemical efficiency.

3. Most Ion exchange materials are in the size range of 20 to 50 mesh or about 0.5mm effective
size. This makes an ion exchange bed a very effective filter, a characteristic having both
advantages and disadvantages.

Filtering ability also leads to fouling and unpredictable operating runs. Some times this is
carried by the accumulation of high MICROBIAL POPULATIONS in ion exchanger bed, even when
operating on a chlorinated water supply.

LATEST DEVELOPMENTS IN ION EXCHANGE:

Because of the above limitation, Ion exchange designs are changing. These improvements are
realized by:
1. COUNTER CURRENT TECHNIQUES

2. MULTIPLE STAGES OF TREATMENT

3. MULTIPLE STAGES OF REGENERATION

4. USE OF WEAK EXCHANGERS WHEREVER POSSIBLE

 5. PRETREATMENT OF WATER PRIOR TO ION EXCHANGE (by lime softening, reverse osmosis etc.)
to reduce the ionic load on the ion exchange system.

6. PRETREATMENT TO REDUCE PARTICULATES OR SOLUBLE ORGANIC FOULANTS (e.g. by filtration,

adsorption).

Leakage: It implies slipping of some of the influent ions into the effluent. In fact, unwanted ions
reach the effluent by two different processes.
a. At the beginning of softening run (using Na2X process as an e.g.) there is appreciable Ca left at
the bottom (after rinsing) of the bed. Water entering at the top gets completely softened, as the
only cation being Na. This softened water, in effect a very dilute brine, regenerates the Ca from
the bottom of the bed. So at the beginning of the run the hardness in the effluent is due to Ca
residue as the exchanger from the previous run (see fig. for Na2X process below)

Na2X Process

2+
Ca
C Na+ Ca2+
+
Na
Ca2+ Na+
+ 2+
Na Ca

At exhaustion after brining Rinsing at exhaustion

In case of H2X, Na leakage will be there.

b. As the bed becomes exhausted, the Ca contamination at the bottom of the bed decreases and
the quality continually improves until true leakage – slippage of incoming Ca2+ thro’ the bed into
the effluent – begins to appear. The net effect is shown in fig. below:

Net leakage

Hardness

Re-exchange

Gallons of thro’ put

Slippage
 This same kind of effect is observed with all exchange process having COCURRENT EXHAUSTION
and REGENERATION.

IF THE BED IS REGENERATED COUNTER CURRENT TO THE water flow, the effect is eliminated
and leakage is then due to actual ion slippage.

The improvement of both quality and efficiency by COUNTERFLOW REGENERATION IS

STRIKINGLY illustrated in below figure, showing hydrogen cycle operation with downward
service flow and inflow regeneration with H2SO4.

35

30

25

Effluent water 20

Conductivity 15 cocurrent using 11lb acid/ft3

10

0 20 40 60 80 100

% of operating cycle

Counter current – using 7.4 lb of acid/ft3

A FINAL BACKWASH IS ANOTHER PRCEDURE TO MINIMISE LEAKAGE.

In an idle unit, this is migration of ions between resin particles. This causes a change of water
quality when flow commences again.

HYDROGEN CYCLE EXCHANGE:

The effluent is acid, since it contains CO2 equivalent to the incoming alkalinity and
hydrogen which has been exchanged for substantially all of the cations in the influent, except for
leakage.
Ca (HCO3)2 + H2X → CaX + 2H2O + 2CO2
CaSO4 + H2X → CaX + H2SO4
The strong acidity of the effluent must be corrected. The CO2 is easily removed by
degasification, since THE EQUILIBRIUM CO2 concentration CORRESPONDING TO THE
TYPICAL COMPOSITION OF THE ATOMOSPHERE IS LESS THAN 1 Mg/L. Therefore,
the acidity may be reutilized by the addition of ALKALAI OR BY ANION EXCHANGE.
ACID REGENERATION OF CATION EXCHANGERS:
Why can’t we use H2SO4 for regeneration of SAC, WAC?
We can use H2SO4 but:
A SAC is usually used with H2SO4 regeneration. But the regeneration efficiency is poor.
1. PART OF THE INEFFICIENCY IS DUE TO THE NEED TO KEEP THE CONCENTRATION OF H2SO4 LOW
ENOUGH TO AVOID PRECIPITATION OF CaSO4 in the bed.

2. A second MAJOR FACTOR IN LOW H2SO4 acid efficiency is the INCOMPLETE IONISATION OF THE
ACID AT THE APPLIED CONCENTRATION.

H2SO4 H+ + HSO4- 2H+ + SO42-

In the range of 2 to 8%, appreciable acid is still in the HSO4- form, limiting the mass of
+
H ions available for ion exchange during regeneration.
Also, one more problem in using H2SO4 is as follows:
The spent regenerant requires careful attention for disposal since it contain large amount
of UNUSED ACID plus CaSO4 at concentration far above its solubility, creating a potential
SLUDGE PROBLEM.
The use of HCl avoids the CaSO4 precipitation but in most cases, HCl is too expensive
compared to H2SO4 and special materials of construction are required and HCl vapors must be
properly vented, too.
USING WAC: The utilization of regenerant acid can be considerably improved by incorporating
a CARBOXYLIC EXCHANGER INTO THE SYSTEM.
In such a system the CARBOXYLIC EXCHANGER bed is SIZED TO REACT WITH THE
ALKALINITY OR THE HARDNESS OF THE INCOMING WATER, whichever is lesser. The
SAC is then sized to react with the balance of the cations. The WAC then operates at close to
theoretical efficiency approximately 0.15 lb/kg (or 1.0 kg/kg)
WAC typically have a capacity as high as 60 kg/ft3 (2.8N) (note for SAC, it is 2N. or 44 kg/ft3),
But the operating capacity is usually in the range of 20 to 40 kg/ft3 (0.9 to 1.8N). This compares
with an operation range of only 12 to 18 kg/ft3 (0.6 to 0.8N) for SAC regenerated with H2SO4.
NOTE: The results of treatment whether using a SAC or a combination of WAC (carboxylic)
and SAC are the same. But the advantage of WAC is a reduction in cost by improved acid
efficiency and reduced waste treatment load through reduction of excess acid.
Some systems incorporate layered bonds of carboxylic and sulfuric (SAC) resins in the same
vessel; these are susceptible to fouling because the carboxylic resin is light and difficult to clean
and should be provided with a separate regeneration system to avoid CaSO4 deposition.
WBA cannot remove Weak Acids such as CO2, SiO2, Organic acids. It can remove only strong
acids like H2SO4, HCl, and HNO3.
COUNTER CURRENT REGENERATION OF H2X UNITS:
Another choice is available to improve results and that is to design the exchanger for counter
current regeneration. See the results below of a Canadiametern Plant with equal levels of Na
slippage.
 CATION EXCHANGER regenerated with H2SO4:
Operating Factor Co-current Countercurrent
Regeneration:
a. Acid lb/ft3 6.0 3.7
b. Concentration 2 and 4% 2%
CAPACITY:
a. Kg/ft3 7.7 14.5
b. lb H2SO4/Kg 0.78 0.26
Regeneration:
Acid consumption, as a % of 520% 170%
theoretical

ANION EXCHANGER:
Anion exchangers may be produced from a variety of resinous or plastic skeleton including the
same styrene-divinyl Benzene copolymer as is used for cation exchangers. As with cation
exchangers, two general varieties are used commercially: WEAK BASE acid STRONG BASE
EXCHANGERS.
The functional group of an anion exchanger is an amine, the organic equivalent of Ammonia.
WEAK BASE Exchangers (WBA) contain a secondary or tertiary amine group RR 1 – NH or
RR1 – N – R1, which can adsorb strong acids.
STRONG BASE EXCHANGERS (SBA) contain a quaternary amine, RR 1 RII RIII N+ Cl- which
can exchange all anions. The most common quaternary resin has the formula – R.N(CH3)3.Cl.
WBA exchangers are able to remove only Strong Mineral Acids such as H2SO4, HCl, HNO3
With practically no exchange capacity for WEAK ACIDS such as CO2, SiO2, Organic acids.
The typical reaction is shown as an adsorption, rather than ion exchange process:
HCl + A → A. HCl
(A represents ANION EXCHANGER)
The exhausted Resin is very efficiency reacted with any Alkali, which simply neutralizes the
adsorbed acid and release it as a Neutral Salt.
Two forms of anion resins are there (1) Cl- form (2) OH form
STRONG BASE EXCHANGERS ARE TRUE ION EXCHANGER Materials. Several typical
reactions given below:
Dealkalization with Cl- for exchanger, ACl2
2HCO3- + ACl2 → A (HCO3)2 + 2Cl-
Sulfate removal, with Cl form
SO42- + ACl2 → ASO4 + 2Cl-
The most common use for STRONG BASE EXCHANGERS is COMPLETE ANION
REMOVAL from Hydrogen exchange effluent to produce D.M. Water.
H2SO4 A.SO4
2HCl A.Cl2
2H2CO3 + A (OH) 2 → A (HCO3)2+ 2H2O
2H2SiO3 A (HSiO3)2

THE EXCHANGE RESIN IS NEUTRALISed WITH NaOH. In this form, the exchanger can
also convert Neutral salts to bases known as SALT-SPLITTING.
 2NaCl + A (OH) 2 → ACl2 + 2NaOH
The selectivity of Anion Exchanger was given earlier from that it is clear that SILICA WILL
LEAK FIRST AND THE EXHAUSTE BED will have the composition as shown below:
Mol% Mol%
Top SO4
Cl
Flow O CO2
SiO2
H
Bottom
New OH form resin At Exhaustion

Mol% Mol% Mol%

Mol% SO4 OH SO4
Cl Cl
FlowCO2 flow
OH CO2
SiO2 SiO2 SiO2

S
After Backwash after NaOH elution after rinsing at
exhaustion
COCURRENT REGENERATION

By far the most common form in which anion exchangers are used is the HYDROXIDE
FORM, WITH CAUSTIC SODA (NaOH) being used for regeneration. In this process, the
anions in the cation effluent are exchanged for Hydroxide, if there are cations present; such as
Sodium, the effluent will contain NaOH and this is the most prominent factor affecting the
quality of finished water.
Why CO2 degassifer? One of the common methods for reducing loading ON THE
ANION EXCHANGERS is the removal of CO2 by degasification so that it need not be removed
by Ion Exchange.
Advantage of WBA: WBA exchangers can be installed in DM system both to relieve load on the
strong anion exchangers and also to improve the economy of operation. WBA exchangers
remove only strong mineral acids, such as HCl, H2SO4, HNO3 and the alkali used for
regeneration neutralizes these adsorbed acids so that the regeneration is close to 100% efficient.
FOR REGENERATION OF WBA, A VARIETY OF CHEMICALS (ALKALIES) CAN BE
USED FOR THIS OPERATION. THE FOLLOWING ALKALIES CAN BE USED FOR
REGENERATION OF WBA: NH3, NaOH, Na2CO3
TYPICAL WBA CAPACITIES:
Chemical Dosage lb/ft3 Capacity kg/ft3 Usage lb/kg
NH3 1.5 20.0 0.08
NaOH 3.0 21.3 0.14
Na2CO3 6.6 19.6 0.34

NaOH is preferred when effective elution organics and high quality of treated water are required.
NOTE:
 1. CATION EXCHANGER RINSE CAN BE USED FOR COOLING TOWER MAKE UP FOR ALKALINITY
REDUCTION.

2. REGENERANT CONCENTRATION IS IMPORTANT: In correct chemical application is a cause of

poor resin performance.

CAPACITY LOSS is due to the following reasons:

1. Material (Resin) loss because of excessive back wash or rinsing or mechanical failure of internal
distribution.

2. Dirty Ion exchanger beds and this is usually caused by improper back wash.

3. Channeling: which can be detected fairly by surface appearance. If the surface is uneven,
channeling will take place. Another cause of channeling is low flow.

4. Incorrect chemical application is another cause for poor performance of resin.

Good elution

Plug flow

Poor elution due to dilution or channeling

effluent

salinity %NaCl

Minutes after start of rinsing

5. Anion resins are generally much more sensitive to degradation than cation resins, particularly
thro’ irreversible fouling with organic material.

HOW TO PREVENT ORGANIC FOULING:

CERTAIN REACTIVE ORGANIC MATERIALS DIFFUSE INTO THE GEL
STRUCTURE OF STRONGLY BASIC ANION EXCHANGERS (SBA) and WBA, and then
polymerize into molecules so large that they are trapped in the gel, unable to diffuse again. So,
1. MAXIMUM REDUCTION OF ORGANIC MATTER BY PRETREATMENT
 2. Application of a CLEANING AGENT DURING EACH BACK WASH to disperse Organic matter and
reduce its opportunity to diffuse into the gel structure.

IN ADDITION, PERIODIC TREATMENT OF WBA WITH STRONG ALKALI AND WAC, SAC WITH
STRONG ACIDS, CAUSES THE ANION & CATION EXCHANGERS RESIN TO SHRINK, EXPELLING
WATER THAT CARRIES WITH IT SOME OF THE ORGANIC MATTER, LIKE SQEEZING A SPONGE.

DEPOSIT CONTROL

Deposits are conglomerates that accumulate on water and wetted surfaces and interfere
with system performance.
Deposits include SCALE, FOULANTS or a combination of the two.
Scale forms when the concentration of a dissolved mineral exceeds its solubility limit and
the mineral precipitates such as CaCO3 scale – at points where velocities are too low to support
the material in the stream.
Deposit Sources: may be external or internal. A source of depositing materials, particularly in
an OPEN COOLING TOWERS IS AIR. Cooling towers act as large AIR SCRUBBERS, and
the water is quite effective in capturing dust, MICROBES and other debris from the large
volume of air that it contacts. Because the amount of suspended solids in air is always changing,
the suspended solids level in the quality water also changes considerably from time to time.
Cooling tower is also scrubs industrial gases from air. NH3, H2S, SO2 and other gases are rapidly
absorbed into water, when they react chemically, changing water characteristics. Some times,
this change is so dramatic that scaling, corrosion or microbial matter may suddenly obstruct a
system in a matter of days.
TREATMENT TO CONTROL SYSTEM DEPOSITS:
(a) Threshold inhibitors (b) Dispersants (c) Surface active agents and (d) Crystal modifiers.

a. Threshold Inhibitors: This first class of deposit control chemical includes sequestering agents
such as POLYPOSPHATES, ORGANO PHOSPHOROUS COMPOUNDS AND POLYMER,
(POLYACRYLATES Forms). Then exert a ‘threshold effect’, reducing the POTENTIAL FOR
PRECIPITATION OF CALCIUM, Fe and Mn.
 b. DISPERSANTS: The second group is made up of organic dispersants, including organo
phosphorous compound and polyelectrolyte. These will disperse suspended solids by adsorbing
to the surfaces, then adding an electrostatic charge to each particle, causing mutual repulsion.
In other words, dispersant act oppositely from coagulants.

c. SURFACTANTS: The third category of deposit control agents is surface active materials, Those
that penetrate and disperse biomass are called BIODISPERSANTS. SOME OF THESE ARE ALSO
BIOCIDES AND HELP TO KILL THE SLIME ORGANISMS.

Some surface-active agents are effective wetting agents and anti foulants which help fluidize solids
and keep them moving with the flowing water. STILL others are selected to emulsify Hydrocarbons
so that they can be eliminated from the system by conventional blow down.

d. Crystal Modifiers: The fourth group of control agents includes those chemicals used to modify
the crystal structure of scale. These chemicals which distort or modify crystal growth are also
considered as deposit control agents. These chemicals are widely used in cooling towers and
boilers.

Natural Organics such as LIGNIN and TANNIN were the first organic treatments used to keep the
heat transfer surface clean by crystal modification. They function also as dispersants.

NOTE: CaCO3 precipitates as CALCITE at low temperatures and as ARAGONITE AT HIGH

TEMPERATURES.
E.g. Of crystal modifiers: 1. Polyacrylate (2) sulfonated copolymer crystal modifiers (3)
Blend of Polyacrylate and phosphate.
CONTROL OF MICROBIAC ACTIVITY
CHLORINE DOSING: CHLORINE IS AN OXIDISING BIOCIDE to control MICROBIAL
GROWTH. Cl2 gas, most commonly used biocide, hydrolyzes rapidly when dissolved in water.
Cl2 + H2O → H+ + Cl- + HOCl
Hydrolysis occurs in less than a second at 18oC, Hypochlorous Acid (HOCl) is the active
ingredient formed by this reaction. This weak acid tends to undergo partial dissociation as
follows:
HOCl H+ + OCl-
Producing hypochlorite ion and hydrogen ion. Depending on pH and concentration, Cl 2 in water
exists as free Cl2 gas, hypochlorous acid or hypochlorite ion.
HOCl HAS A FASTER KILLING POWER THAN OCl- (below pH 7.5 and at 7.0 HOCl
predominates) above pH 7.5, hypochlorite ions predominate and they are Exclusive from (won’t
be there) when pH exceed 9.0
The sum of Hypochlorous acid + OCl- is called FREE AVAILABLE CHLORINE (or FRC)
Cl2 is a strong oxidizing agent capable of reacting with many impurities in water including NH3,
AMINO ACIDS, PROTEINS, CARBONACEOUS MATERIAL, Fe2+, Mn2+, S2 – and CN-.
The amount of Cl2 needed to react with these substances is called “Chlorine demand”.
CHLOROAMINE compounds also have biocidal properties, than referred to as the combined
residual chlorine. Cl2 reacts with NH3 to form these different chloramines.
HOCl + NH3 → NH2Cl + H2O (Mono chloramine)
NH2Cl + HOCl → NHCl2 + H2O (dichloramine)
NHCl2 + HOCl → NCl3 + H2O (trichloramine)
But Chloramines are slower acting than FRC, but have the advantage of being more effective at
pH value above 10.

COOLING WATER TREATMENT

The tube wall temp, called Skin Temperature, is the most IMPORTANT VARIABLE
CONTROLLING CORROSION AND DEPOSITION. The individual controlling factors of
water velocity, heat flux and water and process temps, all combine to define Skin Temperature
For eg., where high skin temps, occurs (above 93oC) the plant can find the most probable
locations for scale formation and corrosion, because many compounds found in water-formed
deposits are less soluble at increased temps, and corrosion reactions proceed faster at elevated
temps.
To help keep the walls free of suspended solid deposition, C.W. velocity should be above 2-3
ft/sec (0.6 to 0.9M/sec) to a high as 7 to 8 ft/sec (2.1 to 2.4 m/sec).
Open Recirculation Systems:- How to calculate performance:
1. Recirculation rate QC → flow of cooling water pumped by a pump.

2. Temperature differential or Range ( T): (Inlet – Outlet)

3. Evaporation E: E is the water lost to atmosphere in the cooling process M 3/min. The
Evaporation loss depends on amount of water being cooled QC and T. AS A THUMB RULE: For
each 10oF (5.6oC) temperature drop across the evaporative process, 1% of the recirculation rate
QC is evaporated.

E = QC x (T2 – T1)/1000

E = QC (M3/Min) x (metric)

4. Make Up: (M): The input of water required to replace the water lost by evaporation of that
being lost through Blow down, tower drift and other miscellaneous losses. It can be found out
by:

M=Ex where

CR = CONCENTRATION RATIO

CONCENTRATION RATIO (or cycles of concentration): (OR) Makeup contains dissolved

impurities. The evaporating water produces pure H2O vapor, leaving behind these impurities,

CR =
i.e CR = CB/CM
Since the input solids = output solids
M x CM = B x CB where M = Make up flow
B = loss of concentrated water by blow down, drift, other leakage.
Hence, CR = CB/CM = M/B = Make up/Total loss of water.
The CR should be calculated for several individual components in the water to determine if the
system is in “balance”.
IMP → IN GENERAL, IDEAL CASE, THE SYSTEM IS BALANCED WHEN THE CR OF
ALL IONS (Ca, Mg, alkalinity etc. ARE EQUAL
IF THE CRs are NOT EQUAL, IT CAN INDICATE THAT SOME MINERAL (CaCO 3, SiO2
etc.) IS PRECIPITATING FROM THE RECIRCULATING COOLING WATER. For eg. If CR
for Ca or alkalinity is 0.5 below that of Mg, then CaCO3 is probably precipitating in CWS.
NOTE: Because of addition of chemicals CRs of certain will vary.
For e.g. As we are dosing H2SO4, CR of SO42- will be higher. Also CR for alkalinity decreases
at the same time, as ALKALINITY IS DESTROYED BY ACID ADDED TO TOWER. (2)
Chlorination will increase CR of Cl-. CR based conductivity will also be increased by some of
the added chemicals.
TOTAL LOSSES IN A C.T:
1. Blow down

2. Drift loss

3. Evaporation

4. Leakages

1. Blow down: (BR) is calculated and controlled to remove dissolved solids at the same rate at
which they are introduced by make up. In total Blow down calculation, drift BD and leakages BL
are included.

B = BR + BD + BL

So, M = B + E B=M–E

And B = (M/CR)

DRIFT BD: Carry over of water mist with air (mist and drift eliminators are used). Mist and drift
eliminators are used to reduce the loss to 0.0005% of the re-circulation rate. Normal loss = 0.05
to 0.2%. Since drift contains dissolved solids, it is really a portion of blowdown.
Holding capacity of system V = Sump Volume + 20 to 30% for water contained in lines and
equipment.
Time/Cycle €: Time required for water to make one trip around the loop (one cycle) t = V/QC
HOLDING TIME INDEX: (HTI): is an expression of the half life of a treatment chemical added
to an evaporative C.T. This index represents time required to dilute an added chemical to 50%
of its original concentration after the chemical addition is discontinued. It is also the time
required to concentrate the make up solid by a factor of 2.0
It is an important factor in setting control limits where chemical feed may be interrupted.
 It is also important for establishing an effective dosage for BIOLOGICAL CONTROL
AGENTS, where one slug fed into the system.
For a CT, the half-life depends primarily on the system capacity and Blowdown rate.

H.T.I = 0.693 x (0.693 = ln2)

But B = E/CR-1

HTI = 0.693 x

Or HTI = 0.693 x
Effect of pH on Cl2 dosing:

1000
Half life or 800
HTI Min. 600
HTI: Holding 400
Time Index 200

0 4.5 5.5 6.5 7.5 8.5 9.5

pH

100
80 Cl2 OCl
Chlorine species 60 HOCl -
In solution(%) 40
20
HOCl
0 OCl
2 4 - 6 8 10
pH
HOCl has a more rapid biocide activity than does the OCl- (Hypo chlorination). The ion
OCl- predominate above a pH of 7.5, penetrates microbial cells less rapidly, then longer contact
times are needed.

Important Cooling Water Variables

1 Ca, Mg Define Scaling tendency of water
2 M-alkalinity, pH, Define concentrations of carbonate and bicarbonate
Temperature and solubility of CaCO3
3 SO4, SiO2 Must be controlled to prevent sulphate and silicate
scales.
4 Suspended Solids Cause fouling, require dispersants.
5 Contaminants:- Hydrocarbon, Cause fouling and microbial growth high Cl2
glycols, NH3, SO2, H2S demand, precipitate chemical treatments.

- Ca and Mg hardness define scaling tendency.

- Total alkalinity, pH and temperature define the concentration of carbonate and bicarbonate ions
in the water, and also solubility of CaCO3. All of these must be controlled within acceptable
limits for each system to ensure scale-free operation.

- Concentration of SO4 and Silica must be controlled at reasonable levels to prevent formation of
gypsum and silica scales.

- System may contain suspended solids which concentrate in the tower and cause fouling.
Dispersants may be used to control this.

Sources:
1. From makeup

2. From air

3. Precipitation products or microbial masses.

- To avoid suspended solids, side stream filter shall be provided to filter a portion of the
circulating water, approximately equal to the evaporation losses.

C.W. System Problems:

1. Corrosion: is a function of water characteristics and the materials in the system. Corrosion
causes premature failure of metals; deposits of corrosion products reduce both heat transfer
and flow rates.
2. Scaling : is caused by precipitation of compounds that become insoluble at higher
temperatures, such as CaCO3. Scale interferes with heat transfer and reduces flow.
3. Fouling: results from settling out of suspended solids, build up of corrosion products, and
growth of microbial masses. Fouling has the same effect on the system as scaling, but
fouling also promotes scaling

CORROSION AND SCALE CONTROL IN C.W.S.:

Corrosion in recirculation C.W.S. is controlled by employing either inorganic or organic
inhibitors.
The four major inorganic inhibitors are Chromate, Zinc, Ortho-phosphate and Polyphosphate.
Minor supplements include molybdate, nitrate, nitrite and various organic nitrogen
compounds, silicate and natural organics.
Inorganic polyphosphates and natural organic materials were the earliest chemical used for
C.W.S.. The concept behind these designs was to add a small amount of acid to control the
stability index to a slightly scale-forming value. (Organic corrosion inhibitors include
organic phosphorous compounds, specific synthetic polymers, organic nitrogen compounds,
and long chain carboxylic acids).
a. Polyphosphates and natural organic materials were added to provide both corrosion protection
and scale inhibition. The scale inhibitors stemmed from the use of polyphosphates as a
threshold treatment.

b. Polyphosphates combine with calcium to form cathodic inhibitor that reduces the corrosion
rate.
c. The natural organic material tends to keep the metal surface relatively clean and aid the
inhibitor (polyphosphate) to form a protective film. It also disperses suspended solids and also
prevents precipitation of calcium carbonate and tri-calcium phosphate.

BUT, the greatest disadvantage of this programme (using polyphosphate + natural organic
materials) IS THE REVERSION OF POLY PHOSPHATE TO ORTHOPHOSPHATE. THIS
ORTHOPHOSPHATE CAN COMBINE WITH CALCIUM TO FORM CALCIUM PHOSPHATE SCALE. FOR
THIS REASON, WE FOLLOW THE FOLLOWING PROGRAMME:

USE BOTH ORTHO AND POLY PHOSPHATES: In this both ortho and poly phosphates are used as
corrosion inhibitors.

To prevent calcium phosphate deposition, the pH is generally controlled at 7.0 and specified
synthetic polymers are added to disperse and stabilize calcium phosphate.

Chromate Treatment: Excellent corrosion inhibitor. Initially chromate was applied at very high
dosages, frequently in the range of 200 to 300 mg/L as CrO4. Acid was added to the system to
lower the pH to between 6 and 7, preventing CaCO3 precipitating.

This treatment was quite effective in both scale inhibition and corrosion protection, but one
shortcoming was that pitting attack tended to occur if the chromate residue becomes low. It
was found that if chromate was considered with other inhibitors, particularly cathodic type (e.g.
Zn, polyphosphate) the chromate level could be reduced to 20 to 30 mg/L CrO 4, with better
results than obtained at 200 – 300 mg/L CrO4 used above. This is called synergized chromate
programme. It also employed acid, controlling pH to 6 to 7. Advantage is the margin of safety
provided against pitting attack, should the chromate be momentarily underfed.

But chromate programme lead to environmental pollution.

4. Organo Zinc Combination was developed. Since Zinc, a Cathodic Inhibitor, has lower film
strength than chromate, the pH of the system for an organo zinc programme was increased to
between 7 and 8 to make the water less corrosive, allowing zinc to form a satisfactory inhibitor
barriers. The organic portion of the treatment was a dispersant to keep the system free of
deposits, thereby encouraging formation of an adequate zinc film. In addition to dispersion,
certain types of organics increased zinc solubility at higher pH required for this method of
treatment.

But as the inhibitor Zn film is not as effective as chromate film at operating pH, it is not useful as
compared to chromate programme.

Advantage of Alkaline treatment of C.W. (i.e. pH in the alkaline):

 1. Advantage of alkaline operation is the buffer capacity provided by the water that reduces the
impact of system upsets on performance.

2. Another advantage is the substantial reduction or occasional elimination of acid feed.

5. Organo Phosphorous Compounds: Like inorganic poly phosphates, these organo phosphates
prevent scale formation by the threshold effect.

a. Inorganic polyphosphates easily revert to ortho phosphates with increasing holding time,
temperature and microbiological attack. Whereas organo phosphorous compounds do not
revert under normal cooling water conditions except under severe microbiological attack.

b. UNLIKE THE INORGANIC POLYPHOSPHATES, THE ORGANO PHOSPHOROUS COMPOUNDS

ARE GENERALLY ABLE TO INHIBIT Precipitation OF CaCO3 and OTHER SCALE-FORMING
SPECIES AT HIGHER pH AND ALKALINITY THAN TOLERATION BY THE INORGANIC
POLYPHOSPHATES.

The basic treatment concept is to raise the pH to 7.5 to 9.0, thereby reducing the corrosivity
of the water. But the decrease of corrosivity is not enough for mild steel exchangers. All
organic inhibitors + organic phosphorous compounds will protect S.S. from corrosion, scale
control and deposit control.

AQUAT 565H – Treatment: CONTAINS ORTHO, META & ORGANIC PHOSPHATES +

ZnSO4 + Synthetic dispersants.
The principle of this treatment is to operate the C.W.S. at high pH and hardness levels, where
scaling is a major problem while corrosion is quite low.
It incorporate specific corrosion inhibitors to assure scale & corrosion protection.
Organo phosphonates are scale inhibitors, which prevent precipitation of scalants by their
threshold effect. Potential scalants are maintained well above their solubility limit.
The dispersant present in Aquat 565H prevent deposition of flocculants such as clay, silt &
corrosion protection with preventing scalant deposition.
CHEMICAL COMPONENTS OF C.W. TREATMENT PROBLEMS
Chemical Treatments Corrosion Scaling Fouling Microbe
1. Chromates
2. Zinc
3. Molybdates
4. Silicates
5. Poly Phosphates
6. Poly Esters
7. All-organic
8. Natural organics
9. Synthetic Polymers
10. Non-oxidising Biocides
 11. Oxiding biocides Cl2/Br2
12. Ozone

Anodic Inhibitors Cathodic Inhibitors Both anodic, cathodic

1. Chromates 1. Polyphosphate 1. Organic filming
amines
2. Ortho phosphates 2. Zinc 2. Phosphonates
3. Nitrites Costly, deposition 3. Na2CO3
4. Silicates problems, Provide
nutrients for
microbial growth

Corrosion inhibitors present in the blend act synergistically to provide anodic and cathodic
protection for low corrosion rate. It is non-toxic.
In addition Aquat 351 (biocides) & 321 is found effective in controlling microbial growth.
Biocide dose rate = 30 ppm
Aquat 565H dose rate to maintain 80 ppm
Aquat 565H contain 7.5% ortho PO4- - -
Ortho PO4 - - - maintained in water is 8-10 ppm
Hardness in CW = 500 ppm
pH = 7- 8
TDS = 1000 – 1500 ppm2
FOULING CONTROL: - (deposits control) Deposits or fouling will effect H.T. rates and flow
rate also.
CONTROL OF DEPOSITS IS OFTEN MORE DIFFICULT IN ALKALINE SYSTEMS THAN
IN LOWER pH systems.
Sources of fouling deposits:
1. The make up water may contain dissolved solids, organic matter and suspended solids, any of
which can contribute to fouling.

2. A system may become grossly contaminated with microbes; for e.g. Make up water with a high
BoD is particularly susceptible to fouling from slime – forming bacteria.

3. Air borne fouling deposits: Dirt, reactive gases like H2S, SO2, NH3, microbial contamination.

Sources of fouling deposits:

Raw Water Airborne Recirculation water
Colloidal organics Dirt Scale: CaCO3, CaSO4, Mg,
Silt, dirt Reactive gases, H2S, SO2, SiO3
NH3
Soluble Iron Corrosion products: Fe2O3
Process leaks – Hydro carbon
Sulphide
Microbial contamination Microbial contamination Microbial contamination

Prevention: Use of proper dispersants

 Synthetic organics, including polymers and surface active agents are generally applied for
disposing microbial and organic deposits. Synthetic polymers such as poly acrylates or poly
acryl amides act as dispersant for silt, sand, iron and other inorganic deposits.
Organo phosphorous compounds including polyol ester and phosphonates are inhibitors
for calcium carbonate and CaSO4 precipitates.
MICROBIAL CONTROL: Microbial deposits lead to fouling. It requires biocides to kill
microbe colonies and dispersants to loosen and wash them away.
Most common oxidizing biocide is Cl2. If FRC of 0.2 to 0.4 ppm is maintained continuously, it
will provide effective control at all C.W. pH values.
Sterilization studies have shown that Cl2 kills faster at pH 7 than above pH 8.0
If FRC exceeds 1 ppm, it will lead to tower timber delignification.
Disadvantage: (Cl2) it can react with some organic materials, particularly phenolic compounds to
form reaction products that are non biodegradable, presenting potential effluent problem.
Br2: is often a more practical treatment than Cl2 because it remains effective at higher pH values
and avoid formation of by-products resulting from chlorination.
Biodispersant – Aquat 321, 351: Although Cl2, Br2 are excellent killing agents, their performance
can be significantly improved by the use of bio dispersants. Biodispersants aid the toxicant by
breaking loose the biofilms and enabling them to contact more microbial organisms.
DM PLANT
1. Mg hardness more than 2.0 ppm leads to scale formation in waste stripper of X.U.

2. EMA (Equivalent Mineral Acidity): It is quantitative capacity of Aqueous Mediameter to react

with Hydroxyl oilys (OH-) to pH 4.3.

Decrease in EMA value is used in determining Na+ slip in demineralised water plant.

EMA = Cl- + SO4- - + NO3- + PO4- -

3. ALKALINITY: It is the quantitative capacity of aqueous mediameter to react with hydrogen ions
(H+)

It is usually imparted by the BICARBONATES, CARBONATES AND HYDROXIDES compounds of

natural or treated water.

4. SILICA: The maximum allowable silica content in BFW at 40 kg/cm2 pressure is 0.5 Mg/lit

Silica is carried away by steam in turbine and if it is more than specified, it may erode the
turbine blades and can even cause imbalance of the turbine.

In case of PFW, it SHOULD NOT BE MORE THAN 3 ppm, to avoid SCALE FORMATION IN WASTE
STRIPPER OF EXCHANGE UNIT. It forms scales in presence of Ca, Mg hardness only.

5. CHLORIDE: Cl- content in PFW is to be controlled to reduce SCC of S.S. The Max allowable limit is
3 mg/lit.

THE ANION RESINS ARE MAINLY SUSCEPTIBLE TO ORGANIC FOULING WHILE CATION RESINS
MAINLY SUSCEPTIBLE TO IRON FOULING. The fouled resin losses the exchange capacity and its
rinse time also increases. The best way to tackle these problems is pre-treatment of raw water
i.e. chlorination, alum dosing and passing the raw water through activated charcoal etc.
 Ejector line: comes from the portion between two sections from one section, liquid will be
collected into a parting box and then redistributed over the below section.

Vacuum Deaeration

Flow 455 M3/hr

O/L O2 content 0.2 ppm at 20oC
Normal operating temperature 20oC
Pressure 20 Ton
Packing Poly propylene packing
Liquid distribution, redistribution are provided (GRP material) Two sections in the packed bed
Vacuum pump Cast iron body, S.S. Shaft
Duty 449 M3/hr at 39.85 mm Hg (or tons)
Seal water flow 7M3/hr (Trip = 3.5 M3/hr)
Air ejection duty 2.67 Kg/hr air/vapor at 14.41 mmHg

Principle of operation: the dissolved gases are removed by subjecting the water to a high
vacuum as it passes in a relatively thin liquid film over the large surface area of the packing.

The dissolved gases exert an equilibrium P.P. over the liquid surface which varies with the
dissolved gas content and temperature of the liquid. By providing a sufficiently large vacuum
source, the actual partial pressure of gases is kept below the equilibrium value and the gases are
continuously removed.

In addition to the dissolved gases, the water itself exerts a vapor pressure and so some water
vapor is always draining off with the gases.

How to treat the fouled resin? By SOAKING

The fouled resin will be restored up to some extent by regular brine alkaline for organic
defouling and acid treatment for iron defouling once in 3 months.

WAC/SAC: Fill the bed with concentrated Acid (98%) and keep it like that for 24 hours for iron
defouling.

WBA: Fill the bed with concentrated (30%) NaOH and keep it like that for 24 hours for organic
defouling.
 CHLORIDE INDUCED SCC:

A specific type of SCC is induced by chloride concentration cell, common with, but not limited
to, STAINLESS STEELS (316…) To occur, it requires a chloride concentration and tensile stress
focused together to cause both intergrannular and transgrannular branch type cracking, this
produces weakening of the metal and eventual failure.

Experience indicates that the concentration of Cl- in water contacting the S.S. is not the critical
factor. The MAIN FACTOR IS THE EXISTENCE OF CONDITIONS THAT ALLOW CHLORINE
CONCENTRATION CELLS TO DEVELOP.

In absence of concentration Cells or STRESS, Cl- levels in excess of 1000 ppm (Mg/L) have not
caused S.S. to crack. In fact, some desalination plants where Cl- concentration exceed 30,000
ppm have not experienced failure WHEN PROPERLY ANNEALED STAINLESS STEEL
CONSTRUCTION WAS USED AND THE SYSTEM KEPT FREE OF DEPOSITS.

THE KEY TO PREVENTING SCC IS ELIMINATING DEPOSITS AND FABRICATING +STRESS - RELIEVED
EQUIPMENT THAT DOES NOT ALLOW CONCENTRATION CELL TO OCCUR.

ONCE CONDITIONS FOR Cl- induced SCC to occur:

1. Cl- concentration + Tensile Stress + deposits:

Elimination:
1. STRESS RELIEVED EQUIPMENT

2. FREE OF DEPOSITS

3. Cl- concentration Low.

6 Chains: 4 in service + 1 regeneration + 1 standby

S.No. WAC SAC WBA
3
Flow from Steam M /hr
01 Normal 288 288 288
Maximum 300 300 300
Minimum 61 61 61
02 Net capacity between regeneration M3 5760 5760 5760
03 Period between regeneration 20 hrs 20 hrs 20 hrs
Chemical per regeneration (kg)
04 30% HCl 4787 4787 -
100% NaOH - - 491
05 Waste water per regeneration 125 61 95
06 Time per regeneration(minutes) 121 121 80
07 Resin Indion 236 Indion 225 Indion 48R
08 Resin liter/unit 10920 11160 10920

WAC reactions: Ca2+ + 2RH → R2Ca +2H+

Mg + 2RH → R2Mg + 2H+
2

SAC reactions: Na+ + RH → RNa + H+

K + RH → RK + H+
+

Regenerant quantity: Ionic Load x Mol.wt (36.5) x 1.2

NOW DM PLANT
WAC: - RESIN: INDION – 236 CONTAINS CARBOXLIC ACID GROUPS
It is based on cross-linked polyacrylic acid and is supplied as moist white beads in the
hydrogen form, and is recommended for the reduction of alkalinity in BFW.
It removes Calcium Bicarbonate alkalinity from water, thus reducing total dissolved
solids. It can also be used to soften water containing sodium alkalinity.
If removal of non-alkaline hardness (chlorides and Sulphates of Ca, Mg) is required, de
alkalinity should be followed by softening using SAC in the sodium form (Indion – 225).
Physical form Moist beads
Wet screen grading
-120 to +30 IS.S. (
- 1.2 mm to 0.3 mm
Voids 40%
Ionic form (as supplied) H+
Max. operating temperature 100oC
Effective pH range 5 – 10
Resistance to oxidizing agents Generally good. Chlorine should not be present and must be
eliminated by chemical dosing or by use of activated carbon
filter.
Resistance to reducing agents good
Total Ion exchange capacity Approx. 210 Kg CaCO3/M3

Exhaustion: It is normally recommended that the operating cycle be terminated when the treated
water alkalinity reaches 30 gr.CaCO3/M3
Feed Water Temperatures: Capacity increase with increased temperature and MAX capacity is
obtained. When feed water temperature is 40oC approximately

UNIT Operation Flow (M3/hr) Time (Minutes)

1 WAC a. Back wash 81.0 5
b. Acid preinjection 48.0 2
c. Acid injection (5% w/w) 57.5 30 Thorough
d. Acid transfer 48.0 14 SAC
 e. Rinse 110.0 40
2 SAC a. Back wash 72.0 5
b. Acid preinjection 48.0 2
c. Acid injection (5% w/w) 57.5 30
d. Acid transfer 48.0 14
e. Rinse 110.0 30
3 WBA a. Back wash 32.0 5
b. Caustic Preinjection 18.0 2
c. Caustic injection (5% w/w) 22.0 33
d. Rinse 115.0 40

1. The purpose of acid preinjection stage is to ensure proper flow of power water is established
before injection of acid commenced.

2. Rinse is to remove excess acid and liberated cation or anions for WAC/SAC or WBA. This
operation is carried out simultaneously and independently for WAC, SAC, and WBA.

Treated Water Quality: The treated water is always alkaline.

100 (Gr.CaCO3/M3)100
Alkalinity Alkalinity
0 Starvation
0
(Gr.CaCO3/M3)EMA
EMA
100 0 50 100 100 0 50
100
% capacity (Exhauster Cycle) Exhaust
cycle
(% capacity up to alkalinity end point
30ppm as caco3)

Bed depth : 0.75 to 2.0 m

Backwash : Until effluent is clear, at a rate to give approximately 40% bed
expansion
Regenerant : Length – 5% (w/w) HCl (0.8% w/w of H2SO4)
Regenerant injection flow rate: 5% HCl → 2M3/hr-M3
(0.8% H2SO4 → 17 M3/hr M3)
Rinse flow rate : 10 M3/hr M3
Rinse time : Normally 40 minutes but dependent on plant design and end point
of
Rinse desired.

EXCHANGE CAPACITY ( If T.H > Total alkalinity) at 25oC

120
110
Capacity
3 (M )
3
 100
90
80
70
60
50
5 10 15 20 25 30
Exhaustion time in hours

EXCHANGE CAPACITY COMPARATIVE FURTHER IF TOTAL ALKALINITY > T.H

1.0
Multiply capacity of

0.8
0.6
0.4
above fig. by

0.2
0
0.2 0.4 0.6 0.8 1.0
Degasser tower: - Packing: pall rings.

I/L gas vent

Over flow line

Air
drain

Select liquid separator (gas

liquid departure)

Deaerator: Each deaerator tower is having two stages packed with poly propylene packing
(Leaver pack)
Vacuum Pump: Impeller is located eccentrically within con. The liquid ring, therefore, acts as a
piston.
Principle of operation of vacuum pumps: Initially the pump casing is partially filled with the seal
liquid (usually water). On first starting up, this liquid is thrown to the periphery of the casing
and forms a liquid ring. This liquid ring seals the space between the impeller blades and casing.
Note that at top position of the impeller, the chargers are completely filled with liquid. As the
impeller rotates, the liquid ring moves away from hub, increasing the space in the piping
chamber. This draws the gas into chamber from the inlet part adjacent to the impeller. As the
impeller continues to rotate, any gas in the impeller chamber is compressed by the liquid ring
and is expelled through the discharge part. This sequence is repeated again with each revolution.
The seal liquid also seals the space between the impeller blade and pump casing, plus absorbs the
heat of companion and condensation (which handling saturated gas steam).
A continuous supply of seal liquid is necessary to remove heat developed by friction, companion
and condensation. If temperature raises, vacuum will come down.

O/L part I/L Part

Space
gas
Eccentric impeller
liquid ring

Exchange Capacity corrective factor for feed water temperature:

1.0
0.9
0.8
0.7
0
5 10 15 20 25
30 Feed water temperature oC

Bed Expansion:
80
Water temperature
% Bed expansion 5 10 15
60
20
40
2025
5 10 15 20
30 Back wash water M3/hr.m
Pressure Loss 2.0
1.0
0.5
Pressure
0.4 water temperatureoC 5 20
(us)
0.3 50
ban/M
0.2
bed depth
0.1
0.05 Flow rate
M3/hr.m
 5 10 20 30 40 50 60

SAC:
Resin:- Indion – 225 (Hydrogen Cycle)
- Contains sulphuric acid groups.

- Based on cross-linked poly styrene and has a gel structure.

- It is supplied moist in the Na+ and H+ form

- Our SAC is H+ form

STRUCTURE: Basic monotone CH2 = CH2monotones

STYRENE (VINYL BENZENE, VB):-

CH2 = CH2
Divinyl Benzene (DVB)

CH2 = CH2
POLYMERISATION OF STYRENE TO POLYSTENE:
- CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 – CH2 -

COPOLYMERISATION OF STYRENE AND DIVINYL BENZENE, showing the role of DVB

in cross linking the Polystyrene chain:
The production of a stable ion exchange resin by copolymerization
- CH2 – CH2– CH2 – CH2– CH2 – CH2 – CH2 – CH2 - CH2 - CH2 - CH2

CH2 - CH2 – CH2 – CH2 – CH2 – CH2

- CH2 - CH2 – CH2
CH2
CH2
- CH2 – CH2 – CH2 – CH2
CH2 – CH2 -
CH2 - CH2 -
CH2
1 Wet Screen grading -120 to +30 I.S.I
= - 1.2 mm to 0.3 mm
2 Voids Approx. 40%
3 Ionic form (as supplied) H+
4 Max. Op. temperature 120oC
5 Effective pH range 0 to 14
6 Resistance to oxidizing agents Generally good. Chlorine should not be present and
must be removed by chemical dosing or by using
an activated carbon filter.
7 Total Ion Exchange Capacity Approx. 100 kg/M3
HYDEROGEN CYCLE: The operating exchange capacity of SAC depends on:
1. Type of acid

2. Concentration of regenerating acid.

3. Regeneration level employed kg acid/M3

4. Na+ and Mg+ + content of feed.

5. ….. Limit ; 100

1. Hydrochloric Acid: The recommended injection strength is 5% w/w and injection should be
carried out at a flow rate of 4 M3/hr M3

2. HNO3: It is an oxidizing agent and hence use of concentrations. Above 10% should be avoided.
Injection strength and flow rate are the same as far HCl. CONSTLY.

3. H2SO4: Leads to CaSO4 precipitation and its rate depends on Ca2+ content of feed water and
content time should also be controlled. COSTLY.

1. (Operating exch. Capacity: - (for …. HCl, HNO3)

Ca + Mg

a. =0 0

Na + K

100

Exchange Capacity 30

Kg CaCO3/M3 70

60/100

40/0 80

20

20 40 60 80 100 120 140 160

Kg HCl/M3

Kg HNO3/M3

35 70 105 140 175 210 240 250

 Ca+Mg
Na+K 0

b. = 0.3 100
30
70 60/100
Exchange Capacity 40/0 80
Kg CaCO3/M3 20

Regeneration level
Kg HCl/M3

Kg HNO3/M3

Na+K Ca+Mg

c. = 0.6 100 0

30

Exchange
Capacity 70 60/100
KgCaCO3/M3 40/0 00

20

Regeneration level

Kg HCl/M3

Kg HNO3/M3

d. = 1.0 Na+K Ca+Mg

 100 0

30
Exchange
Capacity 70
KgCaCO3/M3 60/100

40/0 00

20

Regeneration level

Mixed bed Regeneration:- Anion resin density is less than that of cation resin. First step in
regeneration is air agitation to segregate anion and cation resins. Anionic resin will settle at the
top whereas cationic resin at the bottom. First anion resin regeneration will be done with NaOH,
after regeneration of anionic resin, regeneration and cation regeneration will be done with HCl.

LEAKAGE RATE:- FROM SAC: depends on

1. Regeneration Level (2) Sodium and K content of feed water

50
40 Na+K%Na+K% Ca+Mg%
30 100
20 80
10
9 0
8 60
7 20
6 40
5 20 40
4 60
3 10
2 80
1
Regeneration level

160
Kg HCl/M3
 Kg HNO3/M3
a. Leakage rate as Regeneration level

b. Leakage rate is max. at a particular regeneration Level where Na+K+ comes is high.

WBA: - INDIONN – 48 R (High porosity bead form)

Contain Tertian ammonium groups. Based on cross linked polystyrene
Why degasser before WBA:- To reduce the load on WBA.
Due to its high Regeneration Efficiency, Indion-48K WBA keeps operating costs low.
The inherent quality of WBA is the case with which the absorbed organic matter is readily
removed during regeneration
Exchange Capacity: of WBA depends on
1. The SO4-- - content of the influent water.

2. The concentration Of Free Mineral Acidity (FMA)

3. The exhaustic rate.

WBAs operate at high efficiency and so it is possible to utilize a high % of the total capacity
of the exchange during the service cycle.
Regeneration: WBA can be regenerated with NH3, Caustic Soda (NaOH) or soda ash
(Na2CO3)
NaOH is preferred when effective elution of organics and high quality of treated water are
required.
Treated water quality from WBA: WBA produces treated water with reasonably low
conductivity. The conductivity will be normally about 10 µs/cm at 25oC.
The actual conductivity obtained will depend on the slippage of metallic cations from the
preceding WAC/SAC.
The pH of treated water from WBA depends on the concentration Of CO2 in the water. A
high CO2 content (as in the case of WBA being placed u/s of the degasser) will depress pH of
treated water.
NOTE: All ion exchangers are subject to fouling and blockage of active groups by
precipitated iron. Hence, the iron content of the influent water should be low and the
regenerant alkali must be free from Fe and heavy metals.
All ion exchangers, especially anion exchanges are prone to OXIDATIVE ATTACK,
RESULTING IN SUCH PROBLEMS AS LOSS OF CAPACITY, ION EXCHANGERS
CLUMPING ETC. Therefore alkali, particularly caustic soda (NaOH) should have as low a
CHLORATE CONTENT AS POSSIBLE.

CHARACTERISTICS:
01 Physical form Moist beads
02 Wet screen grading -120 to +30 ISS = -1 .2 mm to 0.3
mm
03 Voids 40% (Approx.)
04 Ionic form Free base
05 Max. Op. temperature 80oC
06 Effective Op. pH range 0 to 7.0
07 Resistance to reducing agents Good
08 Resistance to oxidizing agents Good

TOTAL ION EXCHANGE CAPACITY (SO4- -) = 80 kgCaCO3/M3

01 Pressure Loss Upto 2 bar

02 Back wash 40% bed expn. Flow reqd.
03 Regenerant NaOH
04 Regenerant concentration 1-5% w/w soln. of regenerant
05 Regenerant injection 30 mts. minimum

EXCHANGE CAPACITY: % 100

70
25
60Exchange
capacity Kg 0
3
50CaCO3/M

40 12 16
20
8 Exhaustion time hours

2. EFFECT OF FMA ON CAPACITY:

FMA CAPACITY 150

100
Exchange
capacity %
of above
fig.
50

20 200 500 1000

 40 50 100 FMA PPM CaCO3

3. Bed expansion: Temperature

5oC

10oC
Bed
expansion 20oC
%
40oC

FORMULAE: Work done by Resin = Gross output x Ionic

Load
Exchange capacity can be found out from graph
Now,
RESIN VOLUME = WORK DONE / EXCHANGE CAPACITY

=
So, If resin volume, exchange capacity, ionic load are known we can calculate the gross out put

DESIGN: EXCHANGE CAPACITY:

1. WAC = 79.2 Kg CaCO3/M3 ( 80)

2. SAC = 75.5 Kg CaCO3/M3 ( 75)

3. WBA = 47 Kg CaCO3/M3 ( 45)

Exchange capacity can be increased by increasing the Regeneration level. Not economical
leakage rate of SAC can also be minimized by raising the regeneration level.

Since Gross output =

So, Gross output can be increased by:
1. By increasing resin volume

2. By increasing exchange capacity

3. Exchange capacity can be removed by increasing regenerant level.

CALCULATIONS:- Process Calculations for performance test:-

All units in ppm CaCO3
Design Calculations:
TOTAL CATIONS: TOTAL ANIONS:
Ca → 99 P. Alkalinity = NIL
Mg → 88 TH = 99+88 = M. Alkalinity = 200.2
Na → 91.3 187 Chloride Cl- = 43.5
K → 5.5 Sulphate SO4- - = 33.0
----------------------- Nitrate NO3- = 1.1
TOTAL CATIONS→ 283.8 Phosphates PO4- - - =3.8
---------------
--
TOTAL ANIONS = 283.8
-----------------
EMA = Cl- + SO4 - - + NO3- + PO4- - - = 43.5 + 33 + 1.1 + 3.8 = 83.6 ppm CaCO3
1. WAC: Treatment flow rate = 288 M3/hr

Exhaustic time = 20 hrs.

Net output between regeneration = 5760 M3

Gross output between regeneration = 5760 + 95 + 55 = 5910 M3

Hence, ALKALINITY IS MORE THAN HARDNESS

IONIC LOAD = TOTAL HARDNESS – AVG. HARDNESS SLIP
= 187 – 40 = 147 ppm CaCO3
o
Feed water temperature = 25 C
WORK DONE BY RESIN = GROSS OUTPUT X IONIC LOAD = 5910 x 147/100 =
868.77 kg CaCO3
Resin volume provided = 10.97 M3
Exchange capacity = 79.2 kg CaCO3/M3
2. SAC:-

Treatment flow rate = 288 M3/hr

Exhaustic time = 20 hrs.

Net output between regeneration = 5760 M3

Gross output between regeneration = 5760 + 95 = 5855 M3

 XU feed water quality:
Remarks
pH 7.5 – 9.0 Lower pH causes accelerated
corrosion on C.S
Hardness Ppm (Max) Causes deposits on H.T. surface
TDS <30 ppm
Dissolved O2 0-2 ppm Causes ‘S’ precipitation And …..
Chloride 4ppm S.C.C. on S.S

IONIC LOAD ON SAC = Total Cations – Total Hardness + Avg. hardness slip from WAC
= 283.8 – 187 + 40 = 136.8 ppm CaCO3
= (Total Cation – Ionic load on WAC)

Total Alkalinity/Total Cation in the feed entering SAC:- (200.2 – 187 + 40)/136.8 = 39%
(Na + K)/ Total Cation = (91.3 + 5.5) / 136.8 = 71%.
Regeneration Level = Kg HCl/M3 resin = 128 Kg HCl/M3 of resin.
(This NaCl can’t be removed in WBA)
Exchange Capacity = 75.5 kg CaCO3/M3
Deaerator Capacity = 75.5 x 0.95 = 71.7 kg CaCO3/M3
Work done by resin = (Gross out put x Ionic load) = (5855 x 136.8)/1000 = 800.96 kg CaCO3
Resin Volume = (Work done)/Exch. Capacity = 800.96 / 71.7 = 11.16 M3
3. WBA:

1. Treatment flow rate = 288 M3/hr

2. Exhaustic time = 20 hrs.

3. Net output between regeneration = 5760 M3

4. Gross output between regeneration = 5760 M3

IONIC LOAD ON WBA = FMA

= EMA – Slip from SAC
= 83.6 – 4 = 79.6 ppm CaCO3 = FMA
SO4- -/EMA = 33/83.6 = 39.5%
Deaerator capacity = 47 x 0.9 = 42 kg CaCO3/M3
Work done by resin = Output x Ionic load
= (5760 x 79.6)/1000 = 458.5 kg CaCO3
So, Resin Volume = Work done/Exchange Capacity
= 458.5/42 = 10.92 M3
CALCULATION OF OUTPUT FOR GIVEN ANALYSIS (on 31.03.1988)
All Units are in ppm CaCO3
CATIONS ANIONS
Ca → 76 M. Alkalinity = 198
Mg → 34 TH=11 EMA = 58 (SO4- - + Cl-)
0
 Na → 146 --------------------------------------
-------
--------------------------- TA = 256
TC → 256 --------------------------------------------
---------------------------
1. WAC :- Flow = 288 M3/hr, Exhaust time = 20 hrs.

ALKALINITY IS MORE THAN HARDNESS

Ionic Load = 110 – 40 = 70 ppm CaCO3

Exchange Capacity = 35 kg CaCO3/M3

Expected Output =

= 10970 x 35/70 = 5485 M3 (gross)

2. SAC :- Flow = 288 M3/hr, Exhaust time = 20 hrs

Ionic Load = 256 – 110 + 40 = 186 ppm CaCO3

(Alk/TC) in inplant = (198 – 110 + 40)/186 = 68.8%
Na/TC = 146/186 = 78.6
Regeneration Level = 128 kg HCl M3 of resin
Exch. Capacity = 75 kg CaCO3/M3 (from graphs)
3
3/M

Expected output =
= 11160 x 71.25/186 = 4275 M3 (Gross)
3. WBA : Flow = 288 M3/hr, Exhaust time = 20 hrs

Ionic Load = FMA

= EMA – Slip from SAC

= 58 -4 = 54 ppm CaCO3

SO4 - -/EMA = 41/58 = 0.7 or 70%

FMA = 54

Exch. Capacity (from graph) = 45 kg CaCO3/M3

Deaerator capacity = 40.5 kg CaCO3/M3 = (45 x 0.9)

Expected output =

= = 8190 M3 (Gross)
So,
Design Present
Gross Net Gross Nett
WAC 5910 5760 5485 5485
SAC 5855 5760 4275 4180
WBA 5760 5760 8190 8190

MATERIALS OF CONSTRUCTION
STEELS: The corrosion resistance of steel (combn.) depends upon the form of the oxide surface
film.
Carbon content → 0.2% to 0.4% (High C.Steel)
→ Higher the carbon content, Higher the tensile strength.
ACID USE: 1. C.S should not be used for dilute acid.
H2SO4: Below 90%, C.S. is not recommended
Between 90 – 98%, steel can be used up to boiling point.
But between 80 – 90%, it is serviceable at ROOM TEMPERATURE ONLY.
Above 102%, steel is good up to 140oF
BUT STEEL IS NOT USED WITH HCl, H3PO4, and HNO3 acids.
NaOH: when Iron contamination is permissible, CS can be used for handling NaOH up to about
75% and 212oF. STRESS relieving is sometimes necessary to reduce CAUSTIC
EMDRITTLEMENT.
Tower Shell = A 516 Gr 70, yield strength = 70,000
Silicon kill, lamination,.100%.....
MTS = 304/L
HTS = 316/L (to avoid pitting) – Mo avoids pitting
Rupture disc: Inconel 600 with Teflon coating. (Teflon coating to prevent crevice corrosion)
Halon 1301: C F Cl Br
1 3 0 1
Used here CF3BV
ALLOY STEELS:
Ni increases toughness and improves low temperature props and corrosion resistance.
Cr and Silicon improve Hardness, abrasion resistance, corrosion resistance and resistance to
oxidize.
Mo (Molybdenum) provides strength at elevated temps. Best for pitting corrosion resistance.
STAINLESS STEELS: 1. MARTENSITIC (2) FERRITIC (3) AUSTENITIC
1. MARTENSITIC:

- Low corrosion resistance.

- Contain 12 to 20% of Cr with controlled arrestors, carbon and other additives.

- Can be used in mildly corrosion environment

- AISI 410 is one example.

2. FERRITIC S.S:

- Contains 15 to 30% Cr. With low carbon content 0.1%.

- The higher Cr content improves corrosion resistance

- Type AISI 430 is an example.

- Corrosion resistance is repeal good. But these are not good against reducing agents such as HCl

- Mildly corrosive solutions and oxidizing media are handled without harm.

- 430 type is widely used for HNO3 handling.

3. AUSTENITIC S.S: ARE THE MOST CORROSION RESISTANT OF THE THREE GROUPS.

- Contain 16 to 20% of Cr, 6 to 22% Ni.

- Carbon is kept low (0.08%) to MINIMISE CARBIDE PRECIPITATION

- They are tough and DUCTILE

- Welding heat comes chromic carbide precipitation, which depletes alloy of Cr and lowers its
corrosion resistance in liquid service.

Cr Ni Mo C(Max) Fe
304 19%+ 9% (=28%) 0 0.08% Balance
304L 19% + 10% (= 29%) 0 0.03% Balance
316 18% + 11% (=29%) 2.5% 0.1% Balance
316L 17% + 12% (=29%) 2.0% 0.03% Balance
RK65 19% 25% 4.5% 0.02% Cu= 1.5%

XU:- TOWERS, VESSELS = A516 Gr 70

Mass transfer Trays = SS 304 (L issued when welding is ……
Heat transfer Trays = SS 316
Piping = A 333 Gr 6 (Sulphur low melting point 0.098% Phosphorous
(very
low melting point) 0.05% cold ……. Old
……
Valves = A350L F2 (up to 1 ½ “size)
Valves = A352 LCB (>1 ½ “size)
Pump Impeller = SS316L – Booster ………….. = A352LCB
H2S : Piping from Reaction to K.O drum = 2RK65
Impeller = SS316
Pumps = SS316
STEAM, LPG, DRAING VENT PIPING = A 106 Gr B
HEAT EXCH EX CWX Ch.W.X
Shell SS316L cladded CS CS
Tube SS316 SS316 SS316

SS 304:- Cr →19% Ni →9%, C= 0.03% Max, Rest = Fe

SS 304L:- Cr →19% Ni →10%, C= 0.03% Max, Rest = Fe
SS 316:- Cr →18% Ni →11%, Mo= 2.5% Max, C= 0.1 Max. Rest = Fe
SS 316L:- Cr →17% Ni →12%, Mo=2.0% C= 0.03% Max, Rest = Fe
(But high temperature properties are not effected)
- For mild service, this carbide precipitation is not serious, but for severe corrosion service, the
carbides must be put back into solution by heat treatment. But this is not possible with field-
weld.

- To avoid precipitation, we can use either special S.S. stabilized with titanium, colusice… or
titanium (321, 347, 348) or USING LOW CARBON STEELS (304L, 316L) with 0.03% Max. Carbon.

- Type 302 is the basic alloy of this group. Types 304, 304L are low-carbon versions of 302.

- Type 316, 316L and 317 with 2.5 to 3.5% MO are the MOST CORROSIC RESISTANT.

- Ni greatly improves corrosive resistance over straight CV stainless steels.

INCONEL 600 – High alloy (RD assembly) 80% Ni, 16% Cr, 7% Fe. It contains NO
MOLEBDENUM. THIS CORROSION RESISTANT GRADE IS RECOMMENDED FOR
REDUCING OXIDISING ENVIRONMENT PARTICULARLY AT HIGH TEMPS.
WHEN HEATES IN APR, THE ALLOY RESIST OXIDISATION UPTO 2000OF.
 THE ALLOY IS OUTSTANDING IN RESISTING CORROSION BY GASES, WHEN THESE
GASES ARE ESSENTIALLY FREE OF SULFUR.
LOW TEMPERATURE MATERIALS:-
Most metals lose their ductility and impact strength at low temperatures, although in many cases,
yield and tensile strength increase as temperature goes down.
For low temperature sper…,. A minimum charpoy (impact strength) value of 15ft-lb (keyhole
notch) is specified at operating temperature. For severe loading, a value of 20ft-lb is
recommended.
S.S:-Cr-Ni steels are inherently suitable for service from -300 to -425oF.
Type 304 is the most popular (AUSTENITIC S.S)
Nickel Steel – Low carbon 9% Ni steel is a ferrite alloy can be used in cryogenic equipment up
to -320oF. A 300, A353comes low carbon 9% Nickel steel.
Aluminum: - All alloys have unusual ability to maintain strength and stock resistance at
temperatures as low as -425oF.
Good corrosive resistance, low cost makes these alloys very popular for low temperature
equipment. Type 5000 service are widely used. They are Al-Mg, Al-Mg-Mn alloys.
Cu and alloys: With-few exceptions, the tensile strength of Cu and its alloys increases in
temperature goes down. HOWEVER, COPPER’S LOW STRUCTURAL strength becomes a
problem where constructing large scale equipment. So, alloys must be used. One of the most
successful alloys for low temperatures Is SILICON BRONZE. This alloy can be used to -320oF
with safety.

Nitrogen Plant materials:

COLD BOX: External Shell = C.S
Internal Shell = S.S
Insulation = Slag Wool
Dry gaseous Nitrogen. Pressure of 0.1 kg cm2g is maintained to prevent moisture ingress into
slag wool.
Cold Box Exchanger: - Brazed Aluminum
Distillation Column: Shell = S.S.; Sieve trays = COPPER (50 Nos.)
Vaporizer: Exchanger is made of Aluminum ; Shell = S.S.
Cold Converter: Internal Shell = S.S.; External Shell = C.S
Between these two shells, perlite powder under vacuum is provided. Heat loss for full tank =
0.45% per day.
Low Temperature Materials – carbon and alloy steels:
A.S.T.M. Specification and grade Recommended Min. Service
TemperatureoF
A 353 (9% Ni) -320oF
S.S:- 302, 304L, 304, 310, 347 -425oF
Al alloys: 505L, 508S, 508E, 5154,5456 -425oF
etc.
Cu alloys, Silicon Bronze, 70-30 brass, Cu -320oF

HALON SYSTEM AT CCR

HALON – 1301 used as FIRE EXTINGUISHING AGENT:

C F Cl Br
HALON - 1 3 0 1 = CF3 Br
HALON - 1 2 1 1 = CF2ClBr]
In our system, we are using HALON-1301 why?
1. Halon 1301 is a gas at room temp, wherever Halon 1211 is a liquid at room temperature hence,
1301 requires a small and single piping arrangement.

2. Both are electrically non- conducting so, they can be used for electric firing also.

3. At a concentration of 3-6% (by vol.), Halon 1301 extinguishes the fires. For CO2 extinguishers,
the concentration required = 20%.

4. A concentration Of 80%, Halon 1301 is fatal whereas Halon 1211 is fatal at only 20%
concentration

5. Where water or powder is used as fire extinguishers agents, the secondary damages are rather
extend the cleaning up afterwards is many and expansion. Halon is a gas which can be
ventilated easily.

6. Within 10 seconds, Halon extinguishers the fire.

Only disadvantage: At 500oC, it decomposes into ……..particles which may in combination with
the smoke from fire cause coughing and smarting eyes.
Reactions:-
Reaction 1 : C + O2 → CO2 + Heat
Reaction 2 : H2 + O2 → 2OH
Reaction 3 : 2OH → H2O + O + heat
Reaction 4 : Br + H → HBr
Reaction 5 : HBr + OH → Br + H2O
If halogen is sprayed into the fire, the Halon atoms will split from the carbon atoms and actively
participate in the process of combustion. As can be seen Br reacts with Hydrogen (H) and form,
HBr, which in turn react with OH of the reaction (3). And hence reaction (3) cannot continue
and thus no heat is released to the effect that the process of combustion will stop. Further more,
we got free Bromine atom (5) that can once more react with the H2.

HENCE, WE USE HALON 1301 (CF3Br) AT OUR CCR FOR

FIRE PROTECTION
HOW TO SELECT A PUMP?
(a) Engineering of System requirements.

(b) Selection of pump and driver (c) specification of pump

A. Engineering Of System requirements:-

- Fluid type:- density, viscosity, vapor pressure At suction, conductivity and suspended solids etc.
Total operating range should be concerned.
- Specific material if any required.

- System head curve. Should have good understanding of the system where pump will be
incorporated. Loss of various header no. of values in the pump loop, system of control.
Operation at no flow condition, system head curve which shows flow vs. hydraulic losses.

System head
H System friction curve H
friction loses
Friction loses

System head
Q Q
Alternative Modes of Operation:-
- Continuous or intermittent pumping.

- Fluctuations in head & flow.

- No. of flow paths, whether any flow path needs booster pump.

- Continuity of service expected to decide for standby pump and sizing of no. of pumps.

- Floor space available.

Margin: Specify margin over and above the normal rating to take care of, over long time
operation and fluctuation in suction conditions and power system and etc.
But over sizing of pump has adverse effect in running the pump with minimum flow
recommended by Manufacture.
CENTRIFUGAL PUMPS:
Pumping is the addition of K.E and P.E. to a liquid for the purpose of moving it from one
point to another.
Centrifugal force developed depends on both:
1. Peripheral speed of impeller.

2. Density of the liquid.

But energy imparted per lb. of liquid is independent of the density of the liquid.
But viscosity does affect this imparted energy.
The pressure in a system handling liquids must never be permitted to fall below the vapor
pressure of the liquid.
To deliver a given volume of liquid through the system, a pump must impart energy to the
liquid made up of the following components:
1. Static Head

2. Difference in pressures on liquid surfaces.

3. Friction head

4. Entrance and exit losses

1. STATIC HEAD: refers to a difference in elevation.

Total static head = (liquid level at discharge – liquid level at suction)

Static discharge Head = (discharge Liquid level) – (pump centre line)

Static suction head = (suction liquid level) – (pump centre line)

If suction liquid level is below the pump centre line, STATIC SUCTION HEAD will have negative
valve and it is usually called as STATIC SUCTION LIFT (submergible pump)

2. FRICTION HEAD: is the head required to overcome the friction losses caused by flow of liquid
through piping. Valves, fittings and any other elements such as Heat Exchangers. These losses
vary approximately as V2.

Wear: Even at the end of plant life a pump should be able to deliver capacity. For abrasion
liquid, we should select pumps with liners which can be replaced easily.

Future System Changes: To look into possibility of providing for future system modifications
should affect minimum of running pump. Providing extra flow from the same pump by
increasing the impeller diameter.

Selecting of Pump & Drive:

- Head required and capacity.

- Variation of head with capacity permitted or not.

- Floor space available.

- Pump suction conditions.

- Types of seals/availability of spares.

Pump Characteristics: CONST. HEAD, CONST. CAPACITY → RECIPROCATING PUMP

VARIABLE HEAD, VARIABLE CAPACITY → CENTRIFUGAL PUMP

LOW HEAD, HIGH FLOW → AXIAL PUMP

 3. Entrance and Exit Losses: vary approximately as V2

If the supply of a pump originates in a reservoir, tank, or intake chamber, losses occur at the
point of connection of the suction piping to the source of supply. The magnitude of these losses
depends on the design of the pipe entrance. A well-designed bell-mouth provides the lowest
possible loss.

Similarly on the discharge Side of the system, when the discharge Line terminate at some body
of the liquid, the velocity head of the liquid is entirely lost and must be considered as a part of
the total friction losses.

SYSTEM FRICTION AND SYSTEM HEAD CURVES:-

Head system friction curve

H
Friction losses

Capacity Q
SYSTEM HEAD CURVE: When we confine static header, pressure differences and friction
losses of any system we will get system head. The plot is as follows:
Pump hours Q curve
System head
curve
Head
H Friction losses

TOTAL STATIC HEAD

0 (10) Capacity Q
The point of intersect of system head curve and pump head capacity curve GIVES US THE
CAPACITY THAT WILL BE DELIVERED INTO THE SYSTEM BY THAT PUMP AT
THAT PARTICULAR SPEED.
VARYING STATIC HEADS OR PRESSURE DIFFERENCES:
For these systems, it is possible to construct curves corresponding to the minimum and
maximum conditions. The corresponding intersection gives the minimum and maximum flows,
a pump can deliver into the system at that particular speed pump head capacity curve
system head curve max.

Max static head curve system head

curve, min.
2 Max. Static
head
Head
H 1 min. static head curve Min. static head
 Capacity Q Q at
Min. static head
Q at Max. static head
VARIATIONS IN DESIRED FLOW: A given pump operating in a given system will only
deliver that capacity corresponding to the intersection between the head capacity of the pump
and the system head curves. Hence, in order to vary the capacity, it becomes necessary to
change the shape of either one or both curves.

1. The pump head capacity curve can be changed by operating the pump at VARIABLE SPEED.

2. Or the system head curve can be altered by creating a friction loss thro’ a throttling valve (by
throttling discharge Valve we can vary the capacity now). Also the capacity can be varied by
varying the frequency of the motor.

Head capacity at full speed system

head curve
Head capacity at N2
Head capacity at N3
(a) CHANGE SPEED friction losses

Head H
Static pressure head

Q (Max.)

Head capacity at CONST. SPEED

H3
System head curve H2
System Head Curves H1
H3>H2>H1 throttle
Via throttle valve
Head Friction losses
H
Static Pressure or head
(b) THROTTLE Q3 Q2 Q1 (Max)
Capacity Q
Obviously the diff. between the head developed by the pump and the head required by the
system head curve (H1) represents the wasted energy lost in the throttling process.
AFFINITY LAWS, PUMP PERFORMANCE CURVES:
These are ACTUAL
PERFORMANCE CURVES
VSQ

BHPVSQ
 Best Efficiency Point (BEP)
VSQ ( efficieny of pump
NPSH
Capacity Q
B.E.P : The capacity at which the pump performs its function most efficiently is called the Best
Efficiency Point or BEP.
Water Horse Power – WHP: The useful work done by the pump is the (wt. of liquid pumped in a
period of time) x head developed by the pump and this is called WHP.
i.e.

WHP =
WHP = Water horse power
Q = Pump capacity g[r
H = Total head ft.
Specific Speed: of a pump impeller is the rpm to produce 1-M head at unit B.H.P. under Best
Efficiency Conditions.
1 H.P = 0.736 KW = 736 Watts.
Break Horse Power (B.H.P):- is THE POWER READ TO DRIVE THE PUMP
And B.H.P. = (Water Horse Power)/Pump efficiency

B.H.P = =
Affinity Laws:
1. Q (speed)
2
2. H
3
3. B.H.P. (deviated by P)

2 2 3 3
= , = 2 / 1 , = 2 / 1

(Only for moderate changes in speed)

If D = impeller diameter

2 3
= ; = , =
Specific Speed
NS = /H3/4
NS = Specific speed, = rotation speed rpm, Q = Capacity of pump
H = head ft (head per stage for a multistage pump)
NS equation remains unchanged whether the impeller is single suction or double suction.
- Specific speed No. is independent of rotation speed at which pump is operating.

- The value of specific speed will immediately describe the approximate impeller shape. Also it
will reflect on pump characteristics.
 100 3000-10,000 gpm over 10,000 gpm
90 1000-3000 gpm
80% 500-1000gpm
efficienc 70
y 60 200 – 500 gpm
50 Below 100 gpm 100-200 gpm
40 NS in M.K.S. Units
10 20 40 60 80 100 200 300
NS
Reciprocating and Rotary 40
Specific Speed
1. Reciprocating and Rotary 40

2. Regeneration turbine 10 - 25

3. Centrifugal 40 - 300

4. Mixed flow 300 – 600

5. Axial flow 600 - 1200

H H
H, H,
P
P, P P,
doping
H.V.Q.C curve

Low NS (RADIAMETERL) Q Avg. Sp.

Speed Q

H, H,P, H
P, H P
(dropping HvsQ
curve
 P

High Sp. Speed Q MIXED FLOW

Q

H, P, P H

Axial flow Q
Hence, mixed flow, Axial flow pumps should not be started with its discharge Valves fully
closed. Also a Q , P , for these pumps.
Head
Head H Head
Head H
H power
Power
Q capacity Q Mixed flow Propeller or axial flow
impeller Q
power
efficiency
Centrifugal
(NPSH) required:- is the energy in feet of liquid head required at the pump suction over and
above the vapor pressure of the liquid to permit the pump to deliver a given capacity at a given
speed.
If (NPSH) available > (NPSH) required, changes in (NPSH) …. Won’t affect the pump
performance.
If (NPSH) available falls below (NPSH) required, then cavitation occurs. The performance
curve becomes as shown below (Broken line).
Efficiency
H Head

BE
P
Power NPSH

Q
(The reqd. (NPSH) is lower for hydrocarbons when compared to water)
CAVITATION CURVES:
On set of cavitation
H,
P, Fully developed
cavitation
 Q,

Head
(Hscr) I (Hscr)/II
Both (NPSH)A, (NPSH)R VARY WITH CAPACITY: Ps
Head
H (PS-PUP) (NPSH)r S
hfs+hi A PtA
S (NPSH)A
S+(Ps+Pup) (NPSH)= S+(Ps-Pup)
– (hfs + hi) A
Q (hi = entrance loss
at Pt.A)

(NPSH)a ↓ as Q because of large friction losses in the suction piping, it reduces at larger flows.
(NPSH)r is a function of velocity in the pump suction and at the inlet of impeller. INCREASE
AS THE SQUARE OF CAPACITY.
Qv
INADEQUATE SUCTION CONDITIONS:- HOW TO IMPROVE (NPSH)av and how to reduce
(NPSH) req.
If (NPSH)av is insufficient we can follow this. Improve (NPSH)av or reduce (NPSH)req or do
both.
(a) TO INCREASE (NPSH)av:- we can

1. Raise the liquid level

2. Lower the pump

3. Reduce the friction losses in the suction piping

4. Use a booster pump

5. SUB COOL THE LIQUID

(b) Sub Cool the liquid: This approach INCREASES available (NPSH) by reducing the vapor pressure
of liquid being pumped.

(c) TO REDUCE REQUIRED (NPSH): We can use

1. Slower Speeds

2. A double suction impeller

3. A large impeller …..area

4. An oversize pump.

5. Inducers ahead of conventional impellers

 6. Several smaller pumps in parallel.

1. USE SLOWER SPEEDS: Once a reasonable value of specific speed has been selected, it becomes
obvious that the lower the pump speed, the lower the required NPSH.

But low-speed pump will be more expensive and less efficient than a higher speed pump.
Hence, lowering the speed is not economical.

2. USE A DOUBLE SUCTION IMPELLER: For larger capacities, we usually use double-suction (C.W.
pumps) impeller.

How double suction impeller reduces (NPSH)r?

If we select the same S (specific speed) values for both SINGLE AND DOUBLE-SUCTION impeller
is such that:

1/2 1/2

S= ¾ =

1 → single suction impeller

2→ double suction impeller

Since and if we assume that there Hsv2 = 0.63 Hsv1 or of un…..

Hsv1 = Hsv2 there (n2 = 1.414 n1)

So, by keeping the pump speed same in both cases, we can reduce (NPSH)R by 27% if we use a
double-suction impeller. Alternately, with a given (NPSH)R (same for both types) we can operate
the double suction pump at 41.4% higher speed and hence of high efficiency.

3. USE A LARGER IMPELLER EYE AREA: This solution reduces the required NPSH by reducing the
entrance velocities into the impeller. These lower velocities may have little effect on pump
performance at or near B.E.P. But, when such pumps run at partial load, this practice can lead
to noisy operation, hydraulic surges and premature wear. Hence, this is a dangerous procedure.
 4. USE AVV OVERSILED PUMP: Because (NPSH) required decreases as the capacity is decreased, a
lager pump is occasionally selected. This practice is risky and can lead to undesirable results.

More expensive. And operation will be at low efficiencies. And, operation at a lower % of the
B.E.P. flow can lead to exactly the same problems as above (3).

Uncontrolled excess flow

Head and Q at BEP

Desired

Power capacity system ….curve

At head

(Effect of over sizing) station head

Required flow Q

5. USE AVV INDUCER: An inducer is a low-head axial type impeller with few blades, which is
located in front of the conventional impeller. Any design, it requires considerably less NPSH
than a conventional impeller, so it can be used to reduce (NPSH)req. of a pump. Permissible
operating range of pumps with inducers is generally narrower than with conventional impeller.

6. USE SEVERAL SMALLER PUMPS IN PARALLEL: - Smaller capacity pumps require low (NPSH).

VISCOSITY EFFECTS: - Two of the major head losses in centrifugal pumps are caused by fluid
friction and disk friction. These losses vary with the VISCOSITY OF THE LIUQID.

H 100SSU
32SSU 400SSU
1000SSU
Head.eff↓ as µ 32 SSU
power as µ
4000SSU
– Say bolt
SSU100SSU
Efficiency secondary
400SSUuniversal
2000SSU viscosity1000SSU
in USA
400SS
4000SSU Power 100SSU
U
Q
32SSU

Both Head, efficiency are decreasing with increasing viscosity, power increase as µ
ENTRAINED ARC OR GAS:
If the amount of gas in water is increased to Gas free liquid
6% by volume the effect is almost disastrous. 0%
The dotted line indicates the MINIMUM 1
CAPACITY AT WHICH PUMP CAN BE 2
OPERATED. If pump capacity is reduced 3
further this indicated minimum flow, air or gas 4
Minimum capacity 56
can be longer be partially swept out thro’
discharge and the pump becomes air bound
(6% of gas by volume). Q
%gas by
PARALLEL OPERATION OF TWO PUMPSvolume VS ONE:
The pump in parallel # are there. One was taken at of service. Whenever a single pump is
% head
running, its head capacity curve intersects the system gas by volume
curve at flows in excess of disch.
Capacity. This is called “RUN-OUT POINT”.

Head (2 pumps in parallel) System

head curve
Head (1 pump)

Run
out point

Max.capacity(2 pumps)
Q
Max.capacity (one pump)
Rated capacity
Hence again available (NPSH) at size of the driven must be selected in such a manner as to
satisfy conditions prevailing at run-at point.
OPERATION AT LOW FLOWS: EFFECTS OF OPERATING AT REDUCED FLOWS ARE:
1. Operating at less than Best efficiency (to avoid the use pumps on parallel)
 2. Higher bearing load. If the pump is of the single volute design, it will be subjected to a higher
radiameterl thrust that will increase the load on its radiameterl bearings. A pump that is
expected to operate at such flows must be able to accept this higher bearings load.

3. TEMPERATURE RISE: AS CAPACITY IS REDUCED, THE TEMPERATURE OF LIQUID INCRASES. TO

AVOID EXCEEDING PERMISSIBLE LIMITS, A MINIMUM FLOW BYPASS MUST BE PROVIDED.

4. INTERNAL RECLECULATION: AT CERTAIN FLOWS BELOW THAT AT B.E.P., ALL CENTRIFUGAL

PUMPS ARE SUBJECTED TO INTERNAL RECLECULATION IN BOTH THE SUCTION AND THE
DISCHARGE AREA OF THE IMPELLER. THIS CAN CAUSE HYDRAULIC SURGING AND DAMAGE TO
THE IMPELLER METAL SIMILAR TO THAT CAUSES BY CCAFFIC CAVITATION.

The larger the impeller eye diameter and the larger than area at the impeller suction relative to
its geometry (and so, the lower the required NPSH at a given capacity at speed), the higher the
capacity at which recirculation taken place ( a - % of B.E.P. capacity)

A Flow at suction recirculation eff. With impeller A

Flow at suction recirculation

With impeller B
(NPSH)req. impeller B

(NPSH)req.impeller A
Q

This internal recirculation leads to cavitation, internal pressure pulsations and noise and
can be large to the impeller network.
Hence, to reduce (NPSH)r, if we increase impeller eye area, it will lead to internal
recirculation, at capacities closer to B.E.P. Capacity.
2. HIGHER THE SPECIFIC SPEED FOR A GIVEN SET OF OPERATING CONDITIONS,
THE HIGHER PUMP EFFICIENCY AND THEREFORE THE LOWER THE POWER
CONSUMPTION

100
90 h1/D1 = 0.7
80 0.65
Suction 70 0.6
60 0.55 0.5
recirculation
50 % of BEP 0.45 0
40 flow. 0.25 h1 = hub diameter; D1 = eye diameter
30 Double suction h1/D1 = 0.35 to 0.
20 Multistage h1/D1 = 0.5 to 0.
10
0
6000 800
 Suction specific speed S

S , , Cost P ↓
PUMPS BASIC THEORY

1. Effect of impeller vane angle β on head developed by pump:

Hth = Theoretic head developed

β = Impeller vane angle

β→ 0 90o 180o

Hth → - U22/g +

This theoretic head is strongly affected by vane angle particularly with its smaller and
larger values approaching 0 or 180o
TYPES OF IMPELLER VANES (in a centrifugal pump)
1. Backward curved

2. Radiameterl

3. Forward curved

1. Backward curved of β (vane angle) <90o

2. Radiameterl of β = 90o

3. Forward curved of β >90o

1. Backward curved vane angle β <90o

β β

2. Radiameterl;- β = 90o β
 3. Forward curved β > 90o

The forward vanes add the greatest amount of energy to the flow as compared to other
shapes, yet the dynamic pressure energy predominates in the total amount of energy impacted by
such vanes.
By contrast, it is the potential (static pr.) energy that predominates in the total energy
transferred by backward curved vanes.
Reaction effect: - The capability of impeller vanes to develop a static head is judged normally by
an impeller characteristic called Reaction effect

Reaction effect, ρ = =
Externally forwarded Curved Vanes, ρ = 0, β>90o
For Radiameterl Vanes ρ = ½, β = 90o
Externally Backward curved vanes ρ = β< 90o
The head developed by low-reaction (forward) effect vanes is chiefly dynamic and
therefore, the vanes display high discharge velocities.
Concentrationlusion:- Extremely forward-curved vanes develop the greatest theoretical total
head in the form of dynamic pressure. With the angle β reduced, the Th. Total head decreases as
the reaction effect and static pressure increase. When β = 90 o, the reaction effect is 0.5, and th.
Total head comprises the velocity head and static head, equal in value. As β is further reduced
(Backward), the Th. Total head drops to zero, while the reaction effect grows to unity.
All three types can be used.
CENTRIFUGAL PUMPS EMPLOY MAINLY BACKWARD – CURVED VANES.
Centrifugal Compressors also use Backward Curved Vanes.
CENTRIFUGAL FANS MAY HAVE VANES OF ANY ONE OF THE THREE TYPES
EFFICIENCY:
1. Hydraulic efficiency:

If h = hydraulic losses

H = actual head

Thus, head required of the impeller = H + h = Hth

HYDRAULIC EFFICIENCY = h = H = (h/H + h) = = (1 -

 h is strongly effected by the flow passage configuration of the machines inner surfaces, and
viscosity of the liquid ( Disc friction losses, is a fn. Of viscosity)

( h range from 0.8 to 0.96)

The leakage losses are caused by the liquid (or gas flow from discharge to suction side of the
machine thro’ the impeller – to – casing clearances.

VOLUMETRIC EFFICIENCY: If Q is flow loss for discharge to suction and if Q (m3/sc) is

the delivery from a centrifugal machine, then
Discharge thro’ impeller = Q + Q
Volumetric efficiency = Q/(Q+ Q) =
(Higher than vol, the lower vol the leakage rate) ηv is effected by radiameterl clearance … with
small radiameterl clearance, high ηvol can be obtained. For modern, centrifugal pumps, ηvol
ranges 0.96 to 0.98
Vane efficiency: ηi
Power generated inside the casing by the impeller vanes acting on the flow is

Q = Leakage ratio from suction to discharge

H = actual head
H = head losses because of friction.
But, Machine (or pump) output, Nust = ρgQH only

So vane efficiency ηi = = Nust

Hence, ηi = ηvol x ηh since ηvol = ηh =

So, Ni = =
Vane efficiency takes into account of the leakages and hydraulic losses in the machine
disregarding the disk friction losses.
The power input applied from the driver to machine shaft exceeds the indicated power Ni due to
Mech. Friction in bearings and shaft stuffing boxes and friction between the outer surfaces of the
impeller and surrounding liquid (or gas) (hydraulic friction).
The effect of Mechanical and hydraulic friction can be allowed for by the GROSS MECH.
EFFICIENCY ηM
ηM = Ni/N (range from 0.92 to 0.95)
The use of rolling bearings gives higher
ηM
Hence N = = =

N= – watts
Where ηvol x ηh x ηm = η, the gross efficiency of machine
The power imparted by the shaft to the impeller (Nine)
It includes the indicated power Ni and disc friction power Nfr
Nimp = Ni + Nfr

= + Nfr (KW)
Disc friction pump Nfr = βρR25W3
Where W = angular velocity of machine shaft
β = en..rical coeff. Determined by relative roughness of rotating surface and Reynolds
No.
β can be assumed = (2 to 8) 10-5

R1
R2

MULTISTAGE CENTRIFUGAL PUMPS

AXIAL THRUST BALANCING OF CENTRIFUGAL MACHINES
The impellers of centrifugal machines are subjected to transverse forces (normal to the center
line) and Axial forces (parallel to the centerline)
1. Transverse forces: are caused by the fact that the flow towards the impeller and from the
impeller to diffuser is nonsymmetrical and also if machine rotor is out of static and dynamic
balance. With properly designed approach and diffuser, the transverse forces caused by the
flow asymmetry are rather small.

The static and dynamic unbalance results from the misalignment of geometric axes of the
impeller and shaft and nonsymmetrical main distribution over the impeller.

The assembled rotor of a centrifugal machine is always somewhat out of balance.

To guard against transverse forces induced by unbalance, the rotors are subjected to dynamic
and static balancing by providing bearings.

So the transverse forces are taken care of by machine bearings.

AXIAL FORCES: These arise from unequal, differently directed pressures acting on the front
(facing the suction) and back side of impeller. Also, (in addition), an axial force is induced by
the dynamic action of the flow entering the impeller.

P2P2 P2
C
b RL
 Pw

P2-P1
Rsl P1

P1
P1= Suction pressure ahead of impeller inlet
P2 = Discharge pressure. P2 is transferred via clearances in chambers b and c, upstream and d/s of
impeller.
Actual axial thrust P, at any point on the impeller outer surface, results from the COMBINED
ACTION OF TWO PRESSURES, p2 AND pw. pw IS PRODUCED BY THE CENTRIFUGAL
FORCE EXERTED BY THE LIQUID TRAPPED AND ROTATED BETWEEN THE
IMPELLER OUTER SURFACE AND CASING WALLS.
So, Axial thrust (force) P = P2 + PW
It depends on mainly radical diversion R2 and RSl (suction line) of impeller, its rotation speed
and impeller discharge Pressure (P2).
Axial thrust vs. Load: The less loaded the machine i.e. the lower capacity obtained by throttling,
the greater the axial thrust. Axial thrust is target with closed discharge.
P2 Axial thrust
In multistage machines, axial thrust may be very significant and difficult to be carried on the
thrust bearings at high shaft speed. Only for small-si….machines with a few stages the thrust
bearings can be relied to take care of thrust.
Some of the methods to counter Axial Thrust are:-
a. Liquid flows to both sides of the impeller:

A DOUBLE SUCTION IMPELLER IS SYMMETRICAL AND HENCE TRANSMITS NO AXIAL THRUST TO

THE SHAFT. THIS TYPE OF IMPELLER IS COMMONLY USED IN SINGLE STAGE CENTRIFUGAL PUMP
(E.G. C.W. PUMPS, CH.W.PUMPS)

SO ADVANTAGES OF DOUBLE-SUCTION PUMPS:

(1) Double suction impellers of large centrifugal pumps transmit No Axial Thrust.

(2) Required NPSH is low.

S = η1 Q11/2/Hsr13/4 = η1 Q21/2/Hsr23/4 η1 = single suction (rpm) & η2 = double suction (rpm)

If η1 = η2, Hsr2 = 0.63 Hsr1 (since Q2 = Q1/Q2)

Or if Hsr1 = Hsr2, η2 = 1.414 η1
Hence, if speeds are the same, required NPSH for – double suction impeller is 0.63 times the
NPSh required for a single suction impeller (27% reduction) Also if (NPSH)red. Is the same for
both, the double suction impeller can be operated at higher speed and hence at higher efficiency.
(41.4% high speed).
P2
 P P

P1 P1

Double Suction Impeller

MULTI STAGE MACHINES:

1P 2P 4P
3P

Suction

2P

Stage I Stage II Stage III Stage

IV
Symmetrically arranged double suction multistage pumps
AXIAL THRUST TO THE SHAFT: THIS TYPE OF IMPELLER IS COMMONLY USED IN
SINGLE-STAGE CENTRIFUGAL PUMPS (EG. C.W. PUMPS, CH.W. PUMPS).

So, Advantages of double-suction pumps:-

1. Double suction impellers of large centrifugal pumps transmit NO AXIAL THRUST.

2. Required NPSH is low.

½ 1/2

S= ¾ = 3/4 1 = single suction (rpm): 2 = double suction (rpm)

If 1 = 2, Hsr2 = 0.63 Hsr1 (since Q2 = Q1/2

Or if Hsr1 = Hsr2, 2 = 1.414 1
Hence, if speeds are the same, required NRSH for a double suction impeller is 0.63 times the
NRSH required for a single suction impeller (27% reduction) Also, if (NPSH) reduction Is the
same for both, the double suction impeller can be operated at higher speed and hence at higher
efficiency (41.4% higher speed).
MULTI STAGE MACHINES: In multi stage and multi flow machines, an even no. of impellers
may be used, one half of these having their suction inlets facing in an opposite direction to the
second half. With this arrangement, axial thrust on the first male is compensated by the equal
thrust in the opposite direction by the other half of impellers. This is the reliable, one of the best
methods of axial thrust balancing. A light duty ball thrust bearings will be installed for these
units to fix the rotor in the axial direction and to take the insignificant axial forces due to
inadequate symmetry of the rotor.
Chamber A
P2 Balancing disc
P1 suction
P2
P2

Radiameterl clearance

2. EQUALIZATION OF PRESSURE ON BOTH SIDES OF THE IMPELLER: As we know,

Axial thrust results from the difference of axial pressures u/s and d/s of impeller. With a straight
face wearing ring installed on the back shroud of the impeller along the circumferences of radius
RSL and several holes drilled thro’ the back shroud near the impeller hub, the pressure u/s (at the
I/L) and d/s of the impeller will counter balance each other. But the axial thrust will then only be
caused by its dynamic co…. The dynamic force on the suction side is rather small and can be
taken care of by ball thrust bearing (OR), some times, balancing holes in the shroud connecting
chambers u/s and d/s of the impeller are SOME TIMES REPLACED BY A PIPE
CONNECTION BETWEEN THESE TWO CHAMBERS. This is widely used as its simple.
BUT DISADVANTAGE OF ABOVE METHOD IS DECREASE IN VOLUMETRIC
EFFICIENCY (due to leakage thro’ holes, thro’ pipe).
3. USE BALANCING DISC: (P-1201 A/D, P-201 A/B/C/D/S1/S2): AXIAL THRUST BALANCING can be
driven by using a suitable balancing disc located at the back of the last stage.

The pressure P2 (discharge) is transmitted to the discharge through radiameterl clearance.

One chamber will be provided at the back of the disc, which is kept at a pressure of P 1 (suction)
by means of a line connecting this chamber to suction line.

Here the volumetric efficiency will be affected.

NOTE:
1. From the theoretical Characteristic curves, to obtain a specified theoretical Head and capacity
from a centrifugal pump with impellers having diff. B21 it requires different peripheral velocities
at the impeller discharge or different rotation speeds of impellers of same diameter.

2. To obtain a specified theoretical Head from the impellers of the same diameter, the impeller
with forward curved vanes should rotate at a minimum speed and the one with backward curve
vanes have its rotation speeds at a MAXIMUM.
 FOR THE SAME HEAD (for same impeller diameter):-

FORWARD CURVED VANE SHOULD HAVE MIN. SPEED AND BACKWARD CURVED VANE SHOULD
HAVE MAX. SPEED.

WHY BACKWARD CURVED VANES ARE PREFERRED?

Ref. actual performance curve of B2 > 90 (FORWARD CURVED VANE) peculiarity of forward
curved vane pump is the existence of a max. and hence the ambiguity of the relation H= (Q) for
a given pump with head varying from Hidl to HMax.. Hence, pumps with forward curved vanes
may give UNSTEADY PERFORMANCE WITH SPONTANEOUS VARIATION IN
CAPACITY. Hence, B2 >90 FORWARD CURVED VANE PUMPS ARE UNDESIRABLE.
Again ref. characteristic curve of B2 <90 BACKWARD CURVED VANE. Herein Backward
curved vane pump the relation H = (Q) is NOT AMBIGUOUS. AND THE PUMP IS
CAPABLE OF PERFORMING STEADILY UNDER ANY COONDITIONS.
THEORETICAL CHARACTERISTIC CURVES
H =C–EQ Where C, E are constants
th

2
C= = a constant

E= = constant (lg 2 form 2)

Where Q = 0, i.e. with discharge Valve fully closed Hth = C
Radiameterl. Where 2 (valve angle) = 90o, clg 2 = 0, hence Hth = 0

1. Backward curved vanes: 2 = < , 2nd term of equation H = C-E Q is positive, so, Hth decreases as
capacity Q increases.

2. Forward curved vanes: 2 = < , 2nd term is negative, so, Hth increases with increase in
capacity.

So, THEORETICAL CHARACTERISTIC CURVES ARE:

o
2>90

N (speed) = const.
o
2=90
 o
C 2<90

0 Q

So, the more forward curved the impeller vane, the higher the theoretical head at a given capacity
and speed.
CENTRIFUGAL MACHINE THEORETICAL CURVES FOR CONST. Q AND Hth and
DIFFERENT ANGLES 2
Power KW
29

o
18 2=160 (st.line)
0
90
o
12 2=20
6 Q
20 30 40 60 80 100
Hth
N = cont.
o
2<90

2 o
2>90
Hth
2
( D2n) /3600g Q
Actual performance: Because of head losses, actual curves differ from the:
o
H 2>90 H
o
Th 2<90
o
2<90 Actual Th
Actual
o
2<90
Q
Q

Power W
POWER CURVE Actual

Theoretical
Nth Q
 Power loss

Efficiency = so, = 0 at Q = 0 H=0 because N 0

Specific Speeds:
Rotary and Reciprocating 40
Regenerative turbine → 10 – 25
CENTRIFUGAL → 40 – 30 Q
B.E.
MIXED FLOW →R300 – 600
AXIAL FLOW → 600 - 1200
SURGING OF THE CENTRIFUGAL PUMP: (Axial Flow low)
Because of flow separation from vanes (due to throttling of discharge), and an abrupt change in
the shaft speed (frequency variation), rapidly changing consumption of users, the system will get
upset and this will be responsible for transient operation manifested as spontaneous fluctuations
in the capacity, pressure and power. If these fluctuations decrease rapidly the system is stable.
But under certain circumstances accidental disturbances cause’s fluctuations of increasing
amplitude, the stability is not regained and self-excited, vibration called SURGING is set up in
the system.
Surging is dangerous due to sharp, pressure increase in the flow with a consequent growth of
stresses in the active component of the system.
Design flow rates: (each column)
Feed : 61.4 kg/hr 15%
Product : 6.4 kg/hr 99.89%
Reject : 55.0 kg/hr 5%

Boil up rate (in the Reboiler) =

How to find reflux ratio: G R

G
G
R.R = D/R (reflux ratio)
Boiling rate = ‘G’ (1600 kg/hr)
Reject rate = R known 55.0 kg/hr

So, Reflux Ratio = D/P = =

ASTM REQUIREMENTS FOR REACTOR GRADE D2O

1. Isotopic content = 99.75% + atom present

 2. pH = 7.5 – 8.5

3. Cond. = <15 s/cm at 25oC

4. T = <5 NTU

5. TDS = <12 ppm

6. Cl- = <0.1 ppm

7. Consumption of KMnO4 = < 1 x 10-5 gr/ml

D.U

SEPARATIVE UNIT: Smallest element of isotopic separation plant which effects some
separation of process material e.g. Sieve plates, electrolyte cell, gas cartrifuge.
STAGE: Group of parallelly connected Separative units all fed with material of same
concentration and producing separate streams of same composition.
- Distillation column, XU-I, II, III

- Electrolyte cells in parallel.

CASCADE: When the degree of separation effected by a single stage is less than the degree of
separation desired between product and waste, it is necessary to connect stages in series. SUCH
A SERIALLY CONNECTED GROUP OF STAGE IS CALLED A CASCADE.
X1”
X11 x2”
X
Product
1 UNIT
X1”x2 X31
Feed X1 X1 X11X2”X3 SEP X31
” UNIT UNIT SEP
x2 X21
X1 1 UNIT
X1 1
X1 SEP
UNIT UNIT
STAGE STAGE

CASCADE

ABUNDANCE RATIO :

=
 = Flow Atoms of desired Abundance ratio
rate isotope
Heads X11 Heads L1 X’ ’
B

feed L SEP UNIT X

Feed L X
”
Tails X

= cut = L1/L (Heads/feed) Tails L” X” ”

………………………………………
…→ 2
L = L1 + L”
………………………..→ (3) also LX = L1 X1 + L” X” ………………………………………→
(4)
So, LX = L1 X1 + LX” – L1X1 ………………………………….→ (5)
L (X – X”) = L1 (X1 – X”) …………………………………………→ (6)
Or L1/L =(x-x”)/(x’-x”) = ………………………………………→ (7)
So, X = 1
+ (1 - ……………………………………..→ (8)
STAGE SEPARATION FACTOR, = 1/ ” (Heads/tails)

= 1/ ” = = → (9)
NOTE: STAGE separation factor ‘ ’ is independent of composition. But the ratio X1/X” on the
other hand varies strongly with composition.

HEADS SEPARATION FACTOR :- =

= =

1/ = (1 – X1)/X1 / → (10)
From the definition of and

X1 = = → (11)

X= = (from = ) → (12)

Also, X” = = → (13)
From (7), (8), (9)

–1= → (14)
TYPES OF CASCADE:
(1) SIMPLE CASECADE: No attempt made to reprocess partially depleted tails leaving each stage.

L1”,X1(T
L1”,X1” Ln”,Xn”
ail) L11, Ln1, Xn1
F1XF L11,Xi
P1XP Stage 1 X111 Stage i Stage n

State heads Stage heads Stage

heads

(2) COUNTER CURRENT RECYCLE CASCASE (Most commonly used)

n Ln1Xn1
Product P1XP
L11+1,X11+1
Ln”,Xn
I+1
ENRICHMENT

” Li1 Xi1
L”1+1X”1 i
+1
L”1n” Feed
Nw+
F1XF 1
1

L1j,X1 nw
STRIPPING

j J
L”j 1 stage
X”j W 1 n w

P1Xp, F1XF, W1XW are called EXTERNAL VARIABLES OF THE CASCADE.

Interstage flow rates and compositions are called internal variables of the cascade
Enriching Section:- The purpose of enriching section is to make material of product
concentration
STRIPPING SECTION: The purpose of stripping section is to increase recovery of desired
isotope from feed i.e. to reduce the amount of feed required to make given amount of product.
WHY NO STRIPPING SECTION in XU to increase recovery?
When feed has no value, as with the natural water feed for a deuterium plant, the stripping
section may be eliminated altogether.
Stages are numbered from 1 at waste end of plant to ‘n’ at product end. The highest stage of
stripping section is numbered nw

WMin = (frensky’s for ‘TR’ open)

GENERAL CASCADE EQUATIONS:
Material Balances for external variables:-
F = P + W ……………………………….→ (15)
F XF = Pnp + Wnw…………………………………….→ (16)
It is possible to specify 4 external variables independently by material-balances for internal
variables for each stage.
For enriching section: (i+ 1 stage in fig)
L1i = L”I + 1 + P ……………………………………….→ (17)
L1i X1i = L”I + 1 X”I + 1 + PXp ………………………….→ (18)
STRIPPING SECTION:-
L1j = L”j + 1 – W …………………………………………….→ (19)
L1j X1j = L”j+ 1 X”j+1 – WXw …………………………………..→ (20)
From equations (17) and (18)

X”i+1 – X1i = ……………………………………………..→ (21)

”
Thus n i+1 is less than Xi by an amount which decreases as the reflux ratio L”i+1/P increases. At
the total reflux (L”i+1/P → as f=0 at T.R.), X”i+1 and X1i are equal.
MINIMUM NO. OF STAGES:- When L”i+1/P → (T.R.operation) for a given feed to be
separated into product and waste if specified composition,
X”I+ 1 = X1i → (22)
”i+1 = 1i→ (23)

MIN. No. of stages N =

And
W = XP (1-Xw)/Xw(1-XP) = Overall separation of the cascade
= (XP/1-XP)/(XW/1-XW)
Eg. for Uranium enrichment by gas diffusion = 1.0043 and to make 80% prod. 0.40% waste

NMin = = 1609
NMinINCREASES WITH INCREASING OVERALL SEPRATION REQD AND DECREASE
IN SEPARATION FACTOR 3
i.e. NMin if overall separation (XP/1-XP)/(Xw/1-XW)

NMin if
RMin =
MINIMUM REFLUX RATIO: At Total reflux, difference in composition between
corresponding streams on adjacent stages is MAXIMUM. AS REFLUX RATIO IS
DECREASED, difference in composition decreases and reaches Zero at Min. reflux.
It is clear that Min. reflux ratio increases as the composition departs more from product or waste
composition.
In Isotopic separation where is close to 1.0 Minimum reflux ratio is enormous.
Min R.R , L”/P = (XD-XF)/(X-1)(XP)(1-XP)
= (0.8 – 0.0072)/0.0048 x 0.0072 x 0.928 = 25,800
For Distillation Column ( = 1.045)

(Min) L”/P = = 147

Normal reflux ratio = (BOILUP RATE, not boiling rate)

= = 261
1. In Distillation, same reflux is maintained because the reflux ratio in an adiabatic column remains
merely constant and it is cheaper to add or remove heat at only ends of the column than at a
number of intermediate points.

2. However, in an isotope separation plants, so much can be saved in a way of reducing equipment
sizes and material hold up by reducing reflux ratio at interval between feed and product ends of
the cascade and this is always done. In these cases, increased complexity of a tapered plant is
justified.

Total cost
Annual cost
C.W.
and heat cost
Fixed cost

RMin Roptimum
F1 XF Reflux Ratio
Product

C.T C.T C.T

H.T H.
H.T
W1X T
W

Tapered SQUARE OFF

 XU

IDEAL CASCADE: is
One type of tapered plant which is easy to treat theoretically, which leads to MINIMUM
TOTAL INTERSTAGE FLOW AND WHICH IS APPROXIMATELY BY ALL ISOTOPE
SEPARATION PLANT, DESIGNED FOR MINIMUM COST.
In this, (1) – Heads separation factor is constant
(2) The head streams and tail streams fed to each stage have the same composition
X”1+1 = X11 – 1 = Xi

1
i+L

i+L
1 I+ L
i+1

i+1 ”i+L I+1

”i+1 1
i
i i
1
i-1 ”i

= =
n = {2 ln[(Xp/(1-Xp))/(Xw/(1-Xw))]/ln }- L

nw = ln
…………………………….. -L

ln

enriching section n – nw = ln
Ln
In Ideal cascade, the operating line is almost parallel to the eq. curve because of change of reflux
ratio at every step.
The equation for the flow rates through the cascade.
FLOW RATE THROUGH CASCADE (J) =
J=

]
The above equation states that the total flow in the plant is a product of TWO FACTORS.
1st factor is a FUNCTION OF HEADS SEPARATION FACTOR (i.e.
2nd factor is a function of only flow rates and compositions of feed, product and waste.
1st Factor: a function of heads separation factor, is a measure of relative case or difficulty of the
separation. It is large when is close to UNITY and small where ‘ differs markedly from
unity.
2nd Factor: The 2nd factor is a MEASURE OF MAGNITUDE of the JOB OF SEPARATION.
IT IS PROPORTIONAL TO THE THROUGHPUT AND IS LARGE WHEN PRODUCT AND
WASTE DIFFERS LARGELY, IN COMPOSITION FROM FEED and small when these
compositions are nearly equal.
THIS SECOND FACTOR IS TERMED AS “SEPARATION DUTY” – as it is similar to the
heat duty of an evaporator or feed vaporizer.
SIGNIFICANCE OF SEPARATION DUTY:
1. It indicates the magnitude of the job of separation.

2. COST OF THE plant and holdups increases with increase in separation duty.

3. Large indicates the product and reject concentration Differences.

4. It indicates the size of rotating equipment to be selected.

FOR A PLANT with SINGLE Feed, product and waste streams, the separation duty ‘D’ is given
by;

D =
(same units of flow)

SEPARATIVE POTENTIAL = (2Xi – 1) ln

= (2XF -1) ln
is a function of only composition and is dimensionless. So, → as ni → 0
So, this expresses the fact that a plant of infinite size is required to produce pure isotope.
CHANNELING in a packed column can be caused by:
1. The liquid distributor not dividing the liquid evenly over the column cross section.

2. The liquid moving more easily to the wall than the liquid at the wall to the center. The resulting
channeling along the wall may be accentuated by the vapour condensing because of column
heat losses.

3. The packing geometry inhibiting the lateral distribution.

4. Void variations due to packing being improperly installed.

5. The column being out of vertical alignment.

Effect of channeling on M.T.

Fraction of N = 10
Total plates N = 20
N = 40
N = 100
 0.1
0 1 2 3 4
The above figure shows the effect
5 of5liquid channeling on column efficiency for a system with a
relative volatility of 1.07. Total no. of theoretical Plates N of 10, 20, 40, 100 with tor liquid
come of 90 mole %.
Liuqid migration to the wall appears to be favored by low/column diameter/packing
diameter/ratios (eg. Less than 10) and can be corrected by the use of side wipers or liquid
redistribution.
Causes of channeling:
1. Improper liquid distribution.

2. Void variation

3. Packing geometry inhibiting the lateral distribution.

4. Column is out of verticality (6mm)

SIGNIFICANCE OF
1. It indicates the job involved in separating the miscible components.

= (X/1-X)/(Y/1-Y) =

Pressure drop increases with the boilup of the column and reaches a point where vapours impede
the downward motion of the liquid. This point is called loading point. If boiling is further
increased the P increases much faster rate (initially P square of gas velocity, now it
increases at a rate proportional to gas flow rate raised to the power >2) and reaches a value where
vapour will be bubbling thro’ a pool of liquid filled packup. At this point all the packing area is
wetted and provides a good contact area for mass transfer.
A B C

Flooding point 2 2 Op
Log P/ft of packing
Loading point
1 1 L=0 Dry packing
High liquid flow rate Low liquid flow rate

Log gas velocity

1. The slope of line C (dry packing) = 1.8 to 2.0, indicating turbulent flow of vapour or gas thro’
column packing.

2. At const. vapour velocity, the vapour P increases with an increase in liquid rate because the
free cross sectional area available for the flow vapour is reduced as a result of Navigation of
packing by the liquid.
 Upto point 1, at moderate vapour flow rates for each flow rate of liquid is nearly parallel to that
for dry packing. Hence, up to point 1, P varies a square of gas velocity.

Flooding Point:
1. P is too high and there, P is very sensitive to smell, changes of vapour velocity because of
high P, High energy consumption.

2. As the liquid accumulates rapidly on the packings, the effective surface area available for mass
transfer reduces drastically and hence M.T. efficiency reduces drastically.

At point (1) change in slope status, further change of slope is observed at point (2)
At these point P begins to rise more rapidly than square of gas velocity.
The vapour rate at point 1, where this phenomenon is initiated is called Loading Point.
Beyond the loading point, as the boilup rate is increased thereby increasing the vapour rate, the
liquid hold increase slowly at first and the rapidly (hold up increasing).
At point 2, the liquid phase becomes continuous and vapour bubble thro’ it. At the same time,
the entrainment of liquid by the vapour leaving the packing at the top increasing and the column
is said to be flooded.
NOTE: For each flow rate of liquid, there is a vapour rate at which flooding occurring →
→ Higher for low liquid rates
→ Lower for high liquid rate
Why can’t we operate the column at flooding?
1. It is not practical to operate the column at flooding as P is too high and it is very much
sensitive to the little changes in vapour velocity.

2. Mass transfer efficiency decreases as effective surface for M.T. decreases rapidly. The flooding
condition represents the maximum capacity of column.

3. The PACKED COLUMNS ARE USUALLY DESIGNED TO RUN AT OR JUST BELOW THE LOADING
POINT.

Feed = 246 kgs. 15%

Reject = 5% Product – 99.9%

Total separation =
Separation factor = 1.1596 e- 65.03 T (T – at 120mm Hg 57oC)
= 1.0927

NMin = = 280
N taken = K section x 30 = 360 plates (on experimental basis, 1 section 2.4 Mt = 30 plates)

NTP/M NTP/M
 Vapour boiling rating Vapour
Load

N-NMin/N+1

R-RM/R+!

RMin = = 80
Why structured packing? Why not random packings on sieve trays?
Structured packings are generally more expensive than random packings on an equivalent
column volume. But these offer high performance.
1. High performance.

2. In spite of higher initial cost, they permit greater capacity.

3. Higher efficiency

4. Low P and hence.

5. Lower energy consumption compared to random packed tower or tray tower.

In view of the above gauze structured packings are the best suited for vacuum distillation.
Ours is:- CORRUGATED PHOSPHUR BRONEE COPPER OXIDE COATED (to increase
wettability) WIRE MESH STRUCTURED PACKING.
VACUUM HOLD TEST:
1. Columns:- 40mm Hg for 48 hrs. with an allowable pressure drop = 1mm Hg.

2. Loup:- 40mm Hg for 48 hrs. with an allowable pressure drop of 2 mmHg.

S.No. Plate Column Packing Column

01 No. of stages is high for required separation. Size of the plant is less because of
Hence large size of the plant high efficiency Of the packing
02 High Pressure drop , hence high energy Low pressure drop. Low energy
03 Feed need not be very pure Feed shall be free of impurities
which affects the active surface of
packing.
04 Liquid hold ups are very high Liquid holds up are minimum
05 Can be used for high capacities Effective for lower capacities.

Column Packing Characteristics:-

1. It should have large surface area per unit volume so as to provide a high interfacial area
between vapour and liquid.
 2. It should have large void volume allowing free flow of vapour without excessive pressure drop
( P).

3. It should have good wetting characteristics to promote uniform liquid distribution on the
packing surface.

So,
1. Large surface area per unit volume for better M.T.

2. Large void volume to minimize P.

3. Good wetting characteristics.

Structured Packing:- Billie formula for structured packed tower diameter relating Total
pressure, temperature and mol.wt. of the vapour, vapour load and OPTIMUM CAPACITY
FACTOR which is set equal to 2.4 for gauze packing.
DC = 0.02 [Vm (MT/P)0.5]0.5 where
DC = Column diameter
VM = flow rate of vapour Kg/mole/hr
M = Mol. Wt. of vapour
T = Temperature of vapour K,
P = Pressure of vapour KPa.
HETP-is the highest of packing required to achieve a separation equivalent to that of a single
theoretical plate.

P is structured packing:: Bravo’s equation for P for both gauze and sheet metal packing:-
P = [0.17 + (9.27)/NRe,v)][ev U2v.eff/deq][1/(1-C x Fv)0.5
P = (NRe,V, FV cheque)]
P = Total pressure drop/unit ht. of packing parcel/M
NRe, V= Reynolds No. = (UW.eff x deq)/
Fr = Froude No. for the liquid = UL2/deq.g
UV,eff = effective velocity of vapour M/Sec = UVS/E sin ( angle of channel)
UW.eff = Superficial velocity of vapour M/Sec (E = void fraction of …
C = Const. of the packing = 33.8 for seltzer Bx packing.
deq = equivalent diameter, M
Height of the packing bed: Z = (HOV) (NOV)
HOV = Over all vapor phase height of transfer unit.
NOV = No. of vapor phase transfer units
HV = Vapor phase ht. of T.U. M
HL = Liquid phase ht. of T.U. M
LM = Liquid flow rate mole/sec. VM = Vapor flow rate – meter/sec
MV = slope of eq. line; in case of constant relative volatility
2
M = /[1+( -1)(
Z = Ht. of packing = (HETP) x Nt
HETP: Ht. eq. to th. Plate
Nt = Total no. of Theoretical stages (……
HETP: Hov x ln[ /( -1)]
Where = MV/L = stripping factor, M = 2
HV = V/Kv ae Pv
HL = L/KL ae PL
Ae = effective interfacial area = Total surface area of packing ap on a unit wt. basis.
Kv = vapor M.T. C. eff is a fn. Of NRc, NSc and differencing vapor Dv
KL = Liquid M.T. coefficient is a function of DL (differencing of liquid.
Feed water quality to D.U:-
pH = 6.5 – 8.0
Conductivity = <5 mho/cm
Chloride = 0.5 ppm (max)
Nitrite = <1 ppm
Oil = Nil
H2S = <50 ppb
All Columns are designed for:
1. A temperature of 130oC and

2. Full vacuum and 1.8 kg/cm2g

3. Column is made of SS-304L

Flow Sheet for clean-up Unit: Feed Tank

Activate
Feed D2O from XU.
d carbon
Containing dissolved
bed
H2S, oil and other
impurities (organic
matter)
KMnO4
Int.
C.W KMn
st. O4 st. steam
tan Feed
tank
k evapo-
Condenser
rator
Condenser
C.W

Slurry tank

Product
st. tank
 I X Beds

Feed
buffer
tank

Feed = 15% concentration, rate = 61.4 kg/hr, Product = 99.84+% (isotope purity), rate = 6.4
kg/hr;
Rate = 61.4 – 6.4 = 55 kg/hr
5% concentration Reject is fed back to 3HT of XU.
4 distillation columns:
Each is having a capacity of 50 Te/year
(Annual) Total capacity = 200 Te/year
STREAM FACTOR is the same as that of XU = 7800 hrs. Total unit can be divided into 4
sections.
1. Feed Purification Section.

2. Distillation Columns

3. Bottom product and top reject withdrawal section

4. Vacuum Generation Section.

Feed Purification Section: Operate at atmospheric pressure.

 Feed Feed 13-P-101 A/S P-102 A/S
o Feed water Activated carbon
XU-I, II 15% 35 C storage non-seal centrifugal pump
tank V-101 beds for oil
C-3
tank TK- SS 304L V-104 A/B
removal
101
Product storage 250kg/hr 40oC Feed vapour V-114P-104A/S
int.
C.W.
2 o Feed evaporator
2 E-
tank V-106A/B 2 kg/cm g 100 C,2kg/cm g tank
exchange c.w. 101A/B Jacket
SS 304L 250 kg/hr SS-304L
13-P-105A/S 250kg/hr 40oC shellC.W. E-oC(corrosion allowancetype evaporator
side 39 60mm jacket for steam
3.0 kg/cm2g 15% 102
=1.6mm) S.Side cap=250kg/hr. steam flow=300 kg/hr at 120o 2.7 kg/cm2

Slurry to
Molecular Sieve slurry tank 6kg/hr KMnO4
Ion exchange 304L P-103A/S
columns V-105 KMnO4 storage
Feed Buffer
A/B Over flow of V-101V
Tank V-107 tank
SS-304L 2454 kg/hr V-104
A/B 13P-106A/S capacity=2700 kg/hr
Feed over flow KMnO4 to oxidize any organic matter or SO2 present
in the feed
tank V-108

FLV FLV FCV FCV

VAPOUR FEED HELPS IN CHANGING OVER THE FEED POINT QUICKLY AS AND WHEN
REQUIRED, AND ALSO ENSURES THE PURITY OF FEED.
KMnO4 is added to oxidize organic matter and SO2 present in the feed. It is added before it enters the
feed evaporator E-101 A/B.
Any Isotopic separation plant required large number of theoretical Plates. So, in our distillation units
to reduce the number of plates by running the columns almost at total reflux.

G = 1500 kg/hr (boil up rate) + 61.4 (feed vapour)

L = 1561.4 – 55 (reject) = 1506.4 kg/hr.

L/G slope operating line = (stripping section) = 0.965

Slope of equilibrium line = 1.0427

So, (L/G) slyed…. Qty line, 45 line are almost equal so they are almost parallel. So, min. no. of trays
we will get.
Enriching Section Opt. line sl…. L/G
G1 vapour = 1500 kg/hr (boil up rate)
L1 liquid 1506.4 kg/hr
L/G = 1506.4/1500 = 1
This also parallel to 45 line so no. of plates are minimum
No. of plates of our distillation column = 480 plates (16 NP/M) Z = 2.56x12 =30M
DISTILLATION COLUMNS: 13-C-101 A,B,C,D
Feed = 15% Rate = 61.4 kg/hr
Product = 99.84% Rate = 6.4 kg/hr
Reject = 5% rate = 55.0 kg/hr
Top pressure = 120 mm Hg(abs.), Temperature 54oC
Why top pressure 120 mm Hg (abs)?
Operating pressure of the column is optimized. Separation factor is the ratio of vapour pressures of
the two components. as pressure ↓

1. But by lowering pressure, the specific volume of vapour increases considerably. This leads to very
large tower diameter and in turn increase the capital cost.

2. At the top, we use cooling water for condensation which is at 30oC. Hence for proper condensation
of the vapour, the condenser should get sufficient temperature difference. This sets a lower limit to
the temperature of the vapour and in turn on the pressure of the column.

Considering above factors, it is found to be most economical to design the distillation tower at 120
mm Hg. Abs. at the top.

Pressure drop across each section = 8 mm Hg

So total pressure drop in column = 12 x 8 = 96 mm Hg.

PACKING:
CORRUGATED PHOSPHUR BROZE WIRE MESH PACKING and the surface is activated by
giving coating of copper oxide.
Each section has a lip seal which is seal welded to the other sections.
Advantages of packing tower: Isotopic enrichment always requires large no. of theoretical trays. To
achieve this, sieve tray columns had to be installed in favor to five stage cascade. This entails:
1. Huge hold up
 2. High equilibrium time
3. Large plant volume
4. Large pressure drops
5. High energy requirements
6. High processing & handling losses
7. High capital investment.
IMP NOTES ON DISTILLATION:-
This process can’t be employed for the pre-enrichment section as the separation factor is low
(Relative volatility = 1.04) and very low recovery. Consequently, large plant volume and very large
energy are required. But the same process is best suitable for final enrichment of heavy water and
also for light water extraction from moderator Heavy Water circuit.
Corrugated Ordered Packing Advantages:
1. Large Surface area per unit volume= 800 M2/M3 and hence low H.E.T.P (N.T.P/Mt = 16)
2. Low pressure drop
3. Well defined path for better contact of liquid and vapour
4. Isotopic enrichment always requires large no. of theoretical stages and to achieve this sieve tray
columns had to be installed in favor of five stage cascades. This entails huge hold up, HIGH
EQUILIBRIUM TIME, HEAVY PROCESS AND HANDLING LOSSES BESIDES RESULTING IN ENERGY
INTENSIVE AND HIGH CAPITAL INVESTMENT.

Due to recent advancement in tower packing, sieve tray columns are being replaced by packed
towers.
Our columns ARE MADE OF SS 304L
Inside diameter = 1050 mm + 2.5 mm

TOWER INTERNALS: constitute the following:

1. Tower packing
2. Liquid collection
3. Liquid distributor
4. Top and bottom support rings.
*Low surface tension liquids easily wet the surface. As the surface tension of water (71.97) and that
of D2O (71.93 dynes/cm) are very high, we have to go for special packing. Phosphor bronze
Alternate to phosphor bronze?
Can stainless steel packings with carbide coating be used for our distillation? Most probably YES
Low inventory offsets the high packing cost.
Even though the efficiency of the distillation columns mostly depends on efficiency of the tower
packings, the liquid redistributors, reflux collectors etc. also play a considerable role on the over all
efficiency of the distillation column.
TOWER PACKING CHARACTERISTICS: THE MOST IMPORTANT CHARACTERISTICS OF
TOWER PACKING ARE:
1. High wettability
2. High surface area per unit vol. 800 M2/M3

1
 3. Large void fraction 90 – 95%
4. Low pressure drop
5. Low hold up
Wettability mostly depends on the system property but at the same time, the material of construction
of packing also plays a significant role in achieving the same.
THE SURFACE TENSION OF THE PROCESS FLUID AND THE CONTACT ANGLE FOR A
PARTICULAR FLUID TO THE PACKING ARE THE BASIC FACTORS FOR WETTABILITY.
Extremely large surface area per unit vol. and large void fraction can be achieved for packings
fabricated from WIRE MESH.
DUE TO HIGHER POROSITY, THE FRICTION FACTOR OF THE MESH TYPE PACKING IS
ALWAYS LOWER CONSEQUENTLY, THE PRESSURE DROP IS LOWER → Besides the low
inventory offsets these high packing cost.
MATERIAL OF CONSTRUCTION:-
ESPECIALLY FOR THE WATER/HEAVY WATER SYSTEM, WHERE THE SURFACE
TENSION IS VERY HIGH (71.97/71.93 DYNES/CM AT 25OC RESPECTIVELY) THERE ARE
FEW MATERIALS WHICH CAN BE CHOSEN.
STANLESS STEEL AND POLYPROPYLENE PACKINGS CAN’T BE USED DUE TO THEIR
POOR WETTABILITY.
IT HAS BEEN ESTABLISHED THAT PHOSPHUR-BRONZE IS THE ONLY MATERIAL
WHICH CAN BE USED FOR THE FABRICATION OF TOWER PACKINGS IN VIEW OF ITS
SUPERIORITY OVER COPPER IN MECH STRENGTH, EASE OF FABRICATION AND
MAATERIAL COMPATIBILITY. FURTHER THIS PHOSPHUR-BRONZE CAN EASILY BE
CONVERSTED TO COPPER OXIDE TO YIELD A POROUS SURFACE WHICH ENHANCE
THE WETTABILITY CONSIDERABLY.
HOLLANDER weave 5 shaft wire mesh is the packing.
Description of tower internals:- Cylindrical packing sections suitable for particular diameter are
formed from parallel corrugated strips of woven wire mesh. The corrugations one inclined with
respect to the tower axis and the direction of the corrugations is reversed on the adjacent strips. Two
groups of parallel crossed flow passages of triangular shape are thus formed between adjacent strips.
These tower packings are stacked to the required height in a column section and held in position
tightly by the top and bottom support rings.
WHY LIQUID COLLECTORS AND REFLUX REDISTRIBUTIORS?
IT HAS BEEN OBSERVED THAT THE MAXIMUM PACKED HEIGHT CAN BE OF THE
ORDER OF 2.5 TO 3.0 METERS AS CONSIDERABLE CHANNELING OCCURS BEYOND THE
ABOVE HEIGHT OF THE PACKED BED.
HENCE, IT IS NECESSARY TO INTRODUCE REFLUX COLLECTIORS AND
REDISTRIBUTORS FOR EVERY COLUMN SECTION OF THREE METERS HEIGHT TO
ACHIEVE BETTER PERFORMANCE.
THE LIQUID FLOWING FROM THE BOTTOM OF EACH SECTION IS COLLECTED BY
MEANS OF REFLUX COLLECTORS LOCATED ON THE TOP OF THE LOWER COLUMN
SECTION.
THE PORTION OF LIQUID FLOWING ALONG WITH WALL CAN ALSO BE COLLECTED
AND REDISTRIBUTED.
THE REFLUX COLLECTOR IS SO DESIGNED AND FABRICATED THAT THE DIRECT
CONTACT OF VAPOR AND LIQUID IN THIS COLLECTOR DOES NOT TAKE PLACE SO AS
TO PREVENT ENTRAINMENT.
REFLUX REDISTRIBUTORS (WHY?)
1. It was observed experimentally that if liquid is fed at the center of the packing, it gets uniformly
spread after reaching a certain height from the point where it is fed. The packing up to this point is
not available for mass transfer.

2
2. After a certain height of the packing, the liquid has the tendency to flow towards the wall. It is
necessary that the liquid feed at the top is divided into many substances to evenly spread out thro’
out the entire cross-section such that the entire volume of the packing is made available for M.T.

Cupric oxide film over packing:

Liquid film flows down the column. Hence, high efficiency in mass transfer because of porous cupric
oxide film over the coatings.

These corrugated packings having corrugation at an angle inclined towards the axis of the tower, do
not allow the liquid to flow towards wall but at the same time, the liquid reacting the wall also
retreats towards the center.

However, after a certain height of the packing, the quantity of the liquid flowing on the wall surface
may be considerable and it has become necessary to incorporate a reflux collector and redistributors
for every packed height of 2.5 to 3 meters.

IN ADDITION TO THIS, VERTICALITY AND OVALITY OF THE COLUMN SECTION ALSO HAVE INFLUENCED
ON THE EFFICIENCY OF THE DISTILLATION COLUMN.

BOTH VERTILALITY AND OVALITY SHOULD BE KEPT WITHIN LIMITS.

IF THESE PARAMETERS ARE NOT MAINTAINED, WITHIN LIMITS, THE CONTINUED LOAD GAP BETWEEN
WALL AND PACKING (DUE TO OVALITY) WILL EXIST THRO’ WHICH THE LIQUID WILL BE FLOWING
GIVING RIASE TO CHANNELING. THE SAME EFFECT WILL ALSO BE SEEN IF VETICALITY IS OUT OF
LIMIT.
SURFACE ACTIVATION: IT IS HIGHLY ESSENTIAL TO CREATE THE POROUS OXIDE FILM ON THE
PACKING SURFACE IN ORDER TO GET THE LIQUID SPREAD AS FILM WHICH WILL ENHANCE MASS
TRANSFER RATES.

As WATER/HEAVY WATER, have high surface tensions, they do not wet the packing surface EASILY.
For these systems, it is necessary to make the surface porous and thereby increase the wettability.
To achieve this, the tower internals (packings) are subjected to chemical treatment in situ to obtain a
porous and stable cupric oxide film on the packing surface.

PRE FLOODING: - Before commencing regular operation, it is necessary to ensure that all the packing
surfaces are WET and they are uniformly irrigated.

In order to ensure that boiling rate is increased to the extent that flooding in the section sets in.
After reaching this flooding point, abrupt reduction of boil up rate results in sudden decreasing the
liquid and thereby the whole packing surface is completely wet.

3
liquid collector

Distributor

Top support ring

Packing

Liquid Collector
Bottom support ring

Distributor

1.2 mm perforations

4
 P mmHg/
Mt. of packed
Ht. 1.4 Vapour load Tonne/Hr/M2

18

∆P mt NTP/mt
Of packing of bed

1 2.0 1 2.0
1.4 Vapour load tonne/hr/m2 1.4 Vapour load tonne/hr/m2

18

No.of Theoretical
plates/Mt

5
 (NTP/Mt)
10
1.4 Vapour load tonne/hr/m2 2.0
(1050 mm diameter packed column)
1050 mm diameter; 16 NTP/M; 8mm Hg pressure drop
800 M2/M3 surface area/unit volume, 90-95% void percentage

About our D.U:

Each section can take a vapour load of 1350 kg/hr (1600 kg/hr) and a dynamic load of 150 kgs.
The entire column shall be vertical within 8mm in any orientation. STRAIGHTNESS is maintained
within 1 mm between any two points. 1M apart and 2.5mm on the total 3200mm length of the
section.

Perforations on the distillation = 1.2mm

SUMP: 1.4M I.O; 3.56M High
Capacity of Sump = 3.5 M3 (3.5 tons)

Reboiler: E-106 1-1 shell and tube pan exchanger mounted vertically. Connected to sump.

(steam) Reboiler shell is designed for 7.0 kgcm2g (C.S)

(Process liquid) Tube side = 3.5 kg/cm2 (S.S 304L)

Boil up rate = 1600 kg/hr at 68oC, 0.24 kg/cm2g

Steam requirement = 1730 kg/hr (1.73 te/hr) at 120oC, 2.7 kg/cm2g
Vapour generated is fed back below the first section.

V 107 A/S to D/SD 1600 kg/hr

Sump liquid Reboiler Column
at 68oC,0.248 kg/cm2g
(220mmHg)

Reject Condenser:- E-104 A/B/C/D

1600 kg/hr
Condenser
Vapors at 56oC 35oC liquid column

6
 1600 kg/hr 5%..... C.W-tube side
55 kg/hr
Reject to XU
E-104 A/B/C/D
CHILLED WATER REJECT CONDENSER: E-105 A/B/C/D provided at the top of E-104 A/B/C/D.
It helps in averting any escaped vapor from Reject Condenser or Reflux Condenser E-104 A/B/C/D
inverts from E-105 A/B/c/D are connected to vacuum line of the column.
PRODUCT & REJECT and withdrawal section:
PRODUCT: is drawn in vapour phase and condensed in product condenser. This helps in getting
reactor grade heavy water without further processing.

Ch.W Condensed
liquid E-108
Column (T.S) A/B/C/D
C.W Escaped vapour

Product E-107
A/B/C/D
LCv C.W. S.S. Process Vapour, T.S C C.W.
Over flow
Product Graduated
Storage Tank vessel V-107
V-107A/B A/B/C/D
V-111 A/B are S.S. 304L Vessel storage cap=1200 lts
Col.D Col.C Col.B

Product= 6.4x4 = 25.6 kg/hr for all sections enter V-111 A/B from V-111 A/B, product is pumped to
D2O storage or thro’ Ion Exchange Bed for further purification depending on quality of product.
1600 kg/hr to column
E-104 A/B/C/D
REJECT: 35o 55 kg/hr
Col. C Reject at 35oC

Both graduated vessels (i.e. for Graduated vessel

product and reject) are V-110 A/B/C/D Col.B
connected to a chilled water Col.C
condenser and the condensed Col.D
liquid is draw to Reject storage Reject storage tank
tank V-111 A/B to avoid any V-112 A/B
pumps
loss of D rich gas. P-
V-112A/B Reject St.Tank TK- SS304L
111A/B diagphram
XU 102
Vacuum Generating System:
Vacuum Pumps 108 A/SA, B/SD, C/SC, D/SD
4 will be in operation. 4 standby. Seal water circulation pumps 13-P-109 A/B/C/D

7
2 Nos. of water circulating tanks with heat ex. coils E-111 A/B, 4 Nos. of cyclone separates V-115
A/B/C/D
4 Nos. of Buffer tanks – V-113 A/B/C/D
And two nos. of chilled water exhaust cooler E-109 A/B
VACUUM lines from Equipment/Vessels are connected to buffer tank 13-V-113 A/B/C/D and line of
buffer tank is connected to suction of vacuum Pump. Vapors and inerts are driven out of vacuum
Pumps to cyclone sep. V-115 A/B/C/D, where droplets of water, if any, are separated.

Vap.+inert
Liquid+Vap.inert
inert Cyclone Sep. Ch.W
V-115 A/B Condenser
Buffer
tower Tank
Vacuume pre.liquid
E-109AB condensned
Shell side of water circulating tank E-111A/B liquid
tray

V-112A/B
Reject St. Tank
From E-111A/B, water is pumped to vacuum pump by water circulation pump P-
109A/B/C/D
In E-111A/B, coils are provided thro’ which Ch.W. is circulated to maintain the water temperature
(going to vacuum Pumps) at 32oC
Major Modifications at HWP, Manuguru:
1. Guard Pond recirculation (670KW+2500 M3/hr , Zero Discharge (1000M3/hr), Installation (280KW) of
small Capacity pump = 2500 M3/hr + 1000 M3/hr = 3500 M3/hr

670+280 = 950 KW

Water = 3800M3/hr saving, power saving = 950 KW

2. Trimming (690 KW), Corrocoating (70 KW) of C.W. circulation pumps, Bifurcation (275 KW) of C.W.
circuit:

690 + 70 + 275 = 1035 KW.

3. Trimming of 16 Nos. of process pumps = 390 KW.

4. Waste heat recovery: 5.3 TPH of steam (eff. Temp. dropped by 3oC goes to ETP) + TG cond. heating =
2.2 TPH of LP Steam.

5. Vapor absorption refrigeration: 12 MT/H of steam

LP steam consumption has come down because of various modifications like Waste heat recovery,
steam tracing replacement with heat tracing. Also power consumption has also come down because
of ENCON schemes. So, these used to be throttling losses across LP governing system (HP 30 ata
steam extraction →to LP cylinder of TG) and also enthalpy loss to C.W. of Th. condenser. By
increasing LP steam consumption through VAR, these inefficiencies were automatically taken care of.

6. Replacement of steam tracing with electric heat tracing – 3 MT/hr steam

LP steam consumption: 6T/hr

8
 660 Kcal/kg = 6X 1000 X660/3600X2334 = 0.47MW Heat rate = 2334kcal/kghr

Heat tracing 4KM : 2600M ---33 watt/m, 1400 M ----- 66 watt/m.

So total electric consumption 2600X33 + 1400X66 =178 KW ( 34% n, 2500 kcal/kwh)

LP steam consumption for steam tracing 470 KW Hence 35% energy reduction because of heat
tracing

7. SBA for CO2 removal: 1% increase in gas purity + 1% increase in production. + H2O loss: 4 kg/hr +
Reduction in silica

8. H2S recovery from sour oil = 2.5 Kg/hr (1.5 – 1.8 MT/month)

9. Improvement of system hydraulic of chilled water loop = 250 KW.

Equilibrium time for BEP = 18 months

Eq. time for O18 = 24 months.
In the last decade energy reduction = 40%
1996-97 – 53; 1997-98 – 47, 1998-99 – 40,
2006-07 – 33 GJ/kg
Edutor: At throat – 70 m/sec velocity.
To avoid erosion corrosion, two options are there:
1. Lining with 13% cr (ss) hard facing material or hard facing sleeve – cheap

2. Ceramic lining – costly. (or)

SS 309 Mo lining – which was done downstream of 12-LV-1201 d/s on DP then = 17 kg/cm2g

ISI:
1. Metallographic examination: compare the micro structure with the micro structure of original
material.

2. Surface defects – LPT

3. Sub surface defects (not so deep defects) – MPT (magnetic particle testing)

4. Radiography – real assessment of weld minutes – permanent record – costly.

5. UT: requires skill, cheap compared to radiography.

6. Ultra sound thickness measurement

7. Acoustic emission testing.

FUTURE ENCON SCHEME:

1. Auxiliary steam turbine in the HP steam line to ISG, 30 kg/cm2 (355oC) to 18 kg/cm2, 166 Te/hr, 3.95
MWe

2. Installation of packing in all the towers of XU and VFO, for boosters. One booster can be removed
altogether. Energy saving: 4.6 MW/steam

3. Installation of process heat recovery and waste heat recovery heat exchangers d/s of PPXs and
waste stripper exchangers (E-128, 129 & 130) as the approaches are very high. Saving = 12.5
MT/hr/steam

Approaches: PPX: shell side: 132/86 tube side : 70/114; hot end approach :18oC; cold end :
16oC
E-128/129/130 :- S/S : 155/91, T/S – 70/135 cold end approach: 21oC, hot end: 20oC
4. After installation of VFD for K-105, saving of power = 37% saving of power with packing only in 3CT.
9
 Mellapack 250 Y. Specific area = 250 M2/M3; void = 0.988 (θ=45o)
HETP = C μg0.47 μL 0.4 X ln λ/ λ-1
F (1-Є) (ρg) Dg ap
0.2 0.4 0.77 0.67 0.8

Where µg : gas viscosity

µL : liquid viscosity
F : Vapor load factor (F-factor) = Ug (ρg)0.5
E : Void fraction.
eg : gas density
Dg : gas diffusivity
ap : Packing specific area = 250 M2/M3
𝜆 : Stripping factor = (1/βc)/(L/G)c
(eq.line slope /operating line slope)
Pressure drop = 30 MMWC/M packing.
 Flow path vertically down – self flushing character.

 Very low inventory of liquid

 SS316

 130% of processing capacity.

 Water σ = 75 dynes/cm; wettability a problem

 Process liquid σ = 38 dynes/cm wettability no problem

 Packings are fabricated from this metal of 0.1 to 0.15 mm thick sheets of SS316. The surface is
pressed/punched to generate holes and undulations (or corrugations) for enhancing surface area
and generatic of flow channels.

 Each sheet is rotated 90o with respect to adjacent sheet.

Wettability: Wettability denotes the ability of the liquid to spread on the surface
Wettable : Hydrophilic
Non-wettable : Hydrophobic
Contact angle: is the angle formed by liquid at the three phase boundary where a liquid, gas and solid
intersect.
The lower the contract angle θ the better the wettability.
0 < θ < 90o → good wetting liquid
Θ > 90o → Bad wetting liquid.
A zero contact angle represents complete wetting.
Surface roughness, heterogeneity of surface affect the wettability in the form of contact angles.
Wetting of a solid surface is a complex phenomenon and depends on many parameters like:
a) Liquid properties - µ, ρ, temp. etc.

b) Contact angle, surface roughness

c) Liquid load

Typical contact angles: On extremely hydrophilic surface, a water droplet will completely spread (an
effective contact angle, θ of 0o). This occurs for surface having a large affinity for water (including
materials that absorb water). On many hydrophilic surfaces, water drop lets will exhibit contact
analysis of 10o to 30o.
On highly hydrophilic surfaces, which are in compatible with water, one observes a large contact
angle 70o to 90o.
Θ= 150 – 180o, water droplets simply rest on the surface, without actually wetting to any significant
extent .Wetting directly affects the interfacial area available for M.T. or H.T.
M250Y 1.4 – 1.6
10
 NTSM we can take it as F = 0.18

F factor 0.18 0.2

Packed columns require a minimum liquid load to ensure sufficient M.T. Below this min. loading,
only a very small part of the column is wetted, and so vapor and liquid area are no longer in intimate
contact. So η↓
In practice: Min. liq.loads for dumped packings = 10M3/(Hr)(M2) aq. System
= 5M3/(Hr)(M2) for organic.system
Columns with structured packings (with organic system), Min.liquid load can be as small as 0.2
M3/(Hr)(M2)
Flood point of a column is a gas flow rate at which mass transfer efficiency decreases drastically.
Ideally, the column should be operated on the verge of the flood point to Maximise efficiency and
capacity.
F-Factor, flooding velocity of 3CT tower:
F factor of 3CT : 0.18 (ft/sec) at top, 0.24 ft/sec. at bottom
: 0.17 at MTS bottom HTS bottom
Take F = 0.18 ft/sec.

Flooding velocity V = F = 0.18 = 1.1392 ft/sec = 1.39 ft/sec. = 0.33

M/sec
Q = x 2.32 x 0.4 x 3600 = 6105 M3/hr
At 30oC, 16 kg/m2, ρH2S = 23.23 kg/M3
Flooding M: So, M = Qρ = 5982.8 x 23.23 = 142 Te/Hr
With trays, flow = 115 Te/Hr, % flooding = 80%
With packing flow = 138 Te/Hr % flooding = 97%

Plate type heat exchangers:

They are capable of recovering heat efficiently at low temp. differences of as low as 1 oC
mainly because of high turbulence in these units even at low velocities.
Flat corrugated (or) embossed standardized plates, are arranged in a compact form of heat
exch. Having less weight, require less space, low hold up, and providing high heat transfer coeff. Low
pressure drops.
Limitation: 250oC, pressure = 25 kg/cm2g, gasket materials over the limitation.
The required no. of plates are pressed together within the frame and narrow flow passages are
formed between the plates which are separated from each other by gaskets and plate corrugations.
The basic objective of providing corrugated (or) embossed patterns to the plates is to impart
high turbulence to the flowing fluids which result in H.T. Coeff. AS HIGH AS 2 to 3 TIMES OF
THOSE OBTAINABLE IN SHELL-TUBE UNIT FOR SIMILAR DUTIES. These corrugations also
result in increased surface area and provide additional strength to the plates to withstand diff. pressure
that can exist between the fluids on either side of the plate. To provide deflection, it is necessary to
provide sufficient contact points over the plates.
Gasket materials: Chemical, Temp. resistant, good sealing profess.
With the help of connecting plates, plate heat exch. Can be divided into separate sections to
accommodate more than two fluids in the same plate pack.

F1 F4
Fluid 3 F2
Fluid 2

11
Fluid 3 F4
F1
4-Fluid H.Ex.
Several types of flow patterns can be achieved by appropriate gasket arrangements. Flow pattern(a)
series (b) Parallel
Two basic types.

Series Parallel

Looped – U- arrangement

Looped – Z -
arrangement

Thermal Performance: The plates are two types:

(a) Short duty or soft duty

(b) Long duty or hard plates

Soft (or) Short Plates: Low pressure drop too Low H.T. Coeff.
A short too Wide Plate is of this type.
Hard (or) Long Plates: High Pressure drop too high H.T. Coeff.
Long too narrow plates.
In decisions the type of plate suitable for a given duty, the most convenient use is No. of Transfer
Units (NTU) (or) Performance factor (or) thermal length (or) temp. ratio (TR)
NTU (or) θ2. (or) TR = (ti – to) / tm = 2ApU/WCp
Where Ap = Area of Plate, 2Ap = Area per channel bounded by two plates, M2
ti = channel I/L temp. of process fluid
to = channel O/L temp. of process fluid
tm = Long Mean Temp. diff. (LMTD) between a channel and immediately adjacent channels.
U = overall h.t. coeff.
W = Main flow rate of fluid
Cp = Heat capacity of fluid.
i.e. NTU (or) thermal length is the ratio of temp. drop (or) gain across a channel to LMTD between
that channel and immediately adjacent channel.
NTU can also be defined for exchanger as the ratio of temp. changes for the process fluid to ∆Tlmfor
the exchanger.
12
NTU(across exchanger) = ∆T/ ∆Tlm (across exchanger)
= Uav At/WCp
Hard plates are most suitable for difficult duties such as regeneration, where end temp. differences i.e.
approaches are small so as to achieve a high proportion of heat recovery. Such duties require plates
with high NTU values.
Soft plates are low NTU plates – easier duties – high approaches.
High H.T. Coeff: can be achieved in plate h.ex. at relatively moderate velocities, so that high NTU
duties can be fulfilled in a comparatively small no. of passes. Thus the over all ∆P is minimized. For
very high duties, say with an NTU of 9, a unit may be designed with 3 passes of plates in series each
having an NTU of 3.
An unequal no. of passes is usually adopted when flow rates and permissible ∆P for the two liquid
mealic are different.
One of the problem with plate units is with reference to the exact matching of the thermal duties. It is
very difficult to achieve the required thermal duty and at the same time utilize the available pressure
drop fully. A solution to this problem is to install more than one kind of channel in the same pack
with differing NTU values. The types could be mixed to produce any desired value of NTU between
the highest and the lowest.
The high NTU plate is corrugated with a large included angle chevrons giving a comparatively larger
∆P which the low NTU plate has chevron corrugations with a much smaller included angle leading to
a relatively low ∆P.

Large included angle

small included angle

Medium NTU High NTU

Low NTU
The high NTU plate (NTU-3) provides for lower flow rates and higher h.t. coeffs. Whereas the low
NTU plate (NTU
Eg. For consumption 70% High NTU 2 30% medium NTU plates.
ADV OF PLATE TYPE H.EX:-
- The transition to turbulent flow occurs at Low Re of 10 to 400.

- The high turbulence leads to very high H.T. Coeff. Low fouling rates and reduced size.

- The thin plate cut down metal wall resistance to the minimum.

IMP: These units can use up to 82%of theoretical LMTD, which shell – 2 – tube units are capable
of utilizing only 50% of it, mainly because of cross flow in Shell &Tube H Ex. Absence of cross
flow in plate H.E.
- Over 90% of heat recovery is possible with a plate unit with very close temp. approaches.

- Heat losses to surroundings are Low because only the narrow plate edge and the gasket are exposed.

- As high H.T. Coeffs. Can be achieved at relatively moderate velocities in a plate unit. High NTU duties
can be fulfilled in a comparatively small no. of passes thereby keeping the over all ∆P to the minimum

- Low liquid hold up, compact, occupies less floor space low weight etc.

- Cost wise, a plate unit competes favourably with a tubular one, if the tubes are to be of a costly
material like S.S.

- Multiple duty – More than two liquid it can handle.

LIMITATIONS:
13
- Upper limit on their size, Heat Ex. with larger than 1500 M2 are not normally available.

- Since the flow passages between the plates are thin, high liquid ratio will involve excess ∆Ps, thus
limiting the capacity.

- For special cases, it is possible to have a Max. zero pressure of up to 2.5 MPa (25 kg/m2)

- Operating temps. are limited by the availability of suitable gasket materials upper limit is 250oC.

- The limitations of temp. and pressure are overcome in Heat Exchangers of lamella type in which all
the parallel plates clamped together in a frame are sealed around their edges of the communicating
ports by welding. Although the flexibility of the gasketted unit is lost, the elimination of the gasket
seal enables operation up to 4 MPa (40 kg/m2) in these units.

- Not suitable for air-to-air (or) gas-to-gas applns.

- Liquid with very high µ present problem due to flow distribution effects

No. of channels = No. of plates – 2 (….. sides of first and last plates are not utilized for H.T.)

- Flow velocities <0.1 m/sec give less H.T. coeff. And low H.Excs. µ. As such, velocities <0.1m/sec are
not used in plate H.Ex.

- Not suitable for condensing duties.

- Suitable only for liquid-to-liquid heat duties.

- Viscous liquids which might produce laminar flow in a shell and tube H.Ex. may well be in turbulent
flow in a plate H.Ex.

- High h.t. rates make plate h.ex. ideally suitable for use as chemical reaction.

- Careful choice of fouling factors which designing exchangers is very much necessary in order to
minimize the chances of over (or) under design.

- Over design in addition to costing reduces the flow velocities resulting in increased fouling rates.

- Fouling is much less on plates H.Ex. because of:

a. High turbulence maintain solids in suspension.

b. Velocity profiles across a plate are uniform with areas of low velocity absent.

c. The plate surfaces are smooth and can be further electro polished.

d. Deposits of corrosion products, to which fouling can adhere are absent because of low corrosion
rates.

e. In cooling duties, the high film coeffs. maintain a moderately low metal temps. And this helps
prevent crystalisation growth of the inverse solubility compounds.

NTU of WHR-1 plate unit = 3

- For low viscosity liquids, velocities thro’ the channels in the turbulent region range from 0.3 to
1M/sec. The local velocities may be a high as four times the avg. velocity. All correlation make use of
avg velocity.

- Turbulent region, liquid µ = 0.07 to up to 0.1 ρa.sec.

14
 Laminar region, liquid µ > 0.1 ρa.sec.

- At high viscosities ( 5 ρa.sec), the distribution problems of liquid become predominant and
prediction of laminar heat transfer performance becomes less reliable.

- Laminar region, use Sieder-Tale type equ.

Nu = C (Re PrOe/L)и (µ/µw)и

C = 1.86 to 4.5, n = 0.25 to 0.33, x = 0.1 – 0.2 usually 0.14

n
- Turbulent flow: Nu = =C Prm (µ/µv)x

De =eq dia =

= 4Wb/(2W+2b) b = distance between plates.

De =2b (since b<<w) W = width of plate.
Pressure Drop:
Economic design of plates H.Ex. involves complete utilizing of the permissible pressure drop
which determining the hit area requirement. In these h.exs, the pressure drop requirements can be
closely met due to flexibility involved in the choice of plates w.r.t. their size, configurations and no.
and arrangement of flow passes.
SPECIFIC PRESSURE DROP, J: is a useful parameter is ensuring the performance of a heat exch.
Both w.r.t. hit and pressure drop. It is defined as
For water – water duties
J = ∆P/NTU
For most h.ex. J=20 – 100 kρa/NTU
For water – water duties
For most H.Exs, J is in the range of 0.2 – 1.0 Kg/m2/NTU
Normal value = 0.3 kg/m2/NTU (or) 30 KPa/NTU
- Film Coeff. For water/water duties corresponding to J = 30 will be around 15,000 W/M2 oC

- The max. flow what we get depend on ∆P. In case of low viscosity, pressure drop thro’ the ports is
normally the limiting factor for achieving high flow capacities.

- For viscous liquid gases, the channel ∆P may be more critical.

- It is desirable to provide large port areas to minimize port pr. Drops to improve the h.t. performance
of the h.ex.. As a general rule, port pr. Drop should be kept below 50% of total ∆P. If port loss
exceeds 66% of the total ∆P, the design should be altered.

- Friction factor in a plate channel is 10-60 times that for a tube at the same Re for turbulent flow.

For a typical plate h.ex. f= (34/Re) + 0.8

(laminar flow contribution predominate Re<10)+ turbulent flow contribution becomes predominate
at high Re

LMTD Correction:In a single – pass → pure counter

Current – No LMTD correction.
- A multipass exchanger, if arranged with the same no. of passes for the two fluids, is still essentially in
counter flow – No LMTD correction.

15
- So, when flow thro’ channels is purely counter flow – No LMTD correction.

- Whenever unequal passes are used, the LMTD correction factor will significantly contribute to the
exchanger area (unequal flow conditions).

- If high and low flow rates are to be handled, the necessary velocities must be maintained with the
low fluid flow rate by using an increase no. of passes.

- The Plate Unit is MOST EFF. WHEN THE FLOW RATIO BETWEEN TWO FLUIDS IS IN THE RANGE OF 0.7
TO 1.4.

- For flow ratios other than the above (0.7 to 1.4), unequal no. of passes are used requiring significant
LMTD correction.

PLATE Vs SHELL – AND – TUBE H.EXCHR:

1. For liquid/liquid services, higher h.t. coeff. In plate units.

2. In plate, turbulent flow is obtained at Re as low as 10-400, whereas in shell-tube, critical Re = 2100
(above Re 2100, turbulent flow in shell to tube units).

3. Though tube is the best shape from strength point of view, it is the worst possible shape from H.T.
point of view as it has the smallest h.e. area in comparison to its flow area.

4. Though ∆P in plate unit is as high as 100 times that in a tube at comparable avg. velocities and flow
lengths, the pressure drop is better utilized for H.T. purpose in this plate unit. The plate channel
given considerably higher H.T. Coeff. Than a tube of equivalent ∆P per NTU. The avg. flow velocity in a
plate channel is normally in the range of 0.3 to 0.8 M/sec, which is about half the normal velocity in a
tube.

5. While in a plate unit, the flow channel for both fluids are identical, in a shell & tube unit, the shell
side is inferior from H.T. point of view. For most duties, the no. of passes required in a plate unit are
much less than the no. required on the tube (or) shell side. This reduces the unproductive pressure
drop at entry and exit points.

6. Effective LMTD is usually higher in plate unit. In a plate unit, about 95% of the theoretical LMTD is
achieved, whereas not more than 80%is effectively utilized in shell & tube unit.

The temp. approach in plate unit is as low as 1⁰ C. whereas in shell & tube units, the temp. approach
less than 5oC is not economical.

7. The wall thickness of tube is normally more than twice that of plate and hence metal wall resistance
is much less in plate unit. Fouling resistance is also much less in plate unit.

8. One of the greatest adv. of plate unit is complete accessibility to all parts for inspection, cleaning and
replacement. In tubular unit it is very difficult to inspect tubes and other internal panels.

9. Less space, less weight, low inventory.

For High pressure and temp. applications, SHELL-&-TUBE UNITS. ARE THE BEST CHOICE.
Operation under strained conditions:
1. Tripping of one of the guard pond recirculation pump. We will try to start the standby pump. If it is
not available/doesn’t come in line, we will start the dilution water pump to limit the eff temp <40oC

2. Total failure of Ch.W:In case of complete failure of Ch.W. we will increase the C.T. R. flows keeping a
watch on C.T. temps/pressures.

16
3. Flame failure of flare stack: Normally happens on a windy day, we will try to relit the flare. If it
doesn’t severe implication on safety come in line, will try to light up standby flare, it both are not
available for 2 hrs, we will shut down XUs.

4. Partial failure of C.W: We will reduce h.t. temps, increase CTRs to maintain C.T. temp, start the
standby pumps, watch C.T. pressure.

5. Partial failure of feed water: Reduce h.t. temp, operation the sections at low feed flows. Increase
CTRs monitor CT temp/pr. Start the standby pump.

6. Partial failure of MP Steam: Because if inst. problem, if boiler goes out of service, we will be having
restricted, supply of M.P steam. Increase O/Hs, to H.T. and adjust the H.T. temps.

7. Tripping of one of Inst Air compressors: Isolate plant air, scram air. Try to start S/B compressor, if
not atleast emergency air compressors. Emergency scram air receiver will cater to scramming if any.

8. Hydrate formation

9. Failure of Nitrogen purging to flare: Line up supply from Bullets.

10. Responding to H2S monitors actuation from C.W system, pump sealant outlet etc..

- 200 Mev per fission.

- For 1 watts, 3.1 x 1010 fission/sec

U235 + un1 → fission fragments + 200 Mev + 2n

mass defect = 0.219 amu, which gets converted to energy as per E=MC2.

- Energy release is in the form of Kinetic Energy of fission fragments and neutrons.

- PWR, BWR & PHWR are the thermal reactors when Neutron speed (or) energy is very low, 0.025 ev.

Why Oxides fuel is being used: Oxide Fuel. Can be operated at high temp. and permits higher
burn up than is possible with metallic fuel. The presence of O2 is some what a draw back, since it
partially slows down the neutron and reduces the extent of breeding. (but w.r.t. safety of fast
neutron, slowing down of neutron is some what advantageous Oxides are more stable than
metallic fuel in the presence of neutrons.
Oxides fuel: Adv. High temp. operation, High burn up.
Disadv: . Low breeding.
Hence, R & D is on for metal alloy fuels because of High breeding ratio with metal fuels.
Nat U 0.7% U-235 (fissile), 99.3% → U-238 fertile.
Na : Thermal conductivity – 80 times ‘K’ of water .viscosity lower than water; ρ= 0.9 gr/cc
NPP Fuel Moderator Coolant
CR
1st stage (PHWR) UO2 D2O D2O
B4C
2nd stage (PFBR) (U-Pu)O2 + Th Blanket - Na
B4C
3rd stage (AHWR) (top for 3rd stage) (Th-U)O2 + (Th-Pu)O2 Amorphous carbon in H2O
B4C
Full bundle +
D2O(8o : 20 ratio)
Thermal Breeder Reactors U233 fuel + Light Water Cooled.
17
1stStage :
 Natural Uranium fueled reactors 220 MW, 500 MW Units.

 Total capacity limited to 10,000 MWe based on Uranium reserves 78,000 Te of Uranium reserves.
But low grade uranium in some mines and low tonnage of some mines are the teething problems.

Alternate Sources: Uranium extraction from Lean sources like wet process
 Phosphoric Acid (70 – 150 ppm) (DLEHPA + TBP)

 Monosite sand – by acid leaching and solvent extraction

 From sea water (150 microgram/M3)

 D2O Moderator, coolant, B4C control rods

 Plutonium (U238 + on1 → PU239) fuel will be produced in these reactors by conversion, ratio less
than 1.

2nd Stage:
 FBR with Plutonium as fuel (PU239 from 1st stage).

 Depleted Uranium (or) thorium in the blanket. U238 → PU239, Th232 → U233

 Conversion rate is more than fuel consumption rate, so the normal breeder, ratio 1.2.

Note: Burn-up: the energy extracted from fuel is usually referred to as burn-up of the fuel.
 The fast neutrons (Kev) in the core of a fast reactor have another potential use; for a long time
the disposal of certain types of nuclear waste produced in thermal reactors, which belongs to the
category of elements called “ACTINIDES” has been a problem. By putting this nuclear waste into
the FBRs, it can be broke down into materials, which are more easily, disposed of.

 Liquid metal coolant → Na Excellent heat tr. properties (K= 80 times that of water), viscosity is
less than water.

R&D for Metal Fuel Alloys having high breeding ratio is on

→ Next FBRs should be based on metal fuel alloys.
13 MWe → FBTR, we are using Carbide fuel [(Pu-U) carbide]
PFBR use (Pu-U) oxide fuel, MOX fuel.
 Reprocessing of FBR fuels is complex compared to that of thermal reactor fuels, because of high
Pu and fission product content. The spent fuel discharged from FBTR has 70% Pu as compared to
0.3% in PHWR. This fission products from FBR are also 10 times more than PHWR. Since these
reactors have to be inducted in large nos. in shortest possible time, the spent fuel is to be
reprocessed as quickly as possible.

 In FBR, Pu is produced more than which is consumed. Pu is produced by consuming U238. The
irradiated fuel is reprocessed for recovering U and Pu for reuse in the reactor. In the Fuel
Reprocessing Plant, the fuel pins are dismantled from the subassembly. These pins are then
chopped and dissolved in HNO3. Solvent extraction process with TBP as solvent, is used to
separate U, Pu and fission products.

 The Pu and the U recovered along with fresh Uranium are fabricated as fuel elements in
fabrication plant. This refabricated fuel is used in the reactor. Thus the fuel cycle is closed.

 PFBR is a pool type reactor using MOX fuel of (U-Pu)O2. FBTR is loop type reactor.

18
  FBR breeder thorium, but the breeding rate is not high. Alternate Technologies which offer
shorter doubling times, need to be explored & developed one way is external non-fission source
of neutrons.

ADS → Acceleration driven system – Neutron generated by spallation reaction using a high
energy proton acceleration. (or) by fusion reaction involving O/T nuclei.

PHWR: We get Plutonium → for 2nd stage also 60CO. Cobalt60 → where it is used.
3rd stage: U-233 as fuel and Th-232 as blanket.
 U-233 fuelled thermal reaction will also breed.

 Thorium utilization is the long term core objective of Indian NPP for providing energy security on
sustainable basis.

 The design of thorium fuelled 300 MWe. AHWR will provide a platform for the timely
development, demonstration and optimization of several technologies for the utilizing of thorium
needed for the third stage of Indian NPP. So, AHWR is TDP for thorium utilizing.

 3rd stage reactors will be water cooled thermal reactors as U-233 fuelled thermal reaction also
breeds.

AHWR:Next generation design of PHWR type.

 Developed by BARC

 Aims at using thorium for commercial power generation.

 Vertices pressure tube reactor

 Cooled by BOILING H2O

 Moderator = D2O

Fuel: 52 Pins: 20 pins → (Th – Pu) O2

32 pins → (Th – U233) O2
Primary S/D system : B4C
Secondary S/D system :Lithium Penta Borate solution injected in 32 prism tubes.
LATEST POSITION:
1. NR under operation : 2 BWR + 14 PHWR (3900) + 1 (Commissioning on) (220 MWe)

Commissioning on : 220 MW PHWR – Kaiga – 3

2. NRs under construction: Kaiga 4 (220), RAPS 5,6 (2x220), KK-1,2 (2 PWRs) 2 x 1000 MWe
(kudankalam)

3. New Projects: KK-3,4, Kakrapar, RAPS-X, Jaitapur (mahroli)

4. Plan 2020 – 6 PWRs (1000 MW size) + 4 FBRS (500 MWe size)

Rapid growth of fast reactors is possible only thro’ the deployment of METAL FUEL ALLOYS
rather METAL ALLOY FUELS with high breeding ratio R&D is on
CPP : ‘C’ grade coal consumption : 1300 Te/day (superior quality coal (ash content less) – should not
be ued for power plants as per Govt. of India decision.
‘E’ Grade coal consumption: 2300 Te/day.
VAR
Clausius statement of 2nd Law: “It is impossible to construct a device that will operate in a cycle and
produce no effect other than the transfer of heat from a low temp. body to a high temp. body”.

Tk High Temp. Body TK High Temp. Body

19
 Qk = Qo + Win Q
Possible Win = Qk – Q Impossible R
R
Q₀
Q₀
Low Temp. Body To T₀ To body
Low temp. T₀

Stress should be given to the words “operating in a cycle”. In a single process, it may be possible to
obtain removal of heat from a low temp. body, without doing external work. For eg. Take liquid
Freon at high pressure and expand it thro’ a throttle valve to say 1 bar – 30oC. So, we are getting
refrigeration without doing any work. But this will continue only if infinite supply of high pressure
Freon is available To obtain refrigeration continuously, the refrigerant vapor after evaporation at low
pressure will have to be brought back to initial state of high pressure liquid again. This mean forming
of a complete thermodynamic cycle.

SAT.Vapour at 1 bar -
30⁰ C
Throttle valveQ₀(refrigerant)

Liquid Freon at
High pressure
So, Clausius statement eliminates the possibility of refrigeration without doing work. The statement
necessitates a further clarification regarding heat operated refrigerating machines such as VAR type
or ejector type, using heat directly to produce refrigeration.
Such systems (VAR, Ejector type) may be considered as a combination of a heat engine and a
refrigerating machine. The heat engine part of the system utilizes heat from a body at a high temp.
than the surroundings and delivers the reqd. mech. Work, within the system, which is directly used by
the refrigerating machine part.

HEAT ENGINE, HEAT PUMP AND REFRIGERATING MACHINE:

Heat Engine : Using the heat & producing work power plant cycle is heat engine.

T1
Heat Source
WE
E

T2 T ambient.
Refrigerating Machine: Here by doing work on the system, we transfer heat from low temp. body to
high temp. body.

TK Ta

WR
R

To
Cooled Space
So, a reversible heat engine may be converted into a refrigerating machine by running it in the
reversed direction. So, a refrigerating machine is, schematically, a reversed heat engine.
Heat Pump: There is no difference in cycle of operation between a refrigerating machine and a heat
pump.
So, the same machine can be utilized either:-

20
 TK
Heated space
WH
H

TO Tambient.
a) To absorb heat from a cold body (a cooled space) at temp. To and reject it to the surroundings at
temp. TK Ta (nothing but refrigeration Machine) (or)

b) To absorb heat from the surroundings at temp. To Ta and reject to a hot body ( a heated space) at
temp. TK.

So, Heat Pump can be used either from cooling (or) heating. When used for cooling, it is called
Refrigerating Machine and when used for heating, it is called Heat Pump.
‘R’ operates between ambient temp.
Tamp = TK and a low temp. To
‘H’ operate between ambient temp. Tamp = To and high temp. TK

Heat Source TK
QK
WE Heat space TK
E
QK
Qo WH
QK H
T2 Ta Qo
TK To
Ta Ambient Surroundings
To Ta
WR R

Qo
Cooled Space
To

In R, the heat ex. that absorbs heat is connected to the conditioned space. In H, the heat ex. that
rejects heat is connected to the conditioned space. The other exch. In either case is connected to
the surroundings.
H : The performance of heat engine is described through .
COP : The performance of heat pump (or) refrigerating machine ® is expressed by the ratio of
useful heat to work, called COP (or) Energy ratio, E
R, energy ratio (or) COP (cooling) E c

Ec = =

H, Eh = =

E = Heat engine th = =

Suppose, if th = 30% (say), th = = 0.3

If the heat engine is reversed in operation to work as a “R’ (or) Heat Pump with the operating
conditions unchanged (although in actual practice, the operating temps. Are different), we should
have
21
 → EC = , we know th = = 0.3

→ th = 0.3 = 1- th

So, Ec = = ( Q₀/Qќ) / (1 – (Q₀/Qќ) = = =

2.33

h = = (Qќ/Qќ ) / (Qo/Qќ) – 1 = = 3.33

VAR
MAX COP OF A HEAT OPERATED REFRIGERATING MACHINE
Energy Input = Heat energy thro’ steam qh + pumping work qp
Refrigerating effect = qo (heat extracted from chilled water)

COP =

= neglecting pump work qp ( qo+ qh + qp = qk condenser which is small compared to qh

VAR is a heat operated Refrigerating machine. It may be considered as a combination of a Heat
Energy and a Refrigerating Machine as shown below:
Th Temp. of heat source (LP Steam) (LP
steam)
Qh E
Absorber
condensating
E

QA
Tk Condenser and absorber
temp. Tk
Qc

RQo
To Refrigerating temp.

The energy supplied to the system is in the form of heat Qh at temp. Th. The thermodynamic
cycle is considered to comprise of a Heat Engine Cycle, E, operating between the heat source
temp. Th and the temp. of heat rejection Tk. AND, a Refrigerating Machine K cycle operating
between the refrigeration temp. To and temp. of heat rejectorTk
The work done in the heat engine part of the cycle is equal to the work requirement of
refrigeration part of the cycle. So, the VAR cycle, we may write

COP = = x = th x Ec
So, COP OF HEAT OPERATED REFRIGERATING MACHINE (VAR) IS EQUAL TO THE
PRODUCT OF THE THERMAL EFFICIENCY OF THE HEAT ENGINE PART OF THE
CYCLE AND THE COP FOR COOLING OF THE REFRIGERATION PART OF THE CYCLE.
HENCE, COP OF VAR EXPRESSED BY Qo/Qh SHOULD NOT BE COMPARED WITH COP
OF VCR, which is Qo/W. [In VCR, we are not considering the inefficiencies in generating the
power which is consumed for the operation of compressor].
So, the COP of VAR should be maximum when each of the two terms has a max. value which
would be so when both are equal to their respective Carnot values. Thus:

22
COPMax = th, Carnot x Ec, Carnot (Here it is assume that condenser & absorber temp. are equal, Tk)

= x
So, for max. COP:
1. Temp. of heat source Th should be as high as possible.

2. Temp. of heat sink, Tk should be as LOW as possible.

3. Temp. To of refrigeration should be as HIGH as possible (we don’t want this)

However, VAR system is not a reversible cycle. This is a degree of reversibility due to mixing of
refrigerant and absorbent. So, its COP first, increases with increase of generation temp. it reaches
an optimum value and then, it starts decreasing as a result of increase in irreversibility at high
generation temps.
In VAR, Solution ckt (Libr soln. ckt) –
Generator – Absorber – pump – may be considered to represent the Heat Engine part of the cycle.
On the other hand, Refrigerant ckt (water – represent – ckt)
- Condenser – Expn device – evaporator from the usual refrigeration part of the cycle.

- It may be noted that, in case, the condenser and absorber temp. are not the same and are equal to T c
and Ta respectively, then the MAX possible COP is given by:

COPMAX = x
th carnot x Ec carnot
out VAR, Th = 153.3oC = 426.3oK
o
Absorber Ta = 48.1 C = 310.95oK
Evaporator To = 12.8oC = 285.8oK
o
Condenser Tc = 43 C = 316oK

COPMAX = x
= 0.270 x 9.46
COPMAX = 2.5

What we are getting: COP =

Ch.W.systemCp Cp

Steam flow steam H Cond.H

COP (optg) = 1.4

Prilling water IS 10500, F <1 ppm

H2 based D2O : Large Separate Factor → higher recoveries, flows per unit product → lower fewer
theoretical trays etc. Rate of exchange is very less.
At C.T. Tray GS H2-CH3NH2 H2-NH3
H2-H2O
Gas solubility 830 24 40 8
O/H Rate Const (site) 5000 130 15 1
 Because of low solubility of H2 in CH3NH2, NH3 2H2O, they operate at higher pressure.

23
  Normally hot tower temp in H2 process is limited by vap. Pre. of liquid and C.T. temp. is limited
by minimum practical exchange rate.

GRTN

 Tower Vol. = PKGa

H2S NH3-H2 CH3NH2-H2 H2-H2O

 KG a 0.9 0.008 0.04 0.08

 Low values of KGa are enhanced by using ejector trays, increasing interfacial area varying
considerably and reduce tower volume (V=GRTN/PKGa)

 For H2 based processes: = H/KlRT

 Value of Kl depends both on mass transfer and on chemical reaction, so that kinetic rate const.
enters into its (KG) determination.

Say Kl = M.T. coeff. For liquid phase for combined absorption to chemical reactions.

In slow reaction regime, the exchange reaction occurs in bulk liquid and herein slow reaction
regime,

Kl = Є Kr/ a where Є = Vol. fraction of liquid on the tray

Kr = Kinetic rate const.

a = Interfacial area for M.T.

IMP : In H2 based processes to get high yield, we require high ‘ in cold tower. For high ‘ ’
we require low C.T. trays. But at low temps in C.T. isotopic exchange rate drops to hence tray
drops. To get high exch. Rates at low tower temps, ejector trays are used to get reasonable tray
.
At – 50oC, sieve tray = 0.7%
(CH3NH2-H2 C.T.) ejector tray = 70%
The better performance of ejector tray compared to sieve tray is because of high residence time
(gas phase super final residence time:- sieve tray → 1 sec., ejector → 7.6 sec.) and because of
higher rate of energy dissipation in the ejector producing a much more intimate gas liquid contact.
Pump is required to pump down the liquid to the trays below because of high pressure drop across
each tray.
The reduction in tower volume by a factor of >3, when using the ejector trays more than makes up
for the cost of pumps.
NH3-H2 : C.T. temp. Recovery But as C.T. temp. , reaction rate ↓ so, tray ↓ . Lower
temp. limitation of
– 25oC(for achieving high , high yield) is temp. where we get some practicable exchange rate.
To get high exch. Rates, ejector trays are provided. H.T. temp. is limited to 60 oC by the NH3vap.
Pre. in the gas phase.
In CH3NH2 also C.T. = -50oC for high yields, Because of superior reaction rate compared to
NH3/H2, hence -50oC, HT – 40oC deconvertion of catalyst.

For any bithermal recovery = 1-

24
 For monothermal NH3-H2 recovery = = 5.3-1/5.3 = 80%

Monothermal CH3NH2-H2, R = = 87%

ENRICHMENT RATIO (ER) Vs RECOVERY (OR) YIELD:

7
6 CH3NH2/H2
ER 5
4 NH3/H2
3
2
1
0 H2S/H2O
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Yield (or) Recovery
At ER = 1.0 (no enrichment), the yields are the max. theoretical values of 1- (βh/βc) As the
enrichment ratio increases, theYIELD IS REDUCED. This effect is more marked for H2 based
processes because of less contacting stages are available on C.T. This is the penalty for the
comparatively poor exchange kinetics of the H2 based processes at low temps.
AHER = 4.0, corresponds to optimum condition of the GS plants and NH 3/H2 At this condition
the yeild for NH3/H2 loop is equal to that for GS loop. The yield from CH3NH2-H2 is however
twice as great. This means that normal product from CH3NH2-H2 ( V(40%)) loop requires only
HALF the amount of feed stock of the other two processes.
In GS process, ER has negligible effect on Recovery.
How do you ensure safety of the plant/public:
a. Quarterly leak survey.

b. Environmental monitoring

c. Annual Turn Around : every four years – SHT, SLT

d. ISI

D2O Process figures: 540 Te/Annum (6 plants – 14 PHWRS

Consumption for make up : 12 Te/Reactor/Annum

(in a reactor 6% loss = = 12 Te) = 12 x 14 = 168 Te/annum

Stock piling up = 540 – 168 = 372 Te/annum
Stock at HWPM = 1400 Te
Total stock of HWB = 2000 Te
VSD: Most drives are controlled by a technique called Pulse Width Modulator (PWM), in which
the motor voltage is varied by applying the intermediate d.c. voltage to the motor windings for
longer (or) shorter period of time. The control circuit determines the on and off switching times
and sequence of transistors.
Latest Make up rate : 2% of D2O hold up in PHWR.

Separation Factors:
1 H2O – D2O H2o vs HDO 1.027 at 100oC/1 atm
1.054 at 52oC/ 120 atm
2 O216/ O218 O16 vs O18 1.0078
3 B10 / B11 B10 vs B11 1.016
4 DTo Distillation 1.0125

25
 For HDO vs H2O → = 1.1596 e- 65.43/T
T = OK
So, H2O vs HDo = 1/ HDO – H2O

G.S. Basic :-Kx = = ⇒ [HDO]l = Kn(HDS)g

Kx = 1.01 e233/T
Kx varies with temp, Knc = 2.2, Knh = 1.8
Knc>Knh. This difference in the value of the equilibrium constant allows the liquid in the C.T. to
be in equilibrium with the circulating gas at a higher concn. Than is that in hot tower.
We know, [HDO]l = Kx [HDS]g
Knc>Knh
[HDO]lc> [HDO]lh
must reach the
level of feed concn. And the concn. In the C.T. will attain a value that is somewhat higher. If
product is withdrawn, this will lower the concn. In both towers somewhat the h.t. falling below
the feed and C.T. remaining above. The system thus becomes productive. The feed is split into
two streams, one of higher and one of lower than the initial concn.

C.W. to condense
CW Condense

312 Te/Hr
60% LIBV LIBV 60%

Ch.W24oC
Heat
Recovery
Ch.W14oC LTG
Refrigerant
H2O HTG
Refrigeration pump Heat
CW 55% LIBV Rec.

Absorber Pump line Exchrs.

VAR DIAGRAM
Evaporator : 11 MnHga, 10oC
Condenser : 64 MnHga
HTG : 630 MnHga

The tower dia. Required in M.T. can be decreased by the use of increased tray spacing, so that the
tower cost, which depends on height as well as dia, passes thro’ a minimum at some optimum tray
spacing.

h3

h1
hw
for avoiding flooding:
hw (weight) + h1 (crest over weight) + hw (backup in down,…….) < t (tray space)/2
Off-Site H2S Monitor range = 0 – 20 ppm
5 ppm alerting, 10 ppm danger
26
- About 96% of investment and 93% of the operating costs are associated with the production of 15%
D2O in XU. The remaining costs over by DU.

- ASME Sec.VIIIDiv.I, Design Pressure = x yield strength

- ASEME Sec.VIIIDiv.II, Design Pressure = x yield strength

For our towers, vessel code used: ASME Sec.VIII Div. 2

SHT is normally done at yield strength so, tower, vessel SHT Pr = yield strength = x design pre.
= 1.25 x design pre.
G = 0 → equilibrium reaction
G -ve → reaction occurs (forward reaction)
G +ve → G production > reactants → No reaction
Backward reaction.
H2S:- LOC → Level of Concern =
(IDLH = 300 ppm earlier 1/10 IDLH = 1/10 x 300 = 30 ppm
100 p0pm now (after 1994)
Why On-Site Emergency H2S concn. Limited to 50 ppm?
1. As per US EPA, H2S is extremely hazardous substance and suggests a Level of Concern (LOC) of 30
ppm which is one tenth of IDLH for H2S. Declaration of On-Site Emergency due to H2S release may be
based on H2S- in air values in excess of this LOC. which formulatingemergency plans, a higher/lower
fraction of the LOC value may be decided for declaration of on-site emergency based on practical
condition at site.

2. When 50 ppm concn. Is there in hazardous area, (XU-I or Ii or H2S), the area concn. Out side that area
should be less than 10 ppm so that people can move to BA shetlers without any PPE.

Why Off-Site at low levels: (2-1, 5-2 hrs, 10, 20)

Based on H2S-in-air values in the public domain and other factors, the situation may require in-
place sheltering of the public in their dwelling place (or) may require evacuation of the area.
These intervention levels are generally fixed at lower than LOC. This is because the LOC is
based on the IDLH which is arrived at considering healthy male worker population and DOES
NOT TAKE INTO ACCOUNT EXPOSURE OF MORE SENSITIVE INDIVIDUALS –
CHILDREN, OLD-AGED, preganent woman, whose immune levels are less, should be take into
account. That’s why public TLV (1hr max. avg = 0.1 ppm, 24 hrs daily avg = 0.05 ppm, 24 hrs.
Annual Avg = 0.005 – Limits set by Ministry of Forests & Environment, GoI, in ambient air, H2S
< 6.9 µg/M3)
- May’07 H2S Loss :- 6.4 Te

- Sp. Energy :- 30.5 GJ/Kg D2O

3CT: Design fig. UCIL : L, kg/hr = 30,000

Temp. Liq = 40oC, Vap: 40oC
Q v ft3/sec. = 0.296
V, kg/hr = 108,300, Qv ft3/sec = 36.7
3 3
L; lb/ft = 62.11, V lb/ft = 1.805;
L, cp = 0.77

sec = 0.18
AT, ft2 = 44.7, AA ft2 = 35.7
T, tray spacing: 485 mm = 0.485M

27
 0.5
Flow parameter E = = 0.0473
= 0.0744 t + 0.01173 = 0.047814
= 0.0304t + 0.015 = 0.029744
0.2
log + ) ( = N/M
Csb = 0.0195 M/sec

= 0.633 M/sec = 2.0765 ft/sec

Qv/An
= 36.7 (44.7 – Ad)

Ad = = 4.5
Design velocity = 36.7/(44.7 – 4.7)
= 0.913 ft/sec
So % flooding : 44%
1. NUCLER POWER PROGRAMME
Indian Nuclear Programme comprises of 3 stages for optimized use of domestic Uranium and
Thorium reserves.
 1st Stage - Pressurized Heavy Water Reactors (PHWRs): In the first stage natural uranium
dioxide based fuel is used in heavy water moderated Pressurized Heavy Water Reactors.
 2nd Stage - Fast Breeder Reactor (FBRs) utilizing Plutonium produced in PHWR: In the
second stage, the fissile plutonium, which is separated from the spent fuel generated in
PHWR in fuel processing plants, serves as the main fissile element for fuelling the Fast
Breeder Reactor (FBR). In pursuit of second stage a fast breeder test reactor has been set up
and technology development for a 500 MWe sodium cooled prototype fast breeder reactor is
in progress. In parallel to the above activities, as a part of the second stage of our
programme, it is proposed to use thorium based fuel along with a small feed of plutonium
based fuel in Advanced Heavy Water Reactors (AHWR).
 3rd Stage - Advanced Nuclear Power Systems based on mainly Thorium: In the third stage,
dedicated breeder reactor based on uranium-233 & thorium are planned to construct. This is
the thorium utilization stage. Thorium, when irradiated, gets converted to nuclear
fissionable fuel U-233, which can be used for power generation.
India’s Natural Uranium reserves are limited, whereas Thorium reserves are very large. Projected
indigenous reserves of natural Uranium are adequate to install PHWRs of only about 10,000 MWe.
Natural Uranium consists of
 U235 – 0.7%, fissile material, which involves in fission reaction to produce electricity
 U238 – 99.3%, fertile material: Gets partially converted to fissile Pu239 on absorbing
neutrons
The discharged fuel from PHWR contains about 0.35% Plutonium of which about 70% is fissile.
The unutilized uranium in the discharged fuel is called depleted uranium, contains about 0.2% of U-
235 while the remaining fraction is U-238. This spent fuel is reprocessed. Plutonium and U238 are
separated.
In the Second stage, plutonium and depleted uranium from spent PHWR fuel will be used in
FBRs. These reactors generate more fissile material than consumes by them. The discharged fuel
from FBRs needs to be reprocessed using complex chemical extraction methods.

28
 The third stage requires extensive use of thorium, U-233 in FBRs and AHWRs. Thorium, a fertile
material, cannot be easily fissionable in a nuclear reactor to produce energy. However, like U238,
thorium also gets partially converted to fissile material U233 on collision with neutrons. Kamini
reactor located at IGCAR, Kalpakkam is the only reactor in the world operating with U-233 as fuel.
At present in India, 18 PHWRs, 2 Boiling water reactors and one Pressurized water reactors are under
operation with a total installed capacity of 5780 MWe.

Pursuit of the closed fuel cycle option calls for setting up of reprocessing plants and breeder reactors.
Towards use of thorium for power generation, BARC has been developing Advanced Heavy
Water Reactor (AHWR)
The road map for the 3rd stage is;
i. Advanced Heavy Water Reactor (AHWR)
ii. High temperature reactor based power packs.
iii. Accelerator driven systems (ADS)
i. Advanced Heavy Water Reactors:
AHWR – A vertical pressure tube type reactor cooled by boiling light water and moderated by
Heavy Water which uses both thorium-uranium 233 & thorium plutonium mixed oxide as fuel.
ii. High Temperature Reactor (HTR) based power packs:
This is a programme to design and develop a high temperature reactor system mainly for
processing heat and non-grid based electricity generation application. U-233 is the fuel, liquid
lead based coolant, carbon based structural components, coated particle type nuclear fuel, high
temperature resistant alloys and control systems which can reliably operate under high
temperature conditions include the above.
iii. Accelerator Driven Systems (ADS):
Accelerator driven sub critical systems are those, in which, the nuclear chain reactor is sustained
with the help of neutrons produced by spallation process, using proton beam. An accelerator can
be used to produce several times more electrical energy than that required to run the accelerator.

Boiling Water Reactors (BWR):

To kick start the nuclear power generated programme, the first two plants were of the boiling
water reactor type & were based on imported technology.
Present status:
India’s Nuclear Power Programme has 21operating reactors including 2 Boiling Water Reactors
(BWR) ,18 Pressurized Heavy Water Reactors (PHWR) and 1 Pressurized Water Reactor (PWR).
Operating Reactors:

No. of Reactors & Installed Reactors Under

Place Type
capacity of each, MWe Construction, MWe
BWR 2 X 160 ---
Tarapur
PHWR 2 X 540 ---
Rajasthan PHWR 1 X 100, 1 X 200, 4 X 220 2 X 700
PHWR 2 x 220 ---
Kalpakkam
PFBR --- 1X 500
29
 Narora PHWR 2 x 220 --
Kakrapar PHWR 2 x 220 2 X 700
Kaiga PHWR 4 x 220 ---
Kudankulam VVER (PWR) 1 X 1000 1X 1000
Total installed capacity 5780 4300

Nuclear Fission:
Sustaining of a chain reaction is determined by the probability that a neutron released in fission
will cause a subsequent fission.
 On an average, if less than one neutron involves in the subsequent fission, the rate of fission
will decrease with time and ultimately drop to zero. This situation is called sub critical.
 On an average, if one neutron from fission involves in the subsequent fission, the fission rate
is steady and the reactor is critical. A critical reactor is what is usually desired.
 When more than one neutron causes a subsequent fission, both fission rate and power
generated increase and the situation is termed as super critical. In order to be able to increase
power, reactors are designed to be slightly super critical when all controls are removed.
Reactivity:
If Reactor is
 Super critical Reactivity is positive
 Critical Reactivity is zero
 Sub critical Reactivity is negative
Reactivity can be controlled by:
 Adding or removing fuel.
 Changing the fraction of neutron that leaks from the system.
 Changing the amount of a neutron absorber that competes with fuel for neutrons.
 Reactor control is facilitated by the presence of delayed neutrons. Although, the fraction of
delayed neutron is small, these are sufficient for the types of changes needed to regulate an
operating reactor.

Nuclear Reactors:
Reactors are classified according to the typical energies of the neutrons that cause fission. As
the neutrons collide with nuclei in a reactor, they lose energy. In a thermal reactor, enough
collisions are permitted to occur so that most of the neutrons reach thermal equilibrium with the
atoms of the reactor, at energies of a few hundredths of an electron volt. Neutrons lose energy most
efficiently by colliding with light atoms (moderator).
30
 One disadvantage of thermal reactor is that at low energies U-235 and Pu-238 are not only be
fissionable by thermal (slow) neutron, but they also capture neutrons and restrict them from
undergoing fission. This destroys fissile atoms without any fission. (When neutrons of higher energy
involve in fission, few of these neutrons will only get captured. To achieve this, a reactor can be built
without a moderator.)
Then depending on how many collisions take place with heavier atoms before fission occurs,
the typical fission causing neutrons can have energies in the large of 0.5 ev to thousands of electron
volts (intermediate reactors) or several hundreds thousand electron volts (fast reactors). Such reactors
require higher concentration of fissile material to reach critically than thermal reactors. But these are
more efficient at converting fertile material to fissile material. Indeed they can be designed to produce
more than one new fissile atom for each fissile atom destroyed. Such reactors are called breeders.
Nuclear Fusion:
The process of combining two light atoms to form a heavier atom with less mass than the two
original atoms is called fusion.

Difference between fissile and fertile material:

The fissile material is the one which undergoes nuclear fission (splitting of atom) upon
bombardment by slow/fast neutrons.
Examples for the fissile materials are Uranium 235, Plutonium 239 & Uranium 233.
Fertile material is the one which by itself is not fissionable but will capture the neutron &
will get converted to a fissile material.
Ex: Uranium 238 convert into PU239, Th 232 convert into U233 etc.

Points to be noted:
a) Heavy water or water cannot be used as coolant instead of sodium in FBR because water or
heavy water rapidly decelerates the fast moving fission neutrons to less than the energy
suitable for breeding. Liquid sodium is used because of its high thermal conductivity.
b) Each 220 Mwe nuclear power plant requires about 250 Te of D2O for initial charging & about
8 Te annually as make up.

Decommissioning of a Nuclear reactor:

At the end of its operating life (about 40-50 years) a nuclear power plant contains some radio
active structures & worn out equipment. However a major portion (over 85%) of the plant never
become radioactive and can be demolished or reused without restriction. In the remaining 15%, after
the removal & shifting of highly radioactive spent fuel (contains 99% of the radioactivity) from the
reactor to offsite for disposal, only the reactor vessel and piping are the main concern, because of
induced radioactivity caused by neutron irradiation of structural metals with their specific half lives
for radioactivity.
The three stages of decommissioning nuclear power plants are as follows:
1. Storage and Surveillance: This involves
a) Removal of all irradiated fuel, fuel coolant and other easily accessible radioactive material
b) Strict surveillance & control of reactor vessel, structures inside the containment.
This activity takes about 2 years.
2. Restricted site release:

31
 The radioactive reactor vessel and component are sealed off for a period of about 30 years for
radioactivity to decay and non-active areas are released for other uses.
3. Unrestricted site release:
Major work of dismantling reactor vessel and piping will be done with specialized remote
handling technique. The debris will be taken away for permanent storage in steel lined shallow
land repositories in location duly approved by the regulatory body. The remaining areas of the
plant will be decontaminated & released for restricted occupancy. This may take about 5 yrs.
How are radioactive isotopes produced?
Radioactive isotopes are produced mostly by exposing stable isotopes to the neutrons in a
nuclear reactor. Isotopes produced in this way are neutron rich. Neutron deficient isotopes are
produced by irradiation with protons in an accelerator (Eg. VECC, Calcutta).
In the fast breeder reactor, currently in use, the fuel produced is Pu-239 & there is a blanket of
U-238 around it. Pu-239 undergoes fission and produces energy. At the same time U-238 around it
gets converted to Pu-239 on irradiation with neutrons.
In the next stage of the nuclear programme, Thorium – 232 will be used as a blanket which
will produce U-233, the fissionable fuel.

Cold Fusion
Fusion is the process in which two light nuclei (eg: Deuterium, tritium) merge into each other
to form large nuclei (in this case, helium). During fusion also, the resulting mass is less than the
combined mass of the nuclei, which fuse. The mass destroyed is converted into energy.
Fusion is the process by which the energy is produced in the stars. It requires very high
temperature. At which, matter is in an ionized state called the plasma. The plasma has to be
contained.
It was one stage believed by the scientists that in an electrolytic cell (essentially like that of a
car battery) with the heavy water as the electrolyte, the fusion takes place because of the tremendous
pressure at which deuterium is released. Since fusion is believed to be taking place at room
temperature, it is referred as cold fusion. Now most scientists discover such a possibility, though there
is a reason to believe that neutrons are produced.
Future challenges and strategy for D2O
Three stage programme has been envisaged as a long term strategy for development of nuclear
power in the country. In the first phase natural uranium is to be used in PHWRs for production of
power. In the second stage the plutonium produced in the first stage is to be used in Fast Breeder
Reactor. While in the third phase U-233 produced in the second stage and thorium whose vast
resources available in the country are to be used for power generation.
At present nuclear power forms only about 2% of the total power generated in the country by
various means. It is envisaged that by the year 2020 the contribution of nuclear power should be at
least 6% of the total power generated in the country. Subsequently, when DAE embarks on phase-3
programme is a full-fledged manner, the growth of nuclear power should be at least at a rate
equivalent to 10% of total power. To be able to form 6% contribution in the total power generation
capacity by the year 2020 the Department should have an installed capacity of 18000 MWe.
From the existing scenario, in the year 2020, the total nuclear power from indigenous reactors
would be around 13200 MWe forming about 4.5% of total power generation. Beyond 2020, power
could be added @ 1000 MWe per year based on the plutonium generated on the operating PHWRs as
well as the plutonium held in stock.
Requirement of Heavy Water:

32
 Cumulative requirement of heavy water for setting up of the nuclear power plants, as
envisaged for 8200 MWe would be about 12000 Te by the year 2020. There will be a short fall in
supply of heavy water by the year 2020.

2. ENERGY CONSERVATION

The role of production section in energy conservation is to put efforts for

a. Reduction of the consumption of steam, electric power, chemicals, man hours, and the
downtime of the plant.
b. Reduction in the loss of D2O, H2S and utilities.
c. Increase in production of steam, purity of inputs and production for each system.
d. Total quality management and good house keeping
e. Avoiding nuisance trips and UORs.
 Exchange Units:
a. Control of gas purity.
b. Optimization of the process parameter to maximize the production. (Point to be noted: Hot
tower temperatures are maintained at a maximum value, such that the supply of the steam is
only through extraction, but not from Pressure Reducing Station (PRS). So that excess energy
loss at PRS shall be avoided.)
c. Measures to decrease the consumption of steam.
d. Measures to decrease the loss of H2S and D2O.
e. Measure to decrease the downtime.
f. Trimming of the impeller for the hot tower transfer pumps and some of the cold tower
recirculation pumps
g. Checking the Oil in seal and lube oil system of gas boosters for Total Acid Number (TAN) &
the moisture content. Maintaining the oil quality, as per required specification, by centrifuging
/replacement the same if required.
h. Replacement of steam tracing with Electrical Heat Tracing (EHT) system in phase-1 saved
about 3.0 MT/hr of main steam, which is equivalent to 7.96 GJ/hr of thermal energy.
 Intermediate Steam Generation unit:
a. Maintaining boiler water chemistry.
33
 b. Superheat temperature of a minimum of 5oC is maintained for the HP & LP steam
at the supply end so as to decrease the condensation in the lines & the
resultant condensate loss through traps.
 Cooling water system:
a. Maintain the availability of Cooling Water pumps and fans.
b. If a fan is isolated, hot water supply to that cell is to be isolated to avoid decrease in the
performance of cooling tower.
c. Avoid leakages of C.W through defective asbestos louvers
d. C.W flow through exchangers is kept with in the design values by maintaining DP across
supply and return headers at the battery limit of the XUs to avoid the problem of flow
indicated vibration.
e. C.W recirculation pumps impellers were trimmed & operation of these helped in decrease of
specific energy by 0.7%.

 Chilled water plant:

a. Various operating parameters are maintained and the ratio of KwHr/TR is monitored.
b. To decrease the Freon loss, yearly SLT is carried out and leaks are attended. Then hold on test
is done to ensure that there is no drop in nitrogen pressure. This is followed by evacuation and
vacuum test at 5 mm Hg and Freon is charged only if the raise in pressure is < 1 millibar/hr

 DM Water Plant:
a. Atmospheric degasification removes free CO2 up to solubility limit only and therefore,
Degasser outlet CO2 remains within the range of 5-6 ppm and will exist in carbonic acid form
due to less pH. WBA does not have capacity to remove weak acids like H2CO3 or H2SiO3
and so, D.W water CO2 was always 5-6 ppm only. This CO2 was required to be vented in
purge tower of XUs and during this purging process; H2S goes out as well along with CO2.
Hence, to minimize H2S loss and for improving gas purity for enhanced production, Strong
Base Anion Exchanger Beds (6 nos) have been installed. SBA removes CO2 and brings down
to less than 0.5 ppm CO2.
b. Provision of VFDs for Deaerator feed pumps resulted into an elect. energy saving of 40 KW.

 H2S Generator and Recovery:

a. NaHS solution is used to the maximum extent possible in place of Na2S due to the benefits of
reduction in the cost of material and in the volume of the effluent generated.
Next preference is given to Na2S solution over Na2S flakes due to the benefit of less cost, less
maintenance and no requirement of dissolution.
b. Selection of Na2S flakes or solution is done carefully to have control on the amount of
impurities like Na2SO4 and NaCl, so as to decrease the presence of SO2 and CO2 in the
generated H2S gas.

 Distillation Unit:
a. Only one vacuum pump for all four columns, 3 nos. of dedicated cooling water pump are run
which resulted in savings of 820 KW.

Improvements done

34
 a. Cascading of distillation columns modification of the cascade has resulted in:
 Recovery of distillation unit has increased from the design value of 67% to 82%.
 Feed rate is reduced from 246 Kg/Hr @ 15% conc. to 184 Kg/Hr @ 16.5%, with a net
reactor grade product of 25.6 Kg/Hr. Reject conc. reduced from 5% to 3%.
 Deuterium inventory of columns decreased from 8000 Kg to 5300 Kg.
b. Inter connection of vacuum pump.
c. Two tanks in feed conditioner section are bypassed for avoiding pumping cost.
d. Usage of waste N2 for drying the product containers
e. Dedicated chiller package unit package unit of 24 TR capacities is provided.

Other measures for energy conservation

1. Operation of only one 3rd stage unit in Exchange Units.
Benefits:
a. Savings of 0.6 MW of power, 10 MT/Hr of HP steam, 200 ltrs. Of turbinol-46, 510 M3/Hr of
cooling water and 163 M3/Hr of chilled water.
b. Reduction of H2S inventory by 10 MT.
c. Reduction of D2O inventory by 4MT (100% basis).
d. Reduction of loss of H2S/ D2O during operation.
e. The third stage of other unit can be used for process feed water for further increasing the
production by 0.9 kg/hr.
2. Guard Pond Recirculation Benefits:
a. Stopping of one raw water intake pump, two dilution pumps, two settled water pumps
resulting in power savings of 690 KW.
b. Reduction in intake water resulted in saving of water less to the tune of Rs 4.4 lakh/year.
c. Implementation of zero discharge scheme & prudent water management saved about 1000
m3/hr of water.
3. Water Management:
a. Implementation of zero discharge scheme & prudent water management saved about 1000
m3/hr of water.
b. Due to prudent usage of water, requirement of water in the plant has come down. To capitalize
this one new intake well pump of 2500 m3/hr capacity & 40 MLC was installed. This brought
electrical energy saving of about 280 KW.
4. Increase in gas purity
a. HP N2 sealant to O/H SDV was replaced with water sealant to avoid N2 ingress into system.
b. Installation of SBA at DM plant for removal of CO2 in process feed water resulted into about
1% increase gas purity, which ultimately increased production rate by 1%.

35
 c. Interconnection of vacuum pumps on the suction head helped in maintaining a better vacuum
in vacuum degasser. These steps significantly contributed to increase of gas purity from 92%
to 99% resulting in increased feed processing and decreased specific energy by 7%.
5. Reduction of H2S loss
a. Generated H2S gas is charged to purge tower.
b. The inert from the chillers of H2S unit were routed to the purge tower.
c. Facility for run down of H2S gas boosters, dump tank, CRT/HRT, and H2S storage bullets was
provided.
d. H2S loss recovery from sour oil resulted in reduction of H2S loss to the tune of 1.5 MT/month
through this route.
6. Decrease in loss of D2O
a. Inter connections of dump tanks of both XUs.
b. Dedicated chiller package unit for DU.
c. Provision of jumper line between cold tower and hot tower outlet headers.

Energy conservation in pumps:

The excess head development by the pumping equipment can be reduced by
 Providing speed control mechanism to the drive.
 Providing fluid coupling.
 Trimming of impeller of centrifugal pump.
 Going for new pumping equipment with proper head and flow valves.
In case of trimming of impeller, though there will be a reduction in the pump efficiency on
account of increased clearances due to trimming, the overall power consumption of the pump will
be reduced. When a certain special coating has applied to the internals of the pump, they can
decrease the unwanted clearance and smoother the fluid flow inside the pump thereby improving
the efficiency.
Identification of pumps developing excess head:
1. Measure the liquid flow (Qm) in m3/Hr, total head developed by the pump (Hp) and the
pressure drop across the control valve (dPcv) in kg/cm2g.
2. Ascertain the static head difference (Hs) in kg/cm2g, if any, between the pump suction and
discharge side.
3. Calculate the frictional pressure drop (dPf) in the system excluding the control valve drop
dPf = Hp - dPcv - Hs
4. Ascertain the required flow (Qr) in m3/hr to be transferred by the pump and if Qr is different
compared to the measured flow (Qm) then correct the functional pressure drop as
dPfc = dPf * (Qr/Qm) kg/cm2
5. If the system is prone to fouling in course of time further allowance of 25% of frictional
pressure drop may be given as
dPfc = dPf * (Qr/Qm) * 1.25 kg/cm2
6. The system pressure drop requirement excluding control valve
dPs = dPfc + Hs
36
 7. Considering the desirable pressure drop across the control valve is 25% of total frictional drop
[dPfc + dPcv(desirable)]
dPcv (desirable) = d Pfc * (0.25/0.75)
8. The system head requirement
dPsr = dPfc + dPcv (desirable) + Hs = (1.333 dPfc + Hs) kg/cm2
9. Excess head available in pump = (Hp – 1.333 dPfc - Hs)
10. Excess fluid power being wasted = [(Hp – 1.333 dPfc - Hs) Qm] * [0.02722] kw
Determination of trimming of Impeller of centrifugal pump:
The extent of trimming required is to be carefully determined by trial and error through
affinity laws and also using H Vs Q characteristics of the pump.

1. Ascertain the required flow (Qr) and head (Hr).

2. Assume a reduced diameter (D2) of the impeller and calculate
Q = Qr (D1/D2)
Where D1 is the original diameter of the impeller and read the value of head (H) for the
above flow from H Vs Q curve of the pump.
3. Calculate H2 = H (D1/D2)2
Check whether H2 is same as Hr. Repeat the procedure with different values of reduced
diameter D2 till H2 = Hr.
4. Check from the pump data sheet the suitability of the diameter D2 of the trimmed impeller
into the pump casing. If the reduced diameter of the impeller is within the suitable range of
impeller diameter for casing then impeller may be trimmed.
5. If it is prudent to reduce the impeller diameter in two or more steps, checking the Head at
each diameter in order to arrive at the proper diameter.

Details of trimming of CW recirculation pumps

S. Pump Original Estimated Achieved

No No Impeller Efficiency Impeller Power Impeller Power
dia, mm % dia, mm saving, kw dia mm saving, kw
1 43-P-301A 776 90.8 707 220 707 160
2 43-P-301B 776 90.8 707 220 707 160
3 43-P-301C 776 90.8 707 220 707 160
4 43-P-301D 776 90.8 707 220 707 160
5 43-P-301E 776 90.8 707 220 707 160
6 43-P-301F 776 90.8 707 220 707 190
7 43-P-301G 776 90.8 707 220 707 160
8 43-P-301H 776 90.8 707 220 707 160

 For 43-P-301F corro-coat treatment is done. Due to this, efficiency is improved to 91.2% as
against 78% before corro-coat treatment.
 Trimming of CW pump impellers saved electrical energy of about 690 KW.

Flow Vs Efficiency curve for 43-P-301F

37
Flow Vs Head characteristic curve for 43-P-301F

 CW pump head before trimming was 7 kg/cm2g and after trimming, it was reduced to 5
kg/cm2g
 HT1, HT2 & HT3 transfer pumps trimming was done. Impeller diameter was reduced from
429mm to 385mm. Power consumption reduced from 220KW to 165KW.
 CT1(R), CT2 (R) and 2CTR pumps trimming was done. CT3(R) pump was not trimmed, as
trimmed pumps were unable to give required flow rate with FCV fully open, due to coolers
tube side choking with sulphur.
 Trimming of impellers of these pumps cumulatively resulted into power saving of 390 KW.
 Provision of VFDs for process pumps [HT1(R)/HT2(R)/HT3(R)/HT1(T)/HT2(T)/HT3(T)/
CT1(R)/CT2(R)/2HT(T)/2CT(R)] of both XUs resulted into a saving of 1800 KW of
electrical energy.

38
Optimization of operating parameters in HWP (KOTA):

Before optimization After optimization

H.T temp 1300C 1200C
Recovery 16.8% 15.3%
Steam consumption 135 MT/Hr 110 MT/Hr
Feed rate 415 MT/Hr 415 MT/Hr

As the cooling loads come down due to reduced hot tower temp & also as the CW temp could
be brought down below the design CW temp of 300C, a modification was incorporated to supply
cooling water in chilled water circuit and stop all the operating chillers. This is also helped indirectly
in stopping of one CW pump required for condensation in chiller unit.
Due to low temperature operation, the total power consumption could be brought down to
13.2 MWh from 17.0 MWh. Thus, the revised specific steam & power consumption worked out to be
11.96 MT/kg and 1.66 MT/kg respectively from 12.92 MT/kg & 1.68 MT/kg as achieved before
optimization.
Optimization of system parameters at main plant, HWP (M):

1. Specially designed cross flow sieve tray of exchange columns are designed to process 453
MT/Hr of feed water in each stream at 20kg/cm2g pressure for a rated production of 185
Mt/year based on 7200 on-stream hours. All the associated equipments of Exchange Units
were designed with margin for 10% additional flow over rated capacity.
After a thorough review, gas circulating rate could be increased by 7.5% over the rated value
without causing entrainment which can affect the tray efficiency. Further, refinement of the
process parameters could improve the liquid to gas molar flow rate by 2.5%, resulting in
overall gain in feed rate and production by 10% above the rated value. As the system pressure
is reduced the tray performance was checked and found to be unaffected while handling gas
flow of 107.5% of design.
Thus, the system pressure was reduced to 18.0 kg/cm2g as against the design value of 20
kg/cm2g which has resulted in direct saving in power by 1.36 MWe. This has avoided
throttling requirement of suction side control valves.
Lower system pressure resulted in increased enthalpy requirement in hot towers. Hot tower
temperatures were reduced to 1300C, so that the heat requirements are within the capacity of
the existing heat transfer equipment and also to keep the gas volumetric flow within the
acceptable range to avoid excessive entrainment.
Low pressure operation has facilitated lowering of cold tower temperatures to 320C against the
design value of 330C which partially compensated the loss of recovery due to lower hot tower
temperature.

Heat Recovery:
2. 40 nos. of heat exchangers with heat transfer area of 8469.6 M2 are available for a heat
recovery of 370 GJ/Hr. By proper maintenance of heat exchangers, thermal energy saving of
about 5% over the design intent.
3. Waste heat exchangers (36 nos.) with heat transfer area of 10488 M2 are available with intent
of heat recovery of 570 GJ/Hr. With the proper maintenance of heat exchangers, thermal
energy saving of about 8-9%.

39
4. With the optimized process condition and maintenance of heat exchangers, CW recirculation
could also be reduced from 24000 MT/Hr to about 13200 MT/Hr. This has resulted in a
reduction of electrical energy of about 3 MW.
5. Waste heat recovery is resulted into a saving of 22 GJ/Hr. (Pl Note: This is not GJ/Kg)
6. Reduction of W.S. steam flow from 64 MT/Hr (for each stream of XU) of design value to 38
MT/Hr (for one WS) yields a reduction in total thermal energy requirement for both waste
strippers of about 150 GJ/Hr and also reduced the make up water requirement to the boiler at
CPP by 52 MT/Hr.

40
Waste Heat Recovery

150 m3/hr
67 0C XU-1
CPP 720C 730C 750C

XU-2

320 m3/hr ETP

BF water 56.4 0C
30 0C 44.2 0C

Buffer
vessel 43.2 0C

LP Return condensate
VAR
LP Steam

Estimation of Waste Heat Recovery:

01. Boiler Feed (BF) Make up water : 150 M3/Hr.

02. BF make up water inlet temp : 300C
03. BF make up water outlet temp : 670C
04. Effluent flow rate : 320 M3/hr
05. Effluent temp. inlet : 750C
06. Effluent temp. outlet : 57.20C
07. Total heat recovery : 150 x 103 x 1.0 x (67-30) : 5.55 x 106 Kcal/hr
08. Equivalent LP steam : (5.55 x 106) / (697.7 – 160) : 10.32 Te/Hr
09. Equivalent HP steam : (5.55 x 106) / (794 – 160) : 8.75 Te/Hr.

41
Effect of heat recovery on CPP steam cycle based on efficiency of 0.964

Case I: Initial Operating

Main steam 191.6 T/hr
191.6 T/hr
HP Steam 115 T/hr
LP Steam 29.04 T/hr
21.5 Flow through condenser 47.55 T/hr
MW Power generation 21.5 MW

115
29.04 47.55

Case II: After heat recovery is employed

188.86 T/hr
Main steam 188.86 T/hr
HP Steam 115 T/hr
21.5 LP Steam 24.36 T/hr
MW Flow through condenser 49.5 T/hr
Power generation 21.5 MW
115
24.36
49.5
Actual savings in Main Steam : (191.6 – 188.86) x 2 = 5.48 Te/Hr
Actual savings in LP Steam : (29.04 – 24.36) x 2 = 9.36 Te/Hr

Waste Heat Recovery using Vapor Absorption Refrigeration System:

Subsequent to realization of savings in LP steam consumption through implementation of Waste Heat
Recovery Scheme and through replacing steam tracing with electrical heat tracing of process piping
and impulse lines in Exchange Units, the LP steam is put to use for producing cold energy through
LiBr-H2O based vapour absorption refrigeration cycle of appropriated capacity of 4500 TR to meet
plant chilled water requirement. This had resulted in stoppage of two nos. of Vapour compression
refrigeration machines driven by electrical motors of 2.2 MW each, utilizing Freon-12 as refrigerant,
a ozone depleting substance.

In HWP(M), double effect vapour absorption refrigeration system has been adopted. The system
utilized low pressure saturated steam at 5.0 Kg/cm2g and the LP condensate coming out from the
system is pumped back to CPP.

Benefits:

• Net reduction in power consumption by 3.0 MWe. i.e. equivalent to 12 MT/H of Main steam
• Improvisation in operation stability having minimum running machinery along with drastically
reduced sound levels.

42
Effect of VAR on CPP steam cycle based on efficiency conversion factors of 1.12

1. Total refrigeration possible based on 10.32 Te/Hr of LP Steam = 2415 TR

187.34 T/hr
Main steam 187.34 T/hr
HP Steam 115 T/hr
20.42
LP Steam 29.04 T/hr
MW
Flow through condenser 43.3 T/hr
Power generation 20.42 MW
115 29.04
43.3

2. Additional main steam saving compare to waste heat recovery = (188.86 – 187.34) x 2 = 3.04 T/Hr
Total main steam saving = (191.6 – 187.34) x 2 = 8.52 Te/Hr.

Effect of enhanced VAR on CPP cycle

1. Total refrigeration to be generated= 2800 TR

187.0 T/hr
Main steam 187.0 T/hr
20.42 HP Steam 115 T/hr
MW LP Steam 29.9 T/hr
Flow through condenser 42.13 T/hr
Power generation 20.42 MW
115
29.9
42.13
2. Additional main steam saving compare to waste heat recovery = (188.86 – 187) x 2 = 3.72 Te/Hr
Total main steam saving = (191.6 – 187) x 2 = 9.2 Te/Hr.

Energy aspects in CPP

1. Capacity of boiler 265 TPH of steam generation at 106 kg/cm2 & 4850C
2. TG is single cylinder, double extraction condensing type turbo generation each of rating 30 MWe
3. The TG sets operating conditions were fixed as 101 ata pressure at inlet, 33.5 ata and 8.5 ata at HP
and LP extraction points.
Due to various measures taken, the present operating load is as follows:
Design load Present
HP steam to MP, MT/Hr 375 250
LP steam to MP, MT/Hr 40 20
Power consumption at MP, MW 60 32-33
In House power consumption at CPP, MW 21 9

43
System Modification at CPP:
 Due to the revised lower energy requirement of the plant, total steam requirement of the plant
could be met by TG extraction only, when power generation from TG is 12 MWe above the plant
power requirement.
In the absence of external demand for the additional power generated at CPP, power generation
from TG sets was to be limited to 42 MWe.
With this constant steam from TG extraction was short of plant requirements and the same is
needed to be made up by Pressure Reducing and De-superheating Station (PRDS) where the
steam from SG at 106 ata. is throttled and de-superheated to 32 ata and 8 ata.
This will lead to reduction in TG cycle efficiency. The deficiencies could be corrected by
revising the HP extraction pressure to a lower value of 28 Kg/cm2g as against the design value of
32.5 kg/cm2g and by effecting suitable adjustment in the governing system of TG sets.
 Revision of CMD at CPP: A contract was established with APSEB and maximum demand (CMD)
of 15000 KVA was brought down to less than 10000 KVA. With this the payment on monthly
demand changes and minimum energy charges could be brought down by Rs.10.7 lakhs. Net
energy is being exported to APSEB grid in sufficient quantity such that payments towards CMD
and energy charges to APSEB are made NIL.
 Auxiliary Steam Turbine Generator (TG-4) for generation of 3 MW electricity from available
steam has been installed in CPP to recover the throttling losses in HP steam path to ISG. Savings :
Generation of ~3.4 MW of power and lead to saving of ~10 MT/Hr main steam resulting in
specific energy reduction to the tune of 0.8 GJ/Kg.

44
Energy Conservation Figures

01-02 03-04 04-05 05-06 06-07 07-08 08-09 09-10 10-11 11-12 12-13 13-14
Plant specific energy consumption GJ/Kg 37.6 35.8 32.0 32.6 33.3 32.1 30.9 31.4 31.4 31.1 29.3 29.2
Plant specific power consumption KwHr/Kg 1551 --- --- --- --- --- --- --- --- --- 1146 1143
Specific energy consumption of MP GJ/kg 34 --- --- --- --- --- --- --- --- --- 27.8 27.5
Sp. power consumption of MP KwHr/Kg 1157 --- --- --- --- --- --- --- --- --- 854 854
Specific steam consumption of MP MT/Kg 7.63 --- --- --- --- --- --- --- --- --- 8.86 8.58
Feed process rate Te/Hr 945.4 973.9 973.2 967.3 962.7 965.5 981.6 974.2 946 959.7 980.3 980.1
Stream factor, % 80.3 86.7 95.4 88.1 89.9 94.5 98.1 86.4 96.8 83.5 97.5 88.2
Average Recovery, % 17.67 --- --- --- --- --- --- --- --- --- 18.36 18.67
Avg. system pressure Kg/cm2g 19.2 18.6 19.0 18.8 18.7 19.0 19.1 19.1 19.1 19.1 19.2 19.3
Avg. H2S purity % 97.8 98.0 98.4 98.3 98.3 99.1 99.2 98.8 99.0 99.0 99.3 99.5
HP steam consumption Te/Hr 252.7 243.5 245.3 245.0 248.3 241.3 237.1 248.7 233 244.4 241.1 236.8
LP steam consumption Te/Hr 19.9 19.3 21.3 27.6 26.4 26.0 29.4 29.7 22.1 27.8 29.0 27.4
Thermal energy at MP GJ/Kg 21.4 20.8 19.7 21.0 21.9 21.3 20.0 20.4 19.9 20.6 20.1 19.5
Elec. Energy at MP GJ/Kg 12.6 11.2 9.5 9.1 9.6 9.3 8.7 8.7 9.0 8.7 7.7 8.0
H2S loss, MT/month 10.36 12.25 11.69 9.43 8.9 7.01 9.4 9.8 7.45 7.29 7.7 7.47

45
 ENCON SCHEMES IMPLEMENTED

S.No Scheme Implemented Savings

670 KW & 2500
1 Guard pond Recirculation Oct’98
m3/hr water
2 TG governing system adjustment Oct-99 20 TPH steam
3 Trimming of impellers of C.W pumps Aug-99 690 KW
4 Trimming of impellers of process pumps Jun-02 390 KW
5 Separate drinking water system Apr-00 3.5 TPH steam
6 Reclaimed oil storage facility May-01 1.73 KL oil
7 Capacity utilization of equipment to max. production Nov-00 7.8 TPH steam
8 Waste heat recovery May-02 5.3 TPH steam
9 Zero discharge scheme & water management May-02 1000 m3/hr of water
10 Vapor Absorption Refrigeration system Aug-04 12 MT/H steam
Surge tanks bypassing & common headering of aux.
11 Sep-04 140 KW
CW pumps
12 Replacement of steam tracing with EHT (phase-1) Nov-04 3 MT/H steam
13 additional fire water jockey pumps Mar-05 140 KW
14 Waste heat recovery thru TG condensate heating Mar-05 2.2 MT LP steam
15 One stage blinding of Boiler Feed Pumps Jul-05 280 KW
Installation of new intake well pump of 1800 m3/hr
16 Feb-06 280 KW
& 40 m head
17 Operation of SG with one ID & one FD fan Mar-06 400 KW
1% increase in
18 SBA for removal of CO2 in feed water Jun-06 Production due to 1%
increase in gas purity
19 Small capacity ash slurry pump Jun-06 100 KW
20 H2S loss recovery from sour oil Sep-06 1.5 MT of H2S/month
21 Improvement in system hydraulics of MP Ch.W loop Oct-06 250 KW
22 Bifurcation of Cooling water circuit Oct-06 330 KW
Tapping for De-superheating spray water from 4th
23 Mar-07 60 KW
stage of Boiler Feed Pumps
24 Installation of VFDs for FD fan of SG-2 & SG-3 Mar-07 250 KW/SG
25 Installation of VFDs in CEP of Unit-II at CPP Jul-09 34 KW
26 Aux. steam turbine Mar-11 2500 KW
27 Stoppage of condensate pumps of RXs in XUs Jul-11 60 KW
28 VFDs for SG-1 fans Oct-11 900 KW
29 VFDs for identified process pumps in XUs Jan-12 1800 KW
30 Stopping of service water pumps Oct-12 20 KW
31 VFDs for DM water transfer pumps at CPP Oct-12 20 KW
32 VFDs for Deaerator feed pumps at DMP (MP) Apr-13 40 KW
Replacement of solid aluminum blades in CPP CT
33 Apr-13 70 KW
ID fans with hollow FRP blades
34 VFDs for ID & PA fans of SG-2 & SG-3 Jan-14 550 KW/SG
35 MCS at ETP Mar-14 200 KW

46
Performance of Heavy Water Plants with regard to Energy Conservation:

Year Energy consumption in Gj/kg

Manuguru Kota Hazira Thal Tuticorin
1994-95 57.04 53.3 35.73 41.42 32.55
1995-96 48.79 56.16 34.01 45.85 33.97
1996-97 52.06 60.32 32.09 42.17 35.91
1997-98 51.71 61.10 38.85 42.68 32.65
1998-99 45.61 54.54 31.07 53.05 36.74
1999-2000 40.13 47.95 30.25 39.68 28.68
2000-01 39.5 --- --- --- ---

Specific energy calculation:

I. Total main steam generated=A (MTe)
II. Net energy export=(Export - Import + Colony load)= B(MU)= B×103MWHr
III. Main steam equivalent for 1MWHr of energy = C(MT/MW Hr)
(Presently, 3.9289 MT of steam = 1MWhr)
IV. Main steam equivalent for net energy export = B×103×C = D (MTe)
V. Total main steam consumption in the plant = (Total main steam generated – main steam
equivalent for net energy export) = (A-D) MTe
VI. Production during the period = P kg
VII. Specific main steam consumption = Total main steam consumption in the plant/
production during the period = (A-D)/P MTe/kg = E (MTe/kg)
VIII. Net enthalpy of main steam = (Enthalpy of main steam – Enthalpy of boiler feed water) =
(F-G) = H kcal/kg
IX. Mechanical equivalent of heat,
Joules/sec= watt {1cal=4.184 joules} {1 kcal= 40184 k joules}
X. Specific energy consumption = (specific main stream consumption) × (103) × (net
enthalpy) × (Mech equivalent of heat) = E×103×H×4.184 = (Q)KJ/kg = (Q)(1/106)GJ/kg

Heat rate calculation of boiler

S. Item Quantity Specific enthalpy Total energy
No kcal/kg kcal/hr
1 Main steam generated 206.369 MT/Hr 794.0 163856986
2 HP steam supply to main plant 111.8 MT/Hr 742.0 82955600
3 LP steam supply to main plant 14.0 MT/Hr 697.2 976080
4 Electrical energy generated, MWH 27000 - -
5 HP return condensate from MP to CPP 75 MT/Hr 235.3 17647500
6 LP return condensate from MP to CPP 6 MT/Hr 100.0 600000
7 Make up water to CPP 66.35 MT/Hr 33.0 2189550
8 BFW to boiler 206.369 MT/Hr 159.4 32895218.6

47
Heat rate = [Enthalpy of (Main steam + HPRC + LPRC + Make up water) –
Enthalpy of (BFW to SG+ HP & LP steam to MP) kcal]
Electrical energy generated, KWhr
= [163856986+17647500+600000+2189550] - [32895218.6+82955600+976080]
27000
=2498.8 Kcal/ kwHr
Main steam equivalent to MWhr of energy = Heat rate/ [Enthalpy of main steam- Enthalpy of BFW]
= 2498.8 / (794-158) = 3.9289 MT/MWH

Procedure for Evaluation of heat exchanger performance:

PARAMETER TUBE SIDE SHELL SIDE

Fluid
Flow rate, MT/Hr
Inlet temp/Outlet temp
Average temp, 0C
Density, ρ, kg/m3
Viscosity, μ, kg m/sec
Thermal conductivity, kw/m0C
Specific heat, cp, J/kg0C
Flow area
Equivalent dia, dc
Velocity, V , m/s
Reynolds number Re
Parallel number, (Pr)
JH Factor
Nunelth number NNu
Heat transfer coefficient(h),
w/m2 0C
Film resistance, m2 0c/w
DT1, DT2 0C
Heat transfer, kw
Mismatch in shell side & tube
side heat transfer, %
20
Tube wall resistance, m C/w d0 ln(d0/di)/(2 X kw), kw: thermal conductivity of wall
Total resistance without TS film resistance + SS film resistance + Tube wall resistance
fouling, m2 0C/w
Input parameter Input parameter
Input parameter Input parameter
Input parameter Input parameter
(Inlet temp + Outlet temp)/2 (Inlet temp + Outlet temp)/2
Curve fitted equation Curve fitted equation
Curve fitted equation Curve fitted equation
Curve fitted equation Curve fitted equation
Curve fitted equation Curve fitted equation
n× π× di2/4 (Pt-do)Ds LB/Pt
Pt =Pitch, d0=Tube outside
LB=Tube bundle length
Ds=Shell side dia
di 1) For triangle pitch
De=1.1(Pt2 - 0.917 d02)/d0
2) For square pitch
De=1.27(Pt2 - 0.785 d02)/d0
Main flow / (ρ × flow area) Main flow / (ρ × flow area)
ρdiv/μ ρDev/μ
Cpμ/k Cpμ/k
Curve fitted Curve fitted
0.023(Re)0.8 (Pr)0.33 JH × Re ×(Pr)0.333
NNu ×k/di NNu ×k/De
d0 / (hi × di) 1/h0
Terminal temp difference Terminal temp difference
M × Cp (Tin – Tout) M × Cp (Tin – Tout)
{(TS heat transfer – SS heat transfer)/{(TS heat transfer – SS heat
TS heat transfer} × 100 transfer)/ TS heat transfer} ×
100

48
U calculated without fouling
w/m2 0C
LMTD correction factor
Corrected LMTD, 0C
Heat transfer area, m2
U experimental w/m2 0C
Total resistance measured, m2
0
C/w
Overall dirt factor measured,
m2 0C/w
% difference in overall dirt
factor
1/Total resistance
From graph
Correction factor × (DT1 – DT2) / ln (DT1 - DT2)
No. of shells × π× d0 × L × no. of tubes per shell
(SS heat transfer+ TS heat transfer)/ (2 × LMTD × Area)
1/Uexp
(Total resistance measured) – (Total resistance without fouling)
{[(Dirt factor design)-(Dirt factor measured)]/dirt factor design} ×100

Hagen- Paiseuille equation

▲Ps = 32 ▲L V μ/ gC D2
Its use is in the experimental measurement of viscosity by measuring the pressure drop &
volumetric flow rate through a tube of known length & diameter. From the flow rate, V is calculated
for laminar flow, f = 16/NRe

Heat transfer by forced convection in turbulent flow:

hiD/K = 0.023 ( ρDV/ μ)0.8 (Cpμ/K)1/3 (μ/μw)0.14
In laminar flow heat transfer occurred only by conduction, as there no eddies to carry heat by
convection across isothermal surface.

Heat Transfer by Conduction

Fourier’s law: dq / dA= - K (dT / dx)
A = area of isothermal surface x = distance measured to surface
q = rate of heat flow across surface in the direction normal to surface T= temperature
K = proportionality constant

Overall heat transfer coefficient

dq / dA = U ▲T, U= overall heat transfer coefficient.
If A is taken as outside tube area Ao then U becomes Uo.
Uo/Ui = dAi/dAf = Di/Do

Heat transfer by convection:

hiD/K = 0.023 (ρDV/ μ)0.8 (Cpμ/K)1/3 (μ/μw )0.14

Heat transfer by Radiation:

The fraction of the radiation falling on a body that is reflected is called the reflectivity ρ.
The fraction that is absorbed is called the absorpitivity α.
The fraction that is transmitted is called the transitivity Υ.
The sum of these fraction must be unity or α+ ρ+ Υ= 1.

49
 The max possible absorpitivity is unity attained only if the body absorbs all radiation incident
upon it & reflects or transmits none. A body meeting this requirement is called a blackbody.

Emissivity: A black body has the max attainable emissive power at any given temp and is the
standard to which all other radiators are referred. The ratio of the total emissive power W of a body to
that of a blackbody Wb is the Emissivity, ε, of a body ∈ = W/Wb

Law of black body radiation: The basic relationship for blackbody radiation is the Stefan-boltzman
law which states that the total emissive power of a blackbody is proportional to the fourth power of
the absorbed temp.
Wb = σT4 σ= universal constant.

Kirchhoffs law: At temp equilibrium, the ratio of the total radiating power of any body to the
absorpitivity of that body depends only upon the temp of the body. Then, consider any two bodies in
temp equilibrium with common surrounding.
W1/α1 = W2/α2
W1, W2 = total radiating power of two bodies
α1, α2 = the absorptivities of two bodies

Radiation between surfaces: The total radiation from a unit area of an opaque body of area A1,
Emissivity ∈, and absolute temperature T1 is q/A1 = σ∈ T14

50
 3. WATER MANAGEMENT & ZERO DISCHARGE

Guard Pond Recirculation scheme:

From intake well pump
house at Godavari River

Sump
From dilution
pumps, NaOH
2500 m3/hr Main CT
blow down dosing
Chlorine
CT
To CPP Sump Drop Chlorination
for ash Flash
chamber channel
disposal Process drain mixer
disposal
Effluent
from XU

Sump Surface
aerators
Recirculation
2800 m3/hr
Guard pond
capacity: 16000 m3

Modifications carried out

Treated effluent
to Nullah

This modification was carried out at a total cost of Rs.65 lakhs resulting the following benefits:
1. The rate of drawal of water from Godavari River is reduced by about 2900 M3/hr.
2. By avoiding multiple pumping of water, the energy saving due to the above works out to be
about 16,500 units every day which is equivalent to a cost saving of Rs.67.5 lakhs every year.
3. The outflow of the treated effluent from ETP reduced from 3500 M3/Hr to 600 M3/Hr.
4. There is a reduction in Cl2 consumption at ETP due to recirculation of the effluent water.
5. A good reduction of about Rs.3 lakhs was achieved in the annual water cess and royalty bills
by virtue of decreased drawal of water from river.
Zero discharge scheme: (Figure)
1. By implementation of Guard Pond Recirculation Scheme, Raw Water Intake has been reduced
from 5600 M3/hr to 3000 M3/hr.
2. Present raw water intake is about 2800 - 3000 M3/hr and the final guard pond and outlet water
is presently in the order of 600 M3/hr.
3. In the initial stage, it was proposed to use about 700 M3/hr of water for ash disposal purpose
and about 100 M3/hr on CPP cooling water make up and about 175 M 3/hr for main plant
cooling water make up.
However, based on problem faced in maintaining calcium hardness in cooling water
recirculation and presence of traces of oil in GP water review of the system was done.
4. New scheme: An amount of 970 M3/hr from guard pond was proposed to be recycled and 55
M3/hr of overflow from guard pond will be carried out.
5. This 970 M3/hr will be routed through settled water pumps.
51
6. 200 M3/hr will be used for CPP cooling water tower out of which 40 M3/hr blow down is to be
recycled for ash disposal system. 160M3/hr will be used as feed water to CPP DM Plant. Rest
of water will be used as service water and for ash disposal. Out of total 140M3/hr of the
service water used, 85 M3/hr will be deviated to ash disposal.
7. After incorporation of the above, the raw water consumption comes down to 1800 M3/Hr.

55

970

595
470

52
Pre-requisites for this scheme:
1. Waste heat recovery scheme shall be commissioned so that two GPR pumps can cater to the
requirement of recirculation of 1600 M3/hr and diversion of 970 M3/hr for use at CPP.
2. The existing impeller of the settled water pump can give a flow of about 500 M3/hr with
around 2MLC head loss of from the operating value of 30 MLC system. However, the existing
motor for these pumps are of 45 KW rating and need replacement with motor of 65 KW.
Then it was proposed to use two settled water pumps for transfer of 970 M3/Hr flow to CPP
with higher KW motors.
To facilitate the above transfer of liquid a 14” jumper connection is proposed from the effluent
dilution pumps discharge line going to ETP and the settled water pumps suction.

Use of GP water for CW system at CPP and as feed water to CPP DM Plant:
01. For use of GP water for cooling water system at CPP, it is essential to ensure that H 2S and oil
traces are totally removed. On line H2S analysis of low range of APPLICON is being installed on
guard pond inlet line. Further, to take care of oil traces, GP water is proposed to be passed through
charcoal beds available at CPP DM plant along with DM plant feed.
It is seen that with one ppm of oil at continuous basis, the charcoal bed need total replacement
after a period of 4½ months. Certain piping modifications are also proposed to facilitate transfer
of GP water to cooling water make up at CPP after passing through charcoal beds.
02. In order to use the GP water as feed water to CPP DM Plant, laboratory studies were carried out
to check the effectiveness of the ion exchange beds available at CPP and the cost benefit by
implementation of the scheme. The filtered water storage tanks at CPP are proposed to be epoxy
painted internally as to take care of the corrosive nature of the GP water.

Points to be noted:
01. Another modification is done for separate treatment of process drain tanks content.
02. Corrosion coupon studies for GP water transfer line.
The initial coupon has shown 25MPY which is on the higher side. However, it is seen that the GP
recirculation Line at ETP is in service for more than 3 years and the recent thickness measurement
taken indicated no thickness reduction. It is felt that due to initial general corrosion, subsequent
corrosion rate is getting reduced. Further the GP hold up pH is being controlled on alkaline range.
Corrosion coupons are kept in GP water circulation line and the corrosion rate will be reassessed
over a longer period of time to arrive at thickness reduction.
03. Presently potable and service water are interchangeably used at CPP as both supplies are from
filtered water system of Main Plant. Common overhead tank with internal partition is provided for
the storage of service water and drinking water.
Hence, GP water and drinking water segregation is done and CPP will be getting drinking water
from MP drinking water overhead tank.

53
 4. PERFORMANCE / LOSS INDICATORS

1 Cost of steam loss through a 7 kg/cm2g : Rs 305/day

defective steam trap at line pressure of 15 kg/cm2g : Rs 600/day
30 kg/cm2g : Rs 1040/day
100 kg/cm2g : Rs 2720/day
2 Cost of leakage of intake air Rs 0.65/Nm3
3 Cost of N2 Rs 2.86/Nm3
4 Cost of leakage of filtered water Rs 0.90/m3
5 Cost of DM water at MP Rs 7.50/m3
6 Cost of DM water at CPP Rs 12.75/m3
7 Cost of oil spillage @ one drop/sec Rs 2.0 lakhs/year

Emissions of gaseous parameters/day through CPP stock

a) CO2 2533 MT/day

b) SO2 4.8 MT/day
c) NOx 8.3 Kg/day
d) SPM 840 Kg/day

One unit of electricity (KWHr) consumed at HWPM results in

a) Burning of coal 0.72 Kg

b) Release of Pollution 1.08 Kg
c) Release of ash 0.29 Kg
d) Release of heat 2500 Kcal

About 400 MT of ash is generated every day which is disposed into ash pond. A small quantity is
used for manufacturing bricks.

H2S Losses

The possible reasons for H2S loss:

a. System pressure is being maintained at 19.0 - 19.5 Kg/cm2g, the H2S loss is expected to be on
higher side in comparison where system pressure was 18.0 - 18.5 Kg/cm2g.
b. On account of higher purity, the loss rate is also on increase through normal drain & vent
routes. Nowadays, the purity is maintained around >99% wt/wt by high purge rate.
c. De-choking of CW & Ch.W exchangers, decontamination of pumps for maintenance & very
minor leakages from various valves, flanges etc.

54
The following routes were identified for H2S loss during 2000-2001:
a. Loss through waste stripper effluents 0.2 Kg/hr based on 200 ppb of H2S conc. in effluent.
b. Around 1 Kg/hr of H2S through Purge Tower to maintain system purity.
c. 0.05 gm/hr of H2S through prod. Stripper along with product based on 200 ppb of H2s conc.
d. 2.5 Kg/hr of H2S loss through sour oil generation from gas booster.
e. 0.545 Kg/hr is consumed by the input O2 through process feed water (average 0.27 ppm
during 2000-2001)
f. Apart from the above H2S is also lost from:
- Tower draining.
- Gas booster draining
- Permissible joints leakage.
- Loss of H2S from the process liquid while releasing the equipment for maintenance.

55
 5. HEAVY WATER ENRICHMENT PROCESSES

Selecting Heavy Water Processes:

1 Distillation Size excessive except H2

2 Chemical Exchange Most promising
3 Diffusion Barrier or Membranes costs excessive; high energy
4 Electrolysis Excessive energy
5 Gravitational Excessive energy
6 Absorption High absorbent volume
7 Biological Excessive volume
8 Crystallization Impractical on large scale
9 Selective photochemical Promising if selectivity operation 104

Separation factor

α = (D/H)A / (D/H)B
Where A and B are either enriched and depleted streams from a separating device or two
phases in physical equilibrium or two compounds in chemical equilibrium. Separation factor varies
from Unity (no separation) to about 30 (low temp. electrolysis of Ammonia).
The relative tower volume is proportional to, V α T/[P (α – 1)2 m]
T = abs. temp, P = Pr, α = separation factor; m = no. of Hydrogen atoms per molecule,
(α- 1)2 dominate the above expression

Chemical Exchange Processes:

GS Amine NH3/H2 H2O/H2
Pressure MPa 2 7 7 10
Temp. K 303 / 400 220 / 315 230 / 330 300 / 440
Catalyst --- CH3NHK NH2K Pt/C
*Rate Const. S-1 5000 130 15 1
*Gas solubility (mol/m3.MPa) 830 24 10 8

At cold tower temperature, because of the low solubility of H2, the hydrogen based processes operate
at high pressure.
In simple terms the tower volume is given by, Volume = GRTN/PKG a
G = gas flow mol/sec
R = gas low const. (MPa m3/ mol. K)
T = Temp. in K
N= no. of theoretical transfer
P = Pressure in MPa
KG= Over all mass transfer coefficient m/s
a = Interfacial area per unit volume (m2/m3)
56
 The overall mass transfer coefficient can be related to gas phase mass through coefficient Kg
and the liquid phase mass transfer coefficient Kl by
(1/KG) = (1/ Kg) + (H/ KlRT)
Where H is Henry’s low const. (MPa.m3/mol)
For a soluble gas like H2S, the value of H is small and the gas phase resistance is important and
possibly controlling.
For hydrogen, H is larger and Kg also increases then only liquid phase resistance need to be
considered.
11
Monothermal
NH3/H2 Electrolysis
Bithermal
NH3/H2
H2 distillation CECE
Separation factor

H2O-H2 GS
H2 diffusion

H2O distillation

H2O crystallization

1 Equivalent of thermal energy, Gj/kg 1000

Synthesis Gas for Monothermal H2/NH3 Exchange Process:

The feed of ‘D’ is H2 & N2 mixture of Ammonia synthesis gas. This feed gas is drawn from
the adjacent fertilizer plants and after recovery of the ‘D’ content the gas is returned back to fertilizer
plants. In the fertilizer plants, the ammonia synthesis gas is made by “Steam reforming Process of
Naphtha/Natural gas”.
Steam reforming process of Naptha/Natural gas:
Primary Reformer Naptha & 750 0C
Natural gas + Steam H2 + CO
Ni Catalyst

Naptha &
Secondary Reformer Natural gas + H2O + O2 H2 + CO + CO2
(air)
450 0C
HT shift conversion CO + H2O H2 + CO2
Fe Catalyst
250 0C
LT shift conversion CO + H2O H2 + CO2
Cu+ Zn
Catalyst
Ni Catalyst CH4 + H2O
CO + H2
CO2 absorption Methanation CO2 + H2 CH4 + H2O
250 – 350 0C
Synthesis

57
 Except the primary reformer reaction, all other reactions are exothermic. In the primary
reformer, heat is externally supplied. The requisite quantity of N2 is supplied in the secondary
reformer. The gases at the exit of Methanation contain traces of unconverted CO & CO2 up to 2 to 3
ppm and H2O is saturated condition.
This gas is compressed in four stages up to ̴ 200 kg/cm2g from around 30 kg/cm2g. This is
drawn to HWP. This synthesis gas contains H2 and N2 in 3:1 ratios along with other components

Monothermal H2/NH3 Process:

Mono-thermal exchange process is employed at Heavy water plants of Baroda, Tuticorin, Thal and
Hazira.
Feed: Synthesis gas from fertilizer unit with typical composition of
H2 : 74.12 %
N2 : 24.74 %
Argon : 0.3 %
CH4 : 0.84 %
CO, CO2, O2 : < 2 vpm
H2O : Saturated at 400C
D2 : 115 vpm D/(D+H)
Deuterium content in synthesis gas is low compared to natural abundance, because ‘D” depletion
takes place in shift-converters of NH3 plant as per steam – H2 exchange reaction.
HD + H2O H2 + HDO
If this condensate is recycled properly, the ‘D’ content of synthesis gas can be increased to 125 vpm
The following sequence of activities is carried out:
Intake of synthesis gas from the host fertilizer plant, and the gas is first boosted of its pressure by
about 45 kg/cm2 in order to overcome the pressure drop through various equipments.
 Feed purification and cooling:
As the synthesis gas contains many impurities as listed above, which react with KNH2 catalyst
forming solids which can severely choke the exchange towers, the synthesis gas require
elaborate purification steps. Purification consists of cooling the gas to 50C to remove condensed
water, then gas is dried in Alumina gel dryer.
This and cooled to about -20oC in an NH3 cooler and passed through purifier, which contain a
single ejector tray assembly. In the purifier, all the oxygen bearing impurities like CO, CO2 &
traces of H2O are removed by reaction with K –Ammonia solution. Here the synthesis gas is
also saturated with NH3 before the gas enters into the exchange tower.
K NH2 + H2O KOH + NH3
CO + KNH2 KCO NH2

CO2 + KNH2 KCOO NH2

3O2 + 4 KNH2 KOH + 2 KNO2 + 2 NH3

58
 Deuterium Exchange process:
The gas entering the plant contains around 105 to 115 ppm of D/(D + H). The gas leaving tower
T1 contains around 18 to 20 ppm of D/(D + H). The leaving gas is passed through NH3
converter and the converted NH3 is separated and used as reflux/liquid feed to the tower. The
unconverted gases are sent to fertilizer plant.
The synthesis gas at -250C is fed at the bottom of the exchange tower 12T1 wherein the
synthesis gas is contacted with ‘D’ –depleted liquid ammonia containing KNH2 catalyst flowing
downwards the tower. Catalyst amide solution is separately added in the 15th stage (2nd from
top). Transfer of Deuterium takes place from H2 of synthesis gas to liquid ammonia.
- 25 0C
NH3 + HD NH2 D + H2
0 0C
Separation factor at -25oC = 5.0, at 0oC = 4.25
The exchange tower consists of 15 no. of ejector trays which bring about intimate contact of gas
and liquid streams. Each ejector tray consists of no. of convergent nozzles i.e ejector nozzles
through which the synthesis gas enters the tray with high velocity to break the liquid into fine
droplets. The important feature of ejector trays is very high pressure drops across the trays,
because of which the liquid can not flow down by gravity to the next lower tray. This
necessitates provision of pumps on each tray inside the tower, for pumping the liquid to the next
lower tray.
In the extraction tower, liquid ammonia gets enriched to 5N i.e 5 times the ‘D’ content of the
feed. The liquid leaving the bottom of tower T1 is sent to tower T2 operating at a lower pressure
≈ 110 to 120 kg/cm2g for further enrichment. Tower T2 contains 10 ejector stages. The tower T2
temp is maintained at around 0oC to +2oC. The liquid is enriched to around 200N by contacting
with enriched D2 produced by cracking of the enriched ammonia. The enriched ammonia liquid
is further enriched to in the final enrichment section using the same principles.
 Cracking of enriched ammonia:
Part of the enriched ammonia (200N) is separated of its KNH2 catalyst in the catalyst separation
unit, and then fed to the ammonia cracking unit where the ND3 is cracked into D2 and N2 as per
the following reaction at a temperature of 6000C
2 ND3 3 D2 + N2
The cracker unit consists of a gas-fired furnace, in which cracker tubes, filled with catalyst,
(DNK-2, a special ceramic based iron catalyst) are vertically arranged. The cracking of
ammonia is an endothermic reaction which is sustained by supply of external heat through
furnace.
The cracked D2 gas is cooled, and fed at the bottom of the enrichment tower 12T2 as reflux, in
which the enriched ammonia liquid (5N) is contacted with the D-rich synthesis gas. This will
further enrich the ammonia liquid to 200N.
 Ammonia synthesis:
The feed gas after transferring its ‘D’ content, comes out of the extraction tower 12T1 as ‘D’
depleted gas. This depleted gas is fed to an ammonia synthesis unit where part of the gas is
converted to ammonia with low ‘D’ content, while major part of the depleted synthesis gas is
sent back to the host-fertilizer plant. The depleted NH3 is liquefied and fed to top of the
extraction tower 12T1 in order to extract D from the feed synthesis gas.
The enriched ammonia liquid (200N) is further enriched in final enrichment towers T3 & T4 to
produce nuclear grade ND3. The enriched ND3 is cracked to produce D2 gas and N2 which is
burnt with O2 to produce nuclear grade heavy water. The synthesis gas from fertilizer plant with
traces of impurities as CO & CO2 up to 3 ppm and moisture content at saturated condition at
180 kg/cm2g & 40oC is boosted to a pressure of 230 kg/cm2g to overcome the system pr. drop.
59
Return to
Fertilizer plant
Ammonia
Converter Pr: 120
D/(D+H):
kg/cm2g
18 to 25 ppm
Pr: 120
kg/cm2g

Amide
T1 T2

(-) 250C (-) 00C

Pr: 220 Burner
T3 T4
kg/cm2g α = 5.0 α = 5.0
D2O product
50 – 60%

Purifier Mini
Cracker

~ 5%
~ 1.5% Cracker K-separation
D/(D+H)
D/(D+H) unit
Gas from
Fertilizer plant Rich amide
K-separation Rich
D/(D+H):
unit K-free amide to T2
103 to 115 ppm
Pr: 26
‘D’ stripped kg/cm2g
rich amide

Mono-thermal H2/NH3 exchange process

60
Recovery in a Montothermal Process:
In a bi-thermal process ‘D’ enriched liquid from a cold tower is sent to hot tower for stripping
of the liquid and also to generate a ‘D’ rich gas. The extent to which D stripping/generation of D rich
gas depend on αh. Similarly the enriched liquid from tower T2 is cracked to obtain a rich gas. Since
while cracking the D/(D+H) of liquid & gas is same.
αh for mono-thermal can be taken as 1.
Therefore Recovery = α- 1/α
% R = (5.0-1)/5.0 = 80%

Bi-thermal H2/NH3 exchange process (HWP, Talcher):

The gas was available from the adjacent coal based fertilizer plant, where coal gasification
process was used for making syntheses gas.

Coal gasification process:

Coal gasification
CO H2 CO2 H2S
57% 28% 14% 1%

H2S Removal

Shift conversion CO + H2O H2 + CO2

(Steam)

CO2 removal

Liquid N2 wash
(For removal CO & traces of CO2)

Synthesis gas

The synthesis gas obtained in this process is free from moisture & CO2 due to liquid N2 wash at
very low temperatures. However traces of O2 & Co are present in the gas.
The gas which is drawn from fertilizer plant is passed through a De-oxo vessel, where O2 reacts
with H2 to from H2O which is then separated by washing with liquid ammonia at the bottom of the
purification tower. The gas also gets humidified at the bottom of the purification column and in the
upper section of the purification column K-amide solution is circulated for removal of oxygenated
impurities.
The purified gas is sent to primary exchange tower where the ‘D’ lean liquid from 1st stage
enrichment gets enriched with ‘D’. The enriched liquid is further enriched in a combination of hot &
cold towers up to = 17% (design). The ‘D’ rich liquid after separation of amide is processed in an
ammonia waste exchange column, where the ‘D’ rich waste HDO free from ammonia is taken out
from the bottom of the column and sent to D2O column for further up-gradation.
61
 Isotopic exchange reaction

-300C
HD + NH3 NH2D + H2
+650C

K- Amide catalyst
αc = 5.3
αh = 2.9

+300C
NH2D (G) + H2O (l) ←→ NH3 (g) + H2O (l)

HWP (Baroda) Front End Process

Water after demineralization/degassing is first fed to ammonia absorption columns of absorption

refrigeration system. It absorbs the ammonia vapours and is thus saturated with Ammonia, prior to
feeding to Exchange Columns of front end unit.
The exit water from the ammonia absorption system is preheated and fed to exchange columns
of front end, which is operating at 20 kg/cm2g and temp. 1300C, where deuterium from the water is
transferred to counter flowing deuterium less ammonia vapour. This ammonia required to be enriched
in front end is received from existing synthesis section of the plant.
After recovery of deuterium from the water, the ammonia contained in the depleted water is
stripped off in stripper by steam heating. The water exit from the stripper which is completely free
from ammonia is discarded after proper heat recovery and used as make up water for boiler feed
water and/or cooling water.
Moisture from vapour ammonia carrying out from the top of the exchange column is remained
in Ammonia distillation column.
Moisture free enriched product ammonia from front end is fed to preliminary isotopic
extraction tower 12T1 and a small quantity of product ammonia is also drawn to 14S3 for 14C2 and
other auxiliary requirements of ammonia in the plant.
Both isotopic exchange towers 12T1 and 12T2 operate in series at MP pressure and low temp.
They operate at equal L/G ratio (=1). Ammonia is further enriched in 12T1/T2 by extraction of
deuterium from syngas coming from pre-enriched ammonia cracking in presence of potassium amide
(KNH2) catalyst. The deuterium lean syngas exit from the top of 12T1 is completely synthesized to
ammonia in the modified synthesis section of plant and enriched in front end.

62
 TRANSFER
COLUMN
COLD
TOWER
STRIPPER
HEAT EXCHANGER

DEPLETED

TOWER -2

TOWER -3
SYN. GAS COLD LEAN WATER

COLD

COLD
TO FCI TOWER FROM DU
1

NH3-H2O
CONTACT
TOWER
PURIFICATION
DEOXO UNIT

COLUMN

HOT
TOWER
1

TOWER -3
ENRICHED

HOT
WATER TO
DU

SYN. GAS
FROM FCI HOT
TOWER
STRIPPER

SCHEMATIC FLOW DIAGRAM OF TALCHER PLANT

63
 Data of XU Towers at HWP (M) plant

CT1 HT1 CT2 HT2 CT3 HT3 2HT 2CT 3HT 3CT
1 Column diameter, m 4.25 4.5 4.25 4.5 4.25 4.5 4.5 4.25 2.3 2.3
2 Shell thickness, mm 40-42 42-48 40-42 42-48 40-42 40-48 42-45 38-42 25-38 28-32
3 Corrosion allowance, mm 6 6 6 6 6 6 6 6 6 6
3
4 Column volume, m 661.5 777.5 661.5 777.5 661.5 777.5 572.5 677 223 221.9
5 Column liquid hold up, Te 80.31 101.868 80.31 101.868 89.58 89.717 53.801 90.87 40.695 29.665
6 Column Gas hold up, Te 16.43 13.9 16.43 13.9 16.229 14.149 10.787 17.2687 3.739 5.3828
7 No. of trays [MT/HT] 64/14 61/18 64/14 61/18 64/14 61/18 58 68/14 78/18 78/14
8 Tray spacing, mm 485/485 485/485 485/485 485/485 485/485 485/485 485 485/485 485/485 485/485
9 Tray perforation dia, mm 6.3/6.3 6.3/6.3 6.3/6.3 6.3/6.3 6.3/6.3 6.3/6.3 6.3 6.3/6.3 6.3/6.3 6.3/6.3
10 Tray thickness, mm 2/2 2/2 2/2 2/2 2/2 2/2 2 2/2 2/2 2/2
O/L weir height, (MT/HT), 38/75(1-6) 38/75(1-6) 38/75(1-6)
11 85/90 85/90 85/90 85 38/90 105/90 89/90
mm (tray nos. in bracket) 90(7-14) 90(7-14) 90(7-14)
Pr. Drop per tray, (MT/HT), 99.4/ 114/ 99.4/ 114/ 119.8/ 114.5/ 101.2/ 100.8/ 97.131/
12 115.8
mm WC 88.39 87.3 88.39 87.3 88.4 87.3 84.8 82.3 82.3
13 L, Te/Hr 155 -166 216 155 – 166 216 155 – 166 216 216 155 – 166 --- 30 – 44
14 G, Te/Hr 598 – 640 --- 598 – 640 --- 598 – 640 --- --- 598 – 640 --- 105 – 112
0.54/ 0.6456/ 0.54/ 0.6456/ 0.54/ 0.6456/ 0.5183/ 0.1755/ 0.183/
15 Tray liquid hold up, Te 0.6093
0.458 0.643 0.458 0.6515 0.655 0.6515 0.5665 0.185 0.1882
0.307/ 0.3175/ 0.3077/ 0.318/ 0.3/ 0.3182/ 0.3079/ 0.0755/ 0.0901/
16 Down comer liquid hold up, Te 0.3181
0.1096 0.1096 0.0825 0.105 0.085 0.1052 0.0892 0.04292 0.0226
52.847/ 58.745/ 52.847/ 58.78/ 53.76/ 58.796/ 56.189/ 19.58/ 21.13/
17 Total tray hold up, Te 53.801
7.427 13.549 7.427 13.617 10.36 13.636 9.181 3.278 2.9509

64
 6. DU COLUMN

DU column Internals

1. Distillation process can not be employed for the pre-enrichment section as:
a. Separation factor is low (Relative volatility = 1.04)
b. Very low recovery
c. Large plant volume
d. Large energy requirement.
2. Corrugated ordered packing ensures:
a. High surface area (hence low HETP)
b. Less pressure drop
c. Well defined path for better contact of liquid and vapour.
3. Isotopic enrichment always requires large no. of theoretical stages and to achieve this sieve
tray columns had to be installed in 4 or 5 stage cascades. This entails:
a. Huge hold up.
b. High equilibrium time
c. Handling losses
d. Energy intensive
e. High capital investment.
4. Tower internals constitute:
a. Tower packing.
b. Liquid collector
c. Liquid distributor & re-distributors
d. Packing supporting grid
e. Packing holding ring
5. Tower packing characteristics:
a. High wettability
b. High surface area per unit volume
c. Large void fraction.
d. Low pressure drop
e. Low hold up.
6. Wettability mostly depends on the system properties, but at the same time the material of
construction also plays role.
The surface tension of the process fluid and the contact angle for a particular fluid to the
material of construction are the basic factors for wettability.
7. Extremely large surface area per unit volume and large void fraction can be achieved for
packing fabricated from fine wiremesh.
8. Due to higher porosity, the friction factor of the mesh type packing is always lower.
Consequently the pressure drop is less.
 9. Material of construction
a. For water/heavy water where the surface tension is very high, there are few materials of
construction from which can be chosen.
b. Stainless steel and polypropylene packings can not be used due to their poor wettability.
c. Phosphor bronze is the only material which can be used for the fabrication of tower
internals in view of its superiority over copper in:
- Mechanical strength.
- Ease of fabrication.
- Material compatibility
- This material can be easily converted to copper oxide to yield – porous surface which
enhance the wettability considerably.
10. Cylindrical packing sections, suitable for particular diameter, are prepared from several
parallel corrugated strips of woven wire-mesh. The corrugations are inclined with respect to
the tower axis and the direction of the corrugation is reversed on the adjacent strip. Two
groups of parallel crossed flow passages of triangular shape are thus formed between adjacent
strips.
11. Liquid Collection:
The maximum packed height can be of the order of 2.5 to 3.0 meters as considerable
channeling occurs beyond the above height of the packed bed.
The liquid flowing from the bottom of each section is collected by means of such reflux
collectors located on the top of the lower column section.
The reflux collector is so designed and fabricated such that the direct contact of vapour and
liquid in this collector does not take place so as to prevent entrainment.
12. Liquid Redistribution:
Experimentally it was seen that the liquid, if fed at the centre of the packing, gets uniformly
spread after reaching a certain height from the top. The packing up to this height from the top
is unavailable for mass transfer. Further, after a certain height of the packing the liquid has a
tendency to flow towards the wall.
It is necessary that the liquid fed at the top is divided into many sub streams to evenly spread
through out the entire cross section, such that the entire volume of the packing is available for
mass transfer.
These ordered packings having corrugation at an angle inclined towards the axis of the tower
do not allow the liquid to reach the wall, and at the same time the liquid reaching near the wall
also retreats towards the centre. However, after a certain height of the packing, the quantity of
the liquid flowing on the wall surface may be considerable and it has become necessary to
incorporate a reflux collection and a re-distribution for every packed height of 2.5 to 3 meters.
In addition to this the verticality and Ovality of the column also have influence on the
efficiency of the distillation columns.
If the Ovality is not maintained, the continuous gap between the wall and the packings will
exist, through which the liquid flowing will give raise to channeling. The same effect will be
there, if verticality is not maintained.
Surface Activation:
It is highly essential to create the porous oxide film on the packing surface in order to get the
liquid spread as a film which will enhance the mass transfer rates.
66
 Organic liquid in view of the low surface tension, easily wet the surface of the packing. But
water and heavy water due to their high surface tension do not wet the surface easily. For this
system, it is necessary to make the surface porous and thereby increase the wettability. To
achieve this, the tower internals are subjected to a chemical treatment to obtain a porous and
stable cupric oxide film on the surface.
Pre-flooding:
Before commencing the regular operation in order to ensure that all the packing surfaces are
wet and they are uniformly irrigated, the boil-up rate is increased to the extent that the
flooding in the section set in.
After reaching the flooding point, abrupt reduction of the boil up rate results in sudden
dumping of the liquid and thereby the whole packing surface gets completely wet.

Boiling point diagram showing rectification on ideal plate:

Operating line for distillation rectification section

Yn+1 = [Ln/(Ln+D)]xn + [DXD/(Ln+D)]

Operating for stripping sector

Ym+1 = [Lm/(Lm-B)]xm – [BXb/(Lm-B)]

If both the numerator and denominator are divided by D

Yn+1 = [(Ln/D) /(Ln/D) +1]xn + [xD / (Ln/D) +1]
Ln / D = Reflux ratio , RD
So, Yn+1 = [RD/RD+1]xn + [xD/RD+1]

Fensky equation for minimum no. of trays under total reflux is

Nmin = log[(xD/1-xD) / (xB/1-xB)]
Log αAB -1

67
 7. N.D.T. Methods
1. Radiographic testing (R.T.)
2. Ultrasonic Testing (UT)
3. Eddy Current Testing (E.T)
4. Magnetic Particle Testing (M.P.T)
5. Liquid Penetrant Testing (L.P.T)
6. Visual Testing (V.T)

 First two methods R.T & U.T are volumetric methods and can detect defects inside the material.
 Next two methods ET and MPT can detect surface and sub-surface defects and
 The last two methods LPT and VT can detect only those defects which are open to surface.
 Other NDT methods like leak testing and acoustic emission testing are useful for testing pressure
vessel and other equipment.
01 Radiographic Testing:
Penetrating radiation when passes through the
material gets partly absorbed and partly transmitted. The
amount of transmitted radiation depends on the thickness Void
and density of the material. If there are any defects like
cracks, slag or any voids these will allow more radiation to Specimen
pass through and be indicated as areas of higher density on
the radiographic film. Radioactive source could be X-rays Film
from X-ray machine or gamma rays from radio-isotopes
Darker areas
(When processed)
Such as Co-60, Ir-192, Cs-137 etc. This method finds wide application to find out defects in welds
& castings.
02. Ultrasonic Testing:
This method is known as ultrasonic testing because frequency of sound waves used in this
testing is 500 KHZ to 15 MHZ which is much beyond the audible range. When a beam of these
sound waves passes through material having some internal flaws, part of its energy gests reflected
from the flaw and the resultant beam with reduced energy gets transmitted.
The defect can either be detected by measuring the energy of reflected beam (Reflection &
Pulse echo technique) or by measuring the reduction in the energy of transmitted beam (transmission
technique). Pulse echo technique is most widely used for locating defects in welds and for thickness
measurement.
Major advantage of this method is that the testing can be carried out even when only one
surface is accessible and defect can be located even when these are at an angle to the probing surface.
Amp

Amp

Time Time
Principle of ultrasonic testing
68
03. Eddy Current Testing:
When a test object is placed in alternating magnetic field (Hp), it induces eddy current, in the
test object. These eddy currents in turn produce secondary alternating magnetic field (M s). Any
change in the secondary magnetic field caused by variation in electrical conductivity, magnetic
permeability geometry or due to presence of defect in the test object will change the impedance of the
test coil and consequently the phase and amplitude of generated signal.

This is the only method available for carrying out in service inspection of heat exchangers
tubes to evaluate the damage caused by corrosion and erosion and take necessary corrective action
before it causes failure.

04. Magnetic Particle Testing:

When a ferromagnetic material is magnetized, its field gets distorted, if there is any abrupt
change in the section or when a defect is present. If the defect is on or near the surface it causes
leakage of the magnetic field. When magnetic powder (high permeability iron powder) is sprayed on
the surface, it gets attracted by the leakage flux and forms the indication.
Leakage field Magnetic potential Indicator
jumping air gap

- -- -- - -- -- - ---------------- - - - - - - - - -- - - - - - - - - -
-Flow Line - - - - - - - - - - - - --------------------
This method is used for locating fatigue cracks and steam corrosion cracks.
05. Liquid Penetrant Testing:
Basic Steps:
a. Apply the liquid penetrant on the test area which has been pre-cleared. Pre-clearing is
required to ensure that defects, if any, are open to the surface and not clogged or covered with
oil, grease, rust, corrosion products etc.
b. Allow the penetrant to remain on the test area for sufficiently long time to penetrate even very
close defects like fine cracks.
c. Remove excess penetrant from the test area.
d. Apply a thin coat of developer which acts as blotter and draws the penetrant from the defect.
e. Carry out inspection. Penetrant from the defect appears on the developer coating as defect
indication.

69
06. Visual Testing:
Some codes and standards specify the conditions for proper visual inspection such as amount
of illumination, viewing angle to the surface to be examined, sensitivity etc. Equipment like
boroscopes and fibroscopes can be used for looking into the area which are otherwise inaccessible.

07. Leak Testing:

Most commonly used method

S.No Gross Leak Test Methods Range of leak detection capability Std. CC/Sec
01 Pressure drop test 102 to 10-2
02 Pressure raise test (Vacuum test) 102 to 10-3
03 Ultrasonic Leak detectors 102 to 10-1
04 Bubble test
(a)Air soap solution 100 to 10-3
(b) H2 Alcohol 100 to 10-4
05 Ammonia sensitized paper 100 to 10-4
06 Halogendiode sniffer 100 to 10-5
S.No Fine Leak Test Methods Range of leak detection capability Std.C.C/Sec
07 Helium Mass Spectrometer Leak test
a) Pressure (sniffer method 10-1 to 10-7
b) Vacuum method 10-4 to 10-10
c) Pressure Vacuum test 10-2 to 10-11

08. Acoustic Emission Testing:

When a structure or equipment is subjected to increasing stress, it emits sound waves in
audible and sub-audible range at the location where there is crack indication or crack growth. These
emissions are called acoustic emissions. By sensing and analyzing the direct amplitude and
frequency of these emissions we can find the location and severity of such flaws.
Computerized and automated systems are available for carrying out on line in-service testing.
Its limitations are that it cannot detect static defects. It can detect defect growth only.

70
 8. CONTROL VALVES & INSTRUMENTS

Control Valve size and cost can be minimized with high pressure drop assignment, but
pumping costs and equipment ratings are increased with them. It is essential to calculate minimum,
normal and maximum ‘Cv’ values. With this data, valve size can be selected and reviewed for
rangeability, turndown and for their relationship with valve characteristic or operational curve
Max. controllable flow Normal maximum flow
Rangeability = Turndown =
Min. controllable flow Min. controllable flow

Pv
Valve pressure drop ratio, PR =
Pv + P2
Where Pv = Valve pressure drop & P2 = System friction losses.
Inherent flow characteristic of a valve is defined as the relationship between fractional valve
lift and relative flow through the valve at constant pressure drop. Installed valve characteristic is the
actual characteristic under system’s operating conditions where pressure drop is not constant and is
unique to each specified installed system.
Change in flow
Valve gain, Kc =
Change in stem position

And Kc is the slope of the valve characteristic curve.

1
Flow percent

Valve Characteristics:
The most used and commonly available valves have 2
inherent flow characteristics which fall between quick 3
opening and equal percentage curves. 4 5

 Linear valves have constant gain 1.0

 Equal percentage valve exhibit a low gain at the near
closed position and increased to a high gain at full 0 Stem position, % 100
capacity. 1 – Quick opening
2 – Linear
 The quick opening valve exhibit opposite characteristic 3 – Butterfly
of equal percentage valve, with very light gain at lower 4 – Ball
capacity & zero gain from 50% to 100% steam position. 5 – Equal percentage
Valve Size:
A control valve may be regarded as a variable orifice or restriction and the flow equation may
be developed from the fundamental flow equation.

In the simplest form the flow equation for valves may be written as
For Liquids,

Or

71
 FL = Flow of liquid in gal/hr
CL = discharge Coefficient
d = Valve dia in inch i.e. valve size
P1, P2 = U/s & D/s pressure in Psia

For Gases,

FG = Flow of gas in Std. Cu.ft/hr

CG = disch. coefficient
T = Abs. temperature of flowing gas ( 0F +460)
S = Specific gravity of dry gas relative to air at the same temperature and pressure.
P1, P2 = U/s & D/s pressures in Psia
d = Valve diameter in inches i.e. valve size

For Vapours:

Or

Where F1 = Flow of vapour in lb/Hr

C1 = disch. Coefficient
P1, P2 = U/s & D/s pressure in Psia
d = Valve dia in inches i.e. valve size
V = Sp. Volume of vapour in cu.ft/lb at the D/S condition.

An alternative method of calculating valve sizes is by using the measured hydraulic valve coefficient
known as the ‘Cv’ value. This is the flow of water through the fully open valve, when the pressure
72
drop is maintained at 1 Psi. The required value of Cv for a valve used on liquid flow will then be
given by

When S = Sp. Gravity of liquid

Cv is expressed in U.S. gal/min.
The corresponding equations for gases and vapours are

When the Cv value has been calculated, the required valve size may be obtained from
the manufacturers.

Pressure drop across a valve:

The flow through a valve is proportional to the product of area of the valve port opening and
the square root of the pressure drop across the valve.
The pressure drop in the lines is proportional to the length of the lines and the square of the
velocity through lines. It is obvious that the valve pressure drop is not the only factor tending to
control the flow. However, if the valve pressure drop is to be the dominating factor, it is necessary to
make the pressure drop in the lines small in comparison with the pressure drop in the valve.
As the length of the liner is generally fixed, reduction of the pressure drop in the line may be
achieved only by increasing the line size. The pressure drop proportional to square of the velocity and
velocity is inversely proportional to the square of the pipe diameter. Hence, the pressure drop is
inversely proportional to the fourth power of the pipe diameter. At least 60-70% of the pressure drop
should take place in the valve so that the changes in the pressure drop in the lines are small in
comparison with the pressure drop across the valve.
The larger the line size in comparison with the valve size the better will be the performance of
the Control Valve and in no circumstances should the valve size be greater than the line size.
In general the valve should be at least one size smaller than the line.
i.e. √2 dv = dl ; (dv – valve size and dl - line size)

Valve Positioner:
It is essential that the correcting unit in a control system should respond immediately and in an
accurate manner to small changes in the controller output pressure. Where the pressure of the process
fluid is high, tight packing may be required to prevent leaks around the valve stem and the frictional
force between the stem and pocking tending to resist the motion of the stem will be large.

73
 The force required to move a single port valve where the pressure drop across the valve is
high will be large.
Under these conditions a valve positioner is often installed between the controller and the
correcting unit to enable the controller to apply a very large force to move the valve into the new
position required.
With valve positioner the pressure applied to the diaphragm may be much larger than the
output pressure of the controller so that the force available for moving the valve will be many times
(say 250) greater than that available when a positioner is not used.
A valve positioner therefore not only increases the accuracy with which the valve may be
positioned but also greatly increases the speed with which the final position is achieved.
Proportional Control:
Proportional action is defined as the action of a controller, whose output signal V is
proportional to the measured deviation θ
Then V = - K1θ
K1 is the proportional action factor
K1 α 1 / (Bandwidth of the controller)
α 100/ (% of proportional band)
Proportional Band: The amount of measured value of the controlled variable must change in order
that the valve may be moved from the fully closed position to the fully open position is called the
Proportional Band. In case of automatic controller, it is usually expressed as % of the instruments full
scale. If the scale of the instrument is 0 – 100oC and the temp must change from 70oC to 90oC for the
valve to be moved from fully open to fully closed position, the proportional band is
20/100 x 100 = 20%
Valve position
Controlled
variable

Offset

Time Time

Integral action:
Forced with the problem of offset caused by any change in the set point, the valve shall be operated
slowly in order to reestablish the control point at the desired value. The amount of valve operation
depends upon the size of the deviation and the time for which it permits. That means the rate of the
valve operation is proportional to the deviation; the action is called integral action.
The action of a controller the output signal of which changes at a rate which is proportional to
the measured deviation.

(Or)
K2 is the integral action factor
For a const. deviation, the change of output signal will be proportional to time.

74
Derivative Action:

In addition to the valve operation in a manner which simulates proportional to integral action,
the valve is operated not based on the size of deviation but upon the rate at which the deviation is
changing. Derivative action cannot be used alone. When the deviation is const. it doesn’t matter how
large it may be, derivative action will produce no change in the valve position.
The action of a controller, the output of which, is proportional to the rate at which the
measured derivation changes. Thus

K3 = derivative action factor

P – I action:

The integral action time (T1) of the controller is defined as the time interval in which part of
the output signal due to integral action increases by an amount equal to the part of the output signal
due to proportional action when the deviation is unchanging.
If θ is constant,
P- action, V = - K1θ
I - action, V = - K2 ∫ θ dt
At time T1, if these are equal, On integration, they become - K1 θ = -K2 θ T1
Therefore, T1 = K1 / K2
And V = - K1{θ + (1/T1) ∫ θ dt }

P – D action

V = - K1 θ – K3 (dθ / dt) V = - K1 {θ + (K3/ K1) (dθ / dt)}

The derivative action time T2 of a controller is defined as the time interval in which the part of the
signal due to proportional action in a controller having both P – D action increases by an amount
equal to the part of the output signal due to derivative action, when the deviation is changing at a
const. rate.
Deviation = ∫ (dθ / dt) dt, t is varying from 0 to T2
= T2 (dθ/dt), because (dθ/dt) is constant
At time T2 sec., - K3 T2 (dθ/dt) = - K3 (dθ/dt)
Therefore, T2 = K3/ K1
And V = - K1 {θ + T2 (dθ / dt)}

P – I - D Action :

V = - K1 {θ + [(1/T1) ∫ θ dt] + [T2 (dθ / dt)]}

75
Effect of control actions:

Process load Time

Controlled
variable

Proportional Recovery time

action
Offset

Time
Controlled

Integral
variable

Recovery time
action

Time
Controlled

Proportional
variable

Recovery time
Integral
action

Time
Controlled

Proportional
variable

Integral Recovery time

Derivative
action

Time

76
Forces acting on a Rotameter
Weight acting on the float: w= Vf( ρ2 – ρ1 )
Vf = Volume of the float
ρ1 = density of the liquid
ρ2 = density of the float material

Force acting on downward direction: Fd = P2Af

P2 = Pressure on upper surface
Af = surface area of the float

Force acting in upward direction: Fu = P1Af

P1 = pressure on the downward surface
Af = surface area of the float

Drag force: d = KVlfm

W+Fd = Fu + drag force (negligible)
P1Af= Vf ( ρ2 - ρ1 ) + P2Af

SDV Operation: Open Open

torque permit Open
switch switch SOV

Filter Lubrication 4 way

valve

Close Close
SOV Torque
Valve Positioner: Switch

With the I/P output the beam bends

towards the air supply connection as
back pressure develops in the header, it
actuates the relay and air supply goes to
control valve as it operates till the
balance on the lower beam is
compensated by the spring force
connected to the load.

77
I/P Converter:

4 - 20 mA current flows through

N N
S S
Air Supply
the winding in between the
magnetic poles. Based on the
4 – 20 mA
quantity of current, magnetization
is induced in the core and it gets
attracted towards north pole which
creates a back pressure in the air
3 – 15 Psi supply header and accordingly 3-
15 Psi air supply is generated.

Variable Capacitance method:

FTS, LTS, PTS, DPTS, in HWP (M) are based on variable capacitance method
Capacitance C= εA / d
ε= permeability = dielectric constant in micro faradays,
A = area of the plate
d= distance between the plates
Silicone oil is contained between two plates. There is a
diaphragm between two plates. With the pressure
variations, the diaphragm moves depending on pressure
HP LP difference and the distance between the plates. The other
Silicone parameter A and ε being constant. Capacitances C1 and
oil C2 varies with directly proportional to pressure
C1 C2 difference.

The other method is LVDT: Linear Variable

Differential Transformer due to the pressure
difference the core in between primary and
secondary winding moves up and down. And due
to this the induced voltage in the secondary circuit
E1 and E2 varies. These differences are calibrated
for pressure difference.

78
 9. DESIGN vs PRESENT OPERATING CONDITIONS

Design values As per M/s UCIL Process Flow design

Liquid Feed 412 MT/Hr 453 MT/Hr
CT Gas Flow 546 MT/Hr 595 MT/Hr
HT Gas Flow 597 MT/Hr 658 MT/Hr
F-Factor (CT) (ft/sec) 0.25 0.275
F-Factor(HT) (ft/sec) 0.3 0.33

Other design values:

First stage C.T 65% flooding velocity

First stage H.T 78% flooding velocity
First stage CT fractional entrainment 0.035
First stage HT fractional entrainment 0.06
Second stage CT 67.2% flooding velocity
Second stage HT 81.8% flooding velocity
Second stage CT fractional entrainment 0.036
Second stage HT fractional entrainment 0.07
Third stage CT 46% flooding velocity
Third stage HT 64% flooding velocity

Design efficiencies:

Cold Tower Hot tower

Design expected μ = 61.6% Design expected μ = 70.1%
Design Murphy Efficiency, μ = 63.0% Design Murphy Efficiency μ = 73.4%

Design condition in first stage cold & hot tower (As per UCIL Manual)

Cold Tower Hot tower

1 F factor, ft/sec 0.25 0.30
2 L feed, Te/Hr 144.4 197
3 G feed, Te/Hr 546.8 597.6
3
4 Liquid Density, lb/ ft 62.11 58.48
5 Gas Density, lb/ ft3 2.00 1.38
6 Pr, kg/cm2g 20.6 kg/cm2 21.8
o
7 Temp, C 32 135oC

79
Estimated values for flooding at design conditions:

Cold Tower Hot tower

1 CSB flooding 0.341 0.341
2 Flooding velocity, ft/Sec 1.86 2.2ft/sec
3 Design velocity, ft/sec 1.207 1.72 ft/sec
4 % flooding 65% 78%

Check at 110% higher flow rate of PFD valves

Cold Tower Hot Tower

1. Operating conditions
Pressure 20.6 kg/cm2g 21.8 kg/cm2g
Temperature 32oC 130oC
L 498 MT/Hr ---
Gas 661 MT/Hr 717 Te/Hr
2. Flooding Conditions
CSB flooding 0.341 0.341
Flooding velocity 1.86 ft/Sec 2.25 ft/Sec
Velocity in tower 1.457 ft/sec 2.196 ft/sec
% flooding 78.3% 94.3%
3. Entrainment & Efficiency
Fractional entrainment 0.059 0.22
Expected efficiency 60.6% 60.8%
Drop in design efficiency 1.6% 13.3%

Estimated Entrainment of First stage Hot Tower at different flooding conditions:

85% flooding 90% flooding

1 Gas flow in HT 641 Te/Hr 1 Gas flow in HT 678 Te/Hr
2 % flooding 85% 2 % flooding 90%
3 Fractional entrainment 0.09 3 Fractional entrainment 0.11
4 Expected efficiency 68.4% 4 Expected efficiency 67.2%
5 Drop in efficiency on % of 2.4% 5 Drop in efficiency on % of 3.1%
design design

80
Design capacities of II stage C.T & H.T

II stage C.T II stage H.T

1 F – factor 0.26 1 F factor 0.31
2 L 144.1 Te/Hr 2 L 196.7 Te/Hr
3 G 549.9 Te/Hr 3 G 602.5 Te/Hr
4 Liquid Density 62.11lb/ft3 4 Pressure 21.1 kg/cm2
5 Gas Density 1.9 lb/ft3 5 Temp. 135oC
6 Pressure 19.7 kg/cm2
7 Temp. 32oC
Flooding conditions
1 CSB flooding 0.341 1 CSB flooding 0.341
2 Flooding velocity 1.92 ft/sec 2 Flooding velocity 2.273 ft/sec
3 Design velocity 1.29 ft/sec 3 Design velocity 1.86 ft/sec
4 % flooding 67.2% 4 % flooding 81.8%
Entrainment & efficiency
1 Fractional entrainment 0.035 1 Fractional entrainment 0.07
2 Design expected efficiency 60.5% 2 Design expected efficiency 70.1%
3 Design murphree 61.9% 3 Design murphree 74.0%
efficiency efficiency

Fractional Entrainment = moles liquid entrained/(area) (time)

--------------------------------------------------
L + moles liquid entrained/(area) (time)

Check at 90% flooding velocity for II stage CT & HT

II stage C.T II stage H.T

1 Gas flow 625 Te/Hr 1 Gas flow 678 Te/Hr
2 Pr 19.7 kg/cm2 2 Pr 21.1 Kg/cm2
3 Temp. 32oC 3 Temp. 130oC
Flooding conditions
1 CSB flooding 0.341 1 CSB flooding 0.341
2 Flooding velocity 1.927 ft/sec 2 Flooding velocity 2.29 ft/sec
3 Velocity in tower 1.48 ft/sec 3 Velocity in tower 2.04 ft/sec
4 % flooding 75.5% 4 % flooding 89.1%

II stage C.T II stage H.T

Entrainment & efficiency
1 Fractional entrainment 0.055 1 Fractional entrainment 0.10
2 Expected efficiency 59.8% 2 Expected efficiency 68.4%
3 Drop in design 2.1% 3 Drop in efficiency on % of 1.7%
design

It is concluded that plant can be operated with feed processing rate of 489 MT/Hr i.e. 108% of
PFD flow rate which corresponds to 90% flooding velocity limit in first stage hot tower with design

81
pressure condition. The constraint is that purge tower bottom pumps and CRT transfer pumps to
second stage C.T. Requirements can be met presently by running standby pumps.

Advantage with Staging

Single stage Two stages Three stages

Relative tower volume 1 0.7 0.6
Relative process inventory 1 0.12 0.05

F – Factor

CF = V F
Where,
VF = superficial velocity of the gas; (Volumetric flow rate of gas) /(net cross section for flow), Q/An.
ρL = liquid density
ρG = gas density
‘An’ is the tower cross section At minus the area taken up by the downspouts Ad

Operating characteristics of Sieve Trays

82
 10. VAPOR ABSORPTION REFRIGERATION

Water Lithium Bromide System:

Water Refrigerant
Lithium Bromide Absorbent
Large water ammonia absorption systems are seldom used because of liquid initial cost, overall
complexity, excessive space requirements and large condensing water quantities required.

Water Lithium bromide absorption units utilize two basic factors in producing a refrigeration effect.
1. Water will boil and flash cool itself at low temperature when it is maintained at a high vacuum.
2. Certain substances such as a salt will absorb water vapor lithium bromide solution is a hygroscopic
salt solution which has been found to have the best solubility – vapor pressure relationship to
enable high cycle efficiency.

Boiling point of water at 0.24 inches of Hg ab. In only 39oF (≈ 3.9oC)

83
 The absorption cycle is a two pressure cycle, normally maintaining 45 to 47oF outlet chilled
water 0.27 in Hg ab pressure in the evaporator absorption section and 3.0 in Hg ab in the generator
condenser section. Three circuits are involved water as a refrigerant is pumped to the evaporator.
Lithium bromide as the absorbent is circulated over the absorber tubes, through the heat exchanger
and to the generator.
Cooling water flows in series initially through the absorber tubes and partially through the
condense tubes at about 2/3 of design flow rate. Water to be cooled enters the evaporator (cooler)
tube bundle where it is cooled indirectly by spray water. The water vaporized is absorbed by a strong
solution of lithium bromide at low pressure. The lithium bromide that has absorbed water vapor is
then pumped through the solution heat exchanger to the generator so as to reconstitute the weak
solution low pressure steam (8 to 14 psig) is used in the generator to boil off the water vapor thus
concentrating the salt solution before reentering the absorber. The water boiled off in the generator
then is condensed to a liquid in the condenser section and the condensate is returned to the
evaporator. The limitation in lithium bromide water absorption cycle, if the solution becomes over
concentrated or if excessive non-condensable are present, the absorption cycle will be interrupts
owing to solidification and capacity will not be restores until the unit is de-solidified.
The absorption machine efficiency
Performance ratio = (useful refrigerating effect KJ/Hr)
(Heat input KJ/Hr + Pumping power, kJ/hr)
A performance ratio of single effect VAR is noramlly 0.60 to 0.70.

Lithium Bromide water VAR system:

Absorbent Point 1: The condition of the strong solution in the
HTG
cycle absorber as it starts to absorb Refrigerant.
4 5
Point 2: The condition of the weak solution as it leaves
1500C
HTHE

the absorber and enters the heat exchanger. Line 1-2

1350C represents the decrease in the concentration of the
1200C solution due to absorption of the water vapor from the
CRYSTALLIZATION CURVE

3 6 LTG
1050C evaporator.
LTHE

7 900C Point 3: The condition of the weak solution after it has

2 750C passed through the solution heat exchanger. Line 2-3
1
Absorber 600C represents the heat gained by the solution in the Low
450C Temperature Heat Exchanger.
1 2 3 4 5 6 7
LiBr, 60 55 55 55 57.5 57.5 60
%
Point 4: The condition of the weak solution as it enters
Temp. 48.1
0
41.1 80 136.8 142.5 88.3 86.6 the generator and is being heated. Line 3-4 represents
C
X- axis: LiBr concentration (Wt %) the amount of heat gained by the solution in High
50 52 54 56 58 60 62 64 66 68 Temperature Heat Exchanger..
Point 5: The condition of the strong solution as it leaves the High generator. Line 4-5 represents the
amount of heat required to boil off the water vapors contained in the solution.
Point 6: The condition of the strong solution after it leaves the heat exchanger. Line 5-6 represents the
flow of solution from the generator to the heat exchanger without change in concentration.
Point 7: The condition of the strong solution as it leaves the Low Temperature generator. Line 6-7
represents the heat recovered from water vapors generated in HTG. The solution enters the spray
nozzles of the absorber at the same concentration. Line 7-1 represents the heat further lost by strong
solution before entering into spray nozzles.
The crystallization line indicates the point at which the solution changes from liquid to solid.
Consequently the crystallization line sets the limits of the cycle. If the solution becomes over
concentrated or if excessive non condensable are present the absorption cycle will be interrupted
owing to solidification and capacity will not be restored until the unit is solidified.
84
Capacity Control:

Capacity Control for water- lithium bromide absorption machine can be arranged in one of these three
ways:
1. Throttling of condenser water flow to hold the solution concentration as high as necessary to
produce the refrigerator capacity at the designed chilled water temperature.
2. Throttling the solution flow with a 3-ways diverting valve in the line from the heat exchanger to
the generator.
3. Throttling the steam flow to the generator to vary solution concentration.
Throttling solution flow give lower steam consumption, but the cost of special solution control valves
limits the desirability of thin method condenses water throttling has the disadvantage of higher
cooling water temp at very light flow which accelerate the build up of deposits in the condenser tubes.
So, Throttling of steam flow in the most accepted arrangement

Cooling Water System:

[SHMP + Zn] gives synergic effect for anti corrosion

[HEDP (organic) + poly acrylate] anti scaling
H2SO4 is added to convert CaCO3 which is highly insoluble (and even having reverse solubility
properties with temp) to CaSo4 which is comparatively soluble.
CaCO3 > 10ppm Sludge form
CaSO4 > 2000ppm sludge form

There are 3 layers formed in CWS piping

Inner most layers: Zinc iron phosphate
2nd layers : Zinc phosphate
3rd layers : Calcium phosphate

A minimum of 100ppm ‘Ca’ hardness is essential to maintain the calcium phosphate layer and
otherwise the layers will be eaten away.

85
86
Comparison of COPs and operation parameter for LiBr and NH3 absorption refrigerator
Refrigerator duty = 10×106 Btu/ Hr
Refrigerator temperature = 5.55oC or 42oF
Heating medium = steam condensing at 121oC
Single effect LiBr COP = 0.7179
Ammonia COP = 0.7924
Double effect LiBr COP = 1.0 to 1.2

The Operating Parameter are given below

LiBr NH3
Absorber Pressure 0.133 Psia 70 Psia
Absorber Temperature 111oF / 43.8oC 90oF / 32.2oC
Solution Concentration at 59.5% 53.1%
absorber outlet
Generator outlet concentration 64% 29.4%
Generator Pressure 1.474 Psia 205 Psia
Generator temperature 215oF / 102oC 240oF / 115.5oC
Steam (heat input) 250oF / 121oC 250oF / 121oC

Testing of Vacuum Operated VAR chillers

1. Nitrogen or Soap Test: N2 is charged into the shell side of chiller upto 18 Pascal to 20 Pascal
pressure and soap solution is sprayed.
2. Decay test: The chiller is kept under pressurized condition for 24Hrs by charging tt with N2 up
to 18 Pascal pressure on shell side & pressure drop is noted.
3. Helium spray test: Helium, the next smallest molecule after Hydrogen will leak through very
minute holes. In the test, helium is sprayed on all the joints of the chiller. As the Chiller is
under vacuum, leakage if any will result in the entering of the helium into the Chiller and then
will be be displayed as the screen of helium leak detector.
4 .Helium Strand test: The chiller is fully covered by a polythene sheet and helium is passed from
below to observe the cumulative leak of the entire chiller
5. Hydraulic test: After the chiller passed all the above tests, it is tested for hydraulic test up to
142 Psia pressure on the tube side.

87
 11. ISI CARRIED OUT DURING MTA IN HWP(M)

1. Hardness test : ‘POLDI’ hardness testing

for welded flaw detecting
2. Ultrasonic test
for thickness measurement

3. Eddy current tests for heat exchangers.

4. Metallographic - Crystal lattice examination.

5. Visual inspection.

6. Spring hangers & support.

Towers and vessels material ASTM A516 Cr.70.70 indicates that UTS( Ultimate Testing
Strength) is 70000 Psi and Yielded point: 38000 Psi
Allowable stresses are 17500 Psi
1/4th of UTS (factor of safety)
For bolts & studs allowable stress = 25000 psi
Yield point = 80000 psi
UTS = 100000 psi

Allowable stresses are limited to 25000 psi to avoid SCC.

Torque limits for studs & bolts = T = fLD
f = friction factor = 0.17
L = Bolts load
D = Root dia

Root dia

DD valve seat test pressure = 52 kg/cm2g

Body test = 70 kg/cm2g
Leak rate permitted is 2 ml/(inner dia of disc)(Hr)

88
 12. ELECTRIC MOTORS

Squirrel case induction motor:

Stator is having distributed
winding. When supply is
given to stator, a Rotating
Magnetic Field (RMF) is
induced in stator and revolves
around the Periphery with
synchronous speed. This
RMF cuts the rotor winding
and emf is induced in the
rotor. As the rotor is short
circuited heavy currents flow
in the rotor winding.

The interaction between the RMF and rotor flux will initiate torque and rotates the rotor in the
same direction of RMF.

Slip ring Induction motor:

Because of the variable resistance in rotor

circuit, currents will be limited and p.f will
be improved. So starting torque is improved.
Torque = E2I2cos φ2 .
I2 is induced, cos φ2 is increased and this
increase is dominant.

Synchronous motor:

89
These are not self starting. The rotor/exciter is rotated at a speed nearer to synchronous speed this
external agency. After rotation, DC supply is given. Then, it becomes electromagnet. N & S poles
are generated. Because of this magnetic locking takes place between RMF & exciter and revolves
at constant speed with no slip, Motor run either at synchronous speed or not at all. Dampener
winding is provided to the rotor and short circuited to make rotor self starting and to avoid
dampening.

Variable speed motor:

Either voltage or frequency can be varied or both in combination using thyristor circuit based on
silicon controlled rectifiers to control the speed. (V/f) ratio is maintained to maintain steady flux
generated.

1. Frequency variation (with cyclo-convertor):

2) Voltage variation: 3) Both Voltage & frequency variation:

Cutting made to
reduce voltage

(Change of gate firing angle)

Cutting is done through gate pulse or triggering pulse

Active power = VIcos φ
Reactive power = VIsin φ

DC
AC
E E

Time, t Time, t

With a resistor in the circuit

V & I are
V In phase,
I P.F =1.0

90
With an inductor in the circuit (Inductance will not allow change of current):

V
I Lagging current
For a pure inductor, Ø = 900
Ø

With a capacitor in circuit

V Leading current
I For a pure capacitor, Ø = 900

91
 13. FORMS OF CORROSION

1. Uniform or general attack.

2. Galvanic or two metal corrosion
3. Crevice corrosion
4. Pitting
5. Inter-granular corrosion
6. Selective leaching
7. Erosion corrosion
8. Stress corrosion

Galvanic Corrosion:
A potential difference usually exist between two dissimilar metals when they are
immersed in a corrosive or conductive solution. If these metals are placed in contact or
electrically connected, this potential difference produces electrons flow between them. The less
resistant metal become anode and more resistant metal become cathode.
* EMF series – The potential between metal exposed to solution containing apporox. one gm.
Atomic weight of their respective ion (unit activity) are measured at a constant temp. termed as
EMF series.
* Galvanic series – Since most engineering materials are alloys or galvanic couples usually
include one or two metallic alloys. Under these conditions, galvanic series provides more
accurate prediction these EMF series. The galvanic series has been evaluated based on potential
measurement and galvanic corrosion tests in sea water.

Factors affecting galvanic corrosion:

1. Environmental effects:
 Conductivity of the solution.
 Amount of moisture.
2. Distance effects:
 greater attack near junction
 Velocity.
3. Area Effect: Ratio of anode area to cathode area. Large cathode to small anode is unfavorable.
To prevent select the combination of metal as close together in the galvanic series.

Crevice corrosion:
Intense localized corrosion within crevice and other shielded areas on metal surfaces. This
is associated with a small volume of stagnant solution caused by holes, gasket surface and
crevices under bolts and rivet joints. This is some times called gasket corrosion. Contact between
metallic and non metallic surfaces can cause crevice attack as in the gasket. To function as a
corrosive site, a crevice must be wide enough to permit liquid entry but sufficiently narrow
enough to maintain a stagnant zone.

92
Mechanism:
M M+ + e- (anodic)
O2 + 2 H2O + 4 e- 4 OH- (cathodic)
Once if O2 is depleted, as dissolution M continues to generate more M+, it reacts with chloride
ions in the crevice forming metal chloride within the crevice.
M+ Cl- + H2O → M OH + H+ Cl-
The presence of H+, Cl- increases dissolution rate of “M” leading to auto catalytic process.

Pitting:
Pitting is a form of extremely localized attack that results in holes in the metal.
Auto catalytic nature of pitting:
M → M+ + e-
O2 + 2H2O + 4 e- → 4OH-
M+ + Cl- → M+ Cl- (+H2O)
→ MOH + H+ Cl-
Intergranular corrosion:
Localized attack at and adjacent to grain boundaries with relatively little corrosion of the
grains is intergranular corrosion. The alloy disintegrates (grains fallout) or loses its strength.
Intergranular corrosion can be caused by impurities at the grain boundaries, enrichment of one of
the alloying elements or depletion of one of these elements at the grain boundary areas.
Intergranular corrosion can be associated with welded structure; the material attacked
intergranually is called weld decay.

Selective Leaching: Selective leaching is the removal of one element from a solid alloy by
corrosion process. The most common example is the selective removal of zinc in brass
(dezincification).

Erosion corrosion: The acceleration or increase in rate of deterioration or attack on a metal

because of relative movement between the corrosion field and the metal surface.

Stress Corrosion Cracking: SCC refers cracking caused by simultaneous presence of tensile stress
and a specific corrosive medium. Ex. Season cracking of brass, caustic embattlement.

93
 14. SAFETY

1. Toxicity depends on LC-50 (medium lethal concentration by inhalation route, mg/lit inhalator
in test animals).
Extremely toxic < 0.5 mg/lt
Highly toxic 0.5 to 2.0 mg/lt
Toxic 2.0 – 10.0 mg/lt
For H2S, LC-50 444 ppm (0.618 mg/lit)
For SO2 : LC-50 2520 ppm
For Cl2, LC-50 137 ppm (1 hr)

2. Flammability:
Flammable gases which at 200C and at standard pressure of 101.3 KPa are (a) ignitable when in a
mixture of 13 % or less by volume with air, or (b) have a flammable range with air of at least 12
% points regardless of the lower flammable limits.

Extremely flammable liquids: Chemicals which have flash point lower than or equal to 230C
and initial boiling point less than 350C.

Very highly flammable liquids: Chemicals which have flash point lower than or equal to 230C
and initial boiling point higher than 350C.

Highly flammable liquids: Chemicals which have flash point lower than or equal to 600C but
higher than 230C.

Flammable liquids: Chemicals which have flash point lower than or equal to 600C but higher
than 900C.

Variation of LEL and UEL with temperature and pressure

a) Increasing the temperature reduces the Lower Explosion Limit (LEL) and raises the upper
explosion limit (UEL)
b) Decreasing the temperature increases LEL and reduces UEL.
c) LEL is generally insensitive to changes in pressure except when they are well below
atmosphere. (LEL comes down).
d) UEL is unaffected by sub-atmospheric pressures but broadens as the pressure increases.

3. H2S Properties:
Boiling Point - 60.4oC
Melting point - 85.5oC
Density of liquid 993 kg/M3
Density of gas at 30oC 1.387 kg/M3
Auto ignition temp. 260oC
Flammable limits 4.3% to 46%

94
4. TLV, STEL & IDLH of H2S, Cl2 & SO2:

H2S Cl2 SO2

TLV, ppm 10 ppm 0.5 ppm 2.0 ppm
STEL 15 ppm 1 ppm 5 ppm
IDLH 300 ppm --- ---

5. Threshold limits for H2S, Cl2 & SO2:

H2S Cl2 SO2
Identification & notification of hazards 5 Te 10 Te 15 Te
Safety reports, emergency preparedness 50 Te 25 Te 200 Te

6. Limits for presence in ambient air

H2S = 6.9 μg/M3, SO2 = 80 μg/M3

7. Smell of H2S can be noticed at 0.02 ppm and smell is fairly strong at 0.3 ppm.
At >100 ppm, it causes paralysis of the Olfectory (smelling) nerve and the odor is not felt
thereafter.

8. Toxic effects:
a) Hyper acute  1000 ppm = Lethal within a breath or two
b) Acute  500 to 1000 ppm = 15-30 min. death
c) Sub acute  100 – 500 ppm = within 24 – 48 hrs. death
d) Chronic effects  50 -100 ppm = 90 days – Hyper tension, bronchitis, fatigue

9. H2S inhaled is oxidized to non-toxic sulphates. If O2 is less and H2S is more, it reacts with
metal ion containing proteins of blood thereby ceasing the oxidative metabolism process.
10. Central nervous system depression.

860 0.1 mins – 0.5 mins

H2S conc., ppm

0.5 mins – 10 mins

500

10 mins – 60 mins
290
Threshold for CNS depression
180

Exposure time (mins)

11. Density of liquid Cl2 = 1468 kg/M3
Density of Cl2 gas = 3.2 kg/M3
95
At 0oC & 1 atm, 1 vol. of liquid Cl2 = 457.6 volume of gaseous Cl2

96
Radiation:
Ionising Radiation: alpha, beta, gamma, X, neutrons
Non Ionising radiation : Ultra violet, microwaves
The penetrating capability of the radiation
Cardboard Aluminium Lead Concrete

Alpha ----------------
----------------
Beta
----------------
----------------
Gamma, X-ray ----------------
----------------
Neutrons ----------------

Ultra violet radiation can be cutoff by ordinary glass or spectacles.

Natural Radiation:
Besides manmade radiation we have continuously been subjected to natural or back ground
radiation from:
1. Cosmic radiation – depend upon latitude and height.
2. Naturally occurring radioactive materials present in the earth (uranium & thorium along with
their radioactive decay products like radon, thoron and their daughter products)
3. Radioactive elements present in our bodies (potassium 40, carbon 14 and tritium)
The estimated annual exposure of mass to natural radiation source is 2.5 milli sievert (2.5 mS –
250 m rem)
Radiation Exposure Significance
(mSv)
0.01 Avg. annual dose from radioactive waste
0.1 25 hr jet journey at cruising speed
0.2 Chest X-ray – single exposure
1–2 Avg. annual dose for radiation worker dose limit for public
2 Manmographic examination/ Lumber spine x-ray
2–5 Natural background radiation per year
10 Barium enema (including fluoroscopy)
20 Avg. annual dose limit for radiation worker
500 dose limit for skin & extremities

Effects or radiation
Dose, mSv Effects
Upto 2.5 Natural radiation in 1 year
1 Annual dose limit for individual member of the public
20 Annual dose limit for radiation worker
Up to 500 First identifiable sign of radiation affects appear - vomiting
1000 Radiation sickness appears
2000 Threshold dose for mortality death may occur from radiation sickness
3500 – 5000 50% of exposed persons will die of radiation sickness in 60 days

97
 15. XU-II BOOSTER SEAL

Borsig boosters are provided with Trapped bushing seal for positive gas sealing, which is a non-
contacting liquid seal manufactured under a license agreement with Allis Chalmers.
In static condition of the machine, the seal oil, which is supplied to the seal with excess pressure
over the gas, gets divided into three parts in the seal. The first part, which is 0.3% of total seal oil
supply, flows through the slit between the HP floating ring and the packing sleeve to the seal oil
drain tank (sour oil). The second part, which is 20% of total seal oil supply, flows through the slit
between LP floating ring and the packing sleeve to the atmospheric seal oil drain and this flow
98
depends on the pressure in the casing. The third part, which ~80% of the total seal oil supply,
flows through seal chamber for seal cooling and returns back to the seal oil reservoir.
In dynamic condition, the flow routes of the seal oil are the same as during static condition except
for the route on the gas side. While operating normally, the trapped section of the trapped
bushing seal performs like a pump. During dynamic condition, the sealant buffering the process
gas is whirled by the trapped portion of the seal, which consists of two principal parts: (a) the step
within the stepped dual bushing works in combination with the outer shoulder on the rotating
impeller as a pump (commonly known as pumping bush), to ensure that entire clearance area
between the inner portion of the stepped dual bushing and the impeller is at a positive pressure
level with respect to the gas. (HP floating ring clearance area). Pressure patterns in this clearance
area are similar to those in a lightly loaded journal bearing. (b) The portion of the stator that
meshes with the inner portion of the TBS acts as a dead-end pump, also known as “non-admission
pump” (also commonly known as “de-pumping bush”) . The pumping action of this dead-end
pump just balances the head of the pumping action of the “pumping bush” plus the head due to
the level maintained in S/O overhead tank. Hence there is no pressure differential across the
clearance area between HP floating ring and TBS and because of this, sour oil generation during
dynamic condition is minimum.

99
 16. MISCELLANEOUS

Carnot cycle:

1 Q1

4
Wp
WE
P
2
3
Q2
V
The ideal refrigerator operates on Carnot cycle. It is reversible cycle and consists of the
following steps:
1-2: Adiabatic compression (Isentropic due to reversible character)
2-3: Isothermal rejection of heat at high temperature
3-4: Adiabatic expansion
4-1: Isothermal addition of heat at low temperature
The carnot cycle is an unattainable ideal which serves as a standard of comparison and it
provides a convenient guide to the temperatures that should be maintained to achieve maximum
effectiveness.

Rankine cycle:

QH Although the Carnot cycle has the

maximum possible efficiency for the given
limits of temperature it is not suitable in
steam power plants.
The reversible adiabatic expansion in
the turbine, the constant temperature heat
Win Wout
rejection in the condenser and the reversible
adiabatic compression in the pump are
similar for both Rankine and Carnot cycles.
But whereas the heat addition process
in Rankine cycle is reversible and at a
QL constant pressure in carnot cycle it is
reversible and isothermal.

ɳ carnot > ɳ rankine

1st law efficiency = Output / Input
2nd law efficiency = (Minimum energy intake to perform the given task) / (Actual energy intake to
perform the given task) = Amin / A, (A = available energy or energy)

100
Availability in Chemical Reactions:

1. If the system is in temperature equilibrium with the surroundings before and after process, the
max. work obtainable during a change of state is given by:
Wmax = E1 – E2 – To (S1 – S2)
= {U1 + (m*V12/2) + (m*g*z1)} – { U2 + (m*V22/2) + (m*g*z2)} - To (S1 – S2)
If KE and PE changes are neglected, Wmax = U1 – U2 – To (S1 – S2)
Say, T1 = T2 = To = T, then (WT)max = (U1 – U2) – T (S1 – S2),
F = U – TS, F is defined as Helmholty function
WT ≤ (F1 – F2)
(WT)max = (F1 – F2)T
The max work is done when the process is reversible and equality sign holds. If the process is
irreversible the work is less than the maximum.

2. If both pressure & temp are on equilibrium with the surroundings before and after the process.
When the volume of the system increases, some work is done by the system against the
surroundings (Pdv work)
(Wn)max = A1 – A2
= (U1 – U2) + P0 ( V1 – V2) – To (S1 – S2)
Say, P1 = P2= P0 = P and T1 = T2 = T0 = T
Then, (Wn)max = (U1 – U2)P,T + P(V1 – V2)PT – T (S1 – S2)PT
Gibb’s function: G is defined as
G = H – TS
= U + PV – TS
(G1 – G2)PT = (U1 – U2)P,T + P(V1 – V2)PT – T (S1 – S2)PT
(Wn)max = (G1 – G2)P,T
(Wn)max ≤ (G1 – G2)PT

The decrease in Gibb’s function of a system sets an upper limit to the work that can be performed,
exclusive of Pdv work in any process between two equilibrium system at the same temp and
pressure.
Standard Gibbs function change is ∆G0 = -R T ln(k)

101
Losses in a Centrifugal Pump:

Theoretical head
Head reduction due to
circulatory flow

Actual head Friction losses

Shock losses

Q, flow

102
Integrity/Residual Life Assessment:

Basic Approach:
a. Identification of components for analysis based on process condition, previous operation
history, susceptibility to corrosion, erosion, fatigue etc.
b. Identification of highly stressed components/location due to sustained loads, thermal
stresses/cycling, wind, seismic vibration etc.
c. Metallographic study of stressed components, assessment of mechanical properties and
micro-structural changes due to exposure to process conditions.
d. On line fatigue monitoring of selected locations for estimation of cumulative damage
fraction.
e. Calculation of crack growth rate.

Artificial Intelligence:
Artificial Intelligence falls into three categories:
a) Expert systems
b) Natural Language Processing
c) Robotics
Expert systems try to duplicate human experts and are knowledge based. They are also
called as knowledge systems.
Natural Language processing is concerned with developing computer programmes that can
understand simple commands in natural language as people use every day.
Robotics is concerned with developing visual and tactile programme that allow robots to
perform in a changing environment.
Hazard due to H2S

H2S is a potent inhibitor of cytochrome oxidase (enzyme). It inhibits the enzyme by

binding iron and the oxido-reduction processes are blocked and this inhibitor of cytochrome
enzyme which is essential for cellular respiration may lead to histotoxic hypoxia.
Haemoglobin: Haemoglobin is made up of an Iron Porphyrin compound. Haemo associated with a
protein globin. The most important property of haemoglobin is its ability to readily form a
complex with oxygen when exposed to high oxygen tensions and to dissociate equally readily and
part with the oxygen when exposed to low oxygen tensions in the medium. The oxygen is only
held loosely to the haemo molecule by a redistribution of changes in the molecule. It is hence
called Oxygenation as distinct from oxidation. Oxygen is not reacting with Haemoglobin and
there is no valancy change from ferrous to ferric in haemoglobin and it acts as a carrier of oxygen.

M V M V
103
 CC C C

N M M N M
M
N N Fe N N Fe

P NN V P V

C C C C

P M P M
Globin Globin
Reduced Oxygenated

Structure of Haemoglobin:

M-Methyl group; P- Propionic group; V-Vinyl group.

Cytochrome oxidase:

Cytochrome oxidase is an enzyme which catalysis the oxidative phosphorillation.

Oxydative Phosphorillation:

Aerobic respiration requires atmospheric oxygen. It takes place in presence of oxygen.

During aerobic respiration, respiratory substrata are completely to be oxidized. A large amount of
energy is released out.

Aerobic respiration is represented by;

C6H12O6 + 6O2→ 6CO2 + 6H2O + 674 Kcal.

(Glucose)

When H2S is inhaled it enters into the lungs and diffuses in to the blood. Human being
blood pH is 7.4. When H2S is dissolved in the blood, some part of H2S is dissociated according to
the following reaction
H2S → HS- + H+

Based on the pH of the blood 72% H2S dissociates in the blood. Remaining 28% presents
in the form of un-dissociated H2S. This un-dissociated H2S is caused by haemoglobin by loosely
bounding with it but there is no section and no valiancy change in the heave of haemoglobin.
When the un-dissociated H2S enters the tissue the cytochrome oxidase gets inhibited.

In the brain cells, the internal cellular respiration should be carried continuously without
any interruption once the respiration is stopped energy is also not released for metabolic activities.
Because of H2S inhibition on the respiratory chain man loses sense of smell at 100 ppm H2S conc.
As the conc. increases further, the vital functions like sense of smell, sense of vision gets affected.
At high concentration due to inhibition of cytochrome oxidase the respiratory chain reactions

104
stops and cell death occurs which is irreversible. Hence, Oxygen is to be supplied to the brain
cells within 3 minutes. Oxygen dissociates H2S and it saves the person from irreversible cell
death.

H2S is causing toxic effects on the internal cellular tissues by inhibiting the cellular
respiration. Hence, it is called as histo-toxic. It also reduces the Oxygen carrying capacity of
haemoglobin to the internal tissue causing hypoxia. Hence, the overall effect of H2S on human
being is named as histo-toxic hypoxic.

105
A1& A2:

21oC 38oC
CT HT
Chiller

130oC 85 70oC
Cooler
160oC

115oC

RX

PPX
70oC
130oC
R R

Cold towerHot tower

78 Top most 130oC

68 (Heat of dissolution)

Tray Tray
160oC

14 18th
70oC

30oC Temp 130oC temp

Cold tower Hot tower

150ppm
78

(MC)
Conc .comes down

Tray Tray
due to dissolution

190ppm
(MC)
34

150ppm conc 600ppm 125ppm 152ppm conc 600

106
 30oC
1 CT3 HT3 2HT 2CT
30 30o 130 130
21oC C
21oC
Chiller

33oC 35oC Chiller

33.8 35
Cooler
86o
Cooler
36.5

C
160oC 70oC
PPX
Rx
R 130o
115o C R
C

107
 3CT 3HT
chillerr 180oC
34o
C Chiller 21o
35 C
Cooler
32oC 111o PPX
C T
o R
Chiller R 70 C
35o 111o 180o
C 12
82o C RX C
3CT 70oC 82oC 8
35oC C 118o 70oC
feed
Joining 2HT feed line 2Ct trays C PPX
cooler
130oC

108
Various types of FTs:
1. ∆P transmitter.

2. Turbine flow meter

3. Integral flow meter

4. Pitot tube

5. Annubar

6. Magnetic flow meter

7. Ultrasonic flow meter

8. Target flow meter – DM Plant vacuum pumps set with FT

D D/2

F = CDA F α

∆P is calibrated against flow

Turbine flow meter
Fluid passes thro a turbine, flow is calibrated against flow using number of rotations. A
magnet with coil is provided externally which senses the rotations, whenever the blade comes
nears the magnet it cuts the magnetic flux.
Integral flow meter:
For small sized pipe lines, tapings are taken just in the U/S & D/S of the orifice against
sensor ∆P
Annubar: Basically measures velocity.
P2
=
P
P 1

Q = A-V1 =
Magnetic Flow Meter: e= BDV circuit
N

Magnetic flux
S
109
 Velocity
Emf = B d V Circuit
Distance between electrons
The fluid enters the magnetic flux and the electron horizontally will create emf. Emf
is calibrated against flow No pressure drop.
Ultrasonic
C S1

V
d
Target flow meter:
There is a disk in the fluid flow line depending on the flow the disk rotates which in turn
creates torque. There is a mechanical linkage between disk and flow indication.
LTs
1. Impulse type
Based on ΔP
2. Wafers type Principle

ΔP = level x density
All transmitters have silicone oil with diaphragm. Electrodes

Purge type:
Used for BAT,1&2, BCT,1&2 in DM plant
F.R Diaphragms

Rotameter

Air minimum flow

PT: ΔP principle other end is sealed with atmospheric Pressure.
Temperature sensor:
RTD → Temp variation is reflected in resistance.
Thermo couple → mV generated α Temp.
Two metal alloys are connected together & exposed to the temp.

110
For cold towers, the over all deuterium balance is
F (XP – XF) = G (YP – YF) – (1)
The material balance above stage n
= F (XC(n-1) – XF = G (Ycn – YF) – (2)

Ycn = YF + (XC(n-1) – XF)

As per equation 1

Ycn = YF + (Xc(n-1) – XF)

This is the equation for the operating line in the cold tower, which passes through the points
(XF – YF) are (XP – YP) as the slope

=
In that tower, the equation for the operating line is

Yhn = YF + (Xh(n+1) – Xw)

Yhn = YF + ( ) (Xh(n+1) – Xw)

The line passes thro’ the points (XW ,YF) and (XP , YP)
The minimum number of stages for the separation or the maximum production rate for a
given no. of stages is realized when two conditions are satisfied.
1. The approach to equilibrium at the top of the cold tower equals that at the bottom of hot.

2. The ratio of the slope of the equilibrium line to the slope of the operating line in the hot tower
equals the ratio of the slope of the operating line to the slope of the equilibrium line in the
cold tower.

= BC = = XF

(L/G)n (L/G)h = G2 = L2 BG BC

GL = L = :

XF - XW =
The min. value of gas flow rate required to achieve designed separation is

(G/PXP)mn =

= ≈ 72005

111
 Off-Site Emergency
Exclusion Zone: 1.6 KM
Sterilization Zone: 5.0 KM
With the worst condition of the accidental H2S releases taking into consideration, the
max. GLC of H2Sis arrived to be 10.6 ppm at 5 KM radius, with the values falling off further
along with distance. The emergency plan is therefore prepared to protect population within 5
KM only.
S.No. Intervention levels for H2S Protective Measures
01 2 ppm for 4 Hrs. Alert
02 5 ppm for 1 Hr. Rush to nearest available
shelter/building
03 10 ppm Cover the mouth and nose
with wet cloth and mere
away from prevailing wind
direction
The immediate response to off site emergency comes to the local designated group
called “Off Site Emergency Response Coordination Committee” (OERCC). This is under the
direct control of District Collector, Khammam.
Zone of Operation: For ease of operation and control the region around the plant up to a
distance of 5 KM shall be divided in to 16 sectors and 3 zones. Depending upon the
prevailing wind direction at the time of emergency and the asserted extent of H2S release, the
protective measures shall be implemented in the sector down wind up to a distance of 5 KM.
S. No Source Release scenario Duration for GLC at distance of
strength release 1.5 Km 4.5 Km
(ppm) (ppm)
1 0.5 Te/Hr Failure of gas booster seal 30 min 19.6 4.07
2 1.5 Te/Hr Failure of impulse line 30 min 58.7 12.2
fittings
3 90 Te/Hr From plane stack 30 min 13.5 7.5
4 0.5 Te/Hr Scenario (1) & (3) occurs 30 min 19.5 7.7
& simultaneously
90 Te/Hr
5 150 Kg Failure of 3” line on the Instant 125 9.28
D/S of main inner valve
6 75 Kg Steam failure to waste 5 min 35.2 7.3
stripper

GLC are based on PASQUILL GIFFORD MODEL

112
 SOTP
The annual sour oil generated in both the Exchange Units is estimated to be about 400
m3 and the treatment of the sour oil will lead to annual saving of 360 m3 of Turbinol oil
amounting to net financial benefit of about Rs.100 lakh/annum.
Process:
 Nitrogen purging at a temp. of 120oC to strip off H2S from the contaminated oil
charge to the order of 5.0 ppm.

 Contacting/mixing of copper powder @1% of oil charge by weight at 120oC to form

insoluble solids by reacting with dissolved H2S/sulfur.

H2S + Cu → CuS + H2
 Settling of the solid reaction products & then decantation of the purified oil.

 Filtration by filter media [(10µ)filter] to remove the reacted/un-reacted un-dissolved

solids, formed by the mix of copper powder.

The process removes sulfur/H2S, oil mercaptans

Cu corrosion test:
RBoT: Rotating Bomb Oxidation Test – to test for the life time of the oil for
oxidation.
TAN: Total acid no. mg/KOH/gm of oil.

113
 LP vent
header Cal<2ppm

Sour oil from XU 1,2

40 drum 8m3 Buffered
4 hrs heating & N2

Buffered

0.8m3/l
d
purging

Stripper

Reclaimed oil

Intermediate storage
LP N2 consumption = 60 Nm3/Hr for 0.8m3/Hr of feed tank
N2
purging

114
 Comparison of various process:
10
H2-CH3 NH2
9
H2-NH3
8
7
H2-H2O
β 6
5
4
H2S-H2O
3
2
1
-75 C 0 C 100oC 450oK (177oC)
o o

Temperature OK
GS Amive NH3/H2 H2O/H2
Pressure MPa 2 7 7 10
Temp oK 303/400 220/315 230/330 300/440
Catalyst --- CH3NHK NH2K Pt/C
-1
Rate constant 5 (at cold temp) 5000 130 15 1
3
Gas solubility mol/ (m . map) 830 24 10 8
Henry’s const(Map.m3/mol) 1/830 1/24 1/10 1/8

In simple terms the tower volume is given by

Volume = GRTN/(PKGa)
G = Gas Flow moles/sec. R : gas const. (Mpa M3 mole K)
T = Temp K; N = No. of theoretical plates
P = Pr. in MPa ; KG = over all mass transfer coefficient m/s2
A = interfacial area per unit volume (m3/m3)
The overall mass transfer coefficient can be related to the gas phase mass transfer coefficient
KG by

= +
Where H – Henry’s law constant (Mpa m3/mol)
For a soluble gas like H2S the value of H is small and the gas phase resistance is important and possibly
controlling.
Process comparison:
11
7 NH3/H3 mono thermal Electrolysi
s
5
3 Parasitic CECE
CECE
2
(H2/pd absorption)
Seperation1.6 Bi thermal
Amino/H2
H2
factor ratio1.4 NH3/H2 H2O/H2 Dis
(Bc/Bh) 1.2 ECONOM
1.1 GS
IC H2
1.06 Diagram
1.04 UNECONO H2O Distillation
1.02 H2MIC
O
1.01 crystaltsation
1 3 6 10 30 60 100 300 600 1000
Equivalent thermal energy GJ/Kg

115
 GS process requires 30 GJ/Kg of equivalent thermal energy and Bl/Bh = 1.3. GS process has a
lower separation factor and higher energy consumption than six other processes in the economic
region. It is even an undesirable feature of unit hydrogen sulfide which is corrosive and toxic.
YET THE GS PROCESS DOMINATES HEAVY WATER PRODUCTION AND IS STILL THE
PREFERRED METHOD OF PRODUCTION, Why?
 GS process uses an abundant feed and therefore enjoys the advantage of large scale.

 While the GS processes are expensive they are not too excessive.

 GS process enjoys fast mass transfer rates.

 GS process pressure is not high enough to incur a large cost penalty.

 While the GS process separation factor is not as high as the other processes, it is reasonable.

 The temperature which controls GS process energy input is moderate. Whereas the other
require (mainly H2 distillation and amine-H2) require expensive refrigeration.

 GS is process in independent, not dependent on any other units, hence optimum conditions can
be achieved. Unlike the other process where they are dependent on other fertilizer units.

116
Why Sulfur Precipitates in cold towers:
H2S reacts with the dissolved oxygen in the feed water and forms sulfur.
2H2S + O2→ 2S + 2H2O
The formed sulfur is insoluble in water and denser than water at tries to settle down in cold
tower. At the same time maximum of molten sulfur is carried to hot tower and from hot tower it goes
to waste stripper.
In waster stripper (vapor pr. 4.3 mm Hg) due to high temperature, sulfur partially vaporizes
(vapor pressure of sulfur at 185oC is 1 mm Hg and at 223oC is 5 mm Hg). This partially vaporized
sulfur again goes back to hot tower (vapor pr. 1.3 mm Hg) through O/H gas lines.
It is again carried to cold tower bottom thro’ gas inlet to cold tower and this is in cyclic process.
In cold tower partially molten sulfur settles down and remaining goes to the next stage of cold tower
(2CT). And here as 2CT and 3CT are dead ends, sulfur settles in 2CT and 3CT at the high quantities.
Critical temperature of H2S : 100.4oC
Cirtical pressure of H2S : 88.9 atm.

117
Breathing Air Quality:
Relative Humidity = 30-50%
CO = 5 ppm (max.)
CO2 = 500 ppm (max)
SO2 = 0.05 ppm (max)
H2S = 0.05 ppm (max)
Oil & Other matter = 5 mg/m3
PTP
Purpose: Removal of Impurities like Na2S and Na2SO4.
Feed Composition (Feed to PTP)
Na2SO4 : 10% w/w
Total sulphides as Na2S : 3.0% w/w (present value <1% w/w)
Water insoluble : 0.035% w/w
Cl-as NaCl : 0.059% w/w
Fe, Al compounds : 0.07% w/w
Sodium Hydro sulphides as NaHS : 0.3533% w/w
Excess alkali (as Na2CO3) : 0.283% w/w
Reducing compounds other than
Na2S, NaHS as Na2S2O3 : 0.283% w/w
1. Acid dosing

Na2S + H2SO4→ Na2SO4 + H2S

Na2S2O3 + H2SO4→ Na2SO4 + SO2 + S + H2O
Na2CO3 + H2SO4→ Na2SO4 + CO2 + H2O
Acid dosing is done to attain a pH of 1.5 (to ensure completion of above reactions)
2. Steam stripping: LP steam is fed directly to reactor vessel till solution temp. reaches 90oC steam
consumption is 0.5 Te/batch

3. N2 purging for 10-15 min.

4. The gases produced during acid dosing and steam stripping is taken to the absorber column, via
a cyclone separator. Liquid will come back to reaction vessel. Gases go to absorber column
thro’ a cooler.

H2S + 2NaOH → Na2S + 2H2O

Absorber column is a packed tower with 316L pall rings.
5. Addition of alkali to maintain a pH of 8.0

Evaporation Unit:
Na2SO4 conc. rise from 10% to 25% w/w → Sp.gravity 1.22
No. of effects → 2
Feed rate → 2500 Kg/Hr
Solids in feed → 10%
Inlet temp of feed → 30-60oC
Water evaporation rate → 1500 Kg/Hr
Concentration output (25% w/w) = 2500 – 1500 = 1000 Kg/Hr
Steam consumption = 600 Kg/Hr

118
 Vacuum maintained = 160 mm Hg (abs)/-600 mm Hg g
Economy = No. of Kgs. of water evaporated/Kg. of steam fed
= 1500/600 = 2.5
In a single effect evaporator economy is always < 1.0
Process: The temp of the 10% solution is increased in preheater-1, preheater-2 and preheater-3. The
preheated solution comes to calandria-1 (tube side). LP steam is taken in the shell side of Cal-1. Here
an evaporation rate of 7% takes place.
The concentrated solution from Cal-1 is sent to Cal-2 for further evaporation.
The water vapor separated in Vapor separator- 1 (after Cal-1) is supplied to Cal-2, shell side on heating
media. Here th conc. of solution is brought up to 25% and it goes to CFHT. The vapor produced in
Cal-2 gets separated in vapor separator-2 is used as heating reduce in PH-1.
PH-2 & PH-3 are connected with the shell side of Cal-2 and Cal-1 respectively to get their heating
medium.
All the Vapors are condensed in the condenser. This joins with the condensate of the pre heaters and
calandrias and gets pumped to the drain.
Method of steam economy is by recompressing the vapor from the evaporator and feeding them back in
to the steam chest of an appropriate evaporator effect. Mech. Compression or steam jet ejection may
be used.
In the case of steam jet ejection a High Pr. steam (LP steam only) is used to entrain and compress the
major part of the vapors. Some of the vapors are separately condensed to compensate for the motive
steam added.
In our plant, steam jet ejection is used. It is provided if the steam I/L of Cal-1 to have better steam
economy.
Falling film evaporation:
1. High heat transfer coefficients even at low boiling temps.

2. No problems of hydrostatic heads.

3. Problem is with feed distribution. Distributors are provided in our E.U.

119
Spray Drier Unit:
Vacuum → -40 mm Hg.
Feed rate → 1000 Kg/hr at 80oC
Water evaporation → 750 Kg/Hr
Powder production → 1000-750 = 250 Kg/Hr
Powder production per day → 250 <1U = 6 Te/day
Moisture in powder → 0.5% (max.)
Inlet air temp → 500oC
LDO consumption → 70 Kg/Hr.
Max. Powder emission level in stack → 100 mg/M3 of air
Na2SO4 Powder Specification:
Na2SO4 = 98%
Water Insolubles = 0.5%
Moisture (max.) = 0.5%
-
Cl as NaCl = 2.0%
Iron as Fe (max) = 0.002%
Fe, Al & Cr. Compounds = 0.02%
pH of (10% soln) = 7.5 – 8.0
Interlocks: Set Point Function
o
1. O/L air temp. high 140 C Alarm

2. O/L air temp. very high 160oC trip of burner

3. O/L air temp low 135oC Alarm

4. O/L air temp. very low 120oC Trip of feed pump

5. Atomizer lube oil level low 30% in oiler Alarm

Drying: Transfer of liquid from a wet solid into an unsaturated gas phase.
Hot air enters at the top of drying chamber flow down co-currently with the droplets (Atomized feed)
being dried (Rotary disc atomizer). As the atomized droplets fall, the moisture evaporates into the hot
air, leaving the solid material as dry and cooled particles. Larger particles fall to the bottom of the
drier. Smaller particles go along with the air to a cyclone separator.
Atomizer: Atomizers is of Centrifugal disc type. Centrifugal atomizer produces an extremely uniform
droplet size and does not require a high pressure feed. Centrifugal atomizers are also less effected by
the variations in the feed properties, such as amount of solids, viscosity or even by variation is feed
flow rate.
Air Burner: Inlet oil Pressure = 21 Kg/cm2g
Back pressure, initially = 3 kg/cm2g in steps to be increased to 11 kg/cm2g
Back pressure (LDO return line from burner to tank) = 11 kg/cm2g
The o/l air temp of burner = 500oC
o/l air temp from drying chamber = 140oC
RPM of feed pump = 900 rpm
Supply L.D.O. temp = 40oC

Eddy current coupling: (SDP feed pump)

The coupling has two shaft extensions one shaft which operates at constant speed, is connected
to the motor, while the other shaft providing the adjustable spread out put is connected to the load.

120
 The input, output members are mechanically independent, with the output magnet member is
revolving fully within the input ring or drum member. An air gap separates the two members and a
pair of antifriction bearings maintain their proper relative position.

Magnet member (output member) Input member

Load Motor
(pump)

Tachometer

Speed control mechanism

The magnet member has a field winding which is excited by direct current, usually from a static
power supply.

Application of this field current to the magnet induces eddy currents in the ring. The interaction
between these eddy currents and magnetic flux develops a tangential force tending to turn the magnet
in the same direction as the rotating ring. The net force results in a torque available at the out put shaft
for driving a load.

An increase or decrease in field current will change the value of torque developed thereby
allowing adjustment of the load speed.

121
Simplified Evaporation unit flow sheet:

Condenser

Vacuum
Steam
CAL-1 CAL-2 P.H

VS-1 VS-2

Condensate
Feed

Concentrate

Spray drier:

Feed
Atomizer
Vent

hot
air Vent
500oC
Main cyclar Exhaust fan

Absorber
Cooling converges
Rotary valve fan
Bagge’s
Cyclar

Atmospheric air

Rotary valve

122
Materials of Seals:

Stellite: It is a good working material with a corrosion resistance greater than that of the 300 sewer S.S.

Composition of stellite: Chromium, Cobalt with small % of Nickel, Iron & Tungsten. Stellite is not
recommended for use in water because the water has a tendency to leach out cobalt.

Tungsten Carbide: Seal faces of tungsten carbide possess qualities of superior hardness, Wide range of
chemical inertness and excellent antifriction properties. It is undoubtedly most versatile material. But
its cost is high. Its high modulus of elasticity is a valuable asset in preventing face distortion.

O-ring – Viton – Fluro Carbon Rubber (0oF to 400oF)

Max tolerance of surface finish for a proper seal face

Performance = 3 light bends

= 3 x 11.6 (µ inches)
= 34.8 micro inches.

Rotation part of a seal : Tungsten Carbide.

Stationary point : Graphite

If same material is used for both, it will be subjected to galling effect.

(Molecular adhesiveness, forces will stick to each other)

123
Reactors:

Ideal steady state flow reactors:

01. Plug flow reactor.
02. Mixed reactor for continuous flow stirred tank reactor.

01. Plug Flow Reactor:

Reactants

Product

It is characterized by the fact that the flow of fluid thro’ the reactor is orderly with no element
of fluid overtaking or mixing with any other element ahead or behind.

The necessary and sufficient condition for plug flow is the residence time in the reactor to be
the same for all elements of fluid.

2. CFSTR: It is a reactor in which the contents are well stirred and uniform throughout thus the exit
stream from the reactor has the same composition as the fluid within the reactor.

Feed

Product

Measure of Performance of Flow Reactors:

Reactors time, is the natural measure of the processing rate in a batch reactor, so, the space
time and space velocity are the measures of flow reactors.
Units

Space time = = (Time)

Space Velocity =S= = (time)-1

Ex. A space velocity of 5 hr-1 means that time reactor volumes of feed at specified conditions are being
fed into the reactor per hour.
A space time of 2 min. means that every two minutes one reactor volume of feed at specified
condition is being treated by the reactor.
For zero order reactions, reactor size is independent of type of flow.
For all the reaction orders, the mixed flow reactor is always larger than the plug flow reactor. The ratio
of volumes of CFSTR to PFR increases with the order.

124
Halon 1301:
Halon has ozone depleting potential. Halon replacing agents should have four desirable
characteristics:
01. Low Global Environmental Impact.

- Low Ozone Depletion Potential

- Low Global Warming Potentials

- Low Atmospheric life time

02. Acceptable toxicity

03. Cleanliness/Volatility

04. Effectiveness

Tyco Inert gas: Inert gas blend of Nitrogen, Argon & CO2 will bring down the O2 level to less than
15% below which combustion cannot occurs. Unlike Halon, Inert gas does not participate in the
combustion process and releases no harmful decomposition products. But the gas blend cannot be
compressed to liquid form, so considerably greater storage area.
Another extinguishing agent:
HFC – 227 EA (FH-280) – chemically known as Hepton fluore propane CF3-CHF-CF3
Comparison of HFC – 227EA & Halon-1301:
HFC-227EA Halon 1301
1 Vap.Pr. at 70oF 59 199
2 Ozone depleting potential 0 16
3 Personnel safety Yes Yes
80% by Physical 100% by chemical
4 Fire extinguishing by effect effect
20% by chemical
effect
5 Global warming effect Low -

125
Refrigeration

R-11 → C Cl3 F
R-12 → CCl2 F2
R-22 → CF3 Cl

Effect of increasing compressor discharge pr. H.P, R.E, C.O.P:

3l 2l
P
3
2

4 1

2l

3l 2

T 3

4 1

Refrigeration effect: RE – (h1-h3)

(Enthalpy of vapor leaving the evaporator BTU/lb minus enthalpy of liquid leaving the condenser
BTU/lb)
Heat of Compression: (h2-h1)
(Enthalpy of vapor at compressor discharge minus the enthalpy of vapor leaving the evaporator)

COP:
If discharge Pressure goes up from the figure R.E comes down C.O.P. comes down Heat of compressor
goes up.

Effect of decreasing the suction pressure:

126
 2
3
P

4 1

2l

T
3

4 1

4l 1l

From the figure Heat of compressor goes up – R.E. and C.O.P decrease.

127
Cooling Water System: .

1. SHMP,
2. HEDP,
3. ZnSO4,
4. Poly Acrylates
5. H2SO4,
6. DM water.

New dosing system:

Composition Base chemical used

1 Meta – PO4 10% w/v SodiumHexa Meta Phosphate (SHMP)
2 Organo-PO4 3% W/V Hydroxy ethylene Diphosphonic Acid (HEDP)
3 Zinc 2% W/V Zinc Sulphate
4 Dispersant 2% W/V Poly Acrylate (MW→10000 to 20000)
5 H2SO4 (98%) 1% V/V H2SO4
6 DM water rest DM water

H2SO4 is added in this formulation to avoid precipitation of Zinc Phosphate. Meta Phosphate is
used against Orthophosphate (present in Agent 565H).

Meta Phosphate →Cathode as well as anodic inhibitor

Organo Phosphate →Anodic Inhibitor
Zn → Cathodic Inhibitor.

MBT and Quaternary Ammonium Halide are used at a frequency of once in 10 days as shock
dosing alternatively at a concentration of 20-30 ppm.

MBT: Methylene-Bis-Thiocyanide CNS-CH2-CNS

Cooling Water Chemistry:

1 pH 6.8 – 7.5
2 Total (Meta+ Ortho) 10 ppm as PO4
3 Organo PO4- 3 ppm
4 FRC 0.2 – 0.5
5 Total Hardness <400 ppm
6 TDS <1500 ppm
7 No. of cycles 3-4
8 Fe <0.5 ppm
9 Zn 2-3 ppm
10 Poly acrylate 2 ppm

Aquat 565H New formulation

--
Meta PO4 % W/V Nil 10%
Ortho PO4 % W/V 9.0 0.3
Org. PO4 % W/V 1.0 3.0
Zn++ % W/V 2.8 2.0
Poly Acrylate - 2.0

128
SO4- - %W/V 0.2 4.7
pH <1.0 1.2
Density gm/cc 1.11 1.11

Failure due to presence of sulfur oxidizing Bacteria:

Due to presence of dissolved oxygen, H2S reacts with oxygen to form sulfur.
2H2S + O2→ 2S + 2H2O
Then in the presence of sulfur oxidizing bacteria, we get
2S + 3O2 + 2H2O → 2H2SO4
This H2SO4 gives ferric sulfate by interaction with base metal and due to acidic nature the attack will
continue resulting in failure of material.

129
For a fatal accident man days lost = 6000
Safety

01. Frequency Rate (FR) =

02. Severity Rate (SR) =

03. Injury Index (I I) =

Min. Energy for H2S Ignition = 0.068 milli joules

130
 H2S Generation Unit:

Na2S Composition:

Na2S 58-60%
Na2CO3 0.5%
NaOH 0.5%
Na2S2O3 0.25%
NaCl 0.05%
Fe2O3 0.1%

Reactions: 15% 90%

1. Na2S + H2SO4→ Na2SO4 + H2S (Zero order reaction)
2. 2NAHS + H2SO4→Na2SO4 + 2H2S
3. Na2S2O3 + H2SO4→ Na2SO4 + S + SO2 + H2O
4. Na2CO2 + H2SO4→ Na2SO4 + H2O + CO2
5. SO2 + 2H2S → 3S + H2O
6. 3H2S + H2SO4→4S + 4H2O

# Na2SiO3 leads to sulfur precipitation and formation of SO2 leading to lowering of H2S purity.

# Excess acid leads to sulfur precipitation.

Solubility of Na2S → 27.9 gm/100gm at 10oC (21.3% wt)
151.0 gm/100 gm at 90oC (60% wt)

For 1 kg. of H2S, Na2S (15%) required = 15.29 kgs.

H2SO4 (30%) required = 9.6 kg.

For 220 kg/Hr of H2S, we require

Na2S (15%) = 3.36 Te/Hr
H2SO4 (30%) = 2.1 Te/Hr

Length of the reactor = 6.5 Mt

Dia = 2 inches
Na2S 15% → 3.36 Te/Hr
H2SO4 98% → 0.65 Te/Hr
H2O → 1.45 Te/Hr

Per Ton of H2S produced normally 2 kgs of CO2 – 1.5 kg of SO2 and 8 kgs of ‘S’ are produced.

# ‘S’ formation is controlled by keeping Na2S flow in excess to maintain alkali medium.

U-tube is used because straight pipe occupies more space.

H2S scrubber: Raschig ring packed tower
Stripper : Raschig ring packed tower.

K-101 A/B/C – 3 stage – 1st stage double acting 2nd and 3rd stage single acting.
Packing → glass fiber reinforced Teflon
Piston → Aluminum alloy
Piston rings → glass fiber reinforced Teflon

Na2s supply pumps logics: will not start or will trip if running if
131
 a. H2S compressor is not in operation or trips running
b. Na2Sday tank level low
c. Overload.

H2SO4 pumps logic: will not start or trips if running if

a. Compressor is not in operation or tripped

b. Na2S flow low
c. Dilution water flow low
d. Temp. of diluted acid after cooler is too high
e. Neither of Na2S pump is in operation.
f. Overload
K-101 A/B/S Logics:

1. Suction pressure too low

2. Suction pressure is too high
3. Discharge pressure is too high
4. Suction temp. too high
5. Disch. Temp. is too high
6. C.W. flow to compressor too low
7. Lube oil pressure too low
8. Overload

Solubility of Na2SO4 =10% at 10oC. If the concentration of Na2SO4 goes above 10% at 10oC it
crystallizes. This is the basis for taking Na2S conc. to 14%. If H2SO4 is dosed directly (98%)
without dilution, as the flow thro’ the reaction is mixed flow, it becomes vigorous because of
heat of dilution that too the H2S generation reaction is exothermic and reactor vibrates heavily.

Na2S < 14% → large effluents.

Other Processes:

# 2NaHS + H2SO4→ NasSO4 + 2H2S

This is the best method compared to Na2S. Acid consumption becomes half of that of Na2S
process, also effluent generated is half of that of produced in Na2S process.

# FeS + H2SO4→ FeSO4 + H2S

Sludge forms
650oC
# H2 + S H2 S
Alumina Catalyst

Both H2 and S areexplosive. Hence, chances of explosive are more

H2 generation source must be nearer.
Materials:
1. Acid dilute cooler – Karbate 22 (Compound Graphite Impregnated with phenol resin)

a. High corrosion resistance to H2SO4 of all concentration.

b. Good thermal conductivity.

c. High resistance to thermal shock.

132
2. Scrubber CWX shell side → C.W → C.S.

Tube side → process liq. → SS 316

3. Scrubber chiller shell side → Ch.W →C.S. → SS 316

Tube side→ process liq. → SS 316

4. Stripper Cooler shell side → C.W → C.S.

Tube side → process liq. → 2RK65

5. H2S C.W.X shell side → H2S Gen. → SS 316

Tube side → C.W. → C.S.

6. H2S Chiller shell side → H2S Gen. → SS 316

Tube side → Ch.W. → C.S.

7. Separator → 2 RK 6.5 (B-625 or alloy 20)

8. K.O. Drum→ A516 gr. 70

9. H2S bullets → A516 gr.70

10. Stripper → 2 RK 65 (B-625)

11. Scrubber → 2 RK 65 (B-625)

2RK-65 → Cr: 19%; Ni: 25%; Mo:4.5%; Cu: 1.5%; C: 0.02%; Fe: Rest.

K-101 A/B/S Normal (150 NM3/Hr : 220 Kg/Hr)

1.4 abs → 5 kg/cm2. abs 110oC → 10 kg/cm2. abs 120oC → 33 kg/cm2. abs 140oC

(f =

(750 NM3/Hr) 7 Kgabs → 20 kgabs → 31 kgabs → 33 kgabs.

133
 Nuclear Engineering
Nuclear Fission: Atoms with same atomic number but with different atomic masses are called Isotope.
Isotopes of certain heavier elements tend to become unstable and as a result they split into two
fragments of nearly equal masses. This splitting is accompanied by a loss of matter which is converted
to energy. This process is called Nuclear Fission and the energy thus liberated from the atom is called
Atomic Energy.
The energy liberated is, by Einstein law E = mc2
m = mass of matter disappeared
c = velocity of light.
Chain reaction: When U235 nucleus absorbs a neutron it gets converted to U236.
U92235 + n01→ U92236
This nucleus U236 which is in a highly unstable state, splits into two lighter fragments in
addition to two neutrons. Then two neutrons would then be captured by two more nucleus of U235 to
give rise to 4 neutrons and so on such that a chain reaction is established.
In practice, however, the neutrons moving with high energy escape the neighbouring atom and
hence results in neutron loss and decay of chain reaction. The probability of neutron capture by
neighboring U235 nucleus would be increased, if the neutrons are slowed down. A substance which
slows down the neutron is called a moderator. The slow reaction is called thermal reaction and the
reactor thermal reactor. In contrast reactors where in the neutrons are not moderated or slowed down
are called “Fast Reactors”,
Critical Mass: The minimum spherical mass which ensures adequate nuclei for sustaining a chain
reaction is called critical mass. In the case of U235 the critical mass is of the order of a few kilograms.
500 MWe coal fire station requires 4000 Te/day coal
500 MWe Nuclear power station requires just 200 kg of ‘U’.
Fusion: Atoms of same lighter elements have a tendency to fuse into an atom of heavier element. This
phenomenon is called Fusion Reaction. This too is accompanied by a loss of matter which is converted
into energy.
In the case of fusion, the % loss of the matter being 5 times that in the case of fission, energy
released in fusion is proportionately greater.
Fertile atom: This by itself can’t take part in a nuclear reaction, but can be converted into one that takes
part in a nuclear reaction. Such an atom is called a ‘Fertile atom’ U-238, Th-232 are examples.
+ → +r
→ (Neptunium)
→ (fissile)
Only three nuclides, having sufficient stability to permit storage for a long time, namely U-233, U-235
and Pu-239 are fissionable by neutrons of all energies from thermal neutrons to neutrons of millions of
eV
Of these three U-233, U-235 & PU-239 only U235 is naturally available (~ 0.7%) the other two are
produced artificially from Th232 and U238 by neutron capturing followed by 2 stages of radioactive
decays.
The essential requirements for moderator for thermal reactors are low mass number, small
absorption cross section, and fairly large scattering cross section.
Moderators: Water, Heavy Water, beryllium, Carbon and Zirconium Hydride.
Component Units
# Unit of Activity (radionuclide) is Becquerel (Bq) (1/s)
Tritium content in water = 1 gego Bq.
Curie = 3.7 x 1010 Bq
# Unit of Absorbed dose (radiation) is gray (Gy) (J/Kg)
-2
Rad = 10 Gy.
# Unit of Dose equivalent (radiation) is Sievert (Sv) (I/Kg)
-2
Rem = 10 Sv bv

134
  A sample of radio nuclide decaying at the rate of 1 disintegration per sec (1 dis/s) is defined as
having an activity of 1 Becquerel (1 Bq). One Curie (1Ci) is defined as the activity of a
radionuclide decaying at the rate of 3.7 x 1010 dis/s.

 The radiation dose, more exactly absorbed dose is defined in terms of amount of energy
absorbed by a material by ionizing radiation. Unit rad (radiation absorbed dose) rad is defined
as the amount of radiation that leads to the deposition of 10-2 J of energy per kilogram of the
absorbing material.

 The radiation intensity (Exposure rate) is expressed in terms of roentgens per unit time and the
absorbed dose in rads per unit time.

 The Biological effect of ionizing radiation depends not only on the amount of energy absorbed
per gram (in rads) but also on the other factors. The effect of a given absorbed dose is
expressed in terms of the dose equaivalent for which the unit is rem (radiation equivalent in
man).

If D is the absorbed dose in rads, the dose equivalent in rem is defined by

DE (rem) = D (radi) x QUF x MF
QF = quality factor for the given radiation.
MF = Modifying other factors.
Max doses for occupationally exposed individual
Part of body Rems per quarter
Whole body: Head & 1 (3 rem/quarter is permitted
trunk active blood provided accumulated dose doesn’t
forming organs. Lem of exceed 5 (N-18) rems at age N years)
eye.
Hands and fore arms 18¾
Feet & ankles
Skin of whole body 7½

For general public, the whole body dose to any individual is limited to a max 500 millirems
(mrems) per annum.

135
 On line H2S Analyzer:
One metal oxide semiconductor sensor is existing. Its temp. is maintained at 170oC. When it
adsorbs H2S, its resistance decreases.
It’s calibrated for H2S concentration.
Intrinsic Safety: is defined as a protection technique based upon the restriction of electrical energy
within apparatus and of interconnected wiring, exposed to a potentially explosive atmosphere to a
level below that which can cause ignition by either sparking or heating effects.
Booster Logics:
1. Very low lube oil pressure → 1.2 kg/cm2g

2. S/O O/H tank level very low

3. Cooling water leakage in motor.

4. High High axial displacement: 28 mils.

5. High High radial vibration. 75 (micrometer) (~3 mils)

6. Main Motor stator winding temp high: 120oC

7. Journal bearing temp very high: 120oC

8. S/O temp after cooler temp very high: 55oC (30 mils time delay)

II Remote trip from PLC

1. Scram

2. Class-IV failure

3. If any of the SDVs in the gas loop close

4. Flow low to compressor

5. Very high sump level of C.T & H.T

6. Hand trip from CCR

Start up Interlocks:
1. L/O tank level very low

2. S/o O/H tank level low

3. S/O O/H eng. Tank level low

4. L/O & S/o after cooler temp. low (35oC)

Seal Oil used is Turbinol-46 (ρ = 0.86 gm/cc at 15oC)

Heating oil = Hytherm
H2S solubility in oil = 1952 ppm at 10 atm
= 3915 ppm at 20 atm
XU-I & II Booster differences:
S.No XU-II Borsig XU-I BHEL
01. S/o O/H tank LCV is in the LCV is on S/o I/L line U/s of O/H

136
 cooling oil return line to reservoir tank
02 Oil Consumption Oil Consumption
Running : 15 to 20 lpd Running: 200 lpd
Not running: 150 to 200 lpd Not running: 35 to 40 lpd
03 Seal Cooling Provision No cooling oil provision But LP
side oil taken care of seal cooling
alarm
04 Trapped Bush feed’ Floating oil filter seals
05 2300 KW 2500 KW
06 Seal rotator LP, HP seals are stationary

137
CWS: 1. Langlier Index (LI) = pH –pHS
LI = 0 No. scales, no corrosion
LI = +ve scaling
LI = -ve corrosion
2. Ryznar Index = 2 pHS-pH
RI = 6.5 – 7.5 → No corrosion, no scaling.
RI = <6.5 → Scale formation
RI = >7.5 → Corrosion
pHS → pH at CaCO3 saturation.

138
 DG Set
DG starts automatically when Class-IV power fails. The under voltage relay (<80% of rated
voltage) gets activated and gives signal (24V) to self motor starter (DC motor is there for cranking)
which in turn rotate the flywheel of the engine. At 25% of full speed (1500 rpm) ignition starts
automatically due to high temp.
Both DGs start together when they are in auto mode and load will be taken according to the
selection switch and the other DG stops. In case of any problem of taking the load, other DG which
is running will take the load.
1250 KVA, 415V, 50 HZ, PF=0.8, 24V D.C lead acid battery.

139
 Hydrate formation temp.

T (oK) = 9.3987 ln(p) + 230.15

P = abs. Pr. in KPa
At 18.5 kg/cm hdyrate formation temp is 28.35oC
2

DCV: Each deluge valve can spray water at the rate of 122 M3/Hr.
TLV for H2S = 10 ppm; SO2 = 2 ppm
STEL : for H2S =15ppm; SO2 = 5 ppm
STEL Short Term Exposure Limit: 15 mts.
Time weighed avg. exposure, which shall not exceed at any time during a working day even if the 8
hrs. time weighed avg. is within TLV.
Exposure at STEL should not be larger than 15 mts and should not be repeated more than 4 times per
day. There should be at least 60 mts between successive exposures at the STEL.
Limits for Public: H2S in air (ppm) SO2 in air (ppm)
1. Max. 1 hr. average 0.15 0.14

2. 24 hrs. daily average 0.05 0.05

3. 24 hrs. annual average 0.005 0.013

Effects of H2S
0.15 ppm Min. perceptible odour
10 ppm TLV
27 ppm Strong, Unpleasant odour
50-100 ppm Mild conjunctivitis, respiratory track irritation
in ½ to 1 hr.
100-150 ppm Loss of sense of smell, conjunctivitis, cough,
respiration track irritation 2 to 15 min.
500-600 ppm Cough – Collapse and unconsciousness in 0 to
2 min. death 1 to 4 hrs.
1000 ppm Immediate unconsciousness, rapid death.

Tritium
Max. Permissible concn in air = 2 x 10-7 cubic/M3
Max. Permissible concn in water = 3 x 10-3 cubic/M3
Half life of Tritium = 12 ½ years
Cr% Ni% Mo% C(Max.)% Fe%
SS 304 19 9 0 0.08 Rest
SS 3042 19 10 0 0.03 Rest
SS 316 18 11 2.5 0.1 Rest
SS 3162 17 12 2.0 0.03 Rest
2RK65 19 25 4.5 0.02 Cu1.5

Inconel 600 (RD) Ni. 80%; Cr:16%; Fe.4%

ASTM 516 gr. 70 → Silica – Al Killed?

Silica Killer means adding of silica at approx.. (0.15%-0.3%). Silicon is a deoxidizer element. Silicon
helps in avoiding hydrogen blistering. Al. killed steels have fine grains and higher impact properties at
low temps. Al content is 0.015 to 0.05%

140